National Library of Energy BETA

Sample records for manganese superoxide dismutase

  1. Investigation of the Highly Active Manganese Superoxide Dismutase from Saccharomyces cerevisiae

    SciTech Connect (OSTI)

    Cabelli, D.E.; Barnese, K.; Sheng, Y.; Stich, T.A.; Gralla, E.B.; Britt, R.D.; Valentine, J.S.

    2010-09-15

    Manganese superoxide dismutase (MnSOD) from different species differs in its efficiency in removing high concentrations of superoxide (O{sub 2}{sup -}), due to different levels of product inhibition. Human MnSOD exhibits a substantially higher level of product inhibition than the MnSODs from bacteria. In order to investigate the mechanism of product inhibition and whether it is a feature common to eukaryotic MnSODs, we purified MnSOD from Saccharomyces cerevisiae (ScMnSOD). It was a tetramer with 0.6 equiv of Mn per monomer. The catalytic activity of ScMnSOD was investigated by pulse radiolysis and compared with human and two bacterial (Escherichia coli and Deinococcus radiodurans) MnSODs. To our surprise, ScMnSOD most efficiently facilitates removal of high concentrations of O{sub 2}{sup -} among these MnSODs. The gating value k{sub 2}/k{sub 3} that characterizes the level of product inhibition scales as ScMnSOD > D. radiodurans MnSOD > E. coli MnSOD > human MnSOD. While most MnSODs rest as the oxidized form, ScMnSOD was isolated in the Mn{sup 2+} oxidation state as revealed by its optical and electron paramagnetic resonance spectra. This finding poses the possibility of elucidating the origin of product inhibition by comparing human MnSOD with ScMnSOD.

  2. The structure of the Caenorhabditis elegans manganese superoxide dismutase MnSOD-3-azide complex

    DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)

    Hunter, Gary J.; Trinh, Chi H.; Bonetta, Rosalin; Stewart, Emma E.; Cabelli, Diane E.; Hunter, Therese

    2015-08-27

    C. elegans MnSOD-3 has been implicated in the longevity pathway and its mechanism of catalysis is relevant to the aging process and carcinogenesis. The structures of MnSOD-3 provide unique crystallographic evidence of a dynamic region of the tetrameric interface (residues 41–54). We have determined the structure of the MnSOD-3-azide complex to 1.77-Å resolution. The analysis of this complex shows that the substrate analog, azide, binds end-on to the manganese center as a sixth ligand and that it ligates directly to a third and new solvent molecule also positioned within interacting distance to the His30 and Tyr34 residues of the substratemore » access funnel. This is the first structure of a eukaryotic MnSOD-azide complex that demonstrates the extended, uninterrupted hydrogen-bonded network that forms a proton relay incorporating three outer sphere solvent molecules, the substrate analog, the gateway residues, Gln142, and the solvent ligand. This configuration supports the formation and release of the hydrogen peroxide product in agreement with the 5-6-5 catalytic mechanism for MnSOD. The high product dissociation constant k₄ of MnSOD-3 reflects low product inhibition making this enzyme efficient even at high levels of superoxide.« less

  3. The structure of the Caenorhabditis elegans manganese superoxide dismutase MnSOD-3-azide complex

    SciTech Connect (OSTI)

    Hunter, Gary J.; Trinh, Chi H.; Bonetta, Rosalin; Stewart, Emma E.; Cabelli, Diane E.; Hunter, Therese

    2015-08-27

    C. elegans MnSOD-3 has been implicated in the longevity pathway and its mechanism of catalysis is relevant to the aging process and carcinogenesis. The structures of MnSOD-3 provide unique crystallographic evidence of a dynamic region of the tetrameric interface (residues 4154). We have determined the structure of the MnSOD-3-azide complex to 1.77- resolution. The analysis of this complex shows that the substrate analog, azide, binds end-on to the manganese center as a sixth ligand and that it ligates directly to a third and new solvent molecule also positioned within interacting distance to the His30 and Tyr34 residues of the substrate access funnel. This is the first structure of a eukaryotic MnSOD-azide complex that demonstrates the extended, uninterrupted hydrogen-bonded network that forms a proton relay incorporating three outer sphere solvent molecules, the substrate analog, the gateway residues, Gln142, and the solvent ligand. This configuration supports the formation and release of the hydrogen peroxide product in agreement with the 5-6-5 catalytic mechanism for MnSOD. The high product dissociation constant k? of MnSOD-3 reflects low product inhibition making this enzyme efficient even at high levels of superoxide.

  4. Biologically Relevant Mechanism For Catalytic Removal of Superoxide by Simple Manganese Compounds

    SciTech Connect (OSTI)

    Barnese K.; Cabelli D.; Gralla, E.B.; Valentine, J.S.

    2012-05-01

    Nonenzymatic manganese was first shown to provide protection against superoxide toxicity in vivo in 1981, but the chemical mechanism responsible for this protection subsequently became controversial due to conflicting reports concerning the ability of Mn to catalyze superoxide disproportionation in vitro. In a recent communication, we reported that low concentrations of a simple Mn phosphate salt under physiologically relevant conditions will indeed catalyze superoxide disproportionation in vitro. We report now that two of the four Mn complexes that are expected to be most abundant in vivo, Mn phosphate and Mn carbonate, can catalyze superoxide disproportionation at physiologically relevant concentrations and pH, whereas Mn pyrophosphate and citrate complexes cannot. Additionally, the chemical mechanisms of these reactions have been studied in detail, and the rates of reactions of the catalytic removal of superoxide by Mn phosphate and carbonate have been modeled. Physiologically relevant concentrations of these compounds were found to be sufficient to mimic an effective concentration of enzymatic superoxide dismutase found in vivo. This mechanism provides a likely explanation as to how Mn combats superoxide stress in cellular systems.

  5. Nickel superoxide dismutase: structural and functional roles of His1 and its H-bonding network

    DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)

    Maroney, Michael J.; Cabelli, Diane E.; Ryan, Kelly C.; Guce, Abigail I.; Johnson, Olivia E.; Brunold, Thomas C.; Garman, Scott C.

    2015-01-21

    Crystal structures of nickel-dependent superoxide dismutases (NiSODs) reveal the presence of a H-bonding network formed between the NH group of the apical imidazole ligand from His1 and the Glu17 carboxylate from a neighboring subunit in the hexameric enzyme. This interaction is supported by another intrasubunit H-bond between Glu17 and Arg47. In this study, four mutant NiSOD proteins were produced to experimentally evaluate the roles of this H-bonding network and compare the results with prior predictions from density functional theory calculations. The X-ray crystal structure of H1A-NiSOD, which lacks the apical ligand entirely, reveals that in the absence of the Glu17-His1more » H-bond, the active site is disordered. Characterization of this variant using X-ray absorption spectroscopy (XAS) shows that Ni(II) is bound in the expected N₂S₂ planar coordination site. Despite these structural perturbations, the H1A-NiSOD variant retains 4% of wild-type (WT) NiSOD activity. Three other mutations were designed to preserve the apical imidazole ligand but perturb the H-bonding network: R47A-NiSOD, which lacks the intramolecular H-bonding interaction; E17R/R47A-NiSOD, which retains the intramolecular H-bond but lacks the intermolecular Glu17-His1 H-bond; and E17A/R47ANiSOD, which lacks both H-bonding interactions. These variants were characterized by a combination of techniques, including XAS to probe the nickel site structure, kinetic studies employing pulse-radiolytic production of superoxide, and electron paramagnetic resonance to assess the Ni redox activity. The results indicate that in addition to the roles in redox tuning suggested on the basis of previous computational studies, the Glu17-His1 H-bond plays an important structural role in the proper folding of the “Ni-hook” motif that is a critical feature of the active site.« less

  6. Nickel superoxide dismutase: structural and functional roles of His1 and its H-bonding network

    SciTech Connect (OSTI)

    Maroney, Michael J.; Cabelli, Diane E.; Ryan, Kelly C.; Guce, Abigail I.; Johnson, Olivia E.; Brunold, Thomas C.; Garman, Scott C.

    2015-01-21

    Crystal structures of nickel-dependent superoxide dismutases (NiSODs) reveal the presence of a H-bonding network formed between the NH group of the apical imidazole ligand from His1 and the Glu17 carboxylate from a neighboring subunit in the hexameric enzyme. This interaction is supported by another intrasubunit H-bond between Glu17 and Arg47. In this study, four mutant NiSOD proteins were produced to experimentally evaluate the roles of this H-bonding network and compare the results with prior predictions from density functional theory calculations. The X-ray crystal structure of H1A-NiSOD, which lacks the apical ligand entirely, reveals that in the absence of the Glu17-His1 H-bond, the active site is disordered. Characterization of this variant using X-ray absorption spectroscopy (XAS) shows that Ni(II) is bound in the expected N?S? planar coordination site. Despite these structural perturbations, the H1A-NiSOD variant retains 4% of wild-type (WT) NiSOD activity. Three other mutations were designed to preserve the apical imidazole ligand but perturb the H-bonding network: R47A-NiSOD, which lacks the intramolecular H-bonding interaction; E17R/R47A-NiSOD, which retains the intramolecular H-bond but lacks the intermolecular Glu17-His1 H-bond; and E17A/R47ANiSOD, which lacks both H-bonding interactions. These variants were characterized by a combination of techniques, including XAS to probe the nickel site structure, kinetic studies employing pulse-radiolytic production of superoxide, and electron paramagnetic resonance to assess the Ni redox activity. The results indicate that in addition to the roles in redox tuning suggested on the basis of previous computational studies, the Glu17-His1 H-bond plays an important structural role in the proper folding of the Ni-hook motif that is a critical feature of the active site.

  7. Structural, functional and immunogenic insights on Cu,Zn superoxide dismutase pathogenic virulence factors from Neisseria meningitidis and Brucella abortus

    DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)

    Pratt, Ashley J.; DiDonato, Michael; Shin, David S.; Cabelli, Diane E.; Bruns, Cami K.; Belzer, Carol A.; Gorringe, Andrew R.; Langford, Paul R.; Tabatabai, Louisa B.; Kroll, J. Simon; et al

    2015-10-12

    Bacterial pathogens Neisseria meningitidis and Brucella abortus pose threats to human and animal health worldwide, causing meningococcal disease and brucellosis, respectively. Mortality from acute N. meningitidis infections remains high despite antibiotics, and brucellosis presents alimentary and health consequences. Superoxide dismutases are master regulators of reactive oxygen, general pathogenicity factors and therefore therapeutic targets. Cu,Zn superoxide dismutases (SODs) localized to the periplasm promote survival by detoxifying superoxide radicals generated by major host antimicrobial immune responses. We discovered that passive immunization with an antibody directed at N. meningitidis SOD (NmSOD) was protective in a mouse infection model. To define the relevant atomicmore » details and solution assembly states of this important virulence factor, we report high-resolution and X-ray scattering analyses of NmSOD and SOD from B. abortus (BaSOD). The NmSOD structures revealed an auxiliary tetrahedral Cu-binding site bridging the dimer interface; mutational analyses suggested that this metal site contributes to protein stability, with implications for bacterial defense mechanisms. Biochemical and structural analyses informed us about electrostatic substrate guidance, dimer assembly and an exposed C-terminal epitope in the NmSOD dimer. In contrast, the monomeric BaSOD structure provided insights for extending immunogenic peptide epitopes derived from the protein. These collective results reveal unique contributions of SOD to pathogenic virulence, refine predictive motifs for distinguishing SOD classes and suggest general targets for anti-bacterial immune responses. The identified functional contributions, motifs, and targets distinguishing bacterial and eukaryotic SOD assemblies presented here provide a foundation for efforts to develop SOD-specific inhibitors or vaccines against these harmful pathogens. IMPORTANCE By protecting microbes against reactive oxygen insults, Cu,Zn superoxide dismutases (SODs) aid survival of many bacteria within their hosts. Despite the ubiquity and conservation of these key enzymes, notable species-specific differences relevant to pathogenesis remain undefined. To probe mechanisms that govern the functioning of Neisseria meningitidis and Brucella abortus SODs, we used X-ray structures, enzymology, modeling and murine infection experiments. We identified virulence determinants common to both homologs, assembly differences and a unique metal reservoir within meningococcal SOD that stabilizes the enzyme and may provide a safeguard against copper toxicity. The insights reported here provide a rationale and basis for SOD-specific drugs and extension of immunogen design to target two important pathogens that continue to pose global health threats.« less

  8. Reactive oxygen species on bone mineral density and mechanics in Cu,Zn superoxide dismutase (Sod1) knockout mice

    SciTech Connect (OSTI)

    Smietana, Michael J.; Arruda, Ellen M.; Mechanical Engineering, University of Michigan, 2250 GG Brown, 2350 Hayward, Ann Arbor, MI 48109; Program in Macromolecular Science and Engineering, University of Michigan, 2250 GG Brown, 2350 Hayward, Ann Arbor, MI 48109 ; Faulkner, John A.; Brooks, Susan V.; Molecular and Integrative Physiology, University of Michigan, 2025 BSRB, 109 Zina Pitcher Place, Ann Arbor, MI 48109-2200 ; Larkin, Lisa M.

    2010-12-03

    Research highlights: {yields} Reactive oxygen species (ROS) are considered to be a factor in the onset of a number of age-associated conditions, including loss of BMD. {yields} Cu,Zn-superoxide dismutase (Sod1) deficient mice have increased ROS, reduced bone mineral density, decreased bending stiffness, and decreased strength compared to WT controls. {yields} Increased ROS caused by the deficiency of Sod1, may be responsible for the changes in BMD and bone mechanics and therefore represent an appropriate model for studying mechanisms of age-associated bone loss. -- Abstract: Reactive oxygen species (ROS) play a role in a number of degenerative conditions including osteoporosis. Mice deficient in Cu,Zn-superoxide dismutase (Sod1) (Sod1{sup -/-} mice) have elevated oxidative stress and decreased muscle mass and strength compared to wild-type mice (WT) and appear to have an accelerated muscular aging phenotype. Thus, Sod1{sup -/-} mice may be a good model for evaluating the effects of free radical generation on diseases associated with aging. In this experiment, we tested the hypothesis that the structural integrity of bone as measured by bending stiffness (EI; N/mm{sup 2}) and strength (MPa) is diminished in Sod1{sup -/-} compared to WT mice. Femurs were obtained from male and female WT and Sod1{sup -/-} mice at 8 months of age and three-point bending tests were used to determine bending stiffness and strength. Bones were also analyzed for bone mineral density (BMD; mg/cc) using micro-computed tomography. Femurs were approximately equal in length across all groups, and there were no significant differences in BMD or EI with respect to gender in either genotype. Although male and female mice demonstrated similar properties within each genotype, Sod1{sup -/-} mice exhibited lower BMD and EI of femurs from both males and females compared with gender matched WT mice. Strength of femurs was also lower in Sod1{sup -/-} mice compared to WT as well as between genders. These data indicate that increased oxidative stress, due to the deficiency of Sod1 is associated with decreased bone stiffness and strength and Sod1{sup -/-} mice may represent an appropriate model for studying disease processes in aging bone.

  9. Structural, functional and immunogenic insights on Cu,Zn superoxide dismutase pathogenic virulence factors from Neisseria meningitidis and Brucella abortus

    SciTech Connect (OSTI)

    Pratt, Ashley J.; DiDonato, Michael; Shin, David S.; Cabelli, Diane E.; Bruns, Cami K.; Belzer, Carol A.; Gorringe, Andrew R.; Langford, Paul R.; Tabatabai, Louisa B.; Kroll, J. Simon; Tainer, John A.; Getzoff, Elizabeth D.

    2015-10-12

    Bacterial pathogens Neisseria meningitidis and Brucella abortus pose threats to human and animal health worldwide, causing meningococcal disease and brucellosis, respectively. Mortality from acute N. meningitidis infections remains high despite antibiotics, and brucellosis presents alimentary and health consequences. Superoxide dismutases are master regulators of reactive oxygen, general pathogenicity factors and therefore therapeutic targets. Cu,Zn superoxide dismutases (SODs) localized to the periplasm promote survival by detoxifying superoxide radicals generated by major host antimicrobial immune responses. We discovered that passive immunization with an antibody directed at N. meningitidis SOD (NmSOD) was protective in a mouse infection model. To define the relevant atomic details and solution assembly states of this important virulence factor, we report high-resolution and X-ray scattering analyses of NmSOD and SOD from B. abortus (BaSOD). The NmSOD structures revealed an auxiliary tetrahedral Cu-binding site bridging the dimer interface; mutational analyses suggested that this metal site contributes to protein stability, with implications for bacterial defense mechanisms. Biochemical and structural analyses informed us about electrostatic substrate guidance, dimer assembly and an exposed C-terminal epitope in the NmSOD dimer. In contrast, the monomeric BaSOD structure provided insights for extending immunogenic peptide epitopes derived from the protein. These collective results reveal unique contributions of SOD to pathogenic virulence, refine predictive motifs for distinguishing SOD classes and suggest general targets for anti-bacterial immune responses. The identified functional contributions, motifs, and targets distinguishing bacterial and eukaryotic SOD assemblies presented here provide a foundation for efforts to develop SOD-specific inhibitors or vaccines against these harmful pathogens.

    IMPORTANCE By protecting microbes against reactive oxygen insults, Cu,Zn superoxide dismutases (SODs) aid survival of many bacteria within their hosts. Despite the ubiquity and conservation of these key enzymes, notable species-specific differences relevant to pathogenesis remain undefined. To probe mechanisms that govern the functioning of Neisseria meningitidis and Brucella abortus SODs, we used X-ray structures, enzymology, modeling and murine infection experiments. We identified virulence determinants common to both homologs, assembly differences and a unique metal reservoir within meningococcal SOD that stabilizes the enzyme and may provide a safeguard against copper toxicity. The insights reported here provide a rationale and basis for SOD-specific drugs and extension of immunogen design to target two important pathogens that continue to pose global health threats.

  10. The Superoxide Reductase from the Early Diverging Eukaryote Giardia Intestinalis

    SciTech Connect (OSTI)

    Cabelli, D.E.; Testa, F.; Mastronicola, D.; Bordi, E.; Pucillo, L.P.; Sarti, P.; Saraiva, L.M.; Giuffre, A.; Teixeira, M.

    2011-10-15

    Unlike superoxide dismutases (SODs), superoxidereductases (SORs) eliminate superoxide anion (O{sub 2}{sup {sm_bullet}-}) not through its dismutation, but via reduction to hydrogen peroxide (H{sub 2}O{sub 2}) in the presence of an electron donor. The microaerobic protist Giardia intestinalis, responsible for a common intestinal disease in humans, though lacking SOD and other canonical reactive oxygen species-detoxifying systems, is among the very few eukaryotes encoding a SOR yet identified. In this study, the recombinant SOR from Giardia (SOR{sub Gi}) was purified and characterized by pulse radiolysis and stopped-flow spectrophotometry. The protein, isolated in the reduced state, after oxidation by superoxide or hexachloroiridate(IV), yields a resting species (T{sub final}) with Fe{sup 3+} ligated to glutamate or hydroxide depending on pH (apparent pK{sub a} = 8.7). Although showing negligible SOD activity, reduced SOR{sub Gi} reacts with O{sub 2}{sup {sm_bullet}-} with a pH-independent second-order rate constant k{sub 1} = 1.0 x 10{sup 9} M{sup -1} s{sup -1} and yields the ferric-(hydro)peroxo intermediate T{sub 1}; this in turn rapidly decays to the T{sub final} state with pH-dependent rates, without populating other detectable intermediates. Immunoblotting assays show that SOR{sub Gi} is expressed in the disease-causing trophozoite of Giardia. We propose that the superoxide-scavenging activity of SOR in Giardia may promote the survival of this air-sensitive parasite in the fairly aerobic proximal human small intestine during infection.

  11. Manganese uptake of imprinted polymers

    SciTech Connect (OSTI)

    Susanna Ventura

    2015-09-30

    Batch tests of manganese imprinted polymers of variable composition to assess their ability to extract lithium and manganese from synthetic brines at T=45C . Data on manganese uptake for two consecutive cycles are included.

  12. Structural Determination of Marine Bacteriogenic Manganese Oxides

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    Determination of Marine Bacteriogenic Manganese Oxides John R. Bargar1, Samuel M. Webb2, and Bradley M. Tebo2 1Stanford Synchrotron Radiation Laboratory 2Oregon Health and Sciences University Figure 1. Top: Half of the Earth's annual photosynthetic CO2 fixation budget is attributable to oceanic phytoplankton. Mangan-ese required for this photo-synthetic activity is derived largely from bacteriogenic man-ganese oxides. Bottom: man-ganese oxides precipitated around a spore (cell) of the marine

  13. Superoxide reduction by a superoxide reductase lacking the highly conserved lysine residue

    SciTech Connect (OSTI)

    Teixeira, Miguel; Cabelli, Diane; Pinto, Ana F.; Romao, Celia V.; Pinto, Liliana C.; Huber, Harald; Saraiva, Ligia M.; Todorovic, Smilja

    2014-12-05

    Superoxide reductases (SORs) are the most recently identified superoxide detoxification systems, being found in microorganisms from the three domains of life. These enzymes are characterized by a catalytic mononuclear iron site, with one cysteine and four histidine ligands of the ferrous active form. A lysine residue in the EKHVP motif, located close to the active site, has been considered to be essential for the enzyme function, by contributing to the positive surface patch that attracts the superoxide anion and by controlling the chemistry of the catalytic mechanism through a hydrogen bond network. However, we show here that this residue is substituted by non-equivalent amino acids in several putative SORs from Archaea and unicellular Eukarya. In this work, we focus on mechanistic and spectroscopic studies of one of these less common enzymes, the SOR from the hyperthermophilic crenarchaeon Ignicoccus hospitalis. We employ pulse radiolysis fast kinetics and spectroscopic approaches to study the wild-type enzyme (?E??T??HVP?), and two mutants, T24K and E23A, the later mimicking enzymes lacking both the lysine and glutamate (a ferric ion ligand) of the motif. The efficiency of the wild type protein and mutants in reducing superoxide is comparable to other SORs, revealing the robustness of these enzymes to single mutations.

  14. Superoxide reduction by a superoxide reductase lacking the highly conserved lysine residue

    DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)

    Teixeira, Miguel; Cabelli, Diane; Pinto, Ana F.; Romao, Celia V.; Pinto, Liliana C.; Huber, Harald; Saraiva, Ligia M.; Todorovic, Smilja

    2014-12-05

    Superoxide reductases (SORs) are the most recently identified superoxide detoxification systems, being found in microorganisms from the three domains of life. These enzymes are characterized by a catalytic mononuclear iron site, with one cysteine and four histidine ligands of the ferrous active form. A lysine residue in the –EKHVP– motif, located close to the active site, has been considered to be essential for the enzyme function, by contributing to the positive surface patch that attracts the superoxide anion and by controlling the chemistry of the catalytic mechanism through a hydrogen bond network. However, we show here that this residue ismore » substituted by non-equivalent amino acids in several putative SORs from Archaea and unicellular Eukarya. In this work, we focus on mechanistic and spectroscopic studies of one of these less common enzymes, the SOR from the hyperthermophilic crenarchaeon Ignicoccus hospitalis. We employ pulse radiolysis fast kinetics and spectroscopic approaches to study the wild-type enzyme (₋E₂₃T₂₄HVP₋), and two mutants, T24K and E23A, the later mimicking enzymes lacking both the lysine and glutamate (a ferric ion ligand) of the motif. The efficiency of the wild type protein and mutants in reducing superoxide is comparable to other SORs, revealing the robustness of these enzymes to single mutations.« less

  15. New manganese catalyst for light alkane oxidation

    DOE Patents [OSTI]

    Durante, Vincent A.; Lyons, James E.; Walker, Darrell W.; Marcus, Bonita K.

    1994-01-01

    Aluminophosphates containing manganese in the structural framework are employed for the oxidation of alkanes, for example the vapor phase oxidation of methane to methanol.

  16. Examining Hysteresis in Lithium- and Manganese-Rich Composite...

    Office of Energy Efficiency and Renewable Energy (EERE) Indexed Site

    Hysteresis in Lithium- and Manganese-Rich Composite Cathode Materials Examining Hysteresis in Lithium- and Manganese-Rich Composite Cathode Materials 2013 DOE Hydrogen and Fuel...

  17. Addressing the Voltage Fade Issue with Lithium-Manganese-Rich...

    Office of Energy Efficiency and Renewable Energy (EERE) Indexed Site

    Voltage Fade Issue with Lithium-Manganese-Rich Oxide Cathode Materials Addressing the Voltage Fade Issue with Lithium-Manganese-Rich Oxide Cathode Materials 2012 DOE Hydrogen and...

  18. Addressing the Voltage Fade Issue with Lithium-Manganese-Rich...

    Office of Energy Efficiency and Renewable Energy (EERE) Indexed Site

    Addressing the Voltage Fade Issue with Lithium-Manganese-Rich Oxide Cathode Materials Addressing the Voltage Fade Issue with Lithium-Manganese-Rich Oxide Cathode Materials 2013 DOE...

  19. Molecular Interactions of Plutonium(VI) with SyntheticManganese...

    Office of Scientific and Technical Information (OSTI)

    We chose to study the influence of manganese as a minor component in goethite, because goethite rarely exists as a pure phase in nature. Manganese X-ray absorption near-edge ...

  20. Silver manganese oxide electrodes for lithium batteries

    DOE Patents [OSTI]

    Thackeray, Michael M.; Vaughey, John T.; Dees, Dennis W.

    2006-05-09

    This invention relates to electrodes for non-aqueous lithium cells and batteries with silver manganese oxide positive electrodes, denoted AgxMnOy, in which x and y are such that the manganese ions in the charged or partially charged electrodes cells have an average oxidation state greater than 3.5. The silver manganese oxide electrodes optionally contain silver powder and/or silver foil to assist in current collection at the electrodes and to improve the power capability of the cells or batteries. The invention relates also to a method for preparing AgxMnOy electrodes by decomposition of a permanganate salt, such as AgMnO4, or by the decomposition of KMnO4 or LiMnO4 in the presence of a silver salt.

  1. Manganese Oxide Composite Electrodes for Lithium Batteries | Argonne

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    National Laboratory Manganese Oxide Composite Electrodes for Lithium Batteries Technology available for licensing: Improved spinel-containing "layered-layered" lithium metal oxide electrodes Materials costs reduced with use of manganese Improves "layered-layered" lithium metal oxide electrode spinel has higher voltage, increased stability, minimized voltage fade PDF icon manganese_oxide_electrodes

  2. Suppressing Manganese Dissolution from Lithium Manganese Oxide Spinel Cathodes with Single-Layer Graphene

    SciTech Connect (OSTI)

    Jaber-Ansari, Laila; Puntambekar, Kanan P.; Kim, Soo; Aykol, Muratahan; Luo, Langli; Wu, Jinsong; Myers, Benjamin D.; Iddir, Hakim; Russell, John T.; Saldana, Spencer J.; Kumar, Rajan; Thackeray, Michael M.; Curtiss, Larry A.; Dravid, Vinayak P.; Wolverton, Christopher M.; Hersam, Mark C.

    2015-06-24

    Spinel-structured LiMn 2 O 4 (LMO) is a desirable cathode material for Li-ion batteries due to its low cost, abundance, and high power capability. However, LMO suffers from limited cycle life that is triggered by manganese dissolution into the electrolyte during electrochemical cycling. Here, it is shown that single-layer graphene coatings suppress manganese dissolution, thus enhancing the performance and lifetime of LMO cathodes. Relative to lithium cells with uncoated LMO cathodes, cells with graphene-coated LMO cathodes provide improved capacity retention with enhanced cycling stability. X-ray photoelectron spectroscopy reveals that graphene coatings inhibit manganese depletion from the LMO surface. Additionally, transmission electron microscopy demonstrates that a stable solid electrolyte interphase is formed on graphene, which screens the LMO from direct contact with the electrolyte. Density functional theory calculations provide two mechanisms for the role of graphene in the suppression of manganese dissolution. First, common defects in single-layer graphene are found to allow the transport of lithium while concurrently acting as barriers for manganese diffusion. Second, graphene can chemically interact with Mn 3+ at the LMO electrode surface, promoting an oxidation state change to Mn 4+ , which suppresses dissolution.

  3. Structural Sequestration of Uranium in Bacteriogenic Manganese Oxides

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    Sequestration of Uranium in Bacteriogenic Manganese Oxides Samuel M. Webb (Stanford Synchrotron Radiation Laboratory), Bradley M. Tebo (Oregon Health and Science University), and John Bargar (Stanford Synchrotron Radiation Laboratory). Microbial Respiration Figure 1. Manganese oxides precipitated around a spore (cell) of the marine Mn(II)-oxidizing bacterium, Bacillus sp., strain SG-1. This cell is about 0.5 µm diameter (small axis). Manganese oxides are formed in soils, watersheds, and sea

  4. Manganese oxide nanowires, films, and membranes and methods of making

    DOE Patents [OSTI]

    Suib, Steven Lawrence (Storrs, CT); Yuan, Jikang (Storrs, CT)

    2011-02-15

    Nanowires, films, and membranes comprising ordered porous manganese oxide-based octahedral molecular sieves and methods of making the same are disclosed. A method for forming nanowires includes hydrothermally treating a chemical precursor composition in a hydrothermal treating solvent to form the nanowires, wherein the chemical precursor composition comprises a source of manganese cations and a source of counter cations, and wherein the nanowires comprise ordered porous manganese oxide-based octahedral molecular sieves.

  5. Comparing Well-Defined Manganese, Iron, Cobalt, and Nickel Ketone

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    Hydrosilylation Catalysts Comparing Well-Defined Manganese, Iron, Cobalt, and Nickel Ketone Hydrosilylation Catalysts Authors: Trovitch, R.J. Title: Comparing Well-Defined Manganese, Iron, Cobalt, and Nickel Ketone Hydrosilylation Catalysts Source: Synlett Year: 2014 Volume: published online May 8, 2014 Pages: ABSTRACT: A brief review of manganese-catalyzed hydrosilylation is presented along with a personal account of how the design for the highly active catalyst, (Ph2PPrPDI)Mn, was

  6. Manganese-Based Magnets: Manganese-Based Permanent Magnet with 40 MGOe at 200C

    SciTech Connect (OSTI)

    2012-01-01

    REACT Project: PNNL is working to reduce the cost of wind turbines and EVs by developing a manganese-based nano-composite magnet that could serve as an inexpensive alternative to rare-earth-based magnets. The manganese composite, made from low-cost and abundant materials, could exceed the performance of todays most powerful commercial magnets at temperature higher than 200C. Members of PNNLs research team will leverage comprehensive computer high-performance supercomputer modeling and materials testing to meet this objective. Manganese-based magnets could withstand higher temperatures than their rare earth predecessors and potentially reduce the need for any expensive, bulky engine cooling systems for the motor and generator. This would further contribute to cost savings for both EVs and wind turbines.

  7. Thermodynamic Investigations of Lithium- and Manganese-Rich Transition...

    Office of Energy Efficiency and Renewable Energy (EERE) Indexed Site

    LMR-NMC Materials and Electrodes Examining Hysteresis in Lithium- and Manganese-Rich Composite Cathode Materials Electrochemical Characterization of Voltage Fade in LMR-NMC cells...

  8. Environmental fate of methylcyclopentadienyl manganese tricarbonyl

    SciTech Connect (OSTI)

    Garrison, A.W.; Wolfe, N.L.; Swank, R.R. Jr.; Cipollone, M.G.

    1995-11-01

    Methylcyclopentadienyl manganese tricarbonyl (MMT) has been proposed as an octane booster for unleaded gasoline; such use could result in ecological and human exposure through surface water and groundwater ecosystems. To evaluate the environmental risks from MMT, its environmental fate constants and transformation pathways must be known. Constants for physical parameters that would likely influence MMT fate were collected from the literature or calculated; the compound`s octanol/water partition coefficient and water solubility were determined in the laboratory. Experiments were designed to screen MMT for transformation pathways that are significant over environmentally short time frames. The MMT was found to be fairly stable in the dark in aquifer materials and sediments at various Eh levels; half-lives ranged from 0.2 to 1.5 years in aquifer materials at 25 C. (These matrices were not optimized for biodegradation.) On the other hand, MMT photolyzes rapidly in distilled water; its half-life in midday sunlight in water is approximately 1 min and the disappearance quantum yield is 0.13. Photodegradation products were identified as cyclopentadiene, methyl cyclopentadiene, carbon monoxide, and a manganese carbonyl that readily oxidized to trimanganese tetroxide.

  9. A Lithium-Air Battery Based on Lithium Superoxide | Argonne National

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    Laboratory TEM images of Ir-rGO composite showing Ir nanoparticles less than 2 nm in size. (courtesy of Nature Publishing Group) TEM images of Ir-rGO composite showing Ir nanoparticles less than 2 nm in size. (courtesy of Nature Publishing Group) A Lithium-Air Battery Based on Lithium Superoxide January 20, 2016 Tweet EmailPrint Batteries based on sodium superoxide and on potassium superoxide have recently been reported. However there have been no reports of a battery based on lithium

  10. A highly active manganese precatalyst for the hydrosilylation...

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    precatalyst for the hydrosilylation of ketones and esters Authors: Mukhopadhyay, T.K., Flores, M., Groy, T.L., and Trovitch, R.J. Title: A highly active manganese precatalyst for...

  11. Manganese Reduction-Oxidation Drives Plant Debris Decomposition

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    Manganese Reduction-Oxidation Drives Plant Debris Decomposition Manganese Reduction-Oxidation Drives Plant Debris Decomposition Print Monday, 22 February 2016 00:00 Microbial decomposition of plant debris ("litter") is a keystone ecosystem process because it regulates nutrient availability, ecosystem productivity, and carbon (C) cycling. Historically, climate (primarily temperature and precipitation) has been thought to regulate the rate of litter decomposition, which then influences

  12. Examining Hysteresis in Lithium- and Manganese-Rich Composite Cathode

    Office of Energy Efficiency and Renewable Energy (EERE) Indexed Site

    Materials | Department of Energy Hysteresis in Lithium- and Manganese-Rich Composite Cathode Materials Examining Hysteresis in Lithium- and Manganese-Rich Composite Cathode Materials 2013 DOE Hydrogen and Fuel Cells Program and Vehicle Technologies Program Annual Merit Review and Peer Evaluation Meeting PDF icon es189_gallagher_2013_p.pdf More Documents & Publications Vehicle Technologies Office Merit Review 2014: Electrochemical Modeling of LMR-NMC Materials and Electrodes Vehicle

  13. Thermodynamic Investigations of Lithium- and Manganese-Rich Transition

    Energy Savers [EERE]

    Metal Oxides | Department of Energy Thermodynamic Investigations of Lithium- and Manganese-Rich Transition Metal Oxides Thermodynamic Investigations of Lithium- and Manganese-Rich Transition Metal Oxides 2013 DOE Hydrogen and Fuel Cells Program and Vehicle Technologies Program Annual Merit Review and Peer Evaluation Meeting PDF icon es192_lu_2013_p.pdf More Documents & Publications Vehicle Technologies Office Merit Review 2014: Electrochemical Modeling of LMR-NMC Materials and Electrodes

  14. Studies on Lithium Manganese Rich MNC Composite Cathodes | Department of

    Office of Energy Efficiency and Renewable Energy (EERE) Indexed Site

    Energy Lithium Manganese Rich MNC Composite Cathodes Studies on Lithium Manganese Rich MNC Composite Cathodes 2013 DOE Hydrogen and Fuel Cells Program and Vehicle Technologies Program Annual Merit Review and Peer Evaluation Meeting PDF icon es106_nanda_2013_o.pdf More Documents & Publications Vehicle Technologies Office Merit Review 2014: Electrochemical Modeling of LMR-NMC Materials and Electrodes Vehicle Technologies Office Merit Review 2014: Studies on High Capacity Cathodes for

  15. Kinetic investigation of catalytic disproportionation of superoxide ions in the non-aqueous electrolyte used in Li–air batteries

    DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)

    Wang, Qiang; Zheng, Dong; McKinnon, Meaghan E.; Yang, Xiao -Qing; Qu, Deyang

    2014-10-28

    Superoxide reacts with carbonate solvents in Li–air batteries. Tris(pentafluorophenyl)borane is found to catalyze a more rapid superoxide (O2-) disproportionation reaction than the reaction between superoxide and propylene carbonate (PC). With this catalysis, the negative impact of the reaction between the electrolyte and O2-produced by the O2 reduction can be minimized. A simple kinetic study using ESR spectroscopy was reported to determine reaction orders and rate constants for the reaction between PC and superoxide, and the disproportionation of superoxide catalyzed by Tris(pentafluorophenyl)borane and Li ions. As a result, the reactions are found to be first order and the rate constants aremore »0.033 s-1 M-1, 0.020 s-1 M-1and 0.67 s-1M-1 for reactions with PC, Li ion and Tris(pentafluorophenyl)borane, respectively.« less

  16. Kinetic investigation of catalytic disproportionation of superoxide ions in the non-aqueous electrolyte used in Li-air batteries

    DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)

    Wang, Qiang; Yang, Xiao -Qing; Zheng, Doug; McKinnon, Meaghan E.; Qu, Deyang

    2014-10-28

    Superoxide reacts with carbonate solvents in Liair batteries. Tris(pentafluorophenyl)borane is found to catalyze a more rapid superoxide (O2-) disproportionation reaction than the reaction between superoxide and propylene carbonate (PC). With this catalysis, the negative impact of the reaction between the electrolyte and O2-produced by the O2 reduction can be minimized. A simple kinetic study using ESR spectroscopy was reported to determine reaction orders and rate constants for the reaction between PC and superoxide, and the disproportionation of superoxide catalyzed by Tris(pentafluorophenyl)borane and Li ions. The reactions are found to be first order and the rate constants are 0.033 s-1 M-1,more0.020 s-1 M-1and 0.67 s-1M-1 for reactions with PC, Li ion and Tris(pentafluorophenyl)borane, respectively.less

  17. Compositions containing nucleosides and manganese and their uses

    DOE Patents [OSTI]

    Daly, Michael J.; Gaidamakova, Elena K.; Matrosova, Vera Y.; Levine, Rodney L.; Wehr, Nancy B.

    2015-11-17

    This invention encompasses methods of preserving protein function by contacting a protein with a composition comprising one or more purine or pyrimidine nucleosides (such as e.g., adenosine or uridine) and an antioxidant (such as e.g., manganese). In addition, the invention encompasses methods of treating and/or preventing a side effect of radiation exposure and methods of preventing a side effect of radiotherapy comprising administration of a pharmaceutically effective amount of a composition comprising one or more purine or pyrimidine nucleosides (such as e.g., adenosine or uridine) and an antioxidant (such as e.g., manganese) to a subject in need thereof. The compositions may comprise D. radiodurans extracts.

  18. Manganese oxide nanowires, films, and membranes and methods of making

    DOE Patents [OSTI]

    Suib, Steven Lawrence (Storrs, CT); Yuan, Jikang (Storrs, CT)

    2008-10-21

    Nanowires, films, and membranes comprising ordered porous manganese oxide-based octahedral molecular sieves, and methods of making, are disclosed. A single crystal ultra-long nanowire includes an ordered porous manganese oxide-based octahedral molecular sieve, and has an average length greater than about 10 micrometers and an average diameter of about 5 nanometers to about 100 nanometers. A film comprises a microporous network comprising a plurality of single crystal nanowires in the form of a layer, wherein a plurality of layers is stacked on a surface of a substrate, wherein the nanowires of each layer are substantially axially aligned. A free standing membrane comprises a microporous network comprising a plurality of single crystal nanowires in the form of a layer, wherein a plurality of layers is aggregately stacked, and wherein the nanowires of each layer are substantially axially aligned.

  19. Manganese Reduction-Oxidation Drives Plant Debris Decomposition

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    Manganese Reduction-Oxidation Drives Plant Debris Decomposition Print Microbial decomposition of plant debris ("litter") is a keystone ecosystem process because it regulates nutrient availability, ecosystem productivity, and carbon (C) cycling. Historically, climate (primarily temperature and precipitation) has been thought to regulate the rate of litter decomposition, which then influences the rate at which nutrients become available and C contained in the litter is released back into

  20. Manganese Reduction-Oxidation Drives Plant Debris Decomposition

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    Manganese Reduction-Oxidation Drives Plant Debris Decomposition Print Microbial decomposition of plant debris ("litter") is a keystone ecosystem process because it regulates nutrient availability, ecosystem productivity, and carbon (C) cycling. Historically, climate (primarily temperature and precipitation) has been thought to regulate the rate of litter decomposition, which then influences the rate at which nutrients become available and C contained in the litter is released back into

  1. Manganese Reduction-Oxidation Drives Plant Debris Decomposition

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    Manganese Reduction-Oxidation Drives Plant Debris Decomposition Print Microbial decomposition of plant debris ("litter") is a keystone ecosystem process because it regulates nutrient availability, ecosystem productivity, and carbon (C) cycling. Historically, climate (primarily temperature and precipitation) has been thought to regulate the rate of litter decomposition, which then influences the rate at which nutrients become available and C contained in the litter is released back into

  2. Manganese Reduction-Oxidation Drives Plant Debris Decomposition

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    Manganese Reduction-Oxidation Drives Plant Debris Decomposition Print Microbial decomposition of plant debris ("litter") is a keystone ecosystem process because it regulates nutrient availability, ecosystem productivity, and carbon (C) cycling. Historically, climate (primarily temperature and precipitation) has been thought to regulate the rate of litter decomposition, which then influences the rate at which nutrients become available and C contained in the litter is released back into

  3. Addressing the Voltage Fade Issue with Lithium-Manganese-Rich Oxide Cathode

    Office of Energy Efficiency and Renewable Energy (EERE) Indexed Site

    Materials | Department of Energy Voltage Fade Issue with Lithium-Manganese-Rich Oxide Cathode Materials Addressing the Voltage Fade Issue with Lithium-Manganese-Rich Oxide Cathode Materials 2012 DOE Hydrogen and Fuel Cells Program and Vehicle Technologies Program Annual Merit Review and Peer Evaluation Meeting PDF icon es161_burrell_2012_o.pdf More Documents & Publications Studies on Lithium Manganese Rich MNC Composite Cathodes Vehicle Technologies Office Merit Review 2014:

  4. Photochemical method for generating superoxide radicals (O.sub.2.sup.-) in aqueous solutions

    DOE Patents [OSTI]

    Holroyd, Richard A. (Stony Brook, NY); Bielski, Benon H. J. (Wading River, NY)

    1980-01-01

    A photochemical method and apparatus for generating superoxide radicals (ub.2.sup.-) in an aqueous solution by means of a vacuum-ultraviolet lamp of simple design. The lamp is a microwave powered rare gas device that emits far-ultraviolet light. The lamp includes an inner loop of high purity quartz tubing through which flows an oxygen-saturated sodium formate solution. The inner loop is designed so that the solution is subjected to an intense flux of far-ultraviolet light. This causes the solution to photodecompose and form the product radical (O.sub.2.sup.-).

  5. Kinetic investigation of catalytic disproportionation of superoxide ions in the non-aqueous electrolyte used in Li-air batteries

    SciTech Connect (OSTI)

    Wang, Qiang; Yang, Xiao -Qing; Zheng, Doug; McKinnon, Meaghan E.; Qu, Deyang

    2014-10-28

    Superoxide reacts with carbonate solvents in Liair batteries. Tris(pentafluorophenyl)borane is found to catalyze a more rapid superoxide (O2-) disproportionation reaction than the reaction between superoxide and propylene carbonate (PC). With this catalysis, the negative impact of the reaction between the electrolyte and O2-produced by the O2 reduction can be minimized. A simple kinetic study using ESR spectroscopy was reported to determine reaction orders and rate constants for the reaction between PC and superoxide, and the disproportionation of superoxide catalyzed by Tris(pentafluorophenyl)borane and Li ions. The reactions are found to be first order and the rate constants are 0.033 s-1 M-1, 0.020 s-1 M-1and 0.67 s-1M-1 for reactions with PC, Li ion and Tris(pentafluorophenyl)borane, respectively.

  6. Kinetic investigation of catalytic disproportionation of superoxide ions in the non-aqueous electrolyte used in Liair batteries

    SciTech Connect (OSTI)

    Wang, Qiang; Zheng, Dong; McKinnon, Meaghan E.; Yang, Xiao -Qing; Qu, Deyang

    2014-10-28

    Superoxide reacts with carbonate solvents in Liair batteries. Tris(pentafluorophenyl)borane is found to catalyze a more rapid superoxide (O2-) disproportionation reaction than the reaction between superoxide and propylene carbonate (PC). With this catalysis, the negative impact of the reaction between the electrolyte and O2-produced by the O2 reduction can be minimized. A simple kinetic study using ESR spectroscopy was reported to determine reaction orders and rate constants for the reaction between PC and superoxide, and the disproportionation of superoxide catalyzed by Tris(pentafluorophenyl)borane and Li ions. As a result, the reactions are found to be first order and the rate constants are 0.033 s-1 M-1, 0.020 s-1 M-1and 0.67 s-1M-1 for reactions with PC, Li ion and Tris(pentafluorophenyl)borane, respectively.

  7. Raman Microscopy of Lithium-Manganese-Rich Cathodes

    SciTech Connect (OSTI)

    Ruther, Rose E; Callender, Andrew F.; Zhou, Hui; Martha, Surendra; Nanda, Jagjit

    2014-01-01

    Lithium rich, manganese rich composites with general formula xLi2MnO3 (1-x)LiMO2 are promising candidates for high capacity and high voltage cathodes for lithium ion batteries. Lithium rich oxides crystallize as a nanocomposite of layered phases whose structure further evolves with electrochemical cycling. Raman spectroscopy is potentially a powerful tool to monitor the crystal chemistry and correlate phase changes with electrochemical behavior. While several groups have reported Raman spectra of lithium rich oxides, the data show considerable variability in terms of both the vibrational features observed and their interpretation. In this study Raman microscopy is used to investigate lithium-rich manganese-rich cathodes as a function of average charge and electrochemical cycling. LMR-NMC cycled at elevated temperature (60 C) has a modified crystal structure which may account for some of the observed increase in capacity. Contrary to some reports, no growth of a spinel phase is observed. However, analysis of the Raman spectra does indicate the structure of LMR-NMC deviates significantly from an ideal layered phase. The results also highlight the importance of using low laser power and large sample sizes to obtain consistent data sets.

  8. Raman Microscopy of Lithium-Manganese-Rich Cathodes

    DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)

    Ruther, Rose E; Callender, Andrew F.; Zhou, Hui; Martha, Surendra; Nanda, Jagjit

    2014-01-01

    Lithium rich, manganese rich composites with general formula xLi2MnO3 (1-x)LiMO2 are promising candidates for high capacity and high voltage cathodes for lithium ion batteries. Lithium rich oxides crystallize as a nanocomposite of layered phases whose structure further evolves with electrochemical cycling. Raman spectroscopy is potentially a powerful tool to monitor the crystal chemistry and correlate phase changes with electrochemical behavior. While several groups have reported Raman spectra of lithium rich oxides, the data show considerable variability in terms of both the vibrational features observed and their interpretation. In this study Raman microscopy is used to investigate lithium-rich manganese-rich cathodes asmore » a function of average charge and electrochemical cycling. LMR-NMC cycled at elevated temperature (60 C) has a modified crystal structure which may account for some of the observed increase in capacity. Contrary to some reports, no growth of a spinel phase is observed. However, analysis of the Raman spectra does indicate the structure of LMR-NMC deviates significantly from an ideal layered phase. The results also highlight the importance of using low laser power and large sample sizes to obtain consistent data sets.« less

  9. Hot coal gas desulfurization with manganese-based sorbents. Annual report, September 1992--September 1993

    SciTech Connect (OSTI)

    Hepworth, M.T.

    1993-12-01

    The focus of work being performed on Hot Coal Gas Desulfurization at the Morgantown Energy Technology Center is primarily in the use of zinc ferrite and zinc titanate sorbents; however, prior studies at the US Steel Fundamental Research Laboratories in Monroeville, PA, by E. T. Turkdogan indicated that an alternate sorbent, manganese dioxide-containing ore in mixture with alumina (75 wt % ore + 25 wt % Al{sub 2}O{sub 3}) may be a viable alternative to zinc-based sorbents. Manganese, for example, has a lower vapor pressure in the elemental state than zinc hence it is not as likely to undergo depletion from the sorbent surface upon loading and regeneration cycles. Also manganese oxide is less readily reduced to the elemental state than iron hence the range of reduction potentials for oxygen is somewhat greater than for zinc ferrite. In addition, thermodynamic analysis of the manganese-oxygen-sulfur system shows it to be less amenable to sulfation than zinc ferrite. Potential also exists for utilization of manganese at higher temperatures than zinc ferrite or zinc titanate. This Annual Topical Report documents progress in pelletizing and testing via thermo-gravimetric analysis of individual pellet formulations of manganese ore/ alumina combinations and also manganese carbonate/alumina with two binders, dextrin and bentonite. It includes the prior Quarterly Technical Reports which indicate that the manganese carbonate material, being of higher purity than the manganese ore, has a higher degree of sulfur capacity and more rapid absorption kinetics. A 2-inch fixed-bed reactor has been fabricated and is now ready for subjecting pellets to cyclic loading and regeneration.

  10. Stable "superoxide" opens the door to a new class of batteries | Argonne

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    National Laboratory The lattice match between LiO<sub>2</sub> and Ir<sub>3</sub>Li may be responsible for the LiO<sub>2</sub> discharge product found for the Ir-rGO cathode material. The lattice match between LiO2 and Ir3Li may be responsible for the LiO2 discharge product found for the Ir-rGO cathode material. Stable "superoxide" opens the door to a new class of batteries By Jared Sagoff * January 12, 2016 Tweet EmailPrint While lithium-ion

  11. Uranyl nitrate-exposed rat alveolar macrophages cell death: Influence of superoxide anion and TNF ? mediators

    SciTech Connect (OSTI)

    Orona, N.S.; Tasat, D.R.

    2012-06-15

    Uranium compounds are widely used in the nuclear fuel cycle, military and many other diverse industrial processes. Health risks associated with uranium exposure include nephrotoxicity, cancer, respiratory, and immune disorders. Macrophages present in body tissues are the main cell type involved in the internalization of uranium particles. To better understand the pathological effects associated with depleted uranium (DU) inhalation, we examined the metabolic activity, phagocytosis, genotoxicity and inflammation on DU-exposed rat alveolar macrophages (12.5200 ?M). Stability and dissolution of DU could differ depending on the dissolvent and in turn alter its biological action. We dissolved DU in sodium bicarbonate (NaHCO{sub 3} 100 mM) and in what we consider a more physiological vehicle resembling human internal media: sodium chloride (NaCl 0.9%). We demonstrate that uranyl nitrate in NaCl solubilizes, enters the cell, and elicits its cytotoxic effect similarly to when it is diluted in NaHCO{sub 3}. We show that irrespective of the dissolvent employed, uranyl nitrate impairs cell metabolism, and at low doses induces both phagocytosis and generation of superoxide anion (O{sub 2}{sup ?}). At high doses it provokes the secretion of TNF? and through all the range of doses tested, apoptosis. We herein suggest that at DU low doses O{sub 2}{sup ?} may act as the principal mediator of DNA damage while at higher doses the signaling pathway mediated by O{sub 2}{sup ?} may be blocked, prevailing damage to DNA by the TNF? route. The study of macrophage functions after uranyl nitrate treatment could provide insights into the pathophysiology of uranium?related diseases. -- Highlights: ? Uranyl nitrate effect on cultured macrophages is linked to the doses and independent of its solubility. ? At low doses uranyl nitrate induces generation of superoxide anion. ? At high doses uranyl nitrate provokes secretion of TNF?. ? Uranyl nitrate induces apoptosis through all the range of doses tested.

  12. Process for the electrodeposition of low stress nickel-manganese alloys

    DOE Patents [OSTI]

    Kelly, James John; Goods, Steven Howard; Yang, Nancy Yuan-Chi; Cadden, Charles Henry

    2005-06-07

    A process for electrodepositing a low stress nickel-manganese multilayer alloy on an electrically conductive substrate is provided. The process includes the steps of immersing the substrate in an electrodeposition solution containing a nickel salt and a manganese salt and repeatedly passing an electric current through an immersed surface of the substrate. The electric current is alternately pulsed for predetermined durations between a first electrical current that is effective to electrodeposit nickel and a second electrical current that is effective to electrodeposit nickel and manganese. A multilayered alloy having adjacent layers of nickel and a nickel-manganese alloy on the immersed surface of the substrate is thereby produced. The resulting multilayered alloy exhibits low internal stress, high strength and ductility, and high strength retention upon exposure to heat.

  13. Spin-dependent electron transport in zinc- and manganese-doped adenine molecules

    SciTech Connect (OSTI)

    Simchi, Hamidreza; Esmaeilzadeh, Mahdi Mazidabadi, Hossein

    2014-01-28

    The spin-dependent electron transport properties of zinc- and manganese-doped adenine molecules connected to zigzag graphene leads are studied in the zero bias regime using the non-equilibrium Green's function method. The conductance of the adenine molecule increased and became spin-dependent when a zinc or manganese atom was doped into the molecules. The effects of a transverse electric field on the spin-polarization of the transmitted electrons were investigated and the spin-polarization was controlled by changing the transverse electric field. Under the presence of a transverse electric field, both the zinc- and manganese-doped adenine molecules acted as spin-filters. The maximum spin-polarization of the manganese-doped adenine molecule was greater than the molecule doped with zinc.

  14. Oxidation state of cross-over manganese species on the graphite electrode

    Office of Scientific and Technical Information (OSTI)

    of lithium-ion cells (Journal Article) | SciTech Connect Oxidation state of cross-over manganese species on the graphite electrode of lithium-ion cells Citation Details In-Document Search Title: Oxidation state of cross-over manganese species on the graphite electrode of lithium-ion cells Authors: Gowda, Sanketh R. ; Gallagher, Kevin G. ; Croy, J. R. ; Bettge, Martin ; Thackeray, Michael ; Balasubramanian, Mahalingam Publication Date: 2014-01-01 OSTI Identifier: 1161339 DOE Contract Number:

  15. Role of manganese in red long-lasting phosphorescence of manganese-doped diopside for in vivo imaging

    SciTech Connect (OSTI)

    Lecointre, A.; Bessire, A.; Priolkar, K.R.; Gourier, D.; Wallez, G.; Viana, B.

    2013-05-15

    Highlights: ? Long-lasting phosphorescence of CaMgSi{sub 2}O{sub 6}:Mn is studied for bioimaging application. ? CaMgSi{sub 2}O{sub 6}:Mn yields orange and red luminescence of Mn{sup II}{sub Ca} and Mn{sup II}{sub Mg}, respectively. ? Red Mn{sup II}{sub Mg} emission dominates long-lasting phosphorescence spectra. ? Mn mainly substitutes Mg. ? Mn{sup II}{sub Mg} plays the role of hole trap in the persistent luminescence mechanism. - Abstract: Materials with red long-lasting phosphorescence, such as Mn{sup II}-doped diopsides, can be used for small animal in vivo imaging. CaMgSi{sub 2}O{sub 6}:Mn powders with various amounts of Mn were prepared by solgel to investigate their long-lasting phosphorescence mechanism. X-ray diffraction, X-ray absorption fine and near-edge structure and electron paramagnetic resonance showed that manganese is quantitatively introduced in the structure as Mn{sup II}. Most of the Mn doping ions substitute Mg and possess a highly elongated octahedral environment. While photoluminescence and X-ray excited optical luminescence spectra show both orange (585 nm) and red (685 nm) {sup 4}T{sub 1} ({sup 4}G) ? {sup 6}A{sub 1} ({sup 6}S) emission of Mn{sup II}{sub Ca} and Mn{sup II}{sub Mg}, respectively, Mn{sup II}{sub Mg} red emission dominates long-lasting phosphorescence and thermally stimulated luminescence spectra. These results point to Mn{sup II}{sub Mg} as the preferential hole trap and recombination center in the long-lasting phosphorescence mechanism. An intense persistent red emission suitable for in vivo imaging probes is obtained for the highest nominal Mn content (7.5%)

  16. LOW TEMPERATURE VOC COMBUSTION OVER MANGANESE, COBALT AND ZINC ALPO4 MOLECULAR SIEVES

    SciTech Connect (OSTI)

    Rosemarie Szostak

    2003-03-06

    The objective of this project was to prepare microporous aluminophosphates containing magnesium, manganese, cobalt and zinc (MeAPOs) and to evaluate their performance as oxidation catalysts for the removal of low levels of volatile organic compounds (VOCs) from gas streams. The tasks to be accomplished were as follows: (1) To develop reliable synthesis methods for metal aluminophosphates containing manganese, cobalt and zinc in their framework; (2) To characterize these materials for crystallinity, phase purity, the location and nature of the incorporated metal in the framework; and (3) To evaluate the materials for their catalytic activities in the oxidation of volatile organic environmental pollutants.

  17. Manganese oxide helices, rings, strands, and films, and methods for their preparation

    DOE Patents [OSTI]

    Suib, Steven L. (Storrs, CT); Giraldo, Oscar (Storrs, CT); Marquez, Manuel (Wheeling, IL); Brock, Stephanie (Detroit, MI)

    2003-01-07

    Methods for the preparation of mixed-valence manganese oxide compositions with quaternary ammonium ions are described. The compositions self-assemble into helices, rings, and strands without any imposed concentration gradient. These helices, rings, and strands, as well as films having the same composition, undergo rapid ion exchange to replace the quaternary ammonium ions with various metal ions. And the metal-ion-containing manganese oxide compositions so formed can be heat treated to form semi-conducting materials with high surface areas.

  18. High-Quality Manganese-Doped Zinc Sulfide Quantum Rods with Tunable

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    Dual-Color and Multiphoton Emissions High-Quality Manganese-Doped Zinc Sulfide Quantum Rods with Tunable Dual-Color and Multiphoton Emissions Authors: Deng, Z., Tong, L., Flores, M., Lin, S., Cheng, J.-X., Yan, H., and Liu, Y. Title: High-Quality Manganese-Doped Zinc Sulfide Quantum Rods with Tunable Dual-Color and Multiphoton Emissions Source: Journal of the American Chemical Society Year: 2011 Volume: 133 Pages: 5389-5396 ABSTRACT: We report a simple, fast and green phosphine-free

  19. Water quality evaluation and geochemical assessment of iron, manganese, and arsenic in a landfill site

    SciTech Connect (OSTI)

    Pisigan, R.A. Jr.

    1995-12-31

    Several monitoring wells at a landfill site were sampled for water quality parameters to determine the nature of groundwater contamination. The landfill, located beneath a limestone and dolomitic bedrock, has been used for about 20 years for trash and garbage disposal. The monitoring parameters include major cations and anions, as well as iron, manganese, arsenic, and other parameters measured in the field to characterize the subsurface conditions. Groundwater samples collected near the landfill and downgradient locations had higher levels of iron, manganese, arsenic, alkalinity, hardness than those samples from an upgradient well. The downgradient and on-site samples were also more acidic and turbid, The dissolved oxygen data tend to suggest reducing conditions in the leachate environment. The elevated groundwater concentrations of the three metals, especially iron, were most probably caused by the acidity generated by carbon dioxide and organic acids released from microbial degradation of organic compounds dumped into the landfill. The acidic pH led to the dissolution of iron, manganese, and arsenic bearing mineral phases. The buffering reactions of limestone and dolomite to neutralize the acidic degradation products increased the hardness cations, Ca{sup +2} and Mg{sup +2}. Inorganic speciation modeling indicates that iron, manganese, and arsenic predominantly exist as Fe {sup +2}, Mn{sup +2}, and H{sub 3}AsO{sub 3}. The possible presence of organic complexes of iron was discussed, but could be modeled due to lack of appropriate equilibrium constant data.

  20. Amperometric Biosensors Based on Carbon Paste Electrodes Modified with Nanostructured Mixed-valence Manganese Oxides and Glucose Oxidase

    SciTech Connect (OSTI)

    Cui, Xiaoli; Liu, Guodong; Lin, Yuehe

    2005-06-01

    Nanostructured multivalent manganese oxides octahedral molecular sieve (OMS), including cryptomelane-type manganese oxides and todorokite-type manganese oxides, were synthesized and evaluated for chemical sensing and biosensing at low operating potential. Both cryptomelane-type manganese oxides and todorokite-type manganese oxides are nanofibrous crystals with sub-nanometer open tunnels that provide a unique property for sensing applications. The electrochemical and electrocatalytic performance of OMS for the oxidation of H2O2 have been compared. Both cryptomelane-type manganese oxides and todorokite-type manganese oxides can be used to fabricate sensitive H2O2 sensors. Amperometric glucose biosensors are constructed by bulk modification of carbon paste electrodes (CPEs) with glucose oxidase as a biocomponent and nanostructured OMS as a mediator. A Nafion thin film was applied as an immobilization/encapsulation and protective layer. The biosensors were evaluated as an amperometric glucose detector at phosphate buffer solution with a pH 7.4 at an operating potential of 0.3 V (vs. Ag/AgCl). The biosensor is characterized by a well-reproducible amperometric response, linear signal-to-glucose concentration range up to 3.5 mM and 1.75 mM, and detection limits (S/N = 3) of 0.1 mM and 0.05 mM for todorokite-type manganese oxide and cryptomelane-type manganese oxide modified electrodes, respectively. The biosensors based on OMS exhibit considerable good reproducibility and stability, and the construction and renewal are simple and inexpensive.

  1. Effect of intranasal manganese administration on neurotransmission and spatial learning in rats

    SciTech Connect (OSTI)

    Blecharz-Klin, Kamilla; Piechal, Agnieszka; Joniec-Maciejak, Ilona; Pyrzanowska, Justyna; Widy-Tyszkiewicz, Ewa

    2012-11-15

    The effect of intranasal manganese chloride (MnCl{sub 2}4H{sub 2}O) exposure on spatial learning, memory and motor activity was estimated in Morris water maze task in adult rats. Three-month-old male Wistar rats received for 2 weeks MnCl{sub 2}4H{sub 2}O at two doses the following: 0.2 mg/kg b.w. (Mn0.2) or 0.8 mg/kg b.w. (Mn0.8) per day. Control (Con) and manganese-exposed groups were observed for behavioral performance and learning in water maze. ANOVA for repeated measurements did not show any significant differences in acquisition in the water maze between the groups. However, the results of the probe trial on day 5, exhibited spatial memory deficits following manganese treatment. After completion of the behavioral experiment, the regional brain concentrations of neurotransmitters and their metabolites were determined via HPLC in selected brain regions, i.e. prefrontal cortex, hippocampus and striatum. ANOVA demonstrated significant differences in the content of monoamines and metabolites between the treatment groups compared to the controls. Negative correlations between platform crossings on the previous platform position in Southeast (SE) quadrant during the probe trial and neurotransmitter turnover suggest that impairment of spatial memory and cognitive performance after manganese (Mn) treatment is associated with modulation of the serotonergic, noradrenergic and dopaminergic neurotransmission in the brain. These findings show that intranasally applied Mn can impair spatial memory with significant changes in the tissue level and metabolism of monoamines in several brain regions. -- Highlights: ? Intranasal exposure to manganese in rats impairs spatial memory in the water maze. ? Regional changes in levels of neurotransmitters in the brain have been identified. ? Cognitive disorder correlates with modulation of 5-HT, NA and DA neurotransmission.

  2. Thermodynamic Investigations of Lithium- and Manganese-Rich Transition Metal Oxides

    Office of Energy Efficiency and Renewable Energy (EERE) Indexed Site

    Vehicle Technologies Program Thermodynamic Investigations of Lithium- and Manganese-Rich Transition Metal Oxides Wenquan Lu (PI) Qingliu Wu, Dennis Dees, Kevin Gallagher, Ira Bloom, and Anthony Burrell Electrochemical Energy Storage Chemical Sciences and Engineering Division Argonne National Laboratory This presentation does not contain any proprietary, confidential, or otherwise restricted information Vehicle Technologies Annual Merit Review and Peer Evaluation Washington, D.C. May 13th - 17th

  3. Secondary cell with orthorhombic alkali metal/manganese oxide phase active cathode material

    DOE Patents [OSTI]

    Doeff, M.M.; Peng, M.Y.; Ma, Y.; Visco, S.J.; DeJonghe, L.C.

    1996-09-24

    An alkali metal manganese oxide secondary cell is disclosed which can provide a high rate of discharge, good cycling capabilities, good stability of the cathode material, high specific energy (energy per unit of weight) and high energy density (energy per unit volume). The active material in the anode is an alkali metal and the active material in the cathode comprises an orthorhombic alkali metal manganese oxide which undergoes intercalation and deintercalation without a change in phase, resulting in a substantially linear change in voltage with change in the state of charge of the cell. The active material in the cathode is an orthorhombic structure having the formula M{sub x}Z{sub y}Mn{sub (1{minus}y)}O{sub 2}, where M is an alkali metal; Z is a metal capable of substituting for manganese in the orthorhombic structure such as iron, cobalt or titanium; x ranges from about 0.2 in the fully charged state to about 0.75 in the fully discharged state, and y ranges from 0 to 60 atomic %. Preferably, the cell is constructed with a solid electrolyte, but a liquid or gelatinous electrolyte may also be used in the cell. 11 figs.

  4. Secondary cell with orthorhombic alkali metal/manganese oxide phase active cathode material

    DOE Patents [OSTI]

    Doeff, Marca M.; Peng, Marcus Y.; Ma, Yanping; Visco, Steven J.; DeJonghe, Lutgard C.

    1996-01-01

    An alkali metal manganese oxide secondary cell is disclosed which can provide a high rate of discharge, good cycling capabilities, good stability of the cathode material, high specific energy (energy per unit of weight) and high energy density (energy per unit volume). The active material in the anode is an alkali metal and the active material in the cathode comprises an orthorhombic alkali metal manganese oxide which undergoes intercalation and deintercalation without a change in phase, resulting in a substantially linear change in voltage with change in the state of charge of the cell. The active material in the cathode is an orthorhombic structure having the formula M.sub.x Z.sub.y Mn.sub.(1-y) O.sub.2, where M is an alkali metal; Z is a metal capable of substituting for manganese in the orthorhombic structure such as iron, cobalt or titanium; x ranges from about 0.2 in the fully charged state to about 0.75 in the fully discharged state, and y ranges from 0 to 60 atomic %. Preferably, the cell is constructed with a solid electrolyte, but a liquid or gelatinous electrolyte may also be used in the cell.

