Science.gov

Sample records for bi-mo-ti mixed oxides

  1. Mixed oxide solid solutions

    DOEpatents

    Magno, Scott; Wang, Ruiping; Derouane, Eric

    2003-01-01

    The present invention is a mixed oxide solid solution containing a tetravalent and a pentavalent cation that can be used as a support for a metal combustion catalyst. The invention is furthermore a combustion catalyst containing the mixed oxide solid solution and a method of making the mixed oxide solid solution. The tetravalent cation is zirconium(+4), hafnium(+4) or thorium(+4). In one embodiment, the pentavalent cation is tantalum(+5), niobium(+5) or bismuth(+5). Mixed oxide solid solutions of the present invention exhibit enhanced thermal stability, maintaining relatively high surface areas at high temperatures in the presence of water vapor.

  2. Mixed oxide nanoparticles and method of making

    DOEpatents

    Lauf, Robert J.; Phelps, Tommy J.; Zhang, Chuanlun; Roh, Yul

    2002-09-03

    Methods and apparatus for producing mixed oxide nanoparticulates are disclosed. Selected thermophilic bacteria cultured with suitable reducible metals in the presence of an electron donor may be cultured under conditions that reduce at least one metal to form a doped crystal or mixed oxide composition. The bacteria will form nanoparticles outside the cell, allowing easy recovery. Selection of metals depends on the redox potentials of the reducing agents added to the culture. Typically hydrogen or glucose are used as electron donors.

  3. Nondestructive assay confirmatory assessment experiments: mixed oxide

    SciTech Connect

    Lemming, J.F.

    1980-04-30

    The confirmatory assessment experiments demonstrate traceable nondestructive assay (NDA) measurements of plutonium in mixed oxide powder using commercially available spontaneous-fission assay systems. The experiments illustrate two major concepts: the production of calibration materials using calorimetric assay, and the use of paired measurements for measurement assurance. Two batches of well-characterized mixed oxide powder were used to establish the random and systematic error components. The major components of an NDA measurement assurance technique to establish and maintain traceability are identified and their functions are demonstrated. 20 refs., 10 figs., 10 tabs.

  4. Process for etching mixed metal oxides

    DOEpatents

    Ashby, C.I.H.; Ginley, D.S.

    1994-10-18

    An etching process is described using dicarboxylic and tricarboxylic acids as chelating etchants for mixed metal oxide films such as high temperature superconductors and ferroelectric materials. Undesirable differential etching rates between different metal oxides are avoided by selection of the proper acid or combination of acids. Feature sizes below one micron, excellent quality vertical edges, and film thicknesses in the 100 Angstrom range may be achieved by this method. 1 fig.

  5. Process for etching mixed metal oxides

    DOEpatents

    Ashby, Carol I. H.; Ginley, David S.

    1994-01-01

    An etching process using dicarboxylic and tricarboxylic acids as chelating etchants for mixed metal oxide films such as high temperature superconductors and ferroelectric materials. Undesirable differential etching rates between different metal oxides are avoided by selection of the proper acid or combination of acids. Feature sizes below one micron, excellent quality vertical edges, and film thicknesses in the 100 Angstom range may be achieved by this method.

  6. Alternative oxidation technologies for organic mixed waste

    SciTech Connect

    Borduin, L.C.; Fewell, T.

    1998-07-01

    The Mixed Waste Focus Area (MWFA) is currently supporting the development and demonstration of several alternative oxidation technology (AOT) processes for treatment of combustible mixed low-level wastes. AOTs have been defined as technologies that destroy organic material without using open-flame reactions. AOTs include both thermal and nonthermal processes that oxidize organic wastes but operate under significantly different physical and chemical conditions than incinerators. Nonthermal processes currently being studied include Delphi DETOX and acid digestion at the Savannah River Site (SRS), and direct chemical oxidation at Lawrence Livermore National Laboratory (LLNL). All three technologies are at advanced stages of development or are entering the demonstration phase. Nonflame thermal processes include catalytic chemical oxidation, which is being developed and deployed at Lawrence Berkeley National Laboratory (LBNL), and steam reforming, a commercial process being supported by the Department of Energy (DOE). Although testing is complete on some AOT technologies, most require additional support to complete some or all of the identified development objectives. Brief descriptions, status, and planned paths forward for each of the technologies are presented.

  7. 40 CFR 721.5548 - Mixed metal oxide (generic).

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Mixed metal oxide (generic). 721.5548... Substances § 721.5548 Mixed metal oxide (generic). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as a mixed metal oxide (PMN P-97-956)...

  8. 40 CFR 721.10006 - Mixed metal oxide (generic).

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Mixed metal oxide (generic). 721.10006... Substances § 721.10006 Mixed metal oxide (generic). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as mixed metal oxide (PMN...

  9. 40 CFR 721.10006 - Mixed metal oxide (generic).

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Mixed metal oxide (generic). 721.10006... Substances § 721.10006 Mixed metal oxide (generic). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as mixed metal oxide (PMN...

  10. 40 CFR 721.5548 - Mixed metal oxide (generic).

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Mixed metal oxide (generic). 721.5548... Substances § 721.5548 Mixed metal oxide (generic). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as a mixed metal oxide (PMN P-97-956)...

  11. 40 CFR 721.4610 - Mixed metal oxides (generic).

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Mixed metal oxides (generic). 721.4610... Substances § 721.4610 Mixed metal oxides (generic). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as mixed metal oxides (PMN...

  12. 40 CFR 721.10500 - Acrylated mixed metal oxides (generic).

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Acrylated mixed metal oxides (generic... Specific Chemical Substances § 721.10500 Acrylated mixed metal oxides (generic). (a) Chemical substance and... mixed metal oxides (PMN P-06-341) is subject to reporting under this section for the significant...

  13. 40 CFR 721.10500 - Acrylated mixed metal oxides (generic).

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Acrylated mixed metal oxides (generic... Specific Chemical Substances § 721.10500 Acrylated mixed metal oxides (generic). (a) Chemical substance and... mixed metal oxides (PMN P-06-341) is subject to reporting under this section for the significant...

  14. 40 CFR 721.10006 - Mixed metal oxide (generic).

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Mixed metal oxide (generic). 721.10006... Substances § 721.10006 Mixed metal oxide (generic). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as mixed metal oxide (PMN...

  15. 40 CFR 721.4610 - Mixed metal oxides (generic).

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Mixed metal oxides (generic). 721.4610... Substances § 721.4610 Mixed metal oxides (generic). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as mixed metal oxides (PMN...

  16. 40 CFR 721.4610 - Mixed metal oxides (generic).

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Mixed metal oxides (generic). 721.4610... Substances § 721.4610 Mixed metal oxides (generic). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as mixed metal oxides (PMN...

  17. 40 CFR 721.5548 - Mixed metal oxide (generic).

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Mixed metal oxide (generic). 721.5548... Substances § 721.5548 Mixed metal oxide (generic). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as a mixed metal oxide (PMN P-97-956)...

  18. 40 CFR 721.10006 - Mixed metal oxide (generic).

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Mixed metal oxide (generic). 721.10006... Substances § 721.10006 Mixed metal oxide (generic). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as mixed metal oxide (PMN...

  19. 40 CFR 721.4610 - Mixed metal oxides (generic).

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Mixed metal oxides (generic). 721.4610... Substances § 721.4610 Mixed metal oxides (generic). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as mixed metal oxides (PMN...

  20. 40 CFR 721.5548 - Mixed metal oxide (generic).

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Mixed metal oxide (generic). 721.5548... Substances § 721.5548 Mixed metal oxide (generic). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as a mixed metal oxide (PMN P-97-956)...

  1. 40 CFR 721.4610 - Mixed metal oxides (generic).

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Mixed metal oxides (generic). 721.4610... Substances § 721.4610 Mixed metal oxides (generic). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as mixed metal oxides (PMN...

  2. Critical experiments with mixed oxide fuel

    SciTech Connect

    Harris, D.R.

    1997-06-01

    This paper very briefly outlines technical considerations in performing critical experiments on weapons-grade plutonium mixed oxide fuel assemblies. The experiments proposed would use weapons-grade plutonium and Er{sub 2}O{sub 3} at various dissolved boron levels, and for specific fuel assemblies such as the ABBCE fuel assembly with five large water holes. Technical considerations described include the core, the measurements, safety, security, radiological matters, and licensing. It is concluded that the experiments are feasible at the Rensselaer Polytechnic Institute Reactor Critical Facility. 9 refs.

  3. Investigation of Mixed Oxide Catalysts for NO Oxidation

    SciTech Connect

    Szanyi, Janos; Karim, Ayman M.; Pederson, Larry R.; Kwak, Ja Hun; Mei, Donghai; Tran, Diana N.; Herling, Darrell R.; Muntean, George G.; Peden, Charles HF; Howden, Ken; Qi, Gongshin; Li, Wei

    2014-12-09

    The oxidation of engine-generated NO to NO2 is an important step in the reduction of NOx in lean engine exhaust because NO2 is required for the performance of the LNT technology [2], and it enhances the activities of ammonia selective catalytic reduction (SCR) catalysts [1]. In particular, for SCR catalysts an NO:NO2 ratio of 1:1 is most effective for NOx reduction, whereas for LNT catalysts, NO must be oxidized to NO2 before adsorption on the storage components. However, NO2 typically constitutes less than 10% of NOx in lean exhaust, so catalytic oxidation of NO is essential. Platinum has been found to be especially active for NO oxidation, and is widely used in DOC and LNT catalysts. However, because of the high cost and poor thermal durability of Pt-based catalysts, there is substantial interest in the development of alternatives. The objective of this project, in collaboration with partner General Motors, is to develop mixed metal oxide catalysts for NO oxidation, enabling lower precious metal usage in emission control systems. [1] M. Koebel, G. Madia, and M. Elsener, Catalysis Today 73, 239 (2002). [2] C. H. Kim, G. S. Qi, K. Dahlberg, and W. Li, Science 327, 1624 (2010).

  4. Conversion of mixed plutonium-uranium oxides. [COPRECAL

    SciTech Connect

    Thomas, L.L.

    1980-04-01

    Coprocessing is among the several reprocessing schemes being considered to improve the proliferation resistance of the back end of the nuclear fuel cycle. Coconversion of mixed oxides has been developed but not demonstrated on a production scale. AGNS developed a preliminary conceptual design for a production scale facility to convert mixed plutonium-uranium nitrate to the mixed oxide.

  5. Analytical chemistry methods for mixed oxide fuel, March 1985

    SciTech Connect

    Not Available

    1985-03-01

    This standard provides analytical chemistry methods for the analysis of materials used to produce mixed oxide fuel. These materials are ceramic fuel and insulator pellets and the plutonium and uranium oxides and nitrates used to fabricate these pellets.

  6. 40 CFR 721.10006 - Mixed metal oxide (generic).

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... CONTROL ACT SIGNIFICANT NEW USES OF CHEMICAL SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.10006 Mixed metal oxide (generic). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as mixed metal oxide (PMN...

  7. 40 CFR 721.5548 - Mixed metal oxide (generic).

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... CONTROL ACT SIGNIFICANT NEW USES OF CHEMICAL SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.5548 Mixed metal oxide (generic). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as a mixed metal oxide (PMN P-97-956)...

  8. Mixed Oxide Fresh Fuel Package Auxiliary Equipment

    SciTech Connect

    Yapuncich, F.; Ross, A.; Clark, R.H.; Ammerman, D.

    2008-07-01

    The United States Department of Energy's National Nuclear Security Administration (NNSA) is overseeing the construction the Mixed Oxide (MOX) Fuel Fabrication Facility (MFFF) on the Savannah River Site. The new facility, being constructed by NNSA's contractor Shaw AREVA MOX Services, will fabricate fuel assemblies utilizing surplus plutonium as feedstock. The fuel will be used in designated commercial nuclear reactors. The MOX Fresh Fuel Package (MFFP), which has recently been licensed by the Nuclear Regulatory Commission (NRC) as a type B package (USA/9295/B(U)F-96), will be utilized to transport the fabricated fuel assemblies from the MFFF to the nuclear reactors. It was necessary to develop auxiliary equipment that would be able to efficiently handle the high precision fuel assemblies. Also, the physical constraints of the MFFF and the nuclear power plants require that the equipment be capable of loading and unloading the fuel assemblies both vertically and horizontally. The ability to reconfigure the load/unload evolution builds in a large degree of flexibility for the MFFP for the handling of many types of both fuel and non fuel payloads. The design and analysis met various technical specifications including dynamic and static seismic criteria. The fabrication was completed by three major fabrication facilities within the United States. The testing was conducted by Sandia National Laboratories. The unique design specifications and successful testing sequences will be discussed. (authors)

  9. Optical and electrical studies of cerium mixed oxides

    SciTech Connect

    Sherly, T. R.; Raveendran, R.

    2014-10-15

    The fast development in nanotechnology makes enthusiastic interest in developing nanomaterials having tailor made properties. Cerium mixed oxide materials have received great attention due to their UV absorption property, high reactivity, stability at high temperature, good electrical property etc and these materials find wide applications in solid oxide fuel cells, solar control films, cosmetics, display units, gas sensors etc. In this study cerium mixed oxide compounds were prepared by co-precipitation method. All the samples were doped with Zn (II) and Fe (II). Preliminary characterizations such as XRD, SEM / EDS, TEM were done. UV - Vis, Diffuse reflectance, PL, FT-IR, Raman and ac conductivity studies of the samples were performed.

  10. Optical and electrical studies of cerium mixed oxides

    NASA Astrophysics Data System (ADS)

    Sherly, T. R.; Raveendran, R.

    2014-10-01

    The fast development in nanotechnology makes enthusiastic interest in developing nanomaterials having tailor made properties. Cerium mixed oxide materials have received great attention due to their UV absorption property, high reactivity, stability at high temperature, good electrical property etc and these materials find wide applications in solid oxide fuel cells, solar control films, cosmetics, display units, gas sensors etc. In this study cerium mixed oxide compounds were prepared by co-precipitation method. All the samples were doped with Zn (II) and Fe (II). Preliminary characterizations such as XRD, SEM / EDS, TEM were done. UV - Vis, Diffuse reflectance, PL, FT-IR, Raman and ac conductivity studies of the samples were performed.

  11. Electrically Joining Mixed Conducting Oxides for High Temperature Applications

    SciTech Connect

    Weil, K. Scott; Hardy, John S.

    2003-01-06

    Mixed conducting oxides such as lanthanum strontium cobalt ferrite are currently being investigated for potential use as electrochemically active electrodes and catalytic membranes in a number of high temperature devices, including oxygen generators and solid oxide fuel cells (SOFC). However to take full advantage of the unique properties of these materials, reliable joining techniques need to be developed. What complicates joining in these applications is the requirement that the ceramic-to-metal junction be electrically conductive, so that current can either be drawn from the mixed conducting oxide, in the case of SOFC applications, or be carried to the oxide to initate ionic conduction, as required for oxygen separation and electrocatalysis. This paper outlines a new technique that is being developed to electrically join an oxide conductor to a metal current collector for high temperature electrochemical application.

  12. Composite mixed oxide ionic and electronic conductors for hydrogen separation

    DOEpatents

    Gopalan, Srikanth; Pal, Uday B.; Karthikeyan, Annamalai; Hengdong, Cui

    2009-09-15

    A mixed ionic and electronic conducting membrane includes a two-phase solid state ceramic composite, wherein the first phase comprises an oxygen ion conductor and the second phase comprises an n-type electronically conductive oxide, wherein the electronically conductive oxide is stable at an oxygen partial pressure as low as 10.sup.-20 atm and has an electronic conductivity of at least 1 S/cm. A hydrogen separation system and related methods using the mixed ionic and electronic conducting membrane are described.

  13. Microstructure and thermophysical characterization of mixed oxide fuels

    SciTech Connect

    Freibert, Franz J; Salich, Tarik A; Schwartz, Daniel S; Hampel, Fred G; Mitchell, Jeremy N; Davis, Charles C; Neuman, Angelique D; Willson, Steve P; Dunwoody, John T

    2009-01-01

    Pre-irradiated thermodynamic and microstructural properties of nuclear fuels form the necessary set of data against which to gauge fuel performance and irradiation damage evolution. This paper summarizes recent efforts in mixed-oxide and minor actinide-bearing mixed-oxide ceramic fuels fabrication and characterization at Los Alamos National Laboratory. Ceramic fuels (U{sub 1-x-y-z}u{sub x}Am{sub y}Np{sub z})O{sub 2} fabricated in the compositional ranges of 0.19 {le} x {le} 0.3 Pu, 0 {le} y {le} 0.05 Am, and O {le} z {le} O.03 Np exhibited a uniform crystalline face-centered cubic phase with an average grain size of 14{micro}m; however, electron microprobe analysis revealed segregation of NpO{sub 2} in minor actinide-bearing fuels. Immersion density and porosity analysis demonstrated an average density of 92.4% theoretical for mixed-oxide fuels and an average density of 89.5 % theoretical density for minor actinide-bearing mixed-oxide fuels. Examined fuels exhibited mean thermal expansion value of 12.56 x 10{sup -6} C{sup -1} for temperature range (100 C < T < 1500 C) and ambient temperature Young's modulus and Poisson's ratio of 169 GPa and of 0.327, respectively. Internal dissipation as determined from mechanical resonances of these ceramic fuels has shown promise as a tool to gauge microstructural integrity and to interrogate fundamental properties.

  14. Mixed lanthanide oxide nanoparticles as dual imaging agent in biomedicine

    PubMed Central

    Xu, Wenlong; Bony, Badrul Alam; Kim, Cho Rong; Baeck, Jong Su; Chang, Yongmin; Bae, Ji Eun; Chae, Kwon Seok; Kim, Tae Jeong; Lee, Gang Ho

    2013-01-01

    There is no doubt that the molecular imaging is an extremely important technique in diagnosing diseases. Dual imaging is emerging as a step forward in molecular imaging technique because it can provide us with more information useful for diagnosing diseases than single imaging. Therefore, diverse dual imaging modalities should be developed. Molecular imaging generally relies on imaging agents. Mixed lanthanide oxide nanoparticles could be valuable materials for dual magnetic resonance imaging (MRI)-fluorescent imaging (FI) because they have both excellent and diverse magnetic and fluorescent properties useful for dual MRI-FI, depending on lanthanide ions used. Since they are mixed nanoparticles, they are compact, robust, and stable, which is extremely useful for biomedical applications. They can be also easily synthesized with facile composition control. In this study, we explored three systems of ultrasmall mixed lanthanide (Dy/Eu, Ho/Eu, and Ho/Tb) oxide nanoparticles to demonstrate their usefulness as dual T2 MRI–FI agents. PMID:24220641

  15. Photochemical oxidation: A solution for the mixed waste dilemma

    SciTech Connect

    Prellberg, J.W.; Thornton, L.M.; Cheuvront, D.A.

    1995-12-31

    Numerous technologies are available to remove organic contamination from water or wastewater. A variety of techniques also exist that are used to neutralize radioactive waste. However, few technologies can satisfactorily address the treatment of mixed organic/radioactive waste without creating unacceptable secondary waste products or resulting in extremely high treatment costs. An innovative solution to the mixed waste problem is on-site photochemical oxidation. Liquid-phase photochemical oxidation has a long- standing history of successful application to the destruction of organic compounds. By using photochemical oxidation, the organic contaminants are destroyed on-site leaving the water, with radionuclides, that can be reused or disposed of as appropriate. This technology offers advantages that include zero air emissions, no solid or liquid waste formation, and relatively low treatment cost. Discussion of the photochemical process will be described, and several case histories from recent design testing, including cost analyses for the resulting full-scale installations, will be presented as examples.

  16. Catalytic soot oxidation over Ce- and Cu-doped hydrotalcites-derived mesoporous mixed oxides.

    PubMed

    Wang, Zhongpeng; Wang, Liguo; He, Fang; Jiang, Zheng; Xiao, Tiancun; Zhang, Zhaoliang

    2014-09-01

    Ce- and Cu-doped hydrotalcites derived mixed oxides were prepared through co-precipitation and calcination method, and their catalytic activities for soot oxidation with O2 and O2/NO were investigated. The solids were characterized by XRD, TG-DTG, BET, H2-TPR, in situ FTIR and TPO techniques. All the catalysts precursors showed the typical diffraction patterns of hydrotalcite-like materials having layered structure. The derived mixed oxides exhibited mesoporous properties with specific surface area of 45-160 m2/g. After both Ce and Cu incorporated, mixed crystalline phases of CuO (tenorite), CeO2 (fluorite) and MgAl2O4 (spinel) were formed. As a result, the NO(x) adsorption capacity of this catalyst was largely increased to 201 μmol/g, meanwhile, it was also the most effective to convert NO into NO2 in the sorption process due to the enhanced reducibility. The in situ FTIR spectra revealed that NO(x) were stored mainly as chelating bidentate and monodentate nitrate. The interaction effect between Cu and Ce in the mixed oxide resulted in different NO(x) adsorption behavior. Compared with the non-catalyzed soot oxidation, soot conversion curves over the mixed oxides catalysts shift to low temperature in O2. The presence of NO in the gas phase significantly enhanced the soot oxidation activity with ignition temperature decreased to about 320 degrees C, which is due to NO conversion to NO2 over the catalyst followed by the reaction of NO2 with soot. This explains the cooperative effect of Ce and Cu in the mixed oxide on soot oxidation with high activity and 100% selectivity to CO2 formation. PMID:25924375

  17. Design and synthesis of mixed oxides nanoparticles for biofuel applications

    SciTech Connect

    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.

  18. Geometric Frustration in the Mixed Layer Pnictide Oxides

    SciTech Connect

    Enjalran, M.; Scalettar, R.T.; Kauzlarich, S.M.

    2000-06-06

    The authors present results from a Monte Carlo investigation of a simple bilayer model with geometrically frustrated interactions similar to those found in the mixed layer pnictide oxides (Sr{sub 2}Mn{sub 3}Pn{sub 2}O{sub 2}, Pn = As, Sb). The model is composed of two inequivalent square lattices with nearest-neighbor intra- and interlayer interactions. They find a ground state composed of two independent Neel ordered layers when the interlayer exchange is an order of magnitude weaker than the intralayer exchange, as suggested by experiment. Evidence for local orthogonal order between the layers is found, but it occurs in regions of parameter space which are not experimentally realized. Qualitatively similar results were observed in models with a larger number of layers. They conclude that frustration caused by nearest-neighbor interactions in the mixed layer pnictide oxides is not sufficient to explain the long-range orthogonal order that is observed experimentally.

  19. 40 CFR 721.5315 - Nickel, cobalt mixed metal oxide (generic).

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Nickel, cobalt mixed metal oxide... Specific Chemical Substances § 721.5315 Nickel, cobalt mixed metal oxide (generic). (a) Chemical substance... nickel, cobalt mixed metal oxide. (PMN P-02-90) is subject to reporting under this section for...

  20. 40 CFR 721.5315 - Nickel, cobalt mixed metal oxide (generic).

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Nickel, cobalt mixed metal oxide... Specific Chemical Substances § 721.5315 Nickel, cobalt mixed metal oxide (generic). (a) Chemical substance... nickel, cobalt mixed metal oxide. (PMN P-02-90) is subject to reporting under this section for...

  1. 40 CFR 721.5315 - Nickel, cobalt mixed metal oxide (generic).

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Nickel, cobalt mixed metal oxide... Specific Chemical Substances § 721.5315 Nickel, cobalt mixed metal oxide (generic). (a) Chemical substance... nickel, cobalt mixed metal oxide. (PMN P-02-90) is subject to reporting under this section for...

  2. 40 CFR 721.5315 - Nickel, cobalt mixed metal oxide (generic).

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Nickel, cobalt mixed metal oxide... Specific Chemical Substances § 721.5315 Nickel, cobalt mixed metal oxide (generic). (a) Chemical substance... nickel, cobalt mixed metal oxide. (PMN P-02-90) is subject to reporting under this section for...

  3. 40 CFR 721.5315 - Nickel, cobalt mixed metal oxide (generic).

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Nickel, cobalt mixed metal oxide... Specific Chemical Substances § 721.5315 Nickel, cobalt mixed metal oxide (generic). (a) Chemical substance... nickel, cobalt mixed metal oxide. (PMN P-02-90) is subject to reporting under this section for...

  4. 40 CFR 721.10147 - Acrylate derivative of alkoxysilylalkane ester and mixed metal oxides (generic).

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... alkoxysilylalkane ester and mixed metal oxides (generic). 721.10147 Section 721.10147 Protection of Environment... alkoxysilylalkane ester and mixed metal oxides (generic). (a) Chemical substance and significant new uses subject to... ester and mixed metal oxides (PMN P-07-198) is subject to reporting under this section for...

  5. 40 CFR 721.10147 - Acrylate derivative of alkoxysilylalkane ester and mixed metal oxides (generic).

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... alkoxysilylalkane ester and mixed metal oxides (generic). 721.10147 Section 721.10147 Protection of Environment... alkoxysilylalkane ester and mixed metal oxides (generic). (a) Chemical substance and significant new uses subject to... ester and mixed metal oxides (PMN P-07-198) is subject to reporting under this section for...

  6. Flexible Electronics Powered by Mixed Metal Oxide Thin Film Transistors

    NASA Astrophysics Data System (ADS)

    Marrs, Michael

    A low temperature amorphous oxide thin film transistor (TFT) and amorphous silicon PIN diode backplane technology for large area flexible digital x-ray detectors has been developed to create 7.9-in. diagonal backplanes. The critical steps in the evolution of the backplane process include the qualification and optimization of the low temperature (200 °C) metal oxide TFT and a-Si PIN photodiode process, the stability of the devices under forward and reverse bias stress, the transfer of the process to flexible plastic substrates, and the fabrication and assembly of the flexible detectors. Mixed oxide semiconductor TFTs on flexible plastic substrates suffer from performance and stability issues related to the maximum processing temperature limitation of the polymer. A novel device architecture based upon a dual active layer improves both the performance and stability. Devices are directly fabricated below 200 ºC on a polyethylene naphthalate (PEN) substrate using mixed metal oxides of either zinc indium oxide (ZIO) or indium gallium zinc oxide (IGZO) as the active semiconductor. The dual active layer architecture allows for adjustment to the saturation mobility and threshold voltage stability without the requirement of high temperature annealing, which is not compatible with flexible plastic substrates like PEN. The device performance and stability is strongly dependent upon the composition of the mixed metal oxide; this dependency provides a simple route to improving the threshold voltage stability and drive performance. By switching from a single to a dual active layer, the saturation mobility increases from 1.2 cm2/V-s to 18.0 cm2/V-s, while the rate of the threshold voltage shift decreases by an order of magnitude. This approach could assist in enabling the production of devices on flexible substrates using amorphous oxide semiconductors. Low temperature (200°C) processed amorphous silicon photodiodes were developed successfully by balancing the tradeoffs

  7. Direct chemical oxidation of mixed or toxic wastes

    SciTech Connect

    Balazs, G B; Cooper, J F; Farmer, J C; Lewis, P

    1999-05-01

    Direct Chemical Oxidation (DCO) is an ambient-pressure, low-temperature (<100 C), and aqueous-based process for general-purpose destruction of the organic fraction of hazardous or mixed waste. It uses the peroxydisulfate anion (S{sub 2}O{sub 8}{sup 2{minus}}) in acid or base solutions. The byproduct of the oxidation reaction, typically sodium or ammonium hydrogen sulfate, may be recycled electrolytically to produce the oxidant. The oxidation kinetic reaction is first order with respect to the peroxydisulfate concentration, expressed in equivalents. The rate constant is constant for nearly all dissolved organic compounds: k{sub a} = 0.01 {+-} 0.005 min{sup {minus}1}. This reflects a common rate-determining step, which is the decomposition of the peroxydisulfate anion into the chemically active derivative, the sulfate radical anion, SO{sub 4}{sup {minus}}. This decomposition is promoted in DCO by raising the operating temperature into the range of 80-100 C. Rates are given for approximately 30 substances with diverse functional groups at low concentrations, and for a number of solid and liquid wastes typical of nuclear and chemical industries. The process has been scale up for treatment studies on chlorinated hydrocarbons, in which the hydrolysis of solvent mixtures was followed by oxidation of products in a series of stirred tank reactors. Cost estimates, safety considerations, and a comprehensive bibliography are given.

  8. Development of mixed-conducting oxides for gas separation

    SciTech Connect

    Balachandran, U.; Ma, B.; Maiya, P.S.

    1997-08-01

    Mixed-conducting oxides have been used in many applications, including fuel cells, gas separation membranes, sensors, and electrocatalysis. The authors are developing a mixed-conducting, dense ceramic membrane for selectively transporting oxygen and hydrogen. Ceramic membranes made of Sr-Fe-Co oxide, which has high combined electronic and oxygen ionic conductions, can be used to selectively transport oxygen during the partial oxidation of methane to synthesis gas (syngas, CO + H{sub 2}). The authors have measured the steady-state oxygen permeability of SrFeCo{sub 0.5}O{sub x} as a function of oxygen-partial-pressure gradient and temperature. At 900{degrees}C, oxygen permeability was {approx}2.5 scc{center_dot}cm{sup {minus}2}{center_dot}min{sup {minus}1} for a 2.9-mm-thick membrane and this value increases as membrane thickness decreases. The authors have fabricated tubular SrFeCo{sub 0.5}O{sub x} membranes and operated them at 900{degrees}C for >1000 h during conversion of methane into syngas. The hydrogen ion (proton) transport properties of yttria-doped BaCeO{sub 3} were investigated by impedance spectroscopy and open-cell voltage measurements. High proton conductivity and a high protonic transference number make yttria-doped BaCeO{sub 3} a potential membrane for hydrogen separation.

  9. Neutron field characterisation at mixed oxide fuel plant.

    PubMed

    Passmore, C; Million, M; Kirr, M; Bartz, J; Akselrod, M S; Devita, A; Berard, J

    2012-06-01

    A neutron field characterisation was conducted at the AREVA Melox Plant to determine the response of passive and active neutron dosemeters for several stages in the mixed oxide fuel manufacturing process. Landauer Europe provides radiation dosimetry to many contractors working at the Melox site. The studies were conducted to assist in determining the neutron radiation fields the workers are exposed to routinely, evaluate the need for specific neutron correction factors and to ensure that the most accurate neutron dose is reported for the Melox Plant workers. PMID:22028415

  10. Reduction of spalling in mixed metal oxide desulfurization sorbents by addition of a large promoter metal oxide

    DOEpatents

    Poston, James A.

    1997-01-01

    Mixed metal oxide pellets for removing hydrogen sulfide from fuel gas mixes derived from coal are stabilized for operation over repeated cycles of desulfurization and regeneration reactions by addition of a large promoter metal oxide such as lanthanum trioxide. The pellets, which may be principally made up of a mixed metal oxide such as zinc titanate, exhibit physical stability and lack of spalling or decrepitation over repeated cycles without loss of reactivity. The lanthanum oxide is mixed with pellet-forming components in an amount of 1 to 10 weight percent.

  11. Reduction of spalling in mixed metal oxide desulfurization sorbents by addition of a large promoter metal oxide

    DOEpatents

    Poston, J.A.

    1997-12-02

    Mixed metal oxide pellets for removing hydrogen sulfide from fuel gas mixes derived from coal are stabilized for operation over repeated cycles of desulfurization and regeneration reactions by addition of a large promoter metal oxide such as lanthanum trioxide. The pellets, which may be principally made up of a mixed metal oxide such as zinc titanate, exhibit physical stability and lack of spalling or decrepitation over repeated cycles without loss of reactivity. The lanthanum oxide is mixed with pellet-forming components in an amount of 1 to 10 weight percent.

  12. Preparation of uniform nanoparticles of ultra-high purity metal oxides, mixed metal oxides, metals, and metal alloys

    DOEpatents

    Woodfield, Brian F.; Liu, Shengfeng; Boerio-Goates, Juliana; Liu, Qingyuan; Smith, Stacey Janel

    2012-07-03

    In preferred embodiments, metal nanoparticles, mixed-metal (alloy) nanoparticles, metal oxide nanoparticles and mixed-metal oxide nanoparticles are provided. According to embodiments, the nanoparticles may possess narrow size distributions and high purities. In certain preferred embodiments, methods of preparing metal nanoparticles, mixed-metal nanoparticles, metal oxide nanoparticles and mixed-metal nanoparticles are provided. These methods may provide tight control of particle size, size distribution, and oxidation state. Other preferred embodiments relate to a precursor material that may be used to form nanoparticles. In addition, products prepared from such nanoparticles are disclosed.

  13. [Synthesis and characterization of mixed metal oxide pigments].

    PubMed

    Ding, Jie; Yue, Shi-juan; Liu, Cui-ge; Wei, Yong-ju; Meng, Tao; Jiang, Han-jie; Shi, Yong-zheng; Xu, Yi-zhuang; Yu, Jiang; Wu, Jin-guang

    2012-03-01

    In the present work, aluminum chloride and various soluble salts of doping ions were dissolved in water. In addition, urea and polyvinyl pyrrolidone (PVP) were also dissolved in the above aqueous solution under supersonic treatments. Then the solutions were heated to induce the hydrolysis of urea so that soluble aluminum and doping ions convert into insoluble hydroxide or carbonate gels. After calcinations, the obtained gels change to mixed metal oxide pigments whose color is related to type and concentrations of the doping ions. XRD characterization demonstrates that the diffraction patterns of the products are the same as that of alpha-alumina. Diffuse reflectance spectra of samples of the samples in UV-Vis regions show that the absorption bands for d-d transitions of the doping ions undergo considerable change as the coordinate environments change. In addition, L*, a* and b* values of the pigments were measured by using UV-Vis densitometer. SEM results indicate that the size of the pigment powders is in the range 200-300 nm. The pigments are quite stable since no evidence of dissolution was observed after the synthesized pigment is soaked for 24 hours. ICP test shows that very little amount of doped metal occurs in the corresponding filtrate. The above results suggest that these new kinds of mixed metal oxide pigments are stable, non-toxic, environmental friendly and they may be applicable in molten spinning process and provide a new chance for non-aqueous printing and dyeing industry. PMID:22582641

  14. 40 CFR 721.10148 - Acryloxy alkanoic alkane derivative with mixed metal oxides (generic).

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... with mixed metal oxides (generic). 721.10148 Section 721.10148 Protection of Environment ENVIRONMENTAL... mixed metal oxides (generic). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as acryloxy alkanoic alkane derivative with mixed...

  15. 40 CFR 721.10148 - Acryloxy alkanoic alkane derivative with mixed metal oxides (generic).

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... with mixed metal oxides (generic). 721.10148 Section 721.10148 Protection of Environment ENVIRONMENTAL... mixed metal oxides (generic). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as acryloxy alkanoic alkane derivative with mixed...

  16. Oxidation control of fluxes for mixed-valent inorganic oxide materials synthesis

    NASA Astrophysics Data System (ADS)

    Schrier, Marc David

    This dissertation is concerned with controlling the flux synthesis and ensuing physical properties of mixed-valence metal oxides. Molten alkali metal nitrates and hydroxides have been explored to determine and exploit their variable redox chemistries for the synthesis of mixed-valent oxide materials. Cationic and anionic additives have been utilized in these molten salts to control the relative concentrations of the redox-active species present to effectively tune and cap the electrochemical potential of the flux. Atoms like bismuth, copper, and manganese are capable of providing different numbers of electrons for bonding. With appropriate doping near the metal-insulator transition, many of these mixed-valent inorganic metal oxides exhibit extraordinary electronic and magnetic properties. Traditionally, these materials have been prepared by classical high temperature solid state routes where microscopic homogeneity is hard to attain. In these routes, the starting composition dictates the doping level, and in turn, the formal oxidation state achieved. Molten flux syntheses developed in this work have provided the potential for preparing single-phase, homogeneous, and crystalline materials. The redox-active fluxes provide a medium for enhanced doping and mixed-valency control in which the electrochemical potential adjusts the formal oxidation state, and the doping takes place to maintain charge neutrality. The two superconductor systems investigated are: (1) the potassium-doped barium bismuth oxides, and (2) the alkali metal- and alkaline earth metal-doped lanthanum copper oxides. Controlled oxidative doping has been achieved in both systems by two different approaches. The superconducting properties of these materials have been assessed, and the materials have been characterized by powder X-ray diffraction and e-beam microprobe elemental analyses. In the course of these studies, several other materials have been identified. Analysis of these materials, and the

  17. Properties of mixed molybdenum oxide iridium oxide thin films synthesized by spray pyrolysis

    NASA Astrophysics Data System (ADS)

    Patil, P. S.; Kawar, R. K.; Sadale, S. B.; Inamdar, A. I.; Deshmukh, H. P.

    2006-09-01

    Molybdenum-doped iridium oxide thin films have been deposited onto corning glass- and fluorine-doped tin oxide coated corning glass substrates at 350 °C by using a pneumatic spray pyrolysis technique. An aqueous solution of 0.01 M ammonium molybdate was mixed with 0.01 M iridium trichloride solution in different volume proportions and the resultant solution was used as a precursor solution for spraying. The as-deposited samples were annealed at 600 °C in air medium for 1 h. The structural, electrical and optical properties of as-deposited and annealed Mo-doped iridium oxide were studied and values of room temperature electrical resistivity, and thermoelectric power were estimated. The as-deposited samples with 2% Mo doping exhibit more pronounced electrochromism than other samples, including pristine Ir oxide.

  18. Ion beam mixed oxidation protective coating on Zry-4 cladding

    NASA Astrophysics Data System (ADS)

    Park, Jae-Won; Kim, Jae-Un; Park, Jeong-Yong

    2016-06-01

    In this study, SiC was coated on the surface of Zry-4 cladding to improve the oxidation protectiveness. In the coating of SiC onto Zry-4, the prime concern was adhesion at an elevated temperature. Here, a 70 keV N ion beam was irradiated onto a SiC coating layer of ∼100 nm in thickness; this was deposited via the e-beam evaporation method. Additional coating to a target thickness was then carried out. The films deposited without ion-beam mixing (IBM) often peeled-off at an elevated temperature, while the IBM SiC film always adhered to Zry-4, even after heating to ∼1000 °C; at such a temperature, however, cracks formed in the film. X-ray photoelectron spectroscopy (XPS) analysis showed that the deposited SiC film contained about 20 at.% of O, while after annealing in air, 76 at.% of O was found on the surface layer. This implied that both the surface of SiC film and Zry-4 in the crack lines were oxidized. Comparing the Zr3d peak positions across the interface, a shift of binding energy by ∼1 eV was detected, representing that, in view of favorable thermodynamics, SiC/Zry-4 seems to be an acceptable system to apply IBM. To heal the crack, the process of IBM for a 1 μm thick coating and annealing was repeated. High-resolution field emission secondary electron microscopy (FE-SEM) showed that the crack lines, the main places at which oxidation occurred, were gradually covered as the process was repeated, ensuring enhanced oxidation protectiveness.

  19. 40 CFR 721.10148 - Acryloxy alkanoic alkane derivative with mixed metal oxides (generic).

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... PROTECTION AGENCY (CONTINUED) TOXIC SUBSTANCES CONTROL ACT SIGNIFICANT NEW USES OF CHEMICAL SUBSTANCES... mixed metal oxides (generic). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as acryloxy alkanoic alkane derivative with mixed...

  20. Melting behavior of mixed U-Pu oxides under oxidizing conditions

    NASA Astrophysics Data System (ADS)

    Strach, Michal; Manara, Dario; Belin, Renaud C.; Rogez, Jacques

    2016-05-01

    In order to use mixed U-Pu oxide ceramics in present and future nuclear reactors, their physical and chemical properties need to be well determined. The behavior of stoichiometric (U,Pu)O2 compounds is relatively well understood, but the effects of oxygen stoichiometry on the fuel performance and stability are often still obscure. In the present work, a series of laser melting experiments were carried out to determine the impact of an oxidizing atmosphere, and in consequence the departure from a stoichiometric composition on the melting behavior of six mixed uranium plutonium oxides with Pu content ranging from 14 to 62 wt%. The starting materials were disks cut from sintered stoichiometric pellets. For each composition we have performed two laser melting experiments in pressurized air, each consisting of four shots of different duration and intensity. During the experiments we recorded the temperature at the surface of the sample with a pyrometer. Phase transitions were qualitatively identified with the help of a reflected blue laser. The observed phase transitions occur at a systematically lower temperature, the lower the Pu content of the studied sample. It is consistent with the fact that uranium dioxide is easily oxidized at elevated temperatures, forming chemical species rich in oxygen, which melt at a lower temperature and are more volatile. To our knowledge this campaign is a first attempt to quantitatively determine the effect of O/M on the melting temperature of MOX.

  1. Highly stable, mesoporous mixed lanthanum-cerium oxides with tailored structure and reducibility

    SciTech Connect

    Liang, Shuang; Broitman, Esteban; Wang, Yanan; Cao, Anmin; Veser, Goetz

    2011-05-01

    Pure and mixed lanthanum and cerium oxides were synthesized via a reverse microemulsion-templated route. This approach yields highly homogeneous and phase-stable mixed oxides with high surface areas across the entire range of La:Ce ratios from pure lanthana to pure ceria. Surprisingly, all mixed oxides show the fluorite crystal structure of ceria, even for lanthanum contents as high as 90%. Varying the La:Ce ratio not only allows tailoring of the oxide morphology (lattice parameter, pore structure, particle size, and surface area), but also results in a fine-tuning of the reducibility of the oxide which can be explained by the creation of oxygen vacancies in the ceria lattice upon La addition. Such finely controlled syntheses, which enable the formation of stable, homogeneous mixed oxides across the entire composition range, open the path towards functional tailoring of oxide materials, such as rational catalyst design via fine-tuning of redox activity.

  2. 76 FR 65544 - Standard Format and Content of License Applications for Mixed Oxide Fuel Fabrication Facilities

    Federal Register 2010, 2011, 2012, 2013, 2014

    2011-10-21

    ... issuance of the guide (74 FR 36780). The comment period closed on September 21, 2009. The staff's responses... COMMISSION Standard Format and Content of License Applications for Mixed Oxide Fuel Fabrication Facilities... Format and Content of License Applications for Mixed Oxide Fuel Fabrication Facilities.'' This...

  3. 40 CFR 721.10147 - Acrylate derivative of alkoxysilylalkane ester and mixed metal oxides (generic).

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... alkoxysilylalkane ester and mixed metal oxides (generic). 721.10147 Section 721.10147 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) TOXIC SUBSTANCES CONTROL ACT SIGNIFICANT NEW USES OF CHEMICAL... alkoxysilylalkane ester and mixed metal oxides (generic). (a) Chemical substance and significant new uses subject...

  4. 40 CFR 721.10574 - Alkylcarboxy polyester acrylate reaction products with mixed metal oxides (generic).

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... reaction products with mixed metal oxides (generic). (a) Chemical substance and significant new uses... reaction products with mixed metal oxides (generic). 721.10574 Section 721.10574 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) TOXIC SUBSTANCES CONTROL ACT SIGNIFICANT NEW USES OF...

  5. 40 CFR 721.10574 - Alkylcarboxy polyester acrylate reaction products with mixed metal oxides (generic).

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... reaction products with mixed metal oxides (generic). (a) Chemical substance and significant new uses... reaction products with mixed metal oxides (generic). 721.10574 Section 721.10574 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) TOXIC SUBSTANCES CONTROL ACT SIGNIFICANT NEW USES OF...

  6. Experience making mixed oxide fuel with plutonium from dismantled weapons

    SciTech Connect

    Blair, H.T.; Ramsey, K.B.

    1995-12-31

    Mixed depleted UO{sub 2} and PuO{sub 2} (MOX) pellets prototypic of fuel proposed for use in commercial power reactors were made with plutonium recovered from dismantled weapons. We characterized plutonium dioxide powders that were produced at the Los Alamos and Lawrence Livermore National Laboratories (LANL and LLNL) using various methods to recover the plutonium from weapons parts and to convert It to oxide. The gallium content of the PUO{sub 2} prepared at LANL was the same as in the weapon alloy while the content of that prepared at LLNL was less. The MOX was prepared with a five weight percent plutonium content. We tested various MOX powders milling methods to improve homogeneity and found vibratory milling superior to ball milling. The sintering behavior of pellets made with the PuO{sub 2} from the two laboratories was similar. We evaluated the effects of gallium and of erbium and gadolinium, that are added to the MOX fuel as deplorable neutron absorbers, on the pellet fabrication process and an the sintered pellets. The gallium content of the sintered pellets was <10 ppm, suggesting that the gallium will not be an issue in the reactor, but that it will be an Issue in the operation of the fuel fabrication processing equipment unless it is removed from the PuO{sub 2} before it is blended with the UO{sub 2}.

  7. Antineutrino monitoring of burning mixed oxide plutonium fuels

    NASA Astrophysics Data System (ADS)

    Hayes, A. C.; Trellue, H. R.; Nieto, Michael Martin; Wilson, W. B.

    2012-02-01

    Background: Antineutrino monitoring of reactors is an enhanced nuclear safeguard that is being explored by several international groups. A key question is whether such a scheme could be used to verify the destruction of plutonium loaded in a reactor as mixed oxide (MOX) fuel.Purpose: To explore the effectiveness of antineutrino monitoring for the purposes of nuclear accountability and safeguarding of MOX plutonium, we examine the magnitude and temporal variation in the antineutrino signals expected for different loadings of MOX fuels.Methods: Reactor burn simulations are carried out for four different MOX fuel loadings and the antineutrino signals as a function of fuel burnup are computed and compared.Results: The antineutrino signals from reactor-grade and weapons-grade MOX are shown to be distinct from those from burning low enriched uranium, and this signal difference increases as the MOX plutonium fraction of the reactor core increases.Conclusion: Antineutrino monitoring could be used to verify the destruction of plutonium in reactors, although verifying the grade of the plutonium being burned is found to be more challenging.

  8. Experience in PWR and BWR mixed-oxide fuel management

    SciTech Connect

    Schlosser, G.J.; Krebs, W.; Urban, P. )

    1993-04-01

    Germany has adopted the strategy of a closed fuel cycle using reprocessing and recycling. The central issue today is plutonium recycling by the use of U-Pu mixed oxide (MOX) in pressurized water reactors (PWRs) and boiling water reactors (BWRs). The design of MOX fuel assemblies and fuel management in MOX-containing cores are strongly influenced by the nuclear properties of the plutonium isotopes. Optimized MOX fuel assembly designs for PWRs currently use up to three types of MOX fuel rods having different plutonium contents with natural uranium or uranium tailings as carrier material but without burnable absorbers. The MOX fuel assembly designs for BWRs use four to six rod types with different plutonium contents and Gd[sub 2]O[sub 3]/UO[sub 2] burnable absorber rods. Both the PWR and the BWR designs attain good burnup equivalence and compatibility with uranium fuel assemblies. High flexibility exists in the loading schemes relative to the position and number of MOX fuel assemblies in the reloads and in the core as a whole. The Siemens experience with MOX fuel assemblies is based on the insertion of 318 MOX fuel assemblies in eight PWRs and 168 in BWRs and pressurized heavy water reactors so far. The primary operating results include information on the cycle length, power distribution, reactivity coefficients, and control rod worth of cores containing MOX fuel assemblies.

  9. CONVERSION OF RUSSIAN WEAPON-GRADE PLUTONIUM INTO OXIDE FOR MIXED OXIDE (MOX) FUEL FABRICATION.

    SciTech Connect

    Glagovski, E.; Kolotilov, Y.; Glagolenko, Y.; Zygmunt, Stanley J.; Mason, C. F. V.; Hahn, W. K.; Durrer, R. E.; Thomas, S.; Sicard, B.; Herlet, N.; Fraize, G.; Villa, A.

    2001-01-01

    Progress has been made in the Russian Federation towards the conversion of weapons-grade plutonium (w-Pu) into plutonium oxide (PuO{sub 2}) suitable for further manufacture into mixed oxide (MOX) fuels. This program is funded both by French Commissariat x 1'Energie Atomique (CEA) and the US National Nuclear Security Administration (NNSA). The French program was started as a way to make available their expertise gained from manufacturing MOX fuel. The US program was started in 1998 in response to US proliferation concerns and the acknowledged international need to decrease available w-Pu. Russia has selected both the conversion process and the manufacturing site. This paper discusses the present state of development towards fulfilling this mission: the demonstration plant designed to process small amounts of Pu and validate all process stages and the industrial plant that will process up to 5 metric tons of Pu per year.

  10. Investigation of the Carbon Monoxide Gas Sensing Characteristics of Tin Oxide Mixed Cerium Oxide Thin Films

    PubMed Central

    Durrani, Sardar M. A.; Al-Kuhaili, Mohammad F.; Bakhtiari, Imran A.; Haider, Muhammad B.