  5. Formation of manganese {delta}-doped atomic layer in wurtzite GaN

    SciTech Connect (OSTI)

    Shi Meng; Chinchore, Abhijit; Wang Kangkang; Mandru, Andrada-Oana; Liu Yinghao; Smith, Arthur R.

    2012-09-01

    We describe the formation of a {delta}-doped manganese layer embedded within c-plane wurtzite gallium nitride using a special molecular beam epitaxy growth process. Manganese is first deposited on the gallium-poor GaN (0001) surface, forming a {radical}(3) Multiplication-Sign {radical}(3)-R30 Degree-Sign reconstructed phase. This well-defined surface reconstruction is then nitrided using plasma nitridation, and gallium nitride is overgrown. The manganese content of the {radical}(3) Multiplication-Sign {radical}(3)-R30 Degree-Sign phase, namely one Mn per each {radical}(3) Multiplication-Sign {radical}(3)-R30 Degree-Sign unit cell, implies that the MnGaN alloy layer has a Mn concentration of up to 33%. The structure and chemical content of the surface are monitored beginning from the initial growth stage up through the overgrowth of 20 additional monolayers (MLs) of GaN. An exponential-like drop-off of the Mn signal with increasing GaN monolayers, as measured by Auger electron spectroscopy, indicates that the highly concentrated Mn layer remains at the {delta}-doped interface. A model of the resultant {delta}-doped structure is formulated based on the experimental data, and implications for possible spintronic applications are discussed.

  6. Two coordination polymers of manganese(II) isophthalate and their preparation, structures, and magnetic properties

    SciTech Connect (OSTI)

    Chen Jinxi; Wang Jingjing; Ohba, Masaaki

    2012-01-15

    Two manganese coordination polymers, [Mn{sub 2}(ip){sub 2}(dmf)]{center_dot}dmf (1) and [Mn{sub 4}(ip){sub 4}(dmf){sub 6}]{center_dot}2dmf (2) (ip=isophthalate; dmf=N,N-dimethylformamide), have been synthesized and characterized. X-ray crystal structural data reveal that compound 1 crystallizes in triclinic space group P-1, a=9.716(3) A, b=12.193(3) A, c=12.576(3) A, {alpha}=62.19(2) Degree-Sign , {beta}=66.423(17) Degree-Sign , {gamma}=72.72(2) Degree-Sign , Z=2, while compound 2 crystallizes in monoclinic space group Cc, a=19.80(3) A, b=20.20(2) A, c=18.01(3) A, {beta}=108.40(4) Degree-Sign , Z=4. Variable-temperature magnetic susceptibilities of compounds 1 and 2 exhibit overall weak antiferromagnetic coupling between the adjacent Mn(II) ions. - Graphical abstract: Three-dimensional porous and two-dimensional layered manganese isophthalates have been prepared. Magnetic susceptibility measurements exhibit overall weak antiferromagnetic interactions between the Mn(II) ions in both compounds. Highlights: Black-Right-Pointing-Pointer Two manganese isophthalates have been prepared. Black-Right-Pointing-Pointer Compound 1 adopts a three-dimensional porous structure. Black-Right-Pointing-Pointer Compound 2 adopts a two-dimensional layered structure. Black-Right-Pointing-Pointer Magnetic properties of both compounds are investigated.

  7. Effects of water hardness on the toxicity of manganese to developing brown trout (Salmo trutta)

    SciTech Connect (OSTI)

    Stubblefield, W.A.; Garrison, T.D.; Hockett, J.R.; Brinkman, S.F.; Davies, P.H.; McIntyre, M.W.

    1997-10-01

    Manganese is a common constituent of point and nonpoint discharges from mining and smelting activities. Available data indicate that Mn is acutely toxic at relatively high aqueous concentrations, when compared with trace metals, and its toxicity is affected by water hardness. Little information is available regarding the chronic toxicity of manganese. Early-life-stage (ELS) tests were conducted to determine the toxicity of manganese to brown trout (Salmo trutta) and to evaluate the extent to which water hardness (ranging from 30 to 450 mg/L as CaCO{sub 3}) affects the chronic toxicity of Mn. Water hardness of significantly affected Mn chronic toxicity, with toxicity decreasing with increasing hardness. Decreased survival was the predominant effect noted in the 30-mg/L hardness experiment, while significant effects on growth (as measured by changes in body weight) were observed in both the 150- and 450-mg/L hardness experiments. Twenty-five percent inhibition concentration (IC25) values, based on the combined endpoints (i.e., survival and body weight), were 4.67, 5.59, and 8.68 mg Mn/L (based on measured Mn concentration) at hardness levels of approximately 30, 150, and 450 mg/L as CaCO{sub 3}, respectively.

  8. Oxidation of alpha-tocopherol in micelles and liposomes by the hydroxyl, perhydroxyl, and superoxide free radicals

    SciTech Connect (OSTI)

    Fukuzawa, K.; Gebicki, J.M.

    1983-10-01

    Rates of oxidation of alpha-tocopherol by the hydroxyl- and superoxide free radicals were measured. The radicals were produced in known yields by radiolysis of aqueous solutions with gamma rays. Two main systems were used to dissolve the tocopherol; micelles, made up from charged and uncharged amphiphiles, and membranes made from dimyristyl phosphatidylcholine which could be charged by addition of stearyl amine or dicetyl phosphate. The HO. radicals were efficient oxidants of alpha-tocopherol in all systems, with up to 83% of radicals generated in micelle and 32% in membrane suspensions initiating the oxidation. The HO/sub 2/ radical was an even more effective oxidant, but when most of it was in the O/sub 2/ form at neutral or alkaline pH, the oxidation rates became low. Tocopherol held in positively charged micelles or membranes was oxidized at a higher rate by the O/sub 2/ than in uncharged or negative particles. Possible biological significance of these results is discussed.

  9. Manganese-Aluminum-Based Magnets: Nanocrystalline t-MnAI Permanent Magnets

    SciTech Connect (OSTI)

    2012-01-01

    REACT Project: Dartmouth is developing specialized alloys with magnetic properties superior to the rare earths used in todays best magnets. EVs and renewable power generators typically use rare earths to turn the axles in their electric motors due to the magnetic strength of these minerals. However, rare earths are difficult and expensive to refine. Dartmouth will swap rare earths for a manganese-aluminum alloy that could demonstrate better performance and cost significantly less. The ultimate goal of this project is to develop an easily scalable process that enables the widespread use of low-cost and abundant materials for the magnets used in EVs and renewable power generators.

  10. Reactivity of biogenic manganese oxide for metal sequestration and photochemistry: Computational solid state physics study

    SciTech Connect (OSTI)

    Kwon, K.D.; Sposito, G.

    2010-02-01

    Many microbes, including both bacteria and fungi, produce manganese (Mn) oxides by oxidizing soluble Mn(II) to form insoluble Mn(IV) oxide minerals, a kinetically much faster process than abiotic oxidation. These biogenic Mn oxides drive the Mn cycle, coupling it with diverse biogeochemical cycles and determining the bioavailability of environmental contaminants, mainly through strong adsorption and redox reactions. This mini review introduces recent findings based on quantum mechanical density functional theory that reveal the detailed mechanisms of toxic metal adsorption at Mn oxide surfaces and the remarkable role of Mn vacancies in the photochemistry of these minerals.

  11. Synthesis and Characterization of Rare-earth-free Magnetic Manganese Bismuth Nanocrystals

    SciTech Connect (OSTI)

    Shen, Jian Q.; Cui, Huizhong; Huang, Xiaopeng; Gong, Maogang; Qin, Wei; Kirkeminde, Alec; Cui, Jun; Ren, Shenqiang

    2015-01-01

    Earth abundant manganese bismuth (MnBi) has long been of interest due to its large magnetocrystalline anisotropy and high energy density for advanced permanent magnet applications. However, solution synthesis of MnBi phase is challenging due to the reduction potential mismatch between Mn and Bi elements. In this study, we show a versatile MnBi synthesis method involving the metal co-reduction followed by thermal annealing. The magnetically hard MnBi crystalline phase is then exchange coupled with magnetically soft cobalt coating. Our processing approach offers a promising strategy for manufacturing rare-earth-free magnetic nanocrystals.

  12. Synthesis and characterization of rare-earth-free magnetic manganese bismuth nanocrystals

    SciTech Connect (OSTI)

    Shen, J; Cui, HZ; Huang, XP; Gong, MG; Qin, W; Kirkeminde, A; Cui, J; Ren, SQ

    2015-01-01

    Earth abundant manganese bismuth (MnBi) has long been of interest due to its largemagnetocrystalline anisotropy and high energy density for advanced permanent magnet applications. However, solution synthesis of MnBi phase is challenging due to the reduction potential mismatch between Mn and Bi elements. In this study, we show a versatile MnBi synthesis method involving the metal co-reduction followed by thermal annealing. The magnetically hard MnBi crystalline phase is then exchange coupled with magnetically soft cobalt coating. Our processing approach offers a promising strategy for manufacturing rare-earth-free magnetic nanocrystals.

  13. Growth and magnetic property of antiperovskite manganese nitride films doped with Cu by molecular beam epitaxy

    SciTech Connect (OSTI)

    Yu, Fengmei; Ren, Lizhu; Meng, Meng; Wang, Yunjia; Yang, Mei; Wu, Shuxiang; Li, Shuwei

    2014-04-07

    Manganese nitrides thin films on MgO (100) substrates with and without Cu-doping have been fabricated by plasma assisted molecular beam epitaxy. Antiperovskite compounds Mn{sub 3.6}Cu{sub 0.4}N have been grown in the case of Cu-doping, and the pure Mn{sub 3}N{sub 2} single crystal has been obtained without Cu-doping. The Mn{sub 3.6}Cu{sub 0.4}N exhibits ferrimagnetism, and the magnetization of Mn{sub 3.6}Cu{sub 0.4}N increases upon the temperature decreasing from 300 K to 5 K, similar to Mn{sub 4}N. The exchange bias (EB) effects emerge in the Mn{sub 3.6}Cu{sub 0.4}N films. The EB behavior is originated from the interfaces between ferrimagnetic Mn{sub 3.6}Cu{sub 0.4}N and antiferromagnetic metal Mn, which is verified to be formed by the data of x-ray photoelectron spectroscopy. The present results not only provide a strategy for producing functional antiperovskite manganese nitrides, but also shed promising light on fabricating the exchange bias part of spintronic devices.

  14. Recovery of manganese oxides from spent alkaline and zinccarbon batteries. An application as catalysts for VOCs elimination

    SciTech Connect (OSTI)

    Gallegos, Mara V.; Falco, Lorena R.; Peluso, Miguel A.; Sambeth, Jorge E.; Thomas, Horacio J.

    2013-06-15

    Highlights: Manganese oxides were synthesized using spent batteries as raw materials. Spent alkaline and zinccarbon size AA batteries were used. A biohydrometallurgical process was employed to bio-lixiviate batteries. Manganese oxides were active in the oxidation of VOCs (ethanol and heptane). - Abstract: Manganese, in the form of oxide, was recovered from spent alkaline and zinccarbon batteries employing a biohydrometallurgy process, using a pilot plant consisting in: an air-lift bioreactor (containing an acid-reducing medium produced by an Acidithiobacillus thiooxidans bacteria immobilized on elemental sulfur); a leaching reactor (were battery powder is mixed with the acid-reducing medium) and a recovery reactor. Two different manganese oxides were recovered from the leachate liquor: one of them by electrolysis (EMO) and the other by a chemical precipitation with KMnO{sub 4} solution (CMO). The non-leached solid residue was also studied (RMO). The solids were compared with a MnO{sub x} synthesized in our laboratory. The characterization by XRD, FTIR and XPS reveal the presence of Mn{sub 2}O{sub 3} in the EMO and the CMO samples, together with some Mn{sup 4+} cations. In the solid not extracted by acidic leaching (RMO) the main phase detected was Mn{sub 3}O{sub 4}. The catalytic performance of the oxides was studied in the complete oxidation of ethanol and heptane. Complete conversion of ethanol occurs at 200 C, while heptane requires more than 400 C. The CMO has the highest oxide selectivity to CO{sub 2}. The results show that manganese oxides obtained using spent alkaline and zinccarbon batteries as raw materials, have an interesting performance as catalysts for elimination of VOCs.

  15. 3-D Atomic-Scale Mapping of Manganese Dopants in Lead Sulfide Nanowires

    SciTech Connect (OSTI)

    Isheim, Dieter; Kaszpurenko, Jason; Yu, Dong; Mao, Zugang; Seidman, David N.; Arslan, Ilke

    2012-03-22

    Dopants in nanowires, whether intentional or unintentional, can ultimately control the material's properties and therefore need to be understood on the atomic scale. We study vapor-liquid-solid grown manganese-doped lead sulfide nanowires by atom-probe tomography for the first time for lead salt materials. The three-dimensional chemical concentration maps at the atomic scale demonstrate a radial distribution profile of Mn ions, with a concentration of only 0.18 at.% and 0.01 at.% for MnCl2 and Mn-acetate precursors, respectively. The ability to characterize these small concentrations of dopant atoms in Pb1-xMnxS nanowires (x = 0.0036 and 0.0002), important for spintronic and thermoelectric devices, sets a platform for similar analyses for all nanostructures. First-principles calculations confirm that Mn atoms substitute for Pb in the PbS structure.

  16. Synthesis, structures and properties of a series of manganese coordination complexes constructed from dicarboxylic fluorene derivatives

    SciTech Connect (OSTI)

    Li Xing; Zhao Xiuhua; Bing Yue; Zha Meiqin; Xie Hongzhen; Guo Zhiyong

    2013-01-15

    Assembly reactions of 9,9-diethylfluorene-2,7-dicarboxylic acid (H{sub 2}DFDC) and Mn(CH{sub 3}COO){sub 2}{center_dot}4H{sub 2}O or MnCl{sub 2}{center_dot}4H{sub 2}O by tuning of various secondary ligands such as 2,2 Prime -bipyridine (2,2 Prime -bpy), 4,4 Prime -bipyridine (4,4 Prime -bpy) or 1,3-bis(4-pyridyl)propane) (bpp), gave rise to four complexes {l_brace} [Mn{sub 2}(DFDC){sub 2}(DMF){sub 2}]{center_dot}H{sub 2}O{r_brace} {sub n} (1), [Mn(DFDC)(2,2 Prime -bpy)]{sub n} (2), {l_brace} [Mn{sub 2}(DFDC){sub 2}(4,4 Prime -bpy){sub 2}]{center_dot}2CH{sub 3}OH{r_brace} {sub n} (3), and {l_brace} [Mn{sub 4}(DFDC){sub 4}(bpp){sub 2}(CH{sub 3}OH){sub 3} (H{sub 2}O){sub 3}]{center_dot}3(CH{sub 3}OH){center_dot}3(H{sub 2}O){r_brace} {sub n} (4). Single crystal X-ray diffraction analysis reveal that complex 1 is three dimensional structure with rhombic channels filled by guest water molecules; 2 presents a close-packed structure with high thermal stability; 3 exhibits a three dimensional framework with micro-porous channels filled by guest methanol molecules and 4 is a two-dimensional structure. The photoluminescent properties of 1-4 have been studied, respectively, showing that the Mn(II) ions, accessorial organic ligands or crystal structures exert important influences on the photoluminescence emissions of H{sub 2}DFDC ligands. Thermogravimetric analysis show that the complexes have remarkably high thermal stability. Magnetic susceptibility measurements have been finished and discussed for the complexes. - Graphical abstract: Assembly of 9,9-diethylfluorene-2,7-dicarboxylic acid and Mn(II) salts by tuning of various accessorial ligands resulted in four manganese complexes with different topological frameworks. Highlights: Black-Right-Pointing-Pointer Four manganese complexes based on 9,9-diethylfluorene-2,7-dicarboxylic acid were obtained. Black-Right-Pointing-Pointer The complexes were structurally characterized by single-crystal X-ray diffraction. Black-Right-Pointing-Pointer The complexes 1-4 display different topological structures. Black-Right-Pointing-Pointer Thermogravimetric analysis show the complexes have remarkably high thermal stability.

  17. Kinetic and Crystallgraphic Studies of a Redesigned Manganese-Binding Site in Cytochrome c Peroxidase

    SciTech Connect (OSTI)

    Pfister,T.; Mirarefi, A.; Gengenbach, A.; Zhao, X.; Danstrom , C.; Conatser, N.; Gao, Y.; Robinson, H.; Zukoski, C.; et al.

    2007-01-01

    Manganese peroxidase (MnP) from the white rot fungus Phanerochaete chrysosporium contains a manganese-binding site that plays a critical role in its function. Previously, a Mn{sup II}-binding site was designed into cytochrome c peroxidase (CcP) based on sequence homology (Yeung et al. in Chem. Biol. 4:215-222, 1997; Gengenbach et al. in Biochemistry 38:11425-11432, 1999). Here, we report a redesign of this site based on X-ray structural comparison of MnP and CcP. The variant, CcP(D37E, V45E, H181E), displays 2.5-fold higher catalytic efficiency (k{sub cat}/k{sub M}) than the variant in the original design, mostly due to a stronger k{sub M} of 1.9 mM (vs. 4.1 mM). High-resolution X-ray crystal structures of a metal-free form and a form with Co{sup II} at the designed Mn{sup II} site were also obtained. The metal ion in the engineered metal-binding site overlays well with Mn{sup II} bound in MnP, suggesting that this variant is the closest structural model of the Mn{sup II}-binding site in MnP for which a crystal structure exists. A major difference arises in the distances of the ligands to the metal; the metal-ligand interactions in the CcP variant are much weaker than the corresponding interactions in MnP, probably owing to partial occupancy of metal ion at the designed site, difference in the identity of metal ions (Co{sup II} rather than Mn{sup II}) and other interactions in the second coordination sphere. These results indicate that the metal ion, the ligands, and the environment around the metal-binding site play important roles in tuning the structure and function of metalloenzymes.

  18. Enhanced power factor of higher manganese silicide via melt spin synthesis method

    SciTech Connect (OSTI)

    Shi, Xiaoya; Shi, Xun; Li, Yulong; He, Ying; Chen, Lidong; Li, Qiang

    2014-12-30

    We report on the thermoelectric properties of the Higher Manganese Silicide MnSi?.?? (HMS) synthesized by means of a one-step non-equilibrium method. The ultrahigh cooling rate generated from the melt-spin technique is found to be effective in reducing second phases, which are inevitable during the traditional solid state diffusion processes. Aside from being detrimental to thermoelectric properties, second phases skew the revealing of the intrinsic properties of this class of materials, for example the optimal level of carrier concentration. With this melt-spin sample, we are able to formulate a simple model based on a single parabolic band that can well describe the carrier concentration dependence of the Seebeck coefficient and power factor of the data reported in the literature. An optimal carrier concentration around 5x10? cm? at 300 K is predicted according to this model. The phase-pure melt-spin sample shows the largest power factor at high temperature, resulting in the highest zT value among the three samples in this paper. And the maximum value is superior to those reported in the literatures.

  19. Anomalous hole injection deterioration of organic light-emitting diodes with a manganese phthalocyanine layer

    SciTech Connect (OSTI)

    Lee, Hyunbok; Lee, Jeihyun; Yi, Yeonjin; Cho, Sang Wan; Kim, Jeong Won

    2015-01-21

    Metal phthalocyanines (MPcs) are well known as an efficient hole injection layer (HIL) in organic devices. They possess a low ionization energy, and so the low-lying highest occupied molecular orbital (HOMO) gives a small hole injection barrier from an anode in organic light-emitting diodes. However, in this study, we show that the hole injection characteristics of MPc are not only determined by the HOMO position but also significantly affected by the wave function distribution of the HOMO. We show that even with the HOMO level of a manganese phthalocyanine (MnPc) HIL located between the Fermi level of an indium tin oxide anode and the HOMO level of a N,N?-bis(1-naphthyl)-N,N?-diphenyl-1,1?-biphenyl-4,4?-diamine hole transport layer the device performance with the MnPc HIL is rather deteriorated. This anomalous hole injection deterioration is due to the contracted HOMO wave function, which leads to small intermolecular electronic coupling. The origin of this contraction is the significant contribution of the Mn d-orbital to the MnPc HOMO.

  20. Magnesium and Manganese Silicides For Efficient And Low Cost Thermo-Electric Power Generation

    SciTech Connect (OSTI)

    Trivedi, Sudhir B.; Kutcher, Susan W.; Rosemeier, Cory A.; Mayers, David; Singh, Jogender

    2013-12-02

    Thermoelectric Power Generation (TEPG) is the most efficient and commercially deployable power generation technology for harvesting wasted heat from such things as automobile exhausts, industrial furnaces, and incinerators, and converting it into usable electrical power. We investigated the materials magnesium silicide (Mg2Si) and manganese silicide (MnSi) for TEG. MgSi2 and MnSi are environmentally friendly, have constituent elements that are abundant in the earth's crust, non-toxic, lighter and cheaper. In Phase I, we successfully produced Mg2Si and MnSi material with good TE properties. We developed a novel technique to synthesize Mg2Si with good crystalline quality, which is normally very difficult due to high Mg vapor pressure and its corrosive nature. We produced n-type Mg2Si and p-type MnSi nanocomposite pellets using FAST. Measurements of resistivity and voltage under a temperature gradient indicated a Seebeck coefficient of roughly 120 V/K on average per leg, which is quite respectable. Results indicated however, that issues related to bonding resulted in high resistivity contacts. Determining a bonding process and bonding material that can provide ohmic contact from room temperature to the operating temperature is an essential part of successful device fabrication. Work continues in the development of a process for reproducibly obtaining low resistance electrical contacts.

  1. Enhanced power factor of higher manganese silicide via melt spin synthesis method

    SciTech Connect (OSTI)

    Shi, Xiaoya; Shi, Xun; Li, Yulong; He, Ying; Chen, Lidong; Li, Qiang

    2014-12-30

    We report on the thermoelectric properties of the Higher Manganese Silicide MnSi?.?? (HMS) synthesized by means of a one-step non-equilibrium method. The ultrahigh cooling rate generated from the melt-spin technique is found to be effective in reducing second phases, which are inevitable during the traditional solid state diffusion processes. Aside from being detrimental to thermoelectric properties, second phases skew the revealing of the intrinsic properties of this class of materials, for example the optimal level of carrier concentration. With this melt-spin sample, we are able to formulate a simple model based on a single parabolic band that can well describe the carrier concentration dependence of the Seebeck coefficient and power factor of the data reported in the literature. An optimal carrier concentration around 5x10? cm? at 300 K is predicted according to this model. The phase-pure melt-spin sample shows the largest power factor at high temperature, resulting in the highest zT value among the three samples in this paper; the maximum value is superior to those reported in the literatures.

  2. Electrodeposited manganese dioxide nanostructures on electro-etched carbon fibers: High performance materials for supercapacitor applications

    SciTech Connect (OSTI)

    Kazemi, Sayed Habib; Maghami, Mostafa Ghaem; Kiani, Mohammad Ali

    2014-12-15

    Highlights: We report a facile method for fabrication of MnO{sub 2} nanostructures on electro-etched carbon fiber. MnO{sub 2}-ECF electrode shows outstanding supercapacitive behavior even at high discharge rates. Exceptional cycle stability was achieved for MnO{sub 2}-ECF electrode. The coulombic efficiency of MnO{sub 2}-ECF electrode is nearly 100%. - Abstract: In this article we introduce a facile, low cost and additive/template free method to fabricate high-rate electrochemical capacitors. Manganese oxide nanostructures were electrodeposited on electro-etched carbon fiber substrate by applying a constant anodic current. Nanostructured MnO{sub 2} on electro-etched carbon fiber was characterized by scanning electron microscopy, X-ray diffraction and energy dispersive X-ray analysis. The electrochemical behavior of MnO{sub 2} electro-etched carbon fiber electrode was investigated by electrochemical techniques including cyclic voltammetry, galvanostatic charge/discharge, and electrochemical impedance spectroscopy. A maximum specific capacitance of 728.5 F g{sup ?1} was achieved at a scan rate of 5 mV s{sup ?1} for MnO{sub 2} electro-etched carbon fiber electrode. Also, this electrode showed exceptional cycle stability, suggesting that it can be considered as a good candidate for supercapacitor electrodes.

  3. Enhanced power factor of higher manganese silicide via melt spin synthesis method

    DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)

    Shi, Xiaoya; Shi, Xun; Li, Yulong; He, Ying; Chen, Lidong; Li, Qiang

    2014-12-30

    We report on the thermoelectric properties of the Higher Manganese Silicide MnSi₁.₇₅ (HMS) synthesized by means of a one-step non-equilibrium method. The ultrahigh cooling rate generated from the melt-spin technique is found to be effective in reducing second phases, which are inevitable during the traditional solid state diffusion processes. Aside from being detrimental to thermoelectric properties, second phases skew the revealing of the intrinsic properties of this class of materials, for example the optimal level of carrier concentration. With this melt-spin sample, we are able to formulate a simple model based on a single parabolic band that can well describemore » the carrier concentration dependence of the Seebeck coefficient and power factor of the data reported in the literature. An optimal carrier concentration around 5x10²⁰ cm⁻³ at 300 K is predicted according to this model. The phase-pure melt-spin sample shows the largest power factor at high temperature, resulting in the highest zT value among the three samples in this paper; the maximum value is superior to those reported in the literatures.« less

  4. Approaching the Minimum Thermal Conductivity in Rhenium-Substituted Higher Manganese Silicides

    SciTech Connect (OSTI)

    Chen, Xi [University of Texas at Austin] [University of Texas at Austin; Girard, S. N. [University of Wisconsin, Madison] [University of Wisconsin, Madison; Meng, F. [University of Wisconsin, Madison] [University of Wisconsin, Madison; Lara-Curzio, Edgar [ORNL] [ORNL; Jin, S [University of Wisconsin, Madison] [University of Wisconsin, Madison; Goodenough, J. B. [University of Texas at Austin] [University of Texas at Austin; Zhou, J. S. [University of Texas at Austin] [University of Texas at Austin; Shi, L [University of Texas at Austin] [University of Texas at Austin

    2014-01-01

    Higher manganese silicides (HMS) made of earth-abundant and non-toxic elements are regarded as promising p-type thermoelectric materials because their complex crystal structure results in low lattice thermal conductivity. It is shown here that the already low thermal conductivity of HMS can be reduced further to approach the minimum thermal conductivity via partial substitu- tion of Mn with heavier rhenium (Re) to increase point defect scattering. The solubility limit of Re in the obtained RexMn1 xSi1.8 is determined to be about x = 0.18. Elemental inhomogeneity and the formation of ReSi1.75 inclusions with 50 200 nm size are found within the HMS matrix. It is found that the power factor does not change markedly at low Re content of x 0.04 before it drops considerably at higher Re contents. Compared to pure HMS, the reduced lattice thermal conductivity in RexMn1 xSi1.8 results in a 25% increase of the peak figure of merit ZT to reach 0.57 0.08 at 800 K for x = 0.04. The suppressed thermal conductivity in the pure RexMn1 xSi1.8 can enable further investigations of the ZT limit of this system by exploring different impurity doping strategies to optimize the carrier concentration and power factor.

  5. Manganese valence and coordination structure in Mn,Mg-codoped {gamma}-AlON green phosphor

    SciTech Connect (OSTI)

    Takeda, Takashi; Xie, Rong-Jun; Hirosaki, Naoto; Matsushita, Yoshitaka; Honma, Tetuso

    2012-10-15

    The valence and coordination structure of manganese in a Mn,Mg-codoped {gamma}-AlON spinel-type oxynitride green phosphor were studied by synchrotron X-ray diffraction and absorption fine structure measurements. The absorption edge position of the XANES revealed the bivalency of Mn. Two cation sites are available in the spinel structure for cation doping: a tetrahedral site and an octahedral site. The pre-edge of the XANES and the distance to the nearest neighbor atoms obtained from the EXAFS measurement showed that Mn was situated at the tetrahedral site. Rietveld analysis showed that the vacancy occupied the octahedral site. The preferential occupation of the tetrahedral site by Mn and the roles of N and Mg are discussed in relation to the spinel crystal structure. - Graphical Abstract: Fourier transform of EXAFS of Mn K-edge for Mn,Mg-codoped green phosphor and Mn coordination structure. Highlights: Black-Right-Pointing-Pointer Mn, Mg-codoped {gamma}-AlON green phosphor for white LED. Black-Right-Pointing-Pointer The valence of Mn is divalent. Black-Right-Pointing-Pointer Mn occupies the tetrahedral site in the spinel structure.

  6. Solar-thermal Water Splitting Using the Sodium Manganese Oxide Process & Preliminary H2A Analysis

    SciTech Connect (OSTI)

    Francis, Todd M; Lichty, Paul R; Perkins, Christopher; Tucker, Melinda; Kreider, Peter B; Funke, Hans H; Lewandowski, A; Weimer, Alan W

    2012-10-24

    There are three primary reactions in the sodium manganese oxide high temperature water splitting cycle. In the first reaction, Mn2O3 is decomposed to MnO at 1,500C and 50 psig. This reaction occurs in a high temperature solar reactor and has a heat of reaction of 173,212 J/mol. Hydrogen is produced in the next step of this cycle. This step occurs at 700C and 1 atm in the presence of sodium hydroxide. Finally, water is added in the hydrolysis step, which removes NaOH and regenerates the original reactant, Mn2O3. The high temperature solar-driven step for decomposing Mn2O3 to MnO can be carried out to high conversion without major complication in an inert environment. The second step to produce H2 in the presence of sodium hydroxide is also straightforward and can be completed. The third step, the low temperature step to recover the sodium hydroxide is the most difficult. The amount of energy required to essentially distill water to recover sodium hydroxide is prohibitive and too costly. Methods must be found for lower cost recovery. This report provides information on the use of ZnO as an additive to improve the recovery of sodium hydroxide.

  7. A fast route to obtain manganese spinel nanoparticles by reduction of K-birnessite

    SciTech Connect (OSTI)

    Giovannelli, F.; Chartier, T.; Autret-Lambert, C.; Delorme, F.; Zaghrioui, M.; Seron, A.

    2009-05-15

    The K-birnessite (K{sub x}MnO{sub 2}.yH{sub 2}O) reduction reaction has been tested in order to obtain manganese spinel nanoparticles. The addition of 0.25 weight percent of hydrazine hydrate, the reducing agent, during 24 hours is efficient to transform the birnessite powder in a hausmanite Mn{sub 3}O{sub 4} powder. Well crystallised square shape nanoparticles are obtained. Different birnessite precursors have been tested and the reaction kinetics is strongly correlated to the crystallinity and granulometry of the precursor. The effects of aging time and hydrazine hydrate amount have been studied. Well crystallised Mn{sub 3}O{sub 4} is obtained in one hour. The presence of feitknechtite (MnO(OH)) and amorphous nanorods has been detected as an intermediate phase during birnessite conversion into hausmanite. The conversion mechanism is discussed. - Graphical abstract: TEM image showing Mn{sub 3}O{sub 4} particle after treatment of birnessite with an addition of hydrazine during 24 hours.

  8. Manganese Doping of Magnetic Iron Oxide Nanoparticles: Tailoring Surface Reactivity for a Regenerable Heavy Metal Sorbent

    SciTech Connect (OSTI)

    Warner, Cynthia L.; Chouyyok, Wilaiwan; Mackie, Katherine E.; Neiner, Doinita; Saraf, Laxmikant; Droubay, Timothy C.; Warner, Marvin G.; Addleman, Raymond S.

    2012-02-28

    A method for tuning the analyte affinity of magnetic, inorganic nanostructured sorbents for heavy metal contaminants is described. The manganese-doped iron oxide nanoparticle sorbents have a remarkably high affinity compared to the precursor material. Sorbent affinity can be tuned toward an analyte of interest simply by adjustment of the dopant quantity. The results show that following the Mn doping process there is a large increase in affinity and capacity for heavy metals (i.e., Co, Ni, Zn, As, Ag, Cd, Hg, and Tl). Capacity measurements were carried out for the removal of cadmium from river water and showed significantly higher loading than the relevant commercial sorbents tested for comparison. The reduction in Cd concentration from 100 ppb spiked river water to 1 ppb (less than the EPA drinking water limit of 5 ppb for Cd) was achieved following treatment with the Mn-doped iron oxide nanoparticles. The Mn-doped iron oxide nanoparticles were able to load 1 ppm of Cd followed by complete stripping and recovery of the Cd with a mild acid wash. The Cd loading and stripping is shown to be consistent through multiple cycles with no loss of sorbent performance.

  9. Synergism between arsenite and proteasome inhibitor MG132 over cell death in myeloid leukaemic cells U937 and the induction of low levels of intracellular superoxide anion

    SciTech Connect (OSTI)

    Lombardo, Toms; Cavaliere, Victoria; Costantino, Susana N.; Kornblihtt, Laura; Alvarez, Elida M.; Blanco, Guillermo A.

    2012-02-01

    Increased oxygen species production has often been cited as a mechanism determining synergism on cell death and growth inhibition effects of arsenic-combined drugs. However the net effect of drug combination may not be easily anticipated solely from available knowledge of drug-induced death mechanisms. We evaluated the combined effect of sodium arsenite with the proteasome inhibitor MG132, and the anti-leukaemic agent CAPE, on growth-inhibition and cell death effect in acute myeloid leukaemic cells U937 and Burkitt's lymphoma-derived Raji cells, by the ChouTalalay method. In addition we explored the association of cytotoxic effect of drugs with changes in intracellular superoxide anion (O{sub 2}{sup ?}) levels. Our results showed that combined arsenite + MG132 produced low levels of O{sub 2}{sup ?} at 6 h and 24 h after exposure and were synergic on cell death induction in U937 cells over the whole dose range, although the combination was antagonistic on growth inhibition effect. Exposure to a constant non-cytotoxic dose of 80 ?M hydrogen peroxide together with arsenite + MG132 changed synergism on cell death to antagonism at all effect levels while increasing O{sub 2}{sup ?} levels. Arsenite + hydrogen peroxide also resulted in antagonism with increased O{sub 2}{sup ?} levels in U937 cells. In Raji cells, arsenite + MG132 also produced low levels of O{sub 2}{sup ?} at 6 h and 24 h but resulted in antagonism on cell death and growth inhibition. By contrast, the combination arsenite + CAPE showed high levels of O{sub 2}{sup ?} production at 6 h and 24 h post exposure but resulted in antagonism over cell death and growth inhibition effects in U937 and Raji cells. We conclude that synergism between arsenite and MG132 in U937 cells is negatively associated to O{sub 2}{sup ?} levels at early time points after exposure. -- Highlights: ? Arsenic combined cytotoxic and anti-proliferative effects by ChouTalalay method. ? Cytotoxic effect associated with superoxide levels as assessed by flow cytometry. ? Synergism between arsenite and MG132 in U937 leukemia cell line. ? Synergism turned into antagonism by low levels of hydrogen peroxide. ? Resistance to arsenic cytotoxicity linked to early superoxide anion increased levels.

  10. Protein Instability and Lou Gehrig's Disease

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    called superoxide dismutase (SOD). The study provides evidence that those proteins linked to more severe forms of the disease are less stable structurally and more prone to...

  11. Search for: All records | SciTech Connect

    Office of Scientific and Technical Information (OSTI)

    ... basal superoxide dismutase (SOD) expression. This data suggests that the regulation of O2?- is located at the crossroads between LDL signaling and cell proliferation. less August

  12. Protein Instability and Lou Gehrig's Disease

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    Light Source, researchers focused on the effects of mutations to a gene coding for a protein called superoxide dismutase (SOD). The study provides evidence that those proteins...

  13. Spatially resolved characterization of biogenic manganese oxideproduction within a bacterial biofilm

    SciTech Connect (OSTI)

    Toner, Brandy; Fakra, Sirine; Villalobos, Mario; Warwick, Tony; Sposito, Garrison

    2004-10-01

    Pseudomonas putida strain MnB1, a biofilm forming bacteria, was used as a model for the study of bacterial Mn oxidation in freshwater and soil environments. The oxidation of Mn{sub (aq)}{sup +2} by P. putida was characterized by spatially and temporally resolving the oxidation state of Mn in the presence of a bacterial biofilm using scanning transmission x-ray microscopy (STXM) combined with near edge x-ray absorption fine structure (NEXAFS) spectroscopy at the Mn-L{sub 2,3} absorption edges. Subsamples were collected from growth flasks containing 0.1 mM and 1 mM total Mn at 16, 24, 36 and 48 hours after inoculation. Immediately after collection, the unprocessed hydrated subsamples were imaged at 40 nm resolution. Manganese NEXAFS spectra were extracted from x-ray energy sequences of STXM images (stacks) and fit with linear combinations of well characterized reference spectra to obtain quantitative relative abundances of Mn(II), Mn(III) and Mn(IV). Careful consideration was given to uncertainty in the normalization of the reference spectra, choice of reference compounds, and chemical changes due to radiation damage. The STXM results confirm that Mn{sub (aq)}{sup +2} was removed from solution by P. putida and was concentrated as Mn(III) and Mn(IV) immediately adjacent to the bacterial cells. The Mn precipitates were completely enveloped by bacterial biofilm material. The distribution of Mn oxidation states was spatially heterogeneous within and between the clusters of bacterial cells. Scanning transmission x-ray microscopy is a promising tool to advance the study of hydrated interfaces between minerals and bacteria, particularly in cases where the structure of bacterial biofilms needs to be maintained.

  14. Structural implications of the C-terminal tail in the catalytic and stability properties of manganese peroxidases from ligninolytic fungi

    SciTech Connect (OSTI)

    Fernndez-Fueyo, Elena [CSIC, Ramiro de Maeztu 9, 28040 Madrid (Spain); Acebes, Sandra [Barcelona Supercomputing Center, Jordi Girona 29, 08034 Barcelona (Spain); Ruiz-Dueas, Francisco J.; Martnez, Mara Jess; Romero, Antonio; Medrano, Francisco Javier, E-mail: fjmedrano@cib.csic.es [CSIC, Ramiro de Maeztu 9, 28040 Madrid (Spain); Guallar, Victor, E-mail: fjmedrano@cib.csic.es [Barcelona Supercomputing Center, Jordi Girona 29, 08034 Barcelona (Spain); ICREA, Passeig Llus Companys 23, 08010 Barcelona (Spain); Martnez, Angel T., E-mail: fjmedrano@cib.csic.es [CSIC, Ramiro de Maeztu 9, 28040 Madrid (Spain)

    2014-12-01

    The variable C-terminal tail of manganese peroxidases, a group of enzymes involved in lignin degradation, is implicated in their catalytic and stability properties, as shown by new crystal structures, molecular-simulation and directed-mutagenesis data. Based on this structuralfunctional evaluation, short and long/extralong manganese peroxidase subfamilies have been accepted; the latter are characterized by exceptional stability, while it is shown for the first time that the former are able to oxidize other substrates at the same site where manganese(II) is oxidized. The genome of Ceriporiopsis subvermispora includes 13 manganese peroxidase (MnP) genes representative of the three subfamilies described in ligninolytic fungi, which share an Mn{sup 2+}-oxidation site and have varying lengths of the C-terminal tail. Short, long and extralong MnPs were heterologously expressed and biochemically characterized, and the first structure of an extralong MnP was solved. Its C-terminal tail surrounds the haem-propionate access channel, contributing to Mn{sup 2+} oxidation by the internal propionate, but prevents the oxidation of 2, 2?-azino-bis(3-ethylbenzothiazoline-6-sulfonate) (ABTS), which is only oxidized by short MnPs and by shortened-tail variants from site-directed mutagenesis. The tail, which is anchored by numerous contacts, not only affects the catalytic properties of long/extralong MnPs but is also associated with their high acidic stability. Cd{sup 2+} binds at the Mn{sup 2+}-oxidation site and competitively inhibits oxidation of both Mn{sup 2+} and ABTS. Moreover, mutations blocking the haem-propionate channel prevent substrate oxidation. This agrees with molecular simulations that position ABTS at an electron-transfer distance from the haem propionates of an in silico shortened-tail form, while it cannot reach this position in the extralong MnP crystal structure. Only small differences exist between the long and the extralong MnPs, which do not justify their classification as two different subfamilies, but they significantly differ from the short MnPs, with the presence/absence of the C-terminal tail extension being implicated in these differences.

  15. Effect of Manganese Addition to the Co-MCM-41 Catalyst in the Selective Synthesis of Single Wall Carbon Nanotubes

    SciTech Connect (OSTI)

    Zoican Loebick, C.; Derrouiche, S; Marinkovic, N; Wang, C; Hennrich, F; Kappes, M; Haller, L; Pfefferle, L

    2009-01-01

    The effect of manganese addition to the Co-MCM-41 catalyst on the synthesis of single wall carbon nanotubes (SWNT) by CO disproportionation was characterized. The ratio between the two metals in the MCM-41 framework was varied, and its effect on the resultant SWNT distribution was studied and compared with the results obtained for the monometallic Co-MCM-41 catalyst. Methods including temperature-programmed reduction, X-ray absorption fine structure, thermogravimetric analysis, TEM imaging, and Raman and fluorescence spectroscopy were employed to characterize the behavior of the catalysts under the SWNT synthesis conditions and the diameter and structure distribution of the resultant nanotubes. We found that addition of Mn to the Co-MCM-41 catalyst promotes the growth of SWNT, leading to synthesis of high yield, small diameter SWNT. Manganese does not act in the nucleation of SWNT but acts as an anchoring site for cobalt particles formed during the synthesis process as shown by X-ray absorption.

  16. Electrodeposited Manganese Oxides on Three-Dimensional Carbon Nanotube Substrate: Supercapacitive Behaviour in Aqueous and Organic Electrolytes

    SciTech Connect (OSTI)

    Nam,K.W.; Yang,X.

    2009-03-01

    Thin amorphous manganese oxide layers with a thickness of 3-5nm are electrodeposited on a carbon nanotube (CNT) film substrate that has a three-dimensional nanoporous structure (denoted asMnO2/CNT electrode). For the purpose of comparison, manganese oxide films are also electrodeposited on a flat Pt-coated Si wafer substrate (denoted as MnO2 film electrode). The pseudocapacitive properties of the MnO2 film and MnO2/CNT electrodes are examined in both aqueous electrolyte (1.0M KCl) and nonaqueousorganic electrolyte (1.0M LiClO4 in propylene carbonate). While both types of electrode showpseudocapacitive behaviour in the aqueous electrolyte, only the MnO2/CNT electrode does so in the organic electrolyte, due to its high oxide/electrolyte interfacial area and improved electron conduction through the CNT substrate. Compared with the MnO2 film electrode, the MnO2/CNT electrode shows a much higher specific capacitance and better high-rate capability, regardless of the electrolyte used.Use of the organic electrolyte results in a ?6 times higher specific energy compared with that obtained with the aqueous electrolyte, while maintaining a similar specific power. The construction of a threedimensional nanoporous network structure consisting of a thin oxide layer on a CNT film substrate at the nm scale and the use of an organic electrolyte are promising approaches to improving the specific energyof supercapacitors.

  17. Studies on the catalytic activity of zirconia promoted with sulfate, iron, and manganese

    SciTech Connect (OSTI)

    Wan, K.T.; Khouw, C.B.; Davis, M.E.

    1996-01-01

    The catalytic properties of iron- and manganese-promoted sulfated zirconia (SFMZ) for the isomerization of n-butane to isobutane are investigated using various catalyst pretreatments and reaction conditions. The n-butane isomerization reactivity at 30{degrees}C is effected by calcination of the catalyst at 650{degrees}C in helium and vacuum treatment at room temperature indicating that superacidity is not likely to be responsible for activity. In addition, SFMZ samples exposed to dry air at over 450{degrees}C are more active than those calcined in helium at a reaction temperature of 30{degrees}C (n-butane conversions of 18.7% vs 0.4%) suggesting the presence of an active site involving a metal {open_quotes}oxy{close_quotes} species. The oxy species is capable of reacting CO to CO{sub 2} at room temperature and is present at a number density of 10-15 {mu}mol/g. At a reaction temperature of 100{degrees}C, SFMZ catalysts calcined in air then activated in helium show similar reactivities to those activated in air up to a preheating temperature of 450{degrees}C; above 450{degrees}C the metal oxy species is formed and provides additional activity (n-butane conversions of 37.1% in air vs 15.4% in He for calcinations at 650{degrees}C). The nature of the active sites on SFMZ are investigated using temperature-programmed desorption of substituted benzenes. The liberation of CO{sub 2} and SO{sub 2} in the benzene TPD profile of SFMZ is attributed to the oxidation of benzene at the redox-active metal sites, resulting in the subsequent decomposition of the reduced iron (II) sulfate. Data from the TPD studies do not suggest the presence of superacidity on SFMZ that could contribute to the low-temperature n-butane isomerization activity. Instead, a bifunctional mechanism that involves a combination of a redox-active metal site and an acid site in close proximity is proposed. 62 refs., 17 figs., 4 tabs.

  18. Effects of (Al,Ge) double doping on the thermoelectric properties of higher manganese silicides

    SciTech Connect (OSTI)

    Chen, Xi; Salta, Daniel; Zhang, Libin [Materials Science and Engineering Program, Texas Materials Institute, The University of Texas at Austin, Austin, Texas 78712 (United States); Weathers, Annie [Department of Mechanical Engineering, The University of Texas at Austin, Austin, Texas 78712 (United States); Zhou, Jianshi; Goodenough, John B.; Shi, Li [Materials Science and Engineering Program, Texas Materials Institute, The University of Texas at Austin, Austin, Texas 78712 (United States); Department of Mechanical Engineering, The University of Texas at Austin, Austin, Texas 78712 (United States)

    2013-11-07

    Experiments and analysis have been carried out to investigate the effects of Al and (Al,Ge) doping on the microstructure and thermoelectric properties of polycrystalline higher manganese silicide (HMS) samples, which were prepared by solid-state reaction, ball milling, and followed by spark plasma sintering. It has been found that Al doping effectively increases the hole concentration, which leads to an increase in the electrical conductivity and power factor. By introducing the second dopant Ge into Al-doped HMS, the electrical conductivity is increased, and the Seebeck coefficient is decreased as a result of further increased hole concentration. The peak power factor is found to occur at a hole concentration between 1.8??10{sup 21} and 2.2??10{sup 21}?cm{sup ?3} measured at room temperature. The (Al,Ge)-doped HMS samples show lower power factors owing to their higher hole concentrations. The mobility of Mn(Al{sub 0.0035}Ge{sub y}Si{sub 0.9965-y}){sub 1.8} with y?=?0.035 varies approximately as T{sup ?3/2} above 200?K, suggesting acoustic phonon scattering is the dominant scattering mechanism. The thermal conductivity of HMS does not change appreciably by Al or (Al,Ge) doping. The maximum ZT of (Al,Ge)-doped HMS is 0.57 at 823?K, which is similar to the highest value found in the Al-doped HMS samples. The ZT values were reduced in the Mn(Al{sub 0.0035}Ge{sub y}Si{sub 0.9965-y}){sub 1.8} samples with high Ge concentration of y?=?0.025 and 0.035, because of reduced power factor. In addition, a two-band model was employed to show that the hole contribution to the thermal conductivity dominates the bipolar and electron contributions for all samples from 300 to 823?K and accounts for about 12% of the total thermal conductivity at about 800?K.

  19. Acute ethanol intake induces superoxide anion generation and mitogen-activated protein kinase phosphorylation in rat aorta: A role for angiotensin type 1 receptor

    SciTech Connect (OSTI)

    Yogi, Alvaro; Callera, Glaucia E.; Mecawi, Andr S.; Batalho, Marcelo E.; Carnio, Evelin C.; Antunes-Rodrigues, Jos; Queiroz, Regina H.; Touyz, Rhian M.; Tirapelli, Carlos R.

    2012-11-01

    Ethanol intake is associated with increase in blood pressure, through unknown mechanisms. We hypothesized that acute ethanol intake enhances vascular oxidative stress and induces vascular dysfunction through reninangiotensin system (RAS) activation. Ethanol (1 g/kg; p.o. gavage) effects were assessed within 30 min in male Wistar rats. The transient decrease in blood pressure induced by ethanol was not affected by the previous administration of losartan (10 mg/kg; p.o. gavage), a selective AT{sub 1} receptor antagonist. Acute ethanol intake increased plasma renin activity (PRA), angiotensin converting enzyme (ACE) activity, plasma angiotensin I (ANG I) and angiotensin II (ANG II) levels. Ethanol induced systemic and vascular oxidative stress, evidenced by increased plasma thiobarbituric acid-reacting substances (TBARS) levels, NAD(P)H oxidase?mediated vascular generation of superoxide anion and p47phox translocation (cytosol to membrane). These effects were prevented by losartan. Isolated aortas from ethanol-treated rats displayed increased p38MAPK and SAPK/JNK phosphorylation. Losartan inhibited ethanol-induced increase in the phosphorylation of these kinases. Ethanol intake decreased acetylcholine-induced relaxation and increased phenylephrine-induced contraction in endothelium-intact aortas. Ethanol significantly decreased plasma and aortic nitrate levels. These changes in vascular reactivity and in the end product of endogenous nitric oxide metabolism were not affected by losartan. Our study provides novel evidence that acute ethanol intake stimulates RAS activity and induces vascular oxidative stress and redox-signaling activation through AT{sub 1}-dependent mechanisms. These findings highlight the importance of RAS in acute ethanol-induced oxidative damage. -- Highlights: ? Acute ethanol intake stimulates RAS activity and vascular oxidative stress. ? RAS plays a role in acute ethanol-induced oxidative damage via AT{sub 1} receptor activation. ? Translocation of p47phox and MAPKs phosphorylation are downstream effectors. ? Acute ethanol consumption increases the risk for acute vascular injury.

  20. Flow-Assisted Alkaline Battery: Low-Cost Grid-Scale Electrical Storage using a Flow-Assisted Rechargeable Zinc-Manganese Dioxide Battery

    SciTech Connect (OSTI)

    2010-09-15

    GRIDS Project: Traditional consumer-grade disposable batteries are made of Zinc and Manganese, 2 inexpensive, abundant, and non-toxic metals. But these disposable batteries can only be used once. If they are recharged, the Zinc in the battery develops filaments called dendrites that grow haphazardly and disrupt battery performance, while the Manganese quickly loses its ability to store energy. CUNY Energy Institute is working to tame dendrite formation and to enhance the lifetime of Manganese in order to create a long-lasting, fully rechargeable battery for grid-scale energy storage. CUNY Energy Institute is also working to reduce dendrite formation by pumping fluid through the battery, enabling researchers to fix the dendrites as theyre forming. The team has already tested its Zinc battery through 3,000 recharge cycles (and counting). CUNY Energy Institute aims to demonstrate a better cycle life than lithium-ion batteries, which can be up to 20 times more expensive than Zinc-based batteries.

  1. X-ray absorption spectroscopy on the calcium cofactor to the manganese cluster in photosynthetic oxygen evolution

    SciTech Connect (OSTI)

    Cinco, Roehl M.

    1999-12-16

    Along with Mn, calcium and chloride ions are necessary cofactors for oxygen evolution in Photosystem II (PS II). To further test and verify whether Ca is close to the Mn cluster, the authors substituted strontium for Ca and probed from the Sr point of view for any nearby Mn. The extended X-ray absorption fine structure (EXAFS) of Sr-reactivated PS II indicates major differences between the intact and NH{sub 2}OH-treated samples. In intact samples, the Fourier transform of the Sr EXAFS shows a Fourier peak that is missing in inactive samples. This peak II is best simulated by two Mn neighbors at a distance of 3.5 Angstrom, confirming the proximity of Ca (Sr) cofactor to the Mn cluster. In addition, polarized Sr EXAFS on oriented Sr-reactivated samples shows this peak II is dichroic: large magnitude at 10 degrees (angle between the PS II membrane normal and the x-ray electric field vector) and small at 80 degrees. Analysis of the dichroism yields the relative angle between the Sr-Mn vector and membrane normal (23 degrees {+-} 4 degrees), and the isotropic coordination number for these layered samples. X-ray absorption spectroscopy has also been employed to assess the degree of similarity between the manganese cluster in PS II and a family of synthetic manganese complexes containing the distorted cubane [Mn{sub 4}O{sub 3}X] core (X = benzoate, acetate, methoxide, hydroxide, azide, fluoride, chloride or bromide). In addition, Mn{sub 4}O{sub 3}Cl complexes containing three or six terminal Cl ligands at three of the Mn were included in this study. The EXAFS method detects the small changes in the core structures as X is varied in this series, and serves to exclude these distorted cubanes of C3v symmetry as a topological model for the Mn catalytic cluster. The sulfur K-edge x-ray absorption near-edge structure (XANES) spectra for the amino acids cysteine, methionine, their corresponding oxidized forms cystine and methionine sulfoxide, and glutathione show distinct differences between the thiol and disulfide forms. Sulfur XANES is also used to detect changes (within 5%) of the thiol-to-disulfide ratio in whole human blood, plasma, and erythrocytes.

  2. Low- and high-order harmonic generation in the extended plasmas produced by laser ablation of zinc and manganese targets

    SciTech Connect (OSTI)

    Ganeev, R. A.; Baba, M.; Suzuki, M.; Yoneya, S.; Kuroda, H.

    2014-12-28

    The systematic studies of the harmonic generation of ultrashort laser pulses in the 5-mm-long Zn and Mn plasmas (i.e., application of nanosecond, picosecond, and femtosecond pulses for ablation, comparison of harmonic generation from atomic, ionic, and cluster-contained species of plasma, variation of plasma length, two-color pump of plasmas, etc.) are presented. The conversion efficiency of the 11th–19th harmonics generated in the Zn plasma was ∼5 × 10{sup −5}. The role of the ionic resonances of Zn near the 9th and 10th harmonics on the enhancement of harmonics is discussed. The enhancement of harmonics was also analyzed using the two-color pump of extended plasmas, which showed similar intensities of the odd and even harmonics along the whole range of generation. The harmonics up to the 107th order were demonstrated in the case of manganese plasma. The comparison of harmonic generation in the 5-mm-long and commonly used short (≤0.5 mm) plasma plumes showed the advanced properties of extended media.

  3. A hard X-ray study of a manganese-terpyridine catalyst in a chromium-based Metal Organic Framework

    SciTech Connect (OSTI)

    Ramsey, Alexandra V.

    2015-08-28

    Hydrogen produced from water splitting is a promising source of clean energy. However, a robust catalyst is necessary to carry out the water oxidation step of water splitting. In this study, the catalyst studied was [(terpy)Mn(?-O)2Mn(terpy)]3+ (MnTD) synthesized in the Metal Organic Framework (MOF) MIL-101(Cr), and the method used for analysis was hard X-ray powder diffraction. The diffraction data was used to detect the presence of MOF in different catalytic stages, and lattice parameters were assigned to the samples containing MOF. Fourier maps were constructed with GSAS II to determine the contents of the MOF as preliminary studies suggested that MnTD may not be present. Results showed that MOF is present before catalysis occurs but disappears by the time 45 minutes of catalysis has ensued. Changes in the MOFs lattice parameters and location of electron density in the Fourier maps suggest attractions between the MOF and catalyst that may lead to MOF degradation. Fourier maps also revealed limited, if any, amounts of MnTD, even before catalysis occurred. Molecular manganese oxide may be the source of the high rate of water oxidation catalysis in the studied system.

  4. A study of a ceria-zirconia-supported manganese oxide catalyst for combustion of Diesel soot particles

    SciTech Connect (OSTI)

    Sanchez Escribano, V.; Fernandez Lopez, E.; del Hoyo Martinez, C.; Pistarino, C.; Panizza, M.; Resini, C.; Busca, G.

    2008-04-15

    A study has been conducted on the structural and morphological characterization of a Ce-Zr mixed oxide-supported Mn oxide as well as on its catalytic activity in the oxidation of particulate matter arising from Diesel engines. X-ray powder diffraction analysis (XRD) and FT-IR and FT-Raman spectroscopy evidence that the support is a fluorite-like ceria-zirconia solid solution, whereas the supported phase corresponds to the manganese oxide denoted as bixbyite ({alpha}-Mn{sub 2}O{sub 3}). Thermal analyses and FT-IR spectra in air at varying temperatures of soot mechanically mixed with the catalyst evidence that the combustion takes place to a total extent in the range 420-720 K, carboxylic species being detected as intermediate compounds. Moreover, the soot oxidation was studied in a flow reactor and was found to be selective to CO{sub 2}, with CO as by-product in the range 420-620 K. The amount of the generated CO decreases significantly with increasing O{sub 2} concentration in the feed. (author)

  5. Low-temperature superacid catalysis: Reactions of n - butane and propane catalyzed by iron- and manganese-promoted sulfated zirconia

    SciTech Connect (OSTI)

    Tsz-Keung, Cheung; d`Itri, J.L.; Lange, F.C.; Gates, B.C.

    1995-12-31

    The primary goal of this project is to evaluate the potential value of solid superacid catalysts of the sulfated zirconia type for light hydrocarbon conversion. The key experiments catalytic testing of the performance of such catalysts in a flow reactor fed with streams containing, for example, n-butane or propane. Fe- and Mn-promoted sulfated zirconia was used to catalyze the conversion of n-butane at atmospheric pressure, 225-450{degrees}C, and n-butane partial pressures in the range of 0.0025-0.01 atm. At temperatures <225{degrees}C, these reactions were accompanied by cracking; at temperatures >350{degrees}C, cracking and isomerization occurred. Catalyst deactivation, resulting at least in part from coke formation, was rapid. The primary cracking products were methane, ethane, ethylene, and propylene. The observation of these products along with an ethane/ethylene molar ratio of nearly 1 at 450{degrees}C is consistent with cracking occurring, at least in part, by the Haag-Dessau mechanism, whereby the strongly acidic catalyst protonates n-butane to give carbonium ions. The rate of methane formation from n-butane cracking catalyzed by Fe- and Mn-promoted sulfated zirconia at 450{degrees}C was about 3 x 10{sup -8} mol/(g of catalyst {center_dot}s). The observation of butanes, pentanes, and methane as products is consistent with Olah superacid chemistry, whereby propane is first protonated by a very strong acid to form a carbonium ion. The carbonium ion then decomposes into methane and an ethyl cation which undergoes oligocondensation reactions with propane to form higher molecular weight alkanes. The results are consistent with the identification of iron- and manganese-promoted sulfated zirconia as a superacid.

  6. Activation of ethane in the presence of solid acids: Sulfated zirconia, iron- and manganese-promoted sulfated zirconia, and zeolites

    SciTech Connect (OSTI)

    Cheung, Tsz-Keung; Gates, B.

    1997-06-01

    Ethane was activated in the presence of solid acids [sulfated zirconia (SZ), iron- and manganese-promoted sulfated zirconia (FMSZ), HZSM-5, and USY zeolite] at 1 atm, 200-450{degrees}C, and ethane partial pressures in the range 0.014.2 atm. The data were measured with a flow reactor at low conversions (<0.005) such that reaction of ethane took place in the near absence of alkenes. Catalysis was demonstrated for ethane conversion in the presence of FMSZ at 450{degrees}C and 0.2 atm ethane partial pressure, but the reactions were not shown to be catalytic for the other solid acids and other conditions. FMSZ was active for converting ethane into methane, ethene, and butane at an ethane partial pressure of 0.2 atm and at temperatures of 200-300{degrees}C; the other solid acids had no detectable activities under these conditions. At higher temperatures, each of the solid acids was active for conversion of ethane into ethene; butane and methane were also formed in the presence of FMSZ, HZSM-5, and USY zeolite, whereas methane was the only other hydrocarbon observed in the presence of SZ. The initial (5 min on stream) selectivities to ethene at approximately 0.1 % conversion, ethane partial pressure of 0.2 atm, and 450{degrees}C were approximately 98, 94, 97, and 99%, for SZ, FMSZ, HZSM-5, and USY zeolite, respectively. Under the same reaction conditions, the initial rates of ethane conversion were 0. 1 5 x 10{sup -8}, 3.5 x 10{sup -8} 3.9 x 10{sup -8}, and 0.56 x 10{sup -8} mol/(s {circ} g) for SZ, FMSZ, HZSM-5, and USY zeolite, respectively. The reactivities are consistent with chemistry analogous to that occurring in superacidic solutions and with the suggestion that FMSZ is a stronger acid than the others investigated here. 25 refs., 13 figs., 1 tab.

  7. Homogeneity testing and quantitative analysis of manganese (Mn) in vitrified Mn-doped glasses by laser-induced breakdown spectroscopy (LIBS)

    SciTech Connect (OSTI)

    Unnikrishnan, V. K.; Nayak, Rajesh; Kartha, V. B.; Santhosh, C. E-mail: unnikrishnan.vk@manipal.edu; Sonavane, M. S.; Yeotikar, R. G.; Shah, M. L.; Gupta, G. P.; Suri, B. M.

    2014-09-15

    Laser-induced breakdown spectroscopy (LIBS), an atomic emission spectroscopy method, has rapidly grown as one of the best elemental analysis techniques over the past two decades. Homogeneity testing and quantitative analysis of manganese (Mn) in manganese-doped glasses have been carried out using an optimized LIBS system employing a nanosecond ultraviolet Nd:YAG laser as the source of excitation. The glass samples have been prepared using conventional vitrification methods. The laser pulse irradiance on the surface of the glass samples placed in air at atmospheric pressure was about 1.710{sup 9} W/cm{sup 2}. The spatially integrated plasma emission was collected and imaged on to the spectrograph slit using an optical-fiber-based collection system. Homogeneity was checked by recording LIBS spectra from different sites on the sample surface and analyzing the elemental emission intensities for concentration determination. Validation of the observed LIBS results was done by comparison with scanning electron microscope- energy dispersive X-ray spectroscopy (SEM-EDX) surface elemental mapping. The analytical performance of the LIBS system has been evaluated through the correlation of the LIBS determined concentrations of Mn with its certified values. The results are found to be in very good agreement with the certified concentrations.

  8. Mapping Phase Transformations in the Heat-Affected-Zone of Carbon Manganese Steel Welds using Spatially Resolved X-Ray Diffraction

    SciTech Connect (OSTI)

    Elmer, J W; Wong, J; Ressler, T; Palmer, T A

    2001-12-04

    Spatially Resolved X-Ray Diffraction (SRXRD) was used to investigate phase transformations that occur in the heat affected zone (HAZ) of gas tungsten arc (GTA) welds in AISI 1005 carbon-manganese steel. In situ SRXRD experiments performed at the Stanford Synchrotron Radiation Laboratory (SSRL) probed the phases present in the HAZ during welding, and these real-time observations of the HAZ phases were used to construct a map of the phase transformations occurring in the HAZ. This map identified 5 principal phase regions between the liquid weld pool and the unaffected base metal for the carbon-manganese steel studied in this investigation. Regions of annealing, recrystallization, partial transformation and complete transformation to {alpha}-Fe, {gamma}-Fe, and {delta}-Fe phases were identified using SRXRD, and the experimental results were combined with a heat flow model of the weld to investigate transformation kinetics under both positive and negative temperature gradients in the HAZ. From the resulting phase transformation map, the kinetics of phase transformations that occur under the highly non-isothermal heating and cooling cycles produced during welding of steels can now be better understood and modeled.

  9. Manganese and Ceria Sorbents for High Temperature Sulfur Removal from Biomass-Derived Syngas -- The Impact of Steam on Capacity and Sorption Mode

    SciTech Connect (OSTI)

    Cheah, S.; Parent, Y. O.; Jablonski, W. S.; Vinzant, T.; Olstad, J. L.

    2012-07-01

    Syngas derived from biomass and coal gasification for fuel synthesis or electricity generation contains sulfur species that are detrimental to downstream catalysts or turbine operation. Sulfur removal in high temperature, high steam conditions has been known to be challenging, but experimental reports on methods to tackle the problem are not often reported. We have developed sorbents that can remove hydrogen sulfide from syngas at high temperature (700 C), both in dry and high steam conditions. The syngas composition chosen for our experiments is derived from statistical analysis of the gasification products of wood under a large variety of conditions. The two sorbents, Cu-ceria and manganese-based, were tested in a variety of conditions. In syngas containing steam, the capacity of the sorbents is much lower, and the impact of the sorbent in lowering H{sub 2}S levels is only evident in low space velocities. Spectroscopic characterization and thermodynamic consideration of the experimental results suggest that in syngas containing 45% steam, the removal of H{sub 2}S is primarily via surface chemisorptions. For the Cu-ceria sorbent, analysis of the amount of H{sub 2}S retained by the sorbent in dry syngas suggests both copper and ceria play a role in H{sub 2}S removal. For the manganese-based sorbent, in dry conditions, there is a solid state transformation of the sorbent, primarily into the sulfide form.

  10. Templated, layered manganese phosphate

    DOE Patents [OSTI]

    Thoma, Steven G.; Bonhomme, Francois R.

    2004-08-17

    A new crystalline maganese phosphate composition having an empirical formula: O). The compound was determined to crystallize in the trigonal space group P-3c1 with a=8.8706(4) .ANG., c=26.1580(2) .ANG., and V (volume)=1783 .ANG..sup.3. The structure consists of sheets of corner sharing Mn(II)O.sub.4 and PO.sub.4 tetrahedra with layers of (H.sub.3 NCH.sub.2 CH.sub.2).sub.3 N and water molecules in-between. The pronated (H.sub.3 NCH.sub.2 CH.sub.2).sub.3 N molecules provide charge balancing for the inorganic sheets. A network of hydrogen bonds between water molecules and the inorganic sheets holds the structure together.

  11. Advanced Recombinant Manganese Peroxidase for Biosynthesis of Lignin Bioproducts, Phase I Final Report, STTR Grant #: DE-SC0007503.