    2012-01-01

    Thin films of tin oxide mixed cerium oxide were grown on unheated substrates by physical vapor deposition. The films were annealed in air at 500 °C for two hours, and were characterized using X-ray photoelectron spectroscopy, atomic force microscopy and optical spectrophotometry. X-ray photoelectron spectroscopy and atomic force microscopy results reveal that the films were highly porous and porosity of our films was found to be in the range of 11.6–21.7%. The films were investigated for the detection of carbon monoxide, and were found to be highly sensitive. We found that 430 °C was the optimum operating temperature for sensing CO gas at concentrations as low as 5 ppm. Our sensors exhibited fast response and recovery times of 26 s and 30 s, respectively. PMID:22736967

  11. Complex catalytic behaviors of CuTiOx mixed-oxide during CO oxidation

    DOE PAGESBeta

    Kim, Hyun You; Liu, Ping

    2015-09-21

    Mixed metal oxides have attracted considerable attention in heterogeneous catalysis due to the unique stability, reactivity, and selectivity. Here, the activity and stability of the CuTiOx monolayer film supported on Cu(111), CuTiOx/Cu(111), during CO oxidation was explored using density functional theory (DFT). The unique structural frame of CuTiOx is able to stabilize and isolate a single Cu+ site on the terrace, which is previously proposed active for CO oxidation. Furthermore, it is not the case, where the reaction via both the Langmuir–Hinshelwood (LH) and the Mars-van Krevelen (M-vK) mechanisms are hindered on such single Cu+ site. Upon the formation ofmore » step-edges, the synergy among Cuδ+ sites, TiOx matrix, and Cu(111) is able to catalyze the reaction well. Depending on temperatures and partial pressure of CO and O2, the surface structure varies, which determines the dominant mechanism. In accordance with our results, the Cuδ+ ion alone does not work well for CO oxidation in the form of single sites, while the synergy among multiple active sites is necessary to facilitate the reaction.« less

  12. Thermodynamic calculations of oxygen self-diffusion in mixed-oxide nuclear fuels

    DOE PAGESBeta

    Parfitt, David C.; Cooper, Michael William; Rushton, Michael J.D.; Christopoulos, S. R.; Fitzpatrick, M. E.; Chroneos, A.

    2016-07-29

    Mixed-oxide fuels containing uranium with thorium and/or plutonium may play an important part in future nuclear fuel cycles. There are, however, significantly less data available for these materials than conventional uranium dioxide fuel. In the present study, we employ molecular dynamics calculations to simulate the elastic properties and thermal expansivity of a range of mixed oxide compositions. These are then used to support equations of state and oxygen self-diffusion models to provide a self-consistent prediction of the behaviour of these mixed oxide fuels at arbitrary compositions.

  13. MnOx-CeO2-Al2O3 mixed oxides for soot oxidation: activity and thermal stability.

    PubMed

    Wu, Xiaodong; Liu, Shuang; Weng, Duan; Lin, Fan; Ran, Rui

    2011-03-15

    MnO(x)-CeO(2)-Al(2)O(3) mixed oxides were prepared by impregnating manganese acetate and cerium nitrate on alumina powders using the sol-gel method. The thermal stabilities of MnO(x)-CeO(2) and Al(2)O(3)-modified mixed oxides were evaluated by treating at 800 °C in dry air flow for 20h. The introduction of Al(2)O(3) markedly increases the textural stability of the catalyst with a relatively high dispersion of MnO(x) and CeO(2), remaining a strong synergistic effect between these two oxides. The NO oxidation activity of the ternary oxides experiences a smaller loss after high-temperature calcination, and a low soot oxidation temperature is attained in the presence of NO. PMID:21276659

  14. Operation of mixed conducting metal oxide membrane systems under transient conditions

    SciTech Connect

    Carolan, Michael Francis

    2008-12-23

    Method of operating an oxygen-permeable mixed conducting membrane having an oxidant feed side, an oxidant feed surface, a permeate side, and a permeate surface, which method comprises controlling the differential strain between the permeate surface and the oxidant feed surface at a value below a selected maximum value by varying the oxygen partial pressure on either or both of the oxidant feed side and the permeate side of the membrane.

  15. Synthesis and Characterization of Mixed Metal Oxide Nanocomposite Energetic Materials

    SciTech Connect

    Gash, A; Pantoya, M; Jr., J S; Zhao, L; Shea, K; Simpson, R; Clapsaddle, B

    2003-11-18

    In the field of composite energetic materials, properties such as ingredient distribution, particle size, and morphology, affect both sensitivity and performance. Since the reaction kinetics of composite energetic materials are typically controlled by the mass transport rates between reactants, one would anticipate new and potentially exceptional performance from energetic nanocomposites. We have developed a new method of making nanostructured energetic materials, specifically explosives, propellants, and pyrotechnics, using sol-gel chemistry. A novel sol-gel approach has proven successful in preparing metal oxide/silicon oxide nanocomposites in which the metal oxide is the major component. Two of the metal oxides are tungsten trioxide and iron(III) oxide, both of which are of interest in the field of energetic materials. Furthermore, due to the large availability of organically functionalized silanes, the silicon oxide phase can be used as a unique way of introducing organic additives into the bulk metal oxide materials. As a result, the desired organic functionality is well dispersed throughout the composite material on the nanoscale. By introducing a fuel metal into the metal oxide/silicon oxide matrix, energetic materials based on thermite reactions can be fabricated. The resulting nanoscale distribution of all the ingredients displays energetic properties not seen in its microscale counterparts due to the expected increase of mass transport rates between the reactants. The synthesis and characterization of these metal oxide/silicon oxide nanocomposites and their performance as energetic materials will be discussed.

  16. Magnetic properties of mesoporous cobalt-silica-alumina ternary mixed oxides

    SciTech Connect

    Pal, Nabanita; Seikh, Md. Motin; Bhaumik, Asim

    2013-02-15

    Mesoporous cobalt-silica-alumina mixed oxides with variable cobalt content have been synthesized through slow evaporation method by using Pluronic F127 non-ionic surfactant as template. N{sub 2} sorption analysis of the template-free mixed oxide samples revealed that these mesoporous materials have high BET surface areas together with large mesopores. Powder XRD, TEM, EDS, FT IR and EPR spectroscopic analysis have been employed to understand the nature of the mesophases, bonding and composition of the materials. Low temperature magnetic measurements of these mixed oxide materials show the presence of ferromagnetic correlation at elevated temperature though at low temperature paramagnetic to ferrimagnetic transition is observed. Highlights: Black-Right-Pointing-Pointer Mesoporous cobalt-silica-alumina ternary mixed oxides. Black-Right-Pointing-Pointer High surface area and mesoporosity in magnetic materials. Black-Right-Pointing-Pointer Ferromagnetic correlation at elevated temperature. Black-Right-Pointing-Pointer Low temperature paramagnetic to ferrimagnetic transition.

  17. PHOTOCHEMICAL OXIDANT AIR POLLUTION EFFECTS ON A MIXED CONIFER FOREST FOREST ECOSYSTEM - A PROGRESS REPORT

    EPA Science Inventory

    Since 1972, twelve scientists representing several research disciplines have collaborated in integrated studies to determine the chronic effects of photochemical oxidant air pollutants on a western mixed conifer forest ecosystem. An enormous amount of data has been collected, des...

  18. Single crystal particles of a mesoporous mixed transition metal oxide with a wormhole structure.

    PubMed

    Lee, B; Lu, D; Kondo, J N; Domen, K

    2001-10-21

    A new type of mesoporous mixed transition metal oxide of Nb and Ta (NbTa-TIT-1) has been prepared through a two-step calcination, which consists of single crystal particles with wormhole mesoporous structure. PMID:12240191

  19. Synthesis and Characterization of Mixed Metal Oxide Nanocomposite Energetic Materials

    SciTech Connect

    Clapsaddle, B; Gash, A; Plantier, K; Pantoya, M; Jr., J S; Simpson, R

    2004-04-27

    In the field of composite energetic materials, properties such as ingredient distribution, particle size, and morphology affect both sensitivity and performance. Since the reaction kinetics of composite energetic materials are typically controlled by the mass transport rates between reactants, one would anticipate new and potentially exceptional performance from energetic nanocomposites. We have developed a new method of making nanostructured energetic materials, specifically explosives, propellants, and pyrotechnics, using sol-gel chemistry. A novel sol-gel approach has proven successful in preparing metal oxide/silicon oxide nanocomposites in which the metal oxide is the major component. By introducing a fuel metal, such as aluminum, into the metal oxide/silicon oxide matrix, energetic materials based on thermite reactions can be fabricated. Two of the metal oxides are tungsten trioxide and iron(III) oxide, both of which are of interest in the field of energetic materials. In addition, due to the large availability of organically functionalized silanes, the silicon oxide phase can be used as a unique way of introducing organic additives into the bulk metal oxide materials. These organic additives can cause the generation of gas upon ignition of the materials, therefore resulting in a composite material that can perform pressure/volume work. Furthermore, the desired organic functionality is well dispersed throughout the composite material on the nanoscale with the other components, and is therefore subject to the same increased reaction kinetics. The resulting nanoscale distribution of all the ingredients displays energetic properties not seen in its microscale counterparts due to the expected increase of mass transport rates between the reactants. The synthesis and characterization of iron(III) oxide/organosilicon oxide nanocomposites and their performance as energetic materials will be discussed.

  20. Molten carbonate fuel cell cathode with mixed oxide coating

    DOEpatents

    Hilmi, Abdelkader; Yuh, Chao-Yi

    2013-05-07

    A molten carbonate fuel cell cathode having a cathode body and a coating of a mixed oxygen ion conductor materials. The mixed oxygen ion conductor materials are formed from ceria or doped ceria, such as gadolinium doped ceria or yttrium doped ceria. The coating is deposited on the cathode body using a sol-gel process, which utilizes as precursors organometallic compounds, organic and inorganic salts, hydroxides or alkoxides and which uses as the solvent water, organic solvent or a mixture of same.

  1. Route of electrochemical oxidation of the antibiotic sulfamethoxazole on a mixed oxide anode.

    PubMed

    Hussain, Sajjad; Gul, Saima; Steter, Juliana R; Miwa, Douglas W; Motheo, Artur J

    2015-10-01

    The appearance of pharmaceutical compounds and their bioactive transformation products in aquatic environments is becoming an issue of increasing concern. In this study, the electrochemical oxidation of the widely used antibiotic sulfamethoxazole (SMX) was investigated using a commercial mixed oxide anode (Ti/Ru0.3Ti0.7O2) and a single compartment filter press-type flow reactor. The kinetics of SMX degradation was determined as a function of electrolyte composition, applied current density, and initial pH. Almost complete (98 %) degradation of SMX could be achieved within 30 min of electrolysis in 0.1 mol L(-1) NaCl solution at pH 3 with applied current densities ≥20 mA cm(-2). Nine major intermediates of the reaction were identified by LC-ESI-Q-TOF-MS (e.g., C6H9NO2S (m/z = 179), C6H4NOCl (m/z = 141), and C6H6O2 (m/z = 110)). The degradation followed various routes involving cleavage of the oxazole and benzene rings by hydroxyl and/or chlorine radicals, processes that could occur before or after rupture of the N-S bond, followed by oxidation of the remaining moieties. Analysis of the total organic carbon content revealed that the antibiotic was partially mineralized under the conditions employed and some inorganic ions, including NO3 (-) and SO4 (2-), could be identified. The results presented herein demonstrate the efficacy of the electrochemical process using a Ti/Ru0.3Ti0.7O2 anode for the remediation of wastewater containing the antibiotic SMX. PMID:26002364

  2. Electrooxidation of nitrite on a silica-cerium mixed oxide carbon paste electrode.

    PubMed

    Silveira, Gustavo; de Morais, Andréia; Villis, Paulo César Mendes; Maroneze, Camila Marchetti; Gushikem, Yoshitaka; Lucho, Alzira Maria Serpa; Pissetti, Fábio Luiz

    2012-03-01

    A silica-cerium mixed oxide (SiCe) was prepared by the sol-gel process, using tetraethylorthosilicate and cerium nitrate as precursors and obtained as an amorphous solid possessing a specific surface area of 459 m(2) g(-1). Infrared spectroscopy of the SiCe material showed the formation of the Si-O-Ce linkage in the mixed oxide. Scanning electron microscopy/energy dispersive spectroscopy indicated that the cerium oxide particles were homogenously dispersed on the matrix surface. X-ray diffraction and (29)Si solid-state nuclear magnetic resonance implied non-crystalline silica matrices with chemical environments that are typical for silica-based mixed oxides. X-ray photoelectron spectroscopy showed that Ce was present in approximately equal amounts of both the 3+ and 4+ oxidation states. Cyclic voltammetry data of electrode prepared from the silica-cerium mixed oxide showed a peak for oxidation of Ce(3+)/Ce(4+) at 0.76 V and electrochemical impedance spectroscopy equivalent circuit indicated a porous structure with low charge transfer resistance. In the presence of nitrite, the SiCe electrode shows an anodic oxidation peak at 0.76 V with a linear response as the concentration of the analyte increases from 3×10(-5) at 3.9×10(-3) mol L(-1). PMID:22192596

  3. Mixed Metal Oxides with the Structure of Perovskite for Anticorrosion Organic Coatings

    NASA Astrophysics Data System (ADS)

    Kantorová, M.; Veselý, D.

    Mixed metal oxides pigments of TiO2.ZnO, 2TiO2.ZnO, Zn2TiO4, MgTiO3, CaTiO3, TiO2.ZnO.MgO, and TiO2.ZnO.SrO were synthesized from corresponding oxides or carbonates at high temperature. The obtained metal mixed oxides were characterized by means of X-fray diffraction analysis, measurement of particle sizes and scanning electron microscopy. The synthesized metal mixed oxides were used to produce epoxy-ester coatings with PVC = 10% for a synthesized pigment. The coatings were tested for physical-mechanical properties and in corrosion atmospheres. The results of corrosion tests were compared with standard alumino zinc phosphomolybdate.

  4. Synthesis and characterization of mixed Fe-Cr oxide pillared {alpha}-zirconium phosphate materials

    SciTech Connect

    Perez-Reina, F.J.; Olivera-Pastor, P.; Rodriguez-Castellon, E.; Jimenez-Lopez, A.

    1996-02-15

    Mixed Fe/Cr hydroxyacetate oligomers ranging in composition from 90/10 to 10/90 have been prepared by mixing Fe{sup 3+} and Cr{sup 3+} nitrate solutions and then adding n-propylammonium acetate up to an acetate/Cr{sup 3+} ratio of 2.8 and pH 4. The oligomers were intercalated into colloidal {alpha}-zirconium phosphate or precipitated with excess n-propylamine. The precipitates are all amorphous and show differential thermal behavior in comparison with the intercalates. Upon calcination in air, the precipitates become crystalline, showing the characteristic XRD peaks of mixed Fe/Cr oxides. These mixed oxides present unusually high BET surface areas (up to 276 m {sup 2}{center_dot}g{sup {minus}1}), especially those with low Fe/Cr ratios. The intercalates are poorly crystalline or amorphous at room temperature and upon calcination at 400{degrees}C in air or under N{sub 2}, which indicates that there is no oxide segregation from the interlayers. From these results it is suggested that mixed Fe/Cr oxides are cross-linked to the phosphate layer, forming a pillared structure. Significantly, the mixed oxides segregated from the phosphate surface at 1000{degrees}C present XRD patterns identical to the mixed oxides obtained from the precipitates with the same Fe/Cr ratios. The pillared materials show high BET surface areas, from 200 to 306 m{sup 2}/g, and narrow pore size distributions with pore radius ranging from 8.5 to 13.8 {Angstrom}. XPS analysis reveals a higher affinity of the phosphate surface for Cr{sup 3+} at high Fe/Cr ratios from 70/30 to 90/10. In these samples the partial oxidation of Cr(III) to Cr(VI) was observed in the XPS spectra, in spite of the materials being calcined under N{sub 2}.

  5. Synergetic effects of mixed copper-iron oxides oxygen carriers in chemical looping combustion

    SciTech Connect

    Siriwardane, Ranjani; Tian, Hanjing; Simonyi, Thomas; Poston, James

    2013-06-01

    Chemical looping combustion (CLC) is an emerging technology for clean energy production from fuels. CLC produces sequestration-ready CO{sub 2}-streams without a significant energy penalty. Development of efficient oxygen carriers is essential to successfully operate a CLC system. Copper and iron oxides are promising candidates for CLC. Copper oxide possesses high reactivity but it has issues with particle agglomeration due to its low melting point. Even though iron oxide is an inexpensive oxygen carrier it has a slower reactivity. In this study, mixed metal oxide carriers containing iron and copper oxides were evaluated for coal and methane CLC. The components of CuO and Fe{sub 2}O{sub 3} were optimized to obtain good reactivity while maintaining physical and chemical stability during cyclic reactions for methane-CLC and solid-fuel CLC. Compared with single metal oxygen carriers, the optimized Cu–Fe mixed oxide oxygen carriers demonstrated high reaction rate, better combustion conversion, greater oxygen usage and improved physical stability. Thermodynamic calculations, XRD, TGA, flow reactor studies and TPR experiments suggested that there is a strong interaction between CuO and Fe{sub 2}O{sub 3} contributing to a synergistic effect during CLC reactions. The amount of oxygen release of the mixed oxide carrier in the absence of a fuel was similar to that of the single metal oxides. However, in the presence of fuels, the oxygen consumption and the reaction profiles of the mixed oxide carriers were significantly better than that of the single metal oxides. The nature of the fuel not only influenced the reactivity, but also the final reduction status of the oxygen carriers during chemical looping combustion. Cu oxide of the mixed oxide was fully reduced metallic copper with both coal and methane. Fe oxide of the mixed oxide was fully reduced Fe metal with methane but it was reduced to only FeO with coal. Possible mechanisms of how the presence of CuO enhances the

  6. How to stabilize highly active Cu+ cations in a mixed-oxide catalyst

    DOE PAGESBeta

    Mudiyanselage, Kumudu; Luo, Si; Kim, Hyun You; Yang, Xiaofang; Baber, Ashleigh E.; Hoffmann, Friedrich M.; Senanayake, Sananayake; Rodriguez, Jose A.; Chen, Jingguang G.; Liu, Ping; et al

    2015-09-12

    Mixed-metal oxides exhibit novel properties that are not present in their isolated constituent metal oxides and play a significant role in heterogeneous catalysis. In this study, a titanium-copper mixed-oxide (TiCuOx) film has been synthesized on Cu(111) and characterized by complementary experimental and theoretical methods. At sub-monolayer coverages of titanium, a Cu2O-like phase coexists with TiCuOx and TiOx domains. When the mixed-oxide surface is exposed at elevated temperatures (600–650 K) to oxygen, the formation of a well-ordered TiCuOx film occurs. Stepwise oxidation of TiCuOx shows that the formation of the mixed-oxide is faster than that of pure Cu2O. As the Timore » coverage increases, Ti-rich islands (TiOx) form. The adsorption of CO has been used to probe the exposed surface sites on the TiOx–CuOx system, indicating the existence of a new Cu+ adsorption site that is not present on Cu2O/Cu(111). Adsorption of CO on Cu+ sites of TiCuOx is thermally more stable than on Cu(111), Cu2O/Cu(111) or TiO2(110). The Cu+ sites in TiCuOx domains are stable under both reducing and oxidizing conditions whereas the Cu2O domains present on sub-monolayer loads of Ti can be reduced or oxidized under mild conditions. Furthermore, the results presented here demonstrate novel properties of TiCuOx films, which are not present on Cu(111), Cu2O/Cu(111), or TiO2(110), and highlight the importance of the preparation and characterization of well-defined mixed-metal oxides in order to understand fundamental processes that could guide the design of new materials.« less

  7. Microwave synthesis and electrochemical characterization of Mn/Ni mixed oxide for supercapacitor application

    SciTech Connect

    Prasankumar, T.; Jose, Sujin P.; Ilangovan, R.; Venkatesh, K. S.

    2015-06-24

    Nanostructured Mn/Ni mixed metal oxide was synthesized at ambient temperature by facile microwave irradiation technique. The crystal structure and surface morphology were characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM), respectively. X-ray diffraction analysis confirmed the formation of Mn/Ni mixed oxide in rhombohedral phase and the grain size calculated was found to be 87 nm. The irregular spherical morphology of the prepared sample was exhibited by the SEM images. The characteristic peaks of FTIR at about 630 cm{sup −1} and 749 cm{sup −1} were attributed to the Mn-O and Ni-O stretching vibrations respectively. The presence of both Mn and Ni in the prepared sample was validated by the EDS spectra which in turn confirmed the formation of mixed oxide. Cyclic voltammetry and galvanostatic chargedischarge measurements were employed to investigate the electrochemical performance of the mixed oxide. The cyclic voltammetry curves demonstrated good capacitive performance of the sample in the potential window −0.2V to 0.9V. The charge discharge study revealed the suitability of the prepared mixed oxide for the fabrication of supercapacitor electrode.

  8. Development of Mixed Ion-Electron Conducting Metal Oxides for Solid Oxide Fuel Cells

    NASA Astrophysics Data System (ADS)

    Kan, Wang Hay

    A solid oxide fuel cell (SOFC) is an energy conversion device, which directly converts chemical fuels (e.g., H2, C xHy) into electricity and heat with high efficiency up to 90%. The by-product of CO2 can be safely sequestrated or subsequently chemically transformed back into fuels (e.g., CO, CH 4) by electrolysis using renewable energy sources such as solar and wind. The state-of-the-art Ni-YSZ anode is de-activated in the presence of ppm level of H2S and forming coke in hydrocarbons. Currently, mixed ion and electron conductors (MIECs) are considered as alternatives for Ni-YSZ in SOFCs. The key goal of the research was to develop mixed ion-electron conducting metal oxides based on B-site disordered perovskite-type Ba(Ca,Nb)1-x MxO3-delta (M = Mn, Fe, Co), the B-site 1:1 ordered perovskite-type (M = Mn, Fe, Co) and the Sr2PbO4-type Sr2Ce1-xPrxO4 for SOFCs. Ba2(Ca,Nb)2-xMxO6-delta was chemically stable in 30 ppm levels of H2S at 600 °C for 24 h and in pure CO2 at 800 °C for 24 h. The thermal expansion coefficients (TEC) of the as-prepared ordered perovskites was found to be comparable to Zr0.84Y0.16O1.92 (YSZ). The near-surface concentration of Fe2+ in Ba2Ca 0.67Fe0.33NbO6-delta was found to be about 3 times higher than that in the bulk sample. The electrochemical performance of Ba2Ca0.67M0.33NbO6-delta was assessed by ac impedance spectroscopy using a YSZ supported half-cell. The area specific polarization resistance (ASR) of all samples was found to decrease with increasing temperature. The ASR for H2 gas oxidation can be correlated to the higher concentration of low valence Fe2+ species near-surface (nano-scale). BaCa0.335M0.165Nb0.5O3-delta crystallizes in the B-site disordered primitive perovskite (space group Pm-3m) at 900 °C in air, which can be converted into the B-site 1:2 ordered perovskite (space group P-3m1) at 1200 °C and the B-site 1:1 ordered double perovskite phase (space group Fm-3m ) at 1300 °C. The chemical stability of the perovskites in CO

  9. Facile preparation of highly-dispersed cobalt-silicon mixed oxide nanosphere and its catalytic application in cyclohexane selective oxidation

    PubMed Central

    2011-01-01

    Highly dispersed cobalt-silicon mixed oxide [Co-SiO2] nanosphere was successfully prepared with a modified reverse-phase microemulsion method. This material was characterized in detail by X-ray diffraction, transmission electron microscopy, Fourier transform infrared, ultraviolet-visible diffuse reflectance spectra, X-ray absorption spectroscopy near-edge structure, and N2 adsorption-desorption measurements. High valence state cobalt could be easily obtained without calcination, which is fascinating for the catalytic application for its strong oxidation ability. In the selective oxidation of cyclohexane, Co-SiO2 acted as an efficient catalyst, and good activity could be obtained under mild conditions. PMID:22067075

  10. Direct imaging of octahedral distortion in a complex molybdenum vanadium mixed oxide.

    PubMed

    Lunkenbein, Thomas; Girgsdies, Frank; Wernbacher, Anna; Noack, Johannes; Auffermann, Gudrun; Yasuhara, Akira; Klein-Hoffmann, Achim; Ueda, Wataru; Eichelbaum, Maik; Trunschke, Annette; Schlögl, Robert; Willinger, Marc G

    2015-06-01

    Complex Mo,V-based mixed oxides that crystallize in the orthorhombic M1-type structure are promising candidates for the selective oxidation of small alkanes. The oxygen sublattice of such a complex oxide has been studied by annular bright field scanning transmission electron microscopy. The recorded micrographs directly display the local distortion in the metal oxygen octahedra. From the degree of distortion we are able to draw conclusions on the distribution of oxidation states in the cation columns at different sites. The results are supported by X-ray diffraction and electron paramagnetic resonance measurements that provide integral details about the crystal structure and spin coupling, respectively. PMID:25914205

  11. Mixed metal oxide films as pH sensing materials

    NASA Astrophysics Data System (ADS)

    Arshak, Khalil; Gill, Edric; Korostynska, Olga; Arshak, Arousian

    2007-05-01

    Due to the demand for accurate, reliable and highly sensitive pH sensors, research is being pursued to find novel materials to achieve this goal. Semiconducting metal oxides, such as TiO, SnO and SnO II and insulating oxides such as Nb IIO 5 and Bi IIO 3, and their mixtures in different proportions are being investigated for this purpose. The films of these materials mixtures are used in conjunction with an interdigitated electrode pattern to produce a conductimetric/capacitive pH sensor. The advantages of this approach include straightforward manufacturing, versatility and cost-effectiveness. It was noted that upon contact with a solution, the electrical parameters of the films, such as resistance etc., change. The correlation of these changes with pH values is the basis for the proposed system development. The ultimate goal is to find materials composition, which would have the highest sensitivity towards the pH level of the solutions. It was found that the materials that produced the highest sensitivity either had a long response time or were unstable over a wide pH range. Those exhibiting lower sensitivities were found to be more stable over a wide pH range. All oxide films tested demonstrated a change in electrical parameters upon contact with buffers of known pH value.

  12. Interspecies comparison of the metabolism and dosimetry of inhaled mixed oxides of plutonium and uranium

    SciTech Connect

    Boecker, B.B.; Mewhinney, J.A.; Eidson, A.F.

    1997-12-01

    Three studies were conducted to provide information on the biological fate, distribution of radiation doses among tissues, and implications for potential health consequences of an inhalation exposure to mixed-oxide nuclear fuel materials. In each study, Fischer-344 rats, beagle dogs, and cynomolgus monkeys inhaled one of three aerosols: 750{degrees}C calcined mixed oxides of UO{sub 2} and PuO{sub 2}, 1750{degrees}C sintered (U,Pu)O{sub 2}, or 850{degrees}C calcined {open_quotes}pure{close_quotes} PuO{sub 2}. These materials were collected from glove-box enclosures immediately after industrial processing of mixed-oxide fuel materials. Lung retention, tissue distribution, and mode of excretion of {sup 238-240}Pu, {sup 241}Am, and uranium (when present) were quantified by radiochemical analysis of tissue and excreta samples from animals sacrificed at selected times to 6.5 yr after inhalation exposure.

  13. Redox state of plutonium in irradiated mixed oxide fuels

    NASA Astrophysics Data System (ADS)

    Degueldre, C.; Pin, S.; Poonoosamy, J.; Kulik, D. A.

    2014-03-01

    Nowadays, MOX fuels are used in about 20 nuclear power plants around the world. After irradiation, plutonium co-exists with uranium oxide. Due to the redox sensitive nature of UO2 other plutonium oxides than PuO2 potentially present in the fuel may interact with the matrix. The aim of this study is to determine which plutonium species are present in heterogeneous and homogeneous MOX. The results provided by X-ray Absorption Near Edge Spectroscopy (XANES) for non-irradiated as well as irradiated (center and periphery) homogeneous MOX fuel were published earlier and are completed by Extended X-ray Fine Structure (EXAFS) analysis in this work. The EXAFS signals have been extracted using the ATHENA code and the analyses were carried using EXCURE98 as performed earlier for an analogous element. EXAFS shows that plutonium redox state remains tetravalent in the solid solution and that the minor fraction of trivalent Pu must be below 10%. Independently, the study of homogeneous MOX was also approached by thermodynamics of solid solution of (U,Pu)O2. Such solid solutions were modeled using the Gibbs Energy Minimisation (GEM)-Selektor code (developed at LES, NES, PSI) supported by the literature data on such solid solutions. A comparative study was performed showing which plutonium oxides in their respective mole fractions are more likely to occur in (U,Pu)O2. In the modeling, these oxides were set as ideal and non-ideal solid solutions, as well as separate pure phases. Pu exists mainly as PuO2 in the case of separate phases, but can exist under its reduced forms, PuO1.61 and PuO1.5 in minor fraction i.e. ~15% in ideal solid solution (unlikely) and ~10% in non-ideal solid solution (likely) and at temperature around 1300 K. This combined thermodynamic and EXAFS studies confirm independently the results obtained so far by Pu XANES for the same MOX samples.

  14. High temperature oxidation behaviour of nanostructured cermet coatings in a mixed CO2 - O2 environment

    NASA Astrophysics Data System (ADS)

    Farrokhzad, M. A.; Khan, T. I.

    2014-06-01

    Nanostructured ceramic-metallic (cermet) coatings composed of nanosized ceramic particles (α-Al2O3 and TiO2) dispersed in a nickel matrix were co-electrodeposited and then oxidized at 500°C, 600°C and 700°C in a mixed gas using a Thermo-gravimetric Analysis (TGA) apparatus. The mixed gas was composed of 15% CO2, 10% O2 and 75% N2. This research investigates the effects of CO2 and O2 partial pressures on time-depended oxidation rates for coatings and compared them to the results from atmospheric oxidation under similar temperatures. The increase in partial pressure of oxygen due to the presence of CO2 at each tested temperature was calculated and correlated to the oxidation rate of the coatings. The results showed that the presence of CO2 in the system increased the oxidation rate of cermet coatings when compared to atmospheric oxidation at the same temperature. It was also shown that the increase in the oxidation rate is not the result of CO2 acting as the primary oxidant but as a secondary oxidant which results in an increase of the total partial pressure of oxygen and consequently higher oxidation rates. The WDS and XRD analyses results showed that the presence of nanosized TiO2 particles in a nickel matrix can improve oxidation behaviour of the coatings by formation of Ni-Ti compounds on oxidizing surface of the coating which was found beneficiary in reducing the oxidation rates for cermet coatings.

  15. Bench-scale operation of the DETOX wet oxidation process for mixed waste

    SciTech Connect

    Dhooge, P.M.

    1993-03-01

    Waste matrices containing organics, radionuclides, and metals pose difficult problems in waste treatment and disposal when the organic compounds and/or metals are considered to be hazardous. A means of destroying hazardous organic components while safely containing and concentrating metals would be extremely useful in mixed waste volume reduction or conversion to a radioactive-only form. Previous studies have found the DETOX, a patented process utilizing a novel catalytic wet oxidation by iron(III) oxidant, cold have successful application to mixed wastes, and to many other waste types. This paper describes the results of bench scale studies of DETOX applied to the components of liquid mixed wastes, with the goal of establishing parameters for the design of a prototype waste treatment unit. Apparent organic reaction rate orders, and the dependence of apparent reaction rate on the contact area, were measured for vacuum pump oil, scintillation fluids, and trichloroethylene. It was found that reaction rate was proportional to contact area above about 2.% w/w loading of organic. Oxidations in a 4 liter. volume, mixed bench top reactor have given destruction efficiencies of 99.9999+% for common organics. Reaction rates achieved in the mixedbench top reactor were one to two orders of magnitude greater than had been achieved in unmixed reactions; a thoroughly mixed reactor should be capable of oxidizing 10. to 100.+ grams of organic per liter-hour,depending on the nature and concentration of the organic.

  16. Bench-scale operation of the DETOX wet oxidation process for mixed waste

    SciTech Connect

    Dhooge, P.M.

    1993-01-01

    Waste matrices containing organics, radionuclides, and metals pose difficult problems in waste treatment and disposal when the organic compounds and/or metals are considered to be hazardous. A means of destroying hazardous organic components while safely containing and concentrating metals would be extremely useful in mixed waste volume reduction or conversion to a radioactive-only form. Previous studies have found the DETOX, a patented process utilizing a novel catalytic wet oxidation by iron(III) oxidant, cold have successful application to mixed wastes, and to many other waste types. This paper describes the results of bench scale studies of DETOX applied to the components of liquid mixed wastes, with the goal of establishing parameters for the design of a prototype waste treatment unit. Apparent organic reaction rate orders, and the dependence of apparent reaction rate on the contact area, were measured for vacuum pump oil, scintillation fluids, and trichloroethylene. It was found that reaction rate was proportional to contact area above about 2.% w/w loading of organic. Oxidations in a 4 liter. volume, mixed bench top reactor have given destruction efficiencies of 99.9999+% for common organics. Reaction rates achieved in the mixedbench top reactor were one to two orders of magnitude greater than had been achieved in unmixed reactions; a thoroughly mixed reactor should be capable of oxidizing 10. to 100.+ grams of organic per liter-hour,depending on the nature and concentration of the organic.

  17. Interatomic potentials for mixed oxide and advanced nuclear fuels

    SciTech Connect

    Tiwary, Pratyush; Walle, Axel van de; Jeon, Byoungseon; Groenbech-Jensen, Niels

    2011-03-01

    We extend our recently developed interatomic potentials for UO{sub 2} to the fuel system (U,Pu,Np)O{sub 2}. We do so by fitting against an extensive database of ab initio results as well as to experimental measurements. The applicability of these interactions to a variety of mixed environments beyond the fitting domain is also assessed. The employed formalism makes these potentials applicable across all interatomic distances without the need for any ambiguous splining to the well-established short-range Ziegler-Biersack-Littmark universal pair potential. We therefore expect these to be reliable potentials for carrying out damage simulations (and molecular dynamics simulations in general) in nuclear fuels of varying compositions for all relevant atomic collision energies.

  18. Storage capacity and oxygen mobility in mixed oxides from transition metals promoted by cerium

    NASA Astrophysics Data System (ADS)

    Perdomo, Camilo; Pérez, Alejandro; Molina, Rafael; Moreno, Sonia

    2016-10-01

    The oxygen mobility and storage capacity of Ce-Co/Cu-MgAl or Ce-MgAl mixed oxides, obtained by hydrotalcite precursors, were evaluated using Toluene-temperature-programmed-reaction, 18O2 isotopic exchange and O2-H2 titration. The presence of oxygen vacancies-related species was evaluated by means of Electron Paramagnetic Resonance. A correlation was found between the studied properties and the catalytic activity of the oxides in total oxidation processes. It was evidenced that catalytic activity depends on two related processes: the facility with which the solid can be reduced and its ability to regenerate itself in the presence of molecular oxygen in the gas phase. These processes are enhanced by Cu-Co cooperative effect in the mixed oxides. Additionally, the incorporation of Ce in the Co-Cu catalysts improved their oxygen transport properties.

  19. Mixed metal oxides as alternate cathodes for high energy density electric propulsion

    SciTech Connect

    Papp, J.E.

    1995-12-31

    Silver (II) oxide is currently the Navy`s cathode of choice in high energy density, high rate batteries for torpedo and mobile target applications, for medium rate applications such as Seal Delivery Vehicles, and may be useful for low rate, long endurance UUV missions. While it is certainly a versatile material, silver (II) oxide is expensive to produce and has a lower faradaic (storage) capacity than desired. New research being conducted at the NUWC electric propulsion laboratory is focused toward developing new, lower cost cathode materials with energy densities at least comparable to silver (II) oxide. Mixed metal oxides, with silver (II) oxide as one component, are under investigation. Other materials, without a silver component, are also being considered. This poster will illustrate recent developments in the modification of the silver (II) oxide cathode for Navy applications.

  20. Oxidation kinetic analysis of a mixed uranium dicarbide and graphite compound

    NASA Astrophysics Data System (ADS)

    Marchand, M.; Fiquet, O.; Brothier, M.

    2013-06-01

    The oxidation of a mixed uranium dicarbide and graphite powder has been investigated by simultaneous thermal gravimetric (TGA) and differential thermal (DTA) analyses coupled with gas phase chromatography. For isothermal oxidation conditions with temperatures below 330 °C, only the UC2 chemical phase is progressively oxidised into U3O8 oxides. Parabolic weight gain curves as a function of oxidation over time were obtained. A detailed kinetic study is proposed to establish a pseudo-steady-state during the oxidation process. Using an experimental method based on the sudden temperature increases, a single rate-limiting step has been validated and then modelled by a 3D diffusion law. An apparent activation energy calculated from the Arrhenius representation has been evaluated at -35 kJ/mol, thus describing the diffusion of oxygen through the oxide layer.

  1. Surface acidity of silica-titania mixed oxides

    SciTech Connect

    Odenbrand, C.U.I.; Brandin, J.G.M. ); Busca, G. )

    1992-06-01

    A study of the acidity of coprecipitated SiO[sub 2]-TiO[sub 2] oxides is presented. The amount of acidity has been determined by ammonia adsorption at 150 C. The acidity was also characterized by TPD of adsorbed ammonia and by infrared spectroscopy of various adsorbed probes, such as pivalonitrile, pyridine, ammonia, and n-butylamine. From the quantitative measurements of adsorption of ammonia and from TPD it was concluded that the SiO[sub 2]-TiO[sub 2] mixture can be regarded as a mechanical mixture of silica and titania. However, the IR investigation showed that Ti enters in small amounts into the silica framework. This results in formation of very strong Lewis acid sites, caused by incomplete tetrahedral coordination of Ti[sup 4[minus

  2. Molten salt oxidation for treating low-level mixed wastes

    SciTech Connect

    Adamson, M G; Ford, T D; Foster, K G; Hipple, D L; Hopper, R W; Hsu, P C

    1998-12-10

    MS0 is a promising alternative to incineration for the treatment of a variety of organic wastes. Lawrence Livermore National Laboratory (LLNL) has prepared a facility (please see the photo attached) in which an integrated pilot-scale MS0 treatment system is being tested and demonstrated. The system consists of a MS0 vessel with a dedicated off-gas treatment system, a salt recycle system, feed preparation equipment, and a ceramic final waste forms immobilization system. The MSO/off-gas system has been operational since December 1997. The salt recycle system and the ceramic final forms immobilization became operational in May and August 1998, respectively. We have tested the MS0 facility with various organic feeds, including chlorinated solvents; tributyl phosphate/kerosene, PCB-contaminated waste oils & solvents, booties, plastic pellets, ion exchange resins, activated carbon, radioactive-spiked organics, and well-characterized low- level liquid mixed wastes. MS0 is a versatile technology for hazardous waste treatment and may be a solution to many waste disposal problems. In this paper we will present our operational experience with MS0 and also discuss its process capabilities as well as performance data with different feeds.

  3. Effect of Co/Ni ratios in cobalt nickel mixed oxide catalysts on methane combustion

    SciTech Connect

    Lim, Tae Hwan; Cho, Sung June; Yang, Hee Sung; Engelhard, Mark H.; Kim, Do Heui

    2015-07-31

    A series of cobalt nickel mixed oxide catalysts with the varying ratios of Co to Ni, prepared by co-precipitation method, were applied to methane combustion. Among the various ratios, cobalt nickel mixed oxides having the ratios of Co to Ni of (50:50) and (67:33) demonstrate the highest activity for methane combustion. Structural analysis obtained from X-ray diffraction (XRD) and extended X-ray absorption fine structure (EXAFS) evidently demonstrates that CoNi (50:50) and (67:33) samples consist of NiCo2O4and NiO phase and, more importantly, NiCo2O4spinel structure is largely distorted, which is attributed to the insertion of Ni2+ions into octahedral sites in Co3O4spinel structure. Such structural dis-order results in the enhanced portion of surface oxygen species, thus leading to the improved reducibility of the catalysts in the low temperature region as evidenced by temperature programmed reduction by hydrogen (H2TPR) and X-ray photoelectron spectroscopy (XPS) O 1s results. They prove that structural disorder in cobalt nickel mixed oxides enhances the catalytic performance for methane combustion. Thus, it is concluded that a strong relationship between structural property and activity in cobalt nickel mixed oxide for methane combustion exists and, more importantly, distorted NiCo2O4spinel structure is found to be an active site for methane combustion.

  4. PHOTOCHEMICAL OXIDANT AIR POLLUTION EFFECTS ON A MIXED CONIFER FOREST ECOSYSTEM

    EPA Science Inventory

    EPA contract 68-03-2442 provided support for three years of the studies to determine the chronic effects of photochemical oxidant air pollutants on a western mixed conifer forest ecosystem. This report deals with the year 1976-77 and is the final publication on EPA contract 68-03...

  5. In vitro dissolution of respirable aerosols of industrial uranium and plutonium mixed-oxide nuclear fuels.

    PubMed

    Eidson, A F; Mewhinney, J A

    1983-12-01

    Dissolution characteristics of mixed-oxide nuclear fuels are important considerations for prediction of biological behavior of inhaled particles. Four representative industrial mixed-oxide powders were obtained from fuel fabrication enclosures. Studies of the dissolution of Pu, Am and U from aerosol particles of these materials in a serum simulant solution and in 0.1M HCl showed: (1) dissolution occurred at a rapid rate initially and slowed at longer times, (2) greater percentages of U dissolved than Pu or Am: with the dissolution rates of U and Pu generally reflecting the physical nature of the UO2-PuO2 matrix, (3) the temperature history of industrial mixed-oxides could not be reliably related to Pu dissolution except for a 3-5% increase when incorporated into a solid solution by sintering at 1750 degrees C, and (4) dissolution in the serum simulant agreed with the in vivo UO2 dissolution rate and suggested the dominant role of mechanical processes in PuO2 clearance from the lung. The rapid initial dissolution rate was shown to be related, in part, to an altered surface layer. The advantages and uses of in vitro solubility data for estimation of biological behavior of inhaled industrial mixed oxides, such as assessing the use of chelation therapy and interpretation of urinary excretion data, are discussed. It was concluded that in vitro solubility tests were useful, simple and easily applied to individual materials potentially inhaled by humans. PMID:6643070

  6. Effect of mixing conditions on irritant potency of zinc oxide and sulfur dioxide. [Guinea pigs

    SciTech Connect

    Amdur, M.O.; McCarthy, J.F.; Gill, M.W.

    1983-01-01

    Measurement of mechanics of respiration in guinea pigs was used to assess the irritant potency of zinc oxide and sulfur dioxide mixed under different conditions of temperature and humidity. Concentrations were 1-2 mg/m/sup 3/ zinc oxide and 1 ppm sulfur dioxide. Dry conditions of mixing (Chamber RH 30%) either at 24/sup 0/C in the exposure chamber or at 480/sup 0/C in a dry furnace gave a biological response which could be completely accounted for by responses to zinc oxide and/or sulfur dioxide alone. Chemical examination of the aerosols did not indicate the formation of particulate sulfur species. Zinc oxide and sulfur dioxide mixed dry at 480/sup 0/C and fed into the exposure chamber at 80% RH reacted to produce an irritant aerosol as evidenced by a rapid increase in resistance to levels 29% above control; reversal was rapid when exposure ended. Chemical studies indicated the presence of sulfite on these aerosols. Addition of water vapor to the furnace during mixing at 480/sup 0/C produced a different irritant aerosol. The resistance rose slowly to 19% above control values and remained elevated during the post-exposure hour. Chemical studies indicated the presence of sulfate, sulfite, and adsorbed sulfur trioxide on these aerosols.

  7. Catalyst support of mixed cerium zirconium titanium oxide, including use and method of making

    DOEpatents

    Willigan, Rhonda R.; Vanderspurt, Thomas Henry; Tulyani, Sonia; Radhakrishnan, Rakesh; Opalka, Susanne Marie; Emerson, Sean C.

    2011-01-18

    A durable catalyst support/catalyst is capable of extended water gas shift operation under conditions of high temperature, pressure, and sulfur levels. The support is a homogeneous, nanocrystalline, mixed metal oxide of at least three metals, the first being cerium, the second being Zr, and/or Hf, and the third importantly being Ti, the three metals comprising at least 80% of the metal constituents of the mixed metal oxide and the Ti being present in a range of 5% to 45% by metals-only atomic percent of the mixed metal oxide. The mixed metal oxide has an average crystallite size less than 6 nm and forms a skeletal structure with pores whose diameters are in the range of 4-9 nm and normally greater than the average crystallite size. The surface area of the skeletal structure per volume of the material of the structure is greater than about 240 m.sup.2/cm.sup.3. The method of making and use are also described.

  8. Effect of cooling rate on achieving thermodynamic equilibrium in uranium-plutonium mixed oxides

    NASA Astrophysics Data System (ADS)

    Vauchy, Romain; Belin, Renaud C.; Robisson, Anne-Charlotte; Hodaj, Fiqiri

    2016-02-01

    In situ X-ray diffraction was used to study the structural changes occurring in uranium-plutonium mixed oxides U1-yPuyO2-x with y = 0.15; 0.28 and 0.45 during cooling from 1773 K to room-temperature under He + 5% H2 atmosphere. We compare the fastest and slowest cooling rates allowed by our apparatus i.e. 2 K s-1 and 0.005 K s-1, respectively. The promptly cooled samples evidenced a phase separation whereas samples cooled slowly did not due to their complete oxidation in contact with the atmosphere during cooling. Besides the composition of the annealing gas mixture, the cooling rate plays a major role on the control of the Oxygen/Metal ratio (O/M) and then on the crystallographic properties of the U1-yPuyO2-x uranium-plutonium mixed oxides.

  9. Catalytic combustion of benzene over CuO-CeO2 mixed oxides.

    PubMed

    Jung, Won Young; Lim, Kwon-Taek; Hong, Seong-Soo

    2014-11-01

    Catalytic combustion of benzene over CuO-CeO2 mixed oxides has been investigated. The CuO-CeO2 mixed oxides were prepared by the combustion method using malic acid as an organic fuel and characterized by XRD, XPS and TPR. For the CuO-CeO2 catalyst with a Cu/(Cu + Ce) molar ratio of more than 0.4, highly dispersed copper oxide species were shown at 2θ = 35.5 degrees and 38.8 degrees. The CuO-CeO2 catalyst prepared using 2.0 M malic acid showed the highest activity, with conversion reaching nearly 100% at 350 degrees C. In addition, the highest activity is shown on Cu0.40 (the index denotes the molar ratio Cu/(Cu + Ce)) sample and then it decreases on Cu0.5 and Cu0.7 samples. PMID:25958554

  10. How to stabilize highly active Cu+ cations in a mixed-oxide catalyst

    SciTech Connect

    Mudiyanselage, Kumudu; Luo, Si; Kim, Hyun You; Yang, Xiaofang; Baber, Ashleigh E.; Hoffmann, Friedrich M.; Senanayake, Sananayake; Rodriguez, Jose A.; Chen, Jingguang G.; Liu, Ping; Stacchiola, Dario J.

    2015-09-12

    Mixed-metal oxides exhibit novel properties that are not present in their isolated constituent metal oxides and play a significant role in heterogeneous catalysis. In this study, a titanium-copper mixed-oxide (TiCuOx) film has been synthesized on Cu(111) and characterized by complementary experimental and theoretical methods. At sub-monolayer coverages of titanium, a Cu2O-like phase coexists with TiCuOx and TiOx domains. When the mixed-oxide surface is exposed at elevated temperatures (600–650 K) to oxygen, the formation of a well-ordered TiCuOx film occurs. Stepwise oxidation of TiCuOx shows that the formation of the mixed-oxide is faster than that of pure Cu2O. As the Ti coverage increases, Ti-rich islands (TiOx) form. The adsorption of CO has been used to probe the exposed surface sites on the TiOx–CuOx system, indicating the existence of a new Cu+ adsorption site that is not present on Cu2O/Cu(111). Adsorption of CO on Cu+ sites of TiCuOx is thermally more stable than on Cu(111), Cu2O/Cu(111) or TiO2(110). The Cu+ sites in TiCuOx domains are stable under both reducing and oxidizing conditions whereas the Cu2O domains present on sub-monolayer loads of Ti can be reduced or oxidized under mild conditions. Furthermore, the results presented here demonstrate novel properties of TiCuOx films, which are not present on Cu(111), Cu2O/Cu(111), or TiO2(110), and highlight the importance of the preparation and characterization of well-defined mixed-metal oxides in order to understand fundamental processes that could guide the design of new materials.

  11. Method of producing homogeneous mixed metal oxides and metal-metal oxide mixtures

    DOEpatents

    Quinby, Thomas C.

    1978-01-01

    Metal powders, metal oxide powders, and mixtures thereof of controlled particle size are provided by reacting an aqueous solution containing dissolved metal values with excess urea. Upon heating, urea reacts with water from the solution leaving a molten urea solution containing the metal values. The molten urea solution is heated to above about 180.degree. C. whereupon metal values precipitate homogeneously as a powder. The powder is reduced to metal or calcined to form oxide particles. One or more metal oxides in a mixture can be selectively reduced to produce metal particles or a mixture of metal and metal oxide particles.

  12. Quantifying mixing, boiling, degassing, oxidation and reactivity of thermal waters at Vonarskard, Iceland

    NASA Astrophysics Data System (ADS)

    Stefánsson, Andri; Keller, Nicole S.; Robin, Jóhann Gunnarsson; Kaasalainen, Hanna; Björnsdóttir, Snædís; Pétursdóttir, Sólveig; Jóhannesson, Haukur; Hreggvidsson, Gudmundur Óli

    2016-01-01

    The chemical composition of geothermal fluids may be altered upon ascent from the reservoir to surface by processes including boiling, degassing, mixing, oxidation and water-rock interaction. In an attempt to quantify these processes, a three step model was developed that includes: (1) defining the composition of the end-member fluid types present in the system, (2) quantifying mixing between the end-members using non-reactive elemental concentrations and enthalpy and (3) quantifying the changes of reactive elements including degassing, oxidation and water-rock interaction. The model was applied to geothermal water at Vonarskard, Iceland, for demonstration having temperatures of 3-98 °C, pH of 2.15-9.95 and TDS of 323-2250 ppm, and was thought to be produced from boiled reservoir water, condensed steam and non-thermal water. Most geothermal water represented mixture of non-thermal water and condensed steam whereas the boiled reservoir water was insignificantly mixed. CO2 and H2S degassing was found to be quantitative in steam-heated water, with oxidation of H2S to SO4 also occurred. In contrast, major rock forming elements are enriched in steam-heated water relative to their mixing ratios, suggesting water-rock interaction in the surface zone. Boiled reservoir water observed in alkaline hot springs have, however, undergone less geochemical changes upon ascent to surface and within the surface zone.

  13. A Thermodynamic Investigation of the Redox Properties of Ceria-Titania Mixed Oxides

    SciTech Connect

    Zhou,G.; Hanson, J.; Gorte, R.

    2008-01-01

    Ceria-titania solutions with compositions of Ce0.9Ti0.1O2 and Ce0.8Ti0.2O2 were prepared by the citric-acid (Pechini) method and characterized using X-ray diffraction (XRD) for structure, coulometric titration for redox thermodynamics, and water-gas-shift (WGS) reaction rates. Following calcination at 973 K, XRD suggests that the mixed oxides exist as single phase, fluorite structures, although there was no significant change in the lattice parameter compared to pure ceria. The mixed oxides are shown to be significantly more reducible than bulk ceria, with enthalpies for re-oxidation being approximately -500 kJ/mol O2, compared to -760 kJ/mol O2 for bulk ceria. However, WGS rates over 1 wt% Pd supported on ceria, Ce0.8Ti0.2O2, and Ce0.8Zr0.2O2 were nearly the same. For calcination at 1323 K, the mixed oxides separated into ceria and titania phases, as indicated by both the XRD and thermodynamic results.

  14. Cu-Mn-Ce ternary mixed-oxide catalysts for catalytic combustion of toluene.

    PubMed

    Lu, Hanfeng; Kong, Xianxian; Huang, Haifeng; Zhou, Ying; Chen, Yinfei

    2015-06-01

    Cu-Mn, Cu-Mn-Ce, and Cu-Ce mixed-oxide catalysts were prepared by a citric acid sol-gel method and then characterized by XRD, BET, H2-TPR and XPS analyses. Their catalytic properties were investigated in the toluene combustion reaction. Results showed that the Cu-Mn-Ce ternary mixed-oxide catalyst with 1:2:4 mole ratios had the highest catalytic activity, and 99% toluene conversion was achieved at temperatures below 220°C. In the Cu-Mn-Ce catalyst, a portion of Cu and Mn species entered into the CeO2 fluorite lattice, which led to the formation of a ceria-based solid solution. Excess Cu and Mn oxides existed on the surface of the ceria-based solid solution. The coexistence of Cu-Mn mixed oxides and the ceria-based solid solution resulted in a better synergetic interaction than the Cu-Mn and Cu-Ce catalysts, which promoted catalyst reducibility, increased oxygen mobility, and enhanced the formation of abundant active oxygen species. PMID:26040736

  15. Superconductivity achieved at over liquid nitrogen temperature by (mixed rare earths)-Ba-Cu oxides

    NASA Astrophysics Data System (ADS)

    Kishio, Kohji; Kuwahara, Kazuyuki; Kitazawa, Koichi; Fueki, Kazuo; Nakamura, Osamu

    1987-05-01

    Superconducting oxides were fabricated by reaction of powders of BaCO3, CuO and mixed rare earth (RE) carbonates at compositions expressed as (RE)1Ba2Cu3O(9-y). Two types of incompletely separated raw materials of mixed rare earths, namely, heavy rare earths (HRE) and medium rare earths (MRE), were examined. The zero-resistivity critical temperatures were observed at 92.5 K for the (HRE)-Ba-Cu-O and 85.0 K for the (MRE)-Ba-Cu-O systems, respectively, both of which were well above the boiling point of liquid nitrogen.

  16. Degradation of organophosphorus pesticide parathion methyl on nanostructured titania-iron mixed oxides

    NASA Astrophysics Data System (ADS)

    Henych, Jiří; Štengl, Václav; Slušná, Michaela; Matys Grygar, Tomáš; Janoš, Pavel; Kuráň, Pavel; Štastný, Martin

    2015-07-01

    Titania-iron mixed oxides with various Ti:Fe ratio were prepared by homogeneous hydrolysis of aqueous solutions of titanium(IV) oxysulphate and iron(III) sulphate with urea as a precipitating agent. The synthesized samples were characterized by X-ray diffraction, Raman and infrared spectroscopy, scanning and transmission electron microscopy, XRF analysis, specific surface area (BET) and porosity determination (BJH). These oxides were used for degradation of organophosporus pesticide parathion methyl. The highest degradation efficiency approaching <70% was found for the samples with Ti:Fe ratio 0.25:1 and 1:0.25. Contrary, parathion methyl was not degraded on the surfaces of pure oxides. In general, the highest degradation rate exhibited samples consisted of the iron or titanium oxide containing a moderate amount of the admixture. However, distinct correlations between the degradation rate and the sorbent composition were not identified.

  17. A hybrid water-splitting cycle using copper sulfate and mixed copper oxides

    NASA Technical Reports Server (NTRS)

    Schreiber, J. D.; Remick, R. J.; Foh, S. E.; Mazumder, M. M.

    1980-01-01

    The Institute of Gas Technology has derived and developed a hybrid thermochemical water-splitting cycle based on mixed copper oxides and copper sulfate. Similar to other metal oxide-metal sulfate cycles that use a metal oxide to 'concentrate' electrolytically produced sulfuric acid, this cycle offers the advantage of producing oxygen (to be vented) and sulfur dioxide (to be recycled) in separate steps, thereby eliminating the need of another step to separate these gases. The conceptual process flow-sheet efficiency of the cycle promises to exceed 50%. It has been completely demonstrated in the laboratory with recycled materials. Research in the electrochemical oxidation of sulfur dioxide to produce sulfuric acid and hydrogen performed at IGT indicates that the cell performance goals of 200 mA/sq cm at 0.5 V will be attainable using relatively inexpensive electrode materials.

  18. Mediated electrochemical oxidation of Rocky Flats combustible low level mixed wastes

    SciTech Connect

    Chiba, Z.

    1992-12-01

    Mediated Electrochemical Oxidation (MEO) was originally developed for dissolution of difficult to dissolve forms of plutonium oxide. It was also found to be effective for oxidizing non-polymerized organic materials. MEO is an inherently safe process since the hazardous and radioactive materials are completely contained in the aqueous phase, and operating temperatures and pressures of the system are low (well below 100 {degree}C and 30 psig). The most commonly used mediator-electrolyte combination is silver in nitric acid. The process produces divalent silver ion, a strong oxidizing agent, which dissolves the radioactive components of mixed wastes and destroys the organic components. In the past, work at LLNL has been focused on understanding the basic science and modeling the dissolution and destruction mechanisms. Reaction rates of water with Ag(H) were measured using spectrophotometric methods, and the diffusivity of silver ions in nitric acid was estimated using a rotating disk electrode.

  19. DetOx: a program for determining anomalous scattering factors of mixed-oxidation-state species.

    PubMed

    Sutton, Karim J; Barnett, Sarah A; Christensen, Kirsten E; Nowell, Harriott; Thompson, Amber L; Allan, David R; Cooper, Richard I

    2013-01-01

    Overlapping absorption edges will occur when an element is present in multiple oxidation states within a material. DetOx is a program for partitioning overlapping X-ray absorption spectra into contributions from individual atomic species and computing the dependence of the anomalous scattering factors on X-ray energy. It is demonstrated how these results can be used in combination with X-ray diffraction data to determine the oxidation state of ions at specific sites in a mixed-valance material, GaCl(2). PMID:23254676

  20. Bi–Mn mixed metal organic oxide: A novel 3d-6p mixed metal coordination network

    SciTech Connect

    Shi, Fa-Nian; Rosa Silva, Ana; Bian, Liang

    2015-05-15

    A new terminology of metal organic oxide (MOO) was given a definition as a type of coordination polymers which possess the feature of inorganic connectivity between metals and the direct bonded atoms and show 1D, 2D or 3D inorganic sub-networks. One such compound was shown as an example. A 3d-6p (Mn–Bi. Named MOOMnBi) mixed metals coordination network has been synthesized via hydrothermal method. The new compound with the molecular formula of [MnBi{sub 2}O(1,3,5-BTC){sub 2}]{sub n} (1,3,5-BTC stands for benzene-1,3,5-tricarboxylate) was characterized via single crystal X-ray diffraction technique that revealed a very interesting 3-dimensional (3D) framework with Bi{sub 4}O{sub 2}(COO){sub 12} clusters which are further connected to Mn(COO){sub 6} fragments into a 2D MOO. The topology study indicates an unprecedented topological type with the net point group of (4{sup 13}.6{sup 2})(4{sup 13}.6{sup 8})(4{sup 16}.6{sup 5})(4{sup 18}.6{sup 10})(4{sup 22}.6{sup 14})(4{sup 3}) corresponding to 3,6,7,7,8,9-c hexa-nodal net. MOOMnBi shows catalytic activity in the synthesis of (E)-α,β-unsaturated ketones. - Graphical abstract: This metal organic framework (MOF) is the essence of a 2D metal organic oxide (MOO). - Highlights: • New concept of metal organic oxide (MOO) was defined and made difference from metal organic framework. • New MOO of MOOMnBi was synthesized by hydrothermal method. • Crystal structure of MOOMnBi was determined by single crystal X-ray analysis. • The catalytic activity of MOOMnBi was studied showing reusable after 2 cycles.

  1. Calculation of parameters for inspection planning and evaluation: mixed-oxide fuel fabrication facilities

    SciTech Connect

    Reardon, P.T.; Mullen, M.F.

    1982-08-01

    As part of Task C.35 (Calculation of Parameters for Inspection Planning and Evaluation) of the US Program of Technical Assistance to IAEA Safeguards, Pacific Northwest Laboratory has performed some quantitative analyses of IAEA inspection activities for mixed-oxide fuel fabrication facilities. There were four distinct efforts involved in this task. These were as follows: show the effect on a material balance verification of using two variables measurement methods in some strata; perform additional calculations for the reference facility described in STR-89; modify the INSPECT computer programs to be used as an after-inspection analysis tool, as well as a preinspection planning tool; provide written comments and explantations of text and graphs of the first draft of STR-89, Safeguards Considerations for Mixed-Oxide Fuel Element Fabrication Facilities, by W. Bahm, T. Shea, and D. Tolchenkov, System Studies Section, IAEA.

  2. Sulfur oxidation activities of pure and mixed thermophiles and sulfur speciation in bioleaching of chalcopyrite.

    PubMed

    Zhu, Wei; Xia, Jin-Lan; Yang, Yi; Nie, Zhen-yuan; Zheng, Lei; Ma, Chen-yan; Zhang, Rui-yong; Peng, An-an; Tang, Lu; Qiu, Guan-zhou

    2011-02-01

    The sulfur oxidation activities of four pure thermophilic archaea Acidianus brierleyi (JCM 8954), Metallosphaera sedula (YN 23), Acidianus manzaensis (YN 25) and Sulfolobus metallicus (YN 24) and their mixture in bioleaching chalcopyrite were compared. Meanwhile, the relevant surface sulfur speciation of chalcopyrite leached with the mixed thermophilic archaea was investigated. The results showed that the mixed culture, with contributing significantly to the raising of leaching rate and accelerating the formation of leaching products, may have a higher sulfur oxidation activity than the pure cultures, and jarosite was the main passivation component hindering the dissolution of chalcopyrite, while elemental sulfur seemed to have no influence on the dissolution of chalcopyrite. In addition, the present results supported the former speculation, i.e., covellite might be converted from chalcocite during the leaching experiments, and the elemental sulfur may partially be the derivation of covellite and chalcocite. PMID:21194927

  3. Errors associated with standard nodal diffusion methods as applied to mixed oxide fuel problems

    SciTech Connect

    Brantley, P. S., LLNL

    1998-07-24

    The evaluation of the disposition of plutonium using light water reactors is receiving increased attention. However, mixed-oxide (MOX) fuel assemblies possess much higher absorption and fission cross- sections when compared to standard UO2 assemblies. Those properties yield very high thermal flux gradients at the interfaces between MOX and UO2 assemblies. It has already been reported that standard flux reconstruction methods (that recover the homogeneous intranodal flux shape using the converged nodal solution) yield large errors in the presence of MOX assemblies. In an accompanying paper, we compare diffusion and simplified PN calculations of a mixed-oxide benchmark problem to a reference transport calculation. In this paper, we examine the errors associated with standard nodal diffusion methods when applied to the same benchmark problem. Our results show that a large portion of the error is associated with the quadratic leakage approximation (QLA) that is commonly used in the standard nodal codes.

  4. Characterization of two oxidatively modified phospholipids in mixed monolayers with DPPC.

    PubMed

    Sabatini, Karen; Mattila, Juha-Pekka; Megli, Francesco M; Kinnunen, Paavo K J

    2006-06-15

    The properties of two oxidatively modified phospholipids viz. 1-palmitoyl-2-(9'-oxo-nonanoyl)-sn-glycero-3-phosphocholine (PoxnoPC) and 1-palmitoyl-2-azelaoyl-sn-glycero-3-phosphocholine (PazePC), were investigated using a Langmuir balance, recording force-area (pi-A) isotherms and surface potential psi. In mixed monolayers with 1,2-dipalmitoyl-sn-glycero-3-phosphocholine (DPPC) a progressive disappearance of the liquid expanded-liquid condensed transition and film expansion was observed with increasing content of the oxidized phospholipids. The above is in agreement with fluorescence microscopy of the monolayers, which revealed an increase in the liquid expanded region of DPPC monolayers. At a critical pressure pi(s) approximately 42 mN/m both Poxo- and PazePC induced a deflection in the pi-A isotherms, which could be rationalized in terms of reorientation of the oxidatively modified acyl chains into aqueous phase (adaptation of the so-called extended conformation), followed upon further film compression by solubilization of the oxidized phospholipids into the aqueous phase. Surface potential displayed a discontinuity at the same value of area/molecule, corresponding to the loss of the oxidized phospholipids from the monolayers. Our data support the view that lipid oxidation modifies both the small-scale structural dynamics of biological membranes as well as their more macroscopic lateral organization. Accordingly, oxidatively modified lipids can be expected to influence the organization and functions of membrane associated proteins. PMID:16581831

  5. Characterization of Two Oxidatively Modified Phospholipids in Mixed Monolayers with DPPC

    PubMed Central

    Sabatini, Karen; Mattila, Juha-Pekka; Megli, Francesco M.; Kinnunen, Paavo K. J.

    2006-01-01

    The properties of two oxidatively modified phospholipids viz. 1-palmitoyl-2-(9′-oxo-nonanoyl)-sn-glycero-3-phosphocholine (PoxnoPC) and 1-palmitoyl-2-azelaoyl-sn-glycero-3-phosphocholine (PazePC), were investigated using a Langmuir balance, recording force-area (π-A) isotherms and surface potential ψ. In mixed monolayers with 1,2-dipalmitoyl-sn-glycero-3-phosphocholine (DPPC) a progressive disappearance of the liquid expanded-liquid condensed transition and film expansion was observed with increasing content of the oxidized phospholipids. The above is in agreement with fluorescence microscopy of the monolayers, which revealed an increase in the liquid expanded region of DPPC monolayers. At a critical pressure πs ∼ 42 mN/m both Poxo- and PazePC induced a deflection in the π-A isotherms, which could be rationalized in terms of reorientation of the oxidatively modified acyl chains into aqueous phase (adaptation of the so-called extended conformation), followed upon further film compression by solubilization of the oxidized phospholipids into the aqueous phase. Surface potential displayed a discontinuity at the same value of area/molecule, corresponding to the loss of the oxidized phospholipids from the monolayers. Our data support the view that lipid oxidation modifies both the small-scale structural dynamics of biological membranes as well as their more macroscopic lateral organization. Accordingly, oxidatively modified lipids can be expected to influence the organization and functions of membrane associated proteins. PMID:16581831

  6. Cluster molecular orbital description of the electronic structures of mixed-valence iron oxides and silicates

    USGS Publications Warehouse

    Sherman, David M.

    1986-01-01

    A molecular orbital description, based on spin-unrestricted X??-scattered wave calculations, is given for the electronic structures of mixed valence iron oxides and silicates. The cluster calculations show that electron hopping and optical intervalence charge-transger result from weak FeFe bonding across shared edges of FeO6 coordination polyhedra. In agreement with Zener's double exchange model, FeFe bonding is found to stabilize ferromagnetic coupling between Fe2+ and Fe3+ cations. ?? 1986.

  7. Ceramic waste form for residues from molten salt oxidation of mixed wastes

    SciTech Connect

    Van Konynenburg, R.A.; Hopper, R.W.; Rard, J.A.

    1995-11-01

    A ceramic waste form based on Synroc-D is under development for the incorporation of the mineral residues from molten salt oxidation treatment of mixed low-level wastes. Samples containing as many as 32 chemical elements have been fabricated, characterized, and leach-tested. Universal Treatment Standards have been satisfied for all regulated elements except and two (lead and vanadium). Efforts are underway to further improve chemical durability.

  8. Development of DIPRES feed for the fabrication of mixed-oxide fuels for fast breeder reactors

    SciTech Connect

    Griffin, C W; Rasmussen, D E; Lloyd, M H

    1983-01-01

    The DIrect PREss Spheroidized feed process combines the conversion of uranium-plutonium solutions into spheres by internal gelation with conventional pellet fabrication techniques. In this manner, gel spheres could replace conventional powders as the feed material for pellet fabrication of nuclear fuels. Objective of the DIPRES feed program is to develop and qualify a process to produce mixed-oxide fuel pellets from gel spheres for fast breeder reactors. This process development includes both conversion and fabrication activities.

  9. Fabrication of uranium-americium mixed oxide pellet from microsphere precursors: Application of CRMP process

    NASA Astrophysics Data System (ADS)

    Remy, E.; Picart, S.; Delahaye, T.; Jobelin, I.; Lebreton, F.; Horlait, D.; Bisel, I.; Blanchart, P.; Ayral, A.

    2014-10-01

    Mixed uranium-americium oxides are one of the materials envisaged for Americium Bearing Blankets dedicated to transmutation in fast neutron reactors. Recently, several processes have been developed in order to validate fabrication flowchart in terms of material specifications such as density and homogeneity but also to suggest simplifications for lowering industrial costs and hazards linked to dust generation of highly contaminating and irradiating compounds. This study deals with the application of an innovative route using mixed oxide microspheres obtained from metal loaded resin bead calcination, called Calcined Resin Microsphere Pelletization (CRMP). The synthesis of mixed oxide microsphere precursor of U0.9Am0.1O2±δ is described as well as its characterisation. The use of this free-flowing precursor allows the pressing and sintering of one pellet of U0.9Am0.1O2±δ. The ceramic obtained was characterised and results showed that its microstructure is dense and homogeneous and its density attains 95% of the theoretical density. This study validates the scientific feasibility of the CRMP process applied to the fabrication of uranium and americium-containing materials.

  10. Investigation of some new hydro(solvo)thermal synthesis routes to nanostructured mixed-metal oxides

    SciTech Connect

    Burnett, David L.; Harunsani, Mohammad H.; Kashtiban, Reza J.; Playford, Helen Y.; Sloan, Jeremy; Hannon, Alex C.; Walton, Richard I.

    2014-06-01

    We present a study of two new solvothermal synthesis approaches to mixed-metal oxide materials and structural characterisation of the products formed. The solvothermal oxidation of metallic gallium by a diethanolamine solution of iron(II) chloride at 240 °C produces a crystalline sample of a spinel-structured material, made up of nano-scale particles typically 20 nm in dimension. XANES spectroscopy at the K-edge shows that the material contains predominantly Fe{sup 2+} in an octahedral environment, but that a small amount of Fe{sup 3+} is also present. Careful analysis using transmission electron microscopy and powder neutron diffraction shows that the sample is actually a mixture of two spinel materials: predominantly (>97%) an Fe{sup 2+} phase Ga{sub 1.8}Fe{sub 1.2}O{sub 3.9}, but with a minor impurity phase that is iron-rich. In contrast, the hydrothermal reaction of titanium bis(ammonium lactato)dihydroxide in water with increasing amounts of Sn(IV) acetate allows nanocrystalline samples of the SnO{sub 2}–TiO{sub 2} solid solution to be prepared directly, as proved by powder XRD and Raman spectroscopy. - Graphical abstract: New solvothermal synthesis approaches to spinel and rutile mixed-metal oxides are reported. - Highlights: • Solvothermal oxidation of gallium metal in organic iron(II) solution gives a novel iron gallate spinel. • Hydrothermal reaction of titanium(IV) complex and tin(IV) acetate produces the complete SnO{sub 2}–TiO{sub 2} solid solution. • Nanostructured mixed-metal oxide phases are produced directly from solution.

  11. Sulfidation of mixed metal oxides in a fluidized-bed reactor

    SciTech Connect

    Christoforou, S.C.; Efthimiadis, E.A.; Vasalos, I.A. )

    1995-01-01

    Mixed metal oxides were used for the removal of hydrogen sulfide from a hot gas stream. Sorbents were prepared according to the dry and wet impregnation techniques. The desulfurization performance of the metal oxide sorbents was experimentally tested in a fluidized-bed reactor system. Sulfidation experiments performed under reaction conditions similar to those at the exit of a coal gasifier showed that the preparation procedure and technique, the type and the amount of the impregnated metal oxide, the type of the solid carrier, and the size of the solid reactant affect the H[sub 2]S removal capacity of the sorbents. The pore structure of fresh and sulfided sorbents was analyzed using mercury porosimetry, nitrogen adsorption, and scanning electron microscopy.

  12. Au-mixed lanthanum/cerium oxide catalysts for water-gas-shift

    SciTech Connect

    Wang, Yanan; Liang, Shuang; Cao, Anmin; Thompson, Robert L; Veser, Goetz

    2010-08-01

    We report on the synthesis of highly homogeneous mixed La/Ce-oxides via a microemulsion-templated approach, and their evaluation as active supports for Au in the water gas shift (WGS) reaction. Both structure and reducibility of the oxides could be tailored by adjusting the La content across the entire range of La:Ce-ratios. The reducibility of the Au-free oxides shows an optimum at ∼25% La content, which can be traced back to improved oxygen mobility due to formation of oxygen vacancies and to the formation of more strongly bound oxygen upon La addition. Deposition of Au onto these oxides gives rise to an additional, low-temperature reduction peak, presumably due to hydrogen spill-over from the noble metal onto the oxide support. The WGS activity of Au/La{sub x}Ce{sub 1−x}O{sub 2−0.5x} catalysts correlates closely with the reducibility of the oxide supports, and hence with La content, demonstrating that carefully controlled synthesis of nanostructured catalysts with uniform, tailored composition allows for fine control of reactive properties of these materials, and might ultimately open the way towards a more rational design of catalysts.

  13. Complex catalytic behaviors of CuTiOx mixed-oxide during CO oxidation

    SciTech Connect

    Kim, Hyun You; Liu, Ping

    2015-09-21

    Mixed metal oxides have attracted considerable attention in heterogeneous catalysis due to the unique stability, reactivity, and selectivity. Here, the activity and stability of the CuTiOx monolayer film supported on Cu(111), CuTiOx/Cu(111), during CO oxidation was explored using density functional theory (DFT). The unique structural frame of CuTiOx is able to stabilize and isolate a single Cu+ site on the terrace, which is previously proposed active for CO oxidation. Furthermore, it is not the case, where the reaction via both the Langmuir–Hinshelwood (LH) and the Mars-van Krevelen (M-vK) mechanisms are hindered on such single Cu+ site. Upon the formation of step-edges, the synergy among Cuδ+ sites, TiOx matrix, and Cu(111) is able to catalyze the reaction well. Depending on temperatures and partial pressure of CO and O2, the surface structure varies, which determines the dominant mechanism. In accordance with our results, the Cuδ+ ion alone does not work well for CO oxidation in the form of single sites, while the synergy among multiple active sites is necessary to facilitate the reaction.

  14. Uranium oxide and sodium oxide aerosol experiments: NSPP mixed-oxide tests 303-307, data record report. [LMFBR

    SciTech Connect

    Adams, R.E.; Kress, T.S.; Tobias, M.L.

    1982-10-01

    This data record report summarizes five tests, involving mixtures of uranium oxide and sodium oxide aerosols, conducted in the Nuclear Safety Pilot Plant project at Oak Ridge National Laboratory. The goal of this project is to establish the validity (or level of conservatism) of the aerosol behavioral code, HAARM-3, and follow-on codes under development at Battelle Columbus Laboratories for the US Nuclear Regulatory Commission. Descriptions of the five tests with tables and graphs summarizing the results are included.

  15. Bi-Mn mixed metal organic oxide: A novel 3d-6p mixed metal coordination network

    NASA Astrophysics Data System (ADS)

    Shi, Fa-Nian; Rosa Silva, Ana; Bian, Liang

    2015-05-01

    A new terminology of metal organic oxide (MOO) was given a definition as a type of coordination polymers which possess the feature of inorganic connectivity between metals and the direct bonded atoms and show 1D, 2D or 3D inorganic sub-networks. One such compound was shown as an example. A 3d-6p (Mn-Bi. Named MOOMnBi) mixed metals coordination network has been synthesized via hydrothermal method. The new compound with the molecular formula of [MnBi2O(1,3,5-BTC)2]n (1,3,5-BTC stands for benzene-1,3,5-tricarboxylate) was characterized via single crystal X-ray diffraction technique that revealed a very interesting 3-dimensional (3D) framework with Bi4O2(COO)12 clusters which are further connected to Mn(COO)6 fragments into a 2D MOO. The topology study indicates an unprecedented topological type with the net point group of {413.62}{413.68}{416.65}{418.610}{422.614}{43} corresponding to 3,6,7,7,8,9-c hexa-nodal net. MOOMnBi shows catalytic activity in the synthesis of (E)-α,β-unsaturated ketones.

  16. Wet oxidation of an azo dye: Lumped kinetics in batch and mixed flow reactors

    SciTech Connect

    Donlagic, J.; Levec, J.

    1999-12-01

    Oxidation of a dilute aqueous solution of a model azo dye pollutant (Orange II) was studied in batch and continuous well-mixed (CSTR) reactors. Both reactors operate at 200--250 C, and total pressures up to 50 bar and at oxygen partial pressure from 10 to 30 bar. The model pollutant concentrations were in a range between 100 and 1,000 mg/L, which may be found in industrial wastewaters. The dye oxidation undergoes parallel-consecutive reaction pathways, in which it first decomposes thermally and oxidatively to aromatic intermediates and via organic acids to the final product carbon dioxide. To develop a kinetic equation capable of predicting organic carbon reduction, all organic species present in solution were lumped by total organic carbon (TOC). The lumped oxidation rate in batch reactor exhibited second-order behavior, whereas in the CSTR is was found linearly proportional to its TOC concentration. The lump behavior in batch reactor was dominated by the refractory low molecular mass aliphatic acids formed during the oxidation.

  17. Poisoning and reactivation processes in oxide-type cathodes: Part I. Polycrystalline mixed oxides

    NASA Astrophysics Data System (ADS)

    Shih, A.; Haas, G. A.

    A study has been made of the poisoning and reactivation characteristics of alkaline earth oxide-type cathodes after extended periods of shelf storage. Both emitted and incident electrons were used to measure changes in the electronics properties, i.e. work function. The variations in work function over the surface were obtained in both distribution form as well as topographic presentation using a scanning low energy electron probe (SLEEP). These measurements were correlated with simultaneously occurring compositional changes using Auger, gas desorption and ion scattering techniques. Measurements were made on realistic cathodes in actual vacuum tube ambients. The results showed that oxide-type cathodes poison within a few hours after shut-down by the adsorption of residual gases contained in the vacuum ambient. (The effects of CO 2 were specifically demonstrated.) These adsorbates are, however, desorbed upon heating and in combination with other reactivation processes (such as formation of surface Ba layers when using reducing substrates), the cathode can reach full activation again by the time the temperature reaches the normal operating temperature. The poisoning and reactivation phenomena are a combination of a number of simultaneous processes, and studies to separate and identify these is the objective of part II of this paper.

  18. Mixed Waste Focus Area alternative oxidation technologies development and demonstration program

    SciTech Connect

    Borduin, L.C.; Fewell, T.; Gombert, D.; Priebe, S.

    1998-07-01

    The Mixed Waste Focus Area (MWFA) is currently supporting the development and demonstration of several alternative oxidation technology (AOT) processes for treatment of combustible mixed low-level wastes. The impetus for this support derives from regulatory and political hurdles frequently encountered by traditional thermal techniques, primarily incinerators. AOTs have been defined as technologies that destroy organic material without using open-flame reactions. Whether thermal or nonthermal, the processes have the potential advantages of relatively low-volume gaseous emissions, generation of few or no dioxin/furan compounds, and operation at low enough temperatures that metals (except mercury) and most radionuclides are not volatilized. Technology development and demonstration are needed to confirm and realize the potential of AOTs and to compare them on an equal basis with their fully demonstrated thermal counterparts. AOTs include both thermal and nonthermal processes that oxidize organic wastes but operate under significantly different physical and chemical conditions than incinerators. Nonthermal processes currently being studied include Delphi DETOX and acid digestion at the Savannah River Site, and direct chemical oxidation at Lawrence Livermore National Laboratory. All three technologies are at advanced stages of development or are entering the demonstration phase. Nonflame thermal processes include catalytic chemical oxidation, which is being developed and deployed at Lawrence Berkeley National Laboratory, and team reforming, a commercial process being supported by Department of Energy. Related technologies include two low-flow, secondary oxidation processes (Phoenix and Thermatrix units) that have been tested at MSE, Inc., in Butte, Montana. Although testing is complete on some AOT technologies, most require additional support to complete some or all of the identified development objectives. Brief descriptions, status, and planned paths forward for each

  19. Microstructure and oxygen evolution of Fe-Ce mixed oxides by redox treatment

    NASA Astrophysics Data System (ADS)

    Li, Kongzhai; Haneda, Masaaki; Ning, Peihong; Wang, Hua; Ozawa, Masakuni

    2014-01-01

    The relationship between structure and reduction/redox properties of Fe-Ce mixed oxides with a Fe content of 5, 10, 20 or 30 mol%, prepared by a coprecipitation method, were investigated by XRD, Raman, TEM, TPR and TPO techniques. It is found that all the iron ions can be incorporated into the ceria lattice to form a solid solution for the FeCe 5 (Fe 5%) sample, but amorphous or crystal Fe2O3 particles were found to be present on the Fe-Ce oxide samples with higher the iron content. The reducibility of single solid solution was much better than the pure CeO2, and the appearance of dispersed Fe2O3 particles improved the surface reducibility of materials. The iron ions incorporated into the CeO2 lattice accelerated the oxygen release from bulk to surface, and surface Fe2O3 particles in close contact to CeO2 acted as a catalyst for the reaction between solid solution and hydrogen. The microstructure of exposed Fe2O3 with Ce-Fe-O solid solution allows the Fe-Ce mixed oxides to own good reducibility and high OSC, which also counteracts the deactivation of the reducibility resulting from the sintering of materials in the redox cycling.

  20. Self-assembled hybrid metal oxide base catalysts prepared by simply mixing with organic modifiers

    PubMed Central

    Tamura, Masazumi; Kishi, Ryota; Nakagawa, Yoshinao; Tomishige, Keiichi

    2015-01-01

    Multidentate materials formed by simply mixing heterogeneous and homogeneous components are promising for construction of versatile active sites on the surface of heterogeneous compounds, however, to the best of our knowledge, there are no reports on such materials. Self-assembly of hetero-hybrid catalytic materials occurs when heterogeneous catalysts having adjacent Lewis acid-Lewis base sites are mixed with an organic modifier that contains at least two Lewis base functional groups. Here we demonstrate the strategy by combining cerium oxide and 2-cyanopyridine that self-assembles to form a charge-transfer complex in methanol that exhibits a 2,000-fold increase in reaction rate for hydromethoxylation of acrylonitrile with high selectivity compared with cerium oxide or 2-cyanopyridine alone. The catalytic system is applied to the transesterification and Knoevenagel condensation affording 14-fold and 11-fold higher activity, respectively, than cerium oxide alone. These results demonstrate the potential versatility of the catalytic system and the generality of the catalyst preparation strategy. PMID:26436638

  1. Electrochemical synthesis of new magnetic mixed oxides of Sr and Fe: Composition, magnetic properties, and microstructure

    SciTech Connect

    Amigo, R.; Asenjo, J.; Krotenko, E.; Torres, F.; Tejada, J.; Brillas, E.

    2000-02-01

    An electrochemical method for the preparation of magnetic nanoparticles of new Sr-Fe oxides is presented in this work. It consists of the electrolysis of nitrate or chloride solutions with Sr{sup 2+} and Fe{sup 3+} salts using commercial Fe electrodes. Magnetic materials are collected as precipitates from nitrate media in the pH range 1-3 and from chloride media within the pH range 1--12. The presence of 100--300 ppm aniline in acidic nitrate media yields a decrease in energy cost and particle size. Inductively coupled plasma analysis of materials and energy-dispersive X-ray spectrometry of single particles confirm that they are composed of mixed oxides of Sr and Fe. All synthesized materials crystallize as inverse cubic spinels, usually with intermediate structures between magnetite and maghemite. They are formed by nanoparticles with average sizes from 2 nm to {approximately} 50 nm, as observed by scanning electron microscopy. The electrogenerated mixed oxides have higher saturation magnetization, but lower remanent magnetization and coercive field, than commercial strontium hexaferrite with micrometric particle size.

  2. Preparation of extrusions of bulk mixed oxide compounds with high macroporosity and mechanical strength

    DOEpatents

    Flytzani-Stephanopoulos, Maria; Jothimurugesan, Kandaswami

    1990-01-01

    A simple and effective method for producing bulk single and mixed oxide absorbents and catalysts is disclosed. The method yields bulk single oxide and mixed oxide absorbent and catalyst materials which combine a high macroporosity with relatively high surface area and good mechanical strength. The materials are prepared in a pellet form using as starting compounds, calcined powders of the desired composition and physical properties these powders are crushed to broad particle size distribution, and, optionally may be combined with an inorganic clay binder. The necessary amount of water is added to form a paste which is extruded, dried and heat treated to yield and desired extrudate strength. The physical properties of the extruded materials (density, macroporosity and surface area) are substantially the same as the constituent powder is the temperature of the heat treatment of the extrudates is approximately the same as the calcination temperature of the powder. If the former is substantially higher than the latter, the surface area decreases, but the macroporosity of the extrusions remains essentially constant.

  3. Self-assembled hybrid metal oxide base catalysts prepared by simply mixing with organic modifiers

    NASA Astrophysics Data System (ADS)

    Tamura, Masazumi; Kishi, Ryota; Nakagawa, Yoshinao; Tomishige, Keiichi

    2015-10-01

    Multidentate materials formed by simply mixing heterogeneous and homogeneous components are promising for construction of versatile active sites on the surface of heterogeneous compounds, however, to the best of our knowledge, there are no reports on such materials. Self-assembly of hetero-hybrid catalytic materials occurs when heterogeneous catalysts having adjacent Lewis acid-Lewis base sites are mixed with an organic modifier that contains at least two Lewis base functional groups. Here we demonstrate the strategy by combining cerium oxide and 2-cyanopyridine that self-assembles to form a charge-transfer complex in methanol that exhibits a 2,000-fold increase in reaction rate for hydromethoxylation of acrylonitrile with high selectivity compared with cerium oxide or 2-cyanopyridine alone. The catalytic system is applied to the transesterification and Knoevenagel condensation affording 14-fold and 11-fold higher activity, respectively, than cerium oxide alone. These results demonstrate the potential versatility of the catalytic system and the generality of the catalyst preparation strategy.

  4. Redox properties and VOC oxidation activity of Cu catalysts supported on Ce₁-xSmxOδ mixed oxides.

    PubMed

    Konsolakis, Michalis; Carabineiro, Sónia A C; Tavares, Pedro B; Figueiredo, José L

    2013-10-15

    A series of Cu catalysts supported on Ce1-xSmxOδ mixed oxides with different molar contents (x=0, 0.25, 0.5, 0.75 and 1), was prepared by wet impregnation and evaluated for volatile organic compounds (VOC) abatement, employing ethyl acetate as model molecule. An extensive characterization study was undertaken in order to correlate the morphological, structural and surface properties of catalysts with their oxidation activity. The optimum performance was obtained with Cu/CeO2 catalyst, which offers complete conversion of ethyl acetate into CO2 at temperatures as low as 260°C. The catalytic performance of Cu/Ce1-xSmxOδ was interpreted on the basis of characterization studies, showing that incorporation of samarium in ceria has a detrimental effect on the textural characteristics and reducibility of catalysts. Moreover, high Sm/Ce atomic ratios (from 1 to 3) resulted in a more reduced copper species, compared to CeO2-rich supports, suggesting the inability of these species to take part in the redox mechanism of VOC abatement. Sm/Ce surface atomic ratios are always much higher than the nominal ratios indicating an impoverishment of catalyst surface in cerium oxide, which is detrimental for VOC activity. PMID:23995554

  5. Polyethylene encapsulation of molten salt oxidation mixed low-level radioactive salt residues

    SciTech Connect

    Lageraaen, P.R.; Kalb, P.D.; Grimmett, D.L.; Gay, R.L.; Newman, C.D.

    1995-10-01

    A limited scope treatability study was conducted for polyethylene encapsulation of salt residues generated by a Molten Salt Oxidation (MSO) technology demonstration at the Energy Technology Engineering Center (ETEC), operated by Rockwell International for the US Department of Energy (DOE). During 1992 and 1993, ETEC performed a demonstration with a prototype MSO unit and treated approximately 50 gallons of mixed waste comprised of radioactively contaminated oils produced by hot cell operations. A sample of the mixed waste contaminated spent salt was used during the BNL polyethylene encapsulation treatability study. A nominal waste loading of 50 wt % was successfully processed and waste form test specimens were made for Toxicity Characteristic Leaching Procedure (TCLP) testing. The encapsulated product was compared with base-line TCLP results for total chromium and was found to be well within allowable EPA guidelines.

  6. Neutronics benchmark for the Quad Cities-1 (Cycle 2) mixed oxide assembly irradiation

    SciTech Connect

    Fisher, S.E.; Difilippo, F.C.

    1998-04-01

    Reactor physics computer programs are important tools that will be used to estimate mixed oxide fuel (MOX) physics performance in support of weapons grade plutonium disposition in US and Russian Federation reactors. Many of the computer programs used today have not undergone calculational comparisons to measured data obtained during reactor operation. Pin power, the buildup of transuranics, and depletion of gadolinium measurements were conducted (under Electric Power Research Institute sponsorship) on uranium and MOX pins irradiated in the Quad Cities-1 reactor in the 1970`s. These measurements are compared to modern computational models for the HELIOS and SCALE computer codes. Good agreement on pin powers was obtained for both MOX and uranium pins. The agreement between measured and calculated values of transuranic isotopes was mixed, depending on the particular isotope.

  7. Method for acid oxidation of radioactive, hazardous, and mixed organic waste materials

    DOEpatents

    Pierce, Robert A.; Smith, James R.; Ramsey, William G.; Cicero-Herman, Connie A.; Bickford, Dennis F.

    1999-01-01

    The present invention is directed to a process for reducing the volume of low level radioactive and mixed waste to enable the waste to be more economically stored in a suitable repository, and for placing the waste into a form suitable for permanent disposal. The invention involves a process for preparing radioactive, hazardous, or mixed waste for storage by contacting the waste starting material containing at least one organic carbon-containing compound and at least one radioactive or hazardous waste component with nitric acid and phosphoric acid simultaneously at a contacting temperature in the range of about 140.degree. C. to about 210 .degree. C. for a period of time sufficient to oxidize at least a portion of the organic carbon-containing compound to gaseous products, thereby producing a residual concentrated waste product containing substantially all of said radioactive or inorganic hazardous waste component; and immobilizing the residual concentrated waste product in a solid phosphate-based ceramic or glass form.

  8. Method for acid oxidation of radioactive, hazardous, and mixed organic waste materials

    SciTech Connect

    Pierce, R.A.; Smith, J.R.; Ramsey, W.G.; Cicero-Herman, C.A.; Bickford, D.F.

    1999-09-28

    The present invention is directed to a process for reducing the volume of low level radioactive and mixed waste to enable the waste to be more economically stored in a suitable repository, and for placing the waste into a form suitable for permanent disposal. The invention involves a process for preparing radioactive, hazardous, or mixed waste for storage by contacting the waste starting material containing at least one organic carbon-containing compound and at least one radioactive or hazardous waste component with nitric acid and phosphoric acid simultaneously at a contacting temperature in the range of about 140 C to about 210 C for a period of time sufficient to oxidize at least a portion of the organic carbon-containing compound to gaseous products, thereby producing a residual concentrated waste product containing substantially all of said radioactive or inorganic hazardous waste component; and immobilizing the residual concentrated waste product in a solid phosphate-based ceramic or glass form.

  9. Molten salt oxidation of mixed waste: Preliminary bench-scale experiments without radioactivity

    SciTech Connect

    Haas, P.A.; Rudolph, J.C.; Bell, J.T.

    1994-06-01

    Molten salt oxidation (MSO) is a process in which organic wastes are oxidized by sparging them with air through a bed of molten sodium carbonate (bp 851 {degrees}C) at {ge} 900{degrees}C. This process is readily applicable to the mixed waste because acidic products from Cl, S, P, etc., in the waste, along with most metals and most radionuclides, are retained within the melt as oxides or salts. Rockwell International has studied the application of MSO to various wastes, including some mixed waste. A unit used by Rockwell to study the mixed waste treatment is presently in use at Oak Ridge National Laboratory (ORNL). ORNL`s studies to date have concentrated on chemical flowsheet questions. Concerns that were studied included carbon monoxide (CO) emissions, NO{sub x}, emissions, and metal retention under a variety of conditions. Initial experiments show that CO emissions increase with increasing NaCl content in the melt, increasing temperature, and increasing airflow. Carbon monoxide content is especially high (> 2000 ppm) with high chlorine content (> 10%). Thermal NO{sub x}, emissions are relatively low ( < 5 ppm) at temperatures < 1000{degrees}C. However, most (85--100%) of the nitrogen in the feed as organic nitrate or amine was released as NO{sub x}, The metal contents of the melt and of knockout pot samples of condensed salt show high volatilities of Cs as CsCl. Average condensed salt concentrations were 60% for barium and 100% for strontium and cobalt. The cerium disappeared -- perhaps from deposition on the alumina reactor walls.

  10. Development of a novel wet oxidation process for hazardous and mixed wastes

    SciTech Connect

    Dhooge, P.M.

    1994-11-01

    This article describes and evaluates the DETOX{sup sm} process for processing of mixed wastes. Many DOE waste streams and remediates contain complex and variable mixtures of organic compounds, toxic metals, and radionuclides, often dispersed in organic or inorganic matrices, such as personal protective equipment, various sludges, soils, and water. The DETOX{sup sm} process, patented by Delphi Research, uses a unique combination of metal catalysts to increase the rate of oxidation of organic materials. Included are the following subject areas: project description (phases I-IV); results of all phases; and future work. 5 figs., 1 tab.

  11. Tunable catalytic properties of bi-functional mixed oxides in ethanol conversion to high value compounds

    DOE PAGESBeta

    Ramasamy, Karthikeyan K.; Gray, Michel; Job, Heather; Smith, Colin; Wang, Yong

    2016-02-03

    Here, a highly versatile ethanol conversion process to selectively generate high value compounds is presented here. By changing the reaction temperature, ethanol can be selectively converted to >C2 alcohols/oxygenates or phenolic compounds over hydrotalcite derived bi-functional MgO–Al2O3 catalyst via complex cascade mechanism. Reaction temperature plays a role in whether aldol condensation or the acetone formation is the path taken in changing the product composition. This article contains the catalytic activity comparison between the mono-functional and physical mixture counterpart to the hydrotalcite derived mixed oxides and the detailed discussion on the reaction mechanisms.

  12. Microstructural modeling of thermal conductivity of high burn-up mixed oxide fuel

    NASA Astrophysics Data System (ADS)

    Teague, Melissa; Tonks, Michael; Novascone, Stephen; Hayes, Steven

    2014-01-01

    Predicting the thermal conductivity of oxide fuels as a function of burn-up and temperature is fundamental to the efficient and safe operation of nuclear reactors. However, modeling the thermal conductivity of fuel is greatly complicated by the radially inhomogeneous nature of irradiated fuel in both composition and microstructure. In this work, radially and temperature-dependent models for effective thermal conductivity were developed utilizing optical micrographs of high burn-up mixed oxide fuel. The micrographs were employed to create finite element meshes with the OOF2 software. The meshes were then used to calculate the effective thermal conductivity of the microstructures using the BISON [1] fuel performance code. The new thermal conductivity models were used to calculate thermal profiles at end of life for the fuel pellets. These results were compared to thermal conductivity models from the literature, and comparison between the new finite element-based thermal conductivity model and the Duriez-Lucuta model was favorable.

  13. Application of a mixed metal oxide catalyst to a metallic substrate

    NASA Technical Reports Server (NTRS)

    Sevener, Kathleen M. (Inventor); Lohner, Kevin A. (Inventor); Mays, Jeffrey A. (Inventor); Wisner, Daniel L. (Inventor)

    2009-01-01

    A method for applying a mixed metal oxide catalyst to a metallic substrate for the creation of a robust, high temperature catalyst system for use in decomposing propellants, particularly hydrogen peroxide propellants, for use in propulsion systems. The method begins by forming a prepared substrate material consisting of a metallic inner substrate and a bound layer of a noble metal intermediate. Alternatively, a bound ceramic coating, or frit, may be introduced between the metallic inner substrate and noble metal intermediate when the metallic substrate is oxidation resistant. A high-activity catalyst slurry is applied to the surface of the prepared substrate and dried to remove the organic solvent. The catalyst layer is then heat treated to bind the catalyst layer to the surface. The bound catalyst layer is then activated using an activation treatment and calcinations to form the high-activity catalyst system.

  14. General Synthesis of Porous Mixed Metal Oxide Hollow Spheres with Enhanced Supercapacitive Properties.

    PubMed

    Wang, Qinghong; Zhu, Yuxuan; Xue, Jing; Zhao, Xinsheng; Guo, Zaiping; Wang, Chao

    2016-07-13

    Porous mixed metal oxide (MMO) hollow spheres present high specific surface areas, abundant electrochemically active sites, and outstanding electrochemical properties, showing potential applications in energy storage. A hydro/solvothermal process, followed by a calcination process, can be a viable method for producing uniform porous metal oxide hollow spheres. Unfortunately, this method usually involves harsh synthetic conditions such as high temperature and intricate processing. Herein, we report a general and facile "ion adsorption-annealing" approach for the fabrication of uniform porous MMO hollow spheres. The size and shell thickness of the as-obtained hollow spheres can be adjusted by the carbohydrate sphere templates and the solution concentration. Electrochemical measurements of the MMO hollow spheres demonstrate excellent supercapacitive properties, which may be due to the small size, ultrathin shells, and fine porous structure. PMID:27322845

  15. Microstructural Modeling of Thermal Conductivity of High Burn-up Mixed Oxide Fuel

    SciTech Connect

    Melissa Teague; Michael Tonks; Stephen Novascone; Steven Hayes

    2014-01-01

    Predicting the thermal conductivity of oxide fuels as a function of burn-up and temperature is fundamental to the efficient and safe operation of nuclear reactors. However, modeling the thermal conductivity of fuel is greatly complicated by the radially inhomogeneous nature of irradiated fuel in both composition and microstructure. In this work, radially and temperature-dependent models for effective thermal conductivity were developed utilizing optical micrographs of high burn-up mixed oxide fuel. The micrographs were employed to create finite element meshes with the OOF2 software. The meshes were then used to calculate the effective thermal conductivity of the microstructures using the BISON fuel performance code. The new thermal conductivity models were used to calculate thermal profiles at end of life for the fuel pellets. These results were compared to thermal conductivity models from the literature, and comparison between the new finite element-based thermal conductivity model and the Duriez–Lucuta model was favorable.

  16. Late-occurring pulmonary pathologies following inhalation of mixed oxide (uranium + plutonium oxide) aerosol in the rat.