    SciTech Connect (OSTI)

    Beatty, Christopher; Kitner, Joshua; Lajoie, Curtis; McClain, Sean; Potochnik, Steve

    2012-12-13

    The core purpose of this Phase I STTR was to evaluate the feasibility of a new method of producing a recombinant version of manganese peroxidase (MnP) enzyme. MnP is a potentially valuable enzyme for producing high value lignin products and also for industrial de-coloring operations such as biobleaching of pulp and color removal from textile dye effluents. This lignin-modifying enzyme is produced in small amounts by the native host, a white rot fungus. Previous work by Oregon State University developed a secreted recombinant version of the enzyme in the yeast Pichia pastoris. Unfortunately, the expression is barely moderate and the enzyme is heavily glycosylated, which inhibits purification. In this work, the gene for the enzyme is given a tag which targets production of the enzyme to the peroxisome. This is a promising approach since this location is also where heme and hydrogen peroxide are sequestered, which are both necessary cofactors for MnP. More than ten recombinant strains were constructed, verified, and expressed in the Pichia system. Constitutive (GAP) and methanol-induced promoters (AOX) were tried for peroxisomal targeted, cytosolic, and secreted versions of MnP. Only the secreted strains showed activity. The amount of expression was not significantly changed. The degree of glycosylation was lessened using the AOX (methanol) promotoer, but the resulting enzyme was still not able to be purified using immobilized metal affinity chromatography. Additional work beyond the scope of the defined Phase I project was undertaken to construct, verify, and express Pichia strains that mutated the MnP glycosylation sites to inhibit this process. These strains did not show significant activity. The cause is not known, but it is possible that these sites are important to the structure of the enzyme. Also beyond the scope proposed for our Phase I STTR, the team collaborated with AbSci, a startup with a new E. coli based expression system focused on the production of antibodies and enzymes containing disulfide bonds and requiring folding/post-translational modification. With only limited time remaining in the Phase I schedule, a single construct was made to produce MnP with this system. The enzyme was produced in the soluble fraction of the cell lysate, but no activity was measured. MnP from the existing recombinant source was used to act on lignin. The lignin was from a Kraft process and had a molecular weight of about 10,000 Da. Using 1000 Da dialysis membranes and UV-visible spectroscopy, no modification of either lignin was evident in the dialysate or the retentate. Assays using 2,6 dimethoxy phenol (DMP) as a substrate showed consistent activity throughout the project. In summary, these results fell far short of our expectations. A Phase II proposal was not submitted. Possible reasons for the failure of peroxisomal targeting include destruction by native hydrogen peroxide, native proteases, or unforeseen causes. The AbSci system was only lighted tested and further work may yield a strain with active enzyme. The lack of evidence for lignin modification may be due to the techniques employed. NMR or GC-MS studies may reveal evidence of modification.

  12. Material and detector properties of cadmium manganese telluride (Cd1-xMnxTe) crystals grown by the modified floating-zone method

    DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)

    Hossain, A.; Gu, G. D.; Bolotnikov, A. E.; Camarda, G. S.; Cui, Y.; Roy, U. N.; Yang, G.; Liu, T.; Zhong, R.; Schneelock, J.; et al

    2014-12-24

    We demonstrated the material- and radiation-detection properties of cadmium manganese telluride (Cd1-xMnxTe; x=0.06), a wide-band-gap semiconductor crystal grown by the modified floating-zone method. We investigated the presence of various bulk defects, such as Te inclusions, twins, and dislocations of several as-grown indium-doped Cd1-xMnxTe crystals using different techniques, viz., IR transmission microscopy, and chemical etching. We then fabricated four planar detectors from selected CdMnTe crystals, characterized their electrical properties, and tested their performance as room-temperature X- and gamma-ray detectors. Thus, our experimental results show that CMT crystals grown by the modified floating zone method apparently are free from Te inclusions. However,more » we still need to optimize our growth parameters to attain high-resistivity, large-volume single-crystal CdMnTe.« less

  13. Stability and Rate Capability of Al Substituted Lithium-Rich High-Manganese Content Oxide Materials for Li-Ion Batteries

    SciTech Connect (OSTI)

    Li, Zheng; Chernova, Natasha A.; Feng, Jijun; Upreti, Shailesh; Omenya, Fredrick; Whittingham, M. Stanley

    2015-10-15

    The structures, electrochemical properties and thermal stability of Al-substituted lithium-excess oxides, Li{sub 1.2}Ni{sub 0.16} Mn{sub 0.56}Co{sub 0.08-y}Al{sub y}O{sub 2} (y = 0, 0.024, 0.048, 0.08), are reported, and compared to the stoichiometric compounds, LiNi{sub z}Mn{sub z}Co{sub 1-2z}O{sub 2}. A solid solution was found up to at least y = 0.06. Aluminum substitution improves the poor thermal stability while preserving the high energy density of lithium-excess oxides. However, these high manganese compositions are inferior to the lithium stoichiometric materials, LiNi{sub z}Mn{sub z}Co{sub 1-2z}O{sub 2} (z = 0.333, 0.4), in terms of both power and thermal stability.

  14. Mapping Phase Transformations in the Heat-Affected-Zone of Carbon Manganese Steel Welds using Spatially Resolved X-Ray Diffraction

    SciTech Connect (OSTI)

    Elmer, J W; Wong, J; Ressler, T; Palmer, T A

    2002-02-12

    Spatially Resolved X-Ray Diffraction (SRXRD) was used to investigate phase transformations that occur in the heat affected zone (HAZ) of gas tungsten arc (GTA) welds in AISI 1005 carbon-manganese steel. In situ SRXRD experiments performed at the Stanford Synchrotron Radiation Laboratory (SSRL) probed the phases present in the HAZ during welding, and these real-time observations of the HAZ phases were used to construct a map of the phase transformations occurring in the HAZ. This map identified 5 principal phase regions between the liquid weld pool and the unaffected base metal. Regions of annealing, recrystallization, partial transformation and complete transformation to {alpha}-Fe, {gamma}-Fe, and {delta}-Fe phases were identified using SRXRD, and the experimental results were combined with a heat flow model of the weld and thermodynamic calculations to compare these results with the important phase transformation isotherms. From the resulting phase transformation map, the kinetics of phase transformations that occur under the highly non-isothermal heating and cooling cycles produced during welding of steels can be better understood and modeled.

  15. Genetic variation in resistance to ionizing radiation

    SciTech Connect (OSTI)

    Ayala, F.J.

    1989-01-01

    The very reactive superoxide anion O[sub 2] is generated during cell respiration as well as during exposure to ionizing radiation. Organisms have evolved different mechanisms to protect against the deleterious effects of reduced oxygen species. The copper-zinc superoxide dismutase is a eukaryotic cytoplasmic enzyme that protects the cell by scavenging superoxide radicals and dismutating them to hydrogen peroxide and molecular oxygen: 20[sub 2][sup [minus

  16. A Hard X-ray Study of a Manganese-Terpyridine Dimer Catalyst in a Chromium-based Metal Organic Framework - Oral Presentation

    SciTech Connect (OSTI)

    Ramsey, Alexandra

    2015-08-25

    Cleaner forms of energy are needed, and H2 produced from water spliFng is a possible source. However, a robust catalyst is necessary to carry out the water oxidaKon reacKon. Plants uKlize Photosystem II to catalyze water oxidaKon as a part of photosynthesis, and many syntheKc water oxidaKon catalysts use Photosystem II as a model. In this study, the catalyst of interest was [(terpy)Mn(?-O)2Mn(terpy)]3+ (MnTD), which was synthesized in a chromium-based Metal Organic Framework (MOF) to avoid degradaKon of MnTD molecules. Hard X-ray powder diffracKon was the primary method of analysis. The diffracKon data was used to detect the presence of MOF in samples at different catalyKc stages, and laFce parameters were assigned to the samples containing MOF. Fourier maps were constructed to determine the contents of the MOF as preliminary studies suggested that MnTD may not be present. Results showed that MOF is present before catalysis occurs, but disappears in the iniKal stages of catalysis. Changes in the MOFs laFce parameters suggest aWracKve interacKons between the MOF and catalyst; these interacKons may lead to the observed MOF degradaKon. Fourier maps also reveal limited, if any, amounts of MnTD in the system. Molecular manganese oxide may be the source of the high rate of water oxidaKon catalysis in the studied system.

  17. Manganese partitioning in low carbon manganese steel during annealing

    SciTech Connect (OSTI)

    Lis, J.; Lis, A. Kolan, C.

    2008-08-15

    For 6Mn16 steel experimental soft annealing at 625 deg. C for periods from 1 h to 60 h and modeling with Thermo-Calc were performed to estimate the partitioning of alloying elements, in particular Mn, between ferrite, cementite and austenite. Using transmission electron microscopy and X-ray analysis it was established that the increase of Mn concentration in carbides to a level 7%-11.2% caused a local decrease of the Ac{sub 1} temperature and led to the presence of austenite around the carbides. Thus, after cooling, small bainite-martensite or bainite-martensite-retained austenite (BM-A) islands were observed. A dispersion of carbides and a coarsening process were observed. The measured amount of Mn in the carbides was in good agreement with theoretical predictions.

  18. Attenuation of acute nitrogen mustard-induced lung injury, inflammation and fibrogenesis by a nitric oxide synthase inhibitor

    SciTech Connect (OSTI)

    Malaviya, Rama; Venosa, Alessandro; Hall, LeRoy; Gow, Andrew J.; Sinko, Patrick J.; Laskin, Jeffrey D.; Laskin, Debra L.

    2012-12-15

    Nitrogen mustard (NM) is a toxic vesicant known to cause damage to the respiratory tract. Injury is associated with increased expression of inducible nitric oxide synthase (iNOS). In these studies we analyzed the effects of transient inhibition of iNOS using aminoguanidine (AG) on NM-induced pulmonary toxicity. Rats were treated intratracheally with 0.125 mg/kg NM or control. Bronchoalveolar lavage fluid (BAL) and lung tissue were collected 1 d28 d later and lung injury, oxidative stress and fibrosis assessed. NM exposure resulted in progressive histopathological changes in the lung including multifocal lesions, perivascular and peribronchial edema, inflammatory cell accumulation, alveolar fibrin deposition, bronchiolization of alveolar septal walls, and fibrosis. This was correlated with trichrome staining and expression of proliferating cell nuclear antigen (PCNA). Expression of heme oxygenase (HO)-1 and manganese superoxide dismutase (Mn-SOD) was also increased in the lung following NM exposure, along with levels of protein and inflammatory cells in BAL, consistent with oxidative stress and alveolar-epithelial injury. Both classically activated proinflammatory (iNOS{sup +} and cyclooxygenase-2{sup +}) and alternatively activated profibrotic (YM-1{sup +} and galectin-3{sup +}) macrophages appeared in the lung following NM administration; this was evident within 1 d, and persisted for 28 d. AG administration (50 mg/kg, 2 /day, 1 d3 d) abrogated NM-induced injury, oxidative stress and inflammation at 1 d and 3 d post exposure, with no effects at 7 d or 28 d. These findings indicate that nitric oxide generated via iNOS contributes to acute NM-induced lung toxicity, however, transient inhibition of iNOS is not sufficient to protect against pulmonary fibrosis. -- Highlights: ? Nitrogen mustard (NM) induces acute lung injury and fibrosis. ? Pulmonary toxicity is associated with increased expression of iNOS. ? Transient inhibition of iNOS attenuates acute lung injury induced by NM.

  19. Manganese containing layer for magnetic recording media

    DOE Patents [OSTI]

    Lambeth, David N. (Pittsburgh, PA); Lee, Li-Lien (Santa Clara, CA); Laughlin, David E. (Pittsburgh, PA)

    1999-01-01

    The present invention provides for a magnetic recording media incorporating Mn-containing layers between a substrate and a magnetic layer to provide media having increased coercivity and lower noise. The Mn-containing layer can be incorporated in a rotating, translating or stationary recording media to operate in conjunction with magnetic transducing heads for recording and reading of magnetic data, as well as other applications. The magnetic recording medium of the invention preferably includes a Co or Co alloy film magnetic layer, and Mn-containing layer, preferably comprised of VMn, TiMn, MnZn, CrMnMo, CrMnW, CrMnV, and CrMnTi, and most preferably a CrMn alloy, disposed between the substrate and the magnetic layer to promote an epitaxial crystalline structure in the magnetic layer. The medium can further include seed layers, preferably polycrystalline MgO for longitudinal media, underlayers, and intermediate layers. Underlayers and intermediate layers are comprised of materials having either an A2 structure or a B2-ordered crystalline structure disposed between the seed layer and the magnetic layer. Materials having an A2 structure are preferably Cr or Cr alloys, such as CrV, CrMo, CrW and CrTi. Materials having a B2-ordered structure having a lattice constant that is substantially comparable to that of Cr, such as those preferably selected from the group consisting of NiAl, AILCo, FeAl, FeTi, CoFe, CoTi, CoHf, CoZr, NiTi, CuBe, CuZn, A-LMn, AlRe, AgMg, and Al.sub.2 FeMn.sub.2, and is most preferably FeAl or NiAl.

  20. Color stable manganese-doped phosphors

    DOE Patents [OSTI]

    Lyons, Robert Joseph; Setlur, Anant Achyut; Deshpande, Anirundha Rajendra; Grigorov, Ljudmil Slavchev

    2014-04-29

    A lighting apparatus capable of emitting white light includes a semiconductor light source; and a phosphor material radiationally coupled to the light source. The phosphor material includes a color-stable Mn.sup.+4 doped phosphor prepared by a process including providing a phosphor of formula I; A.sub.x[MF.sub.y]:Mn.sup.+4 I and contacting the phosphor in particulate form with a saturated solution of a composition of formula II in aqueous hydrofluoric acid; A.sub.x[MF.sub.y]; II wherein A is Li, Na, K, Rb, Cs, NR.sub.4 or a combination thereof; M is Si, Ge, Sn, Ti, Zr, Al, Ga, In, Sc, Y, La, Nb, Ta, Bi, Gd, or a combination thereof; R is H, lower alkyl, or a combination thereof; x is the absolute value of the charge of the [MF.sub.y] ion; and y is 5, 6 or 7. In particular embodiments, M is Si, Ge, Sn, Ti, Zr, or a combination thereof.

  1. Color stable manganese-doped phosphors

    DOE Patents [OSTI]

    Lyons, Robert Joseph; Setlur, Anant Achyut; Deshpande, Anirudha Rajendra; Grigorov, Ljudmil Slavchev

    2012-08-28

    A process for preparing color stable Mn.sup.+4 doped phosphors includes providing a phosphor of formula I; A.sub.x[MF.sub.y]:Mn.sup.+4 I and contacting the phosphor in particulate form with a saturated solution of a composition of formula II in aqueous hydrofluoric acid; A.sub.x[MF.sub.y]; II wherein A is Li, Na, K, Rb, Cs, NR.sub.4 or a combination thereof; M is Si, Ge, Sn, Ti, Zr, Al, Ga, In, Sc, Y, La, Nb, Ta, Bi, Gd, or a combination thereof; R is H, lower alkyl, or a combination thereof; x is the absolute value of the charge of the [MF.sub.y] ion; and y is 5, 6 or 7. In particular embodiments, M is Si, Ge, Sn, Ti, Zr, or a combination thereof. A lighting apparatus capable of emitting white light includes a semiconductor light source; and a phosphor composition radiationally coupled to the light source, and which includes a color stable Mn.sup.+4 doped phosphor.

  2. Manganese oxide composite electrodes for lithium batteries

    DOE Patents [OSTI]

    Johnson, Christopher S. (Naperville, IL); Kang, Sun-Ho (Naperville, IL); Thackeray, Michael M. (Naperville, IL)

    2009-12-22

    An activated electrode for a non-aqueous electrochemical cell is disclosed with a precursor thereof a lithium metal oxide with the formula xLi.sub.2MnO.sub.3.(1-x)LiMn.sub.2-yM.sub.yO.sub.4 for 0.5

  3. Manganese oxide composite electrodes for lithium batteries

    DOE Patents [OSTI]

    Thackeray, Michael M. (Naperville, IL); Johnson, Christopher S. (Naperville, IL); Li, Naichao (Croton on Hudson, NY)

    2007-12-04

    An activated electrode for a non-aqueous electrochemical cell is disclosed with a precursor of a lithium metal oxide with the formula xLi.sub.2MnO.sub.3.(1-x)LiMn.sub.2-yM.sub.yO.sub.4 for 0

  4. Protein Instability and Lou Gehrig's Disease

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    Protein Instability and Lou Gehrig's Disease Print A new study links protein instability with the progression of a lethal degenerative disease: amyotrophic lateral sclerosis (ALS), also known as Lou Gehrig's disease. Using several biophysical techniques as well as small-angle x-ray scattering (SAXS) at the Advanced Light Source, researchers focused on the effects of mutations to a gene coding for a protein called superoxide dismutase (SOD). The study provides evidence that those proteins linked

  5. Protein Instability and Lou Gehrig's Disease

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    Protein Instability and Lou Gehrig's Disease Print A new study links protein instability with the progression of a lethal degenerative disease: amyotrophic lateral sclerosis (ALS), also known as Lou Gehrig's disease. Using several biophysical techniques as well as small-angle x-ray scattering (SAXS) at the Advanced Light Source, researchers focused on the effects of mutations to a gene coding for a protein called superoxide dismutase (SOD). The study provides evidence that those proteins linked

  6. Protein Instability and Lou Gehrig's Disease

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    Protein Instability and Lou Gehrig's Disease Print A new study links protein instability with the progression of a lethal degenerative disease: amyotrophic lateral sclerosis (ALS), also known as Lou Gehrig's disease. Using several biophysical techniques as well as small-angle x-ray scattering (SAXS) at the Advanced Light Source, researchers focused on the effects of mutations to a gene coding for a protein called superoxide dismutase (SOD). The study provides evidence that those proteins linked

  7. Protein Instability and Lou Gehrig's Disease

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    Protein Instability and Lou Gehrig's Disease Print A new study links protein instability with the progression of a lethal degenerative disease: amyotrophic lateral sclerosis (ALS), also known as Lou Gehrig's disease. Using several biophysical techniques as well as small-angle x-ray scattering (SAXS) at the Advanced Light Source, researchers focused on the effects of mutations to a gene coding for a protein called superoxide dismutase (SOD). The study provides evidence that those proteins linked

  8. Genetic variation in resistance to ionizing radiation. [Annual report, 1989

    SciTech Connect (OSTI)

    Ayala, F.J.

    1989-12-31

    The very reactive superoxide anion O{sub 2} is generated during cell respiration as well as during exposure to ionizing radiation. Organisms have evolved different mechanisms to protect against the deleterious effects of reduced oxygen species. The copper-zinc superoxide dismutase is a eukaryotic cytoplasmic enzyme that protects the cell by scavenging superoxide radicals and dismutating them to hydrogen peroxide and molecular oxygen: 20{sub 2}{sup {minus}} + 2H {yields} H{sub 2}O{sub 2} + O{sub 2}. SOD had been shown to protect against ionizing radiation damage to DNA, viruses, bacteria, mammalian cells, whole mice, and Drosophila. Evidence that genetic differences may affect sensitivity to ionizing radiation has been shown in Drosophila since differences have been shown to exist between strains and resistance to radiation can evolve under natural selection.

  9. Biogeochemistry of manganese in ferruginous Lake Matano, Indonesia

    SciTech Connect (OSTI)

    Jones, C.; Crowe, S.A.; Sturm, A.; Leslie, K.L.; MacLean, L.C. W.; Katsev, S.; Henny, C.; Fowle, D.A.; Canfield, D.E.

    2012-12-13

    This study explores Mn biogeochemistry in a stratified, ferruginous lake, a modern analogue to ferruginous oceans. Intense Mn cycling occurs in the chemocline where Mn is recycled at least 15 times before sedimentation. The product of biologically catalyzed Mn oxidation in Lake Matano is birnessite. Although there is evidence for abiotic Mn reduction with Fe(II), Mn reduction likely occurs through a variety of pathways. The flux of Fe(II) is insufficient to balance the reduction of Mn at 125m depth in the water column, and Mn reduction could be a significant contributor to CH{sub 4} oxidation. By combining results from synchrotron-based X-ray fluorescence and X-ray spectroscopy, extractions of sinking particles, and reaction transport modeling, we find the kinetics of Mn reduction in the lake's reducing waters are sufficiently rapid to preclude the deposition of Mn oxides from the water column to the sediments underlying ferruginous water. This has strong implications for the interpretation of the sedimentary Mn record.

  10. Mesoporous Manganese Oxide Nanowires for High-Capacity, High...

    Office of Scientific and Technical Information (OSTI)

    Number: SC0001160 Resource Type: Journal Article Resource Relation: Journal Name: ACS Nano; Journal Volume: 5; Related Information: NEES partners with University of Maryland...

  11. Molecular Interactions of Plutonium(VI) with SyntheticManganese...

    Office of Scientific and Technical Information (OSTI)

    A paper copy of this document is also available for sale to the public from the National ... a minor component in goethite, because goethite rarely exists as a pure phase in nature. ...

  12. Complex deoxidation equilibria of molten steels by titanium and manganese

    SciTech Connect (OSTI)

    Morita, K.; Morioka, Y.; Tsukihashi, F.; Sano, N.

    1996-12-31

    The relationship between the equilibrium composition of Fe-Ti-Mn melts and that of coexisting oxides has been investigated by employing a cold crucible melting at 1,873 K. Using metal compositions and the Gibbs energies of formation of component oxides, iso-activity contours of FeO and MnO for the FeO-TiO{sub 1.5}-MnO melts at 1,873 K were evaluated. The optimal conditions for practical deoxidation processes with Ti-Mn alloys are discussed.

  13. Manganese-stabilized austenitic stainless steels for fusion applications

    DOE Patents [OSTI]

    Klueh, Ronald L. (Knoxville, TN); Maziasz, Philip J. (Oak Ridge, TN)

    1990-01-01

    An austenitic stainless steel that is comprised of Fe, Cr, Mn, C but no Ni or Nb and minimum N. To enhance strength and fabricability minor alloying additions of Ti, W, V, B and P are made. The resulting alloy is one that can be used in fusion reactor environments because the half-lives of the elements are sufficiently short to allow for handling and disposal.

  14. Final Report: Manganese Redox Mediation of UO2 Stability and...

    Office of Scientific and Technical Information (OSTI)

    One strategy to remediate U contamination in the subsurface is the immobilization of U via injection of an electron donor, e.g., acetate, which leads to stimulation of the ...

  15. Iron and Manganese Pyrophosphates as Cathodes for Lithium-Ion...

    Office of Scientific and Technical Information (OSTI)

    a 'wet method', and found to form a solid solution in the P2sub 1a space group. Both thermogravimetric analysis and magnetic susceptibility measurements confirm the 2+...

  16. 1. Lithographically Patterned Gold/Manganese Dioxide Core/Shell...

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    OF MICROSTRUCTURAL AND MECHANICAL PROPERTY CHANGES IN A V2O5 BATTERY ELECTRODE USING A MEMS OPTICAL SENSOR Hyun Jung 1 , Konstantinos Gerasopoulos 1 , Markus Gnerlich 1 , Alec...

  17. Simple Colorimetric Determination of the Manganese Content in Photosynthetic Membranes

    SciTech Connect (OSTI)

    Semin, B. K.; Seibert, M.

    2009-01-01

    The functional Mn content of intact photosystem II membrane fragments was measured as 4.06 {+-} 0.13 Mn/reaction center when determined using a simple, sensitive colorimetric assay that will also work with thylakoids and core complexes. This procedure requires minimal sample material, does not need expensive assay equipment, requires four simple steps, and only takes 20-30 min to perform. These include (a) removal of the adventitious Mn ions by CaCl{sub 2} treatment of the membranes, (b) extraction of the Mn from the O{sub 2}-evolving complex with hydrochloric acid, (c) purification of the extract by centrifugation followed by filtration of the supernatant through an Acrodisc syringe filter (0.2 {micro}m nylon membrane), and (d) colorimetric determination of Mn in the extract using the reaction of the chromogenic agent, 3,3',5,5'-tetramethylbenzidine, with previously oxidized Mn(II) cations carried out at high pH. The colorimetric assay itself has been used previously by Serrat (Mikrochim Acta 129:77-80, 1998) for assaying Mn concentrations in sea water and drinking water.

  18. In vivo measurement of total body magnesium and manganese in rats

    SciTech Connect (OSTI)

    Zhang, R.Q.; Ellis, K.J. )

    1989-11-01

    Mg and Mn are essential minerals in many biological processes. Thus knowledge of their absolute amounts and how those amounts may be altered is important. In the past the in vivo measurement of Mg in animals was limited by both the poor geometry of the counting system and the requirement for multiple counts of the animal over several hours. We have developed a neutron activation technique for the direct in vivo measurement of total body Mg and Mn in the rat. The counting system adapted for the technique has a response that is relatively invariant (+/- 2.5%) to differences in body size. A least-squares curve fitting technique was developed that requires only a single 5-min count of the animal. Our in vivo values for body Mg and Mn were in excellent agreement (+/- 2.0%) with the results of total carcass analysis using atomic absorption. Longitudinal changes in total body Mg and Mn were examined in vivo in two groups of animals maintained on test diets that contained different amounts of Mg.

  19. Chemically bonded phosphate ceramics of trivalent oxides of iron and manganese

    DOE Patents [OSTI]

    Wagh, Arun S. (Orland Park, IL); Jeong, Seung-Young (Westmont, IL)

    2002-01-01

    A new method for combining elemental iron and other metals to form an inexpensive ceramic to stabilize arsenic, alkaline red mud wastes, swarfs, and other iron or metal-based additives, to create products and waste forms which can be poured or dye cast.

  20. Iron and Manganese Pyrophosphates as Cathodes for Lithium-Ion Batteries

    SciTech Connect (OSTI)

    Zhou, Hui; Upreti, Shailesh; Chernova, Natasha A.; Hautier, Geoffroy; Ceder, Gerbrand; Whittingham, M. Stanley

    2015-10-15

    The mixed-metal phases, (Li{sub 2}Mn{sub 1-y}Fe{sub y}P{sub 2}O{sub 7}, 0 {le} y {le} 1), were synthesized using a 'wet method', and found to form a solid solution in the P2{sub 1}/a space group. Both thermogravimetric analysis and magnetic susceptibility measurements confirm the 2+ oxidation state for both the Mn and Fe. The electrochemical capacity improves as the Fe concentration increases, as do the intensities of the redox peaks of the cyclic voltammogram, indicating higher lithium-ion diffusivity in the iron phase. The two Li{sup +} ions in the three-dimensional tunnel structure of the pyrophosphate phase allows for the cycling of more than one lithium per redox center. Cyclic voltammograms show a second oxidation peak at 5 V and 5.3 V, indicative of the extraction of the second lithium ion, in agreement with ab initio computation predictions. Thus, electrochemical capacities exceeding 200 Ah/kg may be achieved if a stable electrolyte is found.

  1. Effectively suppressing dissolution of manganese from spinel lithium manganate via a nanoscale surface-doping approach

    SciTech Connect (OSTI)

    Lu, Jun; Zhan, Chun; Wu, Tianpin; Wen, Jianguo; Lei, Yu; Kropf, A. Jeremy; Wu, Huiming; Miller, Dean J.; Elam, Jeffrey W.; Sun, Yang-Kook; Qiu, Xinping; Amine, Khalil

    2014-12-16

    The capacity fade of lithium manganate-based cells is associated with the dissolution of Mn from cathode/electrolyte interface due to the disproportionation reaction of Mn(III), and the subsequent deposition of Mn(II) on the anode. Suppressing the dissolution of Mn from the cathode is critical to reducing capacity fade of LiMn2O4-based cells. Here we report a nanoscale surface-doping approach that minimizes Mn dissolution from lithium manganate. This approach exploits advantages of both bulk doping and surface-coating methods by stabilizing surface crystal structure of lithium manganate through cationic doping while maintaining bulk lithium manganate structure, and protecting bulk lithium manganate from electrolyte corrosion while maintaining ion and charge transport channels on the surface through the electrochemically active doping layer. Consequently, the surface-doped lithium manganate demonstrates enhanced electrochemical performance. This study provides encouraging evidence that surface doping could be a promising alternative to improve the cycling performance of lithium-ion batteries.

  2. Ferromagnetism of manganese-doped indium tin oxide films deposited on polyethylene naphthalate substrates

    SciTech Connect (OSTI)

    Nakamura, Toshihiro; Isozaki, Shinichi; Tanabe, Kohei; Tachibana, Kunihide

    2009-04-01

    Mn-doped indium tin oxide (ITO) films were deposited on polyethylene naphthalate (PEN) substrates using radio-frequency magnetron sputtering. The magnetic, electrical, and optical properties of the films deposited on PEN substrates were investigated by comparing with the properties of films grown on glass substrates at the same growth conditions. Thin films on PEN substrates exhibited low electrical resistivity of the order of 10{sup -4} {omega} cm and high optical transmittance between 75% and 90% in the visible region. Ferromagnetic hysteresis loops were observed at room temperature for the samples grown on PEN substrates. Mn-doped ITO films can be one of the most promising candidates of transparent ferromagnetic materials for flexible spintronic devices.

  3. Promises and Challenges of Lithium- and Manganese-Rich Transition-Metal Layered-Oxide Cathodes

    Broader source: Energy.gov [DOE]

    2013 DOE Hydrogen and Fuel Cells Program and Vehicle Technologies Program Annual Merit Review and Peer Evaluation Meeting

  4. Addressing the Voltage Fade Issue with Lithium-Manganese-Rich Oxide Cathode Materials

    Broader source: Energy.gov [DOE]

    2013 DOE Hydrogen and Fuel Cells Program and Vehicle Technologies Program Annual Merit Review and Peer Evaluation Meeting

  5. Tuning the reactivity of mononuclear nonheme manganese(iv)-oxo complexes by triflic acid

    DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)

    Chen, Junying; Yoon, Heejung; Lee, Yong -Min; Seo, Mi Sook; Sarangi, Ritimukta; Fukuzumi, Shunichi; Nam, Wonwoo

    2015-04-14

    Triflic acid (HOTf)-bound nonheme Mn(IV)-oxo complexes, [(L)MnIV(O)]2+–(HOTf)2 (L = N4Py and Bn-TPEN; N4Py = N,N-bis(2-pyridylmethyl)-N-bis(2-pyridyl)methylamine and Bn-TPEN = N-benzyl-N,N',N'-tris(2-pyridylmethyl)ethane-1,2-diamine), were synthesized by adding HOTf to the solutions of the [(L)MnIV(O)]2+ complexes and were characterized by various spectroscopies. The one-electron reduction potentials of the MnIV(O) complexes exhibited a significant positive shift upon binding of HOTf. The driving force dependences of electron transfer (ET) from electron donors to the MnIV(O) and MnIV(O)–(HOTf)2 complexes were examined and evaluated in light of the Marcus theory of ET to determine the reorganization energies of ET. The smaller reorganization energies and much more positive reduction potentialsmore » of the [(L)MnIV(O)]2+–(HOTf)2 complexes resulted in greatly enhanced oxidation capacity towards one-electron reductants and para-X-substituted-thioanisoles. The reactivities of the Mn(IV)-oxo complexes were markedly enhanced by binding of HOTf, such as a 6.4 × 105-fold increase in the oxygen atom transfer (OAT) reaction (i.e., sulfoxidation). Such a remarkable acceleration in the OAT reaction results from the enhancement of ET from para-X-substituted-thioanisoles to the MnIV(O) complexes as revealed by the unified ET driving force dependence of the rate constants of OAT and ET reactions of [(L)MnIV(O)]2+–(HOTf)2. In contrast, deceleration was observed in the rate of H-atom transfer (HAT) reaction of [(L)MnIV(O)]2+–(HOTf)2 complexes with 1,4-cyclohexadiene as compared with those of the [(L)MnIV(O)]2+ complexes. Thus, the binding of two HOTf molecules to the MnIV(O) moiety resulted in remarkable acceleration of the ET rate when the ET is thermodynamically feasible. When the ET reaction is highly endergonic, the rate of the HAT reaction is decelerated due to the steric effect of the counter anion of HOTf.« less

  6. Addressing the Voltage Fade Issue with Lithium-Manganese-Rich Oxide Cathode Materials

    Office of Energy Efficiency and Renewable Energy (EERE) Indexed Site

    the Voltage Fade Issue with Li-Mn Rich Oxide Cathode Materials Principal Investigator: Anthony Burrell Ali Abouimrane, Daniel Abraham, Khalil Amine, Mahalingam Balasubramanian, Javier Bareno Garcia-Ontiveros, Ilias Belharouak, Roy Benedek, Ira Bloom, Zonghai Chen, Dennis Dees, Kevin Gallagher, Hakim Iddir, Brian Ingram, Christopher Johnson, Wenquan Lu, Nenad Markovic, Dean Miller, Yan Qin, Yang Ren, Michael Thackeray, Lynn Trahey, and John Vaughey Chemical Sciences and Engineering Division

  7. Tuning the reactivity of mononuclear nonheme manganese(iv)-oxo complexes by triflic acid

    SciTech Connect (OSTI)

    Chen, Junying; Yoon, Heejung; Lee, Yong -Min; Seo, Mi Sook; Sarangi, Ritimukta; Fukuzumi, Shunichi; Nam, Wonwoo

    2015-04-14

    Triflic acid (HOTf)-bound nonheme Mn(IV)-oxo complexes, [(L)MnIV(O)]2+(HOTf)2 (L = N4Py and Bn-TPEN; N4Py = N,N-bis(2-pyridylmethyl)-N-bis(2-pyridyl)methylamine and Bn-TPEN = N-benzyl-N,N',N'-tris(2-pyridylmethyl)ethane-1,2-diamine), were synthesized by adding HOTf to the solutions of the [(L)MnIV(O)]2+ complexes and were characterized by various spectroscopies. The one-electron reduction potentials of the MnIV(O) complexes exhibited a significant positive shift upon binding of HOTf. The driving force dependences of electron transfer (ET) from electron donors to the MnIV(O) and MnIV(O)(HOTf)2 complexes were examined and evaluated in light of the Marcus theory of ET to determine the reorganization energies of ET. The smaller reorganization energies and much more positive reduction potentials of the [(L)MnIV(O)]2+(HOTf)2 complexes resulted in greatly enhanced oxidation capacity towards one-electron reductants and para-X-substituted-thioanisoles. The reactivities of the Mn(IV)-oxo complexes were markedly enhanced by binding of HOTf, such as a 6.4 105-fold increase in the oxygen atom transfer (OAT) reaction (i.e., sulfoxidation). Such a remarkable acceleration in the OAT reaction results from the enhancement of ET from para-X-substituted-thioanisoles to the MnIV(O) complexes as revealed by the unified ET driving force dependence of the rate constants of OAT and ET reactions of [(L)MnIV(O)]2+(HOTf)2. In contrast, deceleration was observed in the rate of H-atom transfer (HAT) reaction of [(L)MnIV(O)]2+(HOTf)2 complexes with 1,4-cyclohexadiene as compared with those of the [(L)MnIV(O)]2+ complexes. Thus, the binding of two HOTf molecules to the MnIV(O) moiety resulted in remarkable acceleration of the ET rate when the ET is thermodynamically feasible. When the ET reaction is highly endergonic, the rate of the HAT reaction is decelerated due to the steric effect of the counter anion of HOTf.

  8. The Synthesis and Characterization of Substituted Olivines and Layered Manganese Oxides

    Broader source: Energy.gov [DOE]

    2010 DOE Vehicle Technologies and Hydrogen Programs Annual Merit Review and Peer Evaluation Meeting, June 7-11, 2010 -- Washington D.C.

  9. The Synthesis and Characterization of Substituted Phosphates and Layered Manganese Oxides

    Broader source: Energy.gov [DOE]

    2011 DOE Hydrogen and Fuel Cells Program, and Vehicle Technologies Program Annual Merit Review and Peer Evaluation

  10. 2-Aminoimidazole Amino Acids as Inhibitors of the Binuclear Manganese Metalloenzyme Human Arginase I

    SciTech Connect (OSTI)

    Ilies, M.; Di Costanzo, L; North, M; Scott, J; Christianson, D

    2010-01-01

    Arginase, a key metalloenzyme of the urea cycle that converts L-arginine into L-ornithine and urea, is presently considered a pharmaceutical target for the management of diseases associated with aberrant L-arginine homeostasis, such as asthma, cardiovascular diseases, and erectile dysfunction. We now report the design, synthesis, and evaluation of a series of 2-aminoimidazole amino acid inhibitors in which the 2-aminoimidazole moiety serves as a guanidine mimetic. These compounds represent a new class of arginase inhibitors. The most potent inhibitor identified in this study, 2-(S)-amino-5-(2-aminoimidazol-1-yl)pentanoic acid (A1P, 10), binds to human arginase I with K{sub d} = 2 {micro}M and significantly attenuates airways hyperresponsiveness in a murine model of allergic airways inflammation. These findings suggest that 2-aminoimidazole amino acids represent new leads for the development of arginase inhibitors with promising pharmacological profiles.

  11. Oxidation state of cross-over manganese species on the graphite...

    Office of Scientific and Technical Information (OSTI)

    Research Org: Energy Frontier Research Centers (EFRC); Center for Electrical Energy Storage (CEES) Sponsoring Org: USDOE SC Office of Basic Energy Sciences (SC-22) Country of ...

  12. Effects of Macromolecular Crowding on the Structure of a Protein Complex

    SciTech Connect (OSTI)

    Rajapaksha Mudalige, Ajith Rathnaweera [ORNL; Stanley, Christopher B [ORNL; Todd, Brian [ORNL

    2015-01-01

    Macromolecular crowding can alter the structure and function of biological macromolecules. We used small angle scattering (SAS) to measure the change in size of a protein complex, superoxide dismutase (SOD), induced by macromolecular crowding. Crowding was induced using 400 MW polyethylene glycol (PEG), triethylene glycol (TEG), methyl- -glucoside ( -MG) and trimethylamine N-oxide (TMAO). Parallel small angle neutron scattering (SANS) and small angle x-ray scattering (SAXS) allowed us to unambiguously attribute apparent changes in radius of gyration to changes in the structure of SOD. For a 40% PEG solution, we find that the volume of SOD was reduced by 9%. Considering the osmotic pressure due to PEG, this deformation corresponds to a highly compressible structure. SAXS done in the presence of TEG suggests that for further deformation beyond a 9% decrease in volume the resistance to deformation may increase dramatically.

  13. Evaluation of remediation of coal mining wastewater by chitosan microspheres using biomarkers

    SciTech Connect (OSTI)

    Benassi, J.C.; Laus, R.; Geremias, R.; Lima, P.L.; Menezes, C.T.B.; Laranjeira, M.C.M.; Wilhelm, D.; Favere, V.T.; Pedrosa, R.C.

    2006-11-15

    The aim of this work was to evaluate the remediation of mining wastewater effluents by chitosan microspheres using biomarkers of exposure and effect. DNA damage (Comet assay) and several biomarkers of oxidative stress, such as lipoperoxidation levels (TBARS), superoxide dismutase (SOD), catalase (CAT), and glutathione S-transferase (GST) activities, and contents of reduced glutathione (GSH), were measured in blood and liver of tilapia (Oreochromis niloticus) exposed for 7, 15, and 30 days to dechlorinated tap water, 10% coal mining wastewater (CMW), and coal mining wastewater treated with chitosan microspheres (RCM). The results obtained indicated that the use of oxidative stress biomarkers were useful tools for the toxicity evaluation of coal mining effluents and also suggest that chitosan microspheres may be used as an alternative approach for remediation of coal mining wastewaters.

  14. Probing The Electrode/Electrolyte Interface in The Lithium Excess Layered Oxide Li1.2Ni0.2Mn0.6O2

    SciTech Connect (OSTI)

    Carroll, Kyler J; Qian, Danna; Fell, Chris; Calvin, Scott; Veith, Gabriel M; Chi, Miaofang; Dudney, Nancy J; Meng, Ying Shirley

    2013-01-01

    A detailed surface investigation of the lithium-excess nickel manganese layered oxide Li1.2Ni0.2Mn0.6O2 structure was carried out using x-ray photoelectron spectroscopy (XPS), total electron yield and transmission x-ray absorption spectroscopy (XAS), and electron energy loss spectroscopy (EELS) during the first two electrochemical cycles. All spectroscopy techniques consistently showed the presence of Mn4+ in the pristine material and a surprising reduction of Mn at the voltage plateau during the first charge. The Mn reduction is accompanied by the oxygen loss revealed by EELS. Upon the first discharge, the Mn at the surface never fully returns back to Mn4+. The electrode/electrolyte interface of this compound consists of the reduced Mn at the crystalline defect-spinel inner layer and an oxidized Mn species simultaneously with the presence of a superoxide species in amorphous outer layer. This proposed model signifies that oxygen vacancy formation and lithium removal result in electrolyte decomposition and superoxide formation, leading to Mn activation/dissolution and surface layer-spinel phase transformation. The results also indicate that the role of oxygen is complex and significant in contributing to the extra capacity of this class of high energy density cathode materials.

  15. Thermal stability in the blended lithium manganese oxide – Lithium nickel cobalt manganese oxide cathode materials: An in situ time-resolved X-Ray diffraction and mass spectroscopy study

    DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)

    Hu, Enyuan; Bak, Seong Min; Senanayake, Sanjaya D.; Yang, Xiao-Qing; Nam, Kyung-Wan; Zhang, Lulu; Shao, Minhua

    2015-03-01

    Thermal stabilities of a series of blended LiMn2O4(LMO)-LiNi1/3Co1/3Mn1/3O2 (NCM) cathode materials with different weight ratios were studied by in situ time-resolved X-ray diffraction (XRD) combined with mass spectroscopy in the temperature range of 25°C-580°C under helium atmosphere. Upon heating, the electrochemically delithiated LMO changed into Mn3O4 phase at around 250°C. Formation of MnO with rocksalt structure started at 520°C. This observation is in contrast to the previous report for chemically delithiate LMO in air, in which a process of λ-MnO2 transforming to β-MnO2 was observed. Oxygen peak was not observed in all cases, presumably as a result of either consumptionmore » by the carbon or detection limit. CO2 profile correlates well with the phase transition and indirectly suggests the oxygen release of the cathode. Introducing NCM into LMO has two effects: first, it makes the high temperature rock-salt phase formation more complicated with more peaks in CO2 profile due to different MO (M = Ni, Mn, Co) phases; secondly, the onset temperature of CO2 release is lowered, implying lowered oxygen release temperature. Upon heating, XRD patterns indicate the NCM part reacts first, followed by the LMO part. This confirms the better thermal stability of LMO over NCM.« less

  16. Thermal stability in the blended lithium manganese oxide Lithium nickel cobalt manganese oxide cathode materials: An in situ time-resolved X-Ray diffraction and mass spectroscopy study

    SciTech Connect (OSTI)

    Hu, Enyuan; Bak, Seong Min; Senanayake, Sanjaya D.; Yang, Xiao-Qing; Nam, Kyung-Wan; Zhang, Lulu; Shao, Minhua

    2015-03-01

    Thermal stabilities of a series of blended LiMn2O4(LMO)-LiNi1/3Co1/3Mn1/3O2 (NCM) cathode materials with different weight ratios were studied by in situ time-resolved X-ray diffraction (XRD) combined with mass spectroscopy in the temperature range of 25C-580C under helium atmosphere. Upon heating, the electrochemically delithiated LMO changed into Mn3O4 phase at around 250C. Formation of MnO with rocksalt structure started at 520C. This observation is in contrast to the previous report for chemically delithiate LMO in air, in which a process of ?-MnO2 transforming to ?-MnO2 was observed. Oxygen peak was not observed in all cases, presumably as a result of either consumption by the carbon or detection limit. CO2 profile correlates well with the phase transition and indirectly suggests the oxygen release of the cathode. Introducing NCM into LMO has two effects: first, it makes the high temperature rock-salt phase formation more complicated with more peaks in CO2 profile due to different MO (M = Ni, Mn, Co) phases; secondly, the onset temperature of CO2 release is lowered, implying lowered oxygen release temperature. Upon heating, XRD patterns indicate the NCM part reacts first, followed by the LMO part. This confirms the better thermal stability of LMO over NCM.

  17. Low-temperature superacid catalysis: Reactions of n-butane catalyzed by iron- and manganese-promoted sulfated zirconia

    SciTech Connect (OSTI)

    Cheung, T.K.; D`Itri, J.L.; Gates, B.C.

    1995-02-01

    Environmental concerns are leading to the replacement of aromatic hydrocarbons in gasoline with high-octane-number branched paraffins and oxygenated compounds such as methyl t-butyl ether, which is produced from methanol and isobutylene. The latter can be formed from n-butane by isomerization followed by dehydrogenation. To meet the need for improved catalysts for isomerization of n-butane and other paraffins, researchers identified solid acids that are noncorrosive and active at low temperatures. Sulfated zirconia catalyzes the isomerization of n-butane even at 25{degrees}C, and the addition of Fe and Mn promoters increases its activity by three orders of magnitude. Little is known about this new catalyst. Here the authors provide evidence of its performance for n-butane conversion, demonstrating that isomerization is accompanied by disproportionation and other, less well understood, acid-catalyzed reactions and undergoes rapid deactivation associated with deposition of carbonaceous material. 10 refs., 3 figs.

  18. ROLE OF MANGANESE REDUCTION/OXIDATION (REDOX) ON FOAMING AND MELT RATE IN HIGH LEVEL WASTE (HLW) MELTERS (U)

    SciTech Connect (OSTI)

    Jantzen, C; Michael Stone, M

    2007-03-30

    High-level nuclear waste is being immobilized at the Savannah River Site (SRS) by vitrification into borosilicate glass at the Defense Waste Processing Facility (DWPF). Control of the Reduction/Oxidation (REDOX) equilibrium in the DWPF melter is critical for processing high level liquid wastes. Foaming, cold cap roll-overs, and off-gas surges all have an impact on pouring and melt rate during processing of high-level waste (HLW) glass. All of these phenomena can impact waste throughput and attainment in Joule heated melters such as the DWPF. These phenomena are caused by gas-glass disequilibrium when components in the melter feeds convert to glass and liberate gases such as H{sub 2}O vapor (steam), CO{sub 2}, O{sub 2}, H{sub 2}, NO{sub x}, and/or N{sub 2}. During the feed-to-glass conversion in the DWPF melter, multiple types of reactions occur in the cold cap and in the melt pool that release gaseous products. The various gaseous products can cause foaming at the melt pool surface. Foaming should be avoided as much as possible because an insulative layer of foam on the melt surface retards heat transfer to the cold cap and results in low melt rates. Uncontrolled foaming can also result in a blockage of critical melter or melter off-gas components. Foaming can also increase the potential for melter pressure surges, which would then make it difficult to maintain a constant pressure differential between the DWPF melter and the pour spout. Pressure surges can cause erratic pour streams and possible pluggage of the bellows as well. For these reasons, the DWPF uses a REDOX strategy and controls the melt REDOX between 0.09 {le} Fe{sup 2+}/{summation}Fe {le} 0.33. Controlling the DWPF melter at an equilibrium of Fe{sup +2}/{summation}Fe {le} 0.33 prevents metallic and sulfide rich species from forming nodules that can accumulate on the floor of the melter. Control of foaming, due to deoxygenation of manganic species, is achieved by converting oxidized MnO{sub 2} or Mn{sub 2}O{sub 3} species to MnO during melter preprocessing. At the lower redox limit of Fe{sup +2}/{summation}Fe {approx} 0.09 about 99% of the Mn{sup +4}/Mn{sup +3} is converted to Mn{sup +2}. Therefore, the lower REDOX limits eliminates melter foaming from deoxygenation.

  19. OPERATION OF A TRITIUM GLOVEBOX CLEAN-UP SYSTEM USING ZIRCONIUM MANGANESE IRON AND ZIRCONIUM TWO IRON METAL GETTERS

    SciTech Connect (OSTI)

    E. LARSON; K. COOK

    2000-08-01

    A metal hydride-based tritium clean-up system has been successfully operated for more than four years on an 11 m{sup 3} helium/nitrogen glovebox which was used for handling metal tritide powders. The clean-up system consists of two beds: (1) a Zr-Mn-Fe (in a 10% by weight Al binder, SAES ST909) bed operating at 675 C followed by (2) a Zr{sub 2}Fe (SAES ST198) bed operating at 250 C. The Zr-Mn-Fe bed serves to condition the gas stream by cracking hydrogenous impurities (such as H{sub 2}O and hydrocarbons) and absorbing oxygen and carbon. The Zr{sub 2}Fe bed absorbs the hydrogen isotopes from the flowing stream by forming a solid hydride compound. These beds contain 3 kilograms of Zr{sub 2}Fe and have been loaded routinely with 230-250 STP liters of hydrogen isotopes in earlier trials. The Zr-Mn-Fe alloy exhibits an anomaly during activation, namely an exotherm upon initial exposure to nitrogen. The purpose of this work is to better understand this reaction. Nitrogen absorption studies were done in order to quantify the nitrogen taken up by the getter and to characterize the reaction kinetics. In addition, ST909 phases before and after the reaction were studied with x-ray diffraction.

  20. Long-term stability of organic carbon-stimulated chromatereduction in contaminated soils, and its relation to manganese redoxstatus

    SciTech Connect (OSTI)

    Tokunaga, Tetsu K.; Wan, Jiamin; Lanzirotti, Antonio; Sutton,Steve R.; Newville, Matthew; Rao, William

    2007-03-13

    In-situ reduction of toxic Cr(V1) to less hazardous Cr(II1)is becoming a popular strategy for remediating contaminated soils.However, the long term stability of reduced Cr remains to be understood,especially given the common presence of MnfIIIJV) oxides that reoxidizeCr(II1). This 4.6 year laboratory study tracked Cr and Mn redoxtransformations in soils contaminated with Cr(V1) which were then treatedwith different amounts of organic carbon (OC). Changes in Cr and Mnoxidation states within soils were directly and nondestructively measuredusing micro X-ray absorption near edge structure spectroscopy. Chromatereduction was roughly lst-order, and the extent of reduction was enhancedwith higher OC additions. However, significant Cr(||1) reoxidationoccurred in soils exposed to the highest Cr(V1) concentrations (2,560 mgkg"'). Transient Cr(II1) reoxidation up to 420 mg kg1 was measured at 1.1years after OC treatment, followed by further reduction. Chromateconcentrations increased by 220 mg kgm1a t the end of the study (4.6years) in one soil. The causal role that Mn oxidation state had inreoxidizing Cr was supported by trends in Mn K-edge energies. Theseresults provide strong evidence for longterm dependence of soil Croxidation states on balances between OC availability and Mn redoxstatus.

  1. Fabrication and characterization of lithium manganese nickel oxide sputtered thin film cathodes for lithium-ion batteries

    SciTech Connect (OSTI)

    Baggetto, Loic; Unocic, Raymond R; Dudney, Nancy J; Veith, Gabriel M

    2012-01-01

    Li-rich and stoichiometric Li1Mn1.5Ni0.5O4 (LMNO) cathode films have been prepared by magnetron sputtering. Sputtering from a Li stoichiometric target yields Li-rich films composed of spinel, layered and monoclinic phases. Films obtained from a Li deficient target are mostly made of a spinel phase and little layered material. The resulting cathode thin films have good capacity retention and very high rate capability. The reaction mechanism has been investigated by XRD and HRTEM and evidences the reversible formation of a spinel phase, as is also found for the powder samples. The film geometry enables to understand the effect of coatings (ZnO or LiPON). Coating high voltage cathodes reduces the coulombic losses but at the price of rate performance. Nonetheless, these coated sputtered electrode thin films offer a higher rate capability than other LMNO thin films obtained by other physical vapor deposition techniques.

  2. Li and Mn uptake data from initial set of imprinted polymers

    SciTech Connect (OSTI)

    Susanna Ventura

    2015-03-27

    Batch tests of crosslinked lithium and manganese imprinted polymers of variable composition to assess their ability to extract lithium and manganese from synthetic brines at T=45C .

  3. The Synthesis and Characterization of Substituted Phosphates...

    Office of Energy Efficiency and Renewable Energy (EERE) Indexed Site

    Phosphates and Layered Manganese Oxides The Synthesis and Characterization of Substituted Phosphates and Layered Manganese Oxides 2011 DOE Hydrogen and Fuel Cells Program, and...

  4. Proposed "OneEERE" Work Plan Structure

    Office of Energy Efficiency and Renewable Energy (EERE) Indexed Site

    ... * Lithium * Manganese * Tellurium * Zinc Uses for Geothermal Strategic Materials * ... lithium, manganese, and zinc from geothermal brines during the power production process. ...

  5. Batteries from Brine | Department of Energy

    Office of Energy Efficiency and Renewable Energy (EERE) Indexed Site

    In fact, minerals like lithium, manganese, and zinc supply the raw materials for cathodes, ... demonstration facility there and mine lithium, manganese, and zinc from geothermal brines. ...

  6. Li and Mn uptake data from initial set of imprinted polymers

    DOE Data Explorer [Office of Scientific and Technical Information (OSTI)]

    Susanna Ventura

    Batch tests of crosslinked lithium and manganese imprinted polymers of variable composition to assess their ability to extract lithium and manganese from synthetic brines at T=45C .

  7. Chlorobenzene induces oxidative stress in human lung epithelial cells in vitro

    SciTech Connect (OSTI)

    Feltens, Ralph; Moegel, Iljana; Roeder-Stolinski, Carmen; Simon, Jan-Christoph; Herberth, Gunda; Lehmann, Irina

    2010-01-01

    Chlorobenzene is a volatile organic compound (VOC) that is widely used as a solvent, degreasing agent and chemical intermediate in many industrial settings. Occupational studies have shown that acute and chronic exposure to chlorobenzene can cause irritation of the mucosa of the upper respiratory tract and eyes. Using in vitro assays, we have shown in a previous study that human bronchial epithelial cells release inflammatory mediators such as the cytokine monocyte chemoattractant protein-1 (MCP-1) in response to chlorobenzene. This response is mediated through the NF-kappaB signaling pathway. Here, we investigated the effects of monochlorobenzene on human lung cells, with emphasis on potential alterations of the redox equilibrium to clarify whether the chlorobenzene-induced inflammatory response in lung epithelial cells is caused via an oxidative stress-dependent mechanism. We found that expression of cellular markers for oxidative stress, such as heme oxygenase 1 (HO-1), glutathione S-transferase pi1 (GSTP1), superoxide dismutase 1 (SOD1), prostaglandin-endoperoxide synthase 2 (PTGS2) and dual specificity phosphatase 1 (DUSP1), were elevated in the presence of monochlorobenzene. Likewise, intracellular reactive oxygen species (ROS) were increased in response to exposure. However, in the presence of the antioxidants N-(2-mercaptopropionyl)-glycine (MPG) or bucillamine, chlorobenzene-induced upregulation of marker proteins and release of the inflammatory mediator MCP-1 are suppressed. These results complement our previous findings and point to an oxidative stress-mediated inflammatory response following chlorobenzene exposure.

  8. In utero and in vitro effects of benzene and its metabolites on erythroid differentiation and the role of reactive oxygen species

    SciTech Connect (OSTI)

    Badham, Helen J.; Winn, Louise M.

    2010-05-01

    Benzene is a ubiquitous occupational and environmental toxicant. Exposures to benzene both prenatally and during adulthood are associated with the development of disorders such as aplastic anemia and leukemia. Mechanisms of benzene toxicity are unknown; however, generation of reactive oxygen species (ROS) by benzene metabolites may play a role. Little is known regarding the effects of benzene metabolites on erythropoiesis. Therefore, to determine the effects of in utero exposure to benzene on the growth and differentiation of fetal erythroid progenitor cells (CFU-E), pregnant CD-1 mice were exposed to benzene and CFU-E numbers were assessed in fetal liver (hematopoietic) tissue. In addition, to determine the effect of benzene metabolite-induced ROS generation on erythropoiesis, HD3 chicken erythroblast cells were exposed to benzene, phenol, or hydroquinone followed by stimulation of erythrocyte differentiation. Our results show that in utero exposure to benzene caused significant alterations in female offspring CFU-E numbers. In addition, exposure to hydroquinone, but not benzene or phenol, significantly reduced the percentage of differentiated HD3 cells, which was associated with an increase in ROS. Pretreatment of HD3 cells with polyethylene glycol-conjugated superoxide dismutase (PEG-SOD) prevented hydroquinone-induced inhibition of erythropoiesis, supporting the hypothesis that ROS generation is involved in the development of benzene erythrotoxicity. In conclusion, this study provided evidence that ROS generated as a result of benzene metabolism may significantly alter erythroid differentiation, potentially leading to the development of Blood Disorders.

  9. A Chandrasekhar mass progenitor for the Type Ia supernova remnant 3C 397 from the enhanced abundances of nickel and manganese

    DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)

    Yamaguchi, Hiroya; Badenes, Carles; Foster, Adam R.; Bravo, Eduardo; Williams, Brian J.; Maeda, Keiichi; Nobukawa, Masayoshi; Eriksen, Kristoffer A.; Brickhouse, Nancy S.; Petre, Robert; et al

    2015-03-12

    Despite decades of intense efforts, many fundamental aspects of Type Ia supernovae (SNe Ia) remain elusive. One of the major open questions is whether the mass of an exploding white dwarf (WD) is close to the Chandrasekhar limit. Here, we report the detection of strong K-shell emission from stable Fe-peak elements in the Suzaku X-ray spectrum of the Type Ia supernova remnant (SNR) 3C 397. The high Ni/Fe and Mn/Fe mass ratios (0.11–0.24 and 0.018–0.033, respectively) in the hot plasma component that dominates the K-shell emission lines indicate a degree of neutronization in the supernova ejecta that can only bemore » achieved by electron capture in the dense cores of exploding WDs with a near-Chandrasekhar mass. This suggests a single-degenerate origin for 3C 397, since Chandrasekhar mass progenitors are expected naturally if the WD accretes mass slowly from a companion. Altogether with other results supporting the double-degenerate scenario, our work adds to the mounting evidence that both progenitor channels make a significant contribution to the SN Ia rate in star-forming galaxies.« less

  10. Identifying surface structural changes in layered Li-excess nickel manganese oxides in high voltage lithium ion batteries: A joint experimental and theoretical study

    SciTech Connect (OSTI)

    Xu, Bo; Fell, Christopher R.; Chi, Miaofang; Meng, Ying Shirley

    2011-09-06

    High voltage cathode materials Li-excess layered oxide compounds Li[Ni{sub x}Li{sub 1/3-2x/3}Mn{sub 2/3-x/3}]O{sub 2} (0 < x < 1/2) are investigated in a joint study combining both computational and experimental methods. The bulk and surface structures of pristine and cycled samples of Li[Ni{sub 1/5}Li{sub 1/5}Mn{sub 3/5}]O{sub 2} are characterized by synchrotron X-Ray diffraction together with aberration corrected Scanning Transmission Electron Microscopy (a-S/TEM). Electron Energy Loss Spectroscopy (EELS) is carried out to investigate the surface changes of the samples before/after electrochemical cycling. Combining first principles computational investigation with our experimental observations, a detailed lithium de-intercalation mechanism is proposed for this family of Li-excess layered oxides. The most striking characteristics in these high voltage high energy density cathode materials are (1) formation of tetrahedral lithium ions at voltage less than 4.45 V and (2) the transition metal (TM) ions migration leading to phase transformation on the surface of the materials. We show clear evidence of a new spinel-like solid phase formed on the surface of the electrode materials after high-voltage cycling. It is proposed that such surface phase transformation is one of the factors contributing to the first cycle irreversible capacity and the main reason for the intrinsic poor rate capability of these materials.

  11. Changes in expression of renal Oat1, Oat3 and Mrp2 in cisplatin-induced acute renal failure after treatment of JBP485 in rats

    SciTech Connect (OSTI)

    Liu, Tao, E-mail: liutaomedical@qq.com [Department of Clinical Pharmacology, College of Pharmacy, Dalian Medical University, 9 West Section, Lvshun South Road, Lvshunkou District, Dalian 116044 (China)] [Department of Clinical Pharmacology, College of Pharmacy, Dalian Medical University, 9 West Section, Lvshun South Road, Lvshunkou District, Dalian 116044 (China); Meng, Qiang, E-mail: mengq531@yahoo.cn [Department of Clinical Pharmacology, College of Pharmacy, Dalian Medical University, 9 West Section, Lvshun South Road, Lvshunkou District, Dalian 116044 (China) [Department of Clinical Pharmacology, College of Pharmacy, Dalian Medical University, 9 West Section, Lvshun South Road, Lvshunkou District, Dalian 116044 (China); Provincial Key Laboratory for Pharmacokinetics and Transport, Liaoning, Dalian Medical University (China); Wang, Changyuan, E-mail: wangcyuan@163.com [Department of Clinical Pharmacology, College of Pharmacy, Dalian Medical University, 9 West Section, Lvshun South Road, Lvshunkou District, Dalian 116044 (China) [Department of Clinical Pharmacology, College of Pharmacy, Dalian Medical University, 9 West Section, Lvshun South Road, Lvshunkou District, Dalian 116044 (China); Provincial Key Laboratory for Pharmacokinetics and Transport, Liaoning, Dalian Medical University (China); Liu, Qi, E-mail: llaqii@yahoo.com.cn [Department of Clinical Pharmacology, College of Pharmacy, Dalian Medical University, 9 West Section, Lvshun South Road, Lvshunkou District, Dalian 116044 (China) [Department of Clinical Pharmacology, College of Pharmacy, Dalian Medical University, 9 West Section, Lvshun South Road, Lvshunkou District, Dalian 116044 (China); Provincial Key Laboratory for Pharmacokinetics and Transport, Liaoning, Dalian Medical University (China); Guo, Xinjin, E-mail: guo.xinjin@163.com [Department of Clinical Pharmacology, College of Pharmacy, Dalian Medical University, 9 West Section, Lvshun South Road, Lvshunkou District, Dalian 116044 (China)] [Department of Clinical Pharmacology, College of Pharmacy, Dalian Medical University, 9 West Section, Lvshun South Road, Lvshunkou District, Dalian 116044 (China); Sun, Huijun, E-mail: sunhuijun@hotmail.com [Department of Clinical Pharmacology, College of Pharmacy, Dalian Medical University, 9 West Section, Lvshun South Road, Lvshunkou District, Dalian 116044 (China) [Department of Clinical Pharmacology, College of Pharmacy, Dalian Medical University, 9 West Section, Lvshun South Road, Lvshunkou District, Dalian 116044 (China); Provincial Key Laboratory for Pharmacokinetics and Transport, Liaoning, Dalian Medical University (China); Peng, Jinyong, E-mail: jinyongpeng2005@163.com [Department of Clinical Pharmacology, College of Pharmacy, Dalian Medical University, 9 West Section, Lvshun South Road, Lvshunkou District, Dalian 116044 (China) [Department of Clinical Pharmacology, College of Pharmacy, Dalian Medical University, 9 West Section, Lvshun South Road, Lvshunkou District, Dalian 116044 (China); Provincial Key Laboratory for Pharmacokinetics and Transport, Liaoning, Dalian Medical University (China); and others

    2012-11-01

    The purpose of this study is to investigate whether the effect of cyclo-trans-4-L-hydroxyprolyl-L-serine (JBP485) on acute renal failure (ARF) induced by cisplatin is related to change in expression of renal Oat1, Oat3 and Mrp2 in rats. JBP485 reduced creatinine, blood urea nitrogen (BUN) and indoxyl sulfate (IS) in plasma and malondialdehyde (MDA) in kidney, and recovered the glomerular filtration rate (GFR) and the activity of superoxide dismutase (SOD) in cisplatin-treated rats. The plasma concentration of PAH (para-aminohippurate) determined by LCMS/MS was increased markedly after intravenous administration of cisplatin, whereas cumulative urinary excretion of PAH and the uptake of PAH in kidney slices were significantly decreased. qRT-PCR and Western-blot showed a decrease in mRNA and protein of Oat1 and Oat3, an increase in mRNA and protein of Mrp2 in cisplatin-treated rats, and an increase in IS (a uremic toxin) after co-treatment with JBP485. It indicated that JBP485 promoted urinary excretion of toxins by upregulating renal Mrp2. This therefore gives in part the explanation about the mechanism by which JBP485 improves ARF induced by cisplatin in rats. -- Highlights: ? Cisplatin induces acute renal failure (ARF). ? The expression of Oat1, Oat3 and Mrp2 were changed during ARF. ? The regulated expression of Oat1, Oat3 and Mrp2 is an adaptive protected response. ? JBP485 could facilitate the adaptive protective action.

  12. A semisynthetic strategy leads to alteration of the backbone amidate ligand in the NiSOD active site

    DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)

    Campeciño, Julius O.; Dudycz, Lech W.; Tumelty, David; Berg, Volker; Cabelli, Diane E.; Maroney, Michael J.

    2015-07-01

    Computational investigations have implicated the amidate ligand in nickel superoxide dismutase (NiSOD) in stabilizing Ni-centered redox catalysis and in preventing cysteine thiolate ligand oxidation. To test these predictions, we have used an experimental approach utilizing a semisynthetic scheme that employs native chemical ligation of a pentapeptide (HCDLP) to recombinant S. coelicolor NiSOD lacking these N-terminal residues, NΔ5-NiSOD. Wild-type enzyme produced in this manner exhibits the characteristic spectral properties of recombinant WT-NiSOD and is as catalytically active. The semisynthetic scheme was also employed to construct a variant where the amidate ligand was converted to a secondary amine, H1*-NiSOD, a novel strategymore » that retains a backbone N-donor atom. The H1*-NiSOD variant was found to have only ~1% of the catalytic activity of the recombinant wild-type enzyme, and had altered spectroscopic properties. X-ray absorption spectroscopy reveals a four-coordinate planar site with N2S2-donor ligands, consistent with electronic absorption spectroscopic results indicating that the Ni center in H1*-NiSOD is mostly reduced in the as-isolated sample, as opposed to 50:50 Ni(II)/Ni(III) mixture that is typical for the recombinant wild-type enzyme. The EPR spectrum of as-isolated H1*-NiSOD accounts for ~11% of the Ni in the sample and is similar to WT-NiSOD, but more axial, with gz < gx,y. 14N-hyperfine is observed on gz« less

  13. Time course of systemic oxidative stress and inflammatory response induced by an acute exposure to Residual Oil Fly Ash

    SciTech Connect (OSTI)

    Marchini, T.; Magnani, N.D.; Paz, M.L.; Vanasco, V.; Tasat, D.; Gonzlez Maglio, D.H.; and others

    2014-01-15

    It is suggested that systemic oxidative stress and inflammation play a central role in the onset and progression of cardiovascular diseases associated with the exposure to particulate matter (PM). The aim of this work was to evaluate the time changes of systemic markers of oxidative stress and inflammation, after an acute exposure to Residual Oil Fly Ash (ROFA). Female Swiss mice were intranasally instilled with a ROFA suspension (1.0 mg/kg body weight) or saline solution, and plasma levels of oxidative damage markers [thiobarbituric acid reactive substances (TBARSs) and protein carbonyls], antioxidant status [reduced (GSH) and oxidized (GSSG) glutathione, ascorbic acid levels, and superoxide dismutase (SOD) activity], cytokines levels, and intravascular leukocyte activation were evaluated after 1, 3 or 5 h of exposure. Oxidative damage to lipids and decreased GSH/GSSG ratio were observed in ROFA-exposed mice as early as 1 h. Afterwards, increased protein oxidation, decreased ascorbic acid content and SOD activity were found in this group at 3 h. The onset of an adaptive response was observed at 5 h after the ROFA exposure, as indicated by decreased TBARS plasma content and increased SOD activity. The observed increase in oxidative damage to plasma macromolecules, together with systemic antioxidants depletion, may be a consequence of a systemic inflammatory response triggered by the ROFA exposure, since increased TNF-? and IL-6 plasma levels and polymorphonuclear leukocytes activation was found at every evaluated time point. These findings contribute to the understanding of the increase in cardiovascular morbidity and mortality, in association with environmental PM inhalation. - Highlights: An acute exposure to ROFA triggers the occurrence of systemic oxidative stress. Changes in plasmatic oxidative stress markers appear as early as 1 h after exposure. ROFA induces proinflammatory cytokines release and intravascular leukocyte activation. PMN activation is a relevant source of reactive oxygen species in this model. These findings may account for previously described cardiopulmonary alterations.