    PubMed

    Griffiths, N M; Van der Meeren, A; Fritsch, P; Abram, M-C; Bernaudin, J-F; Poncy, J L

    2010-09-01

    Accidental exposure by inhalation to alpha-emitting particles from mixed oxide (MOX: uranium and plutonium oxide) fuels is a potential long-term health risk to workers in nuclear fuel fabrication plants. For MOX fuels, the risk of lung cancer development may be different from that assigned to individual components (plutonium, uranium) given different physico-chemical characteristics. The objective of this study was to investigate late effects in rat lungs following inhalation of MOX aerosols of similar particle size containing 2.5 or 7.1% plutonium. Conscious rats were exposed to MOX aerosols and kept for their entire lifespan. Different initial lung burdens (ILBs) were obtained using different amounts of MOX. Lung total alpha activity was determined by external counting and at autopsy for total lung dose calculation. Fixed lung tissue was used for anatomopathological, autoradiographical, and immunohistochemical analyses. Inhalation of MOX at ILBs ranging from 1-20 kBq resulted in lung pathologies (90% of rats) including fibrosis (70%) and malignant lung tumors (45%). High ILBs (4-20 kBq) resulted in reduced survival time (N = 102; p < 0.05) frequently associated with lung fibrosis. Malignant tumor incidence increased linearly with dose (up to 60 Gy) with a risk of 1-1.6% Gy for MOX, similar to results for industrial plutonium oxide alone (1.9% Gy). Staining with antibodies against Surfactant Protein-C, Thyroid Transcription Factor-1, or Oct-4 showed differential labeling of tumor types. In conclusion, late effects following MOX inhalation result in similar risk for development of lung tumors as compared with industrial plutonium oxide. PMID:20699696

  17. Solution processable broadband transparent mixed metal oxide nanofilm optical coatings via substrate diffusion doping

    NASA Astrophysics Data System (ADS)

    Glynn, Colm; Aureau, Damien; Collins, Gillian; O'Hanlon, Sally; Etcheberry, Arnaud; O'Dwyer, Colm

    2015-11-01

    Devices composed of transparent materials, particularly those utilizing metal oxides, are of significant interest due to increased demand from industry for higher fidelity transparent thin film transistors, photovoltaics and a myriad of other optoelectronic devices and optics that require more cost-effective and simplified processing techniques for functional oxides and coatings. Here, we report a facile solution processed technique for the formation of a transparent thin film through an inter-diffusion process involving substrate dopant species at a range of low annealing temperatures compatible with processing conditions required by many state-of-the-art devices. The inter-diffusion process facilitates the movement of Si, Na and O species from the substrate into the as-deposited vanadium oxide thin film forming a composite fully transparent V0.0352O0.547Si0.4078Na0.01. Thin film X-ray diffraction and Raman scattering spectroscopy show the crystalline component of the structure to be α-NaVO3 within a glassy matrix. This optical coating exhibits high broadband transparency, exceeding 90-97% absolute transmission across the UV-to-NIR spectral range, while having low roughness and free of surface defects and pinholes. The production of transparent films for advanced optoelectronic devices, optical coatings, and low- or high-k oxides is important for planar or complex shaped optics or surfaces. It provides opportunities for doping metal oxides to ternary, quaternary or other mixed metal oxides on glass, encapsulants or other substrates that facilitate diffusional movement of dopant species.Devices composed of transparent materials, particularly those utilizing metal oxides, are of significant interest due to increased demand from industry for higher fidelity transparent thin film transistors, photovoltaics and a myriad of other optoelectronic devices and optics that require more cost-effective and simplified processing techniques for functional oxides and coatings

  18. Stable and very sensitive gas sensor based on novel mixed-metal oxides

    NASA Astrophysics Data System (ADS)

    Comini, Elisabetta; Faglia, Guido; Sberveglieri, Giorgio

    2004-03-01

    The material properties of the nano-structured materials show remarkable improvement or deviation from the properties exhibited by the coarser grained material. These unique properties are attributed to the significant increase in grain boundary area due to the small grain size. The possibility to manipulate the properties of a nanosized thin film simply through annealing appears to be of widespread interest for material science. In the gas sensing field of application there is a great effort in reducing the grain dimension and increasing the surface area exposed to the interaction with gaseous species. One of the strategies used is the addition of a second element, which can inhibit the grain growth. Furthermore, there may be a coexistence of two phases and one phase can act as a receptor while the other can act as transducers and an effect on film porosity is also expected, depending on the extent of oxide segregation from the nanosized film. Thin films made of Mo-Ti, Mo-W, Ti-W, Ti-Nb mixed oxides were achieved by reactive sputtering, assisted by thermal treatments. These layers were characterized by means of the electrical measurements in presence of different pollutants and alcohols and with the Kelvin probe at different working temperatures; the good sensing capabilities registered with these mixed oxide compared to their single oxides have to be ascribed to the nanosized structure of these layers. In particular different p-type sensing materials were produced, the opposite behavior of these layer is attractive to ease data processing in sensors arrays.

  19. Plutonium-uranium mixed oxide characterization by coupling micro-X-ray diffraction and absorption investigations

    NASA Astrophysics Data System (ADS)

    Degueldre, C.; Martin, M.; Kuri, G.; Grolimund, D.; Borca, C.

    2011-09-01

    Plutonium-uranium mixed oxide (MOX) fuels are currently used in nuclear reactors. The potential differences of metal redox state and microstructural developments of the matrix before and after irradiation are commonly analysed by electron probe microanalysis. In this work the structure and next-neighbor atomic environments of Pu and U oxide features within unirradiated homogeneous MOX and irradiated (60 MW d kg -1) MOX samples was analysed by micro-X-ray fluorescence (μ-XRF), micro-X-ray diffraction (μ-XRD) and micro-X-ray absorption fine structure (μ-XAFS) spectroscopy. The grain properties, chemical bonding, valences and stoichiometry of Pu and U are determined from the experimental data gained for the unirradiated as well as for irradiated fuel material examined in the center of the fuel as well as in its peripheral zone (rim). The formation of sub-grains is observed as well as their development from the center to the rim (polygonization). In the irradiated sample Pu remains tetravalent (>95%) and no (<5%) Pu(V) or Pu(VI) can be detected while the fuel could undergo slight oxidation in the rim zone. Any slight potential plutonium oxidation is buffered by the uranium dioxide matrix while locally fuel cladding interaction could also affect the redox of the fuel.

  20. Solution processable broadband transparent mixed metal oxide nanofilm optical coatings via substrate diffusion doping.

    PubMed

    Glynn, Colm; Aureau, Damien; Collins, Gillian; O'Hanlon, Sally; Etcheberry, Arnaud; O'Dwyer, Colm

    2015-12-21

    Devices composed of transparent materials, particularly those utilizing metal oxides, are of significant interest due to increased demand from industry for higher fidelity transparent thin film transistors, photovoltaics and a myriad of other optoelectronic devices and optics that require more cost-effective and simplified processing techniques for functional oxides and coatings. Here, we report a facile solution processed technique for the formation of a transparent thin film through an inter-diffusion process involving substrate dopant species at a range of low annealing temperatures compatible with processing conditions required by many state-of-the-art devices. The inter-diffusion process facilitates the movement of Si, Na and O species from the substrate into the as-deposited vanadium oxide thin film forming a composite fully transparent V0.0352O0.547Si0.4078Na0.01. Thin film X-ray diffraction and Raman scattering spectroscopy show the crystalline component of the structure to be α-NaVO3 within a glassy matrix. This optical coating exhibits high broadband transparency, exceeding 90-97% absolute transmission across the UV-to-NIR spectral range, while having low roughness and free of surface defects and pinholes. The production of transparent films for advanced optoelectronic devices, optical coatings, and low- or high-k oxides is important for planar or complex shaped optics or surfaces. It provides opportunities for doping metal oxides to ternary, quaternary or other mixed metal oxides on glass, encapsulants or other substrates that facilitate diffusional movement of dopant species. PMID:26575987

  1. Modeling of thermo-mechanical and irradiation behavior of mixed oxide fuel for sodium fast reactors

    NASA Astrophysics Data System (ADS)

    Karahan, Aydın; Buongiorno, Jacopo

    2010-01-01

    An engineering code to model the irradiation behavior of UO2-PuO2 mixed oxide fuel pins in sodium-cooled fast reactors was developed. The code was named fuel engineering and structural analysis tool (FEAST-OXIDE). FEAST-OXIDE has several modules working in coupled form with an explicit numerical algorithm. These modules describe: (1) fission gas release and swelling, (2) fuel chemistry and restructuring, (3) temperature distribution, (4) fuel-clad chemical interaction and (5) fuel-clad mechanical analysis. Given the fuel pin geometry, composition and irradiation history, FEAST-OXIDE can analyze fuel and cladding thermo-mechanical behavior at both steady-state and design-basis transient scenarios. The code was written in FORTRAN-90 program language. The mechanical analysis module implements the LIFE algorithm. Fission gas release and swelling behavior is described by the OGRES and NEFIG models. However, the original OGRES model has been extended to include the effects of joint oxide gain (JOG) formation on fission gas release and swelling. A detailed fuel chemistry model has been included to describe the cesium radial migration and JOG formation, oxygen and plutonium radial distribution and the axial migration of cesium. The fuel restructuring model includes the effects of as-fabricated porosity migration, irradiation-induced fuel densification, grain growth, hot pressing and fuel cracking and relocation. Finally, a kinetics model is included to predict the clad wastage formation. FEAST-OXIDE predictions have been compared to the available FFTF, EBR-II and JOYO databases, as well as the LIFE-4 code predictions. The agreement was found to be satisfactory for steady-state and slow-ramp over-power accidents.

  2. Thermal and oxidation stability of organo-fluorine compound-mixed electrolyte solutions for lithium ion batteries

    NASA Astrophysics Data System (ADS)

    Nishikawa, Daiki; Nakajima, Tsuyoshi; Ohzawa, Yoshimi; Koh, Meiten; Yamauchi, Akiyoshi; Kagawa, Michiru; Aoyama, Hirokazu

    2013-12-01

    Thermal and oxidation stability of fluorine compound-mixed electrolyte solutions have been investigated. Charge/discharge behavior of natural graphite electrode has been also examined in the same electrolyte solutions. Fluorine compounds demonstrate much lower reactivity with metallic Li than ethylene carbonate/dimethyl carbonate. Fluorine compound-mixed electrolyte solutions show the lower reactivity with LiC6 and the smaller exothermic peaks due to decomposition of electrolyte solutions and surface films than original solutions without fluorine compound. Oxidation currents are also smaller in fluorine compound-mixed electrolyte solutions than in original ones. First coulombic efficiencies in fluorine compound-mixed electrolyte solutions are similar to those in original ethylene carbonate-based solutions except one case. Mixing of fluorine compounds highly increase first coulombic efficiencies of natural graphite electrode in propylene carbonate-containing solution.

  3. Analysis and spectral assignments of mixed actinide oxide samples using laser-induced breakdown spectroscopy (LIBS).

    PubMed

    Barefield, James E; Judge, Elizabeth J; Berg, John M; Willson, Stephen P; Le, Loan A; Lopez, Leon N

    2013-04-01

    In this paper, we report for the first time the identification and assignments of complex atomic emission spectra of mixed actinide oxides using laser-induced plasma spectroscopy or laser-induced breakdown spectroscopy (LIBS). Preliminary results of LIBS measurements on samples of uranium dioxide (UO2)/plutonium dioxide (PuO2) and UO2/PuO2/americium dioxide (AmO2)/neptunium dioxide (NpO2) simulated fuel pellets (or mixed actinide oxide samples) are reported and discussed. We have identified and assigned >800 atomic emission lines for a UO2/PuO2/AmO2/NpO2 fuel pellet thus far. The identification and assignments of spectral emission lines for U, Pu, and Am are consistent with wavelength data from the literature. However, only a few emission lines have been assigned with a high degree of confidence for Np compared with atomic emission data from the literature. We also indicate where atomic emission lines for Cm would most likely appear in the spectral regions shown. Finally, we demonstrate that a LIBS system with a resolving power of approximately 20,000 is adequate for analyzing complex mixtures of actinide elements within the same sample. PMID:23601543

  4. Nitric acid oxide mixing ratio measurements using a rocket launched chemiluminescent instrument

    NASA Technical Reports Server (NTRS)

    Horvath, Jack J.

    1989-01-01

    A total of 18 rocket launched parachute borne nitric oxide instruments were launched from 1977 to 1985. A very precise instrument for the measurement of the nitric oxide mixing ratio was fabricated. No changes were made in the main body of the instruments, i.e., things associated with the reaction volume. Except for the last 4 launches, however, it did not yield the required absolute values that was hoped for. Two major problems were encountered. First, the wrong choice of the background calibration gas, nitrogen, caused the first 10 data sets to be too low in the absolute mixing ratio by nearly the order of 2 to 5 ppbv. The error was realized, and air was substituted for the bias gas measurement. Second, in the desire to extend the measurement to higher altitudes, the problem of contaminating the inlet flow tube with ozone from the reagent gas was encountered. The ozone valve was opened too early in the flight and this caused the pressure in the reaction volume to exceed the pressure at the flow tube entrance, permitting the ozone to migrate backwards. This problem was restricted to an altitude above 45 km.

  5. Evaluation of Co-precipitation Processes for the Synthesis of Mixed-Oxide Fuel Feedstock Materials

    SciTech Connect

    Collins, Emory D; Voit, Stewart L; Vedder, Raymond James

    2011-06-01

    The focus of this report is the evaluation of various co-precipitation processes for use in the synthesis of mixed oxide feedstock powders for the Ceramic Fuels Technology Area within the Fuels Cycle R&D (FCR&D) Program's Advanced Fuels Campaign. The evaluation will include a comparison with standard mechanical mixing of dry powders and as well as other co-conversion methods. The end result will be the down selection of a preferred sequence of co-precipitation process for the preparation of nuclear fuel feedstock materials to be used for comparison with other feedstock preparation methods. A review of the literature was done to identify potential nitrate-to-oxide co-conversion processes which have been applied to mixtures of uranium and plutonium to achieve recycle fuel homogeneity. Recent studies have begun to study the options for co-converting all of the plutonium and neptunium recovered from used nuclear fuels, together with appropriate portions of recovered uranium to produce the desired mixed oxide recycle fuel. The addition of recycled uranium will help reduce the safeguard attractiveness level and improve proliferation resistance of the recycled fuel. The inclusion of neptunium is primarily driven by its chemical similarity to plutonium, thus enabling a simple quick path to recycle. For recycle fuel to thermal-spectrum light water reactors (LWRs), the uranium concentration can be {approx}90% (wt.), and for fast spectrum reactors, the uranium concentration can typically exceed 70% (wt.). However, some of the co-conversion/recycle fuel fabrication processes being developed utilize a two-step process to reach the desired uranium concentration. In these processes, a 50-50 'master-mix' MOX powder is produced by the co-conversion process, and the uranium concentration is adjusted to the desired level for MOX fuel recycle by powder blending (milling) the 'master-mix' with depleted uranium oxide. In general, parameters that must be controlled for co

  6. Computational and Experimental Study of the Thermodynamics of Uranium-Cerium Mixed Oxides

    NASA Astrophysics Data System (ADS)

    Hanken, Benjamin Edward

    The thermophysical properties of mixed oxide (MOX) fuels, and how they are influenced by the incorporation of fission products and other actinides, must be well understood for their safe use in an advanced fuel cycle. Cerium is a common plutonium surrogate in experimental studies of MOX, as it closely matches plutonium's ionic radii in the 3+ and 4+ oxidation states, and is soluble in fluorite-structured UO2. As a fission product, cerium's effects on properties of MOX are also of practical interest. To provide additional insights on structure-dependent behavior, urania solid solutions can be studied via density functional theory (DFT), although approaches beyond standard DFT are needed to properly account for the localized nature of the ƒ-electrons. In this work, DFT with Hubbard-U corrections (DFT+U) was employed to study the energetics of fluorite-structured U1-yCe yO2 mixtures. The employed computational approach makes use of a procedure which facilitates convergence of the calculations to multiple self-consistent DFT+U solutions for a given cation arrangement, corresponding to different charge states for the U and Ce ions in several prototypical cation arrangements. Results indicate a significant dependence of the structural and energetic properties of U1-yCeyO2 on the nature of both charge and cation ordering. With the effective Hubbard-U parameters that reproduce well the measured oxidation-reduction energies for urania and ceria, it was found that charge transfer between U4+ and Ce4+ ions, leading to the formation of U5+ and Ce3+, gives rise to an increase in the mixing energy in the range of 4-14 kJ/mol of the formula unit, depending on the nature of the cation ordering. In conjunction with the computational approach, high-temperature oxide-melt drop-solution calorimetry experiments were performed on eight samples spanning compositions of y = 0.119 to y = 0.815. Room temperature mixing enthalpies of U1-yCeyO2 determined from these experiments show near

  7. Dynamics of nitrogen oxides and ozone above and within a mixed hardwood forest in northern Michigan

    NASA Astrophysics Data System (ADS)

    Seok, B.; Helmig, D.; Ganzeveld, L.; Williams, M. W.; Vogel, C. S.

    2013-08-01

    The dynamic behavior of nitrogen oxides (NOx = NO + NO2) and ozone (O3) above and within the canopy at the University of Michigan Biological Station AmeriFlux (UMBS Flux) site was investigated by continuous multi-height vertical gradient measurements during the summer and the fall of 2008. A daily maximum in nitric oxide (NO) mixing ratios was consistently observed during the morning hours between 06:00 and 09:00 EST above the canopy. Daily NO maxima ranged between 0.1 and 2 ppbv (with a median of 0.3 ppbv), which were 2 to 20 times above the atmospheric background. The sources and causes of the morning NO maximum were evaluated using NOx and O3 measurements and synoptic and micrometeorological data. Numerical simulations with a multi-layer canopy-exchange model were done to further support this analysis. The observations indicated that the morning NO maximum was caused by the photolysis of NO2 from non-local air masses, which were transported into the canopy from aloft during the morning breakup of the nocturnal boundary layer. The analysis of simulated process tendencies indicated that the downward turbulent transport of NOx into the canopy compensates for the removal of NOx through chemistry and dry deposition. The sensitivity of NOx and O3 concentrations to soil and foliage NOx emissions was also assessed with the model. Uncertainties associated with the emissions of NOx from the soil or from leaf-surface nitrate photolysis did not explain the observed diurnal behavior in NOx (and O3) and, in particular, the morning peak in NOx mixing ratios. However, a ~30% increase in early morning NOx and NO peak mixing ratios was simulated when a foliage exchange NO2 compensation point was considered. This increase suggests the potential importance of leaf-level, bidirectional exchange of NO2 in understanding the observed temporal variability in NOx at UMBS.

  8. Co-Al mixed metal oxides/carbon nanotubes nanocomposite prepared via a precursor route and enhanced catalytic property

    SciTech Connect

    Fan Guoli; Wang Hui; Xiang Xu; Li Feng

    2013-01-15

    The present work reported the synthesis of Co-Al mixed metal oxides/carbon nanotubes (CoAl-MMO/CNT) nanocomposite from Co-Al layered double hydroxide/CNTs composite precursor (CoAl-LDH/CNT). The materials were characterized by powder X-ray diffraction (XRD), transmission electron microscopy (TEM), low temperature nitrogen adsorption-desorption experiments, thermogravimetric and differential thermal analyses (TG-DTA), Raman spectra and X-ray photoelectron spectroscopy (XPS). The results revealed that in CoAl-MMO/CNT nanocomposite, the nanoparticles of cobalt oxide (CoO) and Co-containing spinel-type complex metal oxides could be well-dispersed on the surface of CNTs, thus forming the heterostructure of CoAl-MMO and CNTs. Furthermore, as-synthesized CoAl-MMO/CNT nanocomposite was utilized as additives for catalytic thermal decomposition of ammonium perchlorate (AP). Compared to those for pure AP and CoAl-MMO, the peak temperature of AP decomposition for CoAl-MMO/CNT was significantly decreased, which is attributed to the novel heterostructure and synergistic effect of multi-component metal oxides of nanocomposite. - Graphical abstract: Hybrid Co-Al mixed metal oxides/carbon nanotubes nanocomposite showed the enhanced catalytic activity in the thermal decomposition of ammonium perchlorate, as compared to carbon nanotubes and pure Co-Al mixed metal oxides. Highlights: Black-Right-Pointing-Pointer Co-Al mixed metal oxides/carbon nanotubes nanocomposite was synthesized. Black-Right-Pointing-Pointer Co-Al mixed metal oxides consisted of cobalt oxide and Co-containing spinels. Black-Right-Pointing-Pointer Nanocomposite exhibited excellent catalytic activity for the decomposition of AP. Black-Right-Pointing-Pointer The superior catalytic property is related to novel heterostructure and composition.

  9. High temperature X-ray diffraction study of the oxidation products and kinetics of uranium-plutonium mixed oxides.

    PubMed

    Strach, Michal; Belin, Renaud C; Richaud, Jean-Christophe; Rogez, Jacques

    2014-12-15

    The oxidation products and kinetics of two sets of mixed uranium-plutonium dioxides containing 14%, 24%, 35%, 46%, 54%, and 62% plutonium treated in air were studied by means of in situ X-ray diffraction (XRD) from 300 to 1773 K every 100 K. The first set consisted of samples annealed 2 weeks before performing the experiments. The second one consisted of powdered samples that sustained self-irradiation damage. Results were compared with chosen literature data and kinetic models established for UO2. The obtained diffraction patterns were used to determine the temperature of the hexagonal M3O8 (M for metal) phase formation, which was found to increase with Pu content. The maximum observed amount of the hexagonal phase in wt % was found to decrease with Pu addition. We conclude that plutonium stabilizes the cubic phases during oxidation, but the hexagonal phase was observed even for the compositions with 62 mol % Pu. The results indicate that self-irradiation defects have a slight impact on the kinetics of oxidation and the lattice parameter even after the phase transformation. It was concluded that the lattice constant of the high oxygen phase was unaffected by the changes in the overall O/M when it was in equilibrium with small quantities of M3O8. We propose that the observed changes in the high oxygen cubic phase lattice parameter are a result of either cation migration or an increase in the miscibility of oxygen in this phase. The solubility of Pu in the hexagonal phase was estimated to be below 14 mol % even at elevated temperatures. PMID:25412433

  10. Laser-induced breakdown spectroscopy for determination of uranium in thorium-uranium mixed oxide fuel materials.

    PubMed

    Sarkar, Arnab; Alamelu, Devanathan; Aggarwal, Suresh K

    2009-05-15

    Laser-induced breakdown spectroscopy (LIBS) has been developed for determining the percentage of uranium in thorium-uranium mixed oxide fuel samples required as a part of the chemical quality assurance of fuel materials. The experimental parameters were optimized using mixed oxide pellets prepared from 1:1 (w/w) mixture of thorium-uranium mixed oxide standards and using boric acid as a binder. Calibration curves were established using U(II) 263.553 nm, U(II) 367.007 nm, U(II) 447.233 nm and U(II) 454.363 nm emission lines. The uranium amount determined in two synthetic mixed oxide samples using calibration curves agreed well with that of the expected values. Except for U(II) 263.553 nm, all the other emission lines exhibited a saturation effect due to self-absorption when U amount exceeded 20 wt.% in the Th-U mixture. The present method will be useful for fast and routine determination of uranium in mixed oxide samples of Th and U, without the need for dissolution, which is difficult and time consuming due to the refractory nature of ThO(2). The methodology developed is encouraging since a very good analytical agreement was obtained considering the limited resolution of the spectrometer employed in the work. PMID:19269431

  11. Electrochemical sulfide oxidation from domestic wastewater using mixed metal-coated titanium electrodes.

    PubMed

    Pikaar, Ilje; Rozendal, René A; Yuan, Zhiguo; Keller, Jürg; Rabaey, Korneel

    2011-11-01

    Hydrogen sulfide generation is a major issue in sewer management. A novel method based on electrochemical sulfide oxidation was recently shown to be highly effective for sulfide removal from synthetic and real sewage. Here, we compare the performance of five different mixed metal oxide (MMO) coated titanium electrode materials for the electrochemical removal of sulfide from domestic wastewater. All electrode materials performed similarly in terms of sulfide removal, removing 78±5%, 77±1%, 85±4%, 84±1%, and 83±2% at a current density of 10 mA/cm(2) using Ta/Ir, Ru/Ir, Pt/Ir, SnO(2) and PbO(2), respectively. Elevated chloride concentrations, often observed in coastal areas, did not entail any significant difference in performance. Independent of the electrode material used, sulfide oxidation by in situ generated oxygen was the predominant reaction mechanism. Passivation of the electrode surface by deposition of elemental sulfur did not occur. However, scaling was observed in the cathode compartment. This study shows that all the MMO coated titanium electrode materials studied are suitable anodic materials for sulfide removal from wastewater. Ta/Ir and Pt/Ir coated titanium electrodes seem the most suitable electrodes since they possess the lowest overpotential for oxygen evolution, are stable at low chloride concentration and are already used in full scale applications. PMID:21885081

  12. Catalytic combustion of soot over ceria-zinc mixed oxides catalysts supported onto cordierite.

    PubMed

    Nascimento, Leandro Fontanetti; Martins, Renata Figueredo; Silva, Rodrigo Ferreira; Serra, Osvaldo Antonio

    2014-03-01

    Modified substrates as outer heterogeneous catalysts was employed to reduce the soot generated from incomplete combustion of diesel or diesel/biodiesel blends, a process that harms the environment and public health. The unique storage properties of ceria (CeO2) makes it one of the most efficient catalysts available to date. Here, we proposed that ceria-based catalysts can lower the temperature at which soot combustion occurs; more specifically, from 610°C to values included in the diesel exhausts operation range (300-450°C). The sol-gel method was used to synthesize mixed oxide-based catalysts (CeO2:ZnO); the resulting catalysts were deposited onto cordierite substrates. In addition, the morphological and structural properties of the material were evaluated by XRD, BET, TPR-H2, and SEM. Thermogravimetric (TG/DTA) analysis revealed that the presence of the catalyst decreased the soot combustion temperature by 200°C on average, indicating that the oxygen species arise at low temperatures in this situation, promoting highly reactive oxidation reactions. Comparative analysis of soot emission by diffuse reflectance spectroscopy (DRS) showed that catalyst-impregnated cordierite samples efficiently oxidized soot in a diesel/biodiesel stationary motor: soot emission decreased by more than 70%. PMID:25079283

  13. Microbial Ecology Assessment of Mixed Copper Oxide/Sulfide Dump Leach Operation

    SciTech Connect

    Bruhn, D F; Thompson, D N; Noah, K S

    1999-06-01

    Microbial consortia composed of complex mixtures of autotrophic and heterotrophic bacteria are responsible for the dissolution of metals from sulfide minerals. Thus, an efficient copper bioleaching operation depends on the microbial ecology of the system. A microbial ecology study of a mixed oxide/sulfide copper leaching operation was conducted using an "overlay" plating technique to differentiate and identify various bacterial consortium members of the genera Thiobacillus, Leptospirillum, Ferromicrobium, and Acidiphilium. Two temperatures (30C and 45C) were used to select for mesophilic and moderately thermophilic bacteria. Cell numbers varied from 0-106 cells/g dry ore, depending on the sample location and depth. After acid curing for oxide leaching, no viable bacteria were recovered, although inoculation of cells from raffinate re-established a microbial population after three months. Due to the low pH of the operation, very few non-iron-oxidizing acidophilic heterotrophs were recovered. Moderate thermophiles were isolated from the ore samples. Pregnant liquor solutions (PLS) and raffinate both contained a diversity of bacteria. In addition, an intermittently applied waste stream that contained high levels of arsenic and fluoride was tested for toxicity. Twenty vol% waste stream in PLS killed 100% of the cells in 48 hours, indicating substantial toxicity and/or growth inhibition. The data indicate that bacteria populations can recover after acid curing, and that application of the waste stream to the dump should be avoided. Monitoring the microbial ecology of the leaching operation provided significant information that improved copper recovery.

  14. Charge storage and the oxygen evolution reaction in mixed Ni-Li oxides.

    PubMed

    Villa, Marco; Milanese, Chiara; Salvi, Paolo; Nelli, Paolo; Marini, Amedeo; Zangari, Giovanni

    2009-09-21

    Electronic and catalytic properties of mixed oxides of Ni-Li are studied at room temperature with NMR and with electrochemical techniques in alkaline solutions. Our Li(x)Ni(1-x)O (0.04 < or = x < or = 0.2) samples have an f.c.c crystal structure, are in an anti-ferromagnetic phase, and exhibit a substantial conductivity due to a hole-hopping process with a characteristic rate which is essentially independent of composition. Several processes of reduction and oxidation occur in the voltage region between the hydrogen (HER) and oxygen evolution (OER) reactions, which are compared with related phenomena observed in pure Ni electrodes (Ni(OH)2 and NiO). Repeated cycles of reduction and oxidation yield electrodes with a somewhat improved OER activity, and a high charge-storage capacity. Heavy anodic treatments cause irreversible changes of these properties, particularly when coupled with months-long storage in air. The complex behavior of these electrodes is interpreted in terms of formation of a topotactic surface layer with hydrogenated species. PMID:19950507

  15. Microstructural Characterization of High Burn-up Mixed Oxide Fast Reactor Fuel

    SciTech Connect

    Melissa C. Teague; Brian P. Gorman; Steven L. Hayes; Douglas L. Porter; Jeffrey King

    2013-10-01

    High burn-up mixed oxide fuel with local burn-ups of 3.4–23.7% FIMA (fissions per initial metal atom) were destructively examined as part of a research project to understand the performance of oxide fuel at extreme burn-ups. Optical metallography of fuel cross-sections measured the fuel-to-cladding gap, clad thickness, and central void evolution in the samples. The fuel-to-cladding gap closed significantly in samples with burn-ups below 7–9% FIMA. Samples with burn-ups in excess of 7–9% FIMA had a reopening of the fuel-to-cladding gap and evidence of joint oxide-gain (JOG) formation. Signs of axial fuel migration to the top of the fuel column were observed in the fuel pin with a peak burn-up of 23.7% FIMA. Additionally, high burn-up structure (HBS) was observed in the two highest burn-up samples (23.7% and 21.3% FIMA). The HBS layers were found to be 3–5 times thicker than the layers found in typical LWR fuel. The results of the study indicate that formation of JOG and or HBS prevents any significant fuel-cladding mechanical interaction from occurring, thereby extending the potential life of the fuel elements.

  16. Nanoporous composites prepared by a combination of SBA-15 with Mg–Al mixed oxides. Water vapor sorption properties

    PubMed Central

    Pérez-Verdejo, Amaury; Pfeiffer, Heriberto; Ruiz-Reyes, Mayra; Santamaría, Juana-Deisy; Fetter, Geolar

    2014-01-01

    Summary This work presents two easy ways for preparing nanostructured mesoporous composites by interconnecting and combining SBA-15 with mixed oxides derived from a calcined Mg–Al hydrotalcite. Two different Mg–Al hydrotalcite addition procedures were implemented, either after or during the SBA-15 synthesis (in situ method). The first procedure, i.e., the post-synthesis method, produces a composite material with Mg–Al mixed oxides homogeneously dispersed on the SBA-15 nanoporous surface. The resulting composites present textural properties similar to the SBA-15. On the other hand, with the second procedure (in situ method), Mg and Al mixed oxides occur on the porous composite, which displays a cauliflower morphology. This is an important microporosity contribution and micro and mesoporous surfaces coexist in almost the same proportion. Furthermore, the nanostructured mesoporous composites present an extraordinary water vapor sorption capacity. Such composites might be utilized as as acid-base catalysts, adsorbents, sensors or storage nanomaterials. PMID:25161858

  17. Amorphous mixed-metal hydroxide nanostructures for advanced water oxidation catalysts

    NASA Astrophysics Data System (ADS)

    Gao, Y. Q.; Liu, X. Y.; Yang, G. W.

    2016-02-01

    The design of highly efficient, durable, and earth-abundant catalysts for the oxygen evolution reaction (OER) is crucial in order to promote energy conversion and storage processes. Here, we synthesize amorphous mixed-metal (Ni-Fe) hydroxide nanostructures with a homogeneous distribution of Ni/Fe as well as a tunable Ni/Fe ratio by a simple, facile, green and low-cost electrochemical technique, and we demonstrate that the synthesized amorphous nanomaterials possess ultrahigh activity and super long-term cycle stability in the OER process. The amorphous Ni0.71Fe0.29(OH)x nanostructure affords a current density of 10 mA cm-2 at an overpotential of a mere 0.296 V and a small Tafel slope of 58 mV dec-1, while no deactivation is detected in the CV testing even up to 30 000 cycles, which suggests the promising application of these amorphous nanomaterials in electrochemical oxidation. Meanwhile, the distinct catalytic activities among these amorphous Ni-Fe hydroxide nanostructures prompts us to take notice of the composition of the alloy hydroxides/oxides when studying their catalytic properties, which opens an avenue for the rational design and controllable preparation of such amorphous nanomaterials as advanced OER electrocatalysts.The design of highly efficient, durable, and earth-abundant catalysts for the oxygen evolution reaction (OER) is crucial in order to promote energy conversion and storage processes. Here, we synthesize amorphous mixed-metal (Ni-Fe) hydroxide nanostructures with a homogeneous distribution of Ni/Fe as well as a tunable Ni/Fe ratio by a simple, facile, green and low-cost electrochemical technique, and we demonstrate that the synthesized amorphous nanomaterials possess ultrahigh activity and super long-term cycle stability in the OER process. The amorphous Ni0.71Fe0.29(OH)x nanostructure affords a current density of 10 mA cm-2 at an overpotential of a mere 0.296 V and a small Tafel slope of 58 mV dec-1, while no deactivation is detected in the CV

  18. Preparation and characterization of RF sputtered Ce-V mixed oxide thin films

    SciTech Connect

    Malini, D. Rachel; Sanjeeviraja, C.

    2012-06-05

    Cerium-Vanadium mixed oxide thin films were deposited at room temperature by varying RF power in RF magnetron sputtering. The morphology and structural features were studied by taking FESEM and XRD and optical properties were analyzed by taking transmittance and absorption spectra. The crystalline film shows orthorhombic CeVO{sub 3} phase and the observed grain size varies from 89.4nm to 208.7nm. The transmission increases and the absorption edge at 330nm is blue shifted with increase in RF power. The optical band gap is found to increase from 1.59 to 1.94eV. The PL spectra shows blue shift in the emission peak centered at a wavelength of 495nm with increase in RF power.

  19. The underwater coincidence counter for plutonium measurements in mixed-oxide fuel assemblies manual

    SciTech Connect

    G. W. Eccleston; H. O. Menlove; M. Abhold; M. Baker; J. Pecos

    1999-05-01

    This manual describes the Underwater Coincidence Counter (UWCC) that has been designed for the measurement of plutonium in mixed-oxide (MOX) fuel assemblies prior to irradiation. The UWCC uses high-efficiency {sup 3}He neutron detectors to measure the spontaneous-fission and induced-fission rates in the fuel assembly. Measurements can be made on MOX fuel assemblies in air or underwater. The neutron counting rate is analyzed for singles, doubles, and triples time correlations to determine the {sup 240}Pu effective mass per unit length of the fuel assembly. The system can verify the plutonium loading per unit length to a precision of less than 1% in a measurement time of 2 to 3 minutes. System design, components, performance tests, and operational characteristics are described in this manual.

  20. Magnetoelectric behavior of carbonyl iron mixed Mn oxide-coated ferrite nanoparticles

    NASA Astrophysics Data System (ADS)

    Ahad, Faris B. Abdul; Lee, Shang-Fan; Hung, Dung-Shing; Yao, Yeong-Der; Yang, Ruey-Bin; Lin, Chung-Kwei; Tsay, Chien-Yie

    2010-05-01

    The dielectric and magnetic properties of manganese oxide-coated Fe3O4 nanoparticles (NPs) were measured by the cavity perturbation method at x-band microwave frequencies ranging from 7-12.5 GHz with controlled external magnetic field up to 2.2 kOe at room temperature. Different ratios (5%, 10%, and 20% by weight) of coated NPs were prepared by sol-gel method then mixed with carbonyl iron powder in epoxy matrix. The saturation magnetization is inversely proportional to the NPs ratio in the mixture between 150 and 180 emu/g. The real part of the permittivity decreased with increasing NPs concentration, but the permittivity change by magnetic field increased. The tunability behavior is explained by insulator-ferromagnetic interface magnetoelectricity and the large surface volume ratio for the NPs.

  1. Reduction of bromate to bromide coupled to acetate oxidation by anaerobic mixed microbial cultures.

    PubMed

    van Ginkel, C G; van Haperen, A M; van der Togt, B

    2005-01-01

    Bromate, a weakly mutagenic oxidizing agent, exists in surface waters. The biodegradation of bromate was investigated by assessing the ability of mixed cultures of micro-organisms for utilization of bromate as electron acceptor and acetate as electron donor. Reduction of bromate was only observed at relatively low concentrations (<3.0 mM) in the absence of molecular oxygen. Under these conditions bromate was reduced stoichiometrically to bromide. Unadapted sludge from an activated sludge treatment plant and a digester reduced bromate without lag period at a constant rate. Using an enrichment culture adapted to bromate, it was demonstrated that bromate was a terminal electron acceptor for anaerobic growth. Approximately 50% of the acetate was utilized for growth with bromate by the enrichment culture. A doubling of 20 h was estimated from a logarithmic growth curve. Other electron acceptors, like perchlorate, chlorate and nitrate, were not reduced or at negligible rates by bromate-utilizing microorganisms. PMID:15607164

  2. Low temperature photochemical vapor deposition of alloy and mixed metal oxide films

    DOEpatents

    Liu, David K.

    1992-01-01

    Method and apparatus for formation of an alloy thin film, or a mixed metal oxide thin film, on a substrate at relatively low temperatures. Precursor vapor(s) containing the desired thin film constituents is positioned adjacent to the substrate and irradiated by light having wavelengths in a selected wavelength range, to dissociate the gas(es) and provide atoms or molecules containing only the desired constituents. These gases then deposit at relatively low temperatures as a thin film on the substrate. The precursor vapor(s) is formed by vaporization of one or more precursor materials, where the vaporization temperature(s) is selected to control the ratio of concentration of metals present in the precursor vapor(s) and/or the total precursor vapor pressure.

  3. Low temperature photochemical vapor deposition of alloy and mixed metal oxide films

    DOEpatents

    Liu, D.K.

    1992-12-15

    Method and apparatus are described for formation of an alloy thin film, or a mixed metal oxide thin film, on a substrate at relatively low temperatures. Precursor vapor(s) containing the desired thin film constituents is positioned adjacent to the substrate and irradiated by light having wavelengths in a selected wavelength range, to dissociate the gas(es) and provide atoms or molecules containing only the desired constituents. These gases then deposit at relatively low temperatures as a thin film on the substrate. The precursor vapor(s) is formed by vaporization of one or more precursor materials, where the vaporization temperature(s) is selected to control the ratio of concentration of metals present in the precursor vapor(s) and/or the total precursor vapor pressure. 7 figs.

  4. Americium and plutonium release behavior from irradiated mixed oxide fuel during heating

    NASA Astrophysics Data System (ADS)

    Sato, I.; Suto, M.; Miwa, S.; Hirosawa, T.; Koyama, S.

    2013-06-01

    The release behavior of Pu and Am was investigated under the reducing atmosphere expected in sodium cooled fast reactor severe accidents. Irradiated Pu and U mixed oxide fuels were heated at maximum temperatures of 2773 K and 3273 K. EPMA, γ-ray spectrometry and α-ray spectrometry for released and residual materials revealed that Pu and Am can be released more easily than U under the reducing atmosphere. The respective release rate coefficients for Pu and Am were obtained as 3.11 × 10-4 min-1 and 1.60 × 10-4 min-1 at 2773 K under the reducing atmosphere with oxygen partial pressure less than 0.02 Pa. Results of thermochemical calculations indicated that the main released chemical forms would likely be PuO for Pu and Am for Am under quite low oxygen partial pressure.

  5. Solid solubility and thermal expansion studies of uranium-europium mixed oxides

    NASA Astrophysics Data System (ADS)

    Venkata Krishnan, R.; Jogeswararao, G.; Panneerselvam, G.; Antony, M. P.; Ananthasivan, K.

    2015-10-01

    Uranium-europium mixed oxides (U1-yEuy)O2-x (y = 0.2, 0.4, 0.6, 0.65, 0.7, 0.75, 0.8) were prepared by citrate gel-combustion synthesis and characterized by using X-ray diffraction (XRD). The terminal solid solubility of EuO1.5 in UO2 is in the composition range 60-65 mol% EuO1.5. The coefficients of thermal expansions at 1973 K for (U1-yEuy)O2-x (y = 0.2, 0.4, 0.6) measured by using high-temperature X-ray diffraction (HTXRD) were found to be 15.80, 14.81 and 14.30 × 10-6 K-1 respectively.

  6. Ag/Au mixed sites promote oxidative coupling of methanol on the alloy surface.

    PubMed

    Xu, Bingjun; Siler, Cassandra G F; Madix, Robert J; Friend, Cynthia M

    2014-04-14

    Nanoporous gold, a dilute alloy of Ag in Au, activates molecular oxygen and promotes the oxygen-assisted catalytic coupling of methanol. Because this trace amount of Ag inherent to nanoporous gold has been proposed as the source of oxygen activation, a thin film Ag/Au alloy surface was studied as a model system for probing the origin of this reactivity. Thin alloy layers of Ag(x)Au(1-x), with 0.15≤x≤0.40, were examined for dioxygen activation and methanol self-coupling. These alloy surfaces recombine atomic oxygen at different temperatures depending on the alloy composition. Total conversion of methanol to selective oxidation products, that is, formaldehyde and methyl formate, was achieved at low initial oxygen coverage and at low temperature. Reaction channels for methyl formate formation occurred on both Au and Au/Ag mixed sites with a ratio, as was predicted from the local 2-dimensional composition. PMID:24633724

  7. Molecular data of mixed metal oxides with importance in nuclear safety

    NASA Astrophysics Data System (ADS)

    Kovács, Attila; Konings, Rudy J. M.

    2016-08-01

    The gas-phase structural and spectroscopic properties of selected mixed metal oxides (Cs2CrO4, Cs2MnO4, Cs2MoO4, Cs2RuO4, BaMoO4, BaMoO3) have been calculated using Density Functional Theory (DFT). The possible structural isomers have been analyzed and for the found global minima the vibrational (IR, Raman) spectra have been predicted taking into account also anharmonic corrections. The bonding properties have been characterized by means of the Natural Bond Orbital analysis model while the low-lying excited electronic states have been calculated using time-dependent DFT. In order to assess the stability of the target species the dissociation enthalpies have been evaluated.

  8. Dynamics of nitrogen oxides and ozone above and within a mixed hardwood forest in Northern Michigan

    NASA Astrophysics Data System (ADS)

    Seok, B.; Helmig, D.; Ganzeveld, L.; Williams, M. W.; Vogel, C. S.

    2012-12-01

    The dynamic behavior of nitrogen oxides (NOx = NO + NO2) and ozone (O3) above and within the canopy at the University of Michigan Biological Station AmeriFlux (UMBS Flux) site was investigated by continuous multi-height vertical gradient measurements during the summer and the fall of 2008. A daily maximum in nitric oxide (NO) levels was consistently observed during the morning hours between 06:00 and 09:00 EST above the canopy. Daily NO maxima ranged between 0.2 and 2 ppbv (with a median of 0.3 ppbv), which was 2 to 20 times above its atmospheric background. The sources and causes of this NO maximum were evaluated using NOx and O3 measurements and synoptic and micrometeorological data. This analysis was further supported by numerical simulations with a multi-layer canopy exchange model implemented into a single-column chemistry-climate model. The observations indicated that the morning NO maximum was caused by the photolysis of NO2 from non-local air masses, which were transported into the canopy from aloft during the morning breakup of the nocturnal boundary layer. The analysis of simulated process tendencies indicated that the downward turbulent transport of NOx into the canopy compensates for the removal of NOx through chemistry and dry deposition. The sensitivity of NOx and O3 concentrations on soil and foliage NOx emissions was also assessed with the model. Uncertainties associated with the emissions of NOx from the soil or from leaf-surface nitrate photolysis did not explain the observed diurnal behavior in NOx (and O3), and in particular, the morning NOx peak mixing ratio. However, when considering the existence of a NO2 compensation point, an increase in the early morning NOx and NO peak mixing ratios by ~30% was simulated. This increase suggests the potential importance of leaf-level, bi-directional exchange of NO2 in understanding the observed temporal variability in NOx at UMBS.

  9. Shell Model for Atomistic Simulation of Lithium Diffusion in Mixed Mn/Ti Oxides

    SciTech Connect

    Kerisit, Sebastien N.; Chaka, Anne M.; Droubay, Timothy C.; Ilton, Eugene S.

    2014-10-23

    Mixed Mn/Ti oxides present attractive physicochemical properties such as their ability to accommodate Li for application in Li-ion batteries. In this work, atomic parameters for Mn were developed to extend an existing shell model of the Li-Ti-O system and allow simulations of pure and lithiated Mn and mixed Mn/Ti oxide polymorphs. The shell model yielded good agreement with experimentally-derived structures (i.e. lattice parameters and inter-atomic distances) and represented an improvement over existing potential models. The shell model was employed in molecular dynamics (MD) simulations of Li diffusion in the 1×1 c direction channels of LixMn1 yTiyO2 with the rutile structure, where 0 ≤ x ≤ 0.25 and 0 ≤ y ≤ 1. In the infinite dilution limit, the arrangement of Mn and Ti ions in the lattice was found to have a significant effect on the activation energy for Li diffusion in the c channels due to the destabilization of half of the interstitial octahedral sites. Anomalous diffusion was demonstrated for Li concentrations as low as x = 0.125, with a single Li ion positioned in every other c channel. Further increase in Li concentration showed not only the substantial effect of Li-Li repulsive interactions on Li mobility but also their influence on the time dependence of Li diffusion. The results of the MD simulations can inform intrinsic structure-property relationships for the rational design of improved electrode materials for Li-ion batteries.

  10. Evaluation of tubular reactor designs for supercritical water oxidation of U.S. Department of Energy mixed waste

    SciTech Connect

    Barnes, C.M.

    1994-12-01

    Supercritical water oxidation (SCWO) is an emerging technology for industrial waste treatment and is being developed for treatment of the US Department of Energy (DOE) mixed hazardous and radioactive wastes. In the SCWO process, wastes containing organic material are oxidized in the presence of water at conditions of temperature and pressure above the critical point of water, 374 C and 22.1 MPa. DOE mixed wastes consist of a broad spectrum of liquids, sludges, and solids containing a wide variety of organic components plus inorganic components including radionuclides. This report is a review and evaluation of tubular reactor designs for supercritical water oxidation of US Department of Energy mixed waste. Tubular reactors are evaluated against requirements for treatment of US Department of Energy mixed waste. Requirements that play major roles in the evaluation include achieving acceptable corrosion, deposition, and heat removal rates. A general evaluation is made of tubular reactors and specific reactors are discussed. Based on the evaluations, recommendations are made regarding continued development of supercritical water oxidation reactors for US Department of Energy mixed waste.

  11. Role of flue gas components in mercury oxidation over TiO2 supported MnOx-CeO2 mixed-oxide at low temperature.

    PubMed

    Li, Hailong; Wu, Chang-Yu; Li, Ying; Li, Liqing; Zhao, Yongchun; Zhang, Junying

    2012-12-01

    MnO(x)-CeO(2) mixed-oxide supported on TiO(2) (Mn-Ce/Ti) was synthesized by an ultrasound-assisted impregnation method and employed to oxidize elemental mercury (Hg(0)) at 200°C in simulated coal combustion flue gas. Over 90% of Hg(0) oxidation was achieved on the Mn-Ce/Ti catalyst at 200°C under simulated flue gas representing those from burning low-rank coals with a high gas hourly space velocity of 60,000 h(-1). Gas-phase O(2) regenerated the lattice oxygen and replenished the chemisorbed oxygen, which facilitated Hg(0) oxidation. HCl was the most effective flue gas component responsible for Hg(0) oxidation. 10 ppm HCl plus 4% O(2) resulted in 100% Hg(0) oxidation under the experimental conditions. SO(2) competed with Hg(0) for active sites, thus deactivating the catalyst's capability in oxidizing Hg(0). NO covered the active sites and consumed surface oxygen active for Hg(0) oxidation, hence limiting Hg(0) oxidation. Water vapor showed prohibitive effect on Hg(0) oxidation due to its competition with HCl and Hg(0) for active adsorption sites. This study provides information about the promotional or inhibitory effects of individual flue gas components on Hg(0) oxidation over a highly effective Mn-Ce/Ti catalyst. Such knowledge is of fundamental importance for industrial applications of the Mn-Ce/Ti catalyst in coal-fired power plants. PMID:23131500

  12. Ni Mg Mixed Metal Oxides for p-Type Dye-Sensitized Solar Cells.

    PubMed

    Zannotti, Marco; Wood, Christopher J; Summers, Gareth H; Stevens, Lee A; Hall, Matthew R; Snape, Colin E; Giovannetti, Rita; Giovanetti, Rita; Gibson, Elizabeth A

    2015-11-11

    Mg Ni mixed metal oxide photocathodes have been prepared by a mixed NiCl2/MgCl2 sol-gel process. The MgO/NiO electrodes have been extensively characterized using physical and electrochemical methods. Dye-sensitized solar cells have been prepared from these films, and the higher concentrations of MgO improved the photovoltage of these devices; however, there was a notable drop in photocurrent with increasing Mg(2+). Charge extraction and XPS experiments revealed that the cause of this was a positive shift in the energy of the valence band, which decreased the driving force for electron transfer from the NiO film to the dye and, therefore, the photocurrent. In addition, increasing concentrations of MgO increases the volume of pores between 0.500 and 0.050 μm, while reducing pore volumes in the mesopore range (less than 0.050 μm) and lowering BET surface area from approximately 41 down to 30 m(2) g(-1). A MgO concentration of 5% was found to strike a balance between the increased photovoltage and decreased photocurrent, possessing a BET surface area of 35 m(2) g(-1) and a large pore volume in both the meso- and macropore range, which lead to a higher overall power conversion efficiency than NiO alone. PMID:26468918

  13. Mixed alkali effect on the spectroscopic properties of alkali-alkaline earth oxide borate glasses

    NASA Astrophysics Data System (ADS)

    Srinivas, G.; Ramesh, B.; Shareefuddin, Md.; Chary, M. N.; Sayanna, R.