  14. Protective effects and mechanisms of curcumin on podophyllotoxin toxicity in vitro and in vivo

    SciTech Connect (OSTI)

    Li, Juan; Dai, Cai-Xia; Sun, Hua; Jin, Lu; State Key Laboratory of New Drug Research, Shanghai Institute of Materia Medica, Chinese Academy of Sciences, 555 Zu Chong Zhi Road, Shanghai 201203 ; Guo, Chong-Yi; Cao, Wei; Wu, Jie; Tian, Hai-Yan; Luo, Cheng; Ye, Wen-Cai; Jiang, Ren-Wang

    2012-12-01

    Podophyllotoxin (POD) is a naturally occurring lignan with pronounced antineoplastic and antiviral properties. POD binds to tubulin and prevents the formation of mitotic spindle. Although cases of overdose or accidental ingestion are quite often, no specific therapy is currently available to treat the POD intoxication. In the current investigation, the protective effects and mechanisms of curcumin (CUR) on podophyllotoxin toxicity were evaluated in vitro and in vivo. The results showed that CUR could protect POD-induced cytotoxicity by recovering the G2/M arrest and decrease the changes of membrane potential and microtubule structure in Vero cells. A significant decrease of mortality rates was observed in Swiss mice treated by intragastrical administration of POD + CUR as compared with POD alone. The POD + CUR group also exhibited decreases in plasma transaminases, alkaline phosphatase, lactate dehydrogenase, plasma urea, creatinine and malondialdehyde level but elevated superoxide dismutase and glutathione levels as compared to the POD group. Histological examination of the liver and kidney demonstrated less morphological changes in the treatment of POD + CUR as compared with POD alone. The mechanism of the protective effects might be due to the competitive binding of CUR with POD in the same colchicines binding site as revealed by the tubulin polymerization assay and the molecular docking analysis, and the antioxidant activity against the oxidative stress induced by POD. In summary, both in vitro and in vivo data indicated the promising role of CUR as a protective agent against the POD poisoning. Highlights: ? A potential antidote to treat the podophyllotoxin (POD) intoxication is found. ? Curcumin showed promising effects against POD poisoning in vitro and in vivo. ? The mechanisms lie in the antioxidant activity and competitive binding with tubulin.

  15. Evaluation of the pharmacokinetics and cardiotoxicity of doxorubicin in rat receiving nilotinib

    SciTech Connect (OSTI)

    Zhou, Zhi-yong; Wan, Li-li; Yang, Quan-jun; Han, Yong-long; Li, Yan; Yu, Qi; Guo, Cheng; Li, Xiao

    2013-10-01

    Doxorubicin (DOX) is a potent chemotherapy drug with a narrow therapeutic window. Nilotinib, a small-molecule Bcr-Abl tyrosine kinase inhibitor, was reported to reverse multidrug resistance (MDR) mediated by P-glycoprotein (P-gp) transmembrane transporters. The present study aimed to investigate nilotinib's affection on the steady-state pharmacokinetics, disposition and cardiotoxicity of DOX. A total of 24 male SpragueDawley rats were randomized into four groups (6 in each) and received the following regimens: saline, intravenous DOX (5 mg/kg) alone, and DOX co-administrated with either 20 or 40 mg/kg nilotinib. Blood was withdrawn at 12 time points till 72 h after DOX injection and the concentrations of DOX and its metabolite doxorubicinol (DOXol) in serum and cardiac tissue were assayed by LCMSMS method. To determine the cardiotoxicity, the following parameters were investigated: creatine kinase, lactate dehydrogenase, malondialdehyde, and superoxide dismutase. Histopathological examination of heart section was carried out to evaluate the extent of cardiotoxicity after treatments. The results showed that pretreatment of 40 mg/kg nilotinib increased the AUC{sub 0t} and C{sub max} of DOX and DOXol. However, their accumulation in cardiac tissue was significantly decreased when compared with the group that received DOX alone. In addition, biochemical and histopathological results showed that 40 mg/kg nilotinib reduced the cardiotoxicity induced by DOX administration. In conclusion, co-administration of nilotinib increased serum exposure, but significantly decreased the accumulation of DOX in cardiac tissue. Consistent with in vitro profile, oral dose of 40 mg/kg nilotinib significantly decreased the cardiotoxicity of DOX in rat by enhancing P-gp activity in the heart.

  16. A semisynthetic strategy leads to alteration of the backbone amidate ligand in the NiSOD active site

    SciTech Connect (OSTI)

    Campecio, Julius O.; Dudycz, Lech W.; Tumelty, David; Berg, Volker; Cabelli, Diane E.; Maroney, Michael J.

    2015-07-01

    Computational investigations have implicated the amidate ligand in nickel superoxide dismutase (NiSOD) in stabilizing Ni-centered redox catalysis and in preventing cysteine thiolate ligand oxidation. To test these predictions, we have used an experimental approach utilizing a semisynthetic scheme that employs native chemical ligation of a pentapeptide (HCDLP) to recombinant S. coelicolor NiSOD lacking these N-terminal residues, N?5-NiSOD. Wild-type enzyme produced in this manner exhibits the characteristic spectral properties of recombinant WT-NiSOD and is as catalytically active. The semisynthetic scheme was also employed to construct a variant where the amidate ligand was converted to a secondary amine, H1*-NiSOD, a novel strategy that retains a backbone N-donor atom. The H1*-NiSOD variant was found to have only ~1% of the catalytic activity of the recombinant wild-type enzyme, and had altered spectroscopic properties. X-ray absorption spectroscopy reveals a four-coordinate planar site with N2S2-donor ligands, consistent with electronic absorption spectroscopic results indicating that the Ni center in H1*-NiSOD is mostly reduced in the as-isolated sample, as opposed to 50:50 Ni(II)/Ni(III) mixture that is typical for the recombinant wild-type enzyme. The EPR spectrum of as-isolated H1*-NiSOD accounts for ~11% of the Ni in the sample and is similar to WT-NiSOD, but more axial, with gz < gx,y. 14N-hyperfine is observed on gz

  17. Protection of cisplatin-induced spermatotoxicity, DNA damage and chromatin abnormality by selenium nano-particles

    SciTech Connect (OSTI)

    Rezvanfar, Mohammad Amin; Rezvanfar, Mohammad Ali; Shahverdi, Ahmad Reza; Ahmadi, Abbas; Baeeri, Maryam; Mohammadirad, Azadeh; Abdollahi, Mohammad

    2013-02-01

    Cisplatin (CIS), an anticancer alkylating agent, induces DNA adducts and effectively cross links the DNA strands and so affects spermatozoa as a male reproductive toxicant. The present study investigated the cellular/biochemical mechanisms underlying possible protective effect of selenium nano-particles (Nano-Se) as an established strong antioxidant with more bioavailability and less toxicity, on reproductive toxicity of CIS by assessment of sperm characteristics, sperm DNA integrity, chromatin quality and spermatogenic disorders. To determine the role of oxidative stress (OS) in the pathogenesis of CIS gonadotoxicity, the level of lipid peroxidation (LPO), antioxidant enzymes including superoxide dismutase (SOD), catalase (CAT) and glutathione peroxidase (GSH-Px) and peroxynitrite (ONOO) as a marker of nitrosative stress (NS) and testosterone (T) concentration as a biomarker of testicular function were measured in the blood and testes. Thirty-two male Wistar rats were equally divided into four groups. A single IP dose of CIS (7 mg/kg) and protective dose of Nano-Se (2 mg/kg/day) were administered alone or in combination. The CIS-exposed rats showed a significant increase in testicular and serum LPO and ONOO level, along with a significant decrease in enzymatic antioxidants levels, diminished serum T concentration and abnormal histologic findings with impaired sperm quality associated with increased DNA damage and decreased chromatin quality. Coadministration of Nano-Se significantly improved the serum T, sperm quality, and spermatogenesis and reduced CIS-induced free radical toxic stress and spermatic DNA damage. In conclusion, the current study demonstrated that Nano-Se may be useful to prevent CIS-induced gonadotoxicity through its antioxidant potential. Highlights: ? Cisplatin (CIS) affects spermatozoa as a male reproductive toxicant. ? Effect of Nano-Se on CIS-induced spermatotoxicity was investigated. ? CIS-exposure induces oxidative sperm DNA damage and impairs steroidogenesis. ? Nano-Se retained sperm quality against CIS-induced free radicals toxic stress.

  18. Microsoft Word - FR Notice - DOE CMS RFI 02-03-2016 FINAL

    Office of Energy Efficiency and Renewable Energy (EERE) Indexed Site

    ... hafnium, helium, indium, lithium, magnesium, manganese, molybdenum, nickel, rhenium, selenium, silicon, tantalum, tellurium, tungsten, vanadium, and zirconium Technologies and ...

  19. Effect of Cr substitution on the magnetic and magnetic-transport...

    Office of Scientific and Technical Information (OSTI)

    ANTIFERROMAGNETISM; CHROMIUM; CONCENTRATION RATIO; CURIE POINT; ELECTRON-PHONON COUPLING; ELECTRONS; INTERMETALLIC COMPOUNDS; IRON; MAGNETORESISTANCE; MAGNONS; MANGANESE; PHONONS;...

  20. Cast B2-phase iron-aluminum alloys with improved fluidity

    DOE Patents [OSTI]

    Maziasz, Philip J. (122 Clark La., Oak Ridge, TN 37830); Paris, Alan M. (P.O. Box 64, Tarrs, PA 15688); Vought, Joseph D. (124 Cove Point Rd., Rockwood, TN 37854)

    2002-01-01

    Systems and methods are described for iron aluminum alloys. A composition includes iron, aluminum and manganese. A method includes providing an alloy including iron, aluminum and manganese; and processing the alloy. The systems and methods provide advantages because additions of manganese to iron aluminum alloys dramatically increase the fluidity of the alloys prior to solidification during casting.

  1. FISSION PRODUCT REMOVAL FROM ORGANIC SOLUTIONS

    DOE Patents [OSTI]

    Moore, R.H.

    1960-05-10

    The decontamination of organic solvents from fission products and in particular the treatment of solvents that were used for the extraction of uranium and/or plutonium from aqueous acid solutions of neutron-irradiated uranium are treated. The process broadly comprises heating manganese carbonate in air to a temperature of between 300 and 500 deg C whereby manganese dioxide is formed; mixing the manganese dioxide with the fission product-containing organic solvent to be treated whereby the fission products are precipitated on the manganese dioxide; and separating the fission product-containing manganese dioxide from the solvent.

  2. Systemic inflammatory changes and increased oxidative stress in rural Indian women cooking with biomass fuels

    SciTech Connect (OSTI)

    Dutta, Anindita; Department of Experimental Hematology, Chittaranjan National Cancer Institute, 37, S.P. Mukherjee Road, Kolkata-700 026 ; Ray, Manas Ranjan; Banerjee, Anirban

    2012-06-15

    The study was undertaken to investigate whether regular cooking with biomass aggravates systemic inflammation and oxidative stress that might result in increase in the risk of developing cardiovascular disease (CVD) in rural Indian women compared to cooking with a cleaner fuel like liquefied petroleum gas (LPG). A total of 635 women (median age 36 years) who cooked with biomass and 452 age-matched control women who cooked with LPG were enrolled. Serum interleukin-6 (IL-6), C-reactive protein (CRP), tumor necrosis factor-alpha (TNF-?) and interleukin-8 (IL-8) were measured by ELISA. Generation of reactive oxygen species (ROS) by leukocytes was measured by flow cytometry, and erythrocytic superoxide dismutase (SOD) was measured by spectrophotometry. Hypertension was diagnosed following the Seventh Report of the Joint Committee. Tachycardia was determined as pulse rate > 100 beats per minute. Particulate matter of diameter less than 10 and 2.5 ?m (PM{sub 10} and PM{sub 2.5}, respectively) in cooking areas was measured using real-time aerosol monitor. Compared with control, biomass users had more particulate pollution in indoor air, their serum contained significantly elevated levels of IL-6, IL-8, TNF-? and CRP, and ROS generation was increased by 37% while SOD was depleted by 41.5%, greater prevalence of hypertension and tachycardia compared to their LPG-using neighbors. PM{sub 10} and PM{sub 2.5} levels were positively associated with markers of inflammation, oxidative stress and hypertension. Inflammatory markers correlated with raised blood pressure. Cooking with biomass exacerbates systemic inflammation, oxidative stress, hypertension and tachycardia in poor women cooking with biomass fuel and hence, predisposes them to increased risk of CVD development compared to the controls. Systemic inflammation and oxidative stress may be the mechanistic factors involved in the development of CVD. -- Highlights: ? Effect of chronic biomass smoke exposure on cardiovascular health was investigated. ? Serum markers of systemic inflammation and oxidative stress were studied. ? Biomass using women had increased systemic inflammation and oxidative stress. ? Indoor air pollution and observed changes were positively associated.

  3. Cadmium-induced oxidative stress and histological damage in the myocardium. Effects of a soy-based diet

    SciTech Connect (OSTI)

    Ferramola, Mariana L.; Prez Daz, Matas F.F.; Honor, Stella M.; Snchez, Sara S.; Antn, Rosa I.; Anzulovich, Ana C.; Gimnez, Mara S.

    2012-12-15

    Cd exposure has been associated to an augmented risk for cardiovascular disease. We investigated the effects of 15 and 100 ppm of Cd on redox status as well as histological changes in the rat heart and the putative protective effect of a soy-based diet. Male Wistar rats were separated into 6 groups and treated during 60 days as follows: groups (1), (2) and (3) were fed a casein-based diet; groups (4), (5) and (6), a soy-based diet; (1) and (4) were given tap water; (2) and (5) tap water containing 15 ppm of Cd{sup 2+}; and (3) and (6) tap water containing 100 ppm of Cd{sup 2+}. Serum lipid peroxides increased and PON-1 activity decreased in group (3). Lipoperoxidation also increased in the heart of all intoxicated groups; however protein oxidation only augmented in (3) and reduced glutathione levels diminished in (2) and (3). Catalase activity increased in groups (3) and (6) while superoxide dismutase activity increased only in (6). Glutathione peroxidase activity decreased in groups (3) and (6). Nrf2 expression was higher in groups (3) and (6), and MTI expression augmented in (3). Histological examination of the heart tissue showed the development of hypertrophic and fusion of cardiomyocytes along with foci of myocardial fiber necrosis. The transmission electron microscopy analysis showed profound ultra-structural damages. No protection against tissue degeneration was observed in animals fed the soy-based diet. Our findings indicate that even though the intake of a soy-based diet is capable of ameliorating Cd induced oxidative stress, it failed in preventing cardiac damage. -- Highlights: ? Cd intoxication produces extracellular and ultrastructural damage in the myocardium. ? The intake of a soy-based diet ameliorated Cd-induced oxidative stress. ? Cd-induced myocardial damage wasn't prevented by the intake of a soy-based diet. ? Cd-induced myocardial degeneration may not be caused by oxidative stress generation. ? Histology evaluation is needed to establish the extent of Cd-induced cardiac damage.

  4. Comparative developmental toxicity of environmentally relevant oxygenated PAHs

    SciTech Connect (OSTI)

    Knecht, Andrea L.; Goodale, Britton C.; Truong, Lisa; Simonich, Michael T.; Swanson, Annika J.; Matzke, Melissa M.; Anderson, Kim A.; Waters, Katrina M.; Tanguay, Robert L.

    2013-09-01

    Oxygenated polycyclic aromatic hydrocarbons (OPAHs) are byproducts of combustion and photo-oxidation of parent PAHs. OPAHs are widely present in the environment and pose an unknown hazard to human health. The developing zebrafish was used to evaluate a structurally diverse set of 38 OPAHs for malformation induction, gene expression changes and mitochondrial function. Zebrafish embryos were exposed from 6 to 120 h post fertilization (hpf) to a dilution series of 38 different OPAHs and evaluated for 22 developmental endpoints. AHR activation was determined via CYP1A immunohistochemistry. Phenanthrenequinone (9,10-PHEQ), 1,9-benz-10-anthrone (BEZO), xanthone (XAN), benz(a)anthracene-7,12-dione (7,12-B[a]AQ), and 9,10-anthraquinone (9,10-ANTQ) were evaluated for transcriptional responses at 48 hpf, prior to the onset of malformations. qRT-PCR was conducted for a number of oxidative stress genes, including the glutathione transferase(gst), glutathione peroxidase(gpx), and superoxide dismutase(sod) families. Bioenergetics was assayed to measure in vivo oxidative stress and mitochondrial function in 26 hpf embryos exposed to OPAHs. Hierarchical clustering of the structure-activity outcomes indicated that the most toxic of the OPAHs contained adjacent diones on 6-carbon moieties or terminal, para-diones on multi-ring structures. 5-carbon moieties with adjacent diones were among the least toxic OPAHs while the toxicity of multi-ring structures with more centralized para-diones varied considerably. 9,10-PHEQ, BEZO, 7,12-B[a]AQ, and XAN exposures increased expression of several oxidative stress related genes and decreased oxygen consumption rate (OCR), a measurement of mitochondrial respiration. Comprehensive in vivo characterization of 38 structurally diverse OPAHs indicated differential AHR dependency and a prominent role for oxidative stress in the toxicity mechanisms. - Highlights: OPAHs are byproducts of combustion present in the environment. OPAHs pose a largely unknown hazard to human health. We assayed the developmental toxicology of 39 different OPAHs in zebrafish. The most toxic OPAHs contained adjacent diones or terminal, para-diones. AHR dependency varied among OPAHs, and oxidative stress influenced their toxicology.

  5. Role of reactive oxygen species in arsenic-induced transformation of human lung bronchial epithelial (BEAS-2B) cells

    SciTech Connect (OSTI)

    Zhang, Zhuo; Pratheeshkumar, Poyil; Budhraja, Amit; Son, Young-Ok; Kim, Donghern; Shi, Xianglin

    2015-01-09

    Highlights: Short term exposure of cells to arsenic causes ROS generation. Chronical exposure of cells to arsenic causes malignant cell transformation. Inhibition of ROS generation reduces cell transformation by arsenic. Arsenic-transformed cells exhibit reduced capacity of generating ROS. Arsenic-transformed cells exhibit increased levels of antioxidants. - Abstract: Arsenic is an environmental carcinogen, its mechanisms of carcinogenesis remain to be investigated. Reactive oxygen species (ROS) are considered to be important. A previous study (Carpenter et al., 2011) has measured ROS level in human lung bronchial epithelial (BEAS-2B) cells and arsenic-transformed BEAS-2B cells and found that ROS levels were higher in transformed cells than that in parent normal cells. Based on these observations, the authors concluded that cell transformation induced by arsenic is mediated by increased cellular levels of ROS. This conclusion is problematic because this study only measured the basal ROS levels in transformed and parent cells and did not investigate the role of ROS in the process of arsenic-induced cell transformation. The levels of ROS in arsenic-transformed cells represent the result and not the cause of cell transformation. Thus question concerning whether ROS are important in arsenic-induced cell transformation remains to be answered. In the present study, we used expressions of catalase (antioxidant against H{sub 2}O{sub 2}) and superoxide dismutase 2 (SOD2, antioxidant against O{sub 2}{sup ?}) to decrease ROS level and investigated their role in the process of arsenic-induced cell transformation. Our results show that inhibition of ROS by antioxidant enzymes decreased arsenic-induced cell transformation, demonstrating that ROS are important in this process. We have also shown that in arsenic-transformed cells, ROS generation was lower and levels of antioxidants are higher than those in parent cells, in a disagreement with the previous report. The present study has also shown that the arsenic-transformed cells acquired apoptosis resistance. The inhibition of catalase to increase ROS level restored apoptosis capability of arsenic-transformed BEAS-2B cells, further showing that ROS levels are low in these cells. The apoptosis resistance due to the low ROS levels may increase cells proliferation, providing a favorable environment for tumorigenesis of arsenic-transformed cells.

  6. Activation of protein kinase B (PKB/Akt) and risk of lung cancer among rural women in India who cook with biomass fuel

    SciTech Connect (OSTI)

    Roychoudhury, Sanghita; Mondal, Nandan Kumar; Mukherjee, Sayali; Dutta, Anindita; Siddique, Shabana; Ray, Manas Ranjan

    2012-02-15

    The impact of indoor air pollution (IAP) from biomass fuel burning on the risk of carcinogenesis in the airways has been investigated in 187 pre-menopausal women (median age 34 years) from eastern India who cooked exclusively with biomass and 155 age-matched control women from same locality who cooked with cleaner fuel liquefied petroleum gas. Compared with control, Papanicolau-stained sputum samples showed 3-times higher prevalence of metaplasia and 7-times higher prevalence of dysplasia in airway epithelial cell (AEC) of biomass users. Immunocytochemistry showed up-regulation of phosphorylated Akt (p-Akt{sup ser473} and p-Akt{sup thr308}) proteins in AEC of biomass users, especially in metaplastic and dysplastic cells. Compared with LPG users, biomass-using women showed marked rise in reactive oxygen species (ROS) generation and depletion of antioxidant enzyme, superoxide dismutase (SOD) indicating oxidative stress. There were 25 times more particulate pollutants (PM{sub 10} and PM{sub 2.5}), 72% more nitrogen dioxide and 4-times more particulate-laden benzo(a)pyrene, but no change in sulfur dioxide in indoor air of biomass-using households, and high performance liquid chromatography estimated 6-fold rise in the concentration of benzene metabolite trans,trans-muconic acid (t,t-MA) in urine of biomass users. Metaplasia and dysplasia, p-Akt expression and ROS generation were positively associated with PM and t,t-MA levels. It appears that cumulative exposure to biomass smoke increases the risk of lung carcinogenesis via oxidative stress-mediated activation of Akt signal transduction pathway. -- Highlights: ? Carcinogenesis in airway cells was examined in biomass and LPG using women. ? Metaplasia and dysplasia of epithelial cells were more prevalent in biomass users. ? Change in airway cytology was associated with oxidative stress and Akt activation. ? Biomass users had greater exposure to respirable PM, B(a)P and benzene. ? Cooking with biomass increases cancer risk in the airways via Akt activation.

  7. Sodium orthovanadate associated with pharmacological doses of ascorbate causes an increased generation of ROS in tumor cells that inhibits proliferation and triggers apoptosis

    SciTech Connect (OSTI)

    Gnther, T-hat nia Mara Fischer; Kviecinski, Maicon Roberto; Baron, Carla Cristine; Felipe, Karina Bettega; Farias, Mirelle Sifroni; Ourique da Silva, Fabiana; Bcker, Ndia Cristina Falco; Pich, Claus Trger; Ferreira, Eduardo Antonio; Filho, Danilo Wilhelm; Verrax, Julien; Calderon, Pedro Buc; Pedrosa, Rozangela Curi

    2013-01-18

    Graphical abstract: -- Abstract: Pharmacological doses of ascorbate were evaluated for its ability to potentiate the toxicity of sodium orthovanadate (Na{sub 3}VO{sub 4}) in tumor cells. Cytotoxicity, inhibition of cell proliferation, generation of ROS and DNA fragmentation were assessed in T24 cells. Na{sub 3}VO{sub 4} was cytotoxic against T24 cells (EC{sub 50} = 5.8 ?M at 24 h), but in the presence of ascorbate (100 ?M) the EC{sub 50} fell to 3.3 ?M. Na{sub 3}VO{sub 4} plus ascorbate caused a strong inhibition of cell proliferation (up to 20%) and increased the generation of ROS (4-fold). Na{sub 3}VO{sub 4} did not directly cleave plasmid DNA, at this aspect no synergism was found occurring between Na{sub 3}VO{sub 4} and ascorbate once the resulting action of the combination was no greater than that of both substances administered separately. Cells from Ehrlich ascites carcinoma-bearing mice were used to determine the activity of antioxidant enzymes, the extent of the oxidative damage and the type of cell death. Na{sub 3}VO{sub 4} alone, or combined with ascorbate, increased catalase activity, but only Na{sub 3}VO{sub 4} plus ascorbate increased superoxide dismutase activity (up to 4-fold). Oxidative damage on proteins and lipids was higher due to the treatment done with Na{sub 3}VO{sub 4} plus ascorbate (23-fold). Ascorbate potentiated apoptosis in tumor cells from mice treated with Na{sub 3}VO{sub 4}. The results indicate that pharmacological doses of ascorbate enhance the generation of ROS induced by Na{sub 3}VO{sub 4} in tumor cells causing inhibition of proliferation and apoptosis. Apoptosis induced by orthovanadate and ascorbate is closer related to inhibition on Bcl-xL and activation of Bax. Our data apparently rule out a mechanism of cell demise p53-dependent or related to Cdk2 impairment.

  8. Reactive oxygen species mediate Cr(VI)-induced carcinogenesis through PI3K/AKT-dependent activation of GSK-3?/?-catenin signaling

    SciTech Connect (OSTI)

    Son, Young-Ok; Pratheeshkumar, Poyil; Wang, Lei; Wang, Xin; Fan, Jia; Kim, Dong-Hern; Lee, Ju-Yeon; Zhang, Zhuo; Lee, Jeong-Chae; Shi, Xianglin

    2013-09-01

    Cr(VI) compounds are known human carcinogens that primarily target the lungs. Cr(VI) produces reactive oxygen species (ROS), but the exact effects of ROS on the signaling molecules involved in Cr(VI)-induced carcinogenesis have not been extensively studied. Chronic exposure of human bronchial epithelial cells to Cr(VI) at nanomolar concentrations (10100 nM) for 3 months not only induced cell transformation, but also increased the potential of these cells to invade and migrate. Injection of Cr(VI)-stimulated cells into nude mice resulted in the formation of tumors. Chronic exposure to Cr(VI) increased levels of intracellular ROS and antiapoptotic proteins. Transfection with catalase or superoxide dismutase (SOD) prevented Cr(VI)-mediated increases in colony formation, cell invasion, migration, and xenograft tumors. While chronic Cr(VI) exposure led to activation of signaling cascades involving PI3K/AKT/GSK-3?/?-catenin and PI3K/AKT/mTOR, transfection with catalase or SOD markedly inhibited Cr(VI)-mediated activation of these signaling proteins. Inhibitors specific for AKT or ?-catenin almost completely suppressed the Cr(VI)-mediated increase in total and active ?-catenin proteins and colony formation. In particular, Cr(VI) suppressed autophagy of epithelial cells under nutrition deprivation. Furthermore, there was a marked induction of AKT, GSK-3?, ?-catenin, mTOR, and carcinogenic markers in tumor tissues formed in mice after injection with Cr(VI)-stimulated cells. Collectively, our findings suggest that ROS is a key mediator of Cr(VI)-induced carcinogenesis through the activation of PI3K/AKT-dependent GSK-3?/?-catenin signaling and the promotion of cell survival mechanisms via the inhibition of apoptosis and autophagy. - Highlights: Chronic exposure to Cr(VI) induces carcinogenic properties in BEAS-2B cells. ROS play an important role in Cr(VI)-induced tumorigenicity of BEAS-2B cells. PI3K/AKT/GSK-3?/?-catenin signaling involved in Cr(VI) carcinogenesis. The inhibition of apoptosis and autophagy contributes to Cr(VI) carcinogenesis.

  9. A Chandrasekhar mass progenitor for the Type Ia supernova remnant 3C 397

    Office of Scientific and Technical Information (OSTI)

    from the enhanced abundances of nickel and manganese (Journal Article) | SciTech Connect A Chandrasekhar mass progenitor for the Type Ia supernova remnant 3C 397 from the enhanced abundances of nickel and manganese Citation Details In-Document Search Title: A Chandrasekhar mass progenitor for the Type Ia supernova remnant 3C 397 from the enhanced abundances of nickel and manganese Despite decades of intense efforts, many fundamental aspects of Type Ia supernovae (SNe Ia) remain elusive. One

  10. Microsoft Word - Mn.doc

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    5 Structural Determination of Marine Bacteriogenic Manganese Oxides John R. Bargar, Samuel M. Webb (Stanford Synchrotron Radiation Laboratory), and Bradley M. Tebo (Oregon Health and Science University) Bacterial oxidation of Mn(II) impacts the global geochemical cycling of carbon, nitrogen, sulfur, nutrients, and contaminants in the environment. Manganese is abundant in the biosphere (~10 14 Kg of suspended and dissolved manganese in the oceans) and is second only to iron in relative

  11. High-Performance Thermoelectric Devices Based on Abundant Silicide...

    Office of Energy Efficiency and Renewable Energy (EERE) Indexed Site

    Reports of methods to synthesize single-crystal and poly or nano- crystalline p- and n-type higher manganese silicides to reduce lattice thermal conductivity...

  12. --No Title--

    Office of Energy Efficiency and Renewable Energy (EERE) Indexed Site

    exceedance of the manganese standard. Aquatic Resources The assessment of effects to fish habitat along the Colorado River was modeled following the concepts of the Instream...

  13. Shenzhen Soopower Technology Ltd | Open Energy Information

    Open Energy Info (EERE)

    China Product: Shenzhen-based subsidiary of China Airborn Missile Academy, they make Lithium Ferrous Phosphate and Lithium Manganese batteries suitable for e-bikes and power...

  14. Shenzhen Yuanyuan Material Tech Co Ltd | Open Energy Information

    Open Energy Info (EERE)

    Material Tech Co, Ltd Place: China Product: China-based maker of cathode materials for Lithium-ion batteries, their main product is Lithium Manganese cathode materials. References:...

  15. Nanoscale Morphological and Chemical Changes of High Voltage...

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    Nanoscale Morphological and Chemical Changes of High Voltage Lithium-Manganese Rich NMC Composite Cathodes with Cycling Friday, August 29, 2014 Renewable energy is critical for the...

  16. Status of Baseline Sampling for Elements in Soil and Vegetation...

    Open Energy Info (EERE)

    facility indicate that there are not significant differences in soil residue levels of lithium and manganese between the 50 sites. However, there are significant difference between...

  17. Search for: All records | SciTech Connect

    Office of Scientific and Technical Information (OSTI)

    (Al), chromium (Cr), manganese (Mn), lead (Pb), copper (Cu), zinc (Zn), arsenic (As), boron (B), selenium (Se), molybdenum (Mo), cadmium (Cd), and barium (Ba). Outfalls and...

  18. The Synthesis and Characterization of Substituted Olivines and...

    Office of Energy Efficiency and Renewable Energy (EERE) Indexed Site

    -- Washington D.C. PDF icon es22whittingham.pdf More Documents & Publications The Synthesis and Characterization of Substituted Olivines and Layered Manganese Oxides The...

  19. The Synthesis and Characterization of Substituted Olivines and...

    Office of Energy Efficiency and Renewable Energy (EERE) Indexed Site

    D.C. PDF icon es050whittingham2010p.pdf More Documents & Publications The Synthesis and Characterization of Substituted Phosphates and Layered Manganese Oxides The...

  20. Double perovskite catalysts for oxidative coupling

    DOE Patents [OSTI]

    Campbell, Kenneth D.

    1991-01-01

    Alkali metal doped double perovskites containing manganese and at least one of cobalt, iron and nickel are useful in the oxidative coupling of alkane to higher hydrocarbons.

  1. Energy Storage Systems 2014 Peer Review Presentations - Poster...

    Office of Energy Efficiency and Renewable Energy (EERE) Indexed Site

    Zinc Manganese Battery for Grid Scale Application Commercialization Pathway - Sanjoy Banerjee & Alex Couzis, CUNY Energy InstituteUrban Electric Power PDF icon Rechargeable Zinc ...

  2. EERE Success Story-California: Geothermal Plant to Help Meet...

    Office of Energy Efficiency and Renewable Energy (EERE) Indexed Site

    Technologies Office is working with California's Simbol Materials to develop technologies that extract battery materials like lithium, manganese, and zinc from geothermal brines. ...

  3. California Geothermal Power Plant to Help Meet High Lithium Demand...

    Office of Energy Efficiency and Renewable Energy (EERE) Indexed Site

    Simbol Materials to develop technologies that extract battery materials like lithium, manganese, and zinc from geothermal brines produced during the geothermal production process. ...

  4. Search for: All records | SciTech Connect

    Office of Scientific and Technical Information (OSTI)

    ... F. ; Besson, M. ; Descorme, C. ; Khrouz, L. Manganese oxides supported on mesoporous titanium oxides were synthesized via a sol-gel route using block copolymer self-assembly. ...

  5. High-Performance Thermoelectric Devices Based on Abundant Silicide Materials for Vehicle Waste Heat Recovery

    Broader source: Energy.gov [DOE]

    Reports of methods to synthesize single-crystal and poly or nano- crystalline p- and n-type higher manganese silicides to reduce lattice thermal conductivity

  6. Lack of a Jahn-Teller Distortion in La1-xSrxCoO3 Determined by...

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    exhibit a wide range of interesting properties, of which superconductivity in the copper oxides and colossal magnetoresistance in the manganese oxides are perhaps the best...

  7. Energy Saving System to Remove Volatile Organic Compounds (VOCs...

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    at Berkeley Lab have developed a catalyst and deployment devices to improve indoor air quality and reduce ventilation energy needs.Description The catalyst, a manganese...

  8. Cooperative Carbon Capture by a Novel Material that Mimics a...

    Office of Science (SC) Website

    Resources Contact Information Basic Energy Sciences U.S. Department of Energy SC-22... spheres) inserted between the manganese (green sphere) and amine (blue sphere) groups ...

  9. Understanding Nature's Choreography in Batteries | U.S. DOE Office...

    Office of Science (SC) Website

    Advanced Scientific Computing Research U.S. Department of Energy SC-21Germantown Building ... key: red oxygen; green carbon; purple manganese; blue lithium; grey hydrogen). ...

  10. Science Highlights | U.S. DOE Office of Science (SC)

    Office of Science (SC) Website

    ... view of how atom stretches informs microscopic description of nuclear energy production. ... spheres) inserted between the manganese (green sphere) and amine (blue sphere) groups ...

  11. Understanding Nature's Choreography in Batteries | U.S. DOE Office...

    Office of Science (SC) Website

    Understanding Nature's Choreography in Batteries Basic Energy Sciences (BES) BES Home ... key: red oxygen; green carbon; purple manganese; blue lithium; grey hydrogen). ...

  12. Ductile aluminide alloys for high temperature applications

    DOE Patents [OSTI]

    Liu, C.T.; Kock, C.C.

    1983-08-03

    Heat- and corrosion-resistant alloys are described which contain nickel, aluminum, boron, iron and in some instances manganese, niobium and titanium.

  13. Method for digesting a nitro-bearing explosive compound

    DOE Patents [OSTI]

    Shah, Manish M. (Richland, WA)

    2000-01-01

    The present invention is a process wherein superoxide radicals from superoxide salt are used to break down the explosive compounds. The process has an excellent reaction rate for degrading explosives, and operates at ambient temperature and atmospheric pressure in aqueous or non-aqueous conditions. Because the superoxide molecules are small, much smaller than an enzyme molecule for example, they can penetrate the microstructure of plastic explosives faster. The superoxide salt generates reactive hydroxyl radicals, which can destroy other organic contaminants, if necessary, along with digesting the explosive nitro-bearing compound.

  14. Method for refining contaminated iridium

    DOE Patents [OSTI]

    Heshmatpour, B.; Heestand, R.L.

    1982-08-31

    Contaminated iridium is refined by alloying it with an alloying agent selected from the group consisting of manganese and an alloy of manganese and copper, and then dissolving the alloying agent from the formed alloy to provide a purified iridium powder.

  15. Low Mn alloy steel for cryogenic service and method of preparation

    DOE Patents [OSTI]

    Morris, Jr., John W. (Berkeley, CA); Niikura, Masakazu (Yokohama, JP)

    1981-01-01

    A ferritic cryogenic steel which has a relatively low (about 4-6%) manganese content and which has been made suitable for use at cryogenic temperatures by a thermal cycling treatment followed by a final tempering. The steel includes 4-6% manganese, 0.02-0.06% carbon, 0.1-0.4% molybdenum and 0-3% nickel.

  16. The Synthesis and Characterization of Substituted Olivines and Layered

    Office of Energy Efficiency and Renewable Energy (EERE) Indexed Site

    Manganese Oxides | Department of Energy 09 DOE Hydrogen Program and Vehicle Technologies Program Annual Merit Review and Peer Evaluation Meeting, May 18-22, 2009 -- Washington D.C. PDF icon es_22_whittingham.pdf More Documents & Publications The Synthesis and Characterization of Substituted Olivines and Layered Manganese Oxides The Synthesis and Characterization of Substituted Phosphates

  17. Effect of Composition on the Voltage Fade Phenomenon in Lithium-, Manganese-Rich xLiMnO3(1-x)LiNiaMnbCocO2: A Combinatorial Synthesis Approach

    SciTech Connect (OSTI)

    Vu, Anh; Qin, Yan; Bareno, Javier; Lin, Chi-Kai; Abouimrane, Ali; Burrell, Anthony K.; Samuel, Bloom; Bass, Dean; Bloom, Ira

    2015-10-30

    The effect of composition on the voltage fade phenomenon was probed using combinatorial synthesis methods. In compositions that have the general formula, (Li2MnO3)a(LiNiO2)b(LiMnO2)c(LiCoO2)d, where 0 ? a?0.83, 0.15 ? b ? 0.42, 0 ? c ? 0.85, and 0 ? d ? 0.30 (a + b + c + d = 1), the dependence of features in the x-ray diffraction pattern and of voltage fade on composition were identified and mapped. The observed values of voltage fade indicated that it displayed some sensitivity to composition, but that the sensitivity was not large. The values of voltage fade were found to be amenable to statistical modeling. The model indicated that it may be possible to lower the value of voltage fade below 0.01% by adjusting the composition of the system; however, the composition is not expected to have the layeredlayered structure.

  18. Molten salt extraction process for the recovery of valued transition metals from land-based and deep-sea minerals

    DOE Patents [OSTI]

    Maroni, V.A.; von Winbush, S.

    1987-05-01

    A process for extracting transition metals and particularly cobalt and manganese together with iron, copper and nickel from low grade ores (including ocean-floor nodules) by converting the metal oxides or other compositions to chlorides in a molten salt, and subsequently using a combination of selective distillation at temperatures below about 500/degree/C, electrolysis at a voltage not more negative that about /minus/1.5 volt versus Ag/AgCl, and precipitation to separate the desired manganese and cobalt salts from other metals and provide cobalt and manganese in metallic forms or compositions from which these metals may be more easily recovered.

  19. Molten salt extraction process for the recovery of valued transition metals from land-based and deep-sea minerals

    DOE Patents [OSTI]

    Maroni, Victor A. (Naperville, IL); von Winbush, Samuel (Huntington, NY)

    1988-01-01

    A process for extracting transition metals and particularly cobalt and manganese together with iron, copper and nickel from low grade ores (including ocean-floor nodules) by converting the metal oxides or other compositions to chlorides in a molten salt, and subsequently using a combination of selective distillation at temperatures below about 500.degree. C., electrolysis at a voltage not more negative than about -1.5 volt versus Ag/AgCl, and precipitation to separate the desired manganese and cobalt salts from other metals and provide cobalt and manganese in metallic forms or compositions from which these metals may be more easily recovered.

  20. Sorbent for use in hot gas desulfurization

    DOE Patents [OSTI]

    Gasper-Galvin, Lee D. (Washington, PA); Atimtay, Aysel T. (Cankaya, TR)

    1993-01-01

    A multiple metal oxide sorbent supported on a zeolite of substantially silicon oxide is used for the desulfurization of process gas streams, such as from a coal gasifier, at temperatures in the range of about 1200.degree. to about 1600.degree. F. The sorbent is provided by a mixture of copper oxide and manganese oxide and preferably such a mixture with molybdenum oxide. The manganese oxide and the molybdenum are believed to function as promoters for the reaction of hydrogen sulfide with copper oxide. Also, the manganese oxide inhibits the volatilization of the molybdenum oxide at the higher temperatures.

  1. Metal phthalocyanine catalysts

    DOE Patents [OSTI]

    Ellis, P.E. Jr.; Lyons, J.E.

    1994-10-11

    A new composition of matter is described which is an alkali metal or ammonium or tetraalkylammonium diazidoperfluorophthalocyanatoferrate. Other embodiments of the invention comprise compositions wherein the metal of the coordination complex is cobalt, manganese and chromium.

  2. Process for removing technetium from iron and other metals

    DOE Patents [OSTI]

    Leitnaker, J.M.; Trowbridge, L.D.

    1999-03-23

    A process for removing technetium from iron and other metals comprises the steps of converting the molten, alloyed technetium to a sulfide dissolved in manganese sulfide, and removing the sulfide from the molten metal as a slag. 4 figs.

  3. Metal phthalocyanine catalysts

    DOE Patents [OSTI]

    Ellis, Jr., Paul E.; Lyons, James E.

    1994-01-01

    As a new composition of matter, alkali metal or ammonium or tetraalkylammonium diazidoperfluorophthalocyanatoferrate. Other embodiments of the invention comprise compositions wherein the metal of the coordination complex is cobalt, manganese and chromium.

  4. Subtask 3: Fuel production complex | Center for Bio-Inspired...

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    3: Fuel production complex All papers by year Subtask 1 Subtask 2 Subtask 3 Subtask 4 Subtask 5 Trovitch, R.J. (2014) Comparing Well-Defined Manganese, Iron, Cobalt, and Nickel...

  5. Process for removing technetium from iron and other metals

    DOE Patents [OSTI]

    Leitnaker, James M. (Kingston, TN); Trowbridge, Lee D. (Oak Ridge, TN)

    1999-01-01

    A process for removing technetium from iron and other metals comprises the steps of converting the molten, alloyed technetium to a sulfide dissolved in manganese sulfide, and removing the sulfide from the molten metal as a slag.

  6. News Item

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    including oceans, rivers and lakes, sunlight is well known to drive manganese oxide redox chemistry. It had long been assumed that electron-rich organic molecules were required to...

  7. Electronic and magnetic properties of Fe and Mn doped two dimensional hexagonal germanium sheets

    SciTech Connect (OSTI)

    Soni, Himadri R. Jha, Prafulla K.

    2014-04-24

    Using first principles density functional theory calculations, the present paper reports systematic total energy calculations of the electronic properties such as density of states and magnetic moment of pristine and iron and manganese doped two dimensional hexagonal germanium sheets.

  8. EERE PowerPoint 97-2004 Template: Green Version

    Office of Energy Efficiency and Renewable Energy (EERE) Indexed Site

    to leach out the template metal (lithium or manganese) * The amount of metal in the leachate is determined by ICP-OES * By determining the amount of metal leached out from the...

  9. REFRACTORY DIE FOR EXTRUDING URANIUM

    DOE Patents [OSTI]

    Creutz, E.C.

    1959-08-11

    A die is presented for the extrusion of metals, said die being formed of a refractory complex oxide having the composition M/sub n/O/sub m/R/sub x/O/sub y/ where M is magnesium, zinc, manganese, or iron, R is aluminum, chromic chromium, ferric iron, or manganic manganese, and m, n, x, and y are whole numbers. Specific examples are spinel, magnesium aluminate, magnetite, magnesioferrite, chromite, and franklinite.

  10. Perpendicular Magnetism Unparalleled Find in Single Crystal | The Ames

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    Laboratory Perpendicular Magnetism Unparalleled Find in Single Crystal Two distinct types of magnetism aligned perpendicular in a single crystal have been detailed in new measurements on single-crystal and powered samples composed of barium, potassium, manganese, and arsenic. Antiferromagnetism occurs with a checkerboard-style patterning of the total atomic magnetic moments due to the spins of the localized electrons of the manganese atoms (known as 'local-moment magnetism'). Aligning

  11. Nanoscale Morphological and Chemical Changes of High Voltage

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    Lithium-Manganese Rich NMC Composite Cathodes with Cycling | Stanford Synchrotron Radiation Lightsource Nanoscale Morphological and Chemical Changes of High Voltage Lithium-Manganese Rich NMC Composite Cathodes with Cycling Friday, August 29, 2014 Renewable energy is critical for the future of humankind. One bottleneck is energy storage because the harvest and consumption of energy are typically separated in time and/or location. Hence, efficient, low-cost, safe and durable batteries are

  12. Electrochemistry Cell Model | Department of Energy

    Office of Energy Efficiency and Renewable Energy (EERE) Indexed Site

    2 DOE Hydrogen and Fuel Cells Program and Vehicle Technologies Program Annual Merit Review and Peer Evaluation Meeting PDF icon es031_gallagher_2012_o.pdf More Documents & Publications Vehicle Technologies Office Merit Review 2014: Electrochemical Modeling of LMR-NMC Materials and Electrodes Examining Hysteresis in Lithium- and Manganese-Rich Composite Cathode Materials Promises and Challenges of Lithium- and Manganese-Rich Transition-Metal Layered-Oxide Cathodes

  13. On the state of Mn impurity implanted in Si

    SciTech Connect (OSTI)

    Orlov, A. F.; Bublik, V. T.; Vdovin, V. I.; Agafonov, Yu. A.; Balagurov, L. A.; Zinenko, V. I.; Kulemanov, I. V.; Shcherbachev, K. D.

    2009-07-15

    The state of manganese impurity in implanted silicon at implantation doses of up to 5 x 10{sup 16} cm{sup -2} has been investigated by X-ray diffraction and transmission electron microscopy. It is established that, after short-term vacuum annealing at 850{sup o}C, most of the implanted manganese impurities are in microinclusions up to 20 nm in size formed by a tetragonal silicide phase of the Mn{sub 15}Si{sub 26} type.

  14. Metal Cycling by Bacteria: Moving Electrons Around

    ScienceCinema (OSTI)

    Nealson, Ken

    2010-01-08

    About 20 years ago, Shewanella oneidensis MR-1 was isolated from a manganese-rich lack in upstate New York, and subsequently shown to utilize solid forms of oxidized manganese or iron as an electron acceptor. Recent studies of metal-reducing bacterial have unveiled a number of unexpected properties of microbes that have enlarged our view of microbes and their role(s) in natural ecosystems. For example, the processes of metal reduction themselves are fundamental to the carbon cycle in many lakes and sediments, where iron and manganese account for the major portion of organic carbon oxidation in many sediments. On more modest spatial scales, iron and manganese reduction can be linked to the oxidation of a wide variety of carbon compounds, many of them recalcitrant and/or toxic. One remarkable property of metal reducers is their ability to reduce solid, often highly crystalline substrates such as iron and manganese oxides and oxyhydroxides. It is now clear that this is done via the utilization of enzymes located on the outer wall of the bacteria - enzymes that apparently interact directly with these solid substrates. Molecular and genomic studies combined have revealed the genes and protoeins responsible for these activities, and many facets of the regulation. This talk focuses on the general features and properties of these remarkable organisms that seem to communicate via electron transfer across a wide variety of soluable, insoluable, and even "inert" substrates, and the way that these processes may be mechanistically linked.

  15. Metal Cycling by Bacteria: Moving Electrons Around

    SciTech Connect (OSTI)

    Nealson, Ken

    2009-07-06

    About 20 years ago, Shewanella oneidensis MR-1 was isolated from a manganese-rich lack in upstate New York, and subsequently shown to utilize solid forms of oxidized manganese or iron as an electron acceptor. Recent studies of metal-reducing bacterial have unveiled a number of unexpected properties of microbes that have enlarged our view of microbes and their role(s) in natural ecosystems. For example, the processes of metal reduction themselves are fundamental to the carbon cycle in many lakes and sediments, where iron and manganese account for the major portion of organic carbon oxidation in many sediments. On more modest spatial scales, iron and manganese reduction can be linked to the oxidation of a wide variety of carbon compounds, many of them recalcitrant and/or toxic. One remarkable property of metal reducers is their ability to reduce solid, often highly crystalline substrates such as iron and manganese oxides and oxyhydroxides. It is now clear that this is done via the utilization of enzymes located on the outer wall of the bacteria - enzymes that apparently interact directly with these solid substrates. Molecular and genomic studies combined have revealed the genes and protoeins responsible for these activities, and many facets of the regulation. This talk focuses on the general features and properties of these remarkable organisms that seem to communicate via electron transfer across a wide variety of soluable, insoluable, and even "inert" substrates, and the way that these processes may be mechanistically linked.

  16. Sulfur dioxide capture in the combustion of mixtures of lime, refuse-derived fuel, and coal

    SciTech Connect (OSTI)

    Churney, K.L.; Buckley, T.J. . Center for Chemical Technology)

    1990-06-01

    Chlorine and sulfur mass balance studies have been carried out in the combustion of mixtures of lime, refuse-derived fuel, and coal in the NIST multikilogram capacity batch combustor. The catalytic effect of manganese dioxide on the trapping of sulfur dioxide by lime was examined. Under our conditions, only 4% of the chlorine was trapped in the ash and no effect of manganese dioxide was observed. Between 42 and 14% of the total sulfur was trapped in the ash, depending upon the lime concentration. The effect of manganese dioxide on sulfur capture was not detectable. The temperature of the ash was estimated to be near 1200{degrees}C, which was in agreement with that calculated from sulfur dioxide capture thermodynamics. 10 refs., 12 figs., 10 tabs.

  17. Catalytic oxidation of hydrocarbons and alcohols by carbon dioxide on oxide catalysts

    SciTech Connect (OSTI)

    Krylov, O.V. . N.N. Semenov Inst. of Chemical Physics); Mamedov, A.Kh.; Mirzabekova, S.R. . Yu.G. Mamedaliev Inst. of Petrochemical Processes)

    1995-02-01

    The great interest displayed lately in heterogeneous catalytic reactions of carbon dioxide is caused by two reasons: (1) the necessity to fight the greenhouse effect and (2) the exhaust of carbon raw material sources. Reactions of oxidative transformation of organic compounds of different classes (alkanes, alkenes, and alcohols) with a nontraditional oxidant, carbon dioxide, were studied on oxide catalysts Fe-O, Cr-O, Mn-O and on multicomponent systems based on manganese oxide. The supported manganese oxide catalysts are active, selective, and stable in conversion of the CH[sub 4] + CO[sub 2] mixture into synthesis gas and in oxidative dehydrogenation of C[sub 2] [minus] C[sub 7] hydrocarbons and the lower alcohols. Unlike metal catalysts manganese oxide based catalysts do not form a carbon layer during the reaction.

  18. Catalyst and method for reduction of nitrogen oxides

    DOE Patents [OSTI]

    Ott, Kevin C. (Los Alamos, NM)

    2008-08-19

    A Selective Catalytic Reduction (SCR) catalyst was prepared by slurry coating ZSM-5 zeolite onto a cordierite monolith, then subliming an iron salt onto the zeolite, calcining the monolith, and then dipping the monolith either into an aqueous solution of manganese nitrate and cerium nitrate and then calcining, or by similar treatment with separate solutions of manganese nitrate and cerium nitrate. The supported catalyst containing iron, manganese, and cerium showed 80 percent conversion at 113 degrees Celsius of a feed gas containing nitrogen oxides having 4 parts NO to one part NO.sub.2, about one equivalent ammonia, and excess oxygen; conversion improved to 94 percent at 147 degrees Celsius. N.sub.2O was not detected (detection limit: 0.6 percent N.sub.2O).

  19. Catalyst and method for reduction of nitrogen oxides

    DOE Patents [OSTI]

    Ott, Kevin C. (Los Alamos, NM)

    2008-05-27

    A Selective Catalytic Reduction (SCR) catalyst was prepared by slurry coating ZSM-5 zeolite onto a cordierite monolith, then subliming an iron salt onto the zeolite, calcining the monolith, and then dipping the monolith either into an aqueous solution of manganese nitrate and cerium nitrate and then calcining, or by similar treatment with separate solutions of manganese nitrate and cerium nitrate. The supported catalyst containing iron, manganese, and cerium showed 80 percent conversion at 113 degrees Celsius of a feed gas containing nitrogen oxides having 4 parts NO to one part NO.sub.2, about one equivalent ammonia, and excess oxygen; conversion improved to 94 percent at 147 degrees Celsius. N.sub.2O was not detected (detection limit: 0.6 percent N.sub.2O).

  20. Catalyst for reduction of nitrogen oxides

    DOE Patents [OSTI]

    Ott, Kevin C.

    2010-04-06

    A Selective Catalytic Reduction (SCR) catalyst was prepared by slurry coating ZSM-5 zeolite onto a cordierite monolith, then subliming an iron salt onto the zeolite, calcining the monolith, and then dipping the monolith either into an aqueous solution of manganese nitrate and cerium nitrate and then calcining, or by similar treatment with separate solutions of manganese nitrate and cerium nitrate. The supported catalyst containing iron, manganese, and cerium showed 80 percent conversion at 113 degrees Celsius of a feed gas containing nitrogen oxides having 4 parts NO to one part NO.sub.2, about one equivalent ammonia, and excess oxygen; conversion improved to 94 percent at 147 degrees Celsius. N.sub.2O was not detected (detection limit: 0.6 percent N.sub.2O).

  1. Dy-Mn-Si as a representative of family of 'Dy-Transition

    Office of Scientific and Technical Information (OSTI)

    Metal-Si' systems: Its isothermal sections, empirical rProd. Type: FTPules and new rare-earth manganese silicides (Journal Article) | SciTech Connect Dy-Mn-Si as a representative of family of 'Dy-Transition Metal-Si' systems: Its isothermal sections, empirical rProd. Type: FTPules and new rare-earth manganese silicides Citation Details In-Document Search Title: Dy-Mn-Si as a representative of family of 'Dy-Transition Metal-Si' systems: Its isothermal sections, empirical rProd. Type: FTPules

  2. Autogenous electrolyte, non-pyrolytically produced solid capacitor structure

    DOE Patents [OSTI]

    Sharp, D.J.; Armstrong, P.S.; Panitz, J.K.G.

    1998-03-17

    A solid electrolytic capacitor is described having a solid electrolyte comprising manganese dioxide dispersed in an aromatic polyamide capable of further cure to form polyimide linkages, the solid electrolyte being disposed between a first electrode made of valve metal covered by an anodic oxide film and a second electrode opposite the first electrode. The electrolyte autogenously produces water, oxygen, and hydroxyl groups which act as healing substances and is not itself produced pyrolytically. Reduction of the manganese dioxide and the water molecules released by formation of imide linkages result in substantially improved self-healing of anodic dielectric layer defects. 2 figs.

  3. Autogenous electrolyte, non-pyrolytically produced solid capacitor structure

    DOE Patents [OSTI]

    Sharp, Donald J. (Albuquerque, NM); Armstrong, Pamela S. (Abingdon, MD); Panitz, Janda Kirk G. (Edgewood, NM)

    1998-01-01

    A solid electrolytic capacitor having a solid electrolyte comprising manganese dioxide dispersed in an aromatic polyamide capable of further cure to form polyimide linkages, the solid electrolyte being disposed between a first electrode made of valve metal covered by an anodic oxide film and a second electrode opposite the first electrode. The electrolyte autogenously produces water, oxygen, and hydroxyl groups which act as healing substances and is not itself produced pyrolytically. Reduction of the manganese dioxide and the water molecules released by formation of imide linkages result in substantially improved self-healing of anodic dielectric layer defects.

  4. Cyano- and polycyanometallo-porphyrins as catalysts for alkane oxidation

    DOE Patents [OSTI]

    Ellis, P.E. Jr.; Lyons, J.E.

    1993-05-18

    New compositions of matter comprising cyano-substituted metal complexes of porphyrins are catalysts for the oxidation of alkanes. The metal is iron, chromium, manganese, ruthenium, copper or cobalt. The porphyrin ring has cyano groups attached thereto in meso- and/or [beta]-pyrrolic positions.

  5. CX-100010: Categorical Exclusion Determination

    Broader source: Energy.gov [DOE]

    Geothermal Thermoelectric Generation (G-TEG) with integrated Temperature Driven Membrane Distillation and Novel Manganese Oxide for Lithium Extraction Award Number: DE-EE0006746 CX(s) Applied: A9, B3.6 Date: 08/27/2014 Location(s): Georgia Offices(s): Golden Field Office Technology Office: Geothermal Technologies

  6. Nitrated metalloporphyrins as catalysts for alkane oxidation

    DOE Patents [OSTI]

    Ellis, P.E. Jr.; Lyons, J.E.

    1994-01-18

    Compositions of matter comprising nitro-substituted metal complexes of porphyrins are catalysts for the oxidation of alkanes. The metal is iron, chromium, manganese, ruthenium, copper or cobalt. The porphyrin ring has nitro groups attached thereto in meso and/or [beta]-pyrrolic positions.

  7. Cyano- and polycyanometallo-porphyrins as catalysts for alkane oxidation

    DOE Patents [OSTI]

    Ellis, P.E. Jr.; Lyons, J.E.

    1995-01-17

    New compositions of matter comprising cyano-substituted metal complexes of porphyrins are catalysts for the oxidation of alkanes. The metal is iron, chromium, manganese, ruthenium, copper or cobalt. The porphyrin ring has cyano groups attached thereto in meso and/or [beta]-pyrrolic positions.

  8. SSRL HEADLINES Oct 2006

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    4 October, 2006 __________________________________________________________________________ Contents of this Issue: Science Highlight - Uranium-Hungry Bacteria Lead to Safer Water Supply Science Highlight - Uranium Trapped in Bacteriogenic Manganese Oxide Tunnels Roger Kornberg Wins the 2006 Chemistry Nobel Prize Another Successful Users' Meeting SSRL Awards Honor Mike Soltis and Bill Schlotter SSRL Users' Organization Executive Committee Update Ground Breaking New Science NIH-NCRR Officials

  9. Radionuclide trap

    DOE Patents [OSTI]

    McGuire, Joseph C. (Richland, WA)

    1978-01-01

    The deposition of radionuclides manganese-54, cobalt-58 and cobalt-60 from liquid sodium coolant is controlled by providing surfaces of nickel or high nickel alloys to extract the radionuclides from the liquid sodium, and by providing surfaces of tungsten, molybdenum or tantalum to prevent or retard radionuclide deposition.

  10. Cyano- and polycyanometallo-porphyrins as catalysts for alkane oxidation

    DOE Patents [OSTI]

    Ellis, Jr., Paul E.; Lyons, James E.

    1995-01-01

    New compositions of matter comprising cyano-substituted metal complexes of porphyrins are catalysts for the oxidation of alkanes. The metal is iron, chromium, manganese, ruthenium, copper or cobalt. The porphyrin ring has cyano groups attached thereto in meso and/or .beta.-pyrrolic positions.

  11. Nitrated metalloporphyrins as catalysts for alkane oxidation

    DOE Patents [OSTI]

    Ellis, Jr., Paul E.; Lyons, James E.

    1994-01-01

    Compositions of matter comprising nitro-substituted metal complexes of porphyrins are catalysts for the oxidation of alkanes. The metal is iron, chromium, manganese, ruthenium, copper or cobalt. The porphyrin ring has nitro groups attached thereto in meso and/or .beta.-pyrrolic positions.

  12. Cyano- and polycyanometallo-porphyrins as catalysts for alkane oxidation

    DOE Patents [OSTI]

    Ellis, Jr., Paul E.; Lyons, James E.

    1993-01-01

    New compositions of matter comprising cyano-substituted metal complexes of porphyrins are catalysts for the oxidation of alkanes. The metal is iron, chromium, manganese, ruthenium, copper or cobalt. The porphyrin ring has cyano groups attached thereto in meso and/or .beta.-pyrrolic positions.

  13. Method for inhibiting alkali metal corrosion of nickel-containing alloys

    DOE Patents [OSTI]

    DeVan, Jackson H. (Oak Ridge, TN); Selle, James E. (Westminster, CO)

    1983-01-01

    Structural components of nickel-containing alloys within molten alkali metal systems are protected against corrosion during the course of service by dissolving therein sufficient aluminum, silicon, or manganese to cause the formation and maintenance of a corrosion-resistant intermetallic reaction layer created by the interaction of the molten metal, selected metal, and alloy.

  14. Non-Equilibrium Pathways during Electrochemical Phase Transformations...

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    lithium-manganese spinel cathode material - Li1+xMn2-xO4 - is one of the state-of-the-art materials for Li-ion batteries. During the electrochemical reaction, up to 2 mol Li can...

  15. Process for producing dimethyl ether from synthesis gas

    DOE Patents [OSTI]

    Pierantozzi, R.

    1985-06-04

    This invention pertains to a Fischer Tropsch process for converting synthesis gas to an oxygenated hydrocarbon with particular emphasis on dimethyl ether. Synthesis gas comprising carbon monoxide and hydrogen are converted to dimethyl ether by carrying out the reaction in the presence of an alkali metal-manganese-iron carbonyl cluster incorporated onto a zirconia-alumina support.

  16. PHEV Battery Cost Assessment | Department of Energy

    Office of Energy Efficiency and Renewable Energy (EERE) Indexed Site

    2 DOE Hydrogen and Fuel Cells Program and Vehicle Technologies Program Annual Merit Review and Peer Evaluation Meeting PDF icon es111_gallagher_2012_o.pdf More Documents & Publications Promises and Challenges of Lithium- and Manganese-Rich Transition-Metal Layered-Oxide Cathodes PHEV Battery Cost Assessment EV Everywhere Grand Challenge - Battery Status and Cost Reduction Prospects

  17. California Geothermal Power Plant to Help Meet High Lithium Demand

    Broader source: Energy.gov [DOE]

    Ever wonder how we get the materials for the advanced batteries that power our cell phones, laptops, and even some electric vehicles? The U.S. Department of Energy's Geothermal Technologies Program (GTP) is working with California's Simbol Materials to develop technologies that extract battery materials like lithium, manganese, and zinc from geothermal brines produced during the geothermal production process.

  18. Sulfur oxide adsorbents and emissions control

    DOE Patents [OSTI]

    Li, Liyu (Richland, WA); King, David L. (Richland, WA)

    2006-12-26

    High capacity sulfur oxide absorbents utilizing manganese-based octahedral molecular sieve (Mn--OMS) materials are disclosed. An emissions reduction system for a combustion exhaust includes a scrubber 24 containing these high capacity sulfur oxide absorbents located upstream from a NOX filter 26 or particulate trap.

  19. Process for the production of hydrogen and carbonyl sulfide from hydrogen sulfide and carbon monoxide using a metal boride, nitride, carbide and/or silicide catalyst

    SciTech Connect (OSTI)

    McGuiggan, M.F.; Kuch, P.L.

    1984-05-08

    Hydrogen and carbonyl sulfide are produced by a process comprising contacting gaseous hydrogen sulfide with gaseous carbon monoxide in the presence of a metal boride, carbide, nitride and/or silicide catalyst, such as titanium carbide, vanadium boride, manganese nitride or molybdenum silicide.

  20. Process for decomposing lignin in biomass

    DOE Patents [OSTI]

    Rector, Kirk Davin; Lucas, Marcel; Wagner, Gregory Lawrence; Kimball, David Bryan; Hanson, Susan Kloek

    2014-10-28

    A mild inexpensive process for treating lignocellulosic biomass involves oxidative delignification of wood using an aqueous solution prepared by dissolving a catalytic amount of manganese (III) acetate into water and adding hydrogen peroxide. Within 4 days and without agitation, the solution was used to convert poplar wood sections into a fine powder-like delignified, cellulose rich materials that included individual wood cells.

  1. CX-004134: Categorical Exclusion Determination

    Broader source: Energy.gov [DOE]

    Electrodeposited Manganese-Cobalt Alloy Coating for Solid Oxide Fuel Cell InterconnectsCX(s) Applied: B3.6, B5.1Date: 09/17/2010Location(s): Clayton, OhioOffice(s): Energy Efficiency and Renewable Energy

  2. Process for producing dimethyl ether form synthesis gas

    DOE Patents [OSTI]

    Pierantozzi, Ronald (Macungie, PA)

    1985-01-01

    This invention pertains to a Fischer Tropsch process for converting synthesis gas to an oxygenated hydrocarbon with particular emphasis on dimethyl ether. Synthesis gas comprising carbon monoxide and hydrogen are converted to dimethyl ether by carrying out the reaction in the presence of an alkali metal-manganese-iron carbonyl cluster incorporated onto a zirconia-alumina support.

  3. Ductile Binder Phase For Use With Almgb14 And Other Hard Ceramic Materials

    DOE Patents [OSTI]

    Cook, Bruce A. (Ankeny, IA); Russell, Alan (Ames, IA); Harringa, Joel (Ames, IA)

    2005-07-26

    This invention relates to a ductile binder phase for use with AlMgB14 and other hard materials. The ductile binder phase, a cobalt-manganese alloy, is used in appropriate quantities to tailor good hardness and reasonable fracture toughness for hard materials so they can be used suitably in industrial machining and grinding applications.

  4. Conversion of CH4 into H2 at 300 C using Pd/MnO2 catalyst made with an effect of water oxidation

    SciTech Connect (OSTI)

    Koyanaka, Hideki; Takeuchi, K; Kolesnikov, Alexander I

    2014-01-01

    A novel electricity-free deposition of palladium on the surface of manganese dioxide, which has a crystal structure of ramsdellite, was studied. Using the Pd deposition, a nano-particle of Pd/MnO2 was prepared, and it was used for a catalytic performance for reforming methane into hydrogen at 300 C.

  5. Aluminum battery alloys

    DOE Patents [OSTI]

    Thompson, David S. (Richmond, VA); Scott, Darwin H. (Mechanicsville, VA)

    1985-01-01

    Aluminum alloys suitable for use as anode structures in electrochemical cs are disclosed. These alloys include iron levels higher than previously felt possible, due to the presence of controlled amounts of manganese, with possible additions of magnesium and controlled amounts of gallium.