    2016-05-01

    The mixed alkali and alkaline earth oxide borate glass with the composition xK2O - (25-x) Li2O-12.5BaO-12.5MgO-50B2O3 (x = 0, 5, 10, 15, 20 and 25mol %) and doped with 1mol% CuO were prepared by the melt quenching technique. From the optical absorption spectra the optical band gap, electronic polarizability(α02-), interaction parameter (A), theoretical and experimental optical basicity (Λ) values were evaluated. From the Electron Paramagnetic Resonance (EPR) spectral data the number of spins (N) and susceptibility (χ) were evaluated. The values of (α02-), and (Λ) increases with increasing of K2O content and electronic polarizability and interaction parameter show opposite behaviuor which may be due to the creation of non-bridging oxygens and expansion of borate network. The reciprocal of susceptibility (1/χ) and spin concentration (N) as a function of K2O content, varied nonlinearly which may be due to creation of non-bridging oxygens in the present glass system. This may be attributed to mixed alkali effect (MAE).

  14. Criticality experiments with mixed oxide fuel pin arrays in plutonium-uranium nitrate solution

    SciTech Connect

    Lloyd, R.C. ); Smolen, G.R. )

    1988-08-01

    A series of critical experiments was completed with mixed plutonium-uranium solutions having a Pu/(Pu + U) ratio of approximately 0.22 in a boiler tube-type lattice assembly. These experiments were conducted as part of the Criticality Data Development Program between the United States Department of Energy (USDOE) and the Power Reactor and Nuclear Fuel Development Corporation (PNC) of Japan. A complete description of the experiments and data are included in this report. The experiments were performed with an array of mixed oxide fuel pins in aqueous plutonium-uranium solutions. The fuel pins were contained in a boiler tube-type tank and arranged in a 1.4 cm square pitch array which resembled cylindrical geometry. One experiment was perfomed with the fuel pins removed from the vessel. The experiments were performed with a water reflector. The concentration of the solutions in the boiler tube-type tank was varied from 4 to 468 g (Pu + U)/liter. The ratio of plutonium to total heavy metal (plutonium plus uranium) was approximately 0.22 for all experiments.

  15. The incorporation of graphene oxide into polysulfone mixed matrix membrane for CO2/CH4 separation

    NASA Astrophysics Data System (ADS)

    Zahri, K.; Goh, P. S.; Ismail, A. F.

    2016-06-01

    Carbon dioxide (CO2) is often found as the main impurity in natural gas, where methane (CH4) is the major component. The presence of CO2 in natural gas leads to several problems such as reducing the energy content of natural gas and cause pipeline corrosion. Thus it must be removed to meet specifications (CO2 ≤ 2 mol%) before the gas can be delivered to the pipeline. In this work, hollow fiber mixed matrix membrane (MMM) were fabricated by embedding graphene oxide (GO) into a polysulfone (PSf) polymer matrix to improve membrane properties as well as its separation performance towards CO2/CH4 gas. The membrane properties were investigated for pristine membrane and mixed matrix membrane filled with filler loading of 0.25%. The synthesized GO and properties of fabricated membranes were characterized and studied using TEM, AFM, XRD, FTIR and SEM respectively. The permeance of pure gases and ideal selectivity of CO2/CH4 gas were determined using pure gas permeation experiment. GO has affinity towards CO2 gas. The nanosheet structure creates path for small molecule gas and restricted large molecule gas to pass through the membrane. The incorporation of GO in PSf polymer enhanced the permeance of CO 2 and CO2/CH4 separation from 64.47 to 86.80 GPU and from 19 to 25 respectively.

  16. Kinetics and thermodynamics of anaerobic ammonium oxidation process using Brocadia spp. dominated mixed cultures.

    PubMed

    Puyol, D; Carvajal-Arroyo, J M; Garcia, B; Sierra-Alvarez, R; Field, J A

    2014-01-01

    Anaerobic ammonium oxidation (anammox) is a recently discovered microbial process commonly applied to treat ammonium pollution in effluents with low organic carbon content. Modeling anammox processes is important for simulating and controlling full-scale plants. In this study, the anammox process was simulated using three models, and substrate and growth parameters obtained by different research groups. Two Brocadia spp.-dominated mixed cultures, one granular and the other flocculent, were used for this purpose. A very good correlation between experimental data using both sludges and model predictions was achieved by one of the models, obtaining correlation coefficients higher than 0.997. Other models and stoichiometric equations tested were unable to predict the anammox kinetics and stoichiometry. Furthermore, the thermodynamic behavior of the two mixed cultures was compared through the determination of the energy of activation of the anammox conversion at temperatures ranging from 9 to 40 °C. Optimum temperature for anammox activity was established at 30-35 °C in both cases. The energy of activation values calculated for granular sludge and flocculent sludge were 64 and 124 kJ mol(-1), respectively. PMID:24759529

  17. DFT study on the electronic structure and chemical state of Americium in an (Am,U) mixed oxide

    NASA Astrophysics Data System (ADS)

    Suzuki, Chikashi; Nishi, Tsuyoshi; Nakada, Masami; Tsuru, Tomohito; Akabori, Mitsuo; Hirata, Masaru; Kaji, Yoshiyuki

    2013-12-01

    We investigated the electronic state of an (Am,U) mixed oxide with the fluorite structure using the all-electron full potential linear augmented plane wave method and compared it with those of Am2O3, AmO2, UO2, and La0.5U0.5O2. The valence of Am in the mixed oxide was close to that of Am2O3 and the valence of U in the mixed oxide was pentavalent. The electronic structure of AmO2 was different from that of Am2O3, particularly just above the Fermi level. In addition, the electronic states of Am and U in the mixed oxide were similar to those of trivalent Am and pentavalent U oxides. These electronic states reflected the high oxygen potential of AmO2 and the heightened oxygen potential resulting from the addition of Am to UO2 and also suggested the occurrence of charge transfer from Am to U in the solid solution process.

  18. Removal of Hazardous Pollutants from Wastewaters: Applications of TiO 2 -SiO 2 Mixed Oxide Materials

    DOE PAGESBeta

    Rasalingam, Shivatharsiny; Peng, Rui; Koodali, Ranjit T.

    2014-01-01

    The direct release of untreated wastewaters from various industries and households results in the release of toxic pollutants to the aquatic environment. Advanced oxidation processes (AOP) have gained wide attention owing to the prospect of complete mineralization of nonbiodegradable organic substances to environmentally innocuous products by chemical oxidation. In particular, heterogeneous photocatalysis has been demonstrated to have tremendous promise in water purification and treatment of several pollutant materials that include naturally occurring toxins, pesticides, and other deleterious contaminants. In this work, we have reviewed the different removal techniques that have been employed for water purification. In particular, the applicationmore » of TiO 2 -SiO 2 binary mixed oxide materials for wastewater treatment is explained herein, and it is evident from the literature survey that these mixed oxide materials have enhanced abilities to remove a wide variety of pollutants.« less

  19. Catalytic propane dehydrogenation over In₂O₃–Ga₂O₃ mixed oxides

    SciTech Connect

    Tan, Shuai; Gil, Laura Briones; Subramanian, Nachal; Sholl, David S.; Nair, Sankar; Jones, Christopher W.; Moore, Jason S.; Liu, Yujun; Dixit, Ravindra S.; Pendergast, John G.

    2015-08-26

    We have investigated the catalytic performance of novel In₂O₃–Ga₂O₃ mixed oxides synthesized by the alcoholic-coprecipitation method for propane dehydrogenation (PDH). Reactivity measurements reveal that the activities of In₂O₃–Ga₂O₃ catalysts are 1–3-fold (on an active metal basis) and 12–28-fold (on a surface area basis) higher than an In₂O₃–Al₂O₃ catalyst in terms of C₃H₈ conversion. The structure, composition, and surface properties of the In₂O₃–Ga₂O₃ catalysts are thoroughly characterized. NH₃-TPD shows that the binary oxide system generates more acid sites than the corresponding single-component catalysts. Raman spectroscopy suggests that catalysts that produce coke of a more graphitic nature suppress cracking reactions, leading to higher C₃H₆ selectivity. Lower reaction temperature also leads to higher C₃H₆ selectivity by slowing down the rate of side reactions. XRD, XPS, and XANES measurements, strongly suggest that metallic indium and In₂O₃ clusters are formed on the catalyst surface during the reaction. The agglomeration of In₂O₃ domains and formation of a metallic indium phase are found to be irreversible under O₂ or H₂ treatment conditions used here, and may be responsible for loss of activity with increasing time on stream.

  20. High-temperature X-ray diffraction study of uranium-neptunium mixed oxides.

    PubMed

    Chollet, Mélanie; Belin, Renaud C; Richaud, Jean-Christophe; Reynaud, Muriel; Adenot, Frédéric

    2013-03-01

    Incorporating minor actinides (MAs = Am, Np, Cm) in UO2 fertile blankets is a viable option to recycle them. Despite this applied interest, phase equilibria between uranium and MAs still need to be thoroughly investigated, especially at elevated temperatures. In particular, few reports on the U-Np-O system are available. In the present work, we provide for the first time in situ high-temperature X-ray diffraction results obtained during the oxidation of (U1-yNpy)O2 uranium-neptunium mixed oxides up to 1373 K and discuss subsequent phase transformations. We show that (i) neptunium stabilizes the UO2-type fluorite structure at high temperature and that (ii) the U3O8-type orthorhombic structure is observed in a wide range of compositions. We clearly demonstrate the incorporation of neptunium in this phase, which was a controversial question in previous studies up to now. We believe it is the particular stability of the tetravalent state of neptunium that is responsible for the observed phase relationships. PMID:23409700

  1. EBSD and TEM Characterization of High Burn-up Mixed Oxide Fuel

    SciTech Connect

    Teague, Melissa C.; Gorman, Brian P.; Miller, Brandon D.; King, Jeffrey

    2014-01-01

    Understanding and studying the irradiation behavior of high burn-up oxide fuel is critical to licensing of future fast breeder reactors. Advancements in experimental techniques and equipment are allowing for new insights into previously irradiated samples. In this work dual column focused ion beam (FIB)/scanning electron microscope (SEM) was utilized to prepared transmission electron microscope samples from mixed oxide fuel with a burn-up of 6.7% FIMA. Utilizing the FIB/SEM for preparation resulted in samples with a dose rate of <0.5 mRem/h compared to approximately 1.1 R/h for a traditionally prepared TEM sample. The TEM analysis showed that the sample taken from the cooler rim region of the fuel pellet had approximately 2.5x higher dislocation density than that of the sample taken from the mid-radius due to the lower irradiation temperature of the rim. The dual column FIB/SEM was additionally used to prepared and serially slice approximately 25 um cubes. High quality electron back scatter diffraction (EBSD) were collected from the face at each step, showing, for the first time, the ability to obtain EBSD data from high activity irradiated fuel.

  2. Amorphous mixed-metal hydroxide nanostructures for advanced water oxidation catalysts.

    PubMed

    Gao, Y Q; Liu, X Y; Yang, G W

    2016-03-01

    The design of highly efficient, durable, and earth-abundant catalysts for the oxygen evolution reaction (OER) is crucial in order to promote energy conversion and storage processes. Here, we synthesize amorphous mixed-metal (Ni-Fe) hydroxide nanostructures with a homogeneous distribution of Ni/Fe as well as a tunable Ni/Fe ratio by a simple, facile, green and low-cost electrochemical technique, and we demonstrate that the synthesized amorphous nanomaterials possess ultrahigh activity and super long-term cycle stability in the OER process. The amorphous Ni0.71Fe0.29(OH)x nanostructure affords a current density of 10 mA cm(-2) at an overpotential of a mere 0.296 V and a small Tafel slope of 58 mV dec(-1), while no deactivation is detected in the CV testing even up to 30 000 cycles, which suggests the promising application of these amorphous nanomaterials in electrochemical oxidation. Meanwhile, the distinct catalytic activities among these amorphous Ni-Fe hydroxide nanostructures prompts us to take notice of the composition of the alloy hydroxides/oxides when studying their catalytic properties, which opens an avenue for the rational design and controllable preparation of such amorphous nanomaterials as advanced OER electrocatalysts. PMID:26864279

  3. Semi-Coke–Supported Mixed Metal Oxides for Hydrogen Sulfide Removal at High Temperatures

    PubMed Central

    Jie, Mi; Yongyan, Zhang; Yongsheng, Zhu; Ting, Guo; Huiling, Fan

    2012-01-01

    Abstract To improve the desulfurization efficiency of sorbents at low cost, modified semi-coke was used as the substrate for mixed metal oxides (ZFM; oxides of zinc [Zn], iron [Fe], and manganese [Mn]) in hot gas desulfurization. Performance of the prepared ZFM/modified semi-coke (MS) sorbents were evaluated in a fixed-bed reactor in the temperature range 400–550°C. Results showed that the molar ratio of Mn to Zn, effect of the substrate, the calcination temperature, and the sulfidation temperature influenced the performance of the sorbents. Optimum conditions for the preparation of the ZFM/MS sorbents were molar ratio of Mn(NO3)2·6H2O, Zn(NO3)2, and Fe(NO3)3, 0.6:1:2; mass ratio of ZFM0.6 to modified semi-coke support, 1:1; and calcination temperature, 600°C. The ZFM0.6/MS sorbent thus prepared exhibited the best sorption sulfur capacity of 27.46% at 450°C. PMID:22783061

  4. Phase transition and mixed oxide-proton conductivity in germanium oxy-apatites

    SciTech Connect

    Leon-Reina, Laura; Porras-Vazquez, Jose M.; Losilla, Enrique R.; Aranda, Miguel A.G.

    2007-04-15

    La{sub 9.75}{open_square}{sub 0.25}(Ge{sub 6}O{sub 24})O{sub 2.62} oxy-apatite shows a phase transition from triclinic to hexagonal symmetry at approximately 1020 K that has been characterised by high-temperature synchrotron X-ray and neutron powder diffraction, and ionic conductivity measurements. The crystal structure at 1073 K has been determined from joint Rietveld refinements of synchrotron X-ray and neutron powder diffraction data. The study shows that hexagonal-La{sub 9.75}{open_square}{sub 0.25}(Ge{sub 6}O{sub 24})O{sub 2.62} contains interstitial oxygen at the position previously reported for other oxy-germanates. Changes in the oxide conductivity associated with this structural transition are discussed. The thermal analyses showed a weight loss on heating close to 600 K very likely due to water release. The synchrotron thermodiffractometric study shows an anomaly in the cell parameters evolution at that temperature, which indicates that this residual water is located into the apatite channels. The electrical characterisation under different atmospheres (dry and wet synthetic air) indicates that there is a significant proton contribution to the overall conductivity below 600 K, mainly under wet atmosphere. - Graphical abstract: La{sub 9.75}{open_square}{sub 0.25}(Ge{sub 6}O{sub 24})O{sub 2.62} oxide-conductor shows triclinic-hexagonal phase transition (see inset) at {approx}1020 K, meanwhile La{sub 9.55}{open_square}{sub 0.45}(Ge{sub 6}O{sub 24})O{sub 2.32} is hexagonal at all temperatures. Both compounds have mixed proton and oxide conductivities below 600 K.

  5. Microbial Ecology Assessment of Mixed Copper Oxide/Sulfide Dump Leach Operation

    SciTech Connect

    Bruhn, Debby Fox; Thompson, David Neal; Noah, Karl Scott

    1999-06-01

    Microbial consortia composed of complex mixtures of autotrophic and heterotrophic bacteria are responsible for the dissolution of metals from sulfide minerals. Thus, an efficient copper bioleaching operation depends on the microbial ecology of the system. A microbial ecology study of a mixed oxide/sulfide copper leaching operation was conducted using an "overlay" plating technique to differentiate and identify various bacterial consortium members of the genera Thiobacillus, “Leptospirillum”, “Ferromicrobium”, and Acidiphilium. Two temperatures (30°C and 45°C) were used to select for mesophilic and moderately thermophilic bacteria. Cell numbers varied from 0-106 cells/g dry ore, depending on the sample location and depth. After acid curing for oxide leaching, no viable bacteria were recovered, although inoculation of cells from raffinate re-established a microbial population after three months. Due to low the pH of the operation, very few non-iron-oxidizing acidophilic heterotrophs were recovered. Moderate thermophiles were isolated from the ore samples. Pregnant liquor solutions (PLS) and raffinate both contained a diversity of bacteria. In addition, an intermittently applied waste stream that contained high levels of arsenic and fluoride was tested for toxicity. Twenty vol% waste stream in PLS killed 100% of the cells in 48 hours, indicating substantial toxicity and/or growth inhibition. The data indicate that bacteria populations can recover after acid curing, and that application of the waste stream to the dump should be avoided. Monitoring the microbial ecology of the leaching operation provided significant information that improved copper recovery.

  6. 77 FR 70193 - Shaw Areva MOX Services (Mixed Oxide Fuel Fabrication Facility); Notice of Atomic Safety and...

    Federal Register 2010, 2011, 2012, 2013, 2014

    2012-11-23

    ... COMMISSION Shaw Areva MOX Services (Mixed Oxide Fuel Fabrication Facility); Notice of Atomic Safety and Licensing Board Reconstitution Pursuant to 10 CFR 2.313(c) and 2.321(b), the Atomic Safety and Licensing... Administrative Judge, Atomic Safety and Licensing Board Panel. BILLING CODE 7590-01-P...

  7. A stochastic model of turbulent mixing with chemical reaction: Nitric oxide formulation in a plug-flow burner

    NASA Technical Reports Server (NTRS)

    Flagan, R. C.; Appleton, J. P.

    1973-01-01

    A stochastic model of turbulent mixing was developed for a reactor in which mixing is represented by n-body fluid particle interactions. The model was used to justify the assumption (made in previous investigations of the role of turbulent mixing on burner generated thermal nitric oxide and carbon monoxide emissions) that for a simple plug flow reactor, composition nonuniformities can be described by a Gaussian distribution function in the local fuel:air equivalence ratio. Recent extensions of this stochastic model to include the combined effects of turbulent mixing and secondary air entrainment on thermal generation of nitric oxide in gas turbine combustors are discussed. Finally, rate limited upper and lower bounds of the nitric oxide produced by thermal fixation of molecular nitrogen and oxidation of organically bound fuel nitrogen are estimated on the basis of the stochastic model for a plug flow burner; these are compared with experimental measurements obtained using a laboratory burner operated over a wide range of test conditions; good agreement is obtained.

  8. Effect of the conditions of preparing mixed oxide catalyst of Mo-V-Te-Nb-O composition on its activity in the oxidative dehydrogenation of ethane

    NASA Astrophysics Data System (ADS)

    Finashina, E. D.; Kucherov, A. V.; Kustov, L. M.

    2013-12-01

    It is shown that catalytic activity of mixed oxide catalyst of Mo-V-Te-Nb-O composition in oxidative dehydrogenation (OD) of ethane is determined to a substantial degree by the Nb-to-(C2O4)2- ratio in niobium-containing precursors. A pH value of 2.8 to 3.0 for a mixture is optimal when conducting the hydrothermal synthesis of a mixed oxide catalyst; this is achieved by using oxaloniobic acid as a niobium-containing precursor. It is determined that substituting antimony for tellurium results in a loss of catalyst activity during the OD of ethane. The optimum Te content in a catalyst is 0.17 mol %.

  9. Mixed oxide fuels testing in the advanced test reactor to support plutonium disposition

    SciTech Connect

    Ryskamp, J.M.; Sterbentz, J.W.; Chang, G.S.

    1995-09-01

    An intense worldwide effort is now under way to find means of reducing the stockpile of weapons-grade plutonium. One of the most attractive solutions would be to use WGPu as fuel in existing light water reactors (LWRs) in the form of mixed oxide (MOX) fuel - i.e., plutonia (PUO{sub 2}) mixed with urania (UO{sub 2}). Before U.S. reactors could be used for this purpose, their operating licenses would have to be amended. Numerous technical issues must be resolved before LWR operating licenses can be amended to allow the use of MOX fuel. These issues include the following: (1) MOX fuel fabrication process verification, (2) Whether and how to use burnable poisons to depress MOX fuel initial reactivity, which is higher than that of urania, (3) The effects of WGPu isotopic composition, (4) The feasibility of loading MOX fuel with plutonia content up to 7% by weight, (5) The effects of americium and gallium in WGPu, (6) Fission gas release from MOX fuel pellets made from WGPu, (7) Fuel/cladding gap closure, (8) The effects of power cycling and off-normal events on fuel integrity, (9) Development of radial distributions of burnup and fission products, (10) Power spiking near the interfaces of MOX and urania fuel assemblies, and (11) Fuel performance code validation. We have performed calculations to show that the use of hafnium shrouds can produce spectrum adjustments that will bring the flux spectrum in ATR test loops into a good approximation to the spectrum anticipated in a commercial LWR containing MOX fuel while allowing operation of the test fuel assemblies near their optimum values of linear heat generation rate. The ATR would be a nearly ideal test bed for developing data needed to support applications to license LWRs for operation with MOX fuel made from weapons-grade plutonium. The requirements for planning and implementing a test program in the ATR have been identified.

  10. Tunable Mixed Ionic/Electronic Conductivity and Permittivity of Graphene Oxide Paper for Electrochemical Energy Conversion.

    PubMed

    Bayer, Thomas; Bishop, Sean R; Perry, Nicola H; Sasaki, Kazunari; Lyth, Stephen M

    2016-05-11

    Graphene oxide (GO) is a two-dimensional graphitic carbon material functionalized with oxygen-containing surface functional groups. The material is of interest in energy conversion, sensing, chemical processing, gas barrier, and electronics applications. Multilayer GO paper has recently been applied as a new proton conducting membrane in low temperature fuel cells. However, a detailed understanding of the electrical/dielectric properties, including separation of the ionic vs electronic contributions under relevant operating conditions, has so far been lacking. Here, the electrical conductivity and dielectric permittivity of GO paper are investigated in situ from 30 to 120 °C, and from 0 to 100% relative humidity (RH) using impedance spectroscopy. These are related to the water content, measured by thermogravimetric analysis. With the aid of electron blocking measurements, GO is demonstrated to be a mixed electronic-protonic conductor, and the ion transference number is derived for the first time. For RH > 40%, conductivity is dominated by proton transport (with a maximum of 0.5 mS/cm at 90 °C and 100% RH). For RH < 40%, electronic conductivity dominates (with a maximum of 7.4 mS/cm at ∼80 °C and 0% RH). The relative permittivity of GO paper increases with decreasing humidity, from ∼10 at 100% RH to several 1000 at 10% RH. These results underline the potential of GO for application not only as a proton conducting electrolyte but also as a mixed conducting electrode material under appropriate conditions. Such materials are highly applicable in electrochemical energy conversion and storage devices such as fuel cells and electrolyzers. PMID:27088238

  11. The behaviour of transuranic mixed oxide fuel in a Candu-900 reactor

    SciTech Connect

    Morreale, A. C.; Ball, M. R.; Novog, D. R.; Luxat, J. C.

    2012-07-01

    The production of transuranic actinide fuels for use in current thermal reactors provides a useful intermediary step in closing the nuclear fuel cycle. Extraction of actinides reduces the longevity, radiation and heat loads of spent material. The burning of transuranic fuels in current reactors for a limited amount of cycles reduces the infrastructure demand for fast reactors and provides an effective synergy that can result in a reduction of as much as 95% of spent fuel waste while reducing the fast reactor infrastructure needed by a factor of almost 13.5 [1]. This paper examines the features of actinide mixed oxide fuel, TRUMOX, in a CANDU{sup R}* nuclear reactor. The actinide concentrations used were based on extraction from 30 year cooled spent fuel and mixed with natural uranium in 3.1 wt% actinide MOX fuel. Full lattice cell modeling was performed using the WIMS-AECL code, super-cell calculations were analyzed in DRAGON and full core analysis was executed in the RFSP 2-group diffusion code. A time-average full core model was produced and analyzed for reactor coefficients, reactivity device worth and online fuelling impacts. The standard CANDU operational limits were maintained throughout operations. The TRUMOX fuel design achieved a burnup of 27.36 MWd/kg HE. A full TRUMOX fuelled CANDU was shown to operate within acceptable limits and provided a viable intermediary step for burning actinides. The recycling, reprocessing and reuse of spent fuels produces a much more sustainable and efficient nuclear fuel cycle. (authors)

  12. Conversion of ethanol to 1,3-butadiene over Na doped ZnxZryOz mixed metal oxides

    SciTech Connect

    Baylon, Rebecca A.; Sun, Junming; Wang, Yong

    2016-01-01

    Despite numerous studies on different oxide catalysts for the ethanol to 1,3-butadiene reaction, few have identified active sites (i.e., type of acidity) correlated to the catalytic performances. In this work, the type of acidity needed for ethanol to 1,3-butadiene conversion has been studied over Zn/Zr mixed oxide catalysts. Specifically, synthesis method, Zn/Zr ratio, and Na doping have been used to control the surface acid-base properties, as confirmed by characterizations such as NH3-TPD and IR-Py techniques. The 2000 ppm Na doped Zn1Zr10Oz-H with balanced base and weak Bronsted acid sites was found to give not only high selectivity to 1,3-butadiene (47%) at near complete ethanol conversion (97%), but also exhibited a much higher 1,3-butadiene productivity than other mixed oxides studied.

  13. Dual Electrospray Pyrolysis for Mixed Metal Oxide (and Carbon) Composite Nanoparticle Synthesis with Applications in Energy Storage

    NASA Astrophysics Data System (ADS)

    Tang, Justin; Liu, Wen; Wang, Hailiang; Gomez, Alessandro

    We present a novel approach to synthesizing mixed metal oxide nanoparticles with a continuous, scalable aerosol flow process using the electrospray. The electrospray is a liquid atomization technique that generates a monodisperse population of highly charged liquid droplets over a broad size range (nanometric to tens of microns). Each liquid droplet serves as a micro-reactor, containing a payload of suitable precursors (such as metal nitrides), allowing for precise control over particle composition and size. By using two electrosprays of opposite polarities, the two highly charged droplets plumes are electrostatically mixed to produce a charge-neutral aerosol. Electrostatically driven droplet-droplet collisions can also be used to control morphology to some degree. This aerosol is passed through a tubular furnace via carrier gas, pyrolizing the precursors to synthesize nanomaterials. We apply this approach to manganese oxide, cobalt oxide, and carbon composite nanoparticles for use in energy storage applications.

  14. Cu-Ce-O mixed oxides from Ce-containing layered double hydroxide precursors: Controllable preparation and catalytic performance

    NASA Astrophysics Data System (ADS)

    Chang, Zheng; Zhao, Na; Liu, Junfeng; Li, Feng; Evans, David G.; Duan, Xue; Forano, Claude; de Roy, Marie

    2011-12-01

    Cu/Zn/Al layered double hydroxide (LDH) precursors have been synthesized using an anion exchange method with anionic Ce complexes containing the dipicolinate (pyridine-2,6-dicarboxylate) ligand. Cu-Ce-O mixed oxides were obtained by calcination of the Ce-containing LDHs. The materials were characterized by X-ray diffraction, Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, thermogravimetry-differential thermal analysis, elemental analysis, and low temperature N 2 adsorption/desorption measurements. The results reveal that the inclusion of Ce has a significant effect on the specific surface area, pore structure, and chemical state of Cu in the resulting Cu-Ce-O mixed metal oxides. The resulting changes in composition and structure, particularly the interactions between Cu and Ce centers, significantly enhance the activity of the Ce-containing materials as catalysts for the oxidation of phenol by hydrogen peroxide.

  15. Cobalt-silicon mixed oxide nanocomposites by modified sol-gel method

    SciTech Connect

    Esposito, Serena; Turco, Maria; Ramis, Gianguido; Bagnasco, Giovanni; Pernice, Pasquale; Pagliuca, Concetta; Bevilacqua, Maria; Aronne, Antonio

    2007-12-15

    Cobalt-silicon mixed oxide materials (Co/Si=0.111, 0.250 and 0.428) were synthesised starting from Co(NO{sub 3}){sub 2}.6H{sub 2}O and Si(OC{sub 2}H{sub 5}){sub 4} using a modified sol-gel method. Structural, textural and surface chemical properties were investigated by thermogravimetric/differential thermal analyses (TG/DTA), XRD, UV-vis, FT-IR spectroscopy and N{sub 2} adsorption at -196 deg. C. The nature of cobalt species and their interactions with the siloxane matrix were strongly depending on both the cobalt loading and the heat treatment. All dried gels were amorphous and contained Co{sup 2+} ions forming both tetrahedral and octahedral complexes with the siloxane matrix. After treatment at 400 deg. C, the sample with lowest Co content appeared amorphous and contained only Co{sup 2+} tetrahedral complexes, while at higher cobalt loading Co{sub 3}O{sub 4} was present as the only crystalline phase, besides Co{sup 2+} ions strongly interacting with siloxane matrix. At 850 deg. C, in all samples crystalline Co{sub 2}SiO{sub 4} was formed and was the only crystallising phase for the nanocomposite with the lowest cobalt content. All materials retained high surface areas also after treatments at 600 deg. C and exhibited surface Lewis acidity, due to cationic sites. The presence of cobalt affected the textural properties of the siloxane matrix decreasing microporosity and increasing mesoporosity. - Graphical abstract: Highly dispersed cobalt-silicon mixed oxide nanocomposites (Co/Si=0.111, 0.250 and 0.428) were obtained by a modified sol-gel method using almost solely aqueous solutions. The nature of cobalt species and their interactions with the siloxane matrix are strongly depending on both the cobalt loading and the heat treatment. All materials retained high surface areas also after treatments at 600 deg. C and exhibited surface Lewis acidity.

  16. Cu-Ce-O mixed oxides from Ce-containing layered double hydroxide precursors: Controllable preparation and catalytic performance

    SciTech Connect

    Chang Zheng; Zhao Na; Liu Junfeng; Li Feng; Evans, David G.; Duan Xue; Forano, Claude; Roy, Marie de

    2011-12-15

    Cu/Zn/Al layered double hydroxide (LDH) precursors have been synthesized using an anion exchange method with anionic Ce complexes containing the dipicolinate (pyridine-2,6-dicarboxylate) ligand. Cu-Ce-O mixed oxides were obtained by calcination of the Ce-containing LDHs. The materials were characterized by X-ray diffraction, Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, thermogravimetry-differential thermal analysis, elemental analysis, and low temperature N{sub 2} adsorption/desorption measurements. The results reveal that the inclusion of Ce has a significant effect on the specific surface area, pore structure, and chemical state of Cu in the resulting Cu-Ce-O mixed metal oxides. The resulting changes in composition and structure, particularly the interactions between Cu and Ce centers, significantly enhance the activity of the Ce-containing materials as catalysts for the oxidation of phenol by hydrogen peroxide. - Graphical Abstract: Cu-Ce-O mixed oxides calcined from [Ce(dipic){sub 3}]{sup 3-}- intercalated Cu/Zn/Al layered double hydroxides were synthesized and displayed good catalytic performances in phenol oxidation due to the Cu-Ce interactions. Highlights: Black-Right-Pointing-Pointer [Ce(dipic){sub 3}]{sup 3-}-intercalated Cu/Zn/Al layered double hydroxides were synthesized. Black-Right-Pointing-Pointer Cu-Ce-O mixed oxides derivated from the LDHs were characterized as catalysts. Black-Right-Pointing-Pointer Presence of Ce influenced physicochemical property and catalytic performance. Black-Right-Pointing-Pointer Cu-Ce interaction was largely responsible for enhanced catalytic ability.

  17. An experimental study of perovskite-structured mixed ionic- electronic conducting oxides and membranes

    NASA Astrophysics Data System (ADS)

    Zeng, Pingying

    In recent decades, ceramic membranes based on mixed ionic and electronic conducting (MIEC) perovskite-structured oxides have received many attentions for their applications for air separation, or as a membrane reactor for methane oxidation. While numerous perovskite oxide materials have been explored over the past two decades; there are hardly any materials with sufficient practical economic value and performance for large scale applications, which justifies continuing the search for new materials. The main purposes of this thesis study are: (1) develop several novel SrCoO3-delta based MIEC oxides, SrCoCo1-xMxO3-delta, based on which membranes exhibit excellent oxygen permeability; (2) investigate the significant effects of the species and concentration of the dopants M (metal ions with fixed valences) on the various properties of these membranes; (3) investigate the significant effects of sintering temperature on the microstructures and performance of oxygen permeation membranes; and (4) study the performance of oxygen permeation membranes as a membrane reactor for methane combustion. To stabilize the cubic phase structure of the SrCoO3-delta oxide, various amounts of scandium was doped into the B-site of SrCoO 3-delta to form a series of new perovskite oxides, SrScxCoCo 1-xO3-delta (SSCx, x = 0-0.7). The significant effects of scandium-doping concentration on the phase structure, electrical conductivity, sintering performance, thermal and structural stability, cathode performance, and oxygen permeation performance of the SSCx membranes, were systematically studied. Also for a more in-depth understanding, the rate determination steps for the oxygen transport process through the membranes were clarified by theoretical and experimental investigation. It was found that only a minor amount of scandium (5 mol%) doping into the B-site of SrCoO3-delta can effectively stabilize the cubic phase structure, and thus significantly improve the electrical conductivity and

  18. Method of CO and/or CO.sub.2 hydrogenation using doped mixed-metal oxides

    SciTech Connect

    Shekhawat, Dushyant; Berry, David A.; Haynes, Daniel J.; Abdelsayed, Victor; Smith, Mark W.; Spivey, James J.

    2015-10-06

    A method of hydrogenation utilizing a reactant gas mixture comprising a carbon oxide and a hydrogen agent, and a hydrogenation catalyst comprising a mixed-metal oxide containing metal sites supported and/or incorporated into the lattice. The mixed-metal oxide comprises a perovskite, a pyrochlore, a fluorite, a brownmillerite, or mixtures thereof doped at the A-site or the B-site. The metal site may comprise a deposited metal, where the deposited metal is a transition metal, an alkali metal, an alkaline earth metal, or mixtures thereof. Contact between the carbon oxide, hydrogen agent, and hydrogenation catalyst under appropriate conditions of temperature, pressure and gas flow rate generate a hydrogenation reaction and produce a hydrogenated product made up of carbon from the carbon oxide and some portion of the hydrogen agent. The carbon oxide may be CO, CO.sub.2, or mixtures thereof and the hydrogen agent may be H.sub.2. In a particular embodiment, the hydrogenated product comprises an alcohol, an olefin, an aldehyde, a ketone, an ester, an oxo-product, or mixtures thereof.

  19. Thin Film Optical Coatings of Vanadium Oxide and Mixed Tungsten/Vanadium Oxide Deposited by APCVD Employing Precursors of Vanadyl Acetylacetonate and a Mixture with Tungsten Hexacarbonyl

    NASA Astrophysics Data System (ADS)

    Bodurov, Georgi; Ivanova, Tatyana; Abrashev, Miroslav; Nenova, Zoya; Gesheva, Kostadinka

    Thin films of transition metals oxides are studied and comparison is made for two types of mixed precursors, first containing only hexacarbonyls, and second containing tungsten hexacarbonyl and vanadyl acetylacetonate (Vanadium (III) acetylacetonate). The best electrochromic material is WO3, although when deposited by Atmospheric Pressure Chemical Vapour Deposition (APCVD) films of WO3 grow very slowly. In production stage, the growth-rate is very important factor for assuring a flow-through process. Our previous investigations showed that addition of a small fraction of lower temperature precursor such as Mo(CO)6, or V(CO)6, to the basic precursor of W(CO)6 result in higher growth rate of films. Our recent studies on mixed WxV1-xO3 showed excellent substrate coverage and high growth-rate. V(CO)6 is a lower thermally stable precursor that allows the first nuclei-islands to be formed on the hot substrates which further facilitate the tungsten oxide film deposition. However V(CO)6 is much too expensive for large-scale production, thus we adopted another compound as precursor - vanadium acetylacetonate, expecting eventual growth-rate increase. The paper describes optical properties of films of vanadium oxide grown in result of utilizing the acetylacetonate. Besides, the paper describes our attempt to deposit mixed films of tungsten/vanadium using a mixed precursor of vanadyl acetylacetonate and tungsten hexacarbonyl. To our knowledge this is a new mixed precursor based on largely used single precursors namely W(CO)6 and Vanadium acetylacetonate. Efforts were needed to adjust the mixed precursor ratio, keeping in mind the vapour pressures of the two chemicals at the deposition temperatures used. The paper presents the results for the visible transmittance and the film material modulation properties, studied by FTIR and Raman spectra. The dependence of the films optical behavior on APCVD process parameters, substrate temperatures, vapour source temperature

  20. Survey of Worldwide Light Water Reactor Experience with Mixed Uranium-Plutonium Oxide Fuel

    SciTech Connect

    Cowell, B.S.; Fisher, S.E.

    1999-02-01

    The US and the Former Soviet Union (FSU) have recently declared quantities of weapons materials, including weapons-grade (WG) plutonium, excess to strategic requirements. One of the leading candidates for the disposition of excess WG plutonium is irradiation in light water reactors (LWRs) as mixed uranium-plutonium oxide (MOX) fuel. A description of the MOX fuel fabrication techniques in worldwide use is presented. A comprehensive examination of the domestic MOX experience in US reactors obtained during the 1960s, 1970s, and early 1980s is also presented. This experience is described by manufacturer and is also categorized by the reactor facility that irradiated the MOX fuel. A limited summary of the international experience with MOX fuels is also presented. A review of MOX fuel and its performance is conducted in view of the special considerations associated with the disposition of WG plutonium. Based on the available information, it appears that adoption of foreign commercial MOX technology from one of the successful MOX fuel vendors will minimize the technical risks to the overall mission. The conclusion is made that the existing MOX fuel experience base suggests that disposition of excess weapons plutonium through irradiation in LWRs is a technically attractive option.

  1. MCNP analysis of PNL split-table critical experiments containing mixed-oxide fuels

    SciTech Connect

    Abdurrahman, N.M.; Yavuz, M.; Radulescu, G.

    1997-12-01

    Pacific Northwest Laboratory (PNL) Split-Table Critical experiments containing mixed-oxide (MOX) fuels for various core configurations are studied using MCNP4A with the ENDF/B-VI continuous-energy library. These experiments were performed to provide necessary technical information and experimental criticality data that would serve as benchmark data in support of the liquid-metal fast breeder reactor program. Because of the current interest in the utilization of weapons-grade plutonium in the form of MOX fuel in light water reactors, such experimental data are extremely important for checking the performance of the modem computational tools. The {sup 239}Pu content in plutonium of the PNL MOX fuels is {approximately}91 wt%, which is very close to that of the weapons-grade {sup 239}Pu. The MOX fuels used in these critical experiments consist of 30.0, 14.62, and 7.89 wt% Pu and N{sub H}/(N{sub Pu} + Nu) moderation ratios (MRs) of 47.4, 30.6, and 51.8, respectively.

  2. Integrated demonstration of molten salt oxidation with salt recycle for mixed waste treatment

    SciTech Connect

    Hsu, P.C.

    1997-11-01

    Molten Salt Oxidation (MSO) is a thermal, nonflame process that has the inherent capability of completely destroying organic constituents of mixed wastes, hazardous wastes, and energetic materials while retaining inorganic and radioactive constituents in the salt. For this reason, MSO is considered a promising alternative to incineration for the treatment of a variety of organic wastes. Lawrence Livermore National Laboratory (LLNL) has prepared a facility and constructed an integrated pilot-scale MSO treatment system in which tests and demonstrations are performed under carefully controlled (experimental) conditions. The system consists of a MSO processor with dedicated off-gas treatment, a salt recycle system, feed preparation equipment, and equipment for preparing ceramic final waste forms. This integrated system was designed and engineered based on laboratory experience with a smaller engineering-scale reactor unit and extensive laboratory development on salt recycle and final forms preparation. In this paper we present design and engineering details of the system and discuss its capabilities as well as preliminary process demonstration data. A primary purpose of these demonstrations is identification of the most suitable waste streams and waste types for MSO treatment.

  3. Development of ORIGEN Libraries for Mixed Oxide (MOX) Fuel Assembly Designs

    DOE PAGESBeta

    Mertyurek, Ugur; Gauld, Ian C.

    2015-12-24

    In this research, ORIGEN cross section libraries for reactor-grade mixed oxide (MOX) fuel assembly designs have been developed to provide fast and accurate depletion calculations to predict nuclide inventories, radiation sources and thermal decay heat information needed in safety evaluations and safeguards verification measurements of spent nuclear fuel. These ORIGEN libraries are generated using two-dimensional lattice physics assembly models that include enrichment zoning and cross section data based on ENDF/B-VII.0 evaluations. Using the SCALE depletion sequence, burnup-dependent cross sections are created for selected commercial reactor assembly designs and a representative range of reactor operating conditions, fuel enrichments, and fuel burnup.more » The burnup dependent cross sections are then interpolated to provide problem-dependent cross sections for ORIGEN, avoiding the need for time-consuming lattice physics calculations. The ORIGEN libraries for MOX assembly designs are validated against destructive radiochemical assay measurements of MOX fuel from the MALIBU international experimental program. This program included measurements of MOX fuel from a 15 × 15 pressurized water reactor assembly and a 9 × 9 boiling water reactor assembly. The ORIGEN MOX libraries are also compared against detailed assembly calculations from the Phase IV-B numerical MOX fuel burnup credit benchmark coordinated by the Nuclear Energy Agency within the Organization for Economic Cooperation and Development. Finally, the nuclide compositions calculated by ORIGEN using the MOX libraries are shown to be in good agreement with other physics codes and with experimental data.« less

  4. Development of ORIGEN Libraries for Mixed Oxide (MOX) Fuel Assembly Designs

    SciTech Connect

    Mertyurek, Ugur; Gauld, Ian C.

    2015-12-24

    In this research, ORIGEN cross section libraries for reactor-grade mixed oxide (MOX) fuel assembly designs have been developed to provide fast and accurate depletion calculations to predict nuclide inventories, radiation sources and thermal decay heat information needed in safety evaluations and safeguards verification measurements of spent nuclear fuel. These ORIGEN libraries are generated using two-dimensional lattice physics assembly models that include enrichment zoning and cross section data based on ENDF/B-VII.0 evaluations. Using the SCALE depletion sequence, burnup-dependent cross sections are created for selected commercial reactor assembly designs and a representative range of reactor operating conditions, fuel enrichments, and fuel burnup. The burnup dependent cross sections are then interpolated to provide problem-dependent cross sections for ORIGEN, avoiding the need for time-consuming lattice physics calculations. The ORIGEN libraries for MOX assembly designs are validated against destructive radiochemical assay measurements of MOX fuel from the MALIBU international experimental program. This program included measurements of MOX fuel from a 15 × 15 pressurized water reactor assembly and a 9 × 9 boiling water reactor assembly. The ORIGEN MOX libraries are also compared against detailed assembly calculations from the Phase IV-B numerical MOX fuel burnup credit benchmark coordinated by the Nuclear Energy Agency within the Organization for Economic Cooperation and Development. Finally, the nuclide compositions calculated by ORIGEN using the MOX libraries are shown to be in good agreement with other physics codes and with experimental data.

  5. Porous mixed metal oxides: design, formation mechanism, and application in lithium-ion batteries

    NASA Astrophysics Data System (ADS)

    Wu, Fangfang; Bai, Jing; Feng, Jinkui; Xiong, Shenglin

    2015-10-01

    The relentless pursuit of new electrode materials for lithium ion batteries (LIBs) has been conducted for decades. Structures with either porous or nanostructure configurations have been confirmed as advantageous candidates for energy storage/conversion applications. The integration of the two features into one structure can provide another chance to improve the electroactivities. Recently, single-phased mixed metal oxides (MMOs) containing different metal cations, in particular, have confirmed high electrochemical activities because of their complex chemical composition, interfacial effects, and the synergic effects of the multiple metal species. In this review, we will focus on recent research advances of MMOs with porous architectures as anode materials in the matter of structural arrangement and compositional manipulation. Moreover, the application of self-supported MMO-based porous structures as LIB anodes is also explained herein. More importantly, investigations on the synthetic system and formation mechanism of porous MMOs will be highlighted. Some future trends for the innovative design of new electrode materials are also discussed in this review. The challenges and prospects will draw many researchers' attention.

  6. Defect physics vis-à-vis electrochemical performance in layered mixed-metal oxide cathode materials

    NASA Astrophysics Data System (ADS)

    Hoang, Khang; Johannes, Michelle

    Layered mixed-metal oxides with different compositions of (Ni,Co,Mn) [NCM] or (Ni,Co,Al) [NCA] have been used in commercial lithium-ion batteries. Yet their defect physics and chemistry is still not well understood, despite having important implications for the electrochemical performance. In this presentation, we report a hybrid density functional study of intrinsic point defects in the compositions LiNi1/3Co1/3Mn1/3O2 (NCM1/3) and LiNi1/3Co1/3Al1/3O2 (NCA1/3) which can also be regarded as model compounds for NCM and NCA. We will discuss defect landscapes in NCM1/3 and NCA1/3 under relevant synthesis conditions with a focus on the formation of metal antisite defects and its implications on the electrochemical properties and ultimately the design of NCM and NCA cathode materials.

  7. Catalytic combustion of chlorobenzene over Mn-Ce-La-O mixed oxide catalysts.

    PubMed

    Yu, Dai; Xingyi, Wang; Dao, Li; Qiguang, Dai

    2011-04-15

    A series of Mn(x)-CeLa mixed oxide catalysts with different compositions prepared by sol-gel method were tested for the catalytic combustion of chlorobenzene (CB), as a model of chlorinated aromatics. Mn(x)-CeLa catalysts with the ratios of Mn/(Mn + Ce + La) in the range from 0.69 to 0.8 were found to possess high catalytic activity in the catalytic combustion of CB. The stability and deactivation of Mn(x)-CeLa catalysts were studied by other assistant experiments. Mn(x)-CeLa catalysts can deactivate below 330 °C, due to the strong adsorption of Cl species produced during the decomposition of CB. Nevertheless, the increase in oxygen concentration can enhance the resistance to Cl poisoning through the reaction of surface oxygen species with residual chlorine. At 350 °C, high activity, good selectivity and desired stability were observed over Mn(x)-CeLa catalysts. PMID:21320750

  8. Improved layered mixed transition metal oxides for Li-ion batteries

    SciTech Connect

    Doeff, Marca M.; Conry, Thomas; Wilcox, James

    2010-03-05

    Recent work in our laboratory has been directed towards development of mixed layered transition metal oxides with general composition Li[Ni, Co, M, Mn]O2 (M=Al, Ti) for Li ion battery cathodes. Compounds such as Li[Ni1/3Co1/3Mn1/3]O2 (often called NMCs) are currently being commercialized for use in consumer electronic batteries, but the high cobalt content makes them too expensive for vehicular applications such as electric vehicles (EV), plug-in hybrid electric vehicles (PHEVs), or hybrid electric vehicles (HEVs). To reduce materials costs, we have explored partial or full substitution of Co with Al, Ti, and Fe. Fe substitution generally decreases capacity and results in poorer rate and cycling behavior. Interestingly, low levels of substitution with Al or Ti improve aspects of performance with minimal impact on energy densities, for some formulations. High levels of Al substitution compromise specific capacity, however, so further improvements require that the Ni and Mn content be increased and Co correspondingly decreased. Low levels of Al or Ti substitution can then be used offset negative effects induced by the higher Ni content. The structural and electrochemical characterization of substituted NMCs is presented in this paper.

  9. Bulk mixed ion electron conduction in amorphous gallium oxide causes memristive behaviour.

    PubMed

    Aoki, Yoshitaka; Wiemann, Carsten; Feyer, Vitaliy; Kim, Hong-Seok; Schneider, Claus Michael; Ill-Yoo, Han; Martin, Manfred

    2014-01-01

    In thin films of mixed ionic electronic conductors sandwiched by two ion-blocking electrodes, the homogeneous migration of ions and their polarization will modify the electronic carrier distribution across the conductor, thereby enabling homogeneous resistive switching. Here we report non-filamentary memristive switching based on the bulk oxide ion conductivity of amorphous GaOx (x~1.1) thin films. We directly observe reversible enrichment and depletion of oxygen ions at the blocking electrodes responding to the bias polarity by using photoemission and transmission electron microscopies, thus proving that oxygen ion mobility at room temperature causes memristive behaviour. The shape of the hysteresis I-V curves is tunable by the bias history, ranging from narrow counter figure-eight loops to wide hysteresis, triangle loops as found in the mathematically derived memristor model. This dynamical behaviour can be attributed to the coupled ion drift and diffusion motion and the oxygen concentration profile acting as a state function of the memristor. PMID:24632885

  10. Chemical bonds and vibrational properties of ordered (U, Np, Pu) mixed oxides

    NASA Astrophysics Data System (ADS)

    Yang, Yu; Zhang, Ping

    2013-01-01

    We use density functional theory +U to investigate the chemical bonding characters and vibrational properties of the ordered (U, Np, Pu) mixed oxides (MOXs), UNpO4,NpPuO4, and UPuO4. It is found that the 5f electronic states of different actinide elements keep their localized characters in all three MOXs. The occupied 5f electronic states of different actinide elements do not overlap with each other and tend to distribute over the energy band gap of the other actinide element's 5f states. As a result, the three ordered MOXs all show smaller band gaps than those of the component dioxides, with values of 0.91, 1.47, and 0.19 eV for UNpO4,NpPuO4, and UPuO4, respectively. Through careful charge density analysis, we further show that the U-O and Pu-O bonds in MOXs show more ionic character than in UO2 and PuO2, while the Np-O bonds show more covalent character than in NpO2. The change in covalencies in the chemical bonds leads to vibrational frequencies of oxygen atoms that are different in MOXs.