  6. Jianguo Wen | Argonne National Laboratory

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    Jianguo Wen Materials Scientist News Advantages of Microscopy Method for Imaging Nanocatalysts A Lithium-Air Battery Based on Lithium Superoxide Telephone 630.252.3254 E-mail jwen@anl.gov CV/Resume PDF icon Jianguo_Wen.pdf

  7. PCB153 reduces telomerase activity and telomere length in immortalized human skin keratinocytes (HaCaT) but not in human foreskin keratinocytes (NFK)

    SciTech Connect (OSTI)

    Senthilkumar, P.K.; Robertson, L.W.; Department of Occupational and Environmental Health, The University of Iowa, Iowa City, IA ; Ludewig, G.

    2012-02-15

    Polychlorinated biphenyls (PCBs), ubiquitous environmental pollutants, are characterized by long term-persistence in the environment, bioaccumulation, and biomagnification in the food chain. Exposure to PCBs may cause various diseases, affecting many cellular processes. Deregulation of the telomerase and the telomere complex leads to several biological disorders. We investigated the hypothesis that PCB153 modulates telomerase activity, telomeres and reactive oxygen species resulting in the deregulation of cell growth. Exponentially growing immortal human skin keratinocytes (HaCaT) and normal human foreskin keratinocytes (NFK) were incubated with PCB153 for 48 and 24 days, respectively, and telomerase activity, telomere length, superoxide level, cell growth, and cell cycle distribution were determined. In HaCaT cells exposure to PCB153 significantly reduced telomerase activity, telomere length, cell growth and increased intracellular superoxide levels from day 6 to day 48, suggesting that superoxide may be one of the factors regulating telomerase activity, telomere length and cell growth compared to untreated control cells. Results with NFK cells showed no shortening of telomere length but reduced cell growth and increased superoxide levels in PCB153-treated cells compared to untreated controls. As expected, basal levels of telomerase activity were almost undetectable, which made a quantitative comparison of treated and control groups impossible. The significant down regulation of telomerase activity and reduction of telomere length by PCB153 in HaCaT cells suggest that any cell type with significant telomerase activity, like stem cells, may be at risk of premature telomere shortening with potential adverse health effects for the affected organism. -- Highlights: ? Human immortal (HaCaT) and primary (NFK) keratinocytes were exposed to PCB153. ? PCB153 significantly reduced telomerase activity and telomere length in HaCaT. ? No effect on telomere length and telomerase activity was found in NFK. ? Increased intracellular superoxide levels and reduced cell growth was seen in both. ? PCB153 may damage telomerase expressing cells like stem cells.

  8. Photo-induced electron transfer method

    DOE Patents [OSTI]

    Wohlgemuth, Roland (2823 Hillegass Ave., Berkeley, CA 94705); Calvin, Melvin (2683 Buena Vista Way, Berkeley, CA 94708)

    1984-01-01

    The efficiency of photo-induced electron transfer reactions is increased and the back transfer of electrons in such reactions is greatly reduced when a photo-sensitizer zinc porphyrin-surfactant and an electron donor manganese porphyrin-surfactant are admixed into phospho-lipid membranes. The phospholipids comprising said membranes are selected from phospholipids whose head portions are negatively charged. Said membranes are contacted with an aqueous medium in which an essentially neutral viologen electron acceptor is admixed. Catalysts capable of transfering electrons from reduced viologen electron acceptor to hydrogen to produce elemental hydrogen are also included in the aqueous medium. An oxidizable olefin is also admixed in the phospholipid for the purpose of combining with oxygen that coordinates with oxidized electron donor manganese porphyrin-surfactant.

  9. Photo-induced electron transfer method

    DOE Patents [OSTI]

    Wohlgemuth, R.; Calvin, M.

    1984-01-24

    The efficiency of photo-induced electron transfer reactions is increased and the back transfer of electrons in such reactions is greatly reduced when a photo-sensitizer zinc porphyrin-surfactant and an electron donor manganese porphyrin-surfactant are admixed into phospholipid membranes. The phospholipids comprising said membranes are selected from phospholipids whose head portions are negatively charged. Said membranes are contacted with an aqueous medium in which an essentially neutral viologen electron acceptor is admixed. Catalysts capable of transferring electrons from reduced viologen electron acceptor to hydrogen to produce elemental hydrogen are also included in the aqueous medium. An oxidizable olefin is also admixed in the phospholipid for the purpose of combining with oxygen that coordinates with oxidized electron donor manganese porphyrin-surfactant.

  10. Rare-Earth-Free Nanostructure Magnets: Rare-Earth-Free Permanent Magnets for Electric Vehicle Motors and Wind Turbine Generators: Hexagonal Symmetry Based Materials Systems Mn-Bi and M-type Hexaferrite

    SciTech Connect (OSTI)

    2012-01-01

    REACT Project: The University of Alabama is developing new iron- and manganese-based composite materials for use in the electric motors of EVs and renewable power generators that will demonstrate magnetic properties superior to todays best rare-earth-based magnets. Rare earths are difficult and expensive to refine. EVs and renewable power generators typically use rare earths to make their electric motors smaller and more powerful. The University of Alabama has the potential to improve upon the performance of current state-of-the-art rare-earth-based magnets using low-cost and more abundant materials such as manganese and iron. The ultimate goal of this project is to demonstrate improved performance in a full-size prototype magnet at reduced cost.

  11. Mn-Fe base and Mn-Cr-Fe base austenitic alloys

    DOE Patents [OSTI]

    Brager, Howard R. (Richland, WA); Garner, Francis A. (Richland, WA)

    1987-01-01

    Manganese-iron base and manganese-chromium-iron base austenitic alloys designed to have resistance to neutron irradiation induced swelling and low activation have the following compositions (in weight percent): 20 to 40 Mn; up to about 15 Cr; about 0.4 to about 3.0 Si; an austenite stabilizing element selected from C and N, alone or in combination with each other, and in an amount effective to substantially stabilize the austenite phase, but less than about 0.7 C, and less than about 0.3 N; up to about 2.5 V; up to about 0.1 P; up to about 0.01 B; up to about 3.0 Al; up to about 0.5 Ni; up to about 2.0 W; up to about 1.0 Ti; up to about 1.0 Ta; and with the remainder of the alloy being essentially iron.

  12. In search of the dead zone: Use of otoliths for tracking fish exposure to hypoxia

    DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)

    Limburg, Karin E.; Walther, Benjamin D.; Lu, Zunli; Jackman, George; Mohan, John; Walther, Yvonne; Nissling, Anders; Weber, Peter K.; Schmitt, Axel K.

    2015-01-01

    Otolith chemistry is often useful for tracking provenance of fishes, as well as examining migration histories. Whereas elements such as strontium and barium correlate well with salinity and temperature, experiments that examine manganese uptake as a function of these parameters have found no such correlation. Instead, dissolved manganese is available as a redox product, and as such, is indicative of low-oxygen conditions. Here we present evidence for that mechanism in a range of habitats from marine to freshwater, across species, and also present ancillary proxies that support the mechanism as well. For example, iodine is redox-sensitive and varies inversely withmore » Mn; and sulfur stable isotope ratios provide evidence of anoxic sulfate reduction in some circumstances.« less

  13. In search of the dead zone: Use of otoliths for tracking fish exposure to hypoxia

    SciTech Connect (OSTI)

    Limburg, Karin E.; Walther, Benjamin D.; Lu, Zunli; Jackman, George; Mohan, John; Walther, Yvonne; Nissling, Anders; Weber, Peter K.; Schmitt, Axel K.

    2015-01-01

    Otolith chemistry is often useful for tracking provenance of fishes, as well as examining migration histories. Whereas elements such as strontium and barium correlate well with salinity and temperature, experiments that examine manganese uptake as a function of these parameters have found no such correlation. Instead, dissolved manganese is available as a redox product, and as such, is indicative of low-oxygen conditions. Here we present evidence for that mechanism in a range of habitats from marine to freshwater, across species, and also present ancillary proxies that support the mechanism as well. For example, iodine is redox-sensitive and varies inversely with Mn; and sulfur stable isotope ratios provide evidence of anoxic sulfate reduction in some circumstances.

  14. Solid state electrochemical current source

    DOE Patents [OSTI]

    Potanin, Alexander Arkadyevich (Sarov, RU); Vedeneev, Nikolai Ivanovich (Sarov, RU)

    2002-04-30

    A cathode and a solid state electrochemical cell comprising said cathode, a solid anode and solid fluoride ion conducting electrolyte. The cathode comprises a metal oxide and a compound fluoride containing at least two metals with different valences. Representative compound fluorides include solid solutions of bismuth fluoride and potassium fluoride; and lead fluoride and potassium fluoride. Representative metal oxides include copper oxide, lead oxide, manganese oxide, vanadium oxide and silver oxide.

  15. Quality problems in waters used for drinking purposes in Italy

    SciTech Connect (OSTI)

    Funari, E.; Bastone, A.; Bottoni, P.; De Donno, D.; Donati, L. )

    1991-12-01

    With a grant from the Italian Ministry of the Environment, the National Institute of Health (Istituto Superiore di Sanita) promoted and coordinated some activities aimed at determining the extent and the intensity of contamination of waters used for human consumption by some chemical agents, and describing causes and modalities of contamination and human health implications. The chemical agents examined were herbicides, nitrates, trihalomethanes, asbestos, manganese and fluoride. In this paper a first nationwide picture of these problems is reported.

  16. Stabilization of solar films against hi temperature deactivation

    DOE Patents [OSTI]

    Jefferson, Clinton F. (Millburn, NJ)

    1984-03-20

    A multi-layer solar energy collector of improved stability comprising: (1) a solar absorptive film consisting essentially of copper oxide, cobalt oxide and manganese oxide; (2) a substrate of quartz, silicate glass or a stainless steel; and (3) an interlayer of platinum, plus a method for preparing a thermally stable multi-layered solar collector, in which the absorptive layer is undercoated with a thin film of platinum to obtain a stable conductor-dielectric tandem.

  17. Pseudogaps, Polarons, and the Mystery of High-Tc Superconductivity

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    Pseudogaps, Polarons, and the Mystery of High-Tc Superconductivity Print Working at the ALS, a multi-institutional collaboration led by researchers at ALS and Stanford University has identified a pseudogap phase with a nodal-antinodal dichotomy in ferromagnetic manganese oxide materials (manganites). Even though ferromagnetism and superconductivity do not exist together, the pseudogap state found in these manganites is remarkably similar to that found in high-temperature superconducting copper

  18. Pseudogaps, Polarons, and the Mystery of High-Tc Superconductivity

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    Pseudogaps, Polarons, and the Mystery of High-Tc Superconductivity Print Working at the ALS, a multi-institutional collaboration led by researchers at ALS and Stanford University has identified a pseudogap phase with a nodal-antinodal dichotomy in ferromagnetic manganese oxide materials (manganites). Even though ferromagnetism and superconductivity do not exist together, the pseudogap state found in these manganites is remarkably similar to that found in high-temperature superconducting copper

  19. Pseudogaps, Polarons, and the Mystery of High-Tc Superconductivity

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    Pseudogaps, Polarons, and the Mystery of High-Tc Superconductivity Pseudogaps, Polarons, and the Mystery of High-Tc Superconductivity Print Wednesday, 26 April 2006 00:00 Working at the ALS, a multi-institutional collaboration led by researchers at ALS and Stanford University has identified a pseudogap phase with a nodal-antinodal dichotomy in ferromagnetic manganese oxide materials (manganites). Even though ferromagnetism and superconductivity do not exist together, the pseudogap state found in

  20. Process for diffusing metallic coatings into ceramics to improve their voltage withstanding capabilities

    DOE Patents [OSTI]

    Miller, H. Craig (Clearwater, FL); Zuhr, Herbert F. (St. Petersburg, FL)

    1978-01-01

    The disclosure relates to a method for diffusing a coating of manganese powder and titanium powder into a ceramic to improve its voltage hold off withstanding capability. The powder coated ceramic is fired for from about 30 to about 90 minutes within about one atmosphere of wet hydrogen at a temperature within the range of from about 1450.degree. to about 1520.degree. C to cause the mixture to penetrate into the ceramic to a depth on the order of a millimeter.

  1. Method of producing imines

    DOE Patents [OSTI]

    Sithambaram, Shanthakumar (Storrs, CT); Son, Young-Chan (Storrs, CT); Suib, Steven L. (Storrs, CT)

    2008-04-08

    A method for forming an imine comprises reacting a first reactant comprising a hydroxyl functionality, a carbonyl functionality, or both a hydroxyl functionality and a carbonyl functionality with a second reactant having an amine functionality in the presence of ordered porous manganese-based octahedral molecular sieves and an oxygen containing gas at a temperature and for a time sufficient for the imine to be produced.

  2. PHEV Battery Cost Assessment | Department of Energy

    Office of Energy Efficiency and Renewable Energy (EERE) Indexed Site

    1 DOE Hydrogen and Fuel Cells Program, and Vehicle Technologies Program Annual Merit Review and Peer Evaluation PDF icon es111_gallagher_2011_o.pdf More Documents & Publications Promises and Challenges of Lithium- and Manganese-Rich Transition-Metal Layered-Oxide Cathodes Vehicle Technologies Office Merit Review 2014: Electrochemical Modeling of LMR-NMC Materials and Electrodes Validation of Electrode Materials and Cell Chemistries

  3. Zinc oxide varistors and/or resistors

    DOE Patents [OSTI]

    Arnold, Jr., Wesley D.; Bond, Walter D.; Lauf, Robert J.

    1993-01-01

    Varistors and/or resistors that includes doped zinc oxide gel microspheres. The doped zinc oxide gel microspheres preferably have from about 60 to about 95% by weight zinc oxide and from about 5 to about 40% by weight dopants based on the weight of the zinc oxide. The dopants are a plurality of dopants selected from silver salts, boron oxide, silicon oxide and hydrons oxides of aluminum, bismuth, cobalt, chromium, manganese, nickel, and antimony.

  4. Zinc oxide varistors and/or resistors

    DOE Patents [OSTI]

    Arnold, W.D. Jr.; Bond, W.D.; Lauf, R.J.

    1993-07-27

    Varistors and/or resistors are described that include doped zinc oxide gel microspheres. The doped zinc oxide gel microspheres preferably have from about 60 to about 95% by weight zinc oxide and from about 5 to about 40% by weight dopants based on the weight of the zinc oxide. The dopants are a plurality of dopants selected from silver salts, boron oxide, silicon oxide and hydrons oxides of aluminum, bismuth, cobalt, chromium, manganese, nickel, and antimony.

  5. AFV CoverSheet

    Office of Scientific and Technical Information (OSTI)

    193 (Accepted Manuscript) A Chandrasekhar Mass Progenitor for the Type Ia Supernova Remnant 3C 397 from The Enhanced Abundances of Nickel and Manganese Yamaguchi, Hiroya; Badenes, Carles; Foster, Adam R.; Bravo, Eduardo; Williams, Brian J.; Maeda, Keiichi; Nobukawa, Masayoshi; Eriksen, Kristoffer A.; Brickhouse, Nancy S.; Petre, Robert; Koyama, Katsuji Provided by the author(s) and the Los Alamos National Laboratory (2016-02-18). To be published in: ASTROPHYSICAL JOURNAL LETTERS ; Vol.801,

  6. Pseudogaps, Polarons, and the Mystery of High-Tc Superconductivity

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    Pseudogaps, Polarons, and the Mystery of High-Tc Superconductivity Print Working at the ALS, a multi-institutional collaboration led by researchers at ALS and Stanford University has identified a pseudogap phase with a nodal-antinodal dichotomy in ferromagnetic manganese oxide materials (manganites). Even though ferromagnetism and superconductivity do not exist together, the pseudogap state found in these manganites is remarkably similar to that found in high-temperature superconducting copper

  7. Electrode Materials for Rechargeable Lithium-Ion Batteries: A New Synthetic

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    Approach | Argonne National Laboratory Electrode Materials for Rechargeable Lithium-Ion Batteries: A New Synthetic Approach Technology available for licensing: New high-energy cathode materials for use in rechargeable lithium-ion cells and batteries synthesized by using a novel alternative approach Lowers battery pack cost. Layered cathode material contains low-cost manganese, which operates at high rate and high voltage and results in a high-energy-density battery with improved stability.

  8. News Item

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    Battery Mystery Solved: Atomic-Resolution Microscopy Answers Longstanding Questions About Lithium-Rich Cathode Material Using complementary microscopy and spectroscopy techniques, researchers at the Molecular Foundry say they have solved the structure of lithium- and manganese-rich transition metal oxides, a potentially game-changing battery material and the subject of intense debate in the decade since it was discovered. Researchers have been divided into three schools of thought on the

  9. Science Highlights

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    Highlights Science Highlights Science highlights feature research conducted by staff and users at the ALS. If a Power Point summary slide or a PDF handout of the highlight is available, you will find it linked beneath the highlight listing and on the highlight's page. You may also print a version of a highlight by clicking the print icon associated with each highlight. Manganese Reduction-Oxidation Drives Plant Debris Decomposition Print Monday, 22 February 2016 00:00 ALS research has shown that

  10. Superacid catalysis of light hydrocarbon conversion. Final report, August 26, 1993--August 26, 1996

    SciTech Connect (OSTI)

    Gates, B.C.

    1996-12-31

    Motivated by the goal of finding improved catalysts for low- temperature conversion of light alkanes into fuel components or precursors of fuel components, the researchers have investigated sulfated zirconia and promoted sulfated zirconia for conversion of butane, propane, and ethane. Catalyst performance data for sulfated zirconia promoted with iron and manganese show that it is the most active noncorrosive, nonhalide catalyst known for n-butane isomerization, and it is an excellent candidate catalyst for new low- temperature n-butane isomerization processes to make isobutane, which can be converted by established technology into methyl t-butyl ether (MTBE). Various transition metals have been found to work as promoters of sulfated zirconia for n-butane isomerization. The combination of iron and manganese is the best known combination of promoters yet discovered. The iron- and manganese-promoted sulfated zirconia is also a catalyst for conversion of propane and of ethane. Ethane is converted into ethylene and butanes in the presence of the iron- and manganese-promoted sulfated zirconia; propane is also converted into butane, among other products. However, the activities of the catalyst for these reactions are orders of magnitude less than the activity for n-butane conversion, and there is no evidence that the catalyst would be of practical value for conversion of alkanes lighter than butane. The product distribution data for ethane and propane conversion provide new insights into the nature of the catalyst and its acidity. These data suggest the involvement of Olah superacid chemistry, whereby the catalyst protonates the alkane itself, giving carbonium ions (as transition states). The mechanism of protonation of the alkane may also pertain to the conversion of butane, but there is good evidence that the butane conversion also proceeds via alkene intermediates by conventional mechanisms of carbenium ion formation and rearrangement.

  11. Electrochemical Characterization of Voltage Fade in LMR-NMC cells |

    Office of Energy Efficiency and Renewable Energy (EERE) Indexed Site

    Department of Energy Characterization of Voltage Fade in LMR-NMC cells Electrochemical Characterization of Voltage Fade in LMR-NMC cells 2013 DOE Hydrogen and Fuel Cells Program and Vehicle Technologies Program Annual Merit Review and Peer Evaluation Meeting PDF icon es188_abraham_2013_p.pdf More Documents & Publications Thermodynamic Investigations of Lithium- and Manganese-Rich Transition Metal Oxides Vehicle Technologies Office: 2014 Energy Storage R&D Annual Report Vehicle

  12. Model for the Fabrication of Tailored Materials for Lithium-Ion Batteries |

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    Argonne National Laboratory Model for the Fabrication of Tailored Materials for Lithium-Ion Batteries Technology available for licensing: Safe, stable and high-capacity cathodes for lithium-ion batteries using a unique materials gradient. A process technology that yields high-capacity batteries. Unique method creates nickel-rich particles on the inside for a high-capacity battery, and a manganese-rich exterior surface for increased safety and stability. PDF icon

  13. High energy cathode material

    DOE Patents [OSTI]

    Li, Bin; Caldwell, Marissa; Tong, Wei; Kaye, Steven; Bhat, Vinay

    2015-09-01

    A composition for use in a battery electrode comprising a compound including lithium, manganese, nickel, and oxygen. The composition is characterized by a powder X-ray diffraction pattern having peaks including 18.6.+-.0.2, 35.0.+-.0.2, 36.4.+-.0.2, 37.7.+-.0.2, 42.1.+-.0.2, and 44.5.+-.0.2 degrees 2.theta. as measured using Cu K.sub..alpha. radiation.

  14. Duct and cladding alloy

    DOE Patents [OSTI]

    Korenko, Michael K. (Rockville, MD)

    1983-01-01

    An austenitic alloy having good thermal stability and resistance to sodium corrosion at 700.degree. C. consists essentially of 35-45% nickel 7.5-14% chromium 0.8-3.2% molybdenum 0.3-1.0% silicon 0.2-1.0% manganese 0-0.1% zirconium 2.0-3.5% titanium 1.0-2.0% aluminum 0.02-0.1% carbon 0-0.01% boron and the balance iron.

  15. Advanced Light Source

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    Next >> Visitors Access to the ALS Gate Access guest-house Guest House lab-shuttles Lab Shuttles maps-and-directions Maps and Directions Parking Safety Experiment Safety safety-for-staff Safety for Staff In Case of Emergency Resources Acronyms Multimedia Employment staff-intranet Staff Intranet Site Map Contact Digg: ALSBerkeleyLab Facebook Page: 208064938929 Flickr: advancedlightsource Twitter: AdvLightSource YouTube: AdvancedLightSource Recent Science Highlights Manganese

  16. Progress Report for the grant "Hight-Resolution Mineralogical Charaterization and Biogeochemical Modeling of Uranium Reduction Pathways at the NABIR Field-Research Center"

    SciTech Connect (OSTI)

    Veblen, David R.

    2006-06-15

    We have successfully completed a proof-of-concept, one-year grant on a three-year proposal from the former NABIR program. Using a state-of-the-art 300-kV, atomic resolution, Field Emission Gun Transmission Electron Microscope (TEM), we have successfully identified three categories of mineral hosts for uranium in contaminated soils from the Oak Ridge FRC: (1) iron oxides: (2) mixed manganese-iron oxides; and (3) uranium phosphates.

  17. Studies on High Voltage Lithium Rich MNC Composite Cathodes | Department of

    Office of Energy Efficiency and Renewable Energy (EERE) Indexed Site

    Energy High Voltage Lithium Rich MNC Composite Cathodes Studies on High Voltage Lithium Rich MNC Composite Cathodes 2012 DOE Hydrogen and Fuel Cells Program and Vehicle Technologies Program Annual Merit Review and Peer Evaluation Meeting PDF icon es106_nanda_2012_p.pdf More Documents & Publications Studies on Lithium Manganese Rich MNC Composite Cathodes Vehicle Technologies Office Merit Review 2014: High Energy Lithium Batteries for PHEV Applications Vehicle Technologies Office Merit

  18. California: Geothermal Plant to Help Meet High Lithium Demand | Department

    Office of Energy Efficiency and Renewable Energy (EERE) Indexed Site

    of Energy Geothermal Plant to Help Meet High Lithium Demand California: Geothermal Plant to Help Meet High Lithium Demand May 21, 2013 - 5:54pm Addthis Through funding provided by the American Recovery and Reinvestment Act of 2009, EERE's Geothermal Technologies Office is working with California's Simbol Materials to develop technologies that extract battery materials like lithium, manganese, and zinc from geothermal brines. Simbol has the potential to power 300,000-600,000 electric vehicles

  19. Engineering of High Energy Cathode Materials | Department of Energy

    Office of Environmental Management (EM)

    Engineering of High Energy Cathode Materials Engineering of High Energy Cathode Materials 2012 DOE Hydrogen and Fuel Cells Program and Vehicle Technologies Program Annual Merit Review and Peer Evaluation Meeting PDF icon es015_amine_2012_o.pdf More Documents & Publications Studies on Lithium Manganese Rich MNC Composite Cathodes Vehicle Technologies Office Merit Review 2014: Synthetic Solutions for Correcting Voltage Fade in LMR-NMC Cathodes Examining Hysteresis in Lithium- and

  20. EERE Success Story-California: Geothermal Plant to Help Meet High Lithium

    Office of Environmental Management (EM)

    Demand | Department of Energy Geothermal Plant to Help Meet High Lithium Demand EERE Success Story-California: Geothermal Plant to Help Meet High Lithium Demand May 21, 2013 - 5:54pm Addthis Through funding provided by the American Recovery and Reinvestment Act of 2009, EERE's Geothermal Technologies Office is working with California's Simbol Materials to develop technologies that extract battery materials like lithium, manganese, and zinc from geothermal brines. Simbol has the potential to

  1. Archeological Applications of XAFS: Prehistorical Paintings And Medieval Glasses

    SciTech Connect (OSTI)

    Farges, F.; Chalmin, E.; Vignaud, C.; Pallot-Frossard, I.; Susini, J.; Bargar, J.; Brown, G.E., Jr.; Menu, M.; /SLAC, SSRL

    2006-10-27

    High-resolution manganese and iron K-edges XANES spectra were collected on several samples of archeological interest: prehistorical paintings and medieval glasses. XANES spectra were collected at the ID21 facility (ESRF, Grenoble, France) using a micro-beam device and at the 11-2 beamline (SSRL, Stanford, USA) using a submillimetric beam. The medieval glasses studied are from gothic glass windows from Normandy (XIVth century). The aim of this study is to help understand the chemical durability of these materials, exposed to weathering since the XIVth century. They are used as analogues of weathered glasses used to dump metallic wastes. These glasses show surficial enrichment in manganese, due to its oxidation from II (glass) to III/IV (surface), which precipitates as amorphous oxy-hydroxides. Similarly, iron is oxidized on the surface and forms ferrihydrite-type aggregates. The prehistorical paintings are from Lascaux and Ekain (Basque country). We choose in that study the black ones, rich in manganese to search for potential evidences of some 'savoir-faire' that the Paleolithic men could have used to realize their paint in rock art, as shown earlier for Fe-bearing pigments. A large number of highly valuable samples, micrometric scaled, were extracted from these frescoes and show large variation in the mineralogical nature of the black pigments used, from an amorphous psilomelane-type to a well-crystallized pyrolusite. Correlation with the crystals morphology helps understanding the know-how of these early artists.

  2. Conducting Polymer-Inorganic Nanoparticle (CPIN) Nanoarrays for Battery Applications - Final Technical Report

    SciTech Connect (OSTI)

    Buttry, Daniel A.

    2006-06-27

    Our objective was to develop new, self-assembling conducting polymer-inorganic nanoparticle nanoarrays (CPIN nanoarrays) comprised of nanoparticles of inorganic Li+ insertion compounds that are wired together with oligomeric chains of derivatives of polythiophene. Using these nanoarrays, we developed an understanding of the relationship between structure and electrochemical function for nanostructured materials. Such nanoarrays are expected to have extremely high specific energy and specific power for battery applications due to the unique structural characteristics that derive from the nanoarray. Under this award we developed several synthetic approaches to producing manganese dioxide nanoparticles (NPs). We also developed a layer-by-layer approach for immobilizing these NPs so they could be examined electrochemically. We also developed new synthetic procedures for encapsulating manganese dioxide nanoparticles within spheres of polyethylenedioxythiophene (PEDOT), a conducting polymer with excellent charge-discharge stability. These have a unique manganese dioxide core-PEDOT shell structure. We examined the structures of these systems using transmission electron microscopy, various scanning probe microscopies, and electrochemical measurements. Various technical reports have been submitted that describe the work, including conference presentations, publications and patent applications. These reports are available through http://www.osti.gov, the DOE Energy Link System.

  3. Strategies to Suppress Cation Vacancies in Metal Oxide Alloys: Consequences for Solar Energy Conversion

    SciTech Connect (OSTI)

    Toroker, Maytal; Carter, Emily A.

    2015-09-01

    First-row transition metal oxides (TMOs) are promising alternative materials for inexpensive and efficient solar energy conversion. However, their conversion efficiency can be deleteriously affected by material imperfections, such as atomic vacancies. In this work, we provide examples showing that in some iron-containing TMOs, iron cation vacancy formation can be suppressed via alloying. We calculate within density functional theory+U theory the iron vacancy formation energy in binary rock-salt oxide alloys that contain iron, manganese, nickel, zinc, and/or magnesium. We demonstrate that formation of iron vacancies is less favorable if we choose to alloy iron(II) oxide with metals that cannot readily accept vacancy-generated holes, e.g., magnesium, manganese, nickel, or zinc. Since there are less available sites for holes and the holes are forced to reside on iron cations, the driving force for iron vacancy formation decreases. These results are consistent with an experiment observing a sharp drop in cation vacancy concentration upon alloying iron(II) oxide with manganese.

  4. Process for strontium-82 separation

    DOE Patents [OSTI]

    Heaton, Richard C.; Jamriska, Sr., David J.; Taylor, Wayne A.

    1992-01-01

    A process for selective separation of strontium-82 and strontium-85 from proton irradiated molybdenum targets comprises dissolving the molybdenum target in a hydrogen peroxide solution to form a first solution containing ions selected from a group consisting of molybdenum, niobium, technetium, selenium, vanadium, arsenic, germanium, zirconium, rubidium, zinc, beryllium, cobalt, iron, manganese, chromium, strontium, and yttrium; passing the solution through a first cationic resin whereby ions selected from a group consisting of zinc, beryllium, cobalt, iron, manganese, chromium, strontium, yttrium a portion of zirconium and a portion of rubidium are selectively absorbed by the first resin; contacting the first resin with an acid solution to strip and remove the absorbed ions from the first cationic exchange resin to form a second solution; evaporating the second solution for a time sufficient to remove substantially all of the acid and water from the solution whereby a residue remains; dissolving the residue in a dilute acid to form a third solution; passing the third solution through a second cationic resin whereby the ions are absorbed by the second resin; contacting the second resin with a dilute sulfuric acid solution whereby the absorbed ions selected from the group consisting of rubidium, zinc, beryllium, cobalt, iron, manganese, chromium and zirconium are selectively removed from the second resin; and contacting the second resin with a dilute acid solution whereby the absorbed strontium ions are selectively removed.

  5. Process for strontium-82 separation

    DOE Patents [OSTI]

    Heaton, R.C.; Jamriska, D.J. Sr.; Taylor, W.A.

    1992-12-01

    A process for selective separation of strontium-82 and strontium-85 from proton irradiated molybdenum targets comprises dissolving the molybdenum target in a hydrogen peroxide solution to form a first solution containing ions selected from a group consisting of molybdenum, niobium, technetium, selenium, vanadium, arsenic, germanium, zirconium, rubidium, zinc, beryllium, cobalt, iron, manganese, chromium, strontium, and yttrium; passing the solution through a first cationic resin whereby ions selected from a group consisting of zinc, beryllium, cobalt, iron, manganese, chromium, strontium, yttrium a portion of zirconium and a portion of rubidium are selectively absorbed by the first resin; contacting the first resin with an acid solution to strip and remove the absorbed ions from the first cationic exchange resin to form a second solution; evaporating the second solution for a time sufficient to remove substantially all of the acid and water from the solution whereby a residue remains; dissolving the residue in a dilute acid to form a third solution; passing the third solution through a second cationic resin whereby the ions are absorbed by the second resin; contacting the second resin with a dilute sulfuric acid solution whereby the absorbed ions selected from the group consisting of rubidium, zinc, beryllium, cobalt, iron, manganese, chromium and zirconium are selectively removed from the second resin; and contacting the second resin with a dilute acid solution whereby the absorbed strontium ions are selectively removed. 1 fig.

  6. Heat and corrosion resistant cast CF8C stainless steel with improved high temperature strength and ductility

    DOE Patents [OSTI]

    Maziasz, Philip J. (Oak Ridge, TN); McGreevy, Tim (Washington, IL); Pollard, Michael James (Peoria, IL); Siebenaler, Chad W. (Dunlap, IL); Swindeman, Robert W. (Oak Ridge, TN)

    2010-08-17

    A CF8C type stainless steel alloy and articles formed therefrom containing about 18.0 weight percent to about 22.0 weight percent chromium and 11.0 weight percent to about 14.0 weight percent nickel; from about 0.05 weight percent to about 0.15 weight percent carbon; from about 2.0 weight percent to about 10.0 weight percent manganese; and from about 0.3 weight percent to about 1.5 weight percent niobium. The present alloys further include less than 0.15 weight percent sulfur which provides high temperature strength both in the matrix and at the grain boundaries without reducing ductility due to cracking along boundaries with continuous or nearly-continuous carbides. The disclosed alloys also have increased nitrogen solubility thereby enhancing strength at all temperatures because nitride precipitates or nitrogen porosity during casting are not observed. The solubility of nitrogen is dramatically enhanced by the presence of manganese, which also retains or improves the solubility of carbon thereby providing additional solid solution strengthening due to the presence of manganese and nitrogen, and combined carbon.

  7. Heat and corrosion resistant cast CF8C stainless steel with improved high temperature strength and ductility

    DOE Patents [OSTI]

    Maziasz, Philip J.; McGreevy, Tim; Pollard, Michael James; Siebenaler, Chad W.; Swindeman, Robert W.

    2006-12-26

    A CF8C type stainless steel alloy and articles formed therefrom containing about 18.0 weight percent to about 22.0 weight percent chromium and 11.0 weight percent to about 14.0 weight percent nickel; from about 0.05 weight percent to about 0.15 weight percent carbon; from about 2.0 weight percent to about 10.0 weight percent manganese; and from about 0.3 weight percent to about 1.5 weight percent niobium. The present alloys further include less than 0.15 weight percent sulfur which provides high temperature strength both in the matrix and at the grain boundaries without reducing ductility due to cracking along boundaries with continuous or nearly-continuous carbides. The disclosed alloys also have increased nitrogen solubility thereby enhancing strength at all temperatures because nitride precipitates or nitrogen porosity during casting are not observed. The solubility of nitrogen is dramatically enhanced by the presence of manganese, which also retains or improves the solubility of carbon thereby providing additional solid solution strengthening due to the presence of manganese and nitrogen, and combined carbon.

  8. Heat and corrosion resistant cast CN-12 type stainless steel with improved high temperature strength and ductility

    DOE Patents [OSTI]

    Mazias, Philip J. (Oak Ridge, TN); McGreevy, Tim (Morton, IL); Pollard,Michael James (East Peoria, IL); Siebenaler, Chad W. (Peoria, IL); Swindeman, Robert W. (Oak Ridge, TN)

    2007-08-14

    A cast stainless steel alloy and articles formed therefrom containing about 0.5 wt. % to about 10 wt. % manganese, 0.02 wt. % to 0.50 wt. % N, and less than 0.15 wt. % sulfur provides high temperature strength both in the matrix and at the grain boundaries without reducing ductility due to cracking along boundaries with continuous or nearly-continuous carbides. Alloys of the present invention also have increased nitrogen solubility thereby enhancing strength at all temperatures because nitride precipitates or nitrogen porosity during casting are not observed. The solubility of nitrogen is dramatically enhanced by the presence of manganese, which also retains or improves the solubility of carbon thereby providing additional solid solution strengthening due to the presence of manganese and nitrogen, and combined carbon. Such solution strengthening enhances the high temperature precipitation-strengthening benefits of fine dispersions of NbC. Such solid solution effects also enhance the stability of the austenite matrix from resistance to excess sigma phase or chrome carbide formation at higher service temperatures. The presence of sulfides is substantially eliminated.

  9. Center for Nanoscale Materials | Argonne National Laboratory

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    A Lithium-Air Battery Based on Lithium Superoxide More Borophene: Atomically Thin Metallic Boron More Ratiometric Sensing of Toxins using Quantum Dots More One Direction: nanocircuitry with semiconducting graphene nanoribbons More Keys to Access: Argonne-INCREASE partnership opens doors to collaboration More Video Highlight A Look Inside Argonne's Center for Nanoscale Materials BROCHURES & NEWSLETTERS CNM Overview Brochure CNM Fact Sheet Key Research Areas Nanofabrication & Devices

  10. Larry Curtiss | Argonne National Laboratory

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    Larry Curtiss Argonne Distinguished Fellow Ph.D., Carnegie-Mellon University Research in the area of computational chemistry including development of new quantum chemical methods and applications to problems in materials science and chemistry Specific research areas include nanocatalysis, nanocrystalline materials, computational thermochemistry, electron transfer processes; and nanoporous materials News Stable "superoxide" opens the door to a new class of batteries Copper clusters

  11. Technologies for Extracting Valuable Metals and Compounds from Geothermal Fluids

    SciTech Connect (OSTI)

    Harrison, Stephen

    2014-04-30

    Executive Summary Simbol Materials studied various methods of extracting valuable minerals from geothermal brines in the Imperial Valley of California, focusing on the extraction of lithium, manganese, zinc and potassium. New methods were explored for managing the potential impact of silica fouling on mineral extraction equipment, and for converting silica management by-products into commercial products.` Studies at the laboratory and bench scale focused on manganese, zinc and potassium extraction and the conversion of silica management by-products into valuable commercial products. The processes for extracting lithium and producing lithium carbonate and lithium hydroxide products were developed at the laboratory scale and scaled up to pilot-scale. Several sorbents designed to extract lithium as lithium chloride from geothermal brine were developed at the laboratory scale and subsequently scaled-up for testing in the lithium extraction pilot plant. Lithium The results of the lithium studies generated the confidence for Simbol to scale its process to commercial operation. The key steps of the process were demonstrated during its development at pilot scale: 1. Silica management. 2. Lithium extraction. 3. Purification. 4. Concentration. 5. Conversion into lithium hydroxide and lithium carbonate products. Results show that greater than 95% of the lithium can be extracted from geothermal brine as lithium chloride, and that the chemical yield in converting lithium chloride to lithium hydroxide and lithium carbonate products is greater than 90%. The product purity produced from the process is consistent with battery grade lithium carbonate and lithium hydroxide. Manganese and zinc Processes for the extraction of zinc and manganese from geothermal brine were developed. It was shown that they could be converted into zinc metal and electrolytic manganese dioxide after purification. These processes were evaluated for their economic potential, and at the present time Simbol Materials is evaluating other products with greater commercial value. Potassium Silicotitanates, zeolites and other sorbents were evaluated as potential reagents for the extraction of potassium from geothermal brines and production of potassium chloride (potash). It was found that zeolites were effective at removing potassium but the capacity of the zeolites and the form that the potassium is in does not have economic potential. Iron-silica by-product The conversion of iron-silica by-product produced during silica management operations into more valuable materials was studied at the laboratory scale. Results indicate that it is technically feasible to convert the iron-silica by-product into ferric chloride and ferric sulfate solutions which are precursors to a ferric phosphate product. However, additional work to purify the solutions is required to determine the commercial viability of this process. Conclusion Simbol Materials is in the process of designing its first commercial plant based on the technology developed to the pilot scale during this project. The investment in the commercial plant is hundreds of millions of dollars, and construction of the commercial plant will generate hundreds of jobs. Plant construction will be completed in 2016 and the first lithium products will be shipped in 2017. The plant will have a lithium carbonate equivalent production capacity of 15,000 tonnes per year. The gross revenues from the project are expected to be approximately $ 80 to 100 million annually. During this development program Simbol grew from a company of about 10 people to over 60 people today. Simbol is expected to employ more than 100 people once the plant is constructed. Simbol Materials business is scalable in the Imperial Valley region because there are eleven geothermal power plants already in operation, which allows Simbol to expand its business from one plant to multiple plants. Additionally, the scope of the resource is vast in terms of potential products such as lithium, manganese and zinc and potentially potassium.

  12. The effect of sulfide type on the fracture behavior of HY180 steel

    SciTech Connect (OSTI)

    Maloney, James L.; Garrison, Warren M. . E-mail: wmg@andrew.cmu.edu

    2005-01-10

    In this paper are discussed the effects of sulfide type on the fracture toughness of HY180 steel. Manganese was added to one heat and the sulfides in this heat were MnS. Lanthanum additions but no manganese additions were made to the second heat and the sulfur was gettered in this heat as particles of La{sub 2}O{sub 2}S. Neither lanthanum nor manganese additions was made to the other two heats. These two heats were modified by small titanium additions. The sulfur in these two heats was gettered as particles of Ti{sub 2}CS. After the usual heat treatment for HY180 steel the fracture toughness of the heat in which the sulfur was gettered as MnS was 256MPam. The fracture toughness of the heat in which the sulfur was gettered as La{sub 2}O{sub 2}S was 344MPam. The fracture toughness of this heat was greater than the fracture toughness of the heat in which the sulfur is gettered as MnS because the particles of La{sub 2}O{sub 2}S are larger and more widely spaced than the particles of MnS. The fracture toughness of the two titanium modified heats were 478MPam and over 550MPam. Void generation studies indicate that void generation is more difficult at particles of Ti{sub 2}CS than at particles of MnS or La{sub 2}O{sub 2}S. The improved fracture toughness of the heats in which the sulfur is gettered as Ti{sub 2}CS is attributed to the particles of Ti{sub 2}CS having greater resistance to void generation than particles of MnS or La{sub 2}O{sub 2}S.

  13. High strength alloys

    DOE Patents [OSTI]

    Maziasz, Phillip James [Oak Ridge, TN; Shingledecker, John Paul [Knoxville, TN; Santella, Michael Leonard [Knoxville, TN; Schneibel, Joachim Hugo [Knoxville, TN; Sikka, Vinod Kumar [Oak Ridge, TN; Vinegar, Harold J [Bellaire, TX; John, Randy Carl [Houston, TX; Kim, Dong Sub [Sugar Land, TX

    2010-08-31

    High strength metal alloys are described herein. At least one composition of a metal alloy includes chromium, nickel, copper, manganese, silicon, niobium, tungsten and iron. System, methods, and heaters that include the high strength metal alloys are described herein. At least one heater system may include a canister at least partially made from material containing at least one of the metal alloys. At least one system for heating a subterranean formation may include a tubular that is at least partially made from a material containing at least one of the metal alloys.

  14. Effect of Heat-Treatment on the Phases of Ni-Mn-Ga Magnetic Shape Memory Alloys

    SciTech Connect (OSTI)

    Huq, Ashfia; Ari-Gur, Pnina; Kimmel, Giora; Richardson, James W; Sharma, Kapil

    2009-01-01

    The Heusler alloys Ni50Mn25+xGa25-x display magnetic shape memory effect (MSM) with very fast and large reversible strain under magnetic fields. This large strain and the speed of reaction make MSM alloys attractive as smart materials. Our crystallographic investigation of these alloys, focused on non-stoichiometric composition with excess of manganese. Using neutron diffraction, we revealed the necessary processing parameters to achieve and preserve the homogeneous metastable one-phase martensitic structure that is needed for an MSM effect at room temperature.

  15. Small plasma focus as neutron pulsed source for nuclides identification

    SciTech Connect (OSTI)

    Milanese, M.; Moroso, R.; Barbaglia, M.; Universidad del Centro de la Provincia de Buenos Aires , Pinto 399, Tandil 7000, Buenos Aires ; Niedbalski, J.; Mayer, R.; Castillo, F.

    2013-10-15

    In this paper, we present preliminary results on the feasibility of employing a low energy (2 kJ, 31 kV) plasma focus device as a portable source of pulsed neutron beams (2.45 MeV) generated by nuclear fusion reactions D-D, for the in situ analysis of substances by nuclear activation. This source has the relevant advantage of being pulsed at requirement, transportable, not permanently radioactive, without radioactive waste, cheap, among others. We prove the feasibility of using this source showing several spectra of the characteristic emission line for manganese, gold, lead, and silver.

  16. Process for the conversion of lower alcohols to higher branched oxygenates

    DOE Patents [OSTI]

    Barger, P.T.

    1996-09-24

    A process is provided for the production of branched C{sub x} oxygenates from lower alcohols such as methanol, ethanol, propanol and mixtures thereof. The process comprises contacting the lower alcohols with a solid catalyst comprising a mixed metal oxide support having components selected from the group consisting of oxides of zinc, magnesium, zirconia, titanium, manganese, chromium, and lanthanides, and an activation metal selected from the group consisting of Group VIII metal, Group IB metals, and mixtures thereof. The advantage of the process is improved yields and selectivity to isobutanol which can subsequently be employed in the production of high octane motor gasoline.

  17. Long life lithium batteries with stabilized electrodes

    DOE Patents [OSTI]

    Amine, Khalil (Downers Grove, IL); Liu, Jun (Naperville, IL); Vissers, Donald R. (Naperville, IL); Lu, Wenquan (Darien, IL)

    2009-03-24

    The present invention relates to non-aqueous electrolytes having electrode stabilizing additives, stabilized electrodes, and electrochemical devices containing the same. Thus the present invention provides electrolytes containing an alkali metal salt, a polar aprotic solvent, and an electrode stabilizing additive. In some embodiments the additives include a substituted or unsubstituted cyclic or spirocyclic hydrocarbon containing at least one oxygen atom and at least one alkenyl or alkynyl group. When used in electrochemical devices with, e.g., lithium manganese oxide spinel electrodes or olivine or carbon-coated olivine electrodes, the new electrolytes provide batteries with improved calendar and cycle life.

  18. Oxidation resistant alloys, method for producing oxidation resistant alloys

    DOE Patents [OSTI]

    Dunning, John S. (Corvallis, OR); Alman, David E. (Salem, OR)

    2002-11-05

    A method for producing oxidation-resistant austenitic alloys for use at temperatures below 800.degree. C. comprising of: providing an alloy comprising, by weight %: 14-18% chromium, 15-18% nickel, 1-3% manganese, 1-2% molybdenum, 2-4% silicon, 0% aluminum and the balance being iron; heating the alloy to 800.degree. C. for between 175-250 hours prior to use in order to form a continuous silicon oxide film and another oxide film. The method provides a means of producing stainless steels with superior oxidation resistance at temperatures above 700.degree. C. at a low cost

  19. Process for the conversion of lower alcohols to higher branched oxygenates

    DOE Patents [OSTI]

    Barger, Paul T. (Arlington Heights, IL)

    1996-01-01

    A process is provided for the production of branched C.sub.4+ oxygenates from lower alcohols such as methanol, ethanol, propanol and mixtures thereof. The process comprises contacting the lower alcohols with a solid catalyst comprising a mixed metal oxide support having components selected from the group consisting of oxides of zinc, magnesium, zirconia, titanium, manganese, chromium, and lanthanides, and an activation metal selected from the group consisting of Group VIII metal, Group IB metals, and mixtures thereof. The advantage of the process is improved yields and selectivity to isobutanol which can subsequently be employed in the production of high octane motor gasoline.

  20. Method and system for ethanol production

    DOE Patents [OSTI]

    Feder, H.M.; Chen, M.J.

    1980-05-21

    A transition metal carbonyl and a tertiary amine are employed as a homogeneous catalytic system in methanol or a less volatile solvent to react methanol with carbon monoxide and hydrogen gas producing ethanol and carbon dioxide. The gas contains a high carbon monoxide to hydrogen ratio as is present in a typical gasifier product. The reaction has potential for anhydrous ethanol production as carbon dioxide rather than water is produced. The only other significant by-product is methane. Selected transition metal carbonyls include those of iron, ruthenium and possibly manganese and osmium. Selected amines include trimethylamine, N-Methylpyrrolidine, 24-diazabicyclooctane, dimethyneopentylamine and 2-pryidinol.

  1. Method and system for ethanol production

    DOE Patents [OSTI]

    Feder, H.M.; Chen, M.J.

    1981-09-24

    A transition metal carbonyl and a tertiary amine are employed as a homogeneous catalytic system in methanol or a less volatile solvent to react methanol with carbon monoxide and hydrogen gas producing ethanol and carbon dioxide. The gas contains a high carbon monoxide to hydrogen ratio as is present in a typical gasifier product. The reaction has potential for anhydrous ethanol production as carbon dioxide rather than water is produced. Selected transition metal carbonyls include those of iron, rhodium, ruthenium, manganese in combination with iron and possibly osmium. Selected amines include trimethylamine, N-Methylpyrrolidine, 2,4-diazabicyclooctane, dimethylneopentylamine, N-methylpiperidine and derivatives of N-methylpiperidine.

  2. Method and system for ethanol production

    DOE Patents [OSTI]

    Feder, Harold M. (Darien, IL); Chen, Michael J. (Darien, IL)

    1983-01-01

    A transition metal carbonyl and a tertiary amine are employed as a homogeneous catalytic system in methanol or a less volatile solvent to react methanol with carbon monoxide and hydrogen gas producing ethanol and carbon dioxide. The gas contains a high carbon monoxide to hydrogen ratio as is present in a typical gasifier product. The reaction has potential for anhydrous ethanol production as carbon dioxide rather than water is produced. Selected transition metal carbonyls include those of iron, rhodium ruthenium, manganese in combination with iron and possibly osmium. Selected amines include trimethylamine, N-Methylpyrrolidine, 2,4-diazabicyclooctane, dimethylneopentylamine, N-methylpiperidine and derivatives of N-methylpiperidine.

  3. Oxidation resistant alloys, method for producing oxidation resistant alloys

    DOE Patents [OSTI]

    Dunning, John S.; Alman, David E.

    2002-11-05

    A method for producing oxidation-resistant austenitic alloys for use at temperatures below 800 C. comprising of: providing an alloy comprising, by weight %: 14-18% chromium, 15-18% nickel, 1-3% manganese, 1-2% molybdenum, 2-4% silicon, 0% aluminum and the balance being iron; heating the alloy to 800 C. for between 175-250 hours prior to use in order to form a continuous silicon oxide film and another oxide film. The method provides a means of producing stainless steels with superior oxidation resistance at temperatures above 700 C. at a low cost

  4. Porphyrins and their synthesis from dipyrromethanes and aldehydes

    DOE Patents [OSTI]

    Wijesekera, T.; Lyons, J.E.; Ellis, P.E. Jr.

    1998-06-02

    The invention comprises new compositions of matter, which are iron, manganese, cobalt or ruthenium complexes of porphyrins having hydrogen, haloalkyl or haloaryl groups in meso positions, two of the opposed meso atoms or groups being hydrogen or haloaryl, and two of the opposed meso atoms or groups being hydrogen or haloalkyl, but not all four of the meso atoms or groups being hydrogen. The invention also comprises new compositions of matter in which all four of the meso positions are substituted with haloalkyl groups and the beta positions are substituted with halogen atoms. A new method of synthesizing porphyrinogens is also provided.

  5. Porphyrins and their synthesis from dipyrromethanes and aldehydes

    DOE Patents [OSTI]

    Wijesekera, Tilak; Lyons, James E.; Ellis, Jr., Paul E.

    1998-01-01

    The invention comprises new compositions of matter, which are iron, manganese, cobalt or ruthenium complexes of porphyrins having hydrogen, haloalkyl or haloaryl groups in meso positions, two of the opposed meso atoms or groups being hydrogen or haloaryl, and two of the opposed meso atoms or groups being hydrogen or haloalkyl, but not all four of the meso atoms or groups being hydrogen. The invention also comprises new compositions of matter in which all four of the meso positions are substituted with haloalkyl groups and the beta positions are substituted with halogen atoms. A new method of synthesizing porphyrinogens is also provided.

  6. Compositions of corrosion-resistant Fe-based amorphous metals suitable for producing thermal spray coatings

    DOE Patents [OSTI]

    Farmer, Joseph C; Wong, Frank M.G.; Haslam, Jeffery J; Ji, Xiaoyan; Day, Sumner D; Blue, Craig A; Rivard, John D.K.; Aprigliano, Louis F; Kohler, Leslie K; Bayles, Robert; Lemieux, Edward J; Yang, Nancy; Perepezko, John H; Kaufman, Larry; Heuer, Arthur; Lavernia, Enrique J

    2013-09-03

    A method of coating a surface comprising providing a source of amorphous metal that contains manganese (1 to 3 atomic %), yttrium (0.1 to 10 atomic %), and silicon (0.3 to 3.1 atomic %) in the range of composition given in parentheses; and that contains the following elements in the specified range of composition given in parentheses: chromium (15 to 20 atomic %), molybdenum (2 to 15 atomic %), tungsten (1 to 3 atomic %), boron (5 to 16 atomic %), carbon (3 to 16 atomic %), and the balance iron; and applying said amorphous metal to the surface by a spray.

  7. Compositions of corrosion-resistant Fe-based amorphous metals suitable for producing thermal spray coatings

    DOE Patents [OSTI]

    Farmer, Joseph C.; Wong, Frank M. G.; Haslam, Jeffery J.; Ji, Xiaoyan; Day, Sumner D.; Blue, Craig A.; Rivard, John D. K.; Aprigliano, Louis F.; Kohler, Leslie K.; Bayles, Robert; Lemieux, Edward J.; Yang, Nancy; Perepezko, John H.; Kaufman, Larry; Heuer, Arthur; Lavernia, Enrique J.

    2013-07-09

    A method of coating a surface comprising providing a source of amorphous metal that contains manganese (1 to 3 atomic %), yttrium (0.1 to 10 atomic %), and silicon (0.3 to 3.1 atomic %) in the range of composition given in parentheses; and that contains the following elements in the specified range of composition given in parentheses: chromium (15 to 20 atomic %), molybdenum (2 to 15 atomic %), tungsten (1 to 3 atomic %), boron (5 to 16 atomic %), carbon (3 to 16 atomic %), and the balance iron; and applying said amorphous metal to the surface by a spray.

  8. Post-Growth Annealing of Bridgman-grown CdZnTe and CdMnTe Crystals for

    Office of Scientific and Technical Information (OSTI)

    Room-temperature Nuclear Radiation Detectors (Journal Article) | SciTech Connect Post-Growth Annealing of Bridgman-grown CdZnTe and CdMnTe Crystals for Room-temperature Nuclear Radiation Detectors Citation Details In-Document Search Title: Post-Growth Annealing of Bridgman-grown CdZnTe and CdMnTe Crystals for Room-temperature Nuclear Radiation Detectors Bridgman-grown cadmium zinc telluride (CdZnTe or CZT) and cadmium manganese telluride (CdMnTe or CMT) crystals often have Te inclusions that

  9. Iron-nickel-chromium alloy having improved swelling resistance and low neutron absorbence

    DOE Patents [OSTI]

    Korenko, Michael K. (Richland, WA)

    1986-01-01

    An iron-nickel-chromium age-hardenable alloy suitable for use in fast breeder reactor ducts and cladding which utilizes the gamma-double prime strengthening phase and characterized in having a delta or eta phase distributed at or near grain boundaries. The alloy consists essentially of about 33-39.5% nickel, 7.5-16% chromium, 1.5-4% niobium, 0.1-0.7% silicon, 0.01-0.2% zirconium, 1-3% titanium, 0.2-0.6% aluminum, and the remainder essentially all iron. Up to 0.4% manganese and up to 0.010% magnesium can be added to inhibit trace element effects.

  10. Primary explosives

    DOE Patents [OSTI]

    Hiskey, Michael A. (Los Alamos, NM); Huynh, My Hang V. (Los Alamos, NM)

    2011-01-25

    The present invention provides a compound of the formula (Cat).sup.+.sub.z[M.sup.++(5-nitro-1H-tetrazolato-N2).sup.-.sub.x(H.sub.2- O).sub.y] where x is 3 or 4, y is 2 or 3, x+y is 6, z is 1 or 2, and M.sup.++ is selected from the group consisting of iron, cobalt, nickel, copper, zinc, chromium, and manganese, and (Cat).sup.+ is selected from the group consisting of ammonium, sodium, potassium, rubidium and cesium. A method of preparing the compound of that formula is also disclosed.

  11. Microstructure and mechanical behavior of neutron irradiated ultrafine grained ferritic steel

    SciTech Connect (OSTI)

    Ahmad Alsabbagh; Apu Sarkar; Brandon Miller; Jatuporn Burns; Leah Squires; Douglas Porter; James I. Cole; K. L. Murty

    2014-10-01

    Neutron irradiation effects on ultra-fine grain (UFG) low carbon steel prepared by equal channel angular pressing (ECAP) has been examined. Counterpart samples with conventional grain (CG) sizes have been irradiated alongside with the UFG ones for comparison. Samples were irradiated in the Advanced Test Reactor (ATR) at Idaho National Laboratory (INL) to 1.24 dpa. Atom probe tomography revealed manganese, silicon-enriched clusters in both ECAP and CG steel after neutron irradiation. X-ray quantitative analysis showed that dislocation density in CG increased after irradiation. However, no significant change was observed in UFG steel revealing better radiation tolerance.

  12. Zinc phosphate conversion coatings

    DOE Patents [OSTI]

    Sugama, Toshifumi

    1997-01-01

    Zinc phosphate conversion coatings for producing metals which exhibit enhanced corrosion prevention characteristics are prepared by the addition of a transition-metal-compound promoter comprising a manganese, iron, cobalt, nickel, or copper compound and an electrolyte such as polyacrylic acid, polymethacrylic acid, polyitaconic acid and poly-L-glutamic acid to a phosphating solution. These coatings are further improved by the incorporation of Fe ions. Thermal treatment of zinc phosphate coatings to generate .alpha.-phase anhydrous zinc phosphate improves the corrosion prevention qualities of the resulting coated metal.

  13. Zinc phosphate conversion coatings

    DOE Patents [OSTI]

    Sugama, T.

    1997-02-18

    Zinc phosphate conversion coatings for producing metals which exhibit enhanced corrosion prevention characteristics are prepared by the addition of a transition-metal-compound promoter comprising a manganese, iron, cobalt, nickel, or copper compound and an electrolyte such as polyacrylic acid, polymethacrylic acid, polyitaconic acid and poly-L-glutamic acid to a phosphating solution. These coatings are further improved by the incorporation of Fe ions. Thermal treatment of zinc phosphate coatings to generate {alpha}-phase anhydrous zinc phosphate improves the corrosion prevention qualities of the resulting coated metal. 33 figs.

  14. PowerPoint Presentation

    Office of Environmental Management (EM)

    Effect of Various Impurities on the Hydrogen Absorption on SAES ST198 Gregg A. Morgan David W. James 36 th Tritium Focus Group - Fall 2015 Los Alamos, NM November, 3-5, 2015 SRNL-STI-2015-00592 Overview 2 * Tritium Purification System * ST909 * ST198 * Results of ST198 Impurity Testing * Conclusions/Summary TPS Overview 3 ST909 Characteristics 4 * Zr(Mn 0.5 Fe 0.5 ) 2 or Zr-Mn-Fe (40.5% Zr, 24.5% Mn, 25.0% Fe, 10% Al) * Manganese and iron - catalytic active sites for decomposition - CH 4 - NH 3

  15. High strength alloys

    DOE Patents [OSTI]

    Maziasz, Phillip James; Shingledecker, John Paul; Santella, Michael Leonard; Schneibel, Joachim Hugo; Sikka, Vinod Kumar; Vinegar, Harold J.; John, Randy Carl; Kim, Dong Sub

    2012-06-05

    High strength metal alloys are described herein. At least one composition of a metal alloy includes chromium, nickel, copper, manganese, silicon, niobium, tungsten and iron. System, methods, and heaters that include the high strength metal alloys are described herein. At least one heater system may include a canister at least partially made from material containing at least one of the metal alloys. At least one system for heating a subterranean formation may include a tublar that is at least partially made from a material containing at least one of the metal alloys.

  16. Design and Demonstration of a Quasi-monoenergetic Neutron Source

    SciTech Connect (OSTI)

    Joshi, T.; Sangiorgio, Samuele; Mozin, Vladimir V.; Norman, E. B.; Sorensen, Peter F.; Foxe, Michael P.; Bench, G.; Bernstein, A.

    2014-03-05

    The design of a neutron source capable of producing 24 and 70 keV neutron beams with narrow energy spread is presented. The source exploits near-threshold kinematics of the 7Li(p,n)7Be reaction while taking advantage of the interference `notches' found in the scattering cross-sections of iron. The design was implemented and characterized at the Center for Accelerator Mass Spectrometry at Lawrence Livermore National Laboratory. Alternative lters such as vanadium and manganese are also explored and the possibility of studying the response of di*erent materials to low-energy nuclear recoils using the resultant neutron beams is discussed.

  17. Fusion welding process

    DOE Patents [OSTI]

    Thomas, Kenneth C. (Export, PA); Jones, Eric D. (Salem, PA); McBride, Marvin A. (Hempfield Township, Westmoreland County, PA)

    1983-01-01

    A process for the fusion welding of nickel alloy steel members wherein a ferrite containing pellet is inserted into a cavity in one member and melted by a welding torch. The resulting weld nugget, a fusion of the nickel containing alloy from the members to be welded and the pellet, has a composition which is sufficiently low in nickel content such that ferrite phases occur within the weld nugget, resulting in improved weld properties. The steel alloys encompassed also include alloys containing carbon and manganese, considered nickel equivalents.

  18. Hydrogen production using hydrogenase-containing oxygenic photosynthetic organisms

    DOE Patents [OSTI]

    Melis, Anastasios; Zhang, Liping; Benemann, John R.; Forestier, Marc; Ghirardi, Maria; Seibert, Michael

    2006-01-24

    A reversible physiological process provides for the temporal separation of oxygen evolution and hydrogen production in a microorganism, which includes the steps of growing a culture of the microorganism in medium under illuminated conditions to accumulate an endogenous substrate, depleting from the medium a nutrient selected from the group consisting of sulfur, iron, and/or manganese, sealing the culture from atmospheric oxygen, incubating the culture in light whereby a rate of light-induced oxygen production is equal to or less than a rate of respiration, and collecting an evolved gas. The process is particularly useful to accomplish a sustained photobiological hydrogen gas production in cultures of microorganisms, such as Chlamydomonas reinhardtii.

  19. Hydrogen Production Using Hydrogenase-Containing Oxygenic Photosynthetic Organisms

    DOE Patents [OSTI]

    Melis, A.; Zhang, L.; Benemann, J. R.; Forestier, M.; Ghirardi, M.; Seibert, M.

    2006-01-24

    A reversible physiological process provides for the temporal separation of oxygen evolution and hydrogen production in a microorganism, which includes the steps of growing a culture of the microorganism in medium under illuminated conditions to accumulate an endogenous substrate, depleting from the medium a nutrient selected from the group consisting of sulfur, iron, and/or manganese, sealing the culture from atmospheric oxygen, incubating the culture in light whereby a rate of light-induced oxygen production is equal to or less than a rate of respiration, and collecting an evolved gas. The process is particularly useful to accomplish a sustained photobiological hydrogen gas production in cultures of microorganisms, such as Chlamydomonas reinhardtii.

  20. Method and system for ethanol production

    DOE Patents [OSTI]

    Feder, Harold M. (Darien, IL); Chen, Michael J. (Darien, IL)

    1981-01-01

    A transition metal carbonyl and a tertiary amine are employed as a homogeneous catalytic system in methanol or a less volatile solvent to react methanol with carbon monoxide and hydrogen gas producing ethanol and carbon dioxide. The gas contains a high carbon monoxide to hydrogen ratio as is present in a typical gasifier product. The reaction has potential for anhydrous ethanol production as carbon dioxide rather than water is produced. The only other significant by product is methane. Selected transition metal carbonyls include those of iron, ruthenium and possibly manganese and osmium. Selected amines include trimethylamine, N-Methylpyrrolidine, 24-diazabicyclooctane, dimethyneopentylamine and 2-pryidinol.

  1. Design and synthesis of mixed oxides nanoparticles for biofuel applications

    SciTech Connect (OSTI)

    Chen, Senniang

    2010-05-15

    The work in this dissertation presents the synthesis of two mixed metal oxides for biofuel applications and NMR characterization of silica materials. In the chapter 2, high catalytic efficiency of calcium silicate is synthesized for transesterfication of soybean oil to biodisels. Chapter 3 describes the synthesis of a new Rh based catalyst on mesoporous manganese oxides. The new catalyst is found to have higher activity and selectivity towards ethanol. Chapter 4 demonstrates the applications of solid-state Si NMR in the silica materials.

  2. | Center for Bio-Inspired Solar Fuel Production

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    Subtask 1 Subtask 2 Subtask 3 Subtask 4 Subtask 5 Published Research Highlights Submitted to DOE Click on a slide to enlarge Megiatto et al (2014) A bioinspired redox relay that mimics radical interactions of the Tyr-His pairs of photosystem II, Nature Chemistry, Published online 9 Feb, 2014, doi: 10.1038/nchem.1862 Mukhopadhyay et al (2014) A highly active manganese precatalyst for the hydrosilylation of ketones and esters. J. Am. Chem. Soc., 136 (3), 882-885. Lu et al (2012) Charge Transport

  3. Method for rapidly determining a pulp kappa number using spectrophotometry

    DOE Patents [OSTI]

    Chai, Xin-Sheng (Atlanta, GA); Zhu, Jun Yong (Marietta, GA)

    2002-01-01

    A system and method for rapidly determining the pulp kappa number through direct measurement of the potassium permanganate concentration in a pulp-permanganate solution using spectrophotometry. Specifically, the present invention uses strong acidification to carry out the pulp-permanganate oxidation reaction in the pulp-permanganate solution to prevent the precipitation of manganese dioxide (MnO.sub.2). Consequently, spectral interference from the precipitated MnO.sub.2 is eliminated and the oxidation reaction becomes dominant. The spectral intensity of the oxidation reaction is then analyzed to determine the pulp kappa number.

  4. Separations method for polar molecules

    DOE Patents [OSTI]

    Thoma, Steven G.; Bonhomme, Francois R.

    2004-07-27

    A method for separating at least one compound from a liquid mixture containing different compounds where anew crystalline manganese phosphate composition with the formula Mn.sub.3 (PO.sub.4).sub.4.2(H.sub.3 NCH.sub.2 CH.sub.2).sub.3 N.6(H.sub.2 O) is dispersed in the liquid mixture, selectively intercalating one or more compounds into the crystalline structure of the Mn.sub.3 (PO.sub.4).sub.4.2(H.sub.3 NCH.sub.2 CH.sub.2).sub.3 N.6(H.sub.2 O).

  5. Latest News | Critical Materials Institute

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    News News releases CMI in the news News archive CMI social media Latest News News about CMI: How true is conventional wisdon about price volatility of tech metals?, Feb. 11, 2016 Need rare-earths know-how? The Critical Materials Institute offers lower-cost access to experts and research, Dec. 1, 2015 Get schooled in rare-earth metals, Nov. 30, 2015 Speciality Metal Recycling Firm Teams Up with US Critical Materials Institute, Nov. 17, 2015 American Manganese Inc. Enters NDA with U.S.

  6. Primary explosives

    DOE Patents [OSTI]

    Hiskey, Michael A. (Los Alamos, NM); Huynh, My Hang V. (Los Alamos, NM)

    2009-03-03

    The present invention provides a compound of the formula (Cat).sup.+.sub.z[M.sup.++(5-nitro-1H-tetrazolato-N2).sup.-.sub.x(H.sub.2- O).sub.y] where x is 3 or 4, y is 2 or 3, x+y is 6, z is 1 or 2, and M.sup.++ is selected from the group consisting of iron, cobalt, nickel, copper, zinc, chromium, and manganese, and (Cat).sup.+ is selected from the group consisting of ammonium, sodium, potassium, rubidium and cesium. A method of preparing the compound of that formula is also disclosed.

  7. Thermochemical generation of hydrogen and oxygen from water. [NaMnO/sub 2/ and TiO/sub 2/

    DOE Patents [OSTI]

    Robinson, P.R.; Bamberger, C.E.

    1980-02-08

    A thermochemical cyclic process for the production of hydrogen exploits the reaction between sodium manganate (NaMnO/sub 2/) and titanium dioxide (TiO/sub 2/) to form sodium titanate (Na/sub 2/TiO/sub 3/), manganese (II) titanate (MnTiO/sub 3/) and oxygen. The titanate mixture is treated with sodium hydroxide, in the presence of steam, to form sodium titanate, sodium manganate (III), water and hydrogen. The sodium titanate-manganate (III) mixture is treated with water to form sodium manganate (III), titanium dioxide and sodium hydroxide. Sodium manganate (III) and titanium dioxide are recycled following dissolution of sodium hydroxide in water.

  8. Determination of reactive oxygen species from ZnO micro-nano structures with shape-dependent photocatalytic activity

    SciTech Connect (OSTI)

    He, Weiwei; Zhao, Hongxiao; Jia, Huimin; Yin, Jun-Jie; Zheng, Zhi

    2014-05-01

    Graphical abstract: ZnO micro/nano structures with shape dependent photocatalytic activity were prepared by hydrothermal reaction. The generations of hydroxyl radical, superoxide and singlet oxygen from irradiated ZnO were identified precisely by electron spin resonance spectroscopy. The type of reactive oxygen species was determined by band gap structure of ZnO. - Highlights: ZnO micro/nano structures with different morphologies were prepared by solvothermal reaction. Multi-pod like ZnO structures exhibited superior photocatalytic activity. The generations of hydroxyl radical, superoxide and singlet oxygen from irradiated ZnO were characterized precisely by electron spin resonance spectroscopy. The type of reactive oxygen species was determined by band gap structure of ZnO. - Abstract: ZnO micro/nano structures with different morphologies have been prepared by the changing solvents used during their synthesis by solvothermal reaction. Three typical shapes of ZnO structures including hexagonal, bell bottom like and multi-pod formed and were characterized by scanning electron microscopy and X-ray diffraction. Multi pod like ZnO structures exhibited the highest photocatalytic activity toward degradation of methyl orange. Using electron spin resonance spectroscopy coupled with spin trapping techniques, we demonstrate an effective way to identify precisely the generation of hydroxyl radicals, superoxide and singlet oxygen from the irradiated ZnO multi pod structures. The type of reactive oxygen species formed was predictable from the band gap structure of ZnO. These results indicate that the shape of micro-nano structures significantly affects the photocatalytic activity of ZnO, and demonstrate the value of electron spin resonance spectroscopy for characterizing the type of reactive oxygen species formed during photoexcitation of semiconductors.

  9. Transition Metal Oxide Alloys as Potential Solar Energy Conversion Materials

    SciTech Connect (OSTI)

    Toroker, Maytal; Carter, Emily A.

    2013-02-21

    First-row transition metal oxides (TMOs) are inexpensive potentia alternative materials for solar energy conversion devices. However, some TMOs, such as manganese(II) oxide, have band gaps that are too large for efficiently absorbing solar energy. Other TMOs, such as iron(II) oxide, have conduction and valence band edges with the same orbital character that may lead to unfavorably high electronhole recombination rates. Another limitation of iron(II) oxide is that the calculated valence band edge is not positioned well for oxidizing water. We predict that key properties, including band gaps, band edge positions, and possibly electronhole recombination rates, may be improved by alloying TMOs that have different band alignments. A new metric, the band gap center offset, is introduced for simple screening of potential parent materials. The concept is illustrated by calculating the electronic structure of binary oxide alloys that contain manganese, nickel, iron, zinc, and/or magnesium, within density functional theory (DFT)+U and hybrid DFT theories. We conclude that alloys of iron(II) oxide are worth evaluating further as solar energy conversion materials.

  10. Preparation of LiMn{sub 2}O{sub 4} cathode thin films for thin film lithium secondary batteries by a mist CVD process

    SciTech Connect (OSTI)

    Tadanaga, Kiyoharu; Yamaguchi, Akihiro; Sakuda, Atsushi; Hayashi, Akitoshi; Tatsumisago, Masahiro; Duran, Alicia; Aparacio, Mario

    2014-05-01

    Highlights: LiMn{sub 2}O{sub 4} thin films were prepared by using the mist CVD process. An aqueous solution of lithium and manganese acetates is used for the precursor solution. The cell with the LiMn{sub 2}O{sub 4} thin films exhibited a capacity of about 80 mAh/g. The cell showed good cycling performance during 10 cycles. - Abstract: LiMn{sub 2}O{sub 4} cathode thin films for thin film lithium secondary batteries were prepared by using so-called the mist CVD process, employing an aqueous solution of lithium acetate and manganese acetate, as the source of Li and Mn, respectively. The aqueous solution of starting materials was ultrasonically atomized to form mist particles, and mists were transferred by nitrogen gas to silica glass substrate to form thin films. FE-SEM observation revealed that thin films obtained by this process were dense and smooth, and thin films with a thickness of about 750 nm were obtained. The electrochemical cell with the thin films obtained by sintering at 700 C exhibited a capacity of about 80 mAh/g, and the cell showed good cycling performance during 10 cycles.

  11. Ethyl`s MMT ready to hit the road

    SciTech Connect (OSTI)

    Stringer, J.

    1996-01-03

    After spending two decades and about $30 million on the fight to sell the fuel octane booster methylcyclopentadienyl manganese tricarbonyl (MMT), Ethyl has started marketing the product. Ethyl president and chief operating officer Thomas Gottwald says he expects a profit from MMT from the outset. {open_quotes}MMT is a gangbuster new product,{close_quotes} says Paul Raman, an analyst with S.G. Warburg (New York), {open_quotes}and it will be very profitable for Ethyl.{close_quotes} Ethyl`s effort to bring MMT to market faced pressure from EPA and automakers. EPA says MMT should not be marketed until more research is done on health effects of the manganese-based additive. US automakers oppose MMT, fearing it will damage catalytic converters. Last October Ethyl won a federal appeals court decision compelling EPA to approve MMT use. Gottwald says the MMT fight has been well worth it: {open_quotes}We fought with our eye on the bottom line.{close_quotes}

  12. Individual Reactions of Permanganate and Various Reductants - Student Report to the DOE ERULF Program for Work Conducted May to July 2000

    SciTech Connect (OSTI)

    Gauger, Amber M.; Hallen, Richard T.

    2012-09-15

    Tank waste on the Hanford Site contains radioactive elements that need to be removed from solution prior to disposal. One effective way to do this is to precipitate the radioactive elements with manganese solids, produced by permanganate oxidation. When added to tank waste, the permanganate reacts quickly producing manganese (IV) dioxide precipitate. Because of the speed of the reaction it is difficult to tell what exactly is happening. Individual reactions using non-radioactive reductants found in the tanks were done to determine reaction kinetics, what permanganate was reduced to, and what oxidation products were formed. In this project sodium formate, sodium nitrite, glycolic acid, glycine, and sodium oxalate were studied using various concentrations of reductant in alkaline sodium hydroxide solutions. It was determined that formate reacted the quickest, followed by glycine and glycolic acid. Oxalate and nitrite did not appear to react with the permanganate solutions. The products of the oxidation reaction were examined. Formate was oxidized to carbonate and water. Glycolic acid was oxidized slower producing oxalate and water. Glycine reactions formed some ammonia in solution, oxalate, and water. The research reported by Amber Gauger in this report was part of a DOE ERULF student intern program at Pacific Northwest National Laboratory under the direction of Richard Hallen in the summer of 2000.

  13. Magnetism in LithiumOxygen Discharge Product

    SciTech Connect (OSTI)

    Lu, Jun; Jung, Hun-Ji; Lau, Kah Chun; Zhang, Zhengcheng; Schlueter, John A.; Du, Peng; Assary, Rajeev S.; Greeley, Jeffrey P.; Ferguson, Glen A.; Wang, Hsien-Hau; Hassoun, Jusef; Iddir, Hakim; Zhou, Jigang; Zuin, Lucia; Hu, Yongfeng; Sun, Yang-Kook; Scrosati, Bruno; Curtiss, Larry A.; Amine, Khalil

    2013-05-13

    Nonaqueous lithiumoxygen batteries have a much superior theoretical gravimetric energy density compared to conventional lithium-ion batteries, and thus could render long-range electric vehicles a reality. A molecular-level understanding of the reversible formation of lithium peroxide in these batteries, the properties of major/minor discharge products, and the stability of the nonaqueous electrolytes is required to achieve successful lithiumoxygen batteries. We demonstrate that the major discharge product formed in the lithiumoxygen cell, lithium peroxide, exhibits a magnetic moment. These results are based on dc-magnetization measurements and a lithium oxygen cell containing an ether-based electrolyte. The results are unexpected because bulk lithium peroxide has a significant band gap. Density functional calculations predict that superoxide- type surface oxygen groups with unpaired electrons exist on stoichiometric lithium peroxide crystalline surfaces and on nanoparticle surfaces; these computational results are consistent with the magnetic measurement of the discharged lithium peroxide product as well as EPR measurements on commercial lithium peroxide. The presence of superoxide-type surface oxygen groups with spin can play a role in the reversible formation and decomposition of lithium peroxide as well as the reversible formation and decomposition of electrolyte molecules.

  14. Maintenance of cellular ATP level by caloric restriction correlates chronological survival of budding yeast

    SciTech Connect (OSTI)

    Choi, Joon-Seok; Lee, Cheol-Koo

    2013-09-13

    Highlights: CR decreases total ROS and mitochondrial superoxide during the chronological aging. CR does not affect the levels of oxidative damage on protein and DNA. CR contributes extension of chronological lifespan by maintenance of ATP level -- Abstract: The free radical theory of aging emphasizes cumulative oxidative damage in the genome and intracellular proteins due to reactive oxygen species (ROS), which is a major cause for aging. Caloric restriction (CR) has been known as a representative treatment that prevents aging; however, its mechanism of action remains elusive. Here, we show that CR extends the chronological lifespan (CLS) of budding yeast by maintaining cellular energy levels. CR reduced the generation of total ROS and mitochondrial superoxide; however, CR did not reduce the oxidative damage in proteins and DNA. Subsequently, calorie-restricted yeast had higher mitochondrial membrane potential (MMP), and it sustained consistent ATP levels during the process of chronological aging. Our results suggest that CR extends the survival of the chronologically aged cells by improving the efficiency of energy metabolism for the maintenance of the ATP level rather than reducing the global oxidative damage of proteins and DNA.

  15. Unilateral radiation pneumonitis in sheep: Physiological changes and bronchoalveolar lavage

    SciTech Connect (OSTI)

    Tillman, B.F.; Loyd, J.E.; Malcolm, A.W.; Holm, B.A.; Brigham, K.L. )

    1989-03-01

    Radiation pneumonitis is a life-threatening result of therapeutic thoracic irradiation, yet its mechanisms are poorly understood. We studied the effects of unilateral lung irradiation (3,000 rad) in sheep from the immediate response to the later development of radiation pneumonitis. We defined radiation pneumonitis by its diagnostic clinical feature, radiographic infiltration of the irradiated zone with a straight margin corresponding to the radiation port. The immediate response in the few hours after irradiation was characterized by cough, labored respiration, hypoxemia (arterial PO{sub 2} decreased 19 Torr), mild pulmonary hypertension (pulmonary arterial pressure increased 20%), and lymphopenia. Hemodynamics and gas exchange returned to normal by day 2 but became abnormal again before or during radiation pneumonitis at 32 +/- 2 days. Respiratory distress, hypoxemia, and pulmonary hypertension recurred during radiation pneumonitis. Bronchoalveolar lavage during radiation pneumonitis contained increased neutrophils (19 +/- 4%, control = 7%), increased protein (0.27 +/- 0.1 g/dl, control = 0.12 +/- 0.03), and severely impaired ability to lower surface tension. Alveolar macrophages from both lungs during unilateral radiation pneumonitis exhibited impaired generation of superoxide after phorbol myristate (only a 30% increase). Normal control alveolar macrophages increased superoxide production after stimulation greater than 400%. We conclude that unilateral lung irradiation in sheep causes a mild immediate response followed by radiation pneumonitis at 1 mo. Unilateral radiation pneumonitis in this model is associated with ipsilateral neutrophilic alveolitis, increased bronchoalveolar lavage protein, and impaired surfactant function, as well as bilateral functional abnormalities of alveolar macrophages.

  16. Enzymantic Conversion of Coal to Liquid Fuels

    SciTech Connect (OSTI)

    Richard Troiano

    2011-01-31

    The work in this project focused on the conversion of bituminous coal to liquid hydrocarbons. The major steps in this process include mechanical pretreatment, chemical pretreatment, and finally solubilization and conversion of coal to liquid hydrocarbons. Two different types of mechanical pretreatment were considered for the process: hammer mill grinding and jet mill grinding. After research and experimentation, it was decided to use jet mill grinding, which allows for coal to be ground down to particle sizes of 5 {mu}m or less. A Fluid Energy Model 0101 JET-O-MIZER-630 size reduction mill was purchased for this purpose. This machine was completed and final testing was performed on the machine at the Fluid Energy facilities in Telford, PA. The test results from the machine show that it can indeed perform to the required specifications and is able to grind coal down to a mean particle size that is ideal for experimentation. Solubilization and conversion experiments were performed on various pretreated coal samples using 3 different approaches: (1) enzymatic - using extracellular Laccase and Manganese Peroxidase (MnP), (2) chemical - using Ammonium Tartrate and Manganese Peroxidase, and (3) enzymatic - using the live organisms Phanerochaete chrysosporium. Spectral analysis was used to determine how effective each of these methods were in decomposing bituminous coal. After analysis of the results and other considerations, such as cost and environmental impacts, it was determined that the enzymatic approaches, as opposed to the chemical approaches using chelators, were more effective in decomposing coal. The results from the laccase/MnP experiments and Phanerochaete chrysosporium experiments are presented and compared in this final report. Spectra from both enzymatic methods show absorption peaks in the 240nm to 300nm region. These peaks correspond to aromatic intermediates formed when breaking down the coal structure. The peaks then decrease in absorbance over time, corresponding to the consumption of aromatic intermediates as they undergo ring cleavage. The results show that this process happens within 1 hour when using extracellular enzymes, but takes several days when using live organisms. In addition, live organisms require specific culture conditions, control of contaminants and fungicides in order to effectively produce extracellular enzymes that degrade coal. Therefore, when comparing the two enzymatic methods, results show that the process of using extracellular lignin degrading enzymes, such as laccase and manganese peroxidase, appears to be a more efficient method of decomposing bituminous coal.

  17. Superacid catalysis of light hydrocarbon conversion. DOE PETC seventh quarterly progress report, April 1, 1995--July 31, 1995

    SciTech Connect (OSTI)

    Gates, B.C.

    1996-02-01

    Iron- and manganese-promoted sulfated zirconia is a catalyst for the conversion of propane, but the rate of conversion of propane is much less than the rate of conversion of butane. Whereas this catalyst appears to be a good candidate for practical, industrial conversion of butane, it appears to lack sufficient activity for practical conversion of propane. The propane conversion data reported here provide excellent insights into the chemistry of the catalytic conversion. Solid and catalysts, namely, sulfated zirconia, iron- and manganese-promoted sulfated zirconia, and USY zeolite, were tested for conversion of propane at 1 atm, 200-450{degrees}C, and propane partial pressures in the range of 0.01-0.05 atm. Both promoted and unpromoted sulfated zirconia were found to be active for conversion of propane into butanes, pentanes, methane, ethane, ethylene, and propylene in the temperature range of 200-350{degrees}C, but catalyst deactivation was rapid. At the higher temperatures, only cracking and dehydrogenation products were observed. In contrast to the zirconia-supported catalysts, USY zeolite was observed to convert propane (into propylene, methane, and ethylene) only at temperatures {ge}400{degrees}C. The initial (5 min on stream) rates of propane conversion in the presence of iron- and manganese-promoted sulfated zirconia, sulfated zirconia, and USY zeolite at 450{degrees}C and 0.01 atm propane partial pressure were 3.3 x 10{sup -8}, 0.3 x 10{sup -8}, and 0.06 x 10{sup -8} mol/(s{center_dot}g), respectively. The product distributions in the temperature range 200-450{degrees}C are those of acid-base catalysis, being similar to what has been observed in superacid solution chemistry at temperatures <0{degrees}C. If propane conversion at 450{degrees}C can be considered as a probe of acid strength of the catalyst, the activity comparison suggests that the promoted sulfated zirconia is a stronger acid than sulfated zirconia, which is a stronger acid than USY zeolite.

  18. Austenitic alloy and reactor components made thereof

    DOE Patents [OSTI]

    Bates, John F. (Ogden, UT); Brager, Howard R. (Richland, WA); Korenko, Michael K. (Wexford, PA)

    1986-01-01

    An austenitic stainless steel alloy is disclosed, having excellent fast neutron irradiation swelling resistance and good post irradiation ductility, making it especially useful for liquid metal fast breeder reactor applications. The alloy contains: about 0.04 to 0.09 wt. % carbon; about 1.5 to 2.5 wt. % manganese; about 0.5 to 1.6 wt. % silicon; about 0.030 to 0.08 wt. % phosphorus; about 13.3 to 16.5 wt. % chromium; about 13.7 to 16.0 wt. % nickel; about 1.0 to 3.0 wt. % molybdenum; and about 0.10 to 0.35 wt. % titanium.

  19. Survey of electrochemical production of inorganic compounds. Final report

    SciTech Connect (OSTI)

    Not Available

    1980-10-01

    The electrochemical generation of inorganic compounds, excluding chlorine/caustic, has been critically reviewed. About 60 x 10/sup 12/ Btu/y fossil fuel equivalent will be used in the year 2000 for the electrosynthesis of inorganic compounds. Significant energy savings in chlorate production can result from the development of suitable electrocatalysts for lowering the cathodic overpotential. Perchlorates, electrolytic hypochlorite, electrolytic manganese dioxide, fluorine and other miscellaneous compounds use relatively small amounts of electrical energy. Implementation of caustic scrubber technology for stack gas cleanup would result in appreciable amounts of sodium sulfate which could be electrolyzed to regenerate caustic. Hydrogen peroxide, now produced by the alkyl anthraquinone process, could be made electrolytically by a new process coupling anodic oxidation of sulfate with cathodic reduction of oxygen in alkaline solution. Ozone is currently manufactured using energy-inefficient silent discharge equipment. A novel energy-efficient approach which uses an oxygen-enhanced anodic reaction is examined.

  20. Volatile Species Retention During Metallic Fuel Casting

    SciTech Connect (OSTI)

    Randall S. Fielding; Douglas L. Proter

    2013-10-01

    Metallic nuclear fuels are candidate transmutation fuel forms for advanced fuel cycles. Through the operation of the Experimental Breeder Reactor II metallic nuclear fuels have been shown to be robust and easily manufactured. However, concerns have been raised concerning loss of americium during the casting process because of its high vapor pressure. In order to address these concerns a gaseous diffusion model was developed and a series of experiments using both manganese and samarium as surrogates for americium were conducted. The modeling results showed that volatility losses can be controlled to essentially no losses with a modest overpressure. Experimental results also showed volatile species retention down to no detectable losses through overpressure, although the loss values varied from the model results the same trend was seen. Bases on these results it is very probably that americium losses through volatility can be controlled to no detectable losses through application of a modest overpressure during casting.

  1. Steel bonded dense silicon nitride compositions and method for their fabrication

    DOE Patents [OSTI]

    Landingham, R.L.; Shell, T.E.

    1985-05-20

    A two-stage bonding technique for bonding high density silicon nitride and other ceramic materials to stainless steel and other hard metals, and multilayered ceramic-metal composites prepared by the technique are disclosed. The technique involves initially slurry coating a surface of the ceramic material at about 1500/sup 0/C in a vacuum with a refractory material and the stainless steel is then pressure bonded to the metallic coated surface by brazing it with nickel-copper-silver or nickel-copper-manganese alloys at a temperature in the range of about 850/sup 0/ to 950/sup 0/C in a vacuum. The two-stage bonding technique minimizes the temperature-expansion mismatch between the dissimilar materials.

  2. Radiation resistant austenitic stainless steel alloys

    DOE Patents [OSTI]

    Maziasz, P.J.; Braski, D.N.; Rowcliffe, A.F.

    1987-02-11

    An austenitic stainless steel alloy, with improved resistance to radiation-induced swelling and helium embrittlement, and improved resistance to thermal creep at high temperatures, consisting essentially of, by weight percent: from 16 to 18% nickel; from 13 to 17% chromium; from 2 to 3% molybdenum; from 1.5 to 2.5% manganese; from 0.01 to 0.5% silicon; from 0.2 to 0.4% titanium; from 0.1 to 0.2% niobium; from 0.1 to 0.6% vanadium; from 0.06 to 0.12% carbon; from 0.01 to 0.03% nitrogen; from 0.03 to 0.08% phosphorus; from 0.005 to 0.01% boron; and the balance iron, and wherein the alloy may be thermomechanically treated to enhance physical and mechanical properties. 4 figs.

  3. Summary Slides of ALS Science Highlights

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    Summary Slides of ALS Science Highlights Print No. Slide Beamline Full Web Highlight ALSNews Volume 327 Aerosol Oxidation Speeds Up in Smoggy Air 9.0.2 02.24.2016 Vol. 370 326 Porous Framework Electrocatalysts Are Key to CO2... 7.3.3, 10.3.2 02.24.2016 Vol. 370 325 Phonon Polariton Behavior in 2D Materials 5.4.1 01.27.2016 Vol. 369 324 Manganese Reduction-Oxidation Drives Plant Debris... 1.4.3, 9.0.2, 10.3.2 02.24.2016 Vol. 370 323 A New Pathway for Radionuclide Uptake 5.0.1, 5.0.2 01.27.2016

  4. Summary Slides of ALS Science Highlights

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    Science Highlights Print No. Slide Beamline Full Web Highlight ALSNews Volume 327 Aerosol Oxidation Speeds Up in Smoggy Air 9.0.2 02.24.2016 Vol. 370 326 Porous Framework Electrocatalysts Are Key to CO2... 7.3.3, 10.3.2 02.24.2016 Vol. 370 325 Phonon Polariton Behavior in 2D Materials 5.4.1 01.27.2016 Vol. 369 324 Manganese Reduction-Oxidation Drives Plant Debris... 1.4.3, 9.0.2, 10.3.2 02.24.2016 Vol. 370 323 A New Pathway for Radionuclide Uptake 5.0.1, 5.0.2 01.27.2016 Vol. 369 322 Watching a

  5. Summary Slides of ALS Science Highlights

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    Summary Slides of ALS Science Highlights Print No. Slide Beamline Full Web Highlight ALSNews Volume 327 Aerosol Oxidation Speeds Up in Smoggy Air 9.0.2 02.24.2016 Vol. 370 326 Porous Framework Electrocatalysts Are Key to CO2... 7.3.3, 10.3.2 02.24.2016 Vol. 370 325 Phonon Polariton Behavior in 2D Materials 5.4.1 01.27.2016 Vol. 369 324 Manganese Reduction-Oxidation Drives Plant Debris... 1.4.3, 9.0.2, 10.3.2 02.24.2016 Vol. 370 323 A New Pathway for Radionuclide Uptake 5.0.1, 5.0.2 01.27.2016

  6. Creep resistant high temperature martensitic steel

    DOE Patents [OSTI]

    Hawk, Jeffrey A.; Jablonski, Paul D.; Cowen, Christopher J.

    2015-11-13

    The disclosure provides a creep resistant alloy having an overall composition comprised of iron, chromium, molybdenum, carbon, manganese, silicon, nickel, vanadium, niobium, nitrogen, tungsten, cobalt, tantalum, boron, and potentially additional elements. In an embodiment, the creep resistant alloy has a molybdenum equivalent Mo(eq) from 1.475 to 1.700 wt. % and a quantity (C+N) from 0.145 to 0.205. The overall composition ameliorates sources of microstructural instability such as coarsening of M.sub.23C.sub.6 carbides and MX precipitates, and mitigates or eliminates Laves and Z-phase formation. A creep resistant martensitic steel may be fabricated by preparing a melt comprised of the overall composition followed by at least austenizing and tempering. The creep resistant alloy exhibits improved high-temperature creep strength in the temperature environment of around 650.degree. C.

  7. Process for light-driven hydrocarbon oxidation at ambient temperatures

    DOE Patents [OSTI]

    Shelnutt, John A. (Tijeras, NM)

    1990-01-01

    A photochemical reaction for the oxidation of hydrocarbons uses molecular oxygen as the oxidant. A reductive photoredox cycle that uses a tin(IV)- or antimony(V)-porphyrin photosensitizer generates the reducing equivalents required to activate oxygen. This artificial photosynthesis system drives a catalytic cycle, which mimics the cytochrome P.sub.450 reaction, to oxidize hydrocarbons. An iron(III)- or manganese(III)-porphyrin is used as the hydrocarbon-oxidation catalyst. Methylviologen can be used as a redox relay molecule to provide for electron-transfer from the reduced photosensitizer to the Fe or Mn porphyrin. The system is long-lived and may be used in photo-initiated spectroscopic studies of the reaction to determine reaction rates and intermediates.

  8. Phosphorus removal from slow-cooled steelmaking slags: Grain size determination and liberation studies

    SciTech Connect (OSTI)

    Fregeau-Wu, E.; Iwasaki, I.

    1995-07-01

    The major obstacle in recycling steelmaking slags to the blast furnace is their phosphorus content. Removal of the phosphorus, which is primarily associated with the silicate and phosphate phases, would allow for greater recycle of these slags for their iron, manganese, and lime contents. Calculations show that separation of the silicates from the oxide phases would remove nearly 90% of the phosphorus from the slag. The variable grain size of the as-received slag made liberation by fine grinding difficult. Therefore, slow-cooling experiments were undertaken to improve the grain size distribution. The grain size distributions were determined using in-situ image analysis. The samples were ground to their apparent liberation size and high gradient magnetic separation was used to separate the magnetic oxides from the nonmagnetic silicates and phosphates. Liberation analysis and modeling was performed on selected separation products for discussion of benefication characteristics.

  9. Hawaii Geothermal Project annotated bibliography: Biological resources of the geothermal subzones, the transmission corridors and the Puna District, Island of Hawaii

    SciTech Connect (OSTI)

    Miller, S.E.; Burgett, J.M.

    1993-10-01

    Task 1 of the Hawaii Geothermal Project Interagency Agreement between the Fish and Wildlife Service and the Department of Energy-Oak Ridge National Laboratory (DOE) includes an annotated bibliography of published and unpublished documents that cover biological issues related to the lowland rain forest in Puna, adjacent areas, transmission corridors, and in the proposed Hawaii Geothermal Project (HGP). The 51 documents reviewed in this report cover the main body of biological information for these projects. The full table of contents and bibliography for each document is included along with two copies (as requested in the Interagency Agreement) of the biological sections of each document. The documents are reviewed in five main categories: (1) geothermal subzones (29 documents); (2) transmission cable routes (8 documents); (3) commercial satellite launching facility (Spaceport; 1 document); (4) manganese nodule processing facility (2 documents); (5) water resource development (1 document); and (6) ecosystem stability and introduced species (11 documents).

  10. Hydrogeochemical and stream-sediment reconnaissance, orientation study, Ouachita Mountain area, Arkansas. National Uranium Resource Evaluation Program

    SciTech Connect (OSTI)

    Steele, K. F.

    1982-08-01

    A hydrogeochemical ground water orientation study was conducted in the multi-mineralized area of the Ouachita Mountains, Arkansas in order to evaluate the usefulness of ground water as a sampling medium for uranium exploration in similar areas. Ninety-three springs and nine wells were sampled in Clark, Garland, Hot Springs, Howard, Montgomery, Pike, Polk, and Sevier Counties. Manganese, barite, celestite, cinnabar, stibnite, copper, lead, and zinc are present. The following parameters were determined: pH, conductivity, alkalinity, U, Br, Cl, F, He, Mn, Na, V, Al, Dy, NO/sub 3/, NH/sub 3/, SO/sub 4/, and PO/sub 4/. The minerals appear to significantly affect the chemistry of the ground water. This report is issued in draft form, without detailed technical and copy editing. This was done to make the report available to the public before the end of the National Uranium Resource Evaluation.

  11. Solid solution strengthened duct and cladding alloy D9-B1

    DOE Patents [OSTI]

    Korenko, Michael K. (Rockville, MD)

    1983-01-01

    A modified AISI type 316 stainless steel is described for use in an atmosphere where the alloy will be subject to neutron irradiation. The alloy is characterized by its phase stability in both the annealed as well as cold work condition and above all by its superior resistance to radiation induced swelling. Graphical data is included to demonstrate the superior swelling resistance of the alloy which contains from about 0.5% to 2.2% manganese, from about 0.7% to about 1.1% silicon, from about 12.5% to 14% chromium, from about 14.5% to about 16.5% nickel, from about 1.2% to about 1.6% molybdenum, from 0.15% to 0.30% titanium, from 0.02% to 0.08% zirconium, and the balance iron with incidental impurities.

  12. Process for recovery of aluminum from carbonaceous waste products

    SciTech Connect (OSTI)

    Kapolyi, L.

    1984-03-13

    A carbonaceous waste product, preferably containing 30 to 60% mineral substances, 35 to 55% carbonaceous materials, 5 to 20% water, and having a calorific value of 2,000 to 3,500 k cal/kg is fired to produce thermal energy and a combustion residue. The residue is adjusted, if necessary, by addition of mineral containing additives so that it contains 15 to 50% alumina, 15 to 20% silica and 13 to 45% other oxides (mainly iron oxide, manganese oxide and calcium oxide). Sufficient limestone is added to produce a mixture containing 1.8 to 2.2 moles of calcium oxide per mole of silica and 1.1 to 1.3 moles of calcium oxide per mole of alumina. The mixture is then sintered. The total energy requirements of the sintering step are supplied by the energy generated in the firing step. Useful products such as cement and cast stone can be produced from the sintered product.

  13. Public health assessment for Smeltertown/Koppers, Salida, Chaffee County, Colorado, Region 8. Cerclis No. COD983769738. Final report

    SciTech Connect (OSTI)

    1995-03-09

    The Smeltertown (SMT) site near Salida, Colorado, was proposed for inclusion on the National Priorities List in February 1992. Wastes generated on-site included smelter slags, soils contaminated with creosote drippings, other contaminated soils, process water holding ponds and associated sludges, spilled ores, and combined soils and sludges. Site contaminants include a wide array of polynuclear aromatic hydrocarbons (PAHs) and numerous metals which include arsenic, cadmium, chromium, manganese, lead, beryllium, zinc, and copper among others. Although some contaminant sources remain on site, many of the original site contamination sources have been removed from the site. Most off-site contamination in soils (PAHs and metals) has been removed. However, further an evaluation of past air-born deposition of contaminants needs to be made to determine if all contaminated soils have been identified.

  14. The crystal structure of methane B at 8 GPaAn ?-Mn arrangement of molecules

    SciTech Connect (OSTI)

    Maynard-Casely, H. E. Lundegaard, L. F.; Loa, I.; McMahon, M. I.; Gregoryanz, E.; Nelmes, R. J.; Loveday, J. S.

    2014-12-21

    From a combination of powder and single-crystal synchrotron x-ray diffraction data we have determined the carbon substructure of phase B of methane at a pressure of ?8 GPa. We find this substructure to be cubic with space group I4{sup }3m and 58 molecules in the unit cell. The unit cell has a lattice parameter a = 11.911(1) at 8.3(2) GPa, which is a factor of ?2 larger than had previously been proposed by Umemoto et al. [J. Phys.: Condens. Matter 14, 10675 (2002)]. The substructure as now solved is not related to any close-packed arrangement, contrary to previous proposals. Surprisingly, the arrangement of the carbon atoms is isostructural with that of ?-manganese at ambient conditions.

  15. Activation of methane by transition metal-substituted aluminophosphate molecular sieves

    DOE Patents [OSTI]

    Iton, Lennox E. (Downers Grove, IL); Maroni, Victor A. (Naperville, IL)

    1991-01-01

    Aluminophosphate molecular sieves substituted with cobalt, manganese or iron and having the AlPO.sub.4 -34 or AlPO.sub.4 -5, or related AlPO.sub.4 structure activate methane starting at approximately 350.degree. C. Between 400.degree. and 500.degree. C. and at methane pressures .ltoreq.1 atmosphere the rate of methane conversion increases steadily with typical conversion efficiencies at 500.degree. C. approaching 50% and selectivity to the production of C.sub.2+ hydrocarbons approaching 100%. The activation mechanism is based on reduction of the transition metal(III) form of the molecular sieve to the transition metal(II) form with accompanying oxidative dehydrogenation of the methane. Reoxidation of the - transition metal(II) form to the transition metal(III) form can be done either chemically (e.g., using O.sub.2) or electrochemically.

  16. Eliminating Voltage Decay of Lithium-Rich Li1.14Mn0.54Ni0.14Co0.14O2 Cathodes by Controlling the Electrochemical Process

    DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)

    Wei, Z.; Zhu, Y.; Zhang, W.; Wang, F.; Zhang, Q.; Qiu, B.; Han, S.; Xia, Y.; Liu, Z.

    2015-03-27

    Lithium-rich material owns a particularly high capacity owing to the activation of electrochemical inactive Li2MnO3 phase. But at the same time, MnO2 phase formed after Li2MnO3 activation confronts a severe problem of converting to spinel phase, and resulting in voltage decay. To our knowledge, this phenomenon is inherent property of layered manganese oxide materials and can hardly be overcome. Based on this, unlike previous reports, herein we design a method for the first time to accelerate the phase transformation by tuning the charge upper-limit voltage at a high value, so the phase transformation process can be finished in a fewmore » cycles. Then material structure remains stable while cycling at a low upper-limit voltage. By this novel method voltage decay is eliminated significantly.« less

  17. In Situ Formation Of Reactive Barriers For Pollution Control

    DOE Patents [OSTI]

    Gilmore, Tyler J. (Pasco, WA); Riley, Robert G. (West Richland, WA)

    2004-04-27

    A method of treating soil contamination by forming one or more zones of oxidized material in the path of percolating groundwater is disclosed. The zone or barrier region is formed by delivering an oxidizing agent into the ground for reaction with an existing soil component. The oxidizing agent modifies the existing soil component creating the oxidized zone. Subsequently when soil contaminates migrate into the zone, the oxidized material is available to react with the contaminates and degrade them into benign products. The existing soil component can be an oxidizable mineral such as manganese, and the oxidizing agent can be ozone gas or hydrogen peroxide. Soil contaminates can be volatile organic compounds. Oxidized barriers can be used single or in combination with other barriers.

  18. Superconducting composite with multilayer patterns and multiple buffer layers

    DOE Patents [OSTI]

    Wu, X.D.; Muenchausen, R.E.

    1993-10-12

    An article of manufacture is described including a substrate, a patterned interlayer of a material selected from the group consisting of magnesium oxide, barium-titanium oxide or barium-zirconium oxide, the patterned interlayer material overcoated with a secondary interlayer material of yttria-stabilized zirconia or magnesium-aluminum oxide, upon the surface of the substrate whereby an intermediate article with an exposed surface of both the overcoated patterned interlayer and the substrate is formed, a coating of a buffer layer selected from the group consisting of cerium oxide, yttrium oxide, curium oxide, dysprosium oxide, erbium oxide, europium oxide, iron oxide, gadolinium oxide, holmium oxide, indium oxide, lanthanum oxide, manganese oxide, lutetium oxide, neodymium oxide, praseodymium oxide, plutonium oxide, samarium oxide, terbium oxide, thallium oxide, thulium oxide, yttrium oxide and ytterbium oxide over the entire exposed surface of the intermediate article, and, a ceramic superconductor. 5 figures.

  19. Recovery of niobium from irradiated targets

    DOE Patents [OSTI]

    Phillips, Dennis R.; Jamriska, Sr., David J.; Hamilton, Virginia T.

    1994-01-01

    A process for selective separation of niobium from proton irradiated molybdenum targets is provided and includes dissolving the molybdenum target in a hydrogen peroxide solution to form a first ion-containing solution, contacting the first ion-containing solution with a cationic resin whereby ions selected form the group consisting of molybdenum, biobium, technetium, selenium, vanadium, arsenic, germanium, zirconium and rubidium remain in a second ion-containing solution while ions selected from the group consisting of rubidium, zinc, beryllium, cobalt, iron, manganese, chromium, strontium, yttrium and zirconium are selectively adsorbed by the cationic resin; adjusting the pH of the second ion-containing solution to within a range of from about 5.0 to about 6.0; contacting the pH adjusting second ion-containing solution with a dextran-based material for a time to selectively separate niobium from the solution and recovering the niobium from the dextran-based material.

  20. Process for recovering evolved hydrogen enriched with at least one heavy hydrogen isotope

    DOE Patents [OSTI]

    Tanaka, John (Storrs, CT); Reilly, Jr., James J. (Bellport, NY)

    1978-01-01

    This invention relates to a separation means and method for enriching a hydrogen atmosphere with at least one heavy hydrogen isotope by using a solid titaniun alloy hydride. To this end, the titanium alloy hydride containing at least one metal selected from the group consisting of vanadium, chromium, manganese, molybdenum, iron, cobalt and nickel is contacted with a circulating gaseous flow of hydrogen containing at least one heavy hydrogen isotope at a temperature in the range of -20.degree. to +40.degree. C and at a pressure above the dissociation pressure of the hydrided alloy selectively to concentrate at least one of the isotopes of hydrogen in the hydrided metal alloy. The contacting is continued until equilibrium is reached, and then the gaseous flow is isolated while the temperature and pressure of the enriched hydride remain undisturbed selectively to isolate the hydride. Thereafter, the enriched hydrogen is selectively recovered in accordance with the separation factor (S.F.) of the alloy hydride employed.

  1. Porphyrins

    DOE Patents [OSTI]

    Wijesekera, Tilak; Lyons, James E.; Ellis, Jr., Paul E.

    1996-01-01

    The invention comprises new compositions of matter, which are iron, manganese, cobalt or ruthenium complexes of porphyrins having hydrogen, haloalkyl or haloaryl groups in meso positions, two of the opposed meso atoms or groups being hydrogen or haloaryl, and two of the opposed meso atoms or groups being hydrogen or haloalkyl, but not all four of the meso atoms or groups being hydrogen. The invention also comprises new compositions of matter in which all four of the meso positions are substituted with haloalkyl groups and the beta positions are substituted with halogen atoms. A new method of synthesizing porphyrinogens is also provided. The novel compositions and others made according to the process of the invention are useful as hydrocarbon conversion catalysts; for example, for the oxidation of alkanes and the decomposition of hydroperoxides.

  2. Porphyrins

    DOE Patents [OSTI]

    Wijesekera, T.; Lyons, J.E.; Ellis, P.E. Jr.

    1996-11-05

    The invention comprises new compositions of matter, which are iron, manganese, cobalt or ruthenium complexes of porphyrins having hydrogen, haloalkyl or haloaryl groups in meso positions, two of the opposed meso atoms or groups being hydrogen or haloaryl, and two of the opposed meso atoms or groups being hydrogen or haloalkyl, but not all four of the meso atoms or groups being hydrogen. The invention also comprises new compositions of matter in which all four of the meso positions are substituted with haloalkyl groups and the beta positions are substituted with halogen atoms. A new method of synthesizing porphyrinogens is also provided. The novel compositions and others made according to the process of the invention are useful as hydrocarbon conversion catalysts; for example, for the oxidation of alkanes and the decomposition of hydroperoxides.

  3. Extrinsic anomalous Hall effect in epitaxial Mn{sub 4}N films

    SciTech Connect (OSTI)

    Meng, M.; Wu, S. X. Ren, L. Z.; Zhou, W. Q.; Wang, Y. J.; Wang, G. L.; Li, S. W.

    2015-01-19

    Anomalous Hall effect (AHE) in ferrimagnetic Mn{sub 4}N epitaxial films grown by molecular-beam epitaxy is investigated. The longitudinal conductivity σ{sub xx} is within the superclean regime, indicating Mn{sub 4}N is a highly conducting material. We further demonstrate that the AHE signal in 40-nm-thick films is mainly due to the extrinsic contributions based on the analysis fitted by ρ{sub AH}=a′ρ{sub xx0}+bρ{sub xx}{sup 2} and σ{sub AH}∝σ{sub xx}. Our study not only provide a strategy for further theoretical work on antiperovskite manganese nitrides but also shed promising light on utilizing their extrinsic AHE to fabricate spintronic devices.

  4. Local environment of Mn in Mn delta-doped Si layers

    SciTech Connect (OSTI)

    Xiao, Q.F.; Kahwaji, S.; Monchesky, T.L.; Gordon, R.A.; Crozier, E.D.

    2009-11-09

    Dilute magnetic semiconductors combine both magnetic ordering and semiconducting behaviour, leading to potential spintronic applications. Silicon containing dilute Mn impurities is a potential dilute magnetic semiconductor. We have grown Mn delta-doped films by deposition of 0.7 of a monolayer of Mn on Si(001) by molecular beam epitaxy and capping the film with Si. The magnetic properties are likely sensitive to the distribution of Mn on substitutional or interstitial sites and the formation of metallic precipitates. We have used polarization-dependent XAFS to examine the local structure. We compare to a thicker MnSi film grown on Si(111) and also examine the influence of lead on the manganese environment when used as a surfactant in the growth process.

  5. Enlarged Mn 3s splitting and room-temperature ferromagnetism in epitaxially grown oxygen doped Mn{sub 2}N{sub 0.86} films

    SciTech Connect (OSTI)

    Meng, M.; Wu, S. X. Ren, L. Z.; Zhou, W. Q.; Wang, Y. J.; Wang, G. L.; Li, S. W.

    2014-11-07

    Single-phase and oxygen doped Mn{sub 2}N{sub 0.86} thin films have been grown on MgO (111) by plasma-assisted molecular beam epitaxy. The films grow under tensile strain and, remarkably, they show ferromagnetic-like interactions at low temperature and ferromagnetic ordering agreed well with the Bloch-law T{sup 3/2} at room-temperature. We further demonstrate the enlarged Mn 3s splitting (6.46 eV) and its possible relation to the observed ferromagnetism. Our study not only provide a strategy for further theoretical work on oxygen doped manganese nitrides, but also shed promising light on utilizing its room-temperature FM property to fabricate spintronic devices.

  6. PROCESSES OF RECLAIMING URANIUM FROM SOLUTIONS

    DOE Patents [OSTI]

    Zumwalt, L.R.

    1959-02-10

    A process is described for reclaiming residual enriched uranium from calutron wash solutions containing Fe, Cr, Cu, Ni, and Mn as impurities. The solution is adjusted to a pH of between 2 and 4 and is contacted with a metallic reducing agent, such as iron or zinc, in order to reduce the copper to metal and thereby remove it from the solution. At the same time the uranium present is reduced to the uranous state The solution is then contacted with a precipitate of zinc hydroxide or barium carbonate in order to precipitate and carry uranium, iron, and chromium away from the nickel and manganese ions in the solution. The uranium is then recovered fronm this precipitate.

  7. Thermoelectric properties of nano-meso-micro β-MnO₂ powders as a function of electrical resistance

    DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)

    Hedden, Morgan; Francis, Nick; Haraldsen, Jason T.; Ahmed, Towfiq; Constantin, Costel

    2015-07-15

    Particle sizes of manganese oxide (β-MnO₂) powders were modified by using a mortar and pestle ground method for period of times that varied between 15–60 min. Particle size versus ground time clearly shows the existence of a size-induced regime transition (i.e., regime I and II). Thermoelectric properties of β-MnO₂ powders as a function of electrical resistance in the range of RP = 10 - 80Ω were measured. Based on the data presented, we propose a model for the β-MnO₂ system in which nanometer-scale MnO₂ crystallites bond together through weak van der Waals forces to form larger conglomerates that span inmore » size from nanometer to micrometer scale.« less

  8. Pyroprocessing of Oxidized Sodium-Bonded Fast Reactor Fuel -- an Experimental Study of Treatment Options for Degraded EBR-II Fuel

    SciTech Connect (OSTI)

    S. D. Herrmann; L. A. Wurth; N. J. Gese

    2013-09-01

    An experimental study was conducted to assess pyrochemical treatment options for degraded EBR-II fuel. As oxidized material, the degraded fuel would need to be converted back to metal to enable electrorefining within an existing electrometallurgical treatment process. A lithium-based electrolytic reduction process was studied to assess the efficacy of converting oxide materials to metal with a particular focus on the impact of zirconium oxide and sodium oxide on this process. Bench-scale electrolytic reduction experiments were performed in LiCl-Li2O at 650 C with combinations of manganese oxide (used as a surrogate for uranium oxide), zirconium oxide, and sodium oxide. The experimental study illustrated how zirconium oxide and sodium oxide present different challenges to a lithium-based electrolytic reduction system for conversion of select metal oxides to metal.

  9. Simulating Valence-to-Core X-ray Emission Spectroscopy of Transition Metal Complexes with Time-Dependent Density Functional Theory

    SciTech Connect (OSTI)

    Zhang, Yu; Mukamel, Shaul; Khalil, Munira; Govind, Niranjan

    2015-11-09

    Valence-to-core (VtC) X-ray emission spectroscopy (XES) has emerged as a power- ful technique for the structural characterization of complex organometallic compounds in realistic environments. Since the spectrum represents electronic transitions from the ligand molecular orbitals to the core holes of the metal centers, the approach is more chemically sensitive to the metal-ligand bonding character compared with con- ventional X-ray absorption techniques. In this paper we study how linear-response time-dependent density functional theory (LR-TDDFT) can be harnessed to simulate K-edge VtC X-ray emission spectra reliably. LR-TDDFT allows one to go beyond the single-particle picture that has been extensively used to simulate VtC-XES. We con- sider seven low- and high-spin model complexes involving chromium, manganese and iron transition metal centers. Our results are in good agreement with experiment.

  10. Composite catalyst for carbon monoxide and hydrocarbon oxidation

    DOE Patents [OSTI]

    Liu, W.; Flytzani-Stephanopoulos, M.

    1996-03-19

    A method and composition are disclosed for the complete oxidation of carbon monoxide and/or hydrocarbon compounds. The method involves reacting the carbon monoxide and/or hydrocarbons with an oxidizing agent in the presence of a metal oxide composite catalyst. The catalyst is prepared by combining fluorite-type oxygen ion conductors with active transition metals. The fluorite oxide, selected from the group consisting of cerium oxide, zirconium oxide, thorium oxide, hafnium oxide, and uranium oxide, and may be doped by alkaline earth and rare earth oxides. The transition metals, selected from the group consisting of molybdenum, copper, cobalt, manganese, nickel, and silver, are used as additives. The atomic ratio of transition metal to fluorite oxide is less than one.

  11. Steel bonded dense silicon nitride compositions and method for their fabrication

    DOE Patents [OSTI]

    Landingham, Richard L. (Livermore, CA); Shell, Thomas E. (Tracy, CA)

    1987-01-01

    A two-stage bonding technique for bonding high density silicon nitride and other ceramic materials to stainless steel and other hard metals, and multilayered ceramic-metal composites prepared by the technique are disclosed. The technique involves initially slurry coating a surface of the ceramic material at about 1500.degree. C. in a vacuum with a refractory material and the stainless steel is then pressure bonded to the metallic coated surface by brazing it with nickel-copper-silver or nickel-copper-manganese alloys at a temperature in the range of about 850.degree. to 950.degree. C. in a vacuum. The two-stage bonding technique minimizes the temperature-expansion mismatch between the dissimilar materials.

  12. Mesoporous Silica-Supported Metal Oxide-Promoted Rh Nanocatalyst for Selective Production of Ethanol from Syngas

    SciTech Connect (OSTI)

    George Kraus

    2010-09-30

    The objective is to develop a process that will convert synthesis gas from coal into ethanol and then transform the ethanol into hydrogen. Principal investigators from Iowa State University include Dr. George Kraus, Dr. Victor Lin, Marek Pruski, and Dr. Robert Brown. Task 1 involves catalyst development and catalyst scale up. Mesoporous manganese silicate mixed oxide materials will be synthesized, characterized and evaluated. The first-and secondgeneration catalysts have been prepared and scaled up for use in Task 2. The construction of a high-pressure reactor system for producing synthetic liquid fuel from simulated synthesis gas stream has been completed as the first step in Task 2. Using the first- and second generation catalysts, the reactor has demonstrated the production of synthetic liquid fuel from a simulated synthesis gas stream.

  13. Optimization of Rhodium-Based Catalysts for Mixed Alcohol Synthesis -- 2011 Progress Report

    SciTech Connect (OSTI)

    Gerber, Mark A.; Gray, Michel J.; Albrecht, Karl O.; Rummel, Becky L.

    2011-10-01

    Pacific Northwest National Laboratory has been conducting research to investigate the feasibility of producing mixed alcohols from biomass-derived synthesis gas (syngas). In recent years, this research has primarily involved the further development of catalysts containing rhodium and manganese based on the results of earlier catalyst screening tests. Research during FY 2011 continued to examine the performance of RhMn catalysts on alternative supports including selected zeolite, silica, and carbon supports. Catalyst optimization continued using both the Davisil 645 and Merck Grade 7734 silica supports. Research also was initiated in FY 2011, using the both Davisil 645 silica and Hyperion CS-02C-063 carbon supports, to evaluate the potential for further improving catalyst performance, through the addition of one or two additional metals as promoters to the catalysts containing Rh, Mn, and Ir.

  14. Porous desulfurization sorbent pellets containing a reactive metal oxide and an inert zirconium compound

    SciTech Connect (OSTI)

    Gardner, Todd H.; Gasper-Galvin, Lee D.

    1996-12-01

    Sorbent pellets for removing hydrogen sulfide from coal gas are prepared by combining a reactive oxide, in particular zinc oxide, with a zirconium compound such as an oxide, silicate, or aluminate of zirconium, and an inorganic binder and pelletizing and calcining the mixture. Alternately, the zinc oxide may be replaced by copper oxide or a combination of copper, molybdenum, and manganese oxides. The pellet components may be mixed in dry form, moistened to produce a paste, and converted to pellets by forming an aqueous slurry of the components and spray drying the slurry, or the reactive oxide may be formed on existing zirconium-containing catalyst-carrier pellets by infusing a solution of a salt of the active metal onto the existing pellets and firing at a high temperature to produce the oxide. Pellets made according to this invention show a high reactivity with hydrogen sulfide and durability such as to be useful over repeated cycles of sorption and regeneration.

  15. Array-type NH.sub.3 sensor

    DOE Patents [OSTI]

    West, David Lawrence; Montgomery, Frederick Charles; Armstrong, Timothy R; Warmack, Robert J

    2013-12-31

    An array-type sensor that senses NH.sub.3 includes non-Nernstian sensing elements constructed from metal and/or metal-oxide electrodes on an O.sub.2 ion conducting substrate. In one example sensor, one electrode may be made of platinum, another electrode may be made of manganese (III) oxide (Mn.sub.2O.sub.3), and another electrode may be made of tungsten trioxide (WO.sub.3). Some sensing elements may further include an electrode made of La.sub.0.6Sr.sub.0.4Co.sub.0.2Fe.sub0.8O.sub.3 and another electrode made of LaCr.sub.0.95.Mg.sub.0.05O.sub.3.

  16. Radiation resistant austenitic stainless steel alloys

    DOE Patents [OSTI]

    Maziasz, Philip J. (Oak Ridge, TN); Braski, David N. (Oak Ridge, TN); Rowcliffe, Arthur F. (Oak Ridge, TN)

    1989-01-01

    An austenitic stainless steel alloy, with improved resistance to radiation-induced swelling and helium embrittlement, and improved resistance to thermal creep at high temperatures, consisting essentially of, by weight percent: from 16 to 18% nickel; from 13 to 17% chromium; from 2 to 3% molybdenum; from 1.5 to 2.5% manganese; from 0.01 to 0.5% silicon; from 0.2 to 0.4% titanium; from 0.1 to 0.2% niobium; from 0.1 to 0.6% vanadium; from 0.06 to 0.12% carbon; from 0.01% to 0.03% nitrogen; from 0.03 to 0.08% phosphorus; from 0.005 to 0.01% boron; and the balance iron, and wherein the alloy may be thermomechanically treated to enhance physical and mechanical properties.

  17. Fight over fuel additive rekindled

    SciTech Connect (OSTI)

    Stringer, J.

    1996-03-20

    Ethyl and EPA are trading punches over EPA`s doubts about the safety of Ethyl`s gasoline additive methylcyclopentadienyl manganese (MMT). Late last week, EPA released a statement reaffirming its position that there has not been enough research on health effects of MMT and asking gas stations to label pumps that contain the additive so consumers will be aware they are using it. Responding to that statement, Ethyl has written Administrator Carol Browner asking why she appears to be supporting the Environmental Defense Fund`s (EDF; Washington) campaign against MMT and advocating the delay of the additive use in light of its known emission-reducing characteristics. The tension began in the early `90s, when the EPA refused to allow Ethyl to market MMT and required it to perform more long-term health studies. Last October a court ordered the agency to grant Ethyl approval to use MMT in nonreformulated gasoline.

  18. Literature review for oxalate oxidation processes and plutonium oxalate solubility

    SciTech Connect (OSTI)

    Nash, C. A.

    2015-10-01

    A literature review of oxalate oxidation processes finds that manganese(II)-catalyzed nitric acid oxidation of oxalate in precipitate filtrate is a viable and well-documented process. The process has been operated on the large scale at Savannah River in the past, including oxidation of 20 tons of oxalic acid in F-Canyon. Research data under a variety of conditions show the process to be robust. This process is recommended for oxalate destruction in H-Canyon in the upcoming program to produce feed for the MOX facility. Prevention of plutonium oxalate precipitation in filtrate can be achieved by concentrated nitric acid/ferric nitrate sequestration of oxalate. Organic complexants do not appear practical to sequester plutonium. Testing is proposed to confirm the literature and calculation findings of this review at projected operating conditions for the upcoming campaign.

  19. Protective coating on positive lithium-metal-oxide electrodes for lithium batteries

    DOE Patents [OSTI]

    Johnson, Christopher S.; Thackeray, Michael M.; Kahaian, Arthur J.

    2006-05-23

    A positive electrode for a non-aqueous lithium cell comprising a LiMn2-xMxO4 spinel structure in which M is one or more metal cations with an atomic number less than 52, such that the average oxidation state of the manganese ions is equal to or greater than 3.5, and in which 0.ltoreq.x.ltoreq.0.15, having one or more lithium spine oxide LiM'2O4 or lithiated spinel oxide Li1+yM'2O4 compounds on the surface thereof in which M' are cobalt cations and in which 0.ltoreq.y.ltoreq.1.

  20. Optimization of Rhodium-Based Catalysts for Mixed Alcohol Synthesis 2012 Progress Report

    SciTech Connect (OSTI)

    Gerber, Mark A.; Gray, Michel J.; Albrecht, Karl O.; Thompson, Becky L.

    2012-11-01

    Pacific Northwest National Laboratory has been conducting research to investigate the feasibility of producing mixed alcohols from biomass-derived synthesis gas (syngas). In recent years, this research has primarily involved the further development of catalysts containing rhodium and manganese based on the results of earlier catalyst screening tests. Testing continued in FY 2012 to further improve the Ir-promoted RhMn catalysts on both silica and carbon supports for producing mixed oxygenates from synthesis gas. This testing re-examined selected alternative silica and carbon supports to follow up on some uncertainties in the results with previous test results. Additional tests were conducted to further optimize the total and relative concentrations of Rh, Mn, and Ir, and to examine selected promoters and promoter combinations based on earlier results. To establish optimum operating conditions, the effects of the process pressure and the feed gas composition also were evaluated.

  1. Optimization of Rhodium-Based Catalysts for Mixed Alcohol Synthesis -- 2010 Progress Report

    SciTech Connect (OSTI)

    Gerber, Mark A.; Gray, Michel J.; Albrecht, Karl O.; White, J. F.; Rummel, Becky L.; Stevens, Don J.

    2010-10-01

    Pacific Northwest National Laboratory has been conducting research for the U.S. Department of Energy, Energy Efficiency Renewable Energy, Biomass Program to investigate the feasibility of producing mixed alcohols from biomass-derived synthesis gas. In recent years this research has primarily involved the further development of a silica-supported catalyst containing rhodium and manganese that was selected from earlier catalyst screening tests. A major effort during 2010 was to examine alternative catalyst supports to determine whether other supports, besides the Davisil 645 silica, would improve performance. Optimization of the Davisil 645 silica-supported catalyst also was continued with respect to candidate promoters iridium, platinum, and gallium, and examination of selected catalyst preparation and activation alternatives for the baseline RhMn/SiO2 catalyst.

  2. Proximity-induced magnetism in transition-metal substituted graphene

    SciTech Connect (OSTI)

    Crook, Charles B.; Constantin, Costel; Ahmed, Towfiq; Zhu, Jian -Xin; Balatsky, Alexander V.; Haraldsen, Jason T.

    2015-08-03

    We investigate the interactions between two identical magnetic impurities substituted into a graphene superlattice. Using a first-principles approach, we calculate the electronic and magnetic properties for transition-metal substituted graphene systems with varying spatial separation. These calculations are compared for three different magnetic impurities, manganese, chromium, and vanadium. We determine the electronic band structure, density of states, and Millikan populations (magnetic moment) for each atom, as well as calculate the exchange parameter between the two magnetic atoms as a function of spatial separation. We find that the presence of magnetic impurities establishes a distinct magnetic moment in the graphene lattice, where the interactions are highly dependent on the spatial and magnetic characteristic between the magnetic and carbon atoms, which leads to either ferromagnetic or antiferromagnetic behavior. Furthermore, through an analysis of the calculated exchange energies and partial density of states, it is determined that interactions between the magnetic atoms can be classified as an RKKY interaction.

  3. Enhanced ferroelectric properties and thermal stability of nonstoichiometric 0.92(Na{sub 0.5}Bi{sub 0.5})TiO{sub 3}-0.08(K{sub 0.5}Bi{sub 0.5})TiO{sub 3} single crystals

    SciTech Connect (OSTI)

    Zhang, Haiwu E-mail: hsluo@mail.sic.ac.cn; Chen, Chao; Deng, Hao; Li, Long; Graduate University of Chinese Academy of Sciences, Beijing 100049 ; Zhao, Xiangyong; Lin, Di; Li, Xiaobing; Ren, Bo; Luo, Haosu E-mail: hsluo@mail.sic.ac.cn; Yan, Jun

    2013-11-18

    Bi deficient, Mn doped 0.92(Na{sub 0.5}Bi{sub 0.5})TiO{sub 3}-0.08(K{sub 0.5}Bi{sub 0.5})TiO{sub 3} single crystals were grown by carefully controlled top-seeded solution growth method. Local structures were investigated by transmission electron microscopy. The site occupation and valence state of manganese were characterized by electron paramagnetic resonance spectrum. The leakage current density in the as-grown single crystals is effectively depressed. The introduced defect complexes suppress the temperature induced phase transformation, increasing the depolarization temperature (165?C) and thermal stability of ferroelectric properties.

  4. Health hazard evaluation report HETA 85-030-1693, Fruehauf Corporation - Parts Plant, Delphos, Ohio

    SciTech Connect (OSTI)

    Gorman, R.; Ehrenberg, R.; Hunninen, K.

    1986-06-01

    A request was received from union and management at the Fruehauf Corporations Parts Facility in Delphos, Ohio to evaluate possible exposures to total welding fume, metals, carbon-monoxide, oxides of nitrogen, and ozone during welding operations. Total welding fume concentrations in 32 personal breathing zone samples ranged from 1.5 to 23.4 milligrams per cubic meter (mg/m/sup 3/). Nine area samples ranged from 0.4 to 3.7mg/m/sup 3/. Three sample results exceeded OSHA standard of 15mg/m/sup 3/. Iron was the predominant metal found. Measurable quantities of aluminum, chromium, copper, magnesium, manganese, molybdenum, nickel, lead, tin, and vanadium were found. Results of a questionnaire, given to 33 of the 92 welders, indicated a relatively high prevalence of reported symptoms of mucous membrane and respiratory tract irritation, including eye irritation, sinus/nasal congestion, headaches, throat irritation and cough.

  5. Analysis of deformed palladium cathodes resulting from heavy water electrolysis

    SciTech Connect (OSTI)

    An, H.K.; Jeong, E.J.; Hong, J.H.; Lee, Y.

    1995-07-01

    Earlier experiments suggested that large differences in heat release between the two sides of a palladium electrode coated with gold on one side and manganese oxide on the other cause observed electrode deformation with high-pressure D{sub 2} gas loading in an electrolysis-like cell. Similar experiments were repeated using heavy water electrolysis. Palladium/titanium coatings on one side and gold coating on the other were made for the preparation of the palladium electrodes. Biaxial bending, partial discoloration, and microcracks of palladium electrodes were observed after 18 days of electrolysis. Analysis of the deformed palladium cathodes was performed. It was discovered that to convert this configuration to a practical energy-producing cell, a coating technique must be found to reduce outward diffusion of deuterium, i.e., to maintain a high D/Pd ratio over longer periods of time. 33 refs., 7 figs., 1 tab.

  6. Development of MnCoO Coating with New Aluminizing Process for Planar SOFC Stacks

    SciTech Connect (OSTI)

    Choi, Jung-Pyung; Weil, K. Scott; Chou, Y. S.; Stevenson, Jeffry W.; Yang, Zhenguo

    2011-03-22

    Low-cost, chromia-forming steels find widespread use in SOFCs at operating temperatures below 800C, because of their low thermal expansion mismatch and low cost. However, volatile Cr-containing species originating from this scale poison the cathode material in the cells and subsequently cause power degradation in the devices. To prevent this, a conductive manganese cobaltite coating has been developed. However, this coating is not compatible with forming hermetic seals between the interconnect or window frame component and ceramic cell. This coating reacts with sealing materials. Thus, a new aluminizing process has been developed for the sealing regions in these parts, as well as for other metallic stack and balance-of-plant components. From this development, the sealing performance and SOFC stack performance became very stable.

  7. Non-stoichiometric AB5 alloys for metal hydride electrodes

    DOE Patents [OSTI]

    Reilly, James J. (Bellport, NY); Adzic, Gordana D. (Setauket, NY); Johnson, John R. (Calverton, NY); Vogt, Thomas (Cold Spring Harbor, NY); McBreen, James (Bellport, NY)

    2001-01-01

    The present invention provides a non-stoichiometric alloy comprising a composition having the formula AB.sub.5+X an atomic ratio wherein A is selected from the group consisting of the rare earth metals, yttrium, mischmetal, or a combination thereof; B is nickel and tin, or nickel and tin and at least a third element selected from the group consisting of the elements in group IVA of the periodic table, aluminum, manganese, iron, cobalt, copper, antimony or a combination thereof; X is greater than 0 and less than or equal to about 2.0; and wherein at least one substituted A site is occupied by at least one of the B elements. An electrode incorporating said alloy and an electrochemical cell incorporating said electrode are also described.

  8. Eliminating Voltage Decay of Lithium-Rich Li1.14Mn0.54Ni0.14Co0.14O2 Cathodes by Controlling the Electrochemical Process

    SciTech Connect (OSTI)

    Wei, Z.; Zhu, Y.; Zhang, W.; Wang, F.; Zhang, Q.; Qiu, B.; Han, S.; Xia, Y.; Liu, Z.

    2015-03-27

    Lithium-rich material owns a particularly high capacity owing to the activation of electrochemical inactive Li2MnO3 phase. But at the same time, MnO2 phase formed after Li2MnO3 activation confronts a severe problem of converting to spinel phase, and resulting in voltage decay. To our knowledge, this phenomenon is inherent property of layered manganese oxide materials and can hardly be overcome. Based on this, unlike previous reports, herein we design a method for the first time to accelerate the phase transformation by tuning the charge upper-limit voltage at a high value, so the phase transformation process can be finished in a few cycles. Then material structure remains stable while cycling at a low upper-limit voltage. By this novel method voltage decay is eliminated significantly.

  9. Invited Article: In situ comparison of passive radon-thoron discriminative monitors at subsurface workplaces in Hungary

    SciTech Connect (OSTI)

    Kvsi, Norbert; Social Organization for Radioecological Cleanliness, Veszprm ; Vigh, Tams; Manganese Mining Process Ltd., rkt ; Nmeth, Csaba; University of Pannonia, Veszprm ; Ishikawa, Tetsuo; Omori, Yasutaka; Janik, Miroslaw; Yonehara, Hidenori

    2014-02-15

    During a one-year long measurement period, radon and thoron data obtained by two different passive radon-thoron discriminative monitors were compared at subsurface workplaces in Hungary, such as mines (bauxite and manganese ore) and caves (medical and touristic). These workplaces have special environmental conditions, such as, stable and high relative humidity (100%), relatively stable temperature (12C21C), low or high wind speed (max. 2.4 ms{sup ?1}) and low or elevated aerosol concentration (13060000 particles m{sup ?3}). The measured radon and thoron concentrations fluctuated in a wide range among the different workplaces. The respective annual average radon concentrations and their standard deviations (in brackets) measured by the passive radon-thoron discriminative monitor with cellulose filter (CF) and the passive radon-thoron discriminative monitor with sponge filter (SF) were: 350(321) Bqm{sup ?3} and 550(497) Bqm{sup ?3} in the bauxite mine; 887(604) Bqm{sup ?3} and 1258(788) Bqm{sup ?3} in the manganese ore mine; 2510(2341) Bqm{sup ?3} and 3403(3075) Bqm{sup ?3} in the medical cave (Hospital Cave of Tapolca); and 6239(2057) Bq m{sup ?3} and 8512(1955) Bqm{sup ?3} in the touristic cave (Lake Cave of Tapolca). The respective average thoron concentrations and their standard deviation (in brackets) measured by CF and SF monitors were: 154(210) Bqm{sup ?3} and 161(148) Bqm{sup ?3} in the bauxite mine; 187(191) Bqm{sup ?3} and 117(147) Bqm{sup ?3} in the manganese-ore mine; 360(524) Bqm{sup ?3} and 371(789) Bqm{sup ?3} in the medical cave (Hospital Cave of Tapolca); and 1420(1184) Bq m{sup ?3} and 1462(3655) Bqm{sup ?3} in the touristic cave (Lake Cave of Tapolca). Under these circumstances, comparison of the radon data for the SF and CF monitors showed the former were consistently 51% higher in the bauxite mine, 38% higher in the manganese ore mine, and 34% higher in the caves. Consequently, correction is required on previously obtained radon data acquired by CF monitors at subsurface workplaces to gain comparable data for SF monitors. In the case of thoron, the data were unreliable and no significant tendency was seen during the comparison therefore comparison of previously obtained thoron data acquired by either CF or SF is doubtful. There was probable influence by relative humidity on the detection response; however, the effects of the high wind speed and elevated aerosol concentration could not be excluded. The results of this study call attention to the importance of calibration under extreme environmental conditions and the need for using reliable radon-thoron monitors for subsurface workplaces.