  11. Improved mixed oxide fuel calculations with the evaluated nuclear data library JEFF-3.2

    DOE PAGESBeta

    Noguere, G.; Bernard, D.; Blaise, P.; Bouland, O.; Leal, Luiz C.; Leconte, P.; Litaize, O.; Peneliau, Y.; Roque, B.; Santamarina, A.; et al

    2016-02-01

    In this study, an overestimation of the keff values for mixed oxide (MOX) fuels was identified with Monte Carlo (TRIPOLI-4) and deterministic (APOLLO2) calculations based on the Joint Evaluated Fission and Fusion (JEFF) evaluated nuclear data library. The overestimation becomes sizeable with Pit aging, reaching a reactivity change of Delta(p)similar or equal to+700 pcm for integral measurements carried out with MOX fuel containing a large amount of americium. This bias was observed for various critical configurations performed in the zero power reactor EOLE of the Commissariat a l'energie atomique et aux energies alternatives (CEA), Cadarache, France. The present work focusesmore » on the improvements achieved with the new 239PU and 241Am evaluated nuclear data files available in the latest version of the JEFF library (JEFF-3.2). The resolved resonance range of the plutonium evaluation was reevaluated at Oak Ridge National Laboratory (ORNL), Oak Ridge, Tennessee, with the Ski/NH code in collaboration with CEA Cadarache. The resonance parameters of the americium evaluation were obtained with the REFIT code in collaboration with the research institutes Institute for Reference Materials and Measurements aRmm, Geel, Belgium, and Institut de recherche sur les lois fondamentales de l'Univers ofio, Saclay, France.« less

  12. International safeguards for a modern MOX (mixed-oxide) fuel fabrication facility

    SciTech Connect

    Pillay, K.K.S.; Stirpe, D.; Picard, R.R.

    1987-03-01

    Bulk-handling facilities that process plutonium for commercial fuel cycles offer considerable challenges to nuclear materials safeguards. Modern fuel fabrication facilities that handle mixed oxides of plutonium and uranium (MOX) often have large inventories of special nuclear materials in their process lines and in storage areas for feed and product materials. In addition, the remote automated processing prevalent at new MOX facilities, which is necessary to minimize radiation exposures to personnel, tends to limit access for measurements and inspections. The facility design considered in this study incorporates all these features as well as state-of-the-art measurement technologies for materials accounting. Key elements of International Atomic Energy Agency (IAEA) safeguards for such a fuel-cycle facility have been identified in this report, and several issues of primary importance to materials accountancy and IAEA verifications have been examined. We have calculated detection sensitivities for abrupt and protracted diversions of plutonium assuming a single materials balance area for all processing areas. To help achieve optimal use of limited IAEA inspection resources, we have calculated sampling plans for attributes/variables verification. In addition, we have demonstrated the usefulness of calculating sigma/sub (MUF-D)/ and detection probabilities corresponding to specified material-loss scenarios and resource allocations. The data developed and the analyses performed during this study can assist both the facility operator and the IAEA in formulating necessary safeguards approaches and verification procedures to implement international safeguards for special nuclear materials.

  13. Solid dispersion of acetaminophen and poly(ethylene oxide) prepared by hot-melt mixing.

    PubMed

    Yang, Min; Wang, Peng; Huang, Chien-Yueh; Ku, M Sherry; Liu, Huiju; Gogos, Costas

    2010-08-16

    In this study, a model drug, acetaminophen (APAP), was melt mixed with poly(ethylene oxide) (PEO) using a Brabender mixer. APAP was found to recrystallize upon cooling to room temperature for all the drug loadings investigated. Higher drug loading leads to faster recrystallization rate. However, the morphology of the recrystallized drug crystals is identical in samples with different drug loadings and does not change with the storage time. To adjust the drug's dissolution rate, nanoclay Cloisite 15A and 30B were added into the binary mixture. The presence of either of the nanoclay dramatically accelerates the drug's recrystallization rate and slows down the drug's releasing rate. The drop of the releasing rate is mainly due to the decrease of wettability, as supported by the contact angle data. Data analysis of the dissolution results suggests that the addition of nanoclays changes the drug's release mechanism from erosion dominant to diffusion dominant. This study suggests that nanoclays may be utilized to tailor the drug's releasing rate and to improve the dosage form's stability by dramatically shortening the lengthy recrystallization process. PMID:20435110

  14. Calculational assessment of critical experiments with mixed oxide fuel pin arrays moderated by organic solution

    SciTech Connect

    Smolen, G.R.

    1987-01-01

    Critical experiments have been conducted with organic-moderated mixed oxide (MOX) fuel pin assemblies at the Pacific Northwest Laboratory (PNL) Critical Mass Laboratory (CML). These experiments are part of a joint exchange program between the United States Department of Energy (USDOE) and the Power Reactor and Nuclear Fuel Development Corporation (PNC) of Japan in the area of criticality data development. The purpose of these experiments is to benchmark computer codes and cross-section libraries and to assess the reactivity difference between systems moderated by water and those moderated by an organic solution. Past studies have indicated that some organic mixtures may be better moderators than water. This topic is of particular importance to the criticality safety of fuel processing plants where fissile material is dissolved in organic solutions during the solvent extraction process. In the past, it has been assumed that the codes and libraries benchmarked with water-moderated experiments were adequate when performing design and licensing studies of organic-moderated systems. Calculations presented in this paper indicated that the SCALE code system and the 27-energy-group cross-section accurately compute k-effectives for organic moderated MOX fuel-pin assemblies. Furthermore, the reactivity of an organic solution with a 32-vol-% TBP/68-vol-% NPH mixture in a heterogeneous configuration is the same, for practical purposes, as water. 5 refs.

  15. Structural Investigation of (U0.7Pu0.3)O2-x Mixed Oxides.

    PubMed

    Vigier, Jean-François; Martin, Philippe M; Martel, Laura; Prieur, Damien; Scheinost, Andreas C; Somers, Joseph

    2015-06-01

    Uranium-plutonium mixed oxide containing 30% of plutonium is a candidate fuel for several fast neutron and accelerator driven reactor systems. In this work, a detailed structural investigation on sol-gel synthesized stoichiometric U0.7Pu0.3O2.00 and substoichiometric U0.7Pu0.3O2-x, using X-ray diffraction (XRD), oxygen 17 magic angle spinning nuclear magnetic resonance ((17)O MAS NMR) and X-ray absorption spectroscopy is described. As observed by XRD, the stoichiometric U0.7Pu0.3O2.00 is monophasic with a lattice parameter in good agreement with Vegard's law, while the substoichiometric U0.7Pu0.3O2-x material is biphasic. Solid solution ideality in terms of a random distribution of metal atoms is proven for U0.7Pu0.3O2.00 with (17)O MAS NMR. X-ray absorption near-edge structure (XANES) spectroscopy shows the presence of plutonium(III) in U0.7Pu0.3O2-x. Extended X-ray absorption fine-structure (EXAFS) spectroscopy indicates a similar local structure around both cations, and comparison with XRD indicates a close similarity between uranium and plutonium local structures and the long-range ordering. PMID:25984750

  16. Mg-Al layered double hydroxides (LDHs) and their derived mixed oxides grown by laser techniques

    NASA Astrophysics Data System (ADS)

    Matei, A.; Birjega, R.; Nedelcea, A.; Vlad, A.; Colceag, D.; Ionita, M. D.; Luculescu, C.; Dinescu, M.; Zavoianu, R.; Pavel, O. D.

    2011-04-01

    Layered double hydroxides (LDHs) have been widely studied due to their applications as multifunctional materials, catalysts, host materials, anionic exchangers, adsorbents for environmental contaminants and for the immobilization of biological materials. As thin films, LDHs are good candidates for novel applications as sensors, corrosion resistant coatings or components in electro optical devices. For these applications, lamellar orientation-controlled film has to be fabricated. In this work, the successful deposition of LDH and their derived mixed oxides thin films by laser techniques is reported. Pulsed laser deposition (PLD) and matrix assisted pulsed laser evaporation (MAPLE) were the methods used for thin films deposition. The ability of Mg-Al LDHs as a carrier for metallic particles (Ag) has been considered. Frozen targets containing 10% powder in water were used for MAPLE, while for PLD the targets consisted in dry-pressed pellets. The structure and the surface morphology of the deposited films were examined by X-ray Diffraction, Atomic Force Microscopy, Scanning Electron Microscopy and Secondary Ion Mass Spectrometry.

  17. Americium characterization by X-ray fluorescence and absorption spectroscopy in plutonium uranium mixed oxide

    NASA Astrophysics Data System (ADS)

    Degueldre, Claude; Cozzo, Cedric; Martin, Matthias; Grolimund, Daniel; Mieszczynski, Cyprian

    2013-06-01

    Plutonium uranium mixed oxide (MOX) fuels are currently used in nuclear reactors. The actinides in these fuels need to be analyzed after irradiation for assessing their behaviour with regard to their environment and the coolant. In this work the study of the atomic structure and next-neighbour environment of Am in the (Pu,U)O2 lattice in an irradiated (60 MW d kg-1) MOX sample was performed employing micro-X-ray fluorescence (µ-XRF) and micro-X-ray absorption fine structure (µ-XAFS) spectroscopy. The chemical bonds, valences and stoichiometry of Am (˜0.66 wt%) are determined from the experimental data gained for the irradiated fuel material examined in its peripheral zone (rim) of the fuel. In the irradiated sample Am builds up as Am3+ species within an [AmO8]13- coordination environment (e.g. >90%) and no (<10%) Am(IV) or (V) can be detected in the rim zone. The occurrence of americium dioxide is avoided by the redox buffering activity of the uranium dioxide matrix.

  18. Mixed-Valent Mn16-Containing Heteropolyanions: Tuning of Oxidation State and Associated Physicochemical Properties.

    PubMed

    Haider, Ali; Ibrahim, Masooma; Bassil, Bassem S; Carey, Akina M; Viet, Anh Nguyen; Xing, Xiaolin; Ayass, Wassim W; Miñambres, Juan F; Liu, Rongji; Zhang, Guangjin; Keita, Bineta; Mereacre, Valeriu; Powell, Annie K; Balinski, Kamil; N'Diaye, Alpha T; Küpper, Karsten; Chen, Han-Yi; Stimming, Ulrich; Kortz, Ulrich

    2016-03-21

    The two 16-manganese-containing, Keggin-based 36-tungsto-4-silicates [Mn(III)10Mn(II)6O6(OH)6(PO4)4(A-α-SiW9O34)4](28-) (1) and [Mn(III)4Mn(II)12(OH)12(PO4)4(A-α-SiW9O34)4](28-) (2) have been prepared by reaction of the trilacunary Keggin precursor [A-α-SiW9O34](10-) with either Mn(OOCCH3)3·2H2O (for 1) or MnCl2·4H2O (for 2), in aqueous phosphate solution at pH 9. Polyanions 1 and 2 comprise mixed-valent, cationic {Mn(III)10Mn(II)6O6(OH)6}(24+) and {Mn(III)4Mn(II)12(OH)12}(24+) cores, respectively, encapsulated by four phosphate groups and four {SiW9} units in a tetrahedral fashion. Both polyanions were structurally and compositionally characterized by single-crystal XRD, IR, thermogravimetric analysis, and X-ray absorption spectroscopy. Furthermore, studies were performed probing the magnetic, electrochemical, oxidation catalytic, and Li-ion battery performance of 1 and 2. PMID:26931312

  19. Neutron Emission Characteristics of Two Mixed-Oxide Fuels: Simulations and Initial Experiments

    SciTech Connect

    D. L. Chichester; S. A. Pozzi; J. L. Dolan; M. Flaska; J. T. Johnson; E. H. Seabury; E. M. Gantz

    2009-07-01

    Simulations and experiments have been carried out to investigate the neutron emission characteristics of two mixed-oxide (MOX) fuels at Idaho National Laboratory (INL). These activities are part of a project studying advanced instrumentation techniques in support of the U.S. Department of Energy's Fuel Cycle Research and Development program and it's Materials Protection, Accounting, and Control for Transmutation (MPACT) campaign. This analysis used the MCNP-PoliMi Monte Carlo simulation tool to determine the relative strength and energy spectra of the different neutron source terms within these fuels, and then used this data to simulate the detection and measurement of these emissions using an array of liquid scintillator neutron spectrometers. These calculations accounted for neutrons generated from the spontaneous fission of the actinides in the MOX fuel as well as neutrons created via (alpha,n) reactions with oxygen in the MOX fuel. The analysis was carried out to allow for characterization of both neutron energy as well as neutron coincidences between multiple detectors. Coincidences between prompt gamma rays and neutrons were also analyzed. Experiments were performed at INL with the same materials used in the simulations to benchmark and begin validation tests of the simulations. Data was collected in these experiments using an array of four liquid scintillators and a high-speed waveform digitizer. Advanced digital pulse-shape discrimination algorithms were developed and used to collect this data. Results of the simulation and modeling studies are presented together with preliminary results from the experimental campaign.

  20. Nitric Oxide PLIF Visualization of Simulated Fuel-Air Mixing in a Dual-Mode Scramjet

    NASA Technical Reports Server (NTRS)

    Cantu, Luca M. L.; Gallo, Emanuela C. A.; Cutler, Andrew D.; Bathel, Brett F.; Danehy, Paul M.; Rockwell, Robert D.; Goyne, Christopher P.; McDaniel, James C.

    2015-01-01

    Nitric oxide (NO) planar induced laser fluorescence (PLIF) measurements have been performed in a small scale scramjet combustor at the University of Virginia Aerospace Research Laboratory at nominal simulated Mach 5 flight. A mixture of NO and N2 was injected at the upstream end of the inlet isolator as a surrogate for ethylene fuel, and the mixing of this fuel simulant was studied with and without a shock train. The shock train was produced by an air throttle, which simulated the blockage effects of combustion downstream of the cavity flame holder. NO PLIF signal was imaged in a plane orthogonal to the freestream at the leading edge of the cavity. Instantaneous planar images were recorded and analyzed to identify the most uniform cases, which were achieved by varying the location of the fuel injection and shock train. This method was used to screen different possible fueling configurations to provide optimized test conditions for follow-on combustion measurements using ethylene fuel. A theoretical study of the selected NO rotational transitions was performed to obtain a LIF signal that is linear with NO mole fraction and approximately independent of pressure and temperature.

  1. Synthesis of Glycerol Carbonate by Transesterification of Glycerol with Urea Over Zn/Al Mixed Oxide.

    PubMed

    Ryu, Young Bok; Baek, Jae Ho; Kim, Yangdo; Lee, Man Sig

    2015-01-01

    Reactions of glycerol carbonate using glycerol and urea have been carried out previously using ZnSO4 and ZnO catalysts, and high yields have been reported using ZnSO4 as catalyst. However, this salt is soluble in glycerol, and recycling of catalyst is difficult after the reaction. In this study, we prepared a mixed metal oxide catalyst using Zn and Al, and this catalyst consisted of a mixture of ZnO and ZnAl2O4. We confirmed the conversion of glycerol and the yield of glycerol carbonate of the amount of Al. As a result, we obtained a yield of 82.3% and a conversion of 82.7%. In addition we obtained high yield in recycling of catalyst. The yield of the glycerol carbonate increases with an increase of acid and base site of catalysts and the highest catalytic activity was obtained when acid/base ratio was approx. 1. From this result, we may conclude that the acid and base site density and ratio of catalysts were very important parameters in the synthesis of glycerol carbonate from urea and glycerol. PMID:26328352

  2. Luminescence studies of rare earth doped yttrium gadolinium mixed oxide phosphor

    NASA Astrophysics Data System (ADS)

    Som, S.; Choubey, A.; Sharma, S. K.

    2012-09-01

    This paper reports the photoluminescence and thermoluminescence properties of gamma ray induced rare earth doped yttrium gadolinium mixed oxide phosphor. The europium (Eu3+) was used as rare earth dopant. The phosphor was prepared by chemical co-precipitation method according to the formula (Y2-x-yGdx) O3: Euy3+ (x=0.5; y=0.05). The photoluminescence emission spectrum of the prepared phosphor shows intense peaks in the red region at 615 nm for 5D0→7F2 transitions and the photoluminescence excitation spectra show a broad band located around 220-270 nm for the emission wavelength fixed at 615 nm. The thermoluminescence studies were carried out after irradiating the phosphor by gamma rays in the dose range from 100 Gy to 1 KGy. In the thermoluminescence glow curves, one single peak was observed at about 300 °C of which the intensity increases linearly in the studied dose range of gamma rays. The glow peak was deconvoluted by GlowFit program and the kinetic parameters associated with the deconvoluted peaks were calculated. The kinetic parameters were also calculated by various glow curve shape and heating rate methods.

  3. Synthesis, characterization and humidity sensing properties of Cu-Sr-Al mixed metal oxide composites

    SciTech Connect

    Vijaya, J. Judith Kennedy, L. John; Sekaran, G.; Nagaraja, K.S.

    2008-02-05

    Copper-strontium-aluminum mixed metal oxide composites prepared by sol-gel technique was investigated for humidity sensing properties. X-ray diffraction, scanning electron microscopy (SEM), FT-IR spectroscopy and nitrogen adsorption/desorption isotherm at 77 K was employed, respectively, to identify the structural phases, surface morphology, vibrational stretching frequencies and BET surface area of the composites. The composites were prepared with the mole ratios of Cu:Sr as (0.0:1.0, 0.2:0.8, 0.4:06, 0.6:0.4, 0.8:0.2 and 1.0:0.0) keeping the aluminium mole ratio as constant and were labeled as CuSA1, CuSA2, CuSA3, CuSA4, CuSA5 and CuSA6, respectively. The samples sintered at 900 deg. C for 5 h, were subjected to dc resistance measurements as a function of relative humidity (RH) in the range 5-98% and the results revealed that the sensitivity factor of CuSA5 possessed the highest humidity sensitivity of 42,000 while the pure composite copper aluminate (CuSA1) and strontium aluminate (CuSA6) possessed comparatively low sensitivities 10,000 and 20,000, respectively. The response and recovery characteristics of the composites CuSA1, CuSA5 and CuSA6 were studied.

  4. Molecular properties of protonated homogeneous and mixed carbon oxide and carbon dioxide clusters

    NASA Astrophysics Data System (ADS)

    Szymczak, Jaroslaw J.; Roszak, Szczepan; Gora, Robert W.; Leszczynski, Jerzy

    2003-10-01

    The molecular structures and characteristics of CO and CO2 protonated homogeneous and mixed complexes were studied by theoretical, ab initio calculations. The thermodynamics, vibrational properties, charge distribution, and interaction energy decomposition components are investigated as a function of the increasing size of clusters. The study reveals the similarities and differences between homogeneous protonated carbon oxide and protonated carbon dioxide clusters. In the first-order approximation the structural differences between (CO)nH+ and (CO2)nH+ clusters are the consequence of the electronic charge distribution in the protonated OCH+ and OCOH+ core fragments. The symmetry of protonated dimers, constituting the cationic core of clusters is the second important factor in determining the overall structure of extended complexes. The OCH+ as well as the OCOH+ fragments are stabilized by cluster formation. The structures and energetics of complexes emerge as a balance between competing electrostatic, exchange, and covalent interactions. The directional covalent forces prevail and enforce the structure of the complexes, however. A universal approach is proposed which allows for the computation of interaction energies for chemical reactions involving significant relaxation of the reactants.

  5. Mesoporous mixed metal oxides derived from P123-templated Mg-Al layered double hydroxides

    SciTech Connect

    Wang Jun; Zhou Jideng; Li Zhanshuang; He Yang; Lin Shuangshuang; Liu Qi; Zhang Milin; Jiang Zhaohua

    2010-11-15

    We report the preparation of mesoporous mixed metal oxides (MMOs) through a soft template method. Different amounts of P123 were used as structure directing agent to synthesize P123-templated Mg-Al layered double hydroxides (LDHs). After calcination of as-synthesized LDHs at 500 {sup o}C, the ordered mesopores were obtained by removal of P123. The mesoporous Mg-Al MMOs fabricated by using 2 wt% P123 exhibited a high specific surface area of 108.1 m{sup 2}/g, and wide distribution of pore size (2-18 nm). An investigation of the 'memory effect' of the mesoporous MMOs revealed that they were successfully reconstructed to ibuprofen intercalated LDHs having different gallery heights, which indicated different intercalation capacities. Due to their mesoporosity these unique MMOs have particular potential as drug or catalyst carriers. - Graphical abstract: Ordered mesoporous Mg-Al MMOs can be obtained through the calcination of P123-templated Mg-Al-CO{sub 3} LDHs. The pore diameter is 2.2 nm. At the presence of ibuprofen, the Mg-Al MMOs can recover to Mg-Al-IBU LDHs, based on its 'remember effect'. Display Omitted

  6. Removal of exhausted oils by adsorption on mixed Ca and Mg oxides.

    PubMed

    Solisio, Carlo; Lodi, Alessandra; Converti, Attilio; Del, Borghi Marco

    2002-02-01

    Adsorption tests were performed on two different exhausted oils to reduce their polluting and health hazard potential: a "water-insoluble oil", utilised for automotive engine lubrication, and an "emulsified" oil, used as coolant for metal-cutting tools. Dolomite, a low-cost recovery material, was used to prepare two effective adsorbents: (a) a mixed Ca and Mg oxide obtained by thermal decomposition of dolomite at 1800 degrees C, and (b) an activated material obtained by submitting this product to chemical treatment with HCl. Preliminary tests carried out with an excess of the former material showed that the insoluble oil was adsorbed with lower yield (Y = 0.40) than the soluble (emulsified) oil (Y = 0.60). The material activation with HCl remarkably improved the adsorption of soluble oil organic fraction (Y > 0.90), while only a little increase in the removal yield was observed for the insoluble oil (Y = 0.44). The results presented and discussed in this work pointed out that the products of dolomite calcination can successfully replace the conventional adsorbing materials in the removal of organic pollutants, with particular concern to exhausted soluble oils, which cannot usually be recycled, thus reducing the operational costs of their treatment. PMID:11848360

  7. Bulk mixed ion electron conduction in amorphous gallium oxide causes memristive behaviour

    NASA Astrophysics Data System (ADS)

    Aoki, Yoshitaka; Wiemann, Carsten; Feyer, Vitaliy; Kim, Hong-Seok; Schneider, Claus Michael; Ill-Yoo, Han; Martin, Manfred

    2014-03-01

    In thin films of mixed ionic electronic conductors sandwiched by two ion-blocking electrodes, the homogeneous migration of ions and their polarization will modify the electronic carrier distribution across the conductor, thereby enabling homogeneous resistive switching. Here we report non-filamentary memristive switching based on the bulk oxide ion conductivity of amorphous GaOx (x~1.1) thin films. We directly observe reversible enrichment and depletion of oxygen ions at the blocking electrodes responding to the bias polarity by using photoemission and transmission electron microscopies, thus proving that oxygen ion mobility at room temperature causes memristive behaviour. The shape of the hysteresis I-V curves is tunable by the bias history, ranging from narrow counter figure-eight loops to wide hysteresis, triangle loops as found in the mathematically derived memristor model. This dynamical behaviour can be attributed to the coupled ion drift and diffusion motion and the oxygen concentration profile acting as a state function of the memristor.

  8. O/M RATIO MEASUREMENT IN PURE AND MIXED OXIDE FULES - WHERE ARE WE NOW?

    SciTech Connect

    J. RUBIN; ET AL

    2000-12-01

    The oxygen-to-metal (O/M) ratio is one of the most critical parameters of nuclear fuel fabrication, and its measurement is closely monitored for manufacturing process control and to ensure the service behavior of the final product. Thermogravimetry is the most widely used method, the procedure for which has remained largely unchanged since its development some thirty years ago. It was not clear to us, however, that this method is still the optimum one in light of advances in instrumentation, and in the current regulatory environment, particularly with regard to waste management and disposal. As part of the MOX fuel fabrication program at Los Alamos, we conducted a comprehensive review of methods for O/M measurements in UO{sub 2}, PuO{sub 2} and mixed oxide fuels for thermal reactors. A concerted effort was made to access information not available in the open literature. We identified approximately thirty five experimental methods that (a) have been developed with the intent of measuring O/M, (b) provided O/M indirectly by suitable reduction of the measured data, or (c) could provide O/M data with suitable data reduction or when combined with other methods. We will discuss the relative strengths and weaknesses of these methods in their application to current routine and small-lot production environment.

  9. Room-temperature oxidation of hypostoichiometric uranium-plutonium mixed oxides U1-yPuyO2-x - A depth-selective approach

    NASA Astrophysics Data System (ADS)

    Vauchy, Romain; Robisson, Anne-Charlotte; Belin, Renaud C.; Martin, Philippe M.; Scheinost, Andreas C.; Hodaj, Fiqiri

    2015-10-01

    In the present work, TGA, XAS and XRD were used to evidence the spontaneous oxidation of biphasic U1-yPuyO2-x samples, with y = 0.28 and 0.45, at room temperature and upon exposure to low moisture and oxygen contents. The oxidation occurs within very short timescales (e.g. O/M ratio increasing from 1.94 to 1.98 within ∼1 μm surface layer in ∼50 h). The combined use of these three complementary methods offered a depth-selective approach from the sample's bulk to its surface and allowed a thorough understanding of the underlying processes involved during the formation of the oxidized layer and of its thickening with time. We believe our results to be of interest in the prospect of fabricating hypo-stoichiometric uranium-plutonium mixed oxides since mastering the oxygen content is a crucial point for many of the fuel properties.

  10. Decolourisation of Acid Orange 7 recalcitrant auto-oxidation coloured by-products using an acclimatised mixed bacterial culture.

    PubMed

    Bay, Hui Han; Lim, Chi Kim; Kee, Thuan Chien; Ware, Ismail; Chan, Giek Far; Shahir, Shafinaz; Ibrahim, Zaharah

    2014-03-01

    This study focuses on the biodegradation of recalcitrant, coloured compounds resulting from auto-oxidation of Acid Orange 7 (AO7) in a sequential facultative anaerobic-aerobic treatment system. A novel mixed bacterial culture, BAC-ZS, consisting of Brevibacillus panacihumi strain ZB1, Lysinibacillus fusiformis strain ZB2, and Enterococcus faecalis strain ZL bacteria were isolated from environmental samples. The acclimatisation of the mixed culture was carried out in an AO7 decolourised solution. The acclimatised mixed culture showed 98 % decolourisation within 2 h of facultative anaerobic treatment using yeast extract and glucose as co-substrate. Subsequent aerobic post treatment caused auto-oxidation reaction forming dark coloured compounds that reduced the percentage decolourisation to 73 %. Interestingly, further agitations of the mixed culture in the solution over a period of 48 h significantly decolourise the coloured compounds and increased the decolourisation percentage to 90 %. Analyses of the degradation compounds using UV-visible spectrophotometer, Fourier transform infrared spectroscopy (FTIR) and high performance liquid chromatography (HPLC) showed complete degradation of recalcitrant AO7 by the novel BAC-ZS. Phytotoxicity tests using Cucumis sativus confirmed the dye solution after post aerobic treatment were less toxic compared to the parent dye. The quantitative real-time PCR revealed that E. faecalis strain ZL was the dominant strain in the acclimatised mix culture. PMID:24293297

  11. Enhanced magnetization in highly crystalline and atomically mixed bcc Fe-Co nanoalloys prepared by hydrogen reduction of oxide composites

    NASA Astrophysics Data System (ADS)

    Sharif, Md Jafar; Yamauchi, Miho; Toh, Shoichi; Matsumura, Syo; Noro, Shin-Ichiro; Kato, Kenichi; Takata, Masaki; Tsukuda, Tatsuya

    2013-01-01

    FexCo100-x nanoalloys (NAs) with 20 <= x <= 80 were prepared by hydrogen reduction of Fe-Co oxide nano-composites, which were composed of mixed phases (or domains) of Fe2O3 and CoO. In situ X-ray diffraction (XRD) measurements using synchrotron radiation clearly showed development of a solid-solution Fe-Co phase by hydrogen reduction from the oxide composites. High-resolution transmission electron microscopy (TEM), high-angle annular dark-field scanning TEM and powder XRD revealed that Fe-Co NAs form a single crystal structure and the two elements are mixed homogeneously. The saturation magnetization depends on the size and metal composition and shows the highest value (250 emu g-1) for the Fe70Co30 NA in the size range of 30-55 nm, which is comparable to that of the Fe70Co30 bulk alloy (245 emu g-1). This high magnetization is attributable to high crystallinity and homogeneous mixing of constituent atoms, which are attained by thermal treatment of oxide phases under a hydrogen atmosphere.FexCo100-x nanoalloys (NAs) with 20 <= x <= 80 were prepared by hydrogen reduction of Fe-Co oxide nano-composites, which were composed of mixed phases (or domains) of Fe2O3 and CoO. In situ X-ray diffraction (XRD) measurements using synchrotron radiation clearly showed development of a solid-solution Fe-Co phase by hydrogen reduction from the oxide composites. High-resolution transmission electron microscopy (TEM), high-angle annular dark-field scanning TEM and powder XRD revealed that Fe-Co NAs form a single crystal structure and the two elements are mixed homogeneously. The saturation magnetization depends on the size and metal composition and shows the highest value (250 emu g-1) for the Fe70Co30 NA in the size range of 30-55 nm, which is comparable to that of the Fe70Co30 bulk alloy (245 emu g-1). This high magnetization is attributable to high crystallinity and homogeneous mixing of constituent atoms, which are attained by thermal treatment of oxide phases under a hydrogen

  12. Testing of the In Situ, Mixed Iron Oxide (IS-MIO) Alpha Removal Process

    SciTech Connect

    PETERS, THOMAS

    2004-06-29

    One of the throughput limitations for the Actinide Removal Process (ARP) and Salt Waste Processing Facility is the lengthy sorption time of plutonium on monosodium titanate(MST). Argonne National Laboratory (ANL) personnel proposed use of the In-Situ-Mixed Iron Oxide (IS-MIO) process, which removes strontium and actinides from waste streams with faster reaction kinetics than the MST process. The Savannah River National Laboratory and ANL received funding to develop the IS-MIO process for deployment at the Savannah River Site. Personnel performed simulant filtration tests to evaluate the process. They prepared 100 L of simulated SRS high level waste, added IS-MIO solutions to the simulated waste, mixed the solutions for four hours, and filtered the slurry in a bench-scale crossflow filter. The simulant was designed to maximize strontium solubility; it was not designed to match a particular tank composition. The crossflow filter was 3/8 inch internal diameter, 2 feet long, and possessing a 0.196 ft2 internal surface area. Researchers also performed a series of decontamination tests using actual waste. They prepared a multi-tank composite adjusted it to 5.6 M sodium, and allowed it to equilibrate. They used this material in six tests. Four of the tests used IS-MIO solutions, one of the tests used MST, and one test served as a control. In each test, personnel sampled the supernate at regular intervals and analyzed for strontium and actinides to determine the effective removal capability. The conclusions from this work follow. The IS-MIO solids do not produce an increase in filter flux. The increased flux observed in some comparisons is due to differences in operating conditions rather than to improved filterability of the IS-MIO solids. Filter flux with sludge and IS-MIO solids increases with increasing axial velocity. A similar correlation occurred with sludge and MST solids. The IS-MIO particles are initially larger than MST particles. Because of shear, by the end of

  13. Enhanced photoassisted water electrolysis using vertically oriented anodically fabricated Ti-Nb-Zr-O mixed oxide nanotube arrays.

    PubMed

    Allam, Nageh K; Alamgir, Faisal; El-Sayed, Mostafa A

    2010-10-26

    Self-ordered, highly oriented arrays of titanium-niobium-zirconium mixed oxide nanotube films were fabricated by the anodization of Ti(35)Nb(5)Zr alloy in aqueous and formamide electrolytes containing NH(4)F at room temperature. The nanostructure topology was found to depend on the nature of the electrolyte and the applied voltage. Our results demonstrate the possibility to grow mixed oxide nanotube array films possessing several-micrometer-thick layers by a simple and straightforward electrochemical route. The fabricated Ti-Nb-Zr-O nanotubes showed a ∼17.5% increase in the photoelectrochemical water oxidation efficiency as compared to that measured for pure TiO(2) nanotubes under UV illumination (100 mW/cm(2), 320-400 nm, 1 M KOH). This enhancement could be related to a combination of the effect of the thin wall of the fabricated Ti-Nb-Zr-O nanotubes (10 ± 2 nm) and the formation of Zr oxide and Nb oxide layers on the nanotube surface, which seems to slow down the electron-hole recombination in a way similar to that reported for Grätzel solar cells. PMID:20815374

  14. Catalytic oxidation of mixed wastes containing high organic content--emission reduction and the effect of steam.

    PubMed

    Chang, Li-Yang; Than, Chit; Morimoto, Hiromi; Williams, Philip G

    2006-01-01

    To resolve mixed organic and radioactive waste disposal problems, Lawrence Berkeley National Laboratory (LBNL) initiated a treatability study using the catalytic chemical oxidation (CCO) system to oxidize a mixed-waste stream and to confine tritium as part of LBNL's pollution prevention program. LBNL has also adopted a legal approach by seeking an equivalent waste-treatment determination for the CCO process, and by petitioning the United States Environmental Protection Agency (EPA) to delist F-coded treatment residues. The results of this study demonstrate that (1) the CCO process can treat aqueous wastes containing a broad range of organic chemicals and achieve more than 99.999% destruction efficiency; (2) greater than 99.9% trapping efficiency for tritiated water can be achieved using an emission-reduction system that also confines the vapor of hydrochloric acid or nitric acid to the liquid residue; and (3) neutralized treatment residues can be disposed of as low-level radioactive waste at a permitted facility after EPA has approved LBNL's petitions, or the tritium in the residues can be recycled. The high oxidation efficiency of the CCO process is mainly due to the optimized operating conditions of the CCO process and the combined effect of steam reforming in the oxidation cell and the catalytic oxidation of organic mixtures and CO in the Pt/Al2O3 catalyst bed. PMID:16401570

  15. Mixed-oxide fuel decay heat analysis for BWR LOCA safety evaluation

    SciTech Connect

    Chiang, R. T.

    2013-07-01

    The mixed-oxide (MOX) fuel decay heat behavior is analyzed for Boiling Water Reactor (BWR) Loss of Coolant Accident (LOCA) safety evaluation. The physical reasoning on why the decay heat power fractions of MOX fuel fission product (FP) are significantly lower than the corresponding decay heat power fractions of uranium-oxide (UOX) fuel FP is illustrated. This is primarily due to the following physical phenomena. -The recoverable energies per fission of plutonium (Pu)-239 and Pu-241 are significantly higher than those of uranium (U)-235 and U-238. Consequently, the fission rate required to produce the same amount of power in MOX fuel is significantly lower than that in UOX fuel, which leads to lower subsequent FP generation rate and associated decay heat power in MOX fuel than those in UOX fuel. - The effective FP decay energy per fission of Pu-239 is significantly lower than the corresponding effective FP decay energy per fission of U-235, e.g., Pu-239's 10.63 Mega-electron-Volt (MeV) vs. U-235's 12.81 MeV at the cooling time 0.2 second. This also leads to lower decay heat power in MOX fuel than that in UOX fuel. The FP decay heat is shown to account for more than 90% of the total decay heat immediately after shutdown. The FP decay heat results based on the American National Standard Institute (ANSI)/American Nuclear Society (ANS)-5.1-1979 standard method are shown very close to the corresponding FP decay heat results based on the ANSI/ANS-5.1-2005 standard method. The FP decay heat results based on the ANSI/ANS-5.1-1979 simplified method are shown very close to but mostly slightly lower than the corresponding FP decay heat results based on the ANSI/ANS-5.1-1971 method. The FP decay heat results based on the ANSI/ANS-5.1-1979 simplified method or the ANSI/ANS-5.1-1971 method are shown significantly larger than the corresponding FP decay heat results based on the ANSI/ANS-5.1-1979 standard method or the ANSI/ANS-5.1-2005 standard method. (authors)

  16. Mixed micellar nanoparticle of amphotericin B and poly styrene-block-poly ethylene oxide reduces nephrotoxicity but retains antifungal activity.

    PubMed

    Han, Kun; Miah, M A Jalil; Shanmugam, Srinivasan; Yong, Chul Soon; Choi, Han-Gon; Kim, Jung Ae; Yoo, Bong Kyu

    2007-10-01

    Mixed micellar nanoparticle consisting of amphotericin B (AmB) and poly styrene-block-poly ethylene oxide (PS-block-PEO) was prepared by high pressure homogenizer. Nephrotoxicity of the nanoparticle was investigated along with antifungal activity and self-aggregation status of the drug in the nanoparticle. Nephrotoxicity was markedly reduced when AmB was intravenously administered to rats as mixed micellar nanoparticle with PS-block-PEO in terms of transmission electron microscopy of tubular cells and creatinine clearance. Antifungal activity of AmB was not altered when the drug was in the form of mixed micellar nanoparticle compared to both conventional formulation and AmB micelle treated by same procedure without PS-block-PEO. Self-aggregation status of AmB molecules revealed monomeric in the mixed micellar nanoparticle with PS-block-PEO up to the therapeutic level of the drug (1-3 mM). The reduced nephrotoxicity of AmB in mixed micellar nanoparticle may be associated with the existence of the drug as monomeric form in the nanoparticle. Based on our result, formulation of AmB as mixed micellar nanoparticle with PS-block-PEO may be a promising alternative for the treatment of fungal diseases in patients who are at risk of renal dysfunction. PMID:18038914

  17. Surface chemistry study of RuO2/IrO2/TiO2 mixed-oxide electrodes.

    PubMed

    Barison, Simona; Daolio, Sergio; Fabrizio, Monica; De Battisti, Achille

    2004-01-01

    DSA metal oxide electrodes such as the RuO(2)/IrO(2)/TiO(2) mixed system are widely studied for their excellent electrocatalytic activity. In order to understand their catalytic properties, the comprehension of the surface chemistry involved during electrochemical treatments is crucial. With this aim, RuO(2)/IrO(2)/TiO(2) mixed-oxide electrodes having various noble metal contents were studied by means of secondary ion mass spectrometry (SIMS). In particular, cathodic and anodic polarization and O(2) evolution reactions were carried out to test the electrode behaviour and SIMS analyses were performed after all these treatments. In this way, surface changes induced by electrochemical treatments and depending on electrode composition were widely investigated by SIMS, revealing, for example, the presence of hydration or preferential dissolution phenomena induced by electrochemical processing. PMID:14755612

  18. Mixed metal oxides for dye-sensitized solar cell using zinc titanium layered double hydroxide as precursor

    NASA Astrophysics Data System (ADS)

    Liu, Jianqiang; Qin, Yaowei; Zhang, Liangji; Xiao, Hongdi; Song, Jianye; Liu, Dehe; Leng, Mingzhe; Hou, Wanguo; Du, Na

    2013-12-01

    Mixed metal oxides (MMO) are always obtained from layered double hydroxide (LDH) by thermal decomposition. In the present work, a zinc titanium LDH with the zinc titanium molar ratio of 4.25 was prepared by urea method and ZnO-based mixed oxides were obtained by calcining at or over 500°C. The MMO was used as electrodes for dye sensitized solar cell (DSSC). The cells constructed by films of prepared composite materials using a N719 as dye were prepared. The efficiency values of these cells are 0.691%, 0.572% and 0.302% with MMO prepared at 500, 600 and 700°C, respectively.

  19. Use of Raman spectroscopy to assess the efficiency of MgAl mixed oxides in removing cyanide from aqueous solutions

    NASA Astrophysics Data System (ADS)

    Cosano, Daniel; Esquinas, Carlos; Jiménez-Sanchidrián, César; Ruiz, José Rafael

    2016-02-01

    Calcining magnesium/aluminium layered double hydroxides (Mg/Al LDHs) at 450 °C provides excellent sorbents for removing cyanide from aqueous solutions. The process is based on the "memory effect" of LDHs; thus, rehydrating a calcined LDH in an aqueous solution restores its initial structure. The process, which conforms to a first-order kinetics, was examined by Raman spectroscopy. The metal ratio of the LDH was found to have a crucial influence on the adsorption capacity of the resulting mixed oxide. In this work, Raman spectroscopy was for the first time use to monitor the adsorption process. Based on the results, this technique is an effective, expeditious choice for the intended purpose and affords in situ monitoring of the adsorption process. The target solids were characterized by using various instrumental techniques including X-ray diffraction spectroscopy, which confirmed the layered structure of the LDHs and the periclase-like structure of the mixed oxides obtained by calcination.

  20. Preparation and characterization of vanadia-titania mixed oxide for immobilization of Serratia rubidaea CCT 5732 and Klebsiella marcescens bacteria

    SciTech Connect

    Saragiotto Colpini, Leda Maria Correia Goncalves, Regina A.; Goncalves, Jose Eduardo; Maieru Macedo Costa, Creusa

    2008-08-04

    Vanadia-titania mixed oxide was synthesized by sol-gel method and characterized by several techniques. Texturally, it is formed by mesopores and presents high-specific surface area and controlled porosity. Scanning electron microscopy revealed that vanadium is homogeneously distributed in the material. Structurally, it was possible to identify characteristic V=O stretching bands by IR. The analysis of X-ray diffraction showed that the material, particularly vanadium, is highly dispersed. Application experiments were carried out through the immobilization of Serratia rubidae CCT 5732 and Klebsiella marcescens bacteria by adsorption on the surface of mixed oxide. The micrographies revealed that the bacteria were adsorbed on the entire support, with average surface densities of 8.55 x 10{sup 11} cells/m{sup 2} (Serratia rubidae CCT 5732) and 3.40 x 10{sup 11} cells/m{sup 2} (K. marcescens)

  1. 3D carbon/cobalt-nickel mixed-oxide hybrid nanostructured arrays for asymmetric supercapacitors.

    PubMed

    Zhu, Jianhui; Jiang, Jian; Sun, Zhipeng; Luo, Jingshan; Fan, Zhanxi; Huang, Xintang; Zhang, Hua; Yu, Ting

    2014-07-23

    The electrochemical performance of supercapacitors relies not only on the exploitation of high-capacity active materials, but also on the rational design of superior electrode architectures. Herein, a novel supercapacitor electrode comprising 3D hierarchical mixed-oxide nanostructured arrays (NAs) of C/CoNi3 O4 is reported. The network-like C/CoNi3 O4 NAs exhibit a relatively high specific surface area; it is fabricated from ultra-robust Co-Ni hydroxide carbonate precursors through glucose-coating and calcination processes. Thanks to their interconnected three-dimensionally arrayed architecture and mesoporous nature, the C/CoNi3 O4 NA electrode exhibits a large specific capacitance of 1299 F/g and a superior rate performance, demonstrating 78% capacity retention even when the discharge current jumps by 100 times. An optimized asymmetric supercapacitor with the C/CoNi3 O4 NAs as the positive electrode is fabricated. This asymmetric supercapacitor can reversibly cycle at a high potential of 1.8 V, showing excellent cycling durability and also enabling a remarkable power density of ∼13 kW/kg with a high energy density of ∼19.2 W·h/kg. Two such supercapacitors linked in series can simultaneously power four distinct light-emitting diode indicators; they can also drive the motor of remote-controlled model planes. This work not only presents the potential of C/CoNi3 O4 NAs in thin-film supercapacitor applications, but it also demonstrates the superiority of electrodes with such a 3D hierarchical architecture. PMID:24643977

  2. Influence of nutrients on oxidation of low level methane by mixed methanotrophic consortia.

    PubMed

    Karthikeyan, Obulisamy Parthiba; Chidambarampadmavathy, Karthigeyan; Nadarajan, Saravanan; Heimann, Kirsten

    2016-03-01

    Low-level methane emissions from coal mine ventilation air (CMV-CH4; i.e., 1 % CH4) can significantly contribute to global climate change, and therefore, treatment is important to reduce impacts. To investigate CMV-CH4 abatement potential, five different mixed methanotrohic consortia (MMCs) were established from soil/sediment sources, i.e., landfill top cover soil, bio-solid compost, vegetated humus soil, estuarine and marine sediments. Enrichment conditions for MMCs were as follows: nitrate mineral salt (NMS) medium, pH ~ 6.8; 25 °C; 20-25 % CH4; agitation 200 rpm; and culture period 20 days, in mini-bench-top bioreactors. The enriched cultures were supplemented with extra carbon (methanol 0.5-1.5 %, formate 5-15 mM, and acetate 5-15 mM), nitrogen (nitrate 0.5-1.5 g L(-1), ammonium 0.1-0.5 g L(-1), or urea: 0.1-0.5 g L(-1)), and trace elements (copper 1-5 μM, iron 1-5 μM, and zinc 1-5 μM) in different batch experiments to improve low-level CH4 abatement. Average CH4 oxidation capacities (MOCs) of MMCs varied between 1.712 ± 0.032 and 1.963 ± 0.057 mg g(-1)DWbiomass h(-1). Addition of formate improved the MOCs of MMCs, but the dose-response varied for different MMCs. Acetate, nitrate and copper had no significant effect on MOCs, while addition of methanol, ammonium, urea, iron and zinc impacted negatively. Overall, MMCs enriched from marine sediments and landfill top cover soil showed high MOCs which were largely resilient to nutrient supplementation, suggesting a strong potential for biofilter development for industrial low-level CH4 abatement, such as those present in CMV. PMID:26867685

  3. The behavior of SiC and Si3N4 ceramics in mixed oxidation/chlorination environments

    NASA Technical Reports Server (NTRS)

    Marra, John E.; Kreidler, Eric R.; Jacobson, Nathan S.; Fox, Dennis S.

    1989-01-01

    The behavior of silicon-based ceramics in mixed oxidation/chlorination environments was studied. High pressure mass spectrometry was used to quantitatively identify the reaction products. The quantitative identification of the corrosion products was coupled with thermogravimetric analysis and thermodynamic equilibrium calculations run under similar conditions in order to deduce the mechanism of corrosion. Variations in the behavior of the different silicon-based materials are discussed. Direct evidence of the existence of silicon oxychloride compounds is presented.

  4. Electrochemical properties of mixed conducting (La,M)(CoFe) oxide perovskites (M=3DSr, Ca, and Ba)

    SciTech Connect

    Stevenson, J.W.; Armstrong, T.R.; Bates, J.L.

    1996-04-01

    Electrical properties and oxygen permeation properties of solid mixed-conducting electrolytes (La,M)(CoFe) oxide perovskites (M=3DSr, Ca, and Ba) have been characterized. These materials are potentially useful as passive membranes to separate high purity oxygen from air and as the cathode in a fuel cell. Dilatometric linear expansion measurements were performed as a function of temperature and oxygen partial pressure to evaluate the stability.

  5. Magnesium Recycling of Partially Oxidized, Mixed Magnesium-Aluminum Scrap through Combined Refining and Solid Oxide Membrane Electrolysis Processes

    SciTech Connect

    Xiaofei Guan; Peter A. Zink; Uday B. Pal; Adam C. Powell

    2012-01-01

    Pure magnesium (Mg) is recycled from 19g of partially oxidized 50.5wt.% Mg-Aluminum (Al) alloy. During the refining process, potentiodynamic scans (PDS) were performed to determine the electrorefining potential for magnesium. The PDS show that the electrorefining potential increases over time as the magnesium content inside the Mg-Al scrap decreases. Up to 100% percent of magnesium is refined from the Mg-Al scrap by a novel refining process of dissolving magnesium and its oxide into a flux followed by vapor phase removal of dissolved magnesium and subsequently condensing the magnesium vapor. The solid oxide membrane (SOM) electrolysis process is employed in the refining system to enable additional recycling of magnesium from magnesium oxide (MgO) in the partially oxidized Mg-Al scrap. The combination of the refining and SOM processes yields 7.4g of pure magnesium.

  6. Magnesium Recycling of Partially Oxidized, Mixed Magnesium-Aluminum Scrap Through Combined Refining and Solid Oxide Membrane (SOM) Electrolysis Processes

    SciTech Connect

    Guan, Xiaofei; Zink, Peter; Pal, Uday

    2012-03-11

    Pure magnesium (Mg) is recycled from 19g of partially oxidized 50.5wt.%Mg-Aluminum (Al) alloy. During the refining process, potentiodynamic scans (PDS) were performed to determine the electrorefining potential for magnesium. The PDS show that the electrorefining potential increases over time as the Mg content inside the Mg-Al scrap decreases. Up to 100% percent of magnesium is refined from the Mg-Al scrap by a novel refining process of dissolving magnesium and its oxide into a flux followed by vapor phase removal of dissolved magnesium and subsequently condensing the magnesium vapors in a separate condenser. The solid oxide membrane (SOM) electrolysis process is employed in the refining system to enable additional recycling of magnesium from magnesium oxide (MgO) in the partially oxidized Mg-Al scrap. The combination of the refining and SOM processes yields 7.4g of pure magnesium; could not collect and weigh all of the magnesium recovered.