  10. XRD and TEM characterization of cathodic MnO{sub 2} and discharge products in the Li-MnO{sub 2} cell

    SciTech Connect (OSTI)

    Shao, Y.; Hackney, S.A.; Cornilsen, B.C.

    1995-12-31

    The crystal structures of the undischarged, heat-treated electrolytic manganese dioxide (HEMD) and discharge products are characterized by high spatial resolution convergent beam electron diffraction (CBED). The results are compared with the x-ray diffraction (XRD) patterns characterized by broad, diffuse peaks. The CBED results for HEMD show that the starting cathodic material has the pyrolusite space group, but with a range of c/a ratios. The variability of the lattice parameter from grain to grain is found to coincide with the broadening on the low angle side of the XRD peaks. The CBED patterns of discharge products suggest a reduction range in c/a ratios and the formation of another phase.

  11. Precipitation hardenable iron-nickel-chromium alloy having good swelling resistance and low neutron absorbence

    DOE Patents [OSTI]

    Korenko, Michael K. (Richland, WA); Merrick, Howard F. (Suffern, NY); Gibson, Robert C. (Ringwood, NJ)

    1980-01-01

    An iron-nickel-chromium age-hardenable alloy suitable for use in fast breeder reactor ducts and cladding which utilizes the gamma-double prime strengthening phase and characterized in having a morphology of the gamma-double prime phase enveloping the gamma-prime phase and delta phase distributed at or near the grain boundaries. The alloy consists essentially of about 40-50% nickel, 7.5-14% chromium, 1.5-4% niobium, 0.25-0.75% silicon, 1-3% titanium, 0.1-0.5% aluminum, 0.02-0.1% carbon, 0.002-0.015% boron, and the balance iron. Up to 2% manganese and up to 0.01% magnesium may be added to inhibit trace element effects; up to 0.1% zirconium may be added to increase radiation swelling resistance; and up to 3% molybdenum may be added to increase strength.

  12. Bio-inspired Design of Electrocatalysts for Oxalate Oxidation: a Combined Experimental and Computational Study of Mn–N–C Catalysts

    SciTech Connect (OSTI)

    Matanovic, Ivana; Babanova, Sofia; Perry, Albert; Serov, Alexey; Artyushkova, Kateryna; Atanassov, Plamen

    2015-05-28

    We report a novel non-platinum group metal (non-PGM) catalyst derived from Mn and amino- antipyrine (MnAAPyr) that shows electrochemical activity towards the oxidation of oxalic acid comparable to Pt with an onset potential for oxalate oxidation measured to be 0.714 * 0.002 V vs. SHE at pH = 4. The material has been synthesized using a templating Sacrificial Support Method with manganese nitrate and 4-aminoantipyrine as precursors. This catalyst is a nano-structured material in which Mn is atomically dispersed on a nitrogendoped graphene matrix. XPS studies reveal high abundance of pyridinic, Mn–Nx, and pyrrolic nitrogen pointing towards the conclusion that pyridinic nitrogen atoms coordinated to manganese constitute the active centers. Thus, the main features of the MnAAPyr catalyst are it exhibits similarity to the active sites of naturally occurring enzymes that are capable of efficient and selective oxidation of oxalic acid. Density functional theory in plane wave formalism with Perdew, Burke and Ernzerhof functional was further used to study the stability and activity of different one-metal active centers that could exist in the catalyst. The results show that the stability of the Mn–Nx sites changes in the following order: MnN4 4 MnN3C 4 MnN2C2 4 MnN3. Based on the overpotentials of 0.64 V and 0.71 V vs. SHE, calculated using the free energy diagrams for the oxalate oxidation mechanism, we could conclude that the MnN3C and MnN2C2 sites are most probable Mn–Nx sites responsible for the reported catalytic activity of the new catalyst.

  13. Synthesis, crystal structure and properties of [(dien){sub 2}Mn]Ge{sub 2}S{sub 4} with mixed-valent Ge centers

    SciTech Connect (OSTI)

    Yue, Cheng-Yang; Yuan, Zhuang-Dong; Zhang, Lu-Ge; Wang, Ya-Bai; Liu, Guo-Dong; Gong, Liao-Kuo; Lei, Xiao-Wu

    2013-10-15

    One new manganese thiogermanate, [(dien){sub 2}Mn]Ge{sub 2}S{sub 4} (dien=diethylenetriamine), was prepared under mild solvothermal conditions and structurally and spectroscopically characterized. The title compound crystallizes in the orthorhombic system, chiral space group P2{sub 1}2{sub 1}2{sub 1} (no. 19) with a=9.113(4) Å, b=12.475(5) Å, c=17.077(7) Å, V=1941.5(15) Å{sup 3} and Z=4. Its structure features a three-dimensional (3D) network composed of a one-dimensional (1D) [Ge{sub 2}S{sub 4}]{sup 2−} anionic chain and a [(dien){sub 2}Mn]{sup 2+} complex interconnected via various hydrogen bonds. The most interesting structural feature of the compound is the presence of two different oxidation states of germanium centers in the 1D [Ge{sub 2}S{sub 4}]{sup 2−} chain, which is also supported by the result of X-ray photoelectron spectroscopy measurement. The optical property of the title compound has also been studied by UV–vis spectra. - Graphical abstract: One new thiogermanate, [(dien){sub 2}Mn]Ge{sub 2}S{sub 4}, contains a one-dimensional [Ge{sub 2}S{sub 4}]{sup 2−} anionic chain with two different oxidation states of germanium centers. Display Omitted - Highlights: • One new manganese thiogermanate [(dien){sub 2}Mn]Ge{sub 2}S{sub 4} was prepared. • The compound features 1D [Ge{sub 2}S{sub 4}]{sup 2−} chain composed of [Ge{sup II}S{sub 4}] and [Ge{sup IV}S{sub 4}] tetrahedra. • The first example of inorganic–organic hybrid thiogermanates with mixed valent Ge centers.

  14. Effect of Mn doping on structural and magnetic susceptibility of C-type rare earth nano oxides Er{sub 2?x}Mn{sub x}O{sub 3}

    SciTech Connect (OSTI)

    Heiba, Zein K.; Taif University, Faculty of Science, Physics Department ; Mohamed, Mohamed Bakr; Fuess, H.

    2012-12-15

    Graphical abstract: Display Omitted Highlights: ? Er{sub 2?x}Mn{sub x}O{sub 3} (0.0 ? x ? 0.20) prepared by solgel method. ? The change in lattice parameter is not linear with x due to the change in crystallite size with doping. ? Anomalous concentration dependence is found in magnetic susceptibility. ? The effective magnetic moment ?{sub eff} is found to decrease with composition parameter x. ? Superexchange interactions between Er ions depending on the amount of Mn or Er in different sites. -- Abstract: The manganese doped rare earth oxides Er{sub 2?x}Mn{sub x} O{sub 3} (0.0 ? x ? 0.20) were synthesized by a solgel process and analyzed by X-ray diffraction using Rietveld refinement methods. A single phase solid solution is formed up to x = 0.15 while for x ? 0.2 a manganese oxide phase appears in the diffraction pattern. Preferential cationic distribution between the non-equivalent sites 8b and 24d of space group Ia3{sup } is found for all samples but to a different extent. The octahedral volume and average bond length of Er{sub 1}-O for 8b site decrease while both octahedral volume and bond length of Er{sub 2}-O for 24d site increase. Magnetization measurements were done in the temperature range 5300 K. The effective magnetic moment ?{sub eff} is found to decrease with composition parameter x, except for sample x = 0.05 where the magnetization is enhanced. The Curie-Weiss paramagnetic temperatures indicate antiferromagnetic interaction.

  15. Process for separation of zirconium-88, rubidium-83 and yttrium-88

    DOE Patents [OSTI]

    Heaton, Richard C.; Jamriska, Sr., David J.; Taylor, Wayne A.

    1994-01-01

    A process for selective separation of strontium-82 and strontium-85 from proton irradiated molybdenum targets is provided and includes dissolving the molybdenum target in a hydrogen peroxide solution to form a first ion-containing solution, passing the first ion-containing solution through a first cationic resin whereby ions selected from the group consisting of molybdenum, niobium, technetium, selenium, vanadium, arsenic, germanium, zirconium and rubidium remain in the first ion-containing solution while ions selected from the group consisting of rubidium, zinc, beryllium, cobalt, iron, manganese, chromium, strontium, yttrium and zirconium are selectively adsorbed by the first resin, contacting the first resin with an acid solution capable of stripping adsorbed ions from the first cationic exchange resin whereby the adsorbed ions are removed from the first resin to form a second ion-containing solution, evaporating the second ion-containing solution for time sufficient to remove substantially all of the acid and water from the second ion-containing solution whereby a residue remains, dissolving the residue from the evaporated second-ion containing solution in a dilute acid to form a third ion-containing solution, said third ion-containing solution having an acid molarity adapted to permit said ions to be adsorbed by a cationic exchange resin, passing the third ion-containing solution through a second cationic resin whereby the ions are adsorbed by the second resin, contacting the second resin with a dilute sulfuric acid solution whereby the adsorbed ions selected from the group consisting of rubidium, zinc, beryllium, cobalt, iron, manganese, chromium, and zirconium are selectively removed from the second resin, and contacting the second resin with a dilute acid solution whereby the adsorbed strontium ions are selectively removed. Zirconium, rubidium, and yttrium radioisotopes can also be recovered with additional steps.

  16. Material and Energy Flows in the Materials Production, Assembly, and End-of-Life Stages of the Automotive Lithium-Ion Battery Life Cycle

    SciTech Connect (OSTI)

    Dunn, Jennifer B.; Gaines, Linda; Barnes, Matthew; Sullivan, John L.; Wang, Michael

    2014-01-01

    This document contains material and energy flows for lithium-ion batteries with an active cathode material of lithium manganese oxide (LiMn₂O₄). These data are incorporated into Argonne National Laboratory’s Greenhouse gases, Regulated Emissions, and Energy use in Transportation (GREET) model, replacing previous data for lithium-ion batteries that are based on a nickel/cobalt/manganese (Ni/Co/Mn) cathode chemistry. To identify and determine the mass of lithium-ion battery components, we modeled batteries with LiMn₂O₄ as the cathode material using Argonne’s Battery Performance and Cost (BatPaC) model for hybrid electric vehicles, plug-in hybrid electric vehicles, and electric vehicles. As input for GREET, we developed new or updated data for the cathode material and the following materials that are included in its supply chain: soda ash, lime, petroleum-derived ethanol, lithium brine, and lithium carbonate. Also as input to GREET, we calculated new emission factors for equipment (kilns, dryers, and calciners) that were not previously included in the model and developed new material and energy flows for the battery electrolyte, binder, and binder solvent. Finally, we revised the data included in GREET for graphite (the anode active material), battery electronics, and battery assembly. For the first time, we incorporated energy and material flows for battery recycling into GREET, considering four battery recycling processes: pyrometallurgical, hydrometallurgical, intermediate physical, and direct physical. Opportunities for future research include considering alternative battery chemistries and battery packaging. As battery assembly and recycling technologies develop, staying up to date with them will be critical to understanding the energy, materials, and emissions burdens associated with batteries.

  17. Material and energy flows in the materials production, assembly, and end-of-life stages of the automotive lithium-ion battery life cycle

    SciTech Connect (OSTI)

    Dunn, J.B.; Gaines, L.; Barnes, M.; Wang, M.; Sullivan, J.

    2012-06-21

    This document contains material and energy flows for lithium-ion batteries with an active cathode material of lithium manganese oxide (LiMn{sub 2}O{sub 4}). These data are incorporated into Argonne National Laboratory's Greenhouse gases, Regulated Emissions, and Energy use in Transportation (GREET) model, replacing previous data for lithium-ion batteries that are based on a nickel/cobalt/manganese (Ni/Co/Mn) cathode chemistry. To identify and determine the mass of lithium-ion battery components, we modeled batteries with LiMn{sub 2}O{sub 4} as the cathode material using Argonne's Battery Performance and Cost (BatPaC) model for hybrid electric vehicles, plug-in hybrid electric vehicles, and electric vehicles. As input for GREET, we developed new or updated data for the cathode material and the following materials that are included in its supply chain: soda ash, lime, petroleum-derived ethanol, lithium brine, and lithium carbonate. Also as input to GREET, we calculated new emission factors for equipment (kilns, dryers, and calciners) that were not previously included in the model and developed new material and energy flows for the battery electrolyte, binder, and binder solvent. Finally, we revised the data included in GREET for graphite (the anode active material), battery electronics, and battery assembly. For the first time, we incorporated energy and material flows for battery recycling into GREET, considering four battery recycling processes: pyrometallurgical, hydrometallurgical, intermediate physical, and direct physical. Opportunities for future research include considering alternative battery chemistries and battery packaging. As battery assembly and recycling technologies develop, staying up to date with them will be critical to understanding the energy, materials, and emissions burdens associated with batteries.

  18. 100th anniversary special paper: Sedimentary mineral deposits and the evolution of earth's near-surface environments

    SciTech Connect (OSTI)

    Holland, H.D. [Harvard University, Cambridge, MA (United States). Dept. of Earth & Planetary Science

    2005-12-15

    The nature of sedimentary mineral deposits has evolved during Earth's history in concert with changes in the oxidation (redo) state of the ocean-atmosphere system, biological evolution, and the growing importance of geologically young accumulations of ore-grade material. There is now strong evidence that the atmosphere and the oceans were anoxic, or essentially anoxic, before 2.4 Ga. Banded iron formations (BIF) and the detrital uranium ores formed prior to 2.4 Ga are consistent with such a state. The period between 2.4 and 2.0 Ga is called the Great Oxidation Event by some. Its ores bear unmistakable marks of the presence of atmospheric O{sub 2}. Between 1.8 and 0.8 Ga the Earth system seems to have been remarkably stable. Sedimentary ore deposits of this period were influenced by the presence of O{sub 2}. BIF, sedimentary manganese, and phosphorites disappeared ca. 1.8 Ga, but sedimentary exhalative (SEDEX) deposits and unconformity-type uranium deposits flourished, and nonsulfide zinc deposits put in an appearance. The period between 0.8 Ga and the end of the Proterozoic at 0.54 Ga was as turbulent or more so than the Paleoproterozoic. BIF returned, as did sedimentary manganese deposits and phosphorites. A further rise in the O{sub 2} content of the atmosphere and an increase in the sulfate concentration of seawater during this period brought the composition of the atmosphere and of seawater close to their present redox state. The last 540 m.y. of Earth's history have seen the system pass through two supercycles of roughly equal length. Climate, the redox stratification of the oceans ocean mixing, and the nature of sedimentary ores were influenced by tectonically and volcanically driven changes during these supercycles. The evolution of the higher land plants gave rise to coal deposits and sandstone-type uranium ores and was important for the formation of bauxites.

  19. Investigation of the relationship between particulate-bound mercury and properties of fly ash in a full-scale 100 MWe pulverized coal combustion boiler

    SciTech Connect (OSTI)

    Sen Li; Chin-Min Cheng; Bobby Chen; Yan Cao; Jacob Vervynckt; Amanda Adebambo; Wei-Ping Pan

    2007-12-15

    The properties of fly ash in coal-fired boilers influence the emission of mercury from power plants into the environment. In this study, seven different bituminous coals were burned in a full-scale 100 MWe pulverized coal combustion boiler and the derived fly ash samples were collected from a mechanical hopper (MH) and an electrostatic precipitator hopper (ESP). The mercury content, specific surface area (SSA), unburned carbon, and elemental composition of the fly ash samples were analyzed to evaluate the correlation between the concentration of particulate-bound mercury and the properties of coal and fly ash. For a given coal, it was found that the mercury content in the fly ash collected from the ESP was greater than in the fly ash samples collected from the MHP. This phenomenon may be due to a lower temperature of flue gas at the ESP (about 135{sup o}C) compared to the temperature at the air preheater (about 350{sup o}C). Also, a significantly lower SSA observed in MH ash might also contribute to the observation. A comparison of the fly ash samples generated from seven different coals using statistical methods indicates that the mercury adsorbed on ESP fly ashes has a highly positive correlation with the unburned carbon content, manganese content, and SSA of the fly ash. Sulfur content in coal showed a significant negative correlation with the Hg adsorption. Manganese in fly ash is believed to participate in oxidizing volatile elemental mercury (Hg{sup 0}) to ionic mercury (Hg{sup 2+}). The oxidized mercury in flue gas can form a complex with the fly ash and then get removed before the flue gas leaves the stack of the boiler.

  20. Comparative genomics of the white-rot fungi, Phanerochaete carnosa and P. chrysosporium, to elucidate the genetic basis of the distinct wood types they colonize

    SciTech Connect (OSTI)

    Suzuki, Hitoshi; MacDonald, Jacqueline; Syed, Khajamohiddin; Salamov, Asaf; Hori, Chiaki; Aerts, Andrea; Henrissat, Bernard; Wiebenga, Ad; vanKuyk, Patricia A.; Barry, Kerrie; Lindquist, Erika; LaButti, Kurt; Lapidus, Alla; Lucas, Susan; Coutinho, Pedro; Gong, Yunchen; Samejima, Masahiro; Mahadevan, Radhakrishnan; Abou-Zaid, Mamdouh; de Vries, Ronald P.; Igarashi, Kiyohiko; Yadav, Jagit S.; Grigoriev, Igor V.; Master, Emma R.

    2012-02-17

    Background Softwood is the predominant form of land plant biomass in the Northern hemisphere, and is among the most recalcitrant biomass resources to bioprocess technologies. The white rot fungus, Phanerochaete carnosa, has been isolated almost exclusively from softwoods, while most other known white-rot species, including Phanerochaete chrysosporium, were mainly isolated from hardwoods. Accordingly, it is anticipated that P. carnosa encodes a distinct set of enzymes and proteins that promote softwood decomposition. To elucidate the genetic basis of softwood bioconversion by a white-rot fungus, the present study reports the P. carnosa genome sequence and its comparative analysis with the previously reported P. chrysosporium genome. Results P. carnosa encodes a complete set of lignocellulose-active enzymes. Comparative genomic analysis revealed that P. carnosa is enriched with genes encoding manganese peroxidase, and that the most divergent glycoside hydrolase families were predicted to encode hemicellulases and glycoprotein degrading enzymes. Most remarkably, P. carnosa possesses one of the largest P450 contingents (266 P450s) among the sequenced and annotated wood-rotting basidiomycetes, nearly double that of P. chrysosporium. Along with metabolic pathway modeling, comparative growth studies on model compounds and chemical analyses of decomposed wood components showed greater tolerance of P. carnosa to various substrates including coniferous heartwood. Conclusions The P. carnosa genome is enriched with genes that encode P450 monooxygenases that can participate in extractives degradation, and manganese peroxidases involved in lignin degradation. The significant expansion of P450s in P. carnosa, along with differences in carbohydrate- and lignin-degrading enzymes, could be correlated to the utilization of heartwood and sapwood preparations from both coniferous and hardwood species.

  1. Free radicals induced in aqueous solution by non-contact atmospheric-pressure cold plasma

    SciTech Connect (OSTI)

    Tani, Atsushi; Fukui, Satoshi; Ono, Yusuke; Kitano, Katsuhisa; Ikawa, Satoshi

    2012-06-18

    To understand plasma-induced chemical processing in liquids, we investigated the formation of free radicals in aqueous solution exposed to different types of non-contact atmospheric-pressure helium plasma using the spin-trapping technique. Both hydroxyl radical (OH{center_dot}) and superoxide anion radical (O{sub 2}{sup -}{center_dot}) adducts were observed when neutral oxygen gas was additionally supplied to the plasma. In particular, O{sub 2}{sup -}{center_dot} can be dominantly induced in the solution via oxygen flow into the afterglow gas of helium plasma. This type of plasma treatment can potentially be used in medical applications to control infectious diseases, because the O{sub 2}{sup -}{center_dot} is crucial for sterilization of liquids via atmospheric-pressure plasma.

  2. Surface species produced in the radiolysis of zirconia nanoparticles

    SciTech Connect (OSTI)

    Carrasco-Flores, Eduardo A.; LaVerne, Jay A.

    2007-12-21

    Modifications to water-zirconia nanoparticle interfaces induced by {gamma} irradiation have been examined using diffuse reflection infrared Fourier transform (DRIFT), Raman scattering, and electron paramagnetic resonance (EPR) techniques. Spectroscopy with in situ heating was used to probe variations in the dissociatively bound chemisorbed water on the zirconia nanoparticles following evaporation of the physisorbed water. DRIFT spectra show that the bridged Zr-OH-Zr species decreases relative to the terminal Zr-OH species upon irradiation. No variation is observed with Raman scattering, indicating that the zirconia morphology is unchanged. EPR measurements suggest the possible formation of the superoxide ion, presumably by modification of the surface OH groups. Trapped electrons and interstitial H atoms are also observed by EPR.

  3. THERMOCHEMICAL HEAT STORAGE FOR CONCENTRATED SOLAR POWER

    SciTech Connect (OSTI)

    PROJECT STAFF

    2011-10-31

    Thermal energy storage (TES) is an integral part of a concentrated solar power (CSP) system. It enables plant operators to generate electricity beyond on sun hours and supply power to the grid to meet peak demand. Current CSP sensible heat storage systems employ molten salts as both the heat transfer fluid and the heat storage media. These systems have an upper operating temperature limit of around 400 C. Future TES systems are expected to operate at temperatures between 600 C to 1000 C for higher thermal efficiencies which should result in lower electricity cost. To meet future operating temperature and electricity cost requirements, a TES concept utilizing thermochemical cycles (TCs) based on multivalent solid oxides was proposed. The system employs a pair of reduction and oxidation (REDOX) reactions to store and release heat. In the storage step, hot air from the solar receiver is used to reduce the oxidation state of an oxide cation, e.g. Fe3+ to Fe2+. Heat energy is thus stored as chemical bonds and the oxide is charged. To discharge the stored energy, the reduced oxide is re-oxidized in air and heat is released. Air is used as both the heat transfer fluid and reactant and no storage of fluid is needed. This project investigated the engineering and economic feasibility of this proposed TES concept. The DOE storage cost and LCOE targets are $15/kWh and $0.09/kWh respectively. Sixteen pure oxide cycles were identified through thermodynamic calculations and literature information. Data showed the kinetics of re-oxidation of the various oxides to be a key barrier to implementing the proposed concept. A down selection was carried out based on operating temperature, materials costs and preliminary laboratory measurements. Cobalt oxide, manganese oxide and barium oxide were selected for developmental studies to improve their REDOX reaction kinetics. A novel approach utilizing mixed oxides to improve the REDOX kinetics of the selected oxides was proposed. It partially replaces some of the primary oxide cations with selected secondary cations. This causes a lattice charge imbalance and increases the anion vacancy density. Such vacancies enhance the ionic mass transport and lead to faster re-oxidation. Reoxidation fractions of Mn3O4 to Mn2O3 and CoO to Co3O4 were improved by up to 16 fold through the addition of a secondary oxide. However, no improvement was obtained in barium based mixed oxides. In addition to enhancing the short term re-oxidation kinetics, it was found that the use of mixed oxides also help to stabilize or even improve the TES properties after long term thermal cycling. Part of this improvement could be attributed to a reduced grain size in the mixed oxides. Based on the measurement results, manganese-iron, cobalt-aluminum and cobalt iron mixed oxides have been proposed for future engineering scale demonstration. Using the cobalt and manganese mixed oxides, we were able to demonstrate charge and discharge of the TES media in both a bench top fixed bed and a rotary kiln-moving bed reactor. Operations of the fixed bed configuration are straight forward but require a large mass flow rate and higher fluid temperature for charging. The rotary kiln makes direct solar irradiation possible and provides significantly better heat transfer, but designs to transport the TES oxide in and out of the reactor will need to be defined. The final reactor and system design will have to be based on the economics of the CSP plant. A materials compatibility study was also conducted and it identified Inconel 625 as a suitable high temperature engineering material to construct a reactor holding either cobalt or manganese mixed oxides. To assess the economics of such a CSP plant, a packed bed reactor model was established as a baseline. Measured cobalt-aluminum oxide reaction kinetics were applied to the model and the influences of bed properties and process parameters on the overall system design were investigated. The optimal TES system design was found to be a network of eight fixed bed reactors at 18.75 MWth each with charge and discharge temperatures between 1200 C and 600 C, which provides a constant output temperature of 900 C. The charge and discharge time are 8 hours each respectively. This design was integrated into a process flowsheet of a CSP plant and the system's economics were determined using AspenPlus and NREL's Solar Advisory Model. Storage cost is very sensitive to materials cost and was calculated to be based around $40/kWh for cobalt based mixed oxide. It can potentially decrease to $10/kWh based on reduced materials cost on a bulk scale. The corresponding calculated LCOE was between $0.22 and 0.30/kW-h. The high LCOE is a result of the high charging temperature required in this first design and the cost of cobalt oxide. It is expected that a moving bed reactor using manganese oxide will significantly improve the economics of the proposed concept.

  4. REMOVING SLUDGE HEELS FROM SAVANNAH RIVER SITE WASTE TANKS BY OXALIC ACID DISSOLUTION

    SciTech Connect (OSTI)

    Poirier, M; David Herman, D; Fernando Fondeur, F; John Pareizs, J; Michael Hay, M; Bruce Wiersma, B; Kim Crapse, K; Thomas Peters, T; Samuel Fink, S; Donald Thaxton, D

    2009-03-01

    The Savannah River Site (SRS) will remove sludge as part of waste tank closure operations. Typically the bulk sludge is removed by mixing it with supernate to produce a slurry, and transporting the slurry to a downstream tank for processing. Experience shows that a residual heel may remain in the tank that cannot be removed by this conventional technique. In the past, SRS used oxalic acid solutions to disperse or dissolve the sludge heel to complete the waste removal. To better understand the actual conditions of oxalic acid cleaning of waste from carbon steel tanks, the authors developed and conducted an experimental program to determine its effectiveness in dissolving sludge, the hydrogen generation rate, the generation rate of other gases, the carbon steel corrosion rate, the impact of mixing on chemical cleaning, the impact of temperature, and the types of precipitates formed during the neutralization process. The test samples included actual SRS sludge and simulated SRS sludge. The authors performed the simulated waste tests at 25, 50, and 75 C by adding 8 wt % oxalic acid to the sludge over seven days. They conducted the actual waste tests at 50 and 75 C by adding 8 wt % oxalic acid to the sludge as a single batch. Following the testing, SRS conducted chemical cleaning with oxalic acid in two waste tanks. In Tank 5F, the oxalic acid (8 wt %) addition occurred over seven days, followed by inhibited water to ensure the tank contained enough liquid to operate the mixer pumps. The tank temperature during oxalic acid addition and dissolution was approximately 45 C. The authors analyzed samples from the chemical cleaning process and compared it with test data. The conclusions from the work are: (1) Oxalic acid addition proved effective in dissolving sludge heels in the simulant demonstration, the actual waste demonstration, and in SRS Tank 5F. (2) The oxalic acid dissolved {approx} 100% of the uranium, {approx} 100% of the iron, and {approx} 40% of the manganese during a single contact in the simulant demonstration. (The iron dissolution may be high due to corrosion of carbon steel coupons.) (3) The oxalic acid dissolved {approx} 80% of the uranium, {approx} 70% of the iron, {approx} 50% of the manganese, and {approx} 90% of the aluminum in the actual waste demonstration for a single contact. (4) The oxalic acid dissolved {approx} 100% of the uranium, {approx} 15% of the iron, {approx} 40% of the manganese, and {approx} 80% of the aluminum in Tank 5F during the first contact cycle. Except for the iron, these results agree well with the demonstrations. The data suggest that a much larger fraction of the iron in the sludge dissolved, but it re-precipitated with the oxalate added to Tank 5F. (5) The demonstrations produced large volumes (i.e., 2-14 gallons of gas/gallon of oxalic acid) of gas (primarily carbon dioxide) by the reaction of oxalic acid with sludge and carbon steel. (6) The reaction of oxalic acid with carbon steel produced hydrogen in the simulant and actual waste demonstrations. The volume produced varied from 0.00002-0.00100 ft{sup 3} hydrogen/ft{sup 2} carbon steel. The hydrogen production proved higher in unmixed tanks than in mixed tanks.

  5. Superacid catalysis of light hydrocarbon conversion. DOE PETC fourth quarterly report, May 25, 1994--August 24, 1994

    SciTech Connect (OSTI)

    Gates, B.C.

    1995-12-31

    The primary goal of this project is to evaluate the potential value of solid superacid catalysts of the sulfated zirconia type for light hydrocarbon conversion. The key experiments include testing of the performance of such catalysts in a flow reactor fed with streams containing, for example, n-butane or propane. A solid superacid catalyst was prepared by addition of iron and manganese to sulfated zirconium hydroxide followed by calcination. The catalyst was tested for n-butane conversion in a packed-bed flow reactor at temperatures of 40 to 225{degrees}C with the reactant partial pressure in the range of 0.0025-0.01 attn. The predominant catalytic reaction was n-butane isomerization, and this was accompanied at 40{degrees}C by near stoichiometric disproportionation. The C3/C5 molar ratio was generally greater than 1, consistent with conversion of the secondary C5 products. As the temperature increased, the selectivity for isomerization decreased and that for disproportionation increased. In a typical experiment the activity of the catalyst increased for about 1 h on stream and then declined rapidly. The rate maxima as a function of time on stream were taken as a measure of the initial activity of the catalyst. For example, the approximate rate of isomerization of n-butane at the maximum was 4.3 x 10-8 mol/(g of catalyst {center_dot} s) with a feed n-butane partial pressure of 0.0025 atm at 75{degrees}C. With a feed n-butane partial pressure of 0.005 atm at 40{degrees}C and a conversion of 1 1%, the molar ratio of propane to i-butane was 0.03, and with the same feed composition at 100{degrees}C, this ratio at a conversion of 50% was 0.1. The iron- and manganese-promoted solid superacid catalyst is potentially of value for practical low-temperature paraffin isomerization accompanied by disproportionation of n-butane.

  6. Intercalation compounds and electrodes for batteries

    DOE Patents [OSTI]

    Chiang, Yet-Ming; Sadoway, Donald R.; Jang, Young-Il; Huang, Biyan

    2004-09-07

    This invention concerns intercalation compounds and in particular lithium intercalation compounds which have improved properties for use in batteries. Compositions of the invention include particulate metal oxide material having particles of multicomponent metal oxide, each including an oxide core of at least first and second metals in a first ratio, and each including a surface coating of metal oxide or hydroxide that does not include the first and second metals in the first ratio formed by segregation of at least one of the first and second metals from the core. The core may preferably comprise Li.sub.x M.sub.y N.sub.z O.sub.2 wherein M and N are metal atom or main group elements, x, y and z are numbers from about 0 to about 1 and y and z are such that a formal charge on M.sub.y N.sub.z portion of the compound is (4-x), and having a charging voltage of at least about 2.5V. The invention may also be characterized as a multicomponent oxide microstructure usable as a lithium intercalation material including a multiphase oxide core and a surface layer of one material, which is a component of the multiphase oxide core, that protects the underlying intercalation material from chemical dissolution or reaction. In a particular preferred example the multicomponent oxide may be an aluminum-doped lithium manganese oxide composition. Such aluminum-doped lithium manganese oxide compositions, having an orthorhombic structure, also form a part of the invention. In addition, the invention includes articles, particularly electrodes, for batteries formed from the compositions of the invention, and batteries including such electrodes. The invention further relates to a composite intercalation material comprising at least two compounds in which at least one compound has an orthorhombic structure Li.sub.x Al.sub.y Mn.sub.1-y O.sub.2, where y is nonzero, or a mixture of orthorhombic and monoclinic Li.sub.x Al.sub.y Mn.sub.1-y O.sub.2.

  7. High Energy Batteries for Hybrid Buses

    SciTech Connect (OSTI)

    Bruce Lu

    2010-12-31

    EnerDel batteries have already been employed successfully for electric vehicle (EV) applications. Compared to EV applications, hybrid electric vehicle (HEV) bus applications may be less stressful, but are still quite demanding, especially compared to battery applications for consumer products. This program evaluated EnerDel cell and pack system technologies with three different chemistries using real world HEV-Bus drive cycles recorded in three markets covering cold, hot, and mild climates. Cells were designed, developed, and fabricated using each of the following three chemistries: (1) Lithium nickel manganese cobalt oxide (NMC) - hard carbon (HC); (2) Lithium manganese oxide (LMO) - HC; and (3) LMO - lithium titanium oxide (LTO) cells. For each cell chemistry, battery pack systems integrated with an EnerDel battery management system (BMS) were successfully constructed with the following features: real time current monitoring, cell and pack voltage monitoring, cell and pack temperature monitoring, pack state of charge (SOC) reporting, cell balancing, and over voltage protection. These features are all necessary functions for real-world HEV-Bus applications. Drive cycle test data was collected for each of the three cell chemistries using real world drive profiles under hot, mild, and cold climate conditions representing cities like Houston, Seattle, and Minneapolis, respectively. We successfully tested the battery packs using real-world HEV-Bus drive profiles under these various climate conditions. The NMC-HC and LMO-HC based packs successfully completed the drive cycles, while the LMO-LTO based pack did not finish the preliminary testing for the drive cycles. It was concluded that the LMO-HC chemistry is optimal for the hot or mild climates, while the NMC-HC chemistry is optimal for the cold climate. In summary, the objectives were successfully accomplished at the conclusion of the project. This program provided technical data to DOE and the public for assessing EnerDel technology, and helps DOE to evaluate the merits of underlying technology. The successful completion of this program demonstrated the capability of EnerDel battery packs to satisfactorily supply all power and energy requirements of a real-world HEV-Bus drive profile. This program supports green solutions to metropolitan public transportation problems by demonstrating the effectiveness of EnerDel lithium ion batteries for HEV-Bus applications.

  8. IMPACT OF NOBLE METALS AND MERCURY ON HYDROGEN GENERATION DURING HIGH LEVEL WASTE PRETREATMENT AT THE SAVANNAH RIVER SITE

    SciTech Connect (OSTI)

    Stone, M; Tommy Edwards, T; David Koopman, D

    2009-03-03

    The Defense Waste Processing Facility (DWPF) at the Savannah River Site vitrifies radioactive High Level Waste (HLW) for repository internment. The process consists of three major steps: waste pretreatment, vitrification, and canister decontamination/sealing. HLW consists of insoluble metal hydroxides (primarily iron, aluminum, calcium, magnesium, manganese, and uranium) and soluble sodium salts (carbonate, hydroxide, nitrite, nitrate, and sulfate). The pretreatment process in the Chemical Processing Cell (CPC) consists of two process tanks, the Sludge Receipt and Adjustment Tank (SRAT) and the Slurry Mix Evaporator (SME) as well as a melter feed tank. During SRAT processing, nitric and formic acids are added to the sludge to lower pH, destroy nitrite and carbonate ions, and reduce mercury and manganese. During the SME cycle, glass formers are added, and the batch is concentrated to the final solids target prior to vitrification. During these processes, hydrogen can be produced by catalytic decomposition of excess formic acid. The waste contains silver, palladium, rhodium, ruthenium, and mercury, but silver and palladium have been shown to be insignificant factors in catalytic hydrogen generation during the DWPF process. A full factorial experimental design was developed to ensure that the existence of statistically significant two-way interactions could be determined without confounding of the main effects with the two-way interaction effects. Rh ranged from 0.0026-0.013% and Ru ranged from 0.010-0.050% in the dried sludge solids, while initial Hg ranged from 0.5-2.5 wt%, as shown in Table 1. The nominal matrix design consisted of twelve SRAT cycles. Testing included: a three factor (Rh, Ru, and Hg) study at two levels per factor (eight runs), three duplicate midpoint runs, and one additional replicate run to assess reproducibility away from the midpoint. Midpoint testing was used to identify potential quadratic effects from the three factors. A single sludge simulant was used for all tests and was spiked with the required amount of noble metals immediately prior to performing the test. Acid addition was kept effectively constant except to compensate for variations in the starting mercury concentration. SME cycles were also performed during six of the tests.

  9. Oxidase uncoupling in heme monooxygenases: Human cytochrome P450 CYP3A4 in Nanodiscs

    SciTech Connect (OSTI)

    Grinkova, Yelena V.; Denisov, Ilia G.; McLean, Mark A.; Sligar, Stephen G.

    2013-01-25

    Highlights: ? Substantial reducing equivalents are lost in human P450 CYP3A4 via an oxidase channel. ? Substrate binding has a pronounced effect on uncoupling in cytochrome P450. ? Anionic phospholipids improve the overall coupling in CYP3A4 Nanodiscs. -- Abstract: The normal reaction mechanism of cytochrome P450 operates by utilizing two reducing equivalents to reduce atmospheric dioxygen, producing one molecule of water and an oxygenated product in an overall stoichiometry of 2 electrons:1 dioxygen:1 product. However, three alternate unproductive pathways exist where the intermediate ironoxygen states in the catalytic cycle can yield reduced oxygen products without substrate metabolism. The first involves release of superoxide from the oxygenated intermediate while the second occurs after input of the second reducing equivalent. Superoxide rapidly dismutates and hence both processes produce hydrogen peroxide that can be cytotoxic to the organism. In both cases, the formation of hydrogen peroxide involves the same overall stoichiometry as oxygenases catalysis. The key step in the catalytic cycle of cytochrome P450 involves scission of the oxygenoxygen bond of atmospheric dioxygen to produce a higher valent iron-oxo state termed Compound I. This intermediate initiates a radical reaction in the oxygenase pathway but also can uptake two additional reducing equivalents from reduced pyridine nucleotide (NADPH) and the flavoprotein reductase to produce a second molecule of water. This non-productive decay of Compound I thus yields an overall oxygen to NADPH ratio of 1:2 and does not produce hydrocarbon oxidation. This water uncoupling reaction provides one of a limited means to study the reactivity of the critical Compound I intermediate in P450 catalysis. We measured simultaneously the rates of NADPH and oxygen consumption as a function of substrate concentration during the steady-state hydroxylation of testosterone catalyzed by human P450 CYP3A4 reconstituted in Nanodiscs. We discovered that the oxidase uncoupling pathway is also operating in the substrate free form of the enzyme with rate of this pathway substantially increasing with the first substrate binding event. Surprisingly, a large fraction of the reducing equivalents used by the P450 system is wasted in this oxidase pathway. In addition, the overall coupling with testosterone and bromocryptine as substrates is significantly higher in the presence of anionic lipids, which is attributed to the changes in the redox potential of CYP3A4 and reductase.

  10. Surface preparation for high purity alumina ceramics enabling direct brazing in hydrogen atmospheres

    DOE Patents [OSTI]

    Cadden, Charles H. (Danville, CA); Yang, Nancy Yuan Chi (Lafayette, CA); Hosking, Floyd M. (Albuquerque, NM)

    2001-01-01

    The present invention relates to a method for preparing the surface of a high purity alumina ceramic or sapphire specimen that enables direct brazing in a hydrogen atmosphere using an active braze alloy. The present invention also relates to a method for directly brazing a high purity alumina ceramic or sapphire specimen to a ceramic or metal member using this method of surface preparation, and to articles produced by this brazing method. The presence of silicon, in the form of a SiO.sub.2 -containing surface layer, can more than double the tensile bond strength in alumina ceramic joints brazed in a hydrogen atmosphere using an active Au-16Ni-0.75 Mo-1.75V filler metal. A thin silicon coating applied by PVD processing can, after air firing, produce a semi-continuous coverage of the alumina surface with a SiO.sub.2 film. Room temperature tensile strength was found to be proportional to the fraction of air fired surface covered by silicon-containing films. Similarly, the ratio of substrate fracture versus interface separation was also related to the amount of surface silicon present prior to brazing. This process can replace the need to perform a "moly-manganese" metallization step.

  11. Modification of modulated plasma plumes for the quasi-phase-matching of high-order harmonics in different spectral ranges

    SciTech Connect (OSTI)

    Ganeev, R. A.; Boltaev, G. S.; Sobirov, B.; Reyimbaev, S.; Sherniyozov, H.; Usmanov, T.; Suzuki, M.; Yoneya, S.; Kuroda, H.

    2015-01-15

    We demonstrate the technique allowing the fine tuning of the distance between the laser-produced plasma plumes on the surfaces of different materials, as well as the variation of the sizes of these plumes. The modification of plasma formations is based on the tilting of the multi-slit mask placed between the heating laser beam and target surface, as well as the positioning of this mask in the telescope placed on the path of heating radiation. The modulated plasma plumes with the sizes of single plume ranging between 0.1 and 1 mm were produced on the manganese and silver targets. Modification of the geometrical parameters of plasma plumes proved to be useful for the fine tuning of the quasi-phase-matched high-order harmonics generated in such structures during propagation of the ultrashort laser pulses. We show the enhancement of some groups of harmonics along the plateau range and the tuning of maximally enhanced harmonic by variable modulation of the plasma.

  12. Design Insights for Tuning the Electrocatalytic Activity of Perovskite Oxides for the Oxygen Evolution Reaction

    SciTech Connect (OSTI)

    Malkhandi, S; Trinh, P; Manohar, AK; Manivannan, A; Balasubramanian, M; Prakash, GKS; Narayanan, SR

    2015-04-16

    Rechargeable metal-air batteries and water electrolyzers based on aqueous alkaline electrolytes hold the potential to be sustainable solutions to address the challenge of storing large amounts of electrical energy generated from solar and wind resources. For these batteries and electrolyzers to be economically viable, it is essential to have efficient, durable, and inexpensive electrocatalysts for the oxygen evolution reaction. In this article, we describe new insights for predicting and tuning the activity of inexpensive transition metal oxides for designing efficient and inexpensive electrocatalysts. We have focused on understanding the factors determining the electrocatalytic activity for oxygen evolution in a strong alkaline medium. To this end, we have conducted a systematic investigation of nanophase calcium-doped lanthanum cobalt manganese oxide, an example of a mixed metal oxide that can be tuned for its electrocatalytic activity by varying the transition metal composition. Using X-ray absorption spectroscopy (XANES), X-ray photoelectron spectroscopy (XPS), electrochemical polarization experiments, and analysis of mechanisms, we have identified the key determinants of electrocatalytic activity. We have found that the Tafel slopes are determined by the oxidation states and the bond energy of the surface intermediates of Mn-OH and Co-OH bonds while the catalytic activity increased with the average d-electron occupancy of the sigma* orbital of the M-OH bond. We anticipate that such understanding will be very useful in predicting the behavior of other transition metal oxide catalysts.

  13. Geochemical provenance of anomalous metal concentrations in stream sediments in the Ashton 1:250,000 quadrangle, Idaho/Montana/Wyoming

    SciTech Connect (OSTI)

    Shannon, S.S. Jr.

    1982-01-01

    Stream-sediment samples from 1500 sites in the Ashton, Idaho/Montana/Wyoming 1:250,000 quadrangle were analyzed for 45 elements. Almost all samples containing anomalous concentrations (exceeding one standard deviation above the mean value of any element) were derived from drainage basins underlain by Quaternary rhyolite, Tertiary andesite or Precambrian gneiss and schist. Aluminum, barium, calcium, cobalt, iron, nickel, magnesium, scandium, sodium, strontium, and vanadium have no andesite provenance. Most anomalous manganese, europium, hafnium, and zirconium values were derived from Precambrian rocks. All other anomalous elemental concentrations are related to Quaternary rhyolite. This study demonstrates that multielemental stream-sediment analyses can be used to infer the provenance of stream sediments. Such data are available for many parts of the country as a result of the National Uranium Resource Evaluation. This study suggests that stream-sediment samples collected in the Rocky Mountains can be used either as pathfinders or as direct indicators to select targets for mineral exploration for a host of metals.

  14. OXALATE MASS BALANCE DURING CHEMICAL CLEANING IN TANK 6F

    SciTech Connect (OSTI)

    Poirier, M.; Fink, S.

    2011-07-22

    The Savannah River Remediation (SRR) is preparing Tank 6F for closure. The first step in preparing the tank for closure is mechanical sludge removal. Following mechanical sludge removal, SRS performed chemical cleaning with oxalic acid to remove the sludge heel. Personnel are currently assessing the effectiveness of the chemical cleaning to determine whether the tank is ready for closure. SRR personnel collected liquid samples during chemical cleaning and submitted them to Savannah River National Laboratory (SRNL) for analysis. Following chemical cleaning, they collected a solid sample (also known as 'process sample') and submitted it to SRNL for analysis. The authors analyzed these samples to assess the effectiveness of the chemical cleaning process. Analysis of the anions showed the measured oxalate removed from Tank 6F to be approximately 50% of the amount added in the oxalic acid. To close the oxalate mass balance, the author collected solid samples, leached them with nitric acid, and measured the concentration of cations and anions in the leachate. Some conclusions from this work are: (1) Approximately 65% of the oxalate added as oxalic acid was removed with the decanted liquid. (2) Approximately 1% of the oxalate (added to the tank as oxalic acid) formed precipitates with compounds such as nickel, manganese, sodium, and iron (II), and was dissolved with nitric acid. (3) As much as 30% of the oxalate may have decomposed forming carbon dioxide. The balance does not fully account for all the oxalate added. The offset represents the combined uncertainty in the analyses and sampling.

  15. Analysis of the Tank 5F Feed and Bleed Residual Solids

    SciTech Connect (OSTI)

    Poirier, M.; Diprete, D.: Coleman, C.; Washington, A.

    2011-07-07

    Savannah River Remediation (SRR) is preparing Tank 5F for closure. As part of Tank 5F Closure Mechanical Cleaning, SRR conducted a 'Feed and Bleed' process in Tank 5F. Following this 'Feed and Bleed' Mechanical Cleaning in Tank 5F, SRR collected two tank heel samples (referred to as sample 1 and sample 2) under Riser 5 to determine the composition of the material remaining in the tanks. This document describes sample analysis results. The conclusions from this analysis follow. (1) The anions measured all had a concentration less than 250 mg/kg, except for oxalate, which had a concentration of 2100-2400 mg/kg. (2) The measured cations with the highest concentration were iron (432,000-519,000 mg/kg), nickel (54,600-69,300 mg/kg), and manganese (35,200-42,100 mg/kg). All other cations measured less than 13,000 mg/kg. (3) The radionuclides present in the highest concentration are {sup 90}Sr (3.0 x 10{sup 10} dpm/g), {sup 137}Cs (6.8 x 10{sup 8} dpm/g), and {sup 241}Am (1.4 x 10{sup 8} - 1.8 x 10{sup 8} dpm/g). (4) The particle size analysis shows a large fraction of particles greater than 100 {micro}.

  16. Uranium hydrogeochemical and stream sediment reconnaissance data release for the Dubois NTMS Quadrangle, Idaho/Montana, including concentrations of forty-five additional elements

    SciTech Connect (OSTI)

    LaDelfe, C.M.

    1980-08-01

    Totals of 1024 water samples and 1600 sediment samples were collected from 1669 locations in the Dubois quadrangle. Water samples were taken at streams, springs, and wells; sediment samples were collected from streams and springs. All field and analytical data are presented for waters in Appendix I-A and for sediments in I-B. All elemental analyses were performed at the LASL. Water samples were initially analyzed for uranium by fluorometry. All water samples containing more than the upper detection limit of uranium were reanalyzed by delayed neutron counting. Sediments were analyzed for uranium and thorium as well as aluminum, antimony, arsenic, barium, beryllium, bismuth, cadmium, calcium, cerium, cesium, chlorine, chromium, cobalt, copper, dysprosium, europium, gold, hafnium, iron, lanthanum, lead, lithium, lutetium, magnesium, manganese, nickel, niobium, potassium rubidium, samarium, scandium, selenium, silver, sodium, strontium, tantalum, terbium, tin, titanium, tungsten, vanadium, ytterbium, zinc and zirconium. All sediments were analyzed for uranium by delayed-neutron counting. Other elemental concentrations in sediments were determined by neutron-activation analysis for 30 elements, by x-ray fluorescence for 12 elements, and by arc-source emission spectrography for 2 elements. Analytical results for sediments are reported as parts per million.

  17. Hydrogen effect on n-butane isomerization over sulfated zirconia-based catalysts

    SciTech Connect (OSTI)

    Sayari, A.; Yang, Yong; Song, Xuemin

    1997-04-15

    Iron- and manganese-promoted sulfated zirconia (SFMZ) has been tested as an n-butane isomerization catalyst in the temperature range of 35 to 180{degrees}C. The catalytic activity exhibits an induction period whose length is dependent on the reaction conditions. The presence of H{sub 2} in the feed stream strongly suppresses n-butane conversion over unprompted sulfated zirconia (SZ) and over Pt-containing SFMZ (PtSFMZ). However, hydrogen had no effect on n-butane isomerization over SFMZ. These findings were interpreted on the basis of a bimolecular mechanism where unsaturated intermediates (carbenium ions and/or butene) are formed during the break-in period. The role of promoters (Fe and Mn) is not only facilitating the formation of hydrogen-deficient intermediates and their accumulation on the catalyst surface, but also enhancing their stability. The negative effect of hydrogen over PtSFMZ is attributed to the occurrence of atomic hydrogen via the dissociative adsorption of H{sub 2} on Pt. 40 refs., 7 figs., 1 tab.

  18. An Industry/DOE Program to Develop and Benchmark Advanced Diamond Product Drill Bits and HP/HT Drilling Fluids to Significantly Improve Rates of Penetration

    SciTech Connect (OSTI)

    TerraTek

    2007-06-30

    A deep drilling research program titled 'An Industry/DOE Program to Develop and Benchmark Advanced Diamond Product Drill Bits and HP/HT Drilling Fluids to Significantly Improve Rates of Penetration' was conducted at TerraTek's Drilling and Completions Laboratory. Drilling tests were run to simulate deep drilling by using high bore pressures and high confining and overburden stresses. The purpose of this testing was to gain insight into practices that would improve rates of penetration and mechanical specific energy while drilling under high pressure conditions. Thirty-seven test series were run utilizing a variety of drilling parameters which allowed analysis of the performance of drill bits and drilling fluids. Five different drill bit types or styles were tested: four-bladed polycrystalline diamond compact (PDC), 7-bladed PDC in regular and long profile, roller-cone, and impregnated. There were three different rock types used to simulate deep formations: Mancos shale, Carthage marble, and Crab Orchard sandstone. The testing also analyzed various drilling fluids and the extent to which they improved drilling. The PDC drill bits provided the best performance overall. The impregnated and tungsten carbide insert roller-cone drill bits performed poorly under the conditions chosen. The cesium formate drilling fluid outperformed all other drilling muds when drilling in the Carthage marble and Mancos shale with PDC drill bits. The oil base drilling fluid with manganese tetroxide weighting material provided the best performance when drilling the Crab Orchard sandstone.

  19. The Orientation Distributions of Lines, Surfaces, and Interfaces Around Three-Phase Boundaries in Solid Oxide Fuel Cell Cathodes

    SciTech Connect (OSTI)

    Dillon, Shen; Helmick, Lam; Miller, Herbert M.; Johnson, Christopher; Wilson, Lane; Gemmen, Randall; Petrova, Rumyana; Barmak, Katayun; Gerdes, Kirk; Rohrer, Gregory S.; Salvador, Paul A.

    2011-11-01

    Three-dimensional electron backscatter diffraction was used to measure the crystallographic distribution of the electrochemically relevant triple phase boundary lines and surfaces near them in SOFC cathodes made up of a porous mixture of yttria-stabilized zirconia and lanthanum strontium manganese oxide, both before and after mild electrochemical loading. All distributions were observed to be nearly isotropic, but non-random textures above the detection threshold were observed. The distributions differ between the two cells, as do the phase fractions and the electrochemical history. The different distributions are interpreted as evidence that steady-state distributions vary locally with phase fractions or that they evolve during the initial operation of the fuel cell. The rates at which triple lines, pore surfaces, and interface boundaries in the porous mixture approach a steady-state value appear to decrease with the average amount of mass transport required to reorient that specific feature. This work provides initial insights into the crystallography of interfaces in a multiphase ceramic material.

  20. Development of Modeling Methods and Tools for Predicting Coupled Reactive Transport Processes in Porous Media at Multiple Scales

    SciTech Connect (OSTI)

    Clement, T Prabhakar; Barnett, Mark O; Zheng, Chunmiao; Jones, Norman L

    2010-05-05

    DE-FG02-06ER64213: Development of Modeling Methods and Tools for Predicting Coupled Reactive Transport Processes in Porous Media at Multiple Scales Investigators: T. Prabhakar Clement (PD/PI) and Mark O. Barnett (Auburn), Chunmiao Zheng (Univ. of Alabama), and Norman L. Jones (BYU). The objective of this project was to develop scalable modeling approaches for predicting the reactive transport of metal contaminants. We studied two contaminants, a radioactive cation [U(VI)] and a metal(loid) oxyanion system [As(III/V)], and investigated their interactions with two types of subsurface materials, iron and manganese oxyhydroxides. We also developed modeling methods for describing the experimental results. Overall, the project supported 25 researchers at three universities. Produced 15 journal articles, 3 book chapters, 6 PhD dissertations and 6 MS theses. Three key journal articles are: 1) Jeppu et al., A scalable surface complexation modeling framework for predicting arsenate adsorption on goethite-coated sands, Environ. Eng. Sci., 27(2): 147-158, 2010. 2) Loganathan et al., Scaling of adsorption reactions: U(VI) experiments and modeling, Applied Geochemistry, 24 (11), 2051-2060, 2009. 3) Phillippi, et al., Theoretical solid/solution ratio effects on adsorption and transport: uranium (VI) and carbonate, Soil Sci. Soci. of America, 71:329-335, 2007

  1. Defect propagation in one-, two-, and three-dimensional compounds doped by magnetic atoms

    DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)

    Furrer, A.; Podlesnyak, A.; Krämer, K. W.; Strässle, Th.

    2014-10-29

    Inelastic neutron scattering experiments were performed to study manganese(II) dimer excitations in the diluted one-, two-, and three-dimensional compounds CsMnxMg1-xBr3, K2MnxZn1-xF4, and KMnxZn1-xF3 (x≤0.10), respectively. The transitions from the ground-state singlet to the excited triplet, split into a doublet and a singlet due to the single-ion anisotropy, exhibit remarkable fine structures. These unusual features are attributed to local structural inhomogeneities induced by the dopant Mn atoms which act like lattice defects. Statistical models support the theoretically predicted decay of atomic displacements according to 1/r2, 1/r, and constant (for three-, two-, and one-dimensional compounds, respectively) where r denotes the distance ofmore » the displaced atoms from the defect. In conclusion, the observed fine structures allow a direct determination of the local exchange interactions J, and the local intradimer distances R can be derived through the linear law dJ/dR.« less

  2. Correlating Local Structure with Electrochemical Activity in Li2MnO3

    SciTech Connect (OSTI)

    Nanda, Jagjit; Sacci, Robert L.; Veith, Gabriel M.; Dixit, Hemant M.; Cooper, Valentino R.; Pezeshki, Alan M.; Ruther, Rose E.

    2015-07-31

    Li2MnO3 is of interest as one component of the composite lithium-rich oxides, which are under development for high capacity, high voltage cathodes in lithium ion batteries. Despite such practical importance, the mechanism of electrochemical activity in Li2MnO3 is contested in the literature, as are the effects of long-term electrochemical cycling. Here, Raman spectroscopy and mapping are used to follow the chemical and structural changes that occur in Li2MnO3. Both conventional slurry electrodes and thin films are studied as a function of the state of charge (voltage) and cycle number. Thin films have similar electrochemical properties as electrodes prepared from slurries, but allow for spectroscopic investigations on uniform samples without carbon additives. Spectral changes correlate well with electrochemical activity and support a mechanism whereby capacity is lost upon extended cycling due to the formation of new manganese oxide phases. Raman mapping of both thin film and slurry electrodes charged to different voltages reveals significant variation in the local structure. Poor conductivity and slow kinetics associated with a two-phase reaction mechanism contribute to the heterogeneity.

  3. Engineered photocatalysts for detoxification of waste water

    SciTech Connect (OSTI)

    Majumder, S.A.; Prairie, M.R.; Shelnutt, J.A.; Khan, S.U.M.

    1996-12-01

    This report describes progress on the development of engineered photocatalysts for the detoxification of water polluted with toxic organic compounds and heavy metals. We examined a range of different oxide supports (titania, alumina, magnesia and manganese dioxide) for tin uroporphyrin and investigated the efficacy of a few different porphyrins. A water-soluble octaacetic-acid-tetraphenylporphyrin and its derivatives have been synthesized and characterized in an attempt to design a porphyrin catalyst with a larger binding pocket. We have also investigated photocatalytic processes on both single crystal and powder forms of semiconducting SiC with an ultimate goal of developing a dual-semiconductor system combining TiO{sub 2} and SiC. Mathematical modeling was also performed to identify parameters that can improve the efficiency of SiC-based photocatalytic systems. Although the conceptual TiO{sub 2}/SiC photodiode shows some promises for photoreduction processes, SiC itself was found to be an inefficient photocatalyst when combined with TiO{sub 2}. Alternative semiconductors with bandgap and band potentials similar to SiC should be tested in the future for further development and a practical utilization of the dual photodiode concept.

  4. Emerging contaminants: Presentations at the 2009 Toxicology and Risk Assessment Conference

    SciTech Connect (OSTI)

    Murnyak, George; Vandenberg, John; Yaroschak, Paul J.; Williams, Larry; Prabhakaran, Krishnan; Hinz, John

    2011-07-15

    A session entitled 'Emerging Contaminants' was held in April 2009 in Cincinnati, OH at the 2009 Toxicology and Risk Assessment Conference. The purpose of the session was to share information on both programmatic and technical aspects associated with emerging contaminants. Emerging contaminants are chemicals or materials that are characterized by a perceived or real threat to human health or environment, a lack of published health standards or an evolving standard. A contaminant may also be 'emerging' because of the discovery of a new source, a new pathway to humans, or a new detection method or technology. The session included five speakers representing the Department of Defense (DoD), the Environmental Protection Agency (EPA), and each of the military services. The DoD created the Emerging Contaminant Directorate to proactively address environmental, health, and safety concerns associated with emerging contaminants. This session described the scan-watch-action list process, impact assessment methodology, and integrated risk management concept that DoD has implemented to manage emerging contaminants. EPA presented emerging trends in health risk assessment. Researchers made technical presentations on the status of some emerging contaminates in the assessment process (i.e. manganese, RDX, and naphthalene).

  5. Actinium radioisotope products of enhanced purity

    DOE Patents [OSTI]

    Meikrantz, David Herbert; Todd, Terry Allen; Tranter, Troy Joseph; Horwitz, E. Philip

    2010-06-15

    A product includes actinium-225 (.sup.225Ac) and less than about 1 microgram (.mu.g) of iron (Fe) per millicurie (mCi) of actinium-225. The product may have a radioisotopic purity of greater than about 99.99 atomic percent (at %) actinium-225 and daughter isotopes of actinium-225, and may be formed by a method that includes providing a radioisotope mixture solution comprising at least one of uranium-233 (.sup.233U) and thorium-229 (.sup.229Th), extracting the at least one of uranium-233 and thorium-229 into an organic phase, substantially continuously contacting the organic phase with an aqueous phase, substantially continuously extracting actinium-225 into the aqueous phase, and purifying the actinium-225 from the aqueous phase. In some embodiments, the product may include less than about 1 nanogram (ng) of iron per millicurie (mCi) of actinium-225, and may include less than about 1 microgram (.mu.g) each of magnesium (Mg), Chromium (Cr), and manganese (Mn) per millicurie (mCi) of actinium-225.

  6. Emission factors for several toxic air pollutants from fluidized-bed combustion of coal

    SciTech Connect (OSTI)

    Smith, A.E.

    1986-03-01

    Clean coal technologies such as fluidized-bed combustion have the potential to emit the same trace elements as conventional combustors. Since the US Environmental Protection Agency (EPA) is likely to promulgate National Emission Standards for Hazardous Air Pollutants for several trace elements, the feasibility of using fluidized-bed combustors to reduce sulfur dioxide emissions may depend in part on the relative amounts of trace elements emitted by fluidized-bed and conventional combustors. Emissions of trace elements from both atmospheric and pressurized fluidized-bed combustors were compared with those from conventional combustors by developing fluidized-bed emission factors from information available in the literature and comparing them with the emission factors for conventional combustors recommended in a literature search conducted for EPA. The comparisons are based on the mass of emission per unit of heat input for antimony, arsenic, beryllium, cadmium, chromium, cobalt, copper, lead, manganese, mercury, nickel, vanadium, and zinc. When inaccuracies in the data were taken into account, the trace element emissions from atmospheric fluidized-bed combustion seem to be somewhat higher than those from a conventional utility boiler burning pulverized coal and somewhat lower than those from pressurized fluidized-bed combustion.

  7. Performance testing of a Laser-Induced Breakdown Spectroscopy (LIBS) based continuous metal emissions monitor at a pyrolytic waste treatment facility

    SciTech Connect (OSTI)

    Hahn, D.W.; Hencken, K.R.; Johnsen, H.A.

    1997-07-01

    A program was initiated at Sandia National Laboratories to develop and demonstrate an advanced continuous emissions monitor that will provide realtime measurement of metal emissions in the wastestreams of thermal treatment facilities. This effort led to the development of a prototype metals monitor based on an optical technique referred to as laser-induced breakdown spectroscopy (LIBS). The measurements are performed in situ, and are both noninvasive and real-time. The automated software incorporates a new conditional analysis algorithm that utilizes single particle detection. The metal emissions monitor was tested during March 1997 at a pilot scale pyrolytic waste processing facility in Santa Fe Springs, California. This report describes the field test, including the monitor installation, test cycle, and overall instrument performance. The Clean Air Act metals chromium and manganese were recorded at concentrations from approximately 2 to 5 parts per billion. Iron was recorded at concentrations from 40 to 140 parts per billion. The overall accuracy was in very good agreement with contracted EPA Reference Method 29 results. Overall, the LIBS-based metals monitor performed exceptionally well on a waste treatment facility with very low metal emissions levels. 19 refs., 12 tabs., 3 figs.

  8. Synthesis, structure refinement at 296 K and physico-chemical characterizations of KMnHP{sub 3}O{sub 10}

    SciTech Connect (OSTI)

    Mechergui, J.; Belam, W.

    2008-12-01

    Potassium manganese(III) monohydrogentriphosphate KMnHP{sub 3}O{sub 10} was synthesized by flux method and characterized by single-crystal X-ray diffraction, crystallizes in the monoclinic system with centric space group C2/c. The parameters of the unit cell are a = 12.104(1), b = 8.287(1). c = 9.150(1) A, {beta} = 110.97(1) deg. and Z = 4. The structure was solved at 296 K using 893 independent reflections and refined until R(F) = 0.022; wR(F{sup 2}) = 0.045. The atomic arrangement of the title compound consists of MnO{sub 6} octahedra linked by hydrogentriphosphate anions to form a three-dimensional framework containing tunnels parallel to the c-axis where the K{sup +} cations are inserted. The structure of KMnHP{sub 3}O{sub 10} contains a single Mn site which is surrounded by typical Jahn-Teller [2 + 2 + 2] distorted octahedron. The title material has been also characterized by different physico-chemical techniques: powder X-ray diffraction, IR, NMR and CI spectroscopies and DTA-TGA-DSC thermal analysis.

  9. Integrated Removal of NOx with Carbon Monoxide as Reductant, and Capture of Mercury in a Low Temperature Selective Catalytic and Adsorptive Reactor

    SciTech Connect (OSTI)

    Neville Pinto; Panagiotis Smirniotis; Stephen Thiel

    2010-08-31

    Coal will likely continue to be a dominant component of power generation in the foreseeable future. This project addresses the issue of environmental compliance for two important pollutants: NO{sub x} and mercury. Integration of emission control units is in principle possible through a Low Temperature Selective Catalytic and Adsorptive Reactor (LTSCAR) in which NO{sub x} removal is achieved in a traditional SCR mode but at low temperature, and, uniquely, using carbon monoxide as a reductant. The capture of mercury is integrated into the same process unit. Such an arrangement would reduce mercury removal costs significantly, and provide improved control for the ultimate disposal of mercury. The work completed in this project demonstrates that the use of CO as a reductant in LTSCR is technically feasible using supported manganese oxide catalysts, that the simultaneous warm-gas capture of elemental and oxidized mercury is technically feasible using both nanostructured chelating adsorbents and ceria-titania-based materials, and that integrated removal of mercury and NO{sub x} is technically feasible using ceria-titania-based materials.

  10. Recovery of germanium-68 from irradiated targets

    DOE Patents [OSTI]

    Phillips, Dennis R.; Jamriska, Sr., David J.; Hamilton, Virginia T.

    1993-01-01

    A process for selective separation of germanium-68 from proton irradiated molybdenum targets is provided and includes dissolving the molybdenum target in a hydrogen peroxide solution to form a first ion-containing solution, contacting the first ion-containing solution with a cationic resin whereby ions selected from the group consisting of molybdenum, niobium, technetium, selenium, vanadium, arsenic, germanium, zirconium and rubidium remain in a second ion-containing solution while ions selected from the group consisting of rubidium, zinc, beryllium, cobalt, iron, manganese, chromium, strontium, yttrium and zirconium are selectively adsorbed by the first resin, adjusting the pH of the second ion-containing solution to within a range of from about 0.7 to about 3.0, adjusting the soluble metal halide concentration in the second ion-containing solution to a level adapted for subsequent separation of germanium, contacting the pH-adjusted, soluble metal halide-containing second ion-containing solution with a dextran-based material whereby germanium ions are separated by the dextran-based material, and recovering the germanium from the dextran-based material, preferably by distillation.