  7. Electronic Structure and Bonding in Co-Based Single and Mixed Valence Oxides: A Quantum Chemical Perspective.

    PubMed

    Singh, Vijay; Major, Dan Thomas

    2016-04-01

    The mixed valence cobalt oxide, Co3O4, is a potential candidate as a photovoltaic (PV) material, which also exhibits intriguing chemical and catalytic properties. Here, we present a comparative study of the electronic, magnetic, and chemical bonding properties of mixed valence Co3O4 (i.e., Co(2+/3+)) with the related single valence CoO (i.e., Co(2+)) and Co2O3 (i.e., Co(3+)) oxides using density functional theory (DFT). We have employed a range of theoretical methods, including pure DFT, DFT+U, and a range-separated exchange-correlation functional (HSE06). We compare the electronic structure and band gap of the oxide materials, with available photoemission spectroscopy and optical band gaps. Our calculations suggest that the bonding between Co(3+) and O(2-) ions in Co2O3 and Co3O4 and Co(2+) and O(2-) ions in CoO and Co3O4 are rather different. We find that Co2O3 and Co3O4 are weakly correlated materials, whereas CoO is a strongly correlated material. Furthermore, our computed one-electron energy level diagrams reveal that strong Co-O antibonding states are present at the top of the valence band for all the cobalt oxides, hinting at a defect tolerant capacity in these materials. These results, which give a detailed picture of the chemical bonding in related single and mixed valence cobalt oxides, may serve as a guide to enhance the PV or photoelectrochemical activity of Co3O4, by reducing its internal defect states or changing its electronic structure by doping or alloying with suitable elements. PMID:27010797

  8. To study the flow property of seven commercially available zinc oxide eugenol impression material at various time intervals after mixing.

    PubMed

    Katna, Vishal; Suresh, S; Vivek, Sharma; Meenakshi, Khandelwal; Ankita, Gaur

    2014-12-01

    Aims and objective of the study was to evaluate the flow property of seven commercially available zinc oxide eugenol impression materials at various time intervals, after mixing 49 samples (seven groups) were fabricated for flow property of the material. The sample were fabricated as equal length of base and accelerator paste of the test materials was taken on the glass slab and mixed with a rigid stainless steel spatula as per manufacturers recommendation till the homogenous mix was obtained. The mix material was loaded in glass syringe and 0.5 ml material was injected on a cellophane sheet placed on marked glass plate. A cellophane sheet and glass plate 70 and 500 g weight was carefully placed on freshly dispensed zinc oxide eugenol impression paste sequentially. The diameter of the mix was noted after 30 s and 1 min of load application and also after the final set of material. The diameter gives the flow of material. The samples were stored at the room temperature. The data of the flow property was analyzed with analysis of variance, Post hoc test and t test. The flow of the zinc oxide eugenol impression paste after 30 s, 1 min and final set of load application for Group A to Group G was noted. Maximum flow was seen for Group G zinc oxide eugenol impression material followed by Group F, D, E, B, C and A in descending order respectively after 30 s, where as the flow property changed after 1 min in the sequence of maximum for Group G followed by Group E, D, B, A, C, and F. Lastly after final set of the impression material the flow maximum for Group G followed by Group E, D, C, F, A and B in descending order. Based on statistical analysis of the results and within in the limitations of this in-vitro study, the following conclusions were drawn that; the flow of zinc oxide eugenol impression material after 30 s, 1 min and that after the final set was maximum for P.S.P. (Group G) and the flow for PYREX (Group A) was minimum. PMID:25489163

  9. Photo-assisted hetero-fenton decolorization of azo dye from contaminated water by Fe-Si mixed oxide nanocomposite.

    PubMed

    Rasoulifard, M H; Monfared, H Hosseini; Masoudian, S

    2011-10-01

    An aerogel of silica gel dopeyd with 2.86 wt% Fe was prepared by an alkoxide sol-gel method and using tetraethyl orthosilicate as a precursor material. The synthesized aerogel was calcined at 500 degress C to produce nanoparticle solids, and was characterized by XRD, FT-IR and SEM. The nanosized iron-silica gel mixed oxide was tested in the photooxidation of the azo dye Acid Red 14 (AR 14) using 30% aqueous hydrogen peroxide as oxidant and UV light. The 2.86 wt% Fe-loaded SiO2 showed very good efficiency in the decolorization of AR 14. The effects of various parameters including solution pH, catalyst, oxidant and initial dye concentrations on photodegradation were investigated and the optimum conditions were determined. The catalyst was resistant to leaching and could be recycled several times without appreciable loss of activity. PMID:22329154

  10. Nature of Catalytic Active Sites Present on the Surface of Advanced Bulk Tantalum Mixed Oxide Photocatalysts

    SciTech Connect

    Phivilay, Somphonh; Puretzky, Alexander A; Domen, Kazunari Domen; Wachs, Israel

    2013-01-01

    The most active photocatalyst system for water splitting under UV irradiation (270 nm) is the promoted 0.2%NiO/NaTaO3:2%La photocatalyst with optimized photonic efficiency (P.E.) of 56%, but fundamental issues about the nature of the surface catalytic active sites and their involvement in the photocatalytic process still need to be clarified. This is the first study to apply cutting edge surface spectroscopic analyses to determine the surface nature of tantalum mixed oxide photocatalysts. Surface analysis with HR-XPS (1-3nm) and HS-LEIS (0.3nm) spectroscopy indicates that the NiO and La2O3 promoters are concentrated in the surface region of the bulk NaTaO3 phase. The La2O3 is concentrated on the NaTaO3 outermost surface layers while NiO is distributed throughout the NaTaO3 surface region (1-3nm). Raman and UV-vis spectroscopy revealed that the bulk molecular and electronic structures, respectively, of NaTaO3 were not modified by the addition of the La2O3 and NiO promoters, with La2O3 resulting in a slightly more ordered structure. Photoluminescence (PL) spectroscopy reveals that the addition of La2O3 and NiO produces a greater number of electron traps resulting in the suppression of the recombination of excited electrons/holes. In contrast to earlier reports, the La2O3 is only a textural promoter (increasing the BET surface area ~7x by stabilizing smaller NaTaO3 particles), but causes a ~3x decrease in the specific photocatalytic TORs ( mol H2/m2/h) rate because surface La2O3 blocks exposed catalytic active NaTaO3 sites. The NiO promoter was found to be a potent electronic promoter that enhances the NaTaO3 surface normalized TORs by a factor of ~10-50 and TOF by a factor of ~10. The level of NiO promotion is the same in the absence and presence of La2O3 demonstrating that there is no promotional synergistic interaction between the NiO and La2O3 promoters. This study demonstrates the important contributions of the photocatalyst surface properties to the fundamental

  11. Catalytic transformations of biomass substrates using mixed metal oxides derived from substituted hydrotalcites

    NASA Astrophysics Data System (ADS)

    Macala, Gerald Stephen, II

    Fueled by seemingly endless reserves of cheap and easily accessible fossil energy, the industrial age has brought to the developed world tremendous advances in human health and well being. Unfortunately the burning of fossil fuels has also been implicated in increasing atmospheric CO2 concentrations and global climate change. Concerns about short-term and long-term supply further build a case for the need for alternative energy sources. Biomass derived materials are a tantalizing source of fuels and fine chemicals. Unlike petroleum derived hydrocarbons, biomass can be both renewable and carbon neutral. Crops can be regenerated annually or even more often in tropical climates, and since the captured carbon originates as atmospheric CO2, the overall cycle has the potential to be nearly carbon neutral regardless of the final fate of the carbon. In contrast to petroleum derived hydrocarbons, which can often be made more valuable by adding functionality, biomass derived materials are already highly functionalized and can usually be made more valuable by selective removal of functionality. The development of robust catalysts capable of selective defuntionalization of biomass derived substrates remains an important challenge with potentially enormous economic and societal impact. In addition to being robust and selective, catalysts should preferably be heterogeneous to allow for easier removal and regeneration after the reaction is complete. New materials consisting of Mg-Al hydrotalcite-like structures, with a limiting percentage of Mg or Al substituted with other M2+ or M3+ cations, were synthesized by a co-precipitation process in basic aqueous solution with carbonate as counterion. Calcination of these materials at 460 °C resulted in evolution of CO2 and water and yielded high surface area mixed metal oxides with enhanced reactivity. Materials were characterized by ICP for elemental analysis, XRD for structural information, XPS for surface elemental analysis and TEM

  12. Americium characterization by X-ray fluorescence and absorption spectroscopy in plutonium uranium mixed oxide

    SciTech Connect

    Degueldre, Claude Cozzo, Cedric; Martin, Matthias; Grolimund, Daniel; Mieszczynski, Cyprian

    2013-06-01

    Plutonium uranium mixed oxide (MOX) fuels are currently used in nuclear reactors. The actinides in these fuels need to be analyzed after irradiation for assessing their behaviour with regard to their environment and the coolant. In this work the study of the atomic structure and next-neighbour environment of Am in the (Pu,U)O₂ lattice in an irradiated (60 MW d kg⁻¹) MOX sample was performed employing micro-X-ray fluorescence (µ-XRF) and micro-X-ray absorption fine structure (µ-XAFS) spectroscopy. The chemical bonds, valences and stoichiometry of Am (~0.66 wt%) are determined from the experimental data gained for the irradiated fuel material examined in its peripheral zone (rim) of the fuel. In the irradiated sample Am builds up as Am³⁺ species within an [AmO₈]¹³⁻ coordination environment (e.g. >90%) and no (<10%) Am(IV) or (V) can be detected in the rim zone. The occurrence of americium dioxide is avoided by the redox buffering activity of the uranium dioxide matrix. - Graphical abstract: Americium LIII XAFS spectra recorded for the irradiated MOX sub-sample in the rim zone for a 300 μm×300 μm beam size area investigated over six scans of 4 h. The records remain constant during multi-scan. The analysis of the XAFS signal shows that Am is found as trivalent in the UO₂ matrix. This analytical work shall open the door of very challenging analysis (speciation of fission product and actinides) in irradiated nuclear fuels. - Highlights: • Americium was characterized by microX-ray absorption spectroscopy in irradiated MOX fuel. • The americium redox state as determined from XAS data of irradiated fuel material was Am(III). • In the sample, the Am³⁺ face an AmO₈¹³⁻coordination environment in the (Pu,U)O₂ matrix. • The americium dioxide is reduced by the uranium dioxide matrix.

  13. Chemical and Radiochemical Composition of Thermally Stabilized Plutonium Oxide from the Plutonium Finishing Plant Considered as Alternate Feedstock for the Mixed Oxide Fuel Fabrication Facility

    SciTech Connect

    Tingey, Joel M.; Jones, Susan A.

    2005-07-01

    Eighteen plutonium oxide samples originating from the Plutonium Finishing Plant (PFP) on the Hanford Site were analyzed to provide additional data on the suitability of PFP thermally stabilized plutonium oxides and Rocky Flats oxides as alternate feedstock to the Mixed Oxide Fuel Fabrication Facility (MFFF). Radiochemical and chemical analyses were performed on fusions, acid leaches, and water leaches of these 18 samples. The results from these destructive analyses were compared with nondestructive analyses (NDA) performed at PFP and the acceptance criteria for the alternate feedstock. The plutonium oxide materials considered as alternate feedstock at Hanford originated from several different sources including Rocky Flats oxide, scrap from the Remote Mechanical C-Line (RMC) and the Plutonium Reclamation Facility (PRF), and materials from other plutonium conversion processes at Hanford. These materials were received at PFP as metals, oxides, and solutions. All of the material considered as alternate feedstock was converted to PuO2 and thermally stabilized by heating the PuO2 powder at 950 C in an oxidizing environment. The two samples from solutions were converted to PuO2 by precipitation with Mg(OH)2. The 18 plutonium oxide samples were grouped into four categories based on their origin. The Rocky Flats oxide was divided into two categories, low- and high-chloride Rocky Flats oxides. The other two categories were PRF/RMC scrap oxides, which included scrap from both process lines and oxides produced from solutions. The two solution samples came from samples that were being tested at Pacific Northwest National Laboratory because all of the plutonium oxide from solutions at PFP had already been processed and placed in 3013 containers. These samples originated at the PFP and are from plutonium nitrate product and double-pass filtrate solutions after they had been thermally stabilized. The other 16 samples originated from thermal stabilization batches before canning at

  14. Heterogeneously catalysed partial oxidation of acrolein to acrylic acid--structure, function and dynamics of the V-Mo-W mixed oxides.

    PubMed

    Kampe, Philip; Giebeler, Lars; Samuelis, Dominik; Kunert, Jan; Drochner, Alfons; Haass, Frank; Adams, Andreas H; Ott, Joerg; Endres, Silvia; Schimanke, Guido; Buhrmester, Thorsten; Martin, Manfred; Fuess, Hartmut; Vogel, Herbert

    2007-07-21

    The major objective of this research project was to reach a microscopic understanding of the structure, function and dynamics of V-Mo-(W) mixed oxides for the partial oxidation of acrolein to acrylic acid. Different model catalysts (from binary and ternary vanadium molybdenum oxides up to quaternary oxides with additional tungsten) were prepared via a solid state preparation route and hydrochemical preparation of precursors by spray-drying or crystallisation with subsequent calcination. The phase composition was investigated ex situ by XRD and HR-TEM. Solid state prepared samples are characterised by crystalline phases associated to suitable phase diagrams. Samples prepared from crystallised and spray-dried precursors show crystalline phases which are not part of the phase diagram. Amorphous or nanocrystalline structures are only found in tungsten doped samples. The kinetics of the partial oxidation as well as the catalysts' structure have been studied in situ by XAS, XRD, temperature programmed reaction and reduction as well as by a transient isotopic tracing technique (SSITKA). The reduction and re-oxidation kinetics of the bulk phase have been evaluated by XAS. A direct influence not only of the catalysts' composition but also of the preparation route is shown. Altogether correlations are drawn between structure, oxygen dynamics and the catalytic performance in terms of activity, selectivity and long-term stability. A model for the solid state behaviour under reaction conditions has been developed. Furthermore, isotope exchange experiments provided a closer image of the mechanism of the selective acrolein oxidation. Based on the in situ characterisation in combination with micro kinetic modelling a detailed reaction model which describes the oxygen exchange and the processes at the catalyst more precisely is discussed. PMID:17612723

  15. N₂O decomposition over K/Na-promoted Mg/Zn-Ce-cobalt mixed oxides catalysts.

    PubMed

    Zhang, Jinli; Hu, Hui; Xu, Jie; Wu, Gaoming; Zeng, Zhaowei

    2014-07-01

    Three groups of cobalt mixed oxide catalysts (Mg/Zn-Co, Mg/Zn-Ce-C, K/Na-Mg/Zn-Ce-Co) were prepared by sol-gel or impregnation methods. The synergistic effects of transition metal, rare earth metal and alkali metal on cobalt mixed catalysts for nitrous oxide (N₂O) decomposing to N₂ and O₂ were investigated. The experimental results revealed that the catalytic activity for N₂O decomposition was promoted as Co²⁺ was replaced partially by Zn²⁺/Mg²⁺, moreover, the characterization analysis by XRD and XPS showed that Zn²⁺/Mg²⁺ replaced Co²⁺ successfully into the spinel structure of Co3O₄ and promoted significantly the catalytic activity. Especially, the addition of CeO₂ and K₂O/Na₂O decreased the binding energy and resulted in an increase in the density of the electron cloud around Co and an improvement of the catalytic activity. Of the investigated cobalt mixed catalysts, the best catalytic activity was shown by 2% K-Zn0.5-Ce0.05-Co catalyst. PMID:25079992

  16. Effect of hydrothermal treatment on properties of Ni-Al layered double hydroxides and related mixed oxides

    SciTech Connect

    Kovanda, Frantisek Rojka, Tomas; Bezdicka, Petr; Jiratova, Kveta; Obalova, Lucie; Pacultova, Katerina; Bastl, Zdenek; Grygar, Tomas

    2009-01-15

    The Ni-Al layered double hydroxides (LDHs) with Ni/Al molar ratio of 2, 3, and 4 were prepared by coprecipitation and treated under hydrothermal conditions at 180 deg. C for times up to 20 h. Thermal decomposition of the prepared samples was studied using thermal analysis and high-temperature X-ray diffraction. Hydrothermal treatment increased significantly the crystallite size of coprecipitated samples. The characteristic LDH diffraction lines disappeared completely at ca. 350 deg. C and a gradual crystallization of NiO-like mixed oxide was observed at higher temperatures. Hydrothermal treatment improved thermal stability of the Ni2Al and Ni3Al LDHs but only a slight effect of hydrothermal treatment was observed with the Ni4Al sample. The Rietveld refinement of powder XRD patterns of calcination products obtained at 450 deg. C showed a formation of Al-containing NiO-like oxide and a presence of a considerable amount of Al-rich amorphous component. Hydrothermal aging of the LDHs resulted in decreasing content of the amorphous component and enhanced substitution of Al cations into NiO-like structure. The hydrothermally treated samples also exhibited a worse reducibility of Ni{sup 2+} components. The NiAl{sub 2}O{sub 4} spinel and NiO still containing a marked part of Al in the cationic sublattice were detected in the samples calcined at 900 deg. C. The Ni2Al LDHs hydrothermally treated for various times and related mixed oxides obtained at 450 deg. C showed an increase in pore size with increasing time of hydrothermal aging. The hydrothermal treatment of LDH precursor considerably improved the catalytic activity of Ni2Al mixed oxides in N{sub 2}O decomposition, which can be explained by suppressing internal diffusion effect in catalysts grains. - Graphical Abstract: Hydrothermal treatment of Ni-Al LDH precursors influenced the porous structure of related mixed oxides and considerably improved their catalytic activity in N{sub 2}O decomposition; the higher catalytic

  17. Characterization of high surface area Zr-Ce (1:1) mixed oxide prepared by a microemulsion method

    SciTech Connect

    Martinez-Arias, A.; Fernandez-Garcia, M.; Ballesteros, V.; Salamanca, L.N.; Conesa, J.C.; Otero, C.; Soria, J.

    1999-07-06

    A Zr-Ce mixed oxide with ca. a 1:1 atomic ratio is prepared by a microemulsion method and studied by X-ray diffraction, transmission electron microscopy, and Raman, X-ray photoelectron (XPS) and electron paramagnetic resonance (EPR) spectroscopies. The results show the formation of a high surface area material (S{sub BET} = 96 m{sup 2}/g) constituted by homodispersed particles of a major pseudocubic phase t{double_prime} (as shown by Raman); the stabilization of the latter phase, instead of the normally more stable tetragonal phase t{prime}, is probably due to the small crystallite size (ca. 5 nm). XPS indicates a moderate degree of surface enrichment in cerium. An EPR study is carried out on the superoxide species formed on the material by O{sub 2} adsorption after outgassing at temperatures up to T{sub v} = 773 K; this shows that the reduced surface centers thermally formed on this mixed oxide are similar to those found on pure ceria but are generated more easily than on the latter, thus evidencing a surface redox reactivity higher than that of the CeO{sub 2} single oxide.

  18. Effect of animal mixing as a stressor on biomarkers of autophagy and oxidative stress during pig muscle maturation.

    PubMed

    Rubio-González, A; Potes, Y; Illán-Rodríguez, D; Vega-Naredo, I; Sierra, V; Caballero, B; Fàbrega, E; Velarde, A; Dalmau, A; Oliván, M; Coto-Montes, A

    2015-07-01

    The objective of this work was to study the postmortem evolution of potential biomarkers of autophagy (Beclin 1, LC3-II/LC3-I ratio) and oxidative stress (total antioxidant activity, TAA; superoxide dismutase activity, SOD and catalase activity, CAT) in the Longissimus dorsi muscle of entire male ((Large White×Landrace)×Duroc) pigs subjected to different management treatments that may promote stress, such as mixing unfamiliar animals at the farm and/or during transport and lairage before slaughter. During the rearing period at the farm, five animals were never mixed after the initial formation of the experimental groups (unmixed group at the farm, UF), whereas 10 animals were subjected to a common routine of being mixed with unfamiliar animals (mixed group at the farm, MF). Furthermore, two different treatments were used during the transport and lairage before slaughter: 10 pigs were not mixed (unmixed group during transport and lairage, UTL), whereas five pigs were mixed with unfamiliar animals on the lorry and during lairage (mixed group during transport and lairage, MTL). These mixing treatments were then combined into three pre-slaughter treatments - namely, UF-UTL, MF-UTL and MF-MTL. The results show that MF-UTL and MF-MTL increased significantly the muscle antioxidant defense (TAA, SOD and CAT) at short postmortem times (4 and 8 h; P<0.001), followed by an earlier depletion of the antioxidant activity at 24 h postmortem (P<0.05). We also found that mixing unfamiliar animals, both at the farm and during transport and lairage, triggers postmortem muscle autophagy, which showed an earlier activation (higher expression of Beclin 1 and LC3-II/LC3-I ratio at 4 h postmortem followed by a decreasing pattern of this ratio along first 24 h postmortem) in the muscle tissues of animals from the MF-UTL and MF-MTL groups, as an adaptive strategy of the muscle cells for counteracting induced stress. From these results, we propose that monitoring the evolution of the main

  19. Aerosol synthesis and electrochemical analysis of niobium mixed-metal oxides for the ethanol oxidation reaction in acid and alkaline electrolyte

    NASA Astrophysics Data System (ADS)

    Konopka, Daniel A.

    Direct ethanol fuel cells are especially important among emerging electrochemical power systems with the potential to offset a great deal of the energy demand currently met through the use of fossil fuels. Ethanol can be refined from petroleum sources or attained from renewable biomass, and is more easily and safely stored and transported than hydrogen, methanol or gasoline. The full energy potential of ethanol in fuel cells can only be realized if the reaction follows a total oxidation pathway to produce CO2. This must be achieved by the development of advanced catalysts that are electrically conductive, stable in corrosive environments, contain a high surface area on which the reaction can occur, and exhibit a bi-functional effect for the ethanol oxidation reaction (EOR). The latter criterion is achievable in mixed-metal systems. Platinum is an effective metal for catalyzing surface reactions of many adsorbates and is usually implemented in the form of Pt nanoparticles supported on inexpensive carbon. This carbon is believed to be neutral in the catalysis of Pt. Instead, carbon can be replaced with carefully designed metals and metal oxides as co-catalysis or support structures that favorably alter the electronic structure of Pt slightly through a strong metal support interaction, while also acting as an oxygen source near adsorbates to facilitate the total oxidation pathway. Niobium mixed-metal-oxides were explored in this study as bi-functional catalyst supports to Pt nanoparticles. We developed a thermal aerosol synthesis process by which mesoporous powders of mixed-metal-oxides decorated with Pt nanoparticles could be obtained from liquid precursors within ˜5 seconds or less, followed by carefully refined chemical and thermal post-treatments. Exceptionally high surface areas of 170--180m2/g were achieved via a surfactant-templated 3D wormhole-type porosity, comparable on a per volume basis to commercial carbon blacks and high surface area silica supports

  20. Preparation of N-doped graphene by reduction of graphene oxide with mixed microbial system and its haemocompatibility.

    PubMed

    Fan, Mengmeng; Zhu, Chunlin; Feng, Zhang-Qi; Yang, Jiazhi; Liu, Lin; Sun, Dongping

    2014-05-01

    A steady, effective and environment friendly method of introducing nitrogen into graphene is by microbial reduction of graphene oxide with mixed microorganisms from the anode chamber of microbial fuel cells (MFC). Using this method, N-doped graphene is easily obtained under mild conditions and by simple treatment processes, with the N/C ratio reaching 8.14%. Various characterizations demonstrate that the as-prepared N-doped graphene has excellent properties and is comparable with, and in some aspects, even better than, pristine graphene (containing only elemental C) prepared by chemical methods. The N-doped graphene (mainly substitution of C in the plane of the graphene sheet) with uniform distribution of N was haemocompatible, nontoxic, and water-dispersible, all of which are desirable properties for biomaterials and attributable to a synergetic metabolic effect of mixed microorganisms. PMID:24667844

  1. Chemical diffusion of CO in mixed CO + O adlayers and reaction-front propagation in CO oxidation on Pd(100).

    PubMed

    Liu, Da-Jiang; Evans, J W

    2006-08-01

    Within the framework of a realistic atomistic lattice-gas model, we present the theoretical formulation and simulation procedures for precise analysis of the chemical diffusion flux of highly mobile CO within a nonuniform interacting mixed CO + O adlayer on a Pd(100) surface. The approach applies in both regimes of relatively immobile unequilibrated and fairly mobile near-equilibrated O adlayer distributions. Spatiotemporal behavior in surface reactions is controlled by chemical diffusion in mixed adlayers. Thus, we naturally integrate the above analysis with a previously developed multiscale modeling strategy to describe mesoscale reaction front propagation in CO oxidation on Pd(100). This treatment avoids using a simplified prescription of chemical diffusion and reaction kinetics as in traditional mean-field reaction-diffusion equation approaches. PMID:16942243

  2. Deactivation of a mixed oxide catalyst of Mo-V-Te-Nb-O composition in the reaction of oxidative ethane dehydrogenation

    NASA Astrophysics Data System (ADS)

    Mishanin, I. I.; Kalenchuk, A. N.; Maslakov, K. I.; Lunin, V. V.; Koklin, A. E.; Finashina, E. D.; Bogdan, V. I.

    2016-06-01

    The operational stability of a mixed oxide catalyst of Mo-V-Te-Nb-O composition in the oxidative dehydrogenation of ethane (ratio of C2H6: O2 = 3: 1) is studied in a flow reactor at temperatures of 340-400°C, a pressure of 1 atm, and a WHSV of the feed mixture of 800 h-1. It is found that the selectivity toward ethylene is 98% at 340°C, but the conversion of ethane at this temperature is only 6%; when the temperature is raised to 400°C, the conversion of ethane is increased to 37%, while the selectivity toward ethylene is reduced to 85%. Using physical and chemical means (XPS, SEM), it is found that the lack of oxidant in the reaction mixture leads to irreversible changes in the catalyst, i.e., reduced selectivity and activity. Raising the reaction temperature to 400°C allows the reduction of tellurium by ethane, from the +6 oxidation state to the zerovalent state, with its subsequent sublimation and the destruction of the catalytically active and selective phase; in its characteristics, the catalyst becomes similar to the Mo-V-Nb-O system containing no tellurium.

  3. Note: Application of CR-39 plastic nuclear track detectors for quality assurance of mixed oxide fuel pellets

    NASA Astrophysics Data System (ADS)

    Kodaira, S.; Kurano, M.; Hosogane, T.; Ishikawa, F.; Kageyama, T.; Sato, M.; Kayano, M.; Yasuda, N.

    2015-05-01

    A CR-39 plastic nuclear track detector was used for quality assurance of mixed oxide fuel pellets for next-generation nuclear power plants. Plutonium (Pu) spot sizes and concentrations in the pellets are significant parameters for safe use in the plants. We developed an automatic Pu detection system based on dense α-radiation tracks in the CR-39 detectors. This system would greatly improve image processing time and measurement accuracy, and will be a powerful tool for rapid pellet quality assurance screening.

  4. Note: Application of CR-39 plastic nuclear track detectors for quality assurance of mixed oxide fuel pellets

    SciTech Connect

    Kodaira, S. Kurano, M.; Hosogane, T.; Ishikawa, F.; Kageyama, T.; Sato, M.; Kayano, M.; Yasuda, N.

    2015-05-15

    A CR-39 plastic nuclear track detector was used for quality assurance of mixed oxide fuel pellets for next-generation nuclear power plants. Plutonium (Pu) spot sizes and concentrations in the pellets are significant parameters for safe use in the plants. We developed an automatic Pu detection system based on dense α-radiation tracks in the CR-39 detectors. This system would greatly improve image processing time and measurement accuracy, and will be a powerful tool for rapid pellet quality assurance screening.

  5. Catalytic properties of mixed oxides in the Nd-Mg-Cu-Cr-Al-O system in oxidation of carbon monoxide

    SciTech Connect

    Varlamov, V.I.; Komarov, V.S.

    1986-04-10

    Much attention is being devoted to effective catalysts for treatment of exhaust gases having improved activity and thermal and chemical stability. The authors study the influence of individual components of the Nd-Mg-Cu-Cr-Ar-O system on its catalytic properties in oxidation of carbon monoxide. The samples were prepared from analytical-grade neodymium oxalate and 1 M aqueous solutions of nitrates of the corrosponding metals. The compositions and certain physicochemical properties of the synthesized samples are presented with the results of x-ray diffraction and IR-spectroscopic investigations. The results show that formation of crystalline phases in the system is observed at 700 deg, and at 900 deg all samples had well-defined crystalline structure. The sample not containing iron oxide has high thermal stability.

  6. Strain Field in Ultrasmall Gold Nanoparticles Supported on Cerium-Based Mixed Oxides. Key Influence of the Support Redox State.

    PubMed

    López-Haro, Miguel; Yoshida, Kenta; Del Río, Eloy; Pérez-Omil, José A; Boyes, Edward D; Trasobares, Susana; Zuo, Jian-Min; Gai, Pratibha L; Calvino, José J

    2016-05-01

    Using a method that combines experimental and simulated Aberration-Corrected High Resolution Electron Microscopy images with digital image processing and structure modeling, strain distribution maps within gold nanoparticles relevant to real powder type catalysts, i.e., smaller than 3 nm, and supported on a ceria-based mixed oxide have been determined. The influence of the reduction state of the support and particle size has been examined. In this respect, it has been proven that reduction even at low temperatures induces a much larger compressive strain on the first {111} planes at the interface. This increase in compression fully explains, in accordance with previous DFT calculations, the loss of CO adsorption capacity of the interface area previously reported for Au supported on ceria-based oxides. PMID:27058299

  7. Controlling the oxygen potential to improve the densification and the solid solution formation of uranium-plutonium mixed oxides

    NASA Astrophysics Data System (ADS)

    Berzati, Ségolène; Vaudez, Stéphane; Belin, Renaud C.; Léchelle, Jacques; Marc, Yves; Richaud, Jean-Christophe; Heintz, Jean-Marc

    2014-04-01

    Diffusion mechanisms occurring during the sintering of oxide ceramics are affected by the oxygen content of the atmosphere, as it imposes the nature and the concentration of structural defects in the material. Thus, the oxygen partial pressure, p(O2), of the sintering gas has to be precisely controlled, otherwise a large dispersion in various parameters, critical for the manufacturing of ceramics such as nuclear oxides fuels, is likely to occur. In the present work, the densification behaviour and the solid solution formation of a mixed uranium-plutonium oxide (MOX) were investigated. The initial mixture, composed of 70% UO2 + 30% PuO2, was studied at p(O2) ranging from 10-15 to 10-4 atm up to 1873 K both with dilatometry and in situ high temperature X-ray diffraction. This study has shown that the initial oxides UO2+x and PuO2-x first densify during heating and then the solid solution formation starts at about 200 K higher. The densification and the formation of the solid solution both occur at a lower temperature when p(O2) increases. Based on this result, it is possible to better define the sintering atmosphere, eventually leading to optimized parameters such as density, oxygen stoichiometry and cations homogenization of nuclear ceramics and of a wide range of industrial ceramic materials.

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

    NASA Astrophysics Data System (ADS)

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

    2014-08-01

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

  9. DRIFT study of CuO-CeO₂-TiO₂ mixed oxides for NOx reduction with NH₃ at low temperatures.

    PubMed

    Chen, Lei; Si, Zhichun; Wu, Xiaodong; Weng, Duan

    2014-06-11

    A CuO-CeO2-TiO2 catalyst for selective catalytic reduction of NOx with NH3 (NH3-SCR) at low temperatures was prepared by a sol-gel method and characterized by X-ray diffraction, Brunner-Emmett-Teller surface area, ultraviolet-visible spectroscopy, H2 temperature-programmed reduction, scanning electron microscopy and in situ diffuse reflectance infrared Fourier transform spectroscopy (in situ DRIFTS). The CuO-CeO2-TiO2 ternary oxide catalyst shows excellent NH3-SCR activity in a low-temperature range of 150-250 °C. Lewis acid sites generated from Cu(2+) are the main active sites for ammonia activation at low temperature, which is crucial for low temperature NH3-SCR activity. The introduction of ceria results in increased reducibility of CuO species and strong interactions between CuO particles with the matrix. The interactions between copper, cerium and titanium oxides lead to high dispersion of metal oxides with increased active oxygen and enhanced catalyst acidity. Homogeneously mixed metal oxides facilitate the "fast SCR" reaction among Cu(2+)-NO, nitrate (coordinated on cerium sites) and ammonia (on titanium sites) on the CuO-CeO2-TiO2 catalyst at low temperatures. PMID:24848157

  10. Electrochemical energy storage by polyaniline nanofibers: high gravity assisted oxidative polymerization vs. rapid mixing chemical oxidative polymerization.

    PubMed

    Zhao, Yibo; Wei, Huige; Arowo, Moses; Yan, Xingru; Wu, Wei; Chen, Jianfeng; Wang, Yiran; Guo, Zhanhu

    2015-01-14

    Polyaniline (PANI) nanofibers prepared by high gravity chemical oxidative polymerization in a rotating packed bed (RPB) have demonstrated a much higher specific capacitance of 667.6 F g(-1) than 375.9 F g(-1) of the nanofibers produced by a stirred tank reactor (STR) at a gravimetric current of 10 A g(-1). Meanwhile, the cycling stability of the electrode is 62.2 and 65.9% for the nanofibers from RPB and STR after 500 cycles, respectively. PMID:25431883

  11. Mixed proton and electron conduction in graphene oxide films: field effect in a transistor based on graphene oxide

    NASA Astrophysics Data System (ADS)

    Smirnov, V. A.; Mokrushin, A. D.; Vasiliev, V. P.; Denisov, N. N.; Denisova, K. N.

    2016-05-01

    GO films exhibited dual proton and electron conduction. Proton conduction showed the exponential dependence on relative humidity with the activation energy E a = 0.9 ± 0.05 eV. For the electron conductivity (220-273 K) induced by thermolysis and chemical means E a = 1.15 ± 0.05 eV. With increasing humidity, the electron conduction went down, which was associated with recombination phenomena. The GO films can be regarded as a first example of the mixed electron-proton conduction when sample conductivity can be regulated by external influence (humidity). Field effect is detected and studied in the transistor on the basis of the GO in different types of conduction.

  12. Effect of ferric oxide on the high-temperature removal of hydrogen sulfide over ZnO-Fe{sub 2}O{sub 3} mixed metal oxide sorbent

    SciTech Connect

    Lee, Y.S.; Kim, H.T.; Yoo, K.O.

    1995-04-01

    The effect of ferric oxide on the removal of hydrogen sulfide over ZnO-Fe{sub 2}O{sub 3} mixed metal oxide sorbents and on the oxidative regeneration of sulfided sorbents was investigated. When ferric oxide was added to the zinc oxide, the reduction of ZnO was retarded by interaction of ZnO with ZnFe{sub 2}O{sub 4}. This interaction was confirmed by larger binding energies of Zn 2P{sub 3/2} and Zn 2P{sub 1/2}, identified by ESCA, of the ZnO-ZnFe{sub 2}O{sub 4} sorbent than those of ZnO. Zinc ferrite with a spinel structure yielded not only high H{sub 2}S removal capacity but also much SO{sub 2} generation. A linear increase of SO{sub 2} generation was confirmed up to 50 wt % Fe{sub 2}O{sub 3}. Resulting from the thermal decomposition of H{sub 2}S over metal sulfides, H{sub 2} generation increased with respect to Fe{sub 2}O{sub 3} according to a quadratic equation. Channeling, caused by sintering during sulfidation, made the flow path of the reactant change and thus pure ZnO sorbent and the sorbent containing 3 wt % Fe{sub 2}O did not sulfurate completely. Addition of Fe{sub 2}O{sub 3} prevented surface structural change like sintering of ZnO during sulfidation.

  13. Nuclear waste treatment - Studying the mixed ion type effects and concentration on the behaviour of oxide dispersions

    SciTech Connect

    Omokanye, Qanitalillahi; Biggs, Simon

    2007-07-01

    In order to gain good control over a particulate dispersion it is necessary to accurately characterise the strength of inter-particle forces that may be operating. Such control is not routinely used, as yet, in the nuclear industry despite the possible benefits. We are investigating the impact of mixed electrolyte systems, for example NaCl and Na{sub 2}SO{sub 4}, on the stability of oxide simulant particle dispersions. The electro-acoustic zeta potentials and shear yield stresses for concentrated dispersions have been measured across a range of pH conditions and electrolyte concentrations (0.001 M - 1.0 M). This paper summarizes initial data from these studies showing how the shear yield stress of concentrated aqueous oxide particle dispersions, can be adjusted through regulation of pH and the addition of background electrolytes (salt). The yield stress as a function of pH for these dispersions in mixed electrolytes showed a direct correlation with corresponding measurements of the zeta potential. Changes in the background electrolyte concentration or type were seen to cause a shift in the position of the isoelectric point (iep). Measurements of the shear yield stress showed a maximum at the iep corresponding to the position of maximum instability in the suspension. The consequences of these data for the efficient treatment of solid-liquid systems will be discussed. (authors)

  14. Nitric acid oxide mixing ratio measurements using a rocket launched chemiluminescent instrument. Final technical report, September 1986-October 1987

    SciTech Connect

    Horvath, J.J.

    1989-01-01

    A total of 18 rocket launched parachute borne nitric oxide instruments were launched from 1977 to 1985. A very precise instrument for the measurement of the nitric oxide mixing ratio was fabricated. No changes were made in the main body of the instruments, i.e., things associated with the reaction volume. Except for the last 4 launches, however, it did not yield the required absolute values that was hoped for. Two major problems were encountered. First, the wrong choice of the background calibration gas, nitrogen, caused the first 10 data sets to be too low in the absolute mixing ratio by nearly the order of 2 to 5 ppbv. The error was realized, and air was substituted for the bias gas measurement. Second, in the desire to extend the measurement to higher altitudes, the problem of contaminating the inlet flow tube with ozone from the reagent gas was encountered. The ozone valve was opened too early in the flight and this caused the pressure in the reaction volume to exceed the pressure at the flow tube entrance, permitting the ozone to migrate backwards. This problem was restricted to an altitude above 45 km.

  15. Biodiesel production from waste cooking oil catalyzed by TiO2-MgO mixed oxides.

    PubMed

    Wen, Zhenzhong; Yu, Xinhai; Tu, Shan-Tung; Yan, Jinyue; Dahlquist, Erik

    2010-12-01

    Mixed oxides of TiO(2)-MgO obtained by the sol-gel method were used to convert waste cooking oil into biodiesel. Titanium improved the stability of the catalyst because of the defects induced by the substitution of Ti ions for Mg ions in the magnesia lattice. The best catalyst was determined to be MT-1-923, which is comprised of an Mg/Ti molar ratio of 1 and calcined at 923 K, based on an assessment of the activity and stability of the catalyst. The main reaction parameters, including methanol/oil molar ratio, catalyst amount, and temperature, were investigated. The catalytic activity of MT-1-923 decreased slowly in the reuse process. After regeneration, the activity of MT-1-923 slightly increased compared with that of the fresh catalyst due to an increase in the specific surface area and average pore diameter. The mixed oxides catalyst, TiO(2)-MgO, showed good potential in large-scale biodiesel production from waste cooking oil. PMID:20696572

  16. Impact of bioavailable Pb2+ on Fe2+ oxidation in the presence of a mixed culture of Acidithiobacillus ferrooxidans

    NASA Astrophysics Data System (ADS)

    Wang, H.; Yang, X.; Gong, L.; Jiang, Z.

    2009-12-01

    Numerous investigations were conducted on the effects of a variety of metals, including As, Cu, Zn, Cr on the growth of Acidithiobacillus ferrooxidans (an iron oxidizer and indigenous to acidic environment) and Fe2+ oxidation. However, less work was reported concerning the Pb2+ effect due to its quick precipitation as anglesite in SO42--rich solutions. The reported inhibiting concentrations of Pb2+ varied greatly on the oxidizing rate of ferrous in the presence of A. ferrooxidans, and the reasons remain unclear. Comparative studies were conducted between chemical and microbial oxidation of ferrous by a mixed culture of A. ferrooxidans in the presence of different concentration of Pb2+. Eh, pH and Fe2+ concentration were monitored periodically and the final precipitates were analyzed by X-ray diffraction (XRD), scanning electronic microscopy (SEM), and SEM-EDAX (Energy-dispersive X-ray spectroscopy). To check the impact of bioavailable Pb2+ on Fe2+ oxidation, initial precipitation was removed before the microbial inoculation. Our data showed that Pb2+ will exert a remarkable inhibition on microbial oxidation of ferrous when initial Pb2+ concentration reached as high as 5 g/L. However, the bioavailable Pb2+ in this case should be much lower than 5 g/L in the solution due to the precipitation of anglesite (The absolute concentration was under analysis). The threshold of Pb2+ concentrations to inhibit the microbial oxidation varies among the previous studies. This might result from the different microbial strains used or the mistaking of initial concentration as the substantial concentration of bioavailable Pb2+ after precipitation as anglesite. In contrast, Pb2+ does not show any obvious influence on chemical oxidation of ferrous. XRD spectrum of the final precipitates showed that anglesite was the only solid phase detected in chemical systems, while pure jarosite was found in the microbial systems. No lead was detected in jarosite by SEM-EDAX, inferring that Pb was

  17. Ruthenium(VI)-Catalyzed Oxidation of Alcohols by Hexacyanoferrate(III): An Example of Mixed Order

    ERIC Educational Resources Information Center

    Mucientes, Antonio E.; de la Pena, Maria A.

    2006-01-01

    The absorbance decay of hexacyanoferrate(III) as a function of time shows a progressive deviation from zero to first order. This variation follows an experimental rate law that has been analyzed. The change in reaction order is due to a change in the relative rate of substrate oxidation with respect to that of catalyst regeneration. (Contains 2…

  18. Structural and thermal investigation of gadolinium gallium mixed oxides obtained by coprecipitation: Observation of a new metastable phase

    SciTech Connect

    Bazzoni, Marco; Bettinelli, Marco; Daldosso, Matteo; Enzo, Stefano . E-mail: enzo@uniss.it; Serra, Filomena; Speghini, Adolfo

    2005-07-15

    Polycrystalline gadolinium gallium mixed oxides were prepared by coprecipitation and annealing at various temperatures below 1000 deg. C. The oxide materials appear to be X-ray amorphous after a heat treatment at 500 deg. C for 30 h, but after 30 h at 800 and 900 deg. C a major, unreported, hexagonal phase, isostructural with TAlO{sub 3} compounds (where T=Y, Eu, Gd, Tb, Dy, Ho, Er) appears to crystallize. On the other hand, a highly energetic mechanical treatment of the amorphous powder previously annealed at 500 deg. C changes considerably the shape and position of exothermal events occurring in the range from 700 up to 900 deg. C. Subsequent annealing at 900 deg. C of the mechanically treated powder gives rise to the complete formation of the Gd{sub 3}Ga{sub 5}O{sub 12} garnet structure at the expense of the hexagonal phase and of the minor Gd{sub 4}Ga{sub 2}O{sub 9} oxide phase. However, a 7.0 wt% contamination is found to be due to tetragonal zirconia coming from vials and balls colliding media. The garnet phase may have strong deviations from the nominal stoichiometry of the garnet, as suggested by the refined lattice parameter obtained from the powder diffraction patterns and by the remarkable absence of intensity relative to the (220) Bragg peak position.

  19. Structural and thermal investigation of gadolinium gallium mixed oxides obtained by coprecipitation: Observation of a new metastable phase

    NASA Astrophysics Data System (ADS)

    Bazzoni, Marco; Bettinelli, Marco; Daldosso, Matteo; Enzo, Stefano; Serra, Filomena; Speghini, Adolfo

    2005-07-01

    Polycrystalline gadolinium gallium mixed oxides were prepared by coprecipitation and annealing at various temperatures below 1000 °C. The oxide materials appear to be X-ray amorphous after a heat treatment at 500 °C for 30 h, but after 30 h at 800 and 900 °C a major, unreported, hexagonal phase, isostructural with TAlO 3 compounds (where T=Y, Eu, Gd, Tb, Dy, Ho, Er) appears to crystallize. On the other hand, a highly energetic mechanical treatment of the amorphous powder previously annealed at 500 °C changes considerably the shape and position of exothermal events occurring in the range from 700 up to 900 °C. Subsequent annealing at 900 °C of the mechanically treated powder gives rise to the complete formation of the Gd 3Ga 5O 12 garnet structure at the expense of the hexagonal phase and of the minor Gd 4Ga 2O 9 oxide phase. However, a 7.0 wt% contamination is found to be due to tetragonal zirconia coming from vials and balls colliding media. The garnet phase may have strong deviations from the nominal stoichiometry of the garnet, as suggested by the refined lattice parameter obtained from the powder diffraction patterns and by the remarkable absence of intensity relative to the (220) Bragg peak position.

  20. Manganese-Cobalt Mixed Spinel Oxides as Surface Modifiers for Stainless Steel Interconnects of Solid Oxide Fuel Cells

    SciTech Connect

    Xia, Gordon; Yang, Z Gary; Stevenson, Jeffry W.

    2006-11-06

    Ferritic stainless steels are promising candidates for interconnect applications in low- and mid-temperature solid oxide fuel cells (SOFCs). A couple of issues however remain for the particular application, including the chromium poisoning due to chromia evaporation, and long-term surface and electrical stability of the scale grown on these steels. Application of a manganese colbaltite spinel protection layer on the steels appears to be an effective approach to solve the issues. For an optimized performance, Mn{sub 1+x}Co{sub 2-x}O{sub 4} (-1 {le} x {le} 2) spinels were investigated against properties relative for protection coating applications on ferritic SOFC interconnects. Overall it appears that the spinels with x around 0.5 demonstrate a good CTE match to ceramic cell components, a relative high electrical conductivity, and a good thermal stability up to 1,250 C. This was confirmed by a long-term test on the Mn{sub 1.5}Co{sub 1.5}O{sub 4} protection layer that was thermally grown on Crofer22 APU, indicating the spinel protection layer not only significantly decreased the contact resistance between a LSF cathode and the stainless steel interconnects, but also inhibited the sub-scale growth on the stainless steels.

  1. Final Report: Fiscal Year 1997 demonstration of omnivorous non-thermal mixed waste treatment: Direct chemical oxidation of organic solids and liquids using peroxydisulfate

    SciTech Connect

    Cooper, J.F.

    1998-01-01

    Direct Chemical Oxidation (DCO) is a non-thermal, ambient pressure, aqueous-based technology for the oxidative destruction of the organic components of hazardous or mixed waste streams. The process has been developed for applications in waste treatment, chemical demilitarization and decontamination at LLNL since 1992. The process uses solutions of the peroxydisulfate ion (typically sodium or ammonium salts) to completely mineralize the organics to carbon dioxide and water. The expended oxidant may be electrolytically regenerated to minimize secondary waste. The paper briefly describes: free radical and secondary oxidant formation; electrochemical regeneration; offgas stream; and throughput.

  2. Ordered mesoporous ternary mixed oxide materials as potential adsorbent of biomolecules

    NASA Astrophysics Data System (ADS)

    Pal, Nabanita; Bhaumik, Asim

    2012-05-01

    Designing a suitable mesoporous framework material for the selective adsorption or immobilization of biomolecules is a very challenging area of research. Mesoporous ternary Co-Si-Al oxide materials with large mesopore and their nanoscale ordering have been reported. The synthesis of these ternary oxides are accomplished through evaporation induced self-assembly (EISA) method using Pluronic non-ionic surfactant F127 under non-aqueous sol-gel route. N2 sorption study revealed high BET surface areas for these materials. These materials exhibited very efficient and selective adsorption for the essential biomolecules like vitamin C (ascorbic acid), vitamin B6 (pyridoxine) and vitamin B3 (nicotinic acid) from their respective aqueous solutions.

  3. Synthesis, characterization, and crystal structures of uranyl compounds containing mixed chromium oxidation states

    SciTech Connect

    Unruh, Daniel K.; Quicksall, Andrew; Pressprich, Laura; Stoffer, Megan; Qiu, Jie; Nuzhdin, Kirill; Wu, Weiqiang; Vyushkova, Mariya; Burns, Peter C.