  11. Method of generating hydrogen by catalytic decomposition of water

    DOE Patents [OSTI]

    Balachandran, Uthamalingam (Hinsdale, IL); Dorris, Stephen E. (LaGrange Park, IL); Bose, Arun C. (Pittsburgh, PA); Stiegel, Gary J. (Library, PA); Lee, Tae-Hyun (Naperville, IL)

    2002-01-01

    A method for producing hydrogen includes providing a feed stream comprising water; contacting at least one proton conducting membrane adapted to interact with the feed stream; splitting the water into hydrogen and oxygen at a predetermined temperature; and separating the hydrogen from the oxygen. Preferably the proton conducting membrane comprises a proton conductor and a second phase material. Preferable proton conductors suitable for use in a proton conducting membrane include a lanthanide element, a Group VIA element and a Group IA or Group IIA element such as barium, strontium, or combinations of these elements. More preferred proton conductors include yttrium. Preferable second phase materials include platinum, palladium, nickel, cobalt, chromium, manganese, vanadium, silver, gold, copper, rhodium, ruthenium, niobium, zirconium, tantalum, and combinations of these. More preferably second phase materials suitable for use in a proton conducting membrane include nickel, palladium, and combinations of these. The method for generating hydrogen is preferably preformed in the range between about 600.degree. C. and 1,700.degree. C.

  12. Synthesis and Characterization of Lithium Bis(fluoromalonato)borate (LiBFMB) for Lithium Ion Battery Applications

    SciTech Connect (OSTI)

    Liao, Chen; Han, Kee Sung; Baggetto, Loic; Hillesheim, Daniel A; Custelcean, Radu; Lee, Dr. Eun-Sung; Guo, Bingkun; Bi, Zhonghe; Jiang, Deen; Veith, Gabriel M; Hagaman, Edward {Ed} W; Brown, Gilbert M; Bridges, Craig A; Paranthaman, Mariappan Parans; Manthiram, Arumugam; Dai, Sheng; Sun, Xiao-Guang

    2014-01-01

    A new orthochelated salt, lithium bis(monofluoromalonato)borate (LiBFMB), has been synthesized and purified for the first time for application in lithium ion batteries. The presence of fluorine in the borate anion of LiBFMB increases its oxidation potential and also facilitates ion dissociation, as reflected by the ratio of ionic conductivity measured by electrochemical impedance spectroscopy ( exp) and that by ion diffusivity coefficients obtained using pulsed field gradient nuclear magnetic resonance (PFG-NMR) technique ( NMR). Half-cell tests using 5.0 V lithium nickel manganese oxide (LiNi0.5Mn1.5O4) as a cathode and EC/DMC/DEC as a solvent reveals that the impedance of the LiBFMB cell is much larger than those of LiPF6 and LiBOB based cells, which results in lower capacity and poor cycling performance of the former. XPS spectra of the cycled cathode electrode suggest that because of the stability of the LiBFMB salt, the solid electrolyte interphase (SEI) formed on the cathode surface is significantly different from those of LiPF6 and LiBOB based electrolytes, resulting in more solvent decomposition and thicker SEI layer. Initial results also indicate that using high dielectric constant solvent PC alters the surface chemistry, reduces the interfacial impedance, and enhances the performance of LiBFMB based 5.0V cell.

  13. Rate dependence of swelling in lithium-ion cells

    SciTech Connect (OSTI)

    Oh, KY; Siegel, JB; Secondo, L; Kim, SU; Samad, NA; Qin, JW; Anderson, D; Garikipati, K; Knobloch, A; Epureanu, BI; Monroe, CW; Stefanopoulou, A

    2014-12-01

    Swelling of a commercial 5 Ah lithium-ion cell with a nickel/manganese/cobalt-oxide cathode is investigated as a function of the charge state and the charge/discharge rate. In combination with sensitive displacement measurements, knowledge of the electrode configuration within this prismatic cell's interior allows macroscopic deformations of the casing to be correlated to electrochemical and mechanical transformations in individual anode/separator/cathode layers. Thermal expansion and interior charge state are both found to cause significant swelling. At low rates, where thermal expansion is negligible, the electrode sandwich dilates by as much as 1.5% as the charge state swings from 0% to 100% because of lithium-ion intercalation. At high rates a comparably large residual swelling was observed at the end of discharge. Thermal expansion caused by joule heating at high discharge rate results in battery swelling. The changes in displacement with respect to capacity at low rate correlate well with the potential changes known to accompany phase transitions in the electrode materials. Although the potential response changes minimally with the C-rate, the extent of swelling varies significantly, suggesting that measurements of swelling may provide a sensitive gauge for characterizing dynamic operating states. (C) 2014 Elsevier B.V. All rights reserved.

  14. Process for Low Cost Domestic Production of LIB Cathode Materials

    SciTech Connect (OSTI)

    Thurston, Anthony

    2012-10-31

    The objective of the research was to determine the best low cost method for the large scale production of the Nickel-Cobalt-Manganese (NCM) layered cathode materials. The research and development focused on scaling up the licensed technology from Argonne National Laboratory in BASFs battery material pilot plant in Beachwood Ohio. Since BASF did not have experience with the large scale production of the NCM cathode materials there was a significant amount of development that was needed to support BASFs already existing research program. During the three year period BASF was able to develop and validate production processes for the NCM 111, 523 and 424 materials as well as begin development of the High Energy NCM. BASF also used this time period to provide free cathode material samples to numerous manufactures, OEMs and research companies in order to validate the ma-terials. The success of the project can be demonstrated by the construction of the production plant in Elyria Ohio and the successful operation of that facility. The benefit of the project to the public will begin to be apparent as soon as material from the production plant is being used in electric vehicles.

  15. Activation analyses for different fusion structural alloys

    SciTech Connect (OSTI)

    Attaya, H.; Smith, D.

    1991-12-31

    The leading candidate structural materials, viz., the vanadium alloys, the nickel or the manganese stabilized austenitic steels, and the ferritic steels, are analysed in terms of their induced activation in the TPSS fusion power reactor. The TPSS reactor has 1950 MW fusion power and inboard and outboard average neutron wall loading of 3.75 and 5.35 MW/m{sup 2} respectively. The results shows that, after one year of continuous operation, the vanadium alloys have the least radioactivity at reactor shutdown. The maximum difference between the induced radioactivity in the vanadium alloys and in the other iron-based alloys occurs at about 10 years after reactor shutdown. At this time, the total reactor radioactivity, using the vanadium alloys, is about two orders of magnitude less than the total reactor radioactivity utilizing any other alloy. The difference is even larger in the first wall, the FW-vanadium activation is 3 orders of magnitude less than other alloys` FW activation. 2 refs., 7 figs.

  16. Activation characteristics of different steel alloys proposed for near-term fusion reactors

    SciTech Connect (OSTI)

    Attaya, H.; Gohar, Y.; Smith, D.; Baker, C.C.

    1988-08-01

    Analyses have been made for different structural alloys proposed for the International Thermonuclear Experimental Reactor (ITER). Candidate alloys include austenitic steels stabilized with nickel (NiSS) or manganese (MnSS). The radioactivity, the decay heat, and the waste disposal rating of each alloy have been calculated for the inboard shield of the ITER design option utilizing water cooled solid breeder blanket. The results show, for the 55 cm inboard shield and after 3 MW.yr/m2 fluence, that the long term activation problems, e.g., radioactive waste, of the MnSS are much less than that of the NiSS. All the MnSS alloys considered are qualified as Class C or better low level waste. Most of the NiSS alloys are not qualified for near surface burial. However, the short term decay heat generation rate for the MnSS is much higher than that of the NiSS. 6 refs., 8 figs., 2 tabs.

  17. Activation analyses for different fusion structural alloys

    SciTech Connect (OSTI)

    Attaya, H.; Smith, D.

    1991-01-01

    The leading candidate structural materials, viz., the vanadium alloys, the nickel or the manganese stabilized austenitic steels, and the ferritic steels, are analysed in terms of their induced activation in the TPSS fusion power reactor. The TPSS reactor has 1950 MW fusion power and inboard and outboard average neutron wall loading of 3.75 and 5.35 MW/m{sup 2} respectively. The results shows that, after one year of continuous operation, the vanadium alloys have the least radioactivity at reactor shutdown. The maximum difference between the induced radioactivity in the vanadium alloys and in the other iron-based alloys occurs at about 10 years after reactor shutdown. At this time, the total reactor radioactivity, using the vanadium alloys, is about two orders of magnitude less than the total reactor radioactivity utilizing any other alloy. The difference is even larger in the first wall, the FW-vanadium activation is 3 orders of magnitude less than other alloys' FW activation. 2 refs., 7 figs.

  18. Concentrations of 23 trace elements in ground water and surface water at and near the Idaho National Engineering Laboratory, Idaho, 1988--91

    SciTech Connect (OSTI)

    Liszewski, M.J.; Mann, L.J.

    1993-12-31

    Analytical data for 23 trace elements are reported for ground- and surface-water samples collected at and near the Idaho National Engineering Laboratory during 1988--91. Water samples were collected from 148 wells completed in the Snake River Plain aquifer, 18 wells completed in discontinuous deep perched-water zones, and 1 well completed in an alluvial aquifer. Surface-water samples also were collected from three streams, two springs, two ponds, and one lake. Data are categorized by concentrations of total recoverable of dissolved trace elements. Concentrations of total recoverable trace elements are reported for unfiltered water samples and include results for one or more of the following: aluminum, arsenic, barium, beryllium, cadmium, chromium, cobalt, copper, iron, lead, manganese, mercury, nickel, selenium, silver, and zinc. Concentrations of dissolved trace elements are reported for water samples filtered through a nominal 0.45-micron filter and may also include bromide, fluoride, lithium, molybdenum, strontium, thallium, and vanadium. Concentrations of dissolved hexavalent chromium also are reported for many samples. The water samples were analyzed at the US Geological Survey`s National Water Quality Laboratory in Arvada, Colorado. Methods used to collect the water samples and quality assurance instituted for the sampling program are described. Concentrations of chromium equaled or exceeded the maximum contaminant level at 12 ground-water quality monitoring wells. Other trace elements did not exceed their respective maximum contaminant levels.

  19. Graphitic biocarbon from metal-catalyzed hydrothermal carbonization of lignin

    SciTech Connect (OSTI)

    Demir, Muslum; Kahveci, Zafer; Aksoy, Burak; Palapati, Naveen K. R.; Subramanian, Arunkumar; Cullinan, Harry T.; El-Kaderi, Hani M.; Harris, Charles T.; Gupta, Ram B.

    2015-10-09

    Lignin is a high-volume byproduct from the pulp and paper industry and is currently burned to generate electricity and process heat. Moreover, the industry has been searching for high value-added uses of lignin to improve the process economics. In addition, battery manufacturers are seeking nonfossil sources of graphitic carbon for environmental sustainability. In our work, lignin (which is a cross-linked polymer of phenols, a component of biomass) is converted into graphitic porous carbon using a two-step conversion. Lignin is first carbonized in water at 300 C and 1500 psi to produce biochar, which is then graphitized using a metal nitrate catalyst at 9001100 C in an inert gas at 15 psi. Graphitization effectiveness of three different catalystsiron, cobalt, and manganese nitratesis examined. The product is analyzed for morphology, thermal stability, surface properties, and electrical conductivity. Both temperature and catalyst type influenced the degree of graphitization. A good quality graphitic carbon was obtained using catalysis by Mn(NO3)2 at 900 C and Co(NO3)2 at 1100 C.

  20. Coating Strategies to Improve Lithium-ion Battery Safety

    SciTech Connect (OSTI)

    Travis, Jonathan; Orendorff, Christopher J.

    2015-09-01

    This work investigated the effects of Al2O3 ALD coatings on the performance and thermal abuse tolerance of graphite based anodes and Li(NixMnyCoz)O2 (NMC) based cathodes. It was found that 5 cycles of Al2O3 ALD on the graphite anode increased the onset temperature of thermal runaway by approximately 20 C and drastically reduced the anodes contribution to the overall amount of heat released during thermal runaway. Although Al2O3 ALD improves the cycling stability of NMC based cathodes, the thermal abuse tolerance was not greatly improved. A series of conductive aluminum oxide/carbon composites were created and characterized as potential thicker protective coatings for use on NMC based cathode materials. A series of electrodes were coated with manganese monoxide ALD to test the efficacy of an oxygen scavenging coating on NMC based cathodes.

  1. Process for making a martensitic steel alloy fuel cladding product

    DOE Patents [OSTI]

    Johnson, Gerald D. (Kennewick, WA); Lobsinger, Ralph J. (Kennewick, WA); Hamilton, Margaret L. (Richland, WA); Gelles, David S. (West Richland, WA)

    1990-01-01

    This is a very narrowly defined martensitic steel alloy fuel cladding material for liquid metal cooled reactors, and a process for making such a martensitic steel alloy material. The alloy contains about 10.6 wt. % chromium, about 1.5 wt. % molybdenum, about 0.85 wt. % manganese, about 0.2 wt. % niobium, about 0.37 wt. % silicon, about 0.2 wt. % carbon, about 0.2 wt. % vanadium, 0.05 maximum wt. % nickel, about 0.015 wt. % nitrogen, about 0.015 wt. % sulfur, about 0.05 wt. % copper, about 0.007 wt. % boron, about 0.007 wt. % phosphorous, and with the remainder being essentially iron. The process utilizes preparing such an alloy and homogenizing said alloy at about 1000.degree. C. for 16 hours; annealing said homogenized alloy at 1150.degree. C. for 15 minutes; and tempering said annealed alloy at 700.degree. C. for 2 hours. The material exhibits good high temperature strength (especially long stress rupture life) at elevated temperature (500.degree.-760.degree. C.).

  2. Correlating Local Structure with Electrochemical Activity in Li2MnO3

    DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)

    Nanda, Jagjit; Sacci, Robert L.; Veith, Gabriel M.; Dixit, Hemant M.; Cooper, Valentino R.; Pezeshki, Alan M.; Ruther, Rose E.

    2015-07-31

    Li2MnO3 is of interest as one component of the composite lithium-rich oxides, which are under development for high capacity, high voltage cathodes in lithium ion batteries. Despite such practical importance, the mechanism of electrochemical activity in Li2MnO3 is contested in the literature, as are the effects of long-term electrochemical cycling. Here, Raman spectroscopy and mapping are used to follow the chemical and structural changes that occur in Li2MnO3. Both conventional slurry electrodes and thin films are studied as a function of the state of charge (voltage) and cycle number. Thin films have similar electrochemical properties as electrodes prepared from slurries,more » but allow for spectroscopic investigations on uniform samples without carbon additives. Spectral changes correlate well with electrochemical activity and support a mechanism whereby capacity is lost upon extended cycling due to the formation of new manganese oxide phases. Raman mapping of both thin film and slurry electrodes charged to different voltages reveals significant variation in the local structure. Poor conductivity and slow kinetics associated with a two-phase reaction mechanism contribute to the heterogeneity.« less

  3. Evaluation of Neutron Radiography Reactor LEU-Core Start-Up Measurements

    DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)

    Bess, John D.; Maddock, Thomas L.; Smolinski, Andrew T.; Marshall, Margaret A.

    2014-11-04

    Benchmark models were developed to evaluate the cold-critical start-up measurements performed during the fresh core reload of the Neutron Radiography (NRAD) reactor with Low Enriched Uranium (LEU) fuel. Experiments include criticality, control-rod worth measurements, shutdown margin, and excess reactivity for four core loadings with 56, 60, 62, and 64 fuel elements. The worth of four graphite reflector block assemblies and an empty dry tube used for experiment irradiations were also measured and evaluated for the 60-fuel-element core configuration. Dominant uncertainties in the experimental keff come from uncertainties in the manganese content and impurities in the stainless steel fuel cladding asmore » well as the 236U and erbium poison content in the fuel matrix. Calculations with MCNP5 and ENDF/B-VII.0 neutron nuclear data are approximately 1.4% (9σ) greater than the benchmark model eigenvalues, which is commonly seen in Monte Carlo simulations of other TRIGA reactors. Simulations of the worth measurements are within the 2σ uncertainty for most of the benchmark experiment worth values. The complete benchmark evaluation details are available in the 2014 edition of the International Handbook of Evaluated Reactor Physics Benchmark Experiments.« less

  4. Extraction of Plutonium From Spiked INEEL Soil Samples Using the Ligand-Assisted Supercritical Fluid Extraction (LA-SFE) Technique

    SciTech Connect (OSTI)

    Fox, R.V.; Mincher, B.J.; Holmes, R.G.G.

    1999-08-01

    In order to investigate the effectiveness of ligand-assisted supercritical fluid extraction for the removal of transuranic contaminations from soils an Idaho National Engineering and Environmental Laboratory (INEEL) silty-clay soil sample was obtained from near the Radioactive Waste Management Complex area and subjected to three different chemical preparations before being spiked with plutonium. The spiked INEEL soil samples were subjected to a sequential aqueous extraction procedure to determine radionuclide portioning in each sample. Results from those extractions demonstrate that plutonium consistently partitioned into the residual fraction across all three INEEL soil preparations whereas americium partitioned 73% into the iron/manganese fraction for soil preparation A, with the balance partitioning into the residual fraction. Plutonium and americium were extracted from the INEEL soil samples using a ligand-assisted supercritical fluid extraction technique. Initial supercritical fluid extraction runs produced plutonium extraction technique. Initial supercritical fluid extraction runs produced plutonium extraction efficiencies ranging from 14% to 19%. After a second round wherein the initial extraction parameters were changed, the plutonium extraction efficiencies increased to 60% and as high as 80% with the americium level in the post-extracted soil samples dropping near to the detection limits. The third round of experiments are currently underway. These results demonstrate that the ligand-assisted supercritical fluid extraction technique can effectively extract plutonium from the spiked INEEL soil preparations.

  5. Investigation of materials for inert electrodes in aluminum electrodeposition cells

    SciTech Connect (OSTI)

    Haggerty, J. S.; Sadoway, D. R.

    1987-09-14

    Work was divided into major efforts. The first was the growth and characterization of specimens; the second was Hall cell performance testing. Cathode and anode materials were the subject of investigation. Preparation of specimens included growth of single crystals and synthesis of ultra high purity powders. Special attention was paid to ferrites as they were considered to be the most promising anode materials. Ferrite anode corrosion rates were studied and the electrical conductivities of a set of copper-manganese ferrites were measured. Float Zone, Pendant Drop Cryolite Experiments were undertaken because unsatisfactory choices of candidate materials were being made on the basis of a flawed set of selection criteria applied to an incomplete and sometimes inaccurate data base. This experiment was then constructed to determine whether the apparatus used for float zone crystal growth could be adapted to make a variety of important based melts and their interactions with candidate inert anode materials. The third major topic was Non Consumable Anode (Data Base, Candidate Compositions), driven by our perception that the basis for prior selection of candidate materials was inadequate. Results are presented. 162 refs., 39 figs., 18 tabs.

  6. Time-Dependent CO[subscript 2] Sorption Hysteresis in a One-Dimensional Microporous Octahedral Molecular Sieve

    SciTech Connect (OSTI)

    Espinal, Laura; Wong-Ng, Winnie; Kaduk, James A.; Allen, Andrew J.; Snyder, Chad R.; Chiu, Chun; Siderius, Daniel W.; Li, Lan; Cockayne, Eric; Espinal, Anais E.; Suib, Steven L.

    2014-09-24

    The development of sorbents for next-generation CO{sub 2} mitigation technologies will require better understanding of CO{sub 2}/sorbent interactions. Among the sorbents under consideration are shape-selective microporous molecular sieves with hierarchical pore morphologies of reduced dimensionality. We have characterized the non-equilibrium CO{sub 2} sorption of OMS-2, a well-known one-dimensional microporous octahedral molecular sieve with manganese oxide framework. Remarkably, we find that the degree of CO{sub 2} sorption hysteresis increases when the gas/sorbent system is allowed to equilibrate for longer times at each pressure step. Density functional theory calculations indicate a 'gate-keeping' role of the cation in the tunnel, only allowing CO{sub 2} molecules to enter fully into the tunnel via a highly unstable transient state when CO{sub 2} loadings exceed 0.75 mmol/g. The energy barrier associated with the gate-keeping effect suggests an adsorption mechanism in which kinetic trapping of CO{sub 2} is responsible for the observed hysteretic behavior.

  7. Complete genome sequence of Desulfomicrobium baculatum type strain (XT)

    SciTech Connect (OSTI)

    Copeland, Alex; Spring, Stefan; Goker, Markus; Schneider, Susanne; Lapidus, Alla; Glavina Del Rio, Tijana; Tice, Hope; Cheng, Jan-Fang; Lucas, Susan; Chen, Feng; Nolan, Matt; Bruce, David; Goodwin, Lynne; Pitluck, Sam; Ivanova, Natalia; Mavrommatis, Konstantinos; Ovchinnikova, Galina; Pati, Amrita; Chen, Amy; Palaniappan, Krishna; Land, Miriam; Hauser, Loren; Chang, Yun-Juan; Jefferies, Cynthia C; Meincke, Linda; Sims, David; Brettin, Thomas; Detter, John C; Han, Cliff; Chain, Patrick; Bristow, James; Eisen, Jonathan; Markowitz, Victor; Hugenholtz, Philip; Klenk, Hans-Peter; Kyrpides, Nikos C; Lucas, Susan

    2009-05-20

    Desulfomicrobium baculatum is the type species of the genus Desulfomicrobium, which is the type genus of the family Desulfomicrobiaceae. It is of phylogenetic interest because of the isolated location of the family Desulfomicrobiaceae within the order Desulfovibrionales. D. baculatum strain XT is a Gram-negative, motile, sulfate-reducing bacterium isolated from water-saturated manganese carbonate ore. It is strictly anaerobic and does not require NaCl for growth, although NaCl concentrations up to 6percent (w/v) are tolerated. The metabolism is respiratory or fermentative. In the presence of sulfate, pyruvate and lactate are incompletely oxidized to acetate and CO2. Here we describe the features of this organism, together with the complete genome sequence and annotation. This is the first completed genome sequence of a member of the deltaproteobacterial family Desulfomicrobiaceae, and this 3,942,657 bp long single replicon genome with its 3494 protein-coding and 72 RNA genes is part of the Genomic Encyclopedia of Bacteria and Archaea project.

  8. Evaluation of Neutron Radiography Reactor LEU-Core Start-Up Measurements

    SciTech Connect (OSTI)

    Bess, John D.; Maddock, Thomas L.; Smolinski, Andrew T.; Marshall, Margaret A.

    2014-11-04

    Benchmark models were developed to evaluate the cold-critical start-up measurements performed during the fresh core reload of the Neutron Radiography (NRAD) reactor with Low Enriched Uranium (LEU) fuel. Experiments include criticality, control-rod worth measurements, shutdown margin, and excess reactivity for four core loadings with 56, 60, 62, and 64 fuel elements. The worth of four graphite reflector block assemblies and an empty dry tube used for experiment irradiations were also measured and evaluated for the 60-fuel-element core configuration. Dominant uncertainties in the experimental keff come from uncertainties in the manganese content and impurities in the stainless steel fuel cladding as well as the 236U and erbium poison content in the fuel matrix. Calculations with MCNP5 and ENDF/B-VII.0 neutron nuclear data are approximately 1.4% (9?) greater than the benchmark model eigenvalues, which is commonly seen in Monte Carlo simulations of other TRIGA reactors. Simulations of the worth measurements are within the 2? uncertainty for most of the benchmark experiment worth values. The complete benchmark evaluation details are available in the 2014 edition of the International Handbook of Evaluated Reactor Physics Benchmark Experiments.

  9. On the bonding nature of electron states for the Fe-Mo double perovskite

    SciTech Connect (OSTI)

    Carvajal, E.; Cruz-Irisson, M.; Oviedo-Roa, R.; Navarro, O.

    2014-05-15

    The electronic transport as well as the effect of an external magnetic field has been investigated on manganese-based materials, spinels and perovskites. Potential applications of double perovskites go from magnetic sensors to electrodes in solid-oxide fuel cells; besides the practical interests, it is known that small changes in composition modify radically the physical properties of double perovskites. We have studied the Sr{sub 2}FeMoO{sub 6} double perovskite compound (SFMO) using first-principles density functional theory. The calculations were done within the generalized gradient approximation (GGA) scheme with the Perdew-Burke-Ernzerhof (PBE) functional. We have made a detailed analysis of each electronic state and the charge density maps around the Fermi level. For the electronic properties of SFMO it was used a primitive cell, for which we found the characteristic half-metallic behavior density of states composed by e{sub g} and t{sub 2g} electrons from Fe and Mo atoms. Those peaks were tagged as bonding or antibonding around the Fermi level at both, valence and conduction bands.

  10. Correlation between the electronic and atomic structure, transport properties, and oxygen vacancies on La{sub 0.7}Ca{sub 0.3}MnO{sub 3} thin films

    SciTech Connect (OSTI)

    Rubio-Zuazo, J. Onandia, L.; Castro, G. R.

    2014-01-13

    We present a study of the role of oxygen vacancies on the atomic and electronic structure and transport properties on a 20?nm thick La{sub 0.7}Ca{sub 0.3}MnO{sub 3} film grown by the pulsed laser deposition method on a SrTiO{sub 3} (001) substrate. The results show that oxygen vacancies induce an atomic structure modification characterized by the movement of the La/Ca cations to the perovskite regular position, by the reduction of the MnO{sub 6} basal plane rotation, and by a cooperative tilting of the octahedra along the out-of-plane direction. The out-of-plane lattice parameter increases due to the reduction of the Mn valence upon oxygen vacancies creation. As a consequence, a shift of the Metal-to-Insulator transition to lower temperatures is found to occur. We discuss the influence of the competitive phenomena of manganese valence and Mn-O-Mn bond distortion on the transport properties of manganite thin films.

  11. Method of preparing doped oxide catalysts for lean NOx exhaust

    DOE Patents [OSTI]

    Park, Paul W.

    2004-03-09

    The lean NOx catalyst includes a substrate, an oxide support material, preferably .gamma.-alumina deposited on the substrate and a metal or metal oxide promoter or dopant introduced into the oxide support material. The metal promoters or dopants are selected from the group consisting of indium, gallium, tin, silver, germanium, gold, nickel, cobalt, copper, iron, manganese, molybdenum, chromium cerium, and vanadium, and oxides thereof, and any combinations thereof. The .gamma.-alumina preferably has a pore volume of from about 0.5 to about 2.0 cc/g; a surface area of between 80 and 350 m.sup.2 /g; an average pore size diameter of between about 3 to 30 nm; and an impurity level of less than or equal to about 0.2 weight percent. In a preferred embodiment the .gamma.-alumina is prepared by a sol-gel method, with the metal doping of the .gamma.-alumina preferably accomplished using an incipient wetness impregnation technique.

  12. Metal/metal oxide doped oxide catalysts having high deNOx selectivity for lean NOx exhaust aftertreatment systems

    DOE Patents [OSTI]

    Park, Paul W.

    2004-03-16

    A lean NOx catalyst and method of preparing the same is disclosed. The lean NOx catalyst includes a ceramic substrate, an oxide support material, preferably .gamma.-alumina, deposited on the substrate and a metal promoter or dopant introduced into the oxide support material. The metal promoters or dopants are selected from the group consisting of indium, gallium, tin, silver, germanium, gold, nickel, cobalt, copper, iron, manganese, molybdenum, chromium, cerium, vanadium, oxides thereof, and combinations thereof. The .gamma.-alumina preferably has a pore volume of from about 0.5 to about 2.0 cc/g; a surface area of between about 80 to 350 m.sup.2 /g; an average pore size diameter of between about 3 to 30 nm; and an impurity level of less than or equal to 0.2 weight percent. In a preferred embodiment the .gamma.-alumina is prepared by a sol-gel method, with the metal doping of the .gamma.-alumina preferably accomplished using an incipient wetness impregnation technique.

  13. Evaluation of 2.25Cr-1Mo Alloy for Containment of LiCl/KCl Eutectic during the Pyrometallurgical Processing of Used Nuclear Fuel

    SciTech Connect (OSTI)

    B.R. Westphal; S.X. Li; G.L. Fredrickson; D. Vaden; T.A. Johnson; J.C. Wass

    2011-03-01

    Recovery of uranium from the Mk-IV and Mk-V electrorefiner vessels containing a LiCl/KCl eutectic salt has been on-going for 14 and 12 years, respectively, during the pyrometallurgical processing of used nuclear fuel. Although austenitic stainless steels are typically utilized for LiCl/KCl salt systems, the presence of cadmium in the Mk-IV electrorefiner dictates an alternate material. A 2.25Cr-1Mo alloy (ASME SA-387) was chosen due to the absence of nickel in the alloy which has a considerable solubility in cadmium. Using the transition metal impurities (iron, chromium, nickel, molybdenum, and manganese) in the electrorefined uranium products, an algorithm was developed to derive values for the contribution of the transition metals from the various input sources. Weight loss and corrosion rate data for the Mk-V electrorefiner vessel were then generated based on the transition metal impurities in the uranium products. To date, the corrosion rate of the 2.25Cr-1Mo alloy in LiCl/KCl eutectic is outstanding assuming uniform (i.e. non-localized) conditions.

  14. Development of a new casting method to fabricate UZr alloy containing minor actinides

    SciTech Connect (OSTI)

    Jong Hwan Kim; Hoon Song; Hyung Tae Kim; Ki Hwan Kim; Chan Bock Lee; R. S. Fielding

    2014-01-01

    Metal fuel slugs of UZr alloys for a sodium-cooled fast reactor (SFR) have conventionally been fabricated using an injection casting method. However, casting alloys containing volatile radioactive constituents, such as Am, are problematic in a conventional injection casting method. As an alternative fabrication method, low pressure gravity casting has been developed. Casting soundness, microstructural characteristics, alloying composition, density, and fuel losses were evaluated for the following as-cast fuel slugs: U10 wt% Zr, U10 wt% Zr5 wt% RE, and U10 wt% Zr5 wt% RE5 wt% Mn. The U and Zr contents were uniform throughout the matrix, and impurities such as oxyen, carbon, and nitrogen satisfied the specification of total impurities less than 2,000 ppm. The appearance of the fuel slugs was generally sound, and the internal integrity was shown to be satisfactory based on gamma-ray radiography. In a volatile surrogate casting test, the UZrREMn fuel slug showed that nearly all of the manganese was retained when casting was done under an inert atmosphere.

  15. An issue paper on the use of hydrogen getters in transportation packaging

    SciTech Connect (OSTI)

    NIGREY,PAUL J.

    2000-02-01

    The accumulation of hydrogen is usually an undesirable occurrence because buildup in sealed systems pose explosion hazards under certain conditions. Hydrogen scavengers, or getters, can avert these problems by removing hydrogen from such environments. This paper provides a review of a number of reversible and irreversible getters that potentially could be used to reduce the buildup of hydrogen gas in containers for the transport of radioactive materials. In addition to describing getters that have already been used for such purposes, novel getters that might find application in future transport packages are also discussed. This paper also discusses getter material poisoning, the use of getters in packaging, the effects of radiation on getters, the compatibility of getters with packaging, design considerations, regulatory precedents, and makes general recommendations for the materials that have the greatest applicability in transport packaging. At this time, the Pacific Northwest National Laboratory composite getter, DEB [1,4-(phenylethylene)benzene] or similar polymer-based getters, and a manganese dioxide-based getter appear to be attractive candidates that should be further evaluated. These getters potentially can help prevent pressurization from radiolytic reactions in transportation packaging.

  16. Coal quality trends and distribution of Title III trace elements in Eastern Kentucky coals

    SciTech Connect (OSTI)

    Eble, C.F.; Hower, J.C.

    1995-12-31

    The quality characteristics of eastern Kentucky coal beds vary both spatially and stratigraphically. Average total sulfur contents are lowest, and calorific values highest, in the Big Sandy and Upper Cumberland Reserve Districts. Average coal thickness is greatest in these two districts as well. Conversely, the thinnest coal with the highest total sulfur content, and lowest calorific value, on average, occurs in the Princess and Southwest Reserve Districts. Several Title III trace elements, notably arsenic, cadmium, lead, mercury, and nickel, mirror this distribution (lower average concentrations in the Big Sandy and Upper Cumberland Districts, higher average concentrations in the Princess and Southwest Districts), probably because these elements are primarily associated with sulfide minerals in coal. Ash yields and total sulfur contents are observed to increase in a stratigraphically older to younger direction. Several Title III elements, notably cadmium, chromium, lead, and selenium follow this trend, with average concentrations being higher in younger coals. Average chlorine concentration shows a reciprocal distribution, being more abundant in older coals. Some elements, such as arsenic, manganese, mercury, cobalt, and, to a lesser extent, phosphorus show concentration spikes in coal beds directly above, or below, major marine zones. With a few exceptions, average Title III trace element concentrations for eastern Kentucky coals are comparable with element distributions in other Appalachian coal-producing states.

  17. Niagara Falls Storage Site environmental report for calendar year 1992, 1397 Pletcher Road, Lewiston, New York. Formerly Utilized Sites Remedial Action Program (FUSRAP)

    SciTech Connect (OSTI)

    Not Available

    1993-05-01

    This report describes the environmental surveillance program at the Niagara Falls Storage Site (NFSS) and provides the results for 1992. From 1944 to the present, the primary use of NFSS has been storage of radioactive residues produced as a by-product of uranium production. All onsite areas of residual radioactivity above guidelines have been remediated. Materials generated during remediation are stored onsite in the 4-ha (10-acre) waste containment structure (WCS). The WCS is a clay-lined, clay-capped, and grass-covered storage pile. The environmental surveillance program at NFSS includes sampling networks for radon concentrations in air; external gamma radiation exposure; and total uranium and radium-226 concentrations in surface water, sediments, and groundwater. Several chemical parameters, including seven metals, are also routinely measured in groundwater. This surveillance program assists in fulfilling the DOE policy of measuring and monitoring effluents from DOE activities and calculating hypothetical doses. Monitoring results are compared with applicable Environmental Protection Agency (EPA) and New York State Department of Environmental Conservation (NYSDEC) standards, DOE derived concentration guides (DCGs), dose limits, and other DOE requirements. Results of environmental monitoring during 1992 indicate that levels of the parameters measured were in compliance with all but one requirement: Concentrations of iron and manganese in groundwater were above NYSDEC groundwater quality standards. However, these elements occur naturally in the soils and groundwater associated with this region. In 1992 there were no environmental occurrences or reportable quantity releases.

  18. Intrinsic in situ anaerobic biodegradation of chlorinated solvents at an industrial landfill

    SciTech Connect (OSTI)

    Lee, M.D.; Mazierski, P.F.; Buchanan, R.J. Jr.; Ellis, D.E.; Sehayek, L.S.

    1995-12-31

    The DuPont Necco Park Landfill in Niagara Falls, New York, is contaminated with numerous chlorinated solvents at concentrations of up to hundreds of mg/L in the groundwater. An extensive monitoring program was conducted to determine if intrinsic anaerobic biodegradation was occurring at the site, to determine what might limit this activity, and to characterize this activity with depth and distance away from the landfill. It was determined that anaerobic microbial activity was occurring in all zones, based upon the presence of intermediate products of the breakdown of the chlorinated solvents and the presence of final metabolic end products such as ethene and ethane. Aerobic, iron-reducing, manganese-reducing, sulfate-reducing, and methanogenic redox conditions were identified at the site. High levels of nitrogen and biodegradable organic compounds were present in most areas to support cometabolic anaerobic microbial activity against the chlorinated solvents. Intrinsic biodegradation is clearly evident and is effective in reducing the concentrations of chlorinated organic in the groundwater at the site. Groundwater modeling efforts during development of a site conceptual model indicated that microbial degradation was necessary to account for the downgradient reduction of chlorinated volatile organic compounds as compared to chloride, a conservative indicator parameter.

  19. Uranium hydrogeochemical and stream sediment reconnaissance data release for the Elk City NTMS Quadrangle, Idaho/Montana, including concentrations of forty-five additional elements

    SciTech Connect (OSTI)

    Broxton, D.E.; Beyth, M.

    1980-07-01

    Totals of 1580 water and 1720 sediment samples were collected from 1754 locations in the quadrangle. Elemental concentration, field measurement, weather, geologic, and geographic data for each sample location are listed for waters in Appendix I-A and for sediments in Appendix I-B. Uranium/thorium ratios for sediment samples are also included in Appendix I-B. All elemental analyses were performed at the LASL. Water samples were initially analyzed for uranium by fluorometry. All water samples containing more than 40 parts per billion (ppB) uranium were reanalyzed by delayed-neutron counting (DNC). A supplemental report containing the multielement analyses of water samples will be open filed in the near future. Sediments were analyzed for uranium and thorium as well as aluminum, antimony, arsenic, barium, beryllium, bismuth, cadmium, calcium, cerium, cesium, chlorine, chromium, cobalt, copper, dysprosium, europium, gold, hafnium, iron, lanthanum, lead, lithium, lutetium, magnesium, manganese, nickel, niobium, potassium, rubidium, samarium, selenium, scandium, silver, sodium, strontium, tantalum, terbium, tin, titanium, tungsten, vanadium, ytterbium, zinc, and zirconium. Basic statistics for 40 of these elements are presented. All sediments were analyzed for uranium by delayed-neutron counting. Other elemental concentrations in sediments were determined by neutron-activation analysis for 30 elements, by x-ray fluorescence for 12 elements, and by arc-source emission spectrography for 2 elements. Analytical results for sediments are reported as parts per million.

  20. A statistical study of the macroepidemiology of air pollution and total mortality

    SciTech Connect (OSTI)

    Lipfert, F.W.; Malone, R.G.; Daum, M.L.; Mendell, N.R.; Yang, Chin-Chun

    1988-04-01

    A statistical analysis of spatial patterns of 1980 US urban total mortality (all causes) was performed, evaluating demographic, socioeconomic and air pollution factors as predictors. Specific mortality predictors included cigarette smoking, drinking water hardness, heating fuel use, and 1978-1982 annual concentrations of the following air pollutants: ozone, carbon monoxide, sulfate aerosol, particulate concentrations of lead, iron, cadmium, manganese, vanadium, as well as total and fine particle mass concentrations from the inhalable particulate network (dichotomous samplers). In addition, estimates of sulfur dioxide, oxides of nitrogen, and sulfate aerosol were made for each city using the ASTRAP long-range transport diffusion model, and entered into the analysis as independent variables. Because the number of cities with valid air quality and water hardness data varied considerably by pollutant, it was necessary to consider several different data sets, ranging from 48 to 952 cities. The relatively strong associations (ca. 5--10%) shown for 1980 pollution with 1980 total mortality are generally not confirmed by independent studies, for example, in Europe. In addition, the US studies did not find those pollutants with known adverse health effects at the concentrations in question (such as ozone or CO) to be associated with mortality. The question of causality vs. circumstantial association must therefore be regarded as still unresolved. 59 refs., 20 figs., 40 tabs.

  1. Leachate treatment system using constructed wetlands, Town of Fenton sanitary landfill, Broome County, New York. Final report

    SciTech Connect (OSTI)

    Not Available

    1993-11-01

    Municipal sanitary landfills generate leachate that New York State regulations require to be collected and treated to avoid contaminating surface water and groundwater. One option for treating leachate is to haul it to municipal wastewater treatment facility. This option may be expensive, may require excessive energy for transportation, and may require pretreatment to protect the receiving facility`s processes. An alternative is on-site treatment and discharge. Personnel from the Town of Fenton, New York; Hawk Engineering, P.C.; Cornell University; and Ithaca College designed, built, and operated a pilot constructed wetland for treating leachate at the Town of Fenton`s municipal landfill. The system, consisting of two overland flow beds and two subsurface flow beds has been effective for 18 months in reducing levels of ammonia (averaging 85% removal by volatilization and denitrification) and total iron (averaging 95% removal by precipitation and sedimentation), two key constituents of the Fenton landfill`s leachate. The system effects these reductions with zero chemical and energy inputs and minimal maintenance. A third key constituent of the leachate, manganese, apparently passes through the beds with minimal removal. Details and wetland considerations are described.

  2. Coating system to permit direct brazing of ceramics

    DOE Patents [OSTI]

    Cadden, Charles H.; Hosking, F. Michael

    2003-01-01

    This invention relates to a method for preparing the surface of a ceramic component that enables direct brazing using a non-active braze alloy. The present invention also relates to a method for directly brazing a ceramic component to a ceramic or metal member using this method of surface preparation, and to articles produced by using this brazing method. The ceramic can be high purity alumina. The method comprises applying a first coating of a silicon-bearing oxide material (e.g. silicon dioxide or mullite (3Al.sub.2 O.sub.3.2SiO.sub.2) to the ceramic. Next, a thin coating of active metal (e.g. Ti or V) is applied. Finally, a thicker coating of a non-active metal (e.g. Au or Cu) is applied. The coatings can be applied by physical vapor deposition (PVD). Alternatively, the active and non-active metals can be co-deposited (e.g. by sputtering a target made of mullite). After all of the coatings have been applied, the ceramic can be fired at a high temperature in a non-oxidizing environment to promote diffusion, and to enhance bonding of the coatings to the substrate. After firing, the metallized ceramic component can be brazed to other components using a conventional non-active braze alloy. Alternatively, the firing and brazing steps can be combined into a single step. This process can replace the need to perform a "moly-manganese" metallization step.

  3. Basics and prospective of magnetic Heusler compounds

    SciTech Connect (OSTI)

    Felser, Claudia Wollmann, Lukas; Chadov, Stanislav; Fecher, Gerhard H.; Parkin, Stuart S. P.

    2015-04-01

    Heusler compounds are a remarkable class of materials with more than 1000 members and a wide range of extraordinary multi-functionalities including halfmetallic high-temperature ferri- and ferromagnets, multi-ferroics, shape memory alloys, and tunable topological insulators with a high potential for spintronics, energy technologies, and magneto-caloric applications. The tunability of this class of materials is exceptional and nearly every functionality can be designed. Co{sub 2}-Heusler compounds show high spin polarization in tunnel junction devices and spin-resolved photoemission. Manganese-rich Heusler compounds attract much interest in the context of spin transfer torque, spin Hall effect, and rare earth free hard magnets. Most Mn{sub 2}-Heusler compounds crystallize in the inverse structure and are characterized by antiparallel coupling of magnetic moments on Mn atoms; the ferrimagnetic order and the lack of inversion symmetry lead to the emergence of new properties that are absent in ferromagnetic centrosymmetric Heusler structures, such as non-collinear magnetism, topological Hall effect, and skyrmions. Tetragonal Heusler compounds with large magneto crystalline anisotropy can be easily designed by positioning the Fermi energy at the van Hove singularity in one of the spin channels. Here, we give a comprehensive overview and a prospective on the magnetic properties of Heusler materials.

  4. Effect of silver doping on the surface of La{sub 5/8}Ca{sub 3/8}MnO{sub 3} epitaxial films

    SciTech Connect (OSTI)

    Tselev, A. Vasudevan, R. K.; Kalinin, S. V.; Baddorf, A. P.

    2014-09-08

    Thin film manganese oxides (manganites) display remarkable properties, such as colossal magnetoresistance and charge ordered phases, and became a focal point of research in the past two decades owing to potential applications ranging from oxide spintronics to resistive switching-based memories. La{sub x}Ca{sub 1−x}MnO{sub 3} (LCMO), a widely studied manganite, is known to substantially improve its transport properties when doped with Ag. However, despite the abundance of studies on LCMO, the effect of silver on the surface structure is unknown. Here, through in-situ methods, scanning tunneling microscopy (STM) is performed on La{sub 5/8}Ca{sub 3/8}MnO{sub 3} films grown by pulsed laser deposition. Films doped by silver, as confirmed by in-situ X-ray photoelectron spectroscopy, display large-scale reconstructions, interpreted as being of type (√10 × √10)R18.4°, while films lacking silver display a (√2 × √2)R45° reconstruction that may be associated with a surface charge-ordered state. It is posited that the possible cause of the varied reconstructions is due to a vacancy ordering on top of the existing (√2 × √2)R45° reconstruction. These studies highlight the influence of Ag on the surface structure, and therefore a route towards modifying the surface properties of manganites.

  5. Atomic-scale electrochemistry on the surface of a manganite by scanning tunneling microscopy

    SciTech Connect (OSTI)

    Vasudevan, Rama K. Tselev, Alexander; Baddorf, Arthur P.; Gianfrancesco, Anthony G.

    2015-04-06

    The doped manganese oxides (manganites) have been widely studied for their colossal magnetoresistive effects, for potential applications in oxide spintronics, electroforming in resistive switching devices, and are materials of choice as cathodes in modern solid oxide fuel cells. However, little experimental knowledge of the dynamics of the surfaces of perovskite manganites at the atomic scale exists. Here, through in-situ scanning tunneling microscopy (STM), we demonstrate atomic resolution on samples of La{sub 0.625}Ca{sub 0.375}MnO{sub 3} grown on (001) SrTiO{sub 3} by pulsed laser deposition. Furthermore, by applying triangular DC waveforms of increasing amplitude to the STM tip, and measuring the tunneling current, we demonstrate the ability to both perform and monitor surface electrochemical processes at the atomic level, including formation of oxygen vacancies and removal and deposition of individual atomic units or clusters. Our work paves the way for better understanding of surface oxygen reactions in these systems.

  6. Effect of silver doping on the surface of La5/8Ca3/8MnO3 epitaxial films

    SciTech Connect (OSTI)

    Tselev, Alexander; Vasudevan, Rama K; Kalinin, Sergei V; Baddorf, Arthur P

    2014-01-01

    Thin film manganese oxides (manganites) display remarkable properties such as colossal magnetoresistance and charge ordered phases, and became a focal point of research in the past two decades owing to potential applications ranging from oxide spintronics to resistive switching-based memories. LaxCa1-xMnO3 (LCMO), a widely studied manganite, is known to substantially improve its transport properties when doped with Ag. However, despite the abundance of studies on LCMO, the effect of silver on the surface structure is unknown. Here, through in-situ methods, scanning tunneling microscopy (STM) is performed on La5/8Ca3/8MnO3 films grown by pulsed laser deposition. Films doped by silver, as confirmed by in-situ X-ray photoelectron spectroscopy (XPS), display large-scale reconstructions, interpreted as being of type ( 10 10)R18.4 , while films lacking silver display a ( 2 2)R45 reconstruction that may be associated with a surface charge-ordered state. It is posited that the possible cause of the varied reconstructions is due to a vacancy ordering on top of the existing ( 2 2)R45 reconstruction. These studies highlight the influence of Ag on the surface structure, and therefore a route towards modifying the surface properties of manganites.

  7. Development of enhanced sulfur rejection processes. Final technical progress report, third quarter (8. quarterly report), July 1--September 30, 1994

    SciTech Connect (OSTI)

    Yoon, R.H.; Luttrell, G.H.; Tao, D.P.; Lu, M.X.; Richardson, P.E.

    1996-03-20

    Pyrite becomes hydrophobic upon superficial oxidation and floats without a collector. The flotation begins to occur at potentials above the stable potentials identified by the chronoamperometry experiments conducted with freshly fractured pyrite. This finding suggests that iron polysulfide, formed during the initial stages of oxidation, is responsible for the flotation. The collectorless flotation is suppressed above the potential where the mineral is aggressively oxidized, forming iron hydroxide and soluble sulfoxy species. The collectorless flotation is less significant at pH 9.2 than at pH 4.6, possibly due to the formation of iron hydroxide. At pH 9.2, the collectorless flotation increases in the presence of EDTA and hydrocarbon oil. The collectorless flotation of pyrite can be suppressed by galvanically coupling the mineral with reactive metals such as aluminum, manganese, and zinc. This effectively prevents the mineral from oxidation. The microflotation tests conducted with mono-sized pyrite samples show that the collectorless flotation can be suppressed effectively in the presence of metal powders. Bench-scale flotation experiments conducted using Denver laboratory flotation cell and a 2-inch diameter Microcel flotation column, also demonstrates that the collectorless flotation can be suppressed in the presence of the reactive metals. It has been established that the most important parameters determining the effectiveness of suppressing pyrite flotation by the galvanic coupling technique are the surface area of the galvanic contractors and the solids concentration of the slurry during conditioning.

  8. Mutagenicity and genotoxicity of coal fly ash water leachate

    SciTech Connect (OSTI)

    Chakraborty, R.; Mukherjee, A.

    2009-03-15

    Fly ash is a by-product of coal-fired electricity generation plants. The prevalent practice of disposal is as slurry of ash and water to storage or ash ponds located near power stations. This has lain to waste thousands of hectares of land all over the world. Since leaching is often the cause of off-site contamination and pathway of introduction into the human environment, a study on the genotoxic effects of fly ash leachate is essential. Leachate prepared from the fly ash sample was analyzed for metal content, and tested for mutagenicity and genotoxicity. Analyses of metals show predominance of the metals - sodium, silicon, potassium, calcium, magnesium, iron, manganese, zinc, and sulphate. The Ames Salmonella mutagenicity assay, a short-term bacterial reverse mutation assay, was conducted on two-tester strains of Salmonella typhimurium strains TA97a and TA102. For genotoxicity, the alkaline version of comet assay on fly ash leachate was carried in vitro on human blood cells and in vivo on Nicotiana plants. The leachate was directly mutagenic and induced significantconcentration-dependent increases in DNA damage in whole blood cells, lymphocytes, and in Nicotiana plants. The comet parameters show increases in tail DNA percentage (%), tail length (mu m), and olive tail moment (arbitrary units). Our results indicate that leachate from fly ash dumpsites has the genotoxic potential and may lead to adverse effects on vegetation and on the health of exposed human populations.

  9. Deciphering Ni sequestration in soil ferromanganese nodules by combining x-ray fluorescence, absorption and diffraction at micrometer scales of resolution

    SciTech Connect (OSTI)

    Manceau, Alain; Tamura, Nobumichi; Marcus, Matthew A.; MacDowell, Alastair A.; Celestre, Richard S.; Sublett, Robert E.; Sposito, Garrison; Padmore, Howard A.

    2002-11-06

    X-ray microprobes are among the most important new analytical techniques to emerge from third generation synchrotron facilities. Here we show how X-ray fluorescence, diffraction, and absorption can be used in parallel to determine the structural form of trace elements in heterogeneous matrices at the micrometer-scale of resolution. Scanning X-ray microfluorescence (microSXRF) and microdiffraction (microSXRD) first are used to identify the host solid phase by mapping the distributions of elements and solid species, respectively. Micro-extended X-ray absorption fine structure (microEXAFS) spectroscopy is then used to determine the mechanism of trace element binding by the host phase at the molecular scale. To illustrate the complementary application of these three techniques, we studied how nickel is sequestered in soil ferromanganese nodules, an overwhelmingly complex natural matrix consisting of submicrometer to nanometer sized particles with varying structures and chemical composition s. We show that nickel substitutes for Mn3+ in the manganese layer of the MnO2-Al(OH)3 mixed-layer oxide lithiophorite. The affinity of Ni for lithiophorite was characteristic of micromodules sampled from soils across the U.S.A. and Europe. Since many natural and synthetic materials are heterogeneous at nanometer to micrometer scales, the synergistic use of microSXRF, microSXRD and microEXAFS is expected to have broad applications to earth and materials science.

  10. Mechanical design of ceramic beam tube braze joints for NOvA kicker magnets

    SciTech Connect (OSTI)

    Ader, C.R.; Reilly, R.E.; Wilson, J.H.

    2010-05-01

    The NO?A Experiment will construct a detector optimized for electron neutrino detection in the existing NuMI neutrino beam. The NuMI beam line is capable of operating at 400 kW of primary beam power and the upgrade will allow up to 700 kW. Ceramic beam tubes are utilized in numerous kicker magnets in different accelerator rings at Fermi National Accelerator Laboratory. Kovar flanges are brazed onto each beam tube end, since kovar and high alumina ceramic have similar expansion curves. The tube, kovar flange, end piece, and braze foil alloy brazing material are stacked in the furnace and then brazed. The most challenging aspect of fabricating kicker magnets in recent years have been making hermetic vacuum seals on the braze joints between the ceramic and flange. Numerous process variables can influence the robustness of conventional metal/ceramic brazing processes. The ceramic-filler metal interface is normally the weak layer when failure does not occur within the ceramic. Differences between active brazing filler metal and the moly-manganese process will be discussed along with the applicable results of these techniques used for Fermilab production kicker tubes.

  11. Atomic-scale electrochemistry on the surface of a manganite

    DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)

    Vasudevan, Rama K; Tselev, Alexander; Baddorf, Arthur P; Kalinin, Sergei V

    2015-01-01

    The doped manganese oxides (manganites) have been widely studied for their colossal magnetoresistive effects, for potential applications in oxide spintronics, electroforming in resistive switching devices, and are materials of choice as cathodes in modern solid oxide fuel cells. However, little experimental knowledge of the dynamics of the surfaces of perovskite manganites at the atomic scale exists. Here, through in-situ scanning tunnelling microscopy (STM), we demonstrate atomic resolution on samples of La0.625Ca0.375MnO3 grown on (001) SrTiO3 by pulsed laser deposition (PLD). Furthermore, by applying triangular DC waveforms of increasing amplitude to the STM tip, and measuring the tunnelling current, we demonstratemore » the ability to both perform and monitor surface electrochemical processes at the atomic level, including, for the first time in a manganite, formation of single and multiple oxygen vacancies, disruption of the overlying manganite layers, and removal and deposition of individual atomic units or clusters. Our work paves the way for better understanding of surface oxygen reactions in these systems.« less

  12. Using support vector machines to improve elemental ion identification in macromolecular crystal structures

    DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)

    Morshed, Nader; Echols, Nathaniel; Adams, Paul D.

    2015-04-25

    In the process of macromolecular model building, crystallographers must examine electron density for isolated atoms and differentiate sites containing structured solvent molecules from those containing elemental ions. This task requires specific knowledge of metal-binding chemistry and scattering properties and is prone to error. A method has previously been described to identify ions based on manually chosen criteria for a number of elements. Here, the use of support vector machines (SVMs) to automatically classify isolated atoms as either solvent or one of various ions is described. Two data sets of protein crystal structures, one containing manually curated structures deposited with anomalousmore » diffraction data and another with automatically filtered, high-resolution structures, were constructed. On the manually curated data set, an SVM classifier was able to distinguish calcium from manganese, zinc, iron and nickel, as well as all five of these ions from water molecules, with a high degree of accuracy. Additionally, SVMs trained on the automatically curated set of high-resolution structures were able to successfully classify most common elemental ions in an independent validation test set. This method is readily extensible to other elemental ions and can also be used in conjunction with previous methods based on a priori expectations of the chemical environment and X-ray scattering.« less

  13. Metallurgical Laboratory Hazardous Waste Management Facility groundwater monitoring report: First quarter 1992

    SciTech Connect (OSTI)

    Thompson, C.Y.

    1992-06-01

    During first quarter 1992, 18 groundwater monitoring wells of the AMB series at the Metallurgical Laboratory Hazardous Waste Management Facility (Metlab HWMF) at Savannah River Plant were visited for sampling. Groundwater samples were analyzed for certain heavy metals, indicator parameters, radionuclides, volatile organic compounds, and other constituents. This report describes the results that exceeded the US Environmental Protection Agency Primary Drinking Water Standards (PDWS) and the Savannah River Site flagging criteria during the quarter. Tetrachloroethylene exceeded the PDWS in wells AMB 4A, 5, and 7A; trichloroethylene exceeded the PDWS in wells AMB 4A, 4B, 4D, 5, and 7A; and total alpha-emitting radium (radium-224 and radium-226) exceeded the PDWS in well AMB 5. Total organic halogens exceeded the Flag 2 criterion in wells AMB 4A, 5, 6, 7A, 7B, and IODD; manganese was elevated in wells AMB 4D and TODD; iron was elevated in well AMB TODD; and pH was elevated in well AMB 10A.

  14. Graphitic biocarbon from metal-catalyzed hydrothermal carbonization of lignin

    DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)

    Demir, Muslum; Kahveci, Zafer; Aksoy, Burak; Palapati, Naveen K. R.; Subramanian, Arunkumar; Cullinan, Harry T.; El-Kaderi, Hani M.; Harris, Charles T.; Gupta, Ram B.

    2015-10-09

    Lignin is a high-volume byproduct from the pulp and paper industry and is currently burned to generate electricity and process heat. Moreover, the industry has been searching for high value-added uses of lignin to improve the process economics. In addition, battery manufacturers are seeking nonfossil sources of graphitic carbon for environmental sustainability. In our work, lignin (which is a cross-linked polymer of phenols, a component of biomass) is converted into graphitic porous carbon using a two-step conversion. Lignin is first carbonized in water at 300 °C and 1500 psi to produce biochar, which is then graphitized using a metal nitratemore » catalyst at 900–1100 °C in an inert gas at 15 psi. Graphitization effectiveness of three different catalysts—iron, cobalt, and manganese nitrates—is examined. The product is analyzed for morphology, thermal stability, surface properties, and electrical conductivity. Both temperature and catalyst type influenced the degree of graphitization. A good quality graphitic carbon was obtained using catalysis by Mn(NO3)2 at 900 °C and Co(NO3)2 at 1100 °C.« less

  15. Optimization of chemical compositions in low-carbon Al-killed enamel steel produced by ultra-fast continuous annealing

    SciTech Connect (OSTI)

    Dong, Futao; Du, Linxiu; Liu, Xianghua; Xue, Fei

    2013-10-15

    The influence of Mn,S and B contents on microstructural characteristics, mechanical properties and hydrogen trapping ability of low-carbon Al-killed enamel steel was investigated. The materials were produced and processed in a laboratory and the ultra-fast continuous annealing processing was performed using a continuous annealing simulator. It was found that increasing Mn,S contents in steel can improve its hydrogen trapping ability which is attributed by refined ferrite grains, more dispersed cementite and added MnS inclusions. Nevertheless, it deteriorates mechanical properties of steel sheet. Addition of trace boron results in both good mechanical properties and significantly improved hydrogen trapping ability. The boron combined with nitrogen segregating at grain boundaries, cementite and MnS inclusions, provides higher amount of attractive hydrogen trapping sites and raises the activation energy for hydrogen desorption from them. - Highlights: We study microstructures and properties in low-carbon Al-killed enamel steel. Hydrogen diffusion coefficients are measured to reflect fish-scale resistance. Manganese improves hydrogen trapping ability but decrease deep-drawing ability. Boron improves both hydrogen trapping ability and deep-drawing ability. Both excellent mechanical properties and fish-scale resistance can be matched.

  16. Atomic-scale electrochemistry on the surface of a manganite

    SciTech Connect (OSTI)

    Vasudevan, Rama K; Tselev, Alexander; Baddorf, Arthur P; Kalinin, Sergei V

    2015-01-01

    The doped manganese oxides (manganites) have been widely studied for their colossal magnetoresistive effects, for potential applications in oxide spintronics, electroforming in resistive switching devices, and are materials of choice as cathodes in modern solid oxide fuel cells. However, little experimental knowledge of the dynamics of the surfaces of perovskite manganites at the atomic scale exists. Here, through in-situ scanning tunnelling microscopy (STM), we demonstrate atomic resolution on samples of La0.625Ca0.375MnO3 grown on (001) SrTiO3 by pulsed laser deposition (PLD). Furthermore, by applying triangular DC waveforms of increasing amplitude to the STM tip, and measuring the tunnelling current, we demonstrate the ability to both perform and monitor surface electrochemical processes at the atomic level, including, for the first time in a manganite, formation of single and multiple oxygen vacancies, disruption of the overlying manganite layers, and removal and deposition of individual atomic units or clusters. Our work paves the way for better understanding of surface oxygen reactions in these systems.

  17. Superconducting composite with multilayer patterns and multiple buffer layers

    DOE Patents [OSTI]

    Wu, Xin D. (Greenbelt, MD); Muenchausen, Ross E. (Espanola, NM)

    1993-01-01

    An article of manufacture including a substrate, a patterned interlayer of a material selected from the group consisting of magnesium oxide, barium-titanium oxide or barium-zirconium oxide, the patterned interlayer material overcoated with a secondary interlayer material of yttria-stabilized zirconia or magnesium-aluminum oxide, upon the surface of the substrate whereby an intermediate article with an exposed surface of both the overcoated patterned interlayer and the substrate is formed, a coating of a buffer layer selected from the group consisting of cerium oxide, yttrium oxide, curium oxide, dysprosium oxide, erbium oxide, europium oxide, iron oxide, gadolinium oxide, holmium oxide, indium oxide, lanthanum oxide, manganese oxide, lutetium oxide, neodymium oxide, praseodymium oxide, plutonium oxide, samarium oxide, terbium oxide, thallium oxide, thulium oxide, yttrium oxide and ytterbium oxide over the entire exposed surface of the intermediate article, and, a ceramic superco n FIELD OF THE INVENTION The present invention relates to the field of superconducting articles having two distinct regions of superconductive material with differing in-plane orientations whereby the conductivity across the boundary between the two regions can be tailored. This invention is the result of a contract with the Department of Energy (Contract No. W-7405-ENG-36).

  18. Preparation and characterization of nanostructured NiO/MnO{sub 2} composite electrode for electrochemical supercapacitors

    SciTech Connect (OSTI)

    Liu Enhui Li Wen; Li Jian; Meng Xiangyun; Ding Rui; Tan Songting

    2009-05-06

    Nanostructured nickel-manganese oxides composite was prepared by the sol-gel and the chemistry deposition combination new route. The surface morphology and structure of the composite were characterized by scanning electron microscope and X-ray diffraction. The as-synthesized NiO/MnO{sub 2} samples exhibit higher surface area of 130-190 m{sup 2} g{sup -1}. Cyclic voltammetry and galvanostatic charge/discharge measurements were applied to investigate the electrochemical performance of the composite electrodes with different ratios of NiO/MnO{sub 2}. When the mass ratio of MnO{sub 2} and NiO in composite material is 80:20, the specific capacitance value of NiO/MnO{sub 2} calculated from the cyclic voltammetry curves is 453 F g{sup -1}, for pure NiO and MnO{sub 2} are 209, 330 F g{sup -1} in 6 mol L{sup -1} KOH electrolyte and at scan rate of 10 mV s{sup -1}, respectively. The specific capacitance of NiO/MnO{sub 2} electrode is much larger than that of each pristine component. Moreover, the composite electrodes showed high power density and stable electrochemical properties.

  19. Unusual magnetic hysteresis and the weakened transition behavior induced by Sn substitution in Mn{sub 3}SbN

    SciTech Connect (OSTI)

    Sun, Ying, E-mail: sunying@buaa.edu.cn [Center for Condensed Matter and Materials Physics, Department of Physics, Beihang University, Beijing 100191 (China); International Center for Materials Nanoarchitectonics (WPI-MANA), National Institute for Materials Science, Tsukuba, Ibaraki 305-0044 (Japan); Guo, Yanfeng; Li, Jun; Wang, Xia [Superconducting Properties Unit, National Institute for Materials Science, Tsukuba, Ibaraki 305-0044 (Japan); Tsujimoto, Yoshihiro [Materials Processing Unit, National Institute for Materials Science, Tsukuba, Ibaraki 305-0047 (Japan); Wang, Cong [Center for Condensed Matter and Materials Physics, Department of Physics, Beihang University, Beijing 100191 (China); Feng, Hai L.; Sathish, Clastin I.; Yamaura, Kazunari, E-mail: yamaura.kazunari@nims.go.jp [Superconducting Properties Unit, National Institute for Materials Science, Tsukuba, Ibaraki 305-0044 (Japan); Graduate School of Chemical Sciences and Engineering, Hokkaido University, Sapporo, Hokkaido 060-0810 (Japan); Matsushita, Yoshitaka [Analysis Station, National Institute for Materials Science, Tsukuba, Ibaraki 305-0047 (Japan)

    2014-01-28

    Substitution of Sb with Sn was achieved in ferrimagnetic antiperovskite Mn{sub 3}SbN. The experimental results indicate that with an increase in Sn concentration, the magnetization continuously decreases and the crystal structure of Mn{sub 3}Sb{sub 1-x}Sn{sub x}N changes from tetragonal to cubic phase at around x of 0.8. In the doping series, step-like anomaly in the isothermal magnetization was found and this behavior was highlighted at x?=?0.4. The anomaly could be attributed to the magnetic frustration, resulting from competition between the multiple spin configurations in the antiperovskite lattice. Meantime, H{sub c} of 18 kOe was observed at x?=?0.3, which is probably the highest among those of manganese antiperovskite materials reported so far. With increasing Sn content, the abrupt change of resistivity and the sharp peak of heat capacity in Mn{sub 3}SbN were gradually weakened. The crystal structure refinements indicate the weakened change at the magnetic transition is close related to the change of c/a ratio variation from tetragonal to cubic with Sn content. The results derived from this study indicate that the behavior of Mn{sub 3}Sb{sub 1-x}Sn{sub x}N could potentially enhance its scientific and technical applications, such as spin torque transfer and hard magnets.

  20. Development of high frequency spice models for ferrite core inductors and transformers

    SciTech Connect (OSTI)

    Muyshondt, G.P.; Portnoy, W.M. . Dept. of Electrical Engineering)

    1989-01-01

    In this work high frequency SPICE models were developed to simulate the hysteresis and saturation effects of toroidal shaped ferrite core inductors and transformers. The models include the nonlinear, multi-valued B-H characteristic of the core material, leakage flux, stray capacitances, and core losses. The saturation effects were modeled using two diode clamping arrangements in conjunction with nonlinear dependent sources. Two possible controlling schemes were developed for the saturation switch. One of the arrangements used the current flowing through a series RC branch to control the switch, while the other used a NAND gate. The NAND gate implementation of the switch proved to be simpler and the parameters associated with it were easier to determine from the measurements and the B-H characteristics of the material. Lumped parameters were used to simulate the parasitic effects. Techniques for measuring these parasitic are described. The models were verified using manganese-zinc ferrite-type toroidal cores and they have general applicability to all circuit analysis codes equivalent function blocks such as multipliers, adders, and logic components. 7 refs., 22 figs.