    2012-07-15

    The mixed-valence chromium uranyl compounds Li{sub 5}[(UO{sub 2}){sub 4}(Cr(V)O{sub 5})(Cr(VI)O{sub 4}){sub 4}](H{sub 2}O){sub 17} (1), (Mg(H{sub 2}O){sub 6}){sub 5}[(UO{sub 2}){sub 8}(Cr(V)O{sub 5}){sub 2}(Cr(VI)O{sub 4}){sub 8}] (2) and (NH{sub 4}){sub 5}[(UO{sub 2}){sub 4}(Cr(V)O{sub 5})(Cr(VI)O{sub 4}){sub 2}]H{sub 2}O{sub 11} (3) have been synthesized and characterized. Each contains an identical sheet of cation-centered polyhedra. Central to the connectivity of the sheet are four uranyl pentagonal bipyramids that share some of their equatorial vertices, giving a four-membered ring. The Cr(V) cation located near the center of this ring is coordinated by O atoms in a square pyramidal arrangement. The Cr(VI) is tetrahedrally coordinated by O atoms, and these tetrahedra link the four-membered rings of bipyramids. The mixed-valence nature of the sheet was verified by XANES, an EPR spectrum, and bond-valence analysis. Low-valence cations and H{sub 2}O groups reside between the sheets of uranyl and chromate polyhedra, where they provide linkages between adjacent sheets. - Graphical abstract: Three uranyl chromate compounds contain both pentavalent and hexavalent chromium. The unusual topology of the uranyl chromate sheet contains unusual pentavalent chromium in a square pyramidal coordination environment. Highlights: Black-Right-Pointing-Pointer The first uranyl compounds with mixed Cr valences are reported. Black-Right-Pointing-Pointer A sheet of uranyl polyhedra stabilizes pentavalent chromium. Black-Right-Pointing-Pointer Uranyl and chromate polyhedra form a topologically novel sheet.

  4. Ordered mesoporous CoMOx (M = Al or Zr) mixed oxides for Fischer-Tropsch synthesis.

    PubMed

    Ahn, Chang-Il; Lee, Yun Jo; Um, Soong Ho; Bae, Jong Wook

    2016-04-01

    A superior structural stability of the ordered mesoporous CoMOx synthesized by using the KIT-6 template was observed under Fischer-Tropsch reaction conditions. The enhanced stability was attributed to a strong interaction of the irreducible metal oxides with the mesoporous Co3O4 by forming Co3O4-ZrO2 (or Co3O4-Al2O3), which resulted in showing a stable activity. PMID:26963504

  5. Synthesis and catalytic properties of mixed oxides in the Sr-Nd-Cu-Cr-Al-O system in oxidation of carbon monoxide

    SciTech Connect

    Komarov, V.S.; Varlamov, V.I.

    1986-05-10

    Much attention is being devoted to production of effective mixed oxide catalysts for treatment of exhaust gases. It was of interest in this connection to study the influence of the individual components of the Sr-Nd-Cu-Cr-Al-O system on the phase composition and catalytic properties of samples obtained from it. The test samples were prepared from analytical-grade neodymium oxalate and 1 M aqueous solutions of metal nitrates of the same purity grade. Weighed portions of the neodymium salt and of triammonium citrate were added n the required proportions to an a equimolar mixture of these solutions. The reaction mixture was evaporated on a water bath with periodic stirring until a resinous product was obtained; this was decomposed at its ignition temperature with the aid of an incandescent lamp. The resultant mass was powdered and heated in air at 700 and 900 for 6 h.

  6. In Silico Design of Highly Selective Mo-V-Te-Nb-O Mixed Metal Oxide Catalysts for Ammoxidation and Oxidative Dehydrogenation of Propane and Ethane.

    PubMed

    Cheng, Mu-Jeng; Goddard, William A

    2015-10-21

    We used density functional theory quantum mechanics with periodic boundary conditions to determine the atomistic mechanism underlying catalytic activation of propane by the M1 phase of Mo-V-Nb-Te-O mixed metal oxides. We find that propane is activated by Te═O through our recently established reduction-coupled oxo activation mechanism. More importantly, we find that the C-H activation activity of Te═O is controlled by the distribution of nearby V atoms, leading to a range of activation barriers from 34 to 23 kcal/mol. On the basis of the new insight into this mechanism, we propose a synthesis strategy that we expect to form a much more selective single-phase Mo-V-Nb-Te-O catalyst. PMID:26423704

  7. Nitrogen oxide abatement by distributed fuel addition. [Reburning, mixing, effect of concentration of nitrogen

    SciTech Connect

    Wendt, J.O.L.; Mereb, J.B.

    1991-01-02

    Reburning experiments are presented in which the effect of the primary flame mode is examined. The application of reburning downstream of an axial diffusion primary flame without swirl is compared to reburning results in which the primary flame is premixed. The comparison is qualitative and is intended to examine reburning under more realistic conditions of utility boilers, where premixed flames are not common. Experimental results of reburning tests using nitrogen containing reburning fuels (ammonia doped natural gas and coal) are presented. The effect of reburning fuel type and nitrogen content on nitrogenous species profiles in the reburn zone are discussed. The last section is concerned with the applications of the kinetic model to predict overall reburning effectiveness from the primary NO level and to identify configuration for low total fixed nitrogen concentration. The effects of mixing in the early stage of reburning are examined and appropriate corrections are incorporated with the kinetic model to allow the prediction of nitrogenous species concentrations in the region where mixing effects are important. An empirical correlation is used to estimate the conversion of the total fixed nitrogen in the reburn zone to NO in the final stage of reburning. The kinetic model is also applied to the testing of hypothetical fuel-rich configurations to identify kinetic limits that would prevent further reductions in nitrogenous species.

  8. Novel Low Temperature Processing for Enhanced Properties of Ion Implanted Thin Films and Amorphous Mixed Oxide Thin Film Transistors

    NASA Astrophysics Data System (ADS)

    Vemuri, Rajitha

    This research emphasizes the use of low energy and low temperature post processing to improve the performance and lifetime of thin films and thin film transistors, by applying the fundamentals of interaction of materials with conductive heating and electromagnetic radiation. Single frequency microwave anneal is used to rapidly recrystallize the damage induced during ion implantation in Si substrates. Volumetric heating of the sample in the presence of the microwave field facilitates quick absorption of radiation to promote recrystallization at the amorphous-crystalline interface, apart from electrical activation of the dopants due to relocation to the substitutional sites. Structural and electrical characterization confirm recrystallization of heavily implanted Si within 40 seconds anneal time with minimum dopant diffusion compared to rapid thermal annealed samples. The use of microwave anneal to improve performance of multilayer thin film devices, e.g. thin film transistors (TFTs) requires extensive study of interaction of individual layers with electromagnetic radiation. This issue has been addressed by developing detail understanding of thin films and interfaces in TFTs by studying reliability and failure mechanisms upon extensive stress test. Electrical and ambient stresses such as illumination, thermal, and mechanical stresses are inflicted on the mixed oxide based thin film transistors, which are explored due to high mobilities of the mixed oxide (indium zinc oxide, indium gallium zinc oxide) channel layer material. Semiconductor parameter analyzer is employed to extract transfer characteristics, useful to derive mobility, subthreshold, and threshold voltage parameters of the transistors. Low temperature post processing anneals compatible with polymer substrates are performed in several ambients (oxygen, forming gas and vacuum) at 150 °C as a preliminary step. The analysis of the results pre and post low temperature anneals using device physics fundamentals

  9. Use of impure inert gases in the controlled heating and cooling of mixed conducting metal oxide materials

    DOEpatents

    Carolan, Michael Francis; Bernhart, John Charles

    2012-08-21

    Method for processing an article comprising mixed conducting metal oxide material. The method comprises contacting the article with an oxygen-containing gas and either reducing the temperature of the oxygen-containing gas during a cooling period or increasing the temperature of the oxygen-containing gas during a heating period; during the cooling period, reducing the oxygen activity in the oxygen-containing gas during at least a portion of the cooling period and increasing the rate at which the temperature of the oxygen-containing gas is reduced during at least a portion of the cooling period; and during the heating period, increasing the oxygen activity in the oxygen-containing gas during at least a portion of the heating period and decreasing the rate at which the temperature of the oxygen-containing gas is increased during at least a portion of the heating period.

  10. Exchange bias in a mixed metal oxide based magnetocaloric compound YFe0.5Cr0.5O3

    NASA Astrophysics Data System (ADS)

    Sharma, Mohit K.; Singh, Karan; Mukherjee, K.

    2016-09-01

    We report a detailed investigation of magnetization, magnetocaloric effect and exchange bias studies on a mixed metal oxide YFe0.5Cr0.5O3 belonging to perovskite family. Our results reveal that the compound is in canted magnetic state (CMS) where ferromagnetic correlations are present in an antiferromagnetic state. Magnetic entropy change of this compound follows a power law (∆SM∼Hm) dependence of magnetic field. In this compound, inverse magnetocaloric effect (IMCE) is observed below 260 K while conventional magnetocaloric effect (CMCE) above it. The exponent 'm' is found to be independent of temperature and field only in the IMCE region. Investigation of temperature and magnetic field dependence studies of exchange bias, reveal a competition between effective Zeeman energy of the ferromagnetic regions and anisotropic exchange energy at the interface between ferromagnetic and antiferromagnetic regions. Variation of exchange bias due to temperature and field cycling is also investigated.

  11. Laboratory evaluation of a two-stage treatment system for TCE cometabolism by a methane-oxidizing mixed culture

    SciTech Connect

    Smith, L.H.; McCarty, P.L.

    1997-08-20

    The objective of this research was to evaluate several factors affecting the performance of a two-stage treatment system employing methane-oxidizing bacteria for trichloroethylene (TCE) biodegradation. The system consists of a completely mixed growth reactor and a plug-flow transformation reactor in which the TCE is cometabolized. Laboratory studies were conducted with continuous growth reactors and batch experiments simulating transformation reactor conditions. Performance was characterized in terms of TCE transformation capacity (T{sub C}, g TCE/g cells), transformation yield (T{sub Y}, g TCE/g CH{sub 4}), and the rate coefficient ratio k{sub TCE}/K{sub S,TCE} (L/mg-d). The growth reactor variables studied were solids retention time (SRT) and nutrient nitrogen (N) concentration. Formate and methane were evaluated as potential transformation reactor amendments.

  12. Evaluation of existing United States` facilities for use as a mixed-oxide (MOX) fuel fabrication facility for plutonium disposition

    SciTech Connect

    Beard, C.A.; Buksa, J.J.; Chidester, K.; Eaton, S.L.; Motley, F.E.; Siebe, D.A.

    1995-12-31

    A number of existing US facilities were evaluated for use as a mixed-oxide fuel fabrication facility for plutonium disposition. These facilities include the Fuels Material Examination Facility (FMEF) at Hanford, the Washington Power Supply Unit 1 (WNP-1) facility at Hanford, the Barnwell Nuclear Fuel Plant (BNFP) at Barnwell, SC, the Fuel Processing Facility (FPF) at Idaho National Engineering Laboratory (INEL), the Device Assembly Facility (DAF) at the Nevada Test Site (NTS), and the P-reactor at the Savannah River Site (SRS). The study consisted of evaluating each facility in terms of available process space, available building support systems (i.e., HVAC, security systems, existing process equipment, etc.), available regional infrastructure (i.e., emergency response teams, protective force teams, available transportation routes, etc.), and ability to integrate the MOX fabrication process into the facility in an operationally-sound manner that requires a minimum amount of structural modifications.

  13. Enhanced strength in reduced graphene oxide/nickel composites prepared by molecular-level mixing for structural applications

    NASA Astrophysics Data System (ADS)

    Zhao, Chao

    2015-02-01

    An effective molecular-level mixing approach was used to prepare reduced graphene oxide (rGO)/Ni powders, which were directly consolidated into rGO/Ni composites by spark plasma sintering. The rGO/Ni composites were found to exhibit a homogeneous dispersion of rGO and a strong interfacial bonding between the rGO and the Ni matrix. The enhanced interfacial bonding was attributed to the oxygen-mediated bonding generated from the interactions between the residue functional groups of rGO and the Ni atoms. Tensile test revealed that 1.5 wt% rGO/Ni composites demonstrated a 95.2 % increase in tensile strength and a 327.6 % increase in yield strength, while simultaneously retained a 12.1 % of elongation. This study thus proposed an effective way to fabricate rGO/Ni composites with enhanced tensile properties.

  14. Chemical potential of oxygen in (U, Pu) mixed oxide with Pu/(U+Pu) = 0.46

    NASA Astrophysics Data System (ADS)

    Dawar, Rimpi; Chandramouli, V.; Anthonysamy, S.

    2016-05-01

    Chemical potential of oxygen in (U,Pu) mixed oxide with Pu/(U + Pu) = 0.46 was measured for the first time using H2/H2O gas equilibration combined with solid electrolyte EMF technique at 1073, 1273 and 1473 K covering an oxygen potential range of -525 to -325 kJ mol-1. The effect of oxygen potential on the oxygen to metal ratio was determined. Increase in oxygen potential increases the O/M. In this study the minimum O/M obtained was 1.985 below which reduction was not possible. Partial molar enthalpy ΔHbar O2 and entropy ΔSbar O2 of oxygen were calculated from the oxygen potential data. The values of -752.36 kJ mol-1 and 0.25 kJ mol-1 were obtained for ΔHbar O2 and ΔSbar O2 respectively.

  15. Observations of reactive nitrogen oxide fluxes by eddy covariance above a mid-latitude mixed hardwood forest

    NASA Astrophysics Data System (ADS)

    Geddes, J. A.; Murphy, J. G.

    2012-12-01

    Human impacts on the global nitrogen cycle have led to many environmental problems including tropospheric ozone and aerosol production, acidification, and eutrophication. However, accelerated nitrogen deposition may also be fertilizing carbon uptake by the world's forests, reducing the impact of global climate change. The observations presented here are part of a long-term interdisciplinary collaboration investigating carbon and nitrogen cycling at a mid-latitude mixed hardwood forest in central Ontario subject to high nitrogen deposition. This project focused on estimating dry deposition rates of reactive nitrogen oxides, as well as the chemical and meteorological controls on their fluxes. Measurements of NOx (= NO + NO2) and NOy (= NOx + NO3 + HNO3 + HONO + volatile p-NO3- + organic nitrates…) were made by a two-channel chemiluminescent analyzer (Air Quality Design, Inc.), where conversion of NO2 to NO was achieved by blue LED converter, and NOy to NO by a heated molybdenum tube. The inlet system was co-located with eddy covariance instrumentation for flux calculations on the top of a 30 m tower extending about 8 m above the forest canopy. The measurements were conducted between July 21 and October 9, 2011. The site is fairly removed from major NOx sources, with campaign average NOx mixing ratio of 550 ppt, although they reached above 2-3 ppb during more polluted events. Average NOy mixing ratios were 1500 ppt. Using meteorological data and back trajectories, we show that airflow from the south brought the highest concentrations of reactive nitrogen, and significant increases in dry deposition to the forest canopy. The magnitude of dry deposition was found to be proportional to NOy mixing ratios, with a small number of high concentration days contributing disproportionately to campaign-long dry deposition. Overall, dry deposition was estimated to contribute approximately 10% of total nitrate deposition to the forest. Diurnal patterns in the fluxes of air with

  16. XRD monitoring of α self-irradiation in uranium-americium mixed oxides.

    PubMed

    Horlait, Denis; Lebreton, Florent; Roussel, Pascal; Delahaye, Thibaud

    2013-12-16

    The structural evolution under (241)Am self-irradiation of U(1-x)Am(x)O(2±δ) transmutation fuels (with x ≤ 0.5) was studied by X-ray diffraction (XRD). Samples first underwent a preliminary heat treatment performed under a reducing atmosphere (Ar/H2(4%)) aiming to recover the previously accumulated structural defects. Over all measurements (carried out over up to a full year and for integrated doses up to 1.5 × 10(18) α-decay events·g(-1)), only fluorite U(1-x)Am(x)O(2±δ) solid solutions were observed. Within a few days after the end of the heat treatment, each of the five studied samples was slowly oxidized as a consequence of their move to air atmosphere, which is evidenced by XRD by an initial sharp decrease of the unit cell parameter. For the compounds with x ≤ 0.15, this oxidation occurred without any phase transitions, but for U0.6Am0.4O(2±δ) and U0.5Am0.5O(2±δ), this process is accompanied by a transition from a first fluorite solid solution to a second oxidized one, as the latter is thermodynamically stable in ambient conditions. In the meantime and after the oxidation process, (241)Am α self-irradiation caused a structural swelling up to ∼0.8 vol %, independently of the sample composition. The kinetic constants of swelling were also determined by regression of experimental data and are, as expected, dependent on x and thus on the dose rate. The normalization of these kinetic constants by sample α-activity, however, leads to very close swelling rates among the samples. Finally, evolutions of microstrain and crystallite size were also monitored, but for the considered dose rates and cumulated doses, α self-irradiation was found, within the limits of the diffractometer used, to have almost no impact on these characteristics. Microstrain was found to be influenced instead by the americium content in the materials (i.e., by the impurities associated with americium starting material and the increase of cationic charge heterogeneity with

  17. Complex Formation Between Lysozyme and Stabilized Micelles with a Mixed Poly(ethylene oxide)/Poly(acrylic acid) Shell.

    PubMed

    Karayianni, Maria; Gancheva, Valeria; Pispas, Stergios; Petrov, Petar

    2016-03-10

    The electrostatic complexation between lysozyme and stabilized polymeric micelles (SPMs) with a poly(acrylic acid) (PAA) or a mixed poly(ethylene oxide)/poly(acrylic acid) (PEO/PAA) shell (SPMs with a mixed shell, SPMMS) and a temperature-responsive poly(propylene oxide) (PPO) core was investigated by means of dynamic, static, and electrophoretic light scattering. The SPMs and different types of SPMMS used resulted from the self-assembly of PAA-PPO-PAA triblock copolymer chains, or PAA-PPO-PAA and PEO-PPO-PEO triblock copolymer chain mixtures (with varying chain lengths and molar ratios) in aqueous solutions at pH 10 and the subsequent cross-linking of their PPO cores via loading and photo-cross-linking of pentaerythritol tetraacrylate (PETA). The solution behavior, structure and properties of the formed complexes at pH 7 and 0.01 M ionic strength, were studied as a function of the protein concentration in the solution (the concentration of the stabilized micelles was kept constant) or equivalently the ratio of the two components. The complexation process and properties of the complexes proved to be dependent on the protein concentration, while of particular interest was the effect of the structure of the shell of the SPMs on the stability/solubility of the complexes. Finally, the fluorescence and mid infrared spectroscopic investigation of the structure of the complexed protein showed that, although a small stretching of the protein molecules occurred in some cases, no protein denaturation takes place upon complexation. PMID:26881445

  18. Effects of Silver Nanoparticles on Primary Mixed Neural Cell Cultures: Uptake, Oxidative Stress and Acute Calcium Responses

    PubMed Central

    Haase, Andrea; Rott, Stephanie; Mantion, Alexandre; Graf, Philipp; Plendl, Johanna; Thünemann, Andreas F.; Meier, Wolfgang P.; Taubert, Andreas; Luch, Andreas; Reiser, Georg

    2012-01-01

    In the body, nanoparticles can be systemically distributed and then may affect secondary target organs, such as the central nervous system (CNS). Putative adverse effects on the CNS are rarely investigated to date. Here, we used a mixed primary cell model consisting mainly of neurons and astrocytes and a minor proportion of oligodendrocytes to analyze the effects of well-characterized 20 and 40 nm silver nanoparticles (SNP). Similar gold nanoparticles served as control and proved inert for all endpoints tested. SNP induced a strong size-dependent cytotoxicity. Additionally, in the low concentration range (up to 10 μg/ml of SNP), the further differentiated cultures were more sensitive to SNP treatment. For detailed studies, we used low/medium dose concentrations (up to 20 μg/ml) and found strong oxidative stress responses. Reactive oxygen species (ROS) were detected along with the formation of protein carbonyls and the induction of heme oxygenase-1. We observed an acute calcium response, which clearly preceded oxidative stress responses. ROS formation was reduced by antioxidants, whereas the calcium response could not be alleviated by antioxidants. Finally, we looked into the responses of neurons and astrocytes separately. Astrocytes were much more vulnerable to SNP treatment compared with neurons. Consistently, SNP were mainly taken up by astrocytes and not by neurons. Immunofluorescence studies of mixed cell cultures indicated stronger effects on astrocyte morphology. Altogether, we can demonstrate strong effects of SNP associated with calcium dysregulation and ROS formation in primary neural cells, which were detectable already at moderate dosages. PMID:22240980

  19. Transparent conductive oxide films mixed with gallium oxide nanoparticle/single-walled carbon nanotube layer for deep ultraviolet light-emitting diodes

    PubMed Central

    2013-01-01

    We propose a transparent conductive oxide electrode scheme of gallium oxide nanoparticle mixed with a single-walled carbon nanotube (Ga2O3 NP/SWNT) layer for deep ultraviolet light-emitting diodes using spin and dipping methods. We investigated the electrical, optical and morphological properties of the Ga2O3 NP/SWNT layers by increasing the thickness of SWNTs via multiple dipping processes. Compared with the undoped Ga2O3 films (current level 9.9 × 10-9 A @ 1 V, transmittance 68% @ 280 nm), the current level flowing in the Ga2O3 NP/SWNT increased by approximately 4 × 105 times and the transmittance improved by 9% after 15 times dip-coating (current level 4 × 10-4 A at 1 V; transmittance 77.0% at 280 nm). These improvements result from both native high transparency of Ga2O3 NPs and high conductivity and effective current spreading of SWNTs. PMID:24295342

  20. Rod-like CuMnOx transformed from mixed oxide particles by alkaline hydrothermal treatment as a novel catalyst for catalytic combustion of toluene.

    PubMed

    Li, W B; Liu, Z X; Liu, R F; Chen, J L; Xu, B Q

    2016-08-17

    Rod-like copper manganese mixed oxides (CuMnx-NR) have been synthesized from copper manganese mixed oxide particles by sodium hydroxide hydrothermal treatment, and a higher BET surface area of 221 m(2) g(-1) is obtained on the nanorod-like sample, which exhibits superior catalytic activity toward toluene combustion at 210 °C due to the increase in its oxygen mobility of the chemisorbed oxygen species as well as the increase in surface concentrations of higher valance cations, Cu(2+), Mn(3+) and Mn(4+), in the samples. PMID:27498822

  1. Toward the Control of the Creation of Mixed Monolayers on Glassy Carbon Surfaces by Amine Oxidation.

    PubMed

    Groppi, Jessica; Bartlett, Philip N; Kilburn, Jeremy D

    2016-01-18

    A versatile and simple methodology for the creation of mixed monolayers on glassy carbon (GC) surfaces was developed, using an osmium-bipyridyl complex and anthraquinone as model redox probes. The work consisted in the electrochemical grafting on GC of a mixture of mono-protected diamine linkers in varying ratios which, after attachment to the surface, allowed orthogonal deprotection. After optimisation of the deprotection conditions, it was possible to remove one of the protecting groups selectively, couple a suitable osmium complex and cap the residual free amines. The removal of the second protecting group allowed the coupling of anthraquinone. The characterisation of the resulting surfaces by cyclic voltammetry showed the variation of the surface coverage of the two redox centres in relation to the initial ratio of the linking amine in solution. PMID:26637108

  2. Spectroscopic study of mixed oxide SAT 1- x:LA x perovskite crystals

    NASA Astrophysics Data System (ADS)

    Runka, T.; Łapsa, K.; Łapiński, A.; Aleksiyko, R.; Berkowski, M.; Drozdowski, M.

    2004-10-01

    Mixed perovskite crystals have been grown from multicomponent melts using the Czochralski method. The Raman, FT-IR and Brillouin investigations of perovskite (1- x)Sr(Al 0.5Ta 0.5)O 3: xLaAlO 3 crystals are reported. The measurements have been performed for several LA concentrations in the range 0.22≤ x≤0.36 at room temperature. The assignment of vibrational modes of IR and Raman spectra was proposed. The experimental results were correlated with structural data, obtained from X-ray diffraction study. The dependence of hypersonic velocity of transverse and longitudinal modes as a function of LA content was also determined. Spectroscopic investigations confirmed the disordered Al/Ta distribution, which increases with the increase of LA content.

  3. Sputtering deposition of Al-doped zinc oxide thin films using mixed powder targets

    NASA Astrophysics Data System (ADS)

    Ohshima, Tamiko; Maeda, Takashi; Tanaka, Yuki; Kawasaki, Hiroharu; Yagyu, Yoshihito; Ihara, Takeshi; Suda, Yoshiaki

    2016-01-01

    Sputtering deposition generally uses high-density bulk targets. Such a fabrication process has various problems including deterioration of the material during heating and difficulty in mixing a large number of materials in precise proportions. However, these problems can be solved by using a powder target. In this study, we prepared Al-doped ZnO (AZO) as transparent conductive thin films by radio-frequency magnetron sputtering with powder and bulk targets. Both the powder and bulk targets formed crystalline structures. The ZnO (002) peak was observed in the X-ray diffraction measurements. The mean transparency and resistivity of the films prepared with the powder target were 82% and 0.548 Ω · cm, respectively. The deposition rate with the powder target was lower than that with the bulk target.

  4. Spontaneous Emulsification of Triolein Induced by Mixed Micellar Solutions of Sodium Polyoxyethylene Alkyl Ether Sulfate and Dodecyldimethyl Amine Oxide.

    PubMed

    Endo, Chika; Ito, Yoshiko; Akabane, Chika; Kaneko, Yukihiro; Sakai, Hideki

    2015-01-01

    A new mechanism of spontaneous emulsification without any salts or co-solvents is described, and is related to the dilatational behavior. Spontaneous emulsification can reduce the time required to remove oily soils from hard surfaces and enhance the detergency, because this type of emulsification requires no external mechanical work. In this paper, we focused on triolein, the main component of food oils and human sebum soil, and tried to induce spontaneous emulsification by using mixed micellar solutions of sodium polyoxyethylene alkyl ether sulfate and N, N-dimethyldodecylamine oxide (AES/DDAO). We characterized the dilatation of the oil/water interface using dynamic interfacial tension and elasticity measurements. This study confirmed that the degree of spontaneous emulsification can be enhanced by controlling the molar ratio of DDAO to AES. This enhancement can be attributed to an increased rate of decrease in the dynamic interfacial tension (i.e., a decreased interface dilatational elasticity), allowing for much greater suppression of the Marangoni effect. Further, we determined that one of the reasons for the decrease in the interface dilatational elasticity is the increasing number of micelles near the oil drop interface, which results from a decrease in the electrostatic repulsion between the micelles and the drop interface. Therefore, controlling the molar ratio of a mixed anionic/amphoteric surfactant solution is an effective way to induce spontaneous emulsification in the absence of salts or co-solvents. PMID:26250425

  5. MOF-derived binary mixed metal/metal oxide @carbon nanoporous materials and their novel supercapacitive performances.

    PubMed

    Wang, Y C; Li, W B; Zhao, L; Xu, B Q

    2016-07-21

    Mixed cobalt and manganese oxides embedded in the nanoporous carbon framework (M/MO@C) were synthesized by the direct carbonization of a binary mixed-metal organic framework (CoMn-MOF-74) for the first time. The unique M/MO@C carbon materials maintained the primary morphology of CoMn-MOF-74, and showed a uniform dispersibility of Co, MnO and CoO nanoparticles in the carbon matrix, and therefore greatly increased the conductivity of the M/MO@C materials. A series of M/MO@C samples were tested as the electrode materials for supercapacitors, and a remarkable specific capacitance of 800 F g(-1) was obtained using the M/MO@C-700 sample at a current density of 1 A g(-1) in 6 M KOH electrolyte. Moreover, the M/MO@C sample showed a good cycling stability with a capacitance retention of 85% after 1000 cycles. It is also found that the optimized carbonization temperature is a critical parameter to obtain such a M/MO@C nanoporous carbon framework with the best capacitive performances. The present approach is convenient and reproducible, which could be easily extended to the preparation of other M/MO@C composites with excellent electrochemical performances. PMID:27328374

  6. Fractionation of Nitrous Oxide Isotopomers in the Stratosphere: Enrichment Factors and the Effects of Transport and Mixing

    NASA Astrophysics Data System (ADS)

    Griffith, D. W.; Toon, G. C.; Sen, B.; Blavier, J.

    2002-05-01

    We have measured vertical profiles of the mixing ratios of the four most abundant isotopomers of nitrous oxide, 14N14N16O, 14N15N16O, 15N14N16O, and 14N14N18O, by remote sensing during 11 balloon flights of the JPL MkIV Fourier transform interferometer. The measurements span from the tropopause to around 30 km at northern mid-high latitudes between 1992 and 2000, and include two polar vortex flights in the 1999-2000 winter. We present a flight-by-flight analysis of the vertical profiles and enrichment factors and compare them with other recently published profiles and laboratory measurements. The observed profiles adhere well to a Rayleigh distillation model above 20-24 km, consistent with an irreversible sink process for N2O, but we observe some deviation from strictly Rayleigh behaviour in the profiles in the lower stratosphere. By correlation with profiles of CH4 measured from the same spectra, we find these deviations to be consistent with the effects of atmospheric transport and mixing processes.

  7. INVESTIGATION OF MIXED METAL SORBENT/CATALYSTS FOR THE SIMULTANEOUS REMOVAL OF SULFUR AND NITROGEN OXIDES

    SciTech Connect

    Ates Akyurtlu; Jale F. Akyurtle

    2001-08-01

    Simultaneous removal of SO{sub 2} and NO{sub x} using a regenerable solid sorbent will constitute an important improvement over the use of separate processes for the removal of these two pollutants from stack gases and possibly eliminate several shortcomings of the individual SO{sub 2} and NO{sub x} removal operations. The work done at PETC and the DOE-funded investigation of the investigators on the sulfation and regeneration of alumina-supported cerium oxide sorbents have shown that they can perform well at relatively high temperatures (823-900 K) as regenerable desulfurization sorbents. Survey of the recent literature shows that addition of copper oxide to ceria lowers the sulfation temperature of ceria down to 773 K, sulfated ceria-based sorbents can function as selective SCR catalysts even at elevated temperatures, SO{sub 2} can be directly reduced to sulfur by CO on CuO-ceria catalysts, and ceria-based catalysts may have a potential for selective catalytic reduction of NO{sub x} by methane. These observations indicate a possibility of developing a ceria-based sorbent/catalyst which can remove both SO{sub 2} and NO{sub x} from flue gases within a relatively wide temperature window, produce significant amounts of elemental sulfur during regeneration, and use methane for the selective catalytic reduction of NO{sub x}.

  8. Acidic and catalytic properties of SiO{sub 2}-Ta{sub 2}O{sub 5} mixed oxides prepared by the sol-gel method

    SciTech Connect

    Guiu, G.; Grange, P.

    1995-09-15

    The acidic and catalytic properties of a series of silicon-tantalum mixed oxides containing between 0 and 30 at% tantalum were characterized by temperature-programmed desorption of ammonia, by FTIR spectra of adsorbed pyridine, and by the test reaction of 1-butanol dehydration at 250-300{degrees}C. Probe molecule adsorption and catalytic testing show an acid site generation in silicon-tantalum mixed oxides compared to pure tantalum oxide. Both Bronsted and Lewis acid sites are present on the mixed oxide surface. Bronsted and Lewis acid sites seem to be weaker in SiO{sub 2}-Ta{sub 2}O{sub 5} mixed oxide than in analogous SiO{sub 2}-Al{sub 2}O{sub 3}, since a greater reaction temperature is required to achieve the same conversion in the above test reaction. However, a great advantage of this new solid acid is the production of butenes with 100% selectivity. 30 refs., 5 figs., 3 tabs.

  9. Nitrous oxide net exchange in a beech dominated mixed forest in Switzerland measured with a quantum cascade laser spectrometer

    NASA Astrophysics Data System (ADS)

    Eugster, W.; Zeyer, K.; Zeeman, M.; Michna, P.; Zingg, A.; Buchmann, N.; Emmenegger, L.

    2007-04-01

    Nitrous oxide fluxes were measured at the Lägeren CarboEurope IP flux site over the multi-species mixed forest dominated by European beech and Norway spruce. Measurements were carried out during a four-week period in October-November 2005 during leaf senescence. Fluxes were measured with a standard ultrasonic anemometer in combination with a quantum cascade laser absorption spectrometer that measured N2O, CO2, and H2O mixing ratios simultaneously at 5 Hz time resolution. To distinguish insignificant fluxes from significant ones it is proposed to use a new approach based on the significance of the correlation coefficient between vertical wind speed and mixing ratio fluctuations. This procedure eliminated roughly 56% of our half-hourly fluxes. Based on the remaining, quality checked N2O fluxes we quantified the mean efflux at 0.8 ± 0.4 μmol m-2 h-1 (mean ± standard error). Most of the contribution to the N2O flux occurred during a 6.5-h period starting 4.5 h before each precipitation event. No relation with precipitation amount could be found. Visibility data representing fog density and duration at the site indicate that wetting of the canopy may have as strong an effect on N2O effluxes as does below-ground microbial activity. It is speculated that above-ground N2O production from the senescing leaves at high moisture (fog, drizzle, onset of precipitation event) may be responsible for part of the measured flux. In comparison with the annual CO2 budget of -342 g C m-2 yr-1 it is estimated that concurrent N2O fluxes offset at least 5% of the greenhouse forcing reduction via net CO2 uptake.

  10. Strong interfacial polarization in ZnO decorated reduced-graphene oxide synthesized by molecular level mixing.

    PubMed

    Jammula, Rama Krishna; Pittala, Suresh; Srinath, Sanyadhanam; Srikanth, Vadali V S S

    2015-07-14

    Globally, there is a great demand for energy storage materials and devices. In this context, charge storage capacitors are of great prominence. Metal oxide-graphene composites are excellent candidates for charge storage materials. This is because the dielectric properties of these composites can be controlled by the nature, dimensions and spatial distribution of the conductive components in these composites. ZnO decorated reduced-graphene oxide (r-GO) is synthesized and studied in this context. ZnO-r-GO composites are synthesized using molecular-level mixing. The composites are named as ZnO-0.1G, ZnO-0.2G and ZnO-0.3G in the order of increasing r-GO content. At 1 kHz, the dielectric permittivity (ε') values of ZnO-0.1G, ZnO-0.2G and ZnO-0.3G are nearly 11 (ε' = 114), 15 (ε' = 153) and 40 (ε' = 400) times greater than that of ZnO (ε' = 10). The strong interfacial polarization (Maxwell-Wagner polarization) in these composites is attributed to the presence of functional groups (which are polar in nature) on the r-GO sheets and also to the presence of lattice and/or topological defects in the r-GO. Temperature dependent electric modulus (M'') studies further confirm the observed interfacial polarization. PMID:26073161

  11. Curium analysis in plutonium uranium mixed oxide by x-ray fluorescence and absorption fine structure spectroscopy.

    PubMed

    Degueldre, C; Borca, C; Cozzo, C

    2013-10-15

    Plutonium uranium mixed oxide (MOX) fuels are being used in commercial nuclear reactors. The actinides in these fuels need to be analyzed after irradiation for assessing their behaviour with regards to their environment and the coolant. In this work the study of the local occurrence, speciation and next-neighbour environment of curium (Cm) in the (Pu,U)O2 lattice within an irradiated (60 MW d kg(-1) average burn-up) MOX sample was performed employing micro-x-ray fluorescence (µ-XRF) and micro-x-ray absorption fine structure (µ-XAFS) spectroscopy. The chemical bonds, valences and stoichiometry of Cm (≈ 0.7 wt% in the rim and ≈ 0.03 wt% in the centre) are determined from the experimental data gained for the irradiated fuel material examined in its centre and peripheral (rim) zones of the fuel. Curium occurrence is also reduced from the centre (hot) to the periphery (colder) because of the condensation of these volatile oxides. In the irradiated sample Cm builds up as Cm(3+) species (>90%) within a [CmO8](13-) or [CmO7](11-) coordination environment and no (<10%) Cm(IV) can be detected in the rim zone. Curium dioxide is reduced because of the redox buffering activity of the uranium dioxide matrix and of its thermodynamic instability. PMID:24054692

  12. CaFeAl mixed oxide derived heterogeneous catalysts for transesterification of soybean oil to biodiesel.

    PubMed

    Lu, Yongsheng; Zhang, Zaiwu; Xu, Yunfeng; Liu, Qiang; Qian, Guangren

    2015-08-01

    CaAl layered double oxides (LDO) were prepared by co-precipitation and calcined at 750°C, and then applied to biodiesel production by transesterification reaction between methanol and soybean oil. Compared with characteristics of CaFe/LDO and CaAl/LDO, CaFeAl/LDO had the best performance based on prominent catalytic activity and stability, and achieved over 90% biodiesel yield, which stayed stable (over 85%) even after 8 cycles of reaction. The optimal catalytic reaction condition was 12:1M-ratio of methanol/oil, reaction temperatures of 60°C, 270rpm stirring rate, 60min reaction time, and 6% weight-ratio of catalyst/oil. In addition, the CaFeAl/LDO catalyst is insoluble in both methanol and methyl esters and can be easily separated for further reaction, turning it into an excellent alternative for biodiesel synthesis. PMID:25740001

  13. Titania-silica mixed oxides. II. Catalytic behaviour in olefin epoxidation

    SciTech Connect

    Hutter, R.; Mallat, T.; Baiker, A.

    1995-04-15

    Various titania-silica aerogels prepared by an alkoxide-sol-gel route have been tested in the epoxidation of bulky olefins using cumene hydroperoxide as oxidant. The drying method, the titanium content between 2 and 20 wt%, and the calcination temperature between 473 and 1073 K were the most important preparation parameters, influencing the catalytic behaviour of the aerogels. The aerogels dried by semicontinuous extraction with supercritical CO{sub 2} at low temperature (LT aerogel) were found to be much more efficient epoxidation catalysts than aerogels prepared by high-temperature supercritical drying and conventionally dried xerogels. The reaction rate of cyclohexene epoxidation over LT aerogels increased monotonically with increasing Ti content. In the range of 333-363 K the catalysts containing 20 wt% TiO{sub 2} (20LT) showed high activity and selectivity (79-93% to peroxide and 87-100% to epoxide) in the oxidation of various cyclic olefins, including cyclododecene, norbornene, cyclohexene, and limonene. Catalytic experiments, FTIR, and UV-vis spectroscopy indicated that the LT aerogels consist of two different types of active species: titanium well-dispersed in the silica matrix and titania nanodomains. The key factors determining the activity and selectivity of sol-gel titania-silica catalysts are the morphology (surface area and pore size) and the relative proportions of Ti-O-Si and Ti-O-Ti structural parts. A comparative study of the epoxidation of cyclohexene, cyclododecene, and norbornene over structurally different titania-silica catalysts, indicates that 20LT shows better catalytic behaviour in these reactions than Ti zeolites and silica-supported titania. 46 refs., 12 figs., 3 tabs.

  14. Performance of Thorium-Based Mixed Oxide Fuels for the Consumption of Plutonium in Current and Advanced Reactors

    SciTech Connect

    Weaver, Kevan Dean; Herring, James Stephen

    2003-07-01

    A renewed interest in thorium-based fuels has arisen lately based on the need for proliferation resistance, longer fuel cycles, higher burnup, and improved waste form characteristics. Recent studies have been directed toward homogeneously mixed, heterogeneously mixed, and seed-and-blanket thorium-uranium oxide fuel cycles that rely on "in situ" use of the bred-in 233U. However, due to the higher initial enrichment required to achieve acceptable burnups, these fuels are encountering economic constraints. Thorium can nevertheless play a large role in the nuclear fuel cycle, particularly in the reduction of plutonium inventories. While uranium-based mixed-oxide (MOX) fuel will decrease the amount of plutonium in discharged fuel, the reduction is limited due to the breeding of more plutonium (and higher actinides) from the 238U. Here, we present calculational results and a comparison of the potential burnup of a thorium-based and uranium-based mixed-oxide fuel in a light water reactor. Although the uranium-based fuels outperformed the thorium-based fuels in achievable burnup, a depletion comparison of the initially charged plutonium (both reactor and weapons grade) showed that the thorium-based fuels outperformed the uranium-based fuels by more that a factor of 2, where >70% of the total plutonium in the thorium-based fuel is consumed during the cycle. This is significant considering that the achievable burnups of the thorium-based fuels were 1.4 to 4.6 times less than the uranium-based fuels for similar plutonium enrichments. For equal specific burnups of ~60 MWd/kg (i.e., using variable plutonium weight percentages to give the desired burnup), the thorium-based fuels still outperform the uranium-based fuels by more than a factor of 2, where the total plutonium consumption in a three-batch, 18-month cycle was 60 to 70%. This is fairly significant considering that 10 to 15% (by weight) more plutonium is needed in the thorium-based fuels as compared to the uranium

  15. Thin film mixed potential nitrogen oxide sensor development for stationary reciprocating engine applications.

    SciTech Connect

    Brosha, E. L.; Mukundan, R.; Lujan, R.; Garzon, F. H.

    2004-01-01

    Mixed potential sensors using thin film Mg-doped LaCrO{sub 3} working electrodes, Pt counter electrodes, and thin film YSZ electrolytes on Al{sub 2}O{sub 3} polycrystalline substrates were prepared and studied at 600 and 650 C in 10.4% O{sub 2}/N{sub 2} balance and in air atmospheres for NO, NO{sub 2}, CO, and hydrocarbon responses. The lanthanum chromite-based sensors showed preferential sensitivity to NO{sub 2} with cross sensitivity to CO and nonmethane hydrocarbons such as C{sub 3}H{sub 6} and C{sub 3}H{sub 8}. In contrast, sensors with spinel NiCr{sub 2}O{sub 4} working electrodes show minimal sensitivity to NO{sub 2}. The use of a heated Pt black pre-catalyst upstream to the sensor was demonstrated and the use of this pre-catalyst effectively removed the CO and hydrocarbon response however more work needs to be done to understand the NO/NO{sub 2} chemistry post catalyst. Studies conducted for up to 800 hrs at 600 C show minimal aging in these devices.

  16. Processing and property evaluation of tungsten-based mixed oxides for photovoltaics and optoelectronics

    NASA Astrophysics Data System (ADS)

    Vargas, Mirella

    Tungsten Oxide (WO3) films and low-dimensional structures have proven to be promising candidates in the fields of photonics and electronics. WO3 is a well-established n-type semiconductor characterized by unique electrochromic behavior, an ideal optical band gap that permits transparency over a wide spectral range, and high chemical integrity. The plethora of diverse properties endow WO3 to be highly effective in applications related to electrochromism, gas sensing, and deriving economical energy. Compared to the bulk films, a materials system involving WO3 and a related species (elements or metal oxides) offer the opportunity to tailor the electrochromic response, and an overall enhancement of the physio-chemical and optical properties. In the present case, WO3 and TiO2 composite films have been fabricated by reactive magnetron sputtering employing W/Ti alloy targets, and individual W and Ti targets for co-sputtering. Composite WO3-TiO2 films were fabricated with variable chemical composition and the effect of variable bulk chemistry on film structure, surface/interface chemistry and chemical valence state of the W and Ti cations was investigated in detail. The process-property relationships between composition and physical properties for the films deposited by using W/Ti alloy targets of variable Ti content are associated with decreases in the deposition rate of the WO3-TiO2 films due to the lower sputter yield of the strongly bonded TiO2 formed on the target surface. Additionally, for the co-sputtered films using variable tungsten power, the optical properties demonstrate unique optical modulation. The changes associated with the physical color of the films demonstrate the potential to tailor the optical behavior for the design and fabrication of multilayer photovoltaic and catalytic devices. The process-structure-property correlation derived in this work will provide a road-map to optimize and produce W-Ti-O thin films with desired properties for a given

  17. Influence of ion beam mixing on the growth of high temperature oxide superconducting thin film

    SciTech Connect

    Bordes, N.; Rollett, A.D.; Cohen, M.R.; Nastasi, M.

    1989-01-01

    The superconducting properties of high temperature superconductor thin films are dependent on the quality of the substrate used to grow these films. In order to maximize the lattice matching between the superconducting film and the substrate, we have used a YBa{sub 2}Cu{sub 3}O{sub 7} thin film deposited on {l angle}100{r angle} SrTiO{sub 3} as a template. The first film was prepared by coevaporation of Y, BaF{sub 2} and Cu on {l angle}100{r angle} SrTiO{sub 3}, followed by an anneal in wet'' oxygen at 850{degree}C. This film showed a sharp transition at about 90 K. A thicker layer of about 5000 A was then deposited on top of this first 2000 {angstrom} film, using the same procedure. After the post anneal at 850{degree}C, the transition took place at 80 K and no epitaxy of the second film was observed. Ion beam mixing at 400{degree}C, using 400 keV O ions was done at the interface of the two films (the second one being not annealed). After the post anneal, the film displayed an improved Tc at 90K. Moreover, epitaxy was shown to take place from the interface SrTiO{sub 3}-123 film towards the surface and was dependent of the dose. These results will be discussed from the data obtained from Rutherford backscattering spectroscopy (RBS) combined with channeling experiments, x-ray diffraction (XRD) and scanning electron microscopy (SEM) observations. 8 refs., 2 figs., 2 tabs.

  18. Aluminum manganese oxides with mixed crystal structure: high-energy-density cathodes for rechargeable sodium batteries.

    PubMed

    Han, Dong-Wook; Ku, Jun-Hwan; Kim, Ryoung-Hee; Yun, Dong-Jin; Lee, Seok-Soo; Doo, Seok-Gwang

    2014-07-01

    We report a new discovery for enhancing the energy density of manganese oxide (Nax MnO2 ) cathode materials for sodium rechargeable batteries by incorporation of aluminum. The Al incorporation results in NaAl(0.1) Mn(0.9) O2 with a mixture of tunnel and layered crystal structures. NaAl(0.1) Mn(0.9) O2 shows a much higher initial discharge capacity and superior cycling performance compared to pristine Na(0.65) MnO2 . We ascribe this enhancement in performance to the formation of a new orthorhombic layered NaMnO2 phase merged with a small amount of tunnel Na(0.44) MnO2 phase in NaAl(0.1) Mn(0.9) O2 , and to improvements in the surface stability of the NaAl(0.1) Mn(0.9) O2 particles caused by the formation of Al-O bonds on their surfaces. Our findings regarding the phase transformation and structure stabilization induced by incorporation of aluminum, closely related to the structural analogy between orthorhombic Na(0.44) MnO2 and NaAl(0.1) Mn(0.9) O2 , suggest a strategy for achieving sodium rechargeable batteries with high energy density and stability. PMID:24797956

  19. Textural, structural, and morphological characterizations and catalytic activity of nanosized CeO(2)-MO(x) (M=Mg(2+), Al(3+), Si(4+)) mixed oxides for CO oxidation.

    PubMed

    Yu, Qiang; Wu, Xiaoxia; Tang, Changjin; Qi, Lei; Liu, Bin; Gao, Fei; Sun, Keqin; Dong, Lin; Chen, Yi

    2011-02-01

    The present work focuses on the combination of ceria with another oxide of different ionic valences from period 3 (Mg(2+), Al(3+), and Si(4+)) using coprecipitation method, followed by calcination at 450 and 750°C, respectively. The textural, structural, morphological and redox properties of nanosized ceria-magnesia, ceria-alumina and ceria-silica mixed oxides have been investigated by means of N(2) physisorption, XRD, Raman, HRTEM, DRS, FT-IR, and H(2)-TPR technologies. XRD results of these mixed oxides reveal that only nanocrystalline ceria (ca. 3-6nm for the 450°C calcined samples) could be observed. The grain size of ceria increases with the increasing calcination temperature from 450 to 750°C due to sintering effect. The highest specific surface area is obtained at CeO(2)-Al(2)O(3) mixed oxides when calcination temperature reaches 750°C. Raman spectra display the cubic fluorite structure of ceria and the existence of oxygen vacancies, and displacement of oxygen ions from their normal lattice positions in the ceria-based mixed oxides. DRS measurements confirm that the smaller the grain size of the ceria, the higher indirect band gap energy. H(2)-TPR results suggest that the reductions of surface and bulk oxygen of ceria were predominant at low and high calcination temperature, respectively. Finally, CO oxidation were performed over these ceria-based mixed oxides, and the combination of CeO(2)-Al(2)O(3) exhibited highest activity irrespective of calcination temperature, which may due to excellent textural/structural properties, good homogeneity, and redox abilities. PMID:21074167

  20. Formation of Prussian-Blue-Analog Nanocages via a Direct Etching Method and their Conversion into Ni-Co-Mixed Oxide for Enhanced Oxygen Evolution.

    PubMed

    Han, Lei; Yu, Xin-Yao; Lou, Xiong Wen David

    2016-06-01

    Novel Ni-Co-Prussian-blue-analog nano-cages consisting of pyramid-like walls were prepared via a facile chemical etching process with ammonia at room temperature. After annealing in air, the derived Ni-Co mixed oxide nanocages exhibit enhanced electrocatalytic activity and excellent stability toward the oxygen-evolution reaction. PMID:27008038

  1. Molybdenum-based additives to mixed-metal oxides for use in hot gas cleanup sorbents for the catalytic decomposition of ammonia in coal gases

    DOEpatents

    Ayala, Raul E.

    1993-01-01

    This invention relates to additives to mixed-metal oxides that act simultaneously as sorbents and catalysts in cleanup systems for hot coal gases. Such additives of this type, generally, act as a sorbent to remove sulfur from the coal gases while substantially simultaneously, catalytically decomposing appreciable amounts of ammonia from the coal gases.

  2. Oxygen surface exchange kinetics of SrTi(1-x)Fe(x)O(3-δ) mixed conducting oxides.

    PubMed

    Yoo, Chung-Yul; Bouwmeester, Henny J M

    2012-09-01

    The oxygen surface exchange kinetics of mixed conducting perovskite oxides SrTi(1-x)Fe(x)O(3-δ) (x = 0, 0.01, 0.05, 0.35, 0.5) has been investigated as a function of temperature and oxygen partial pressure using the pulse-response (18)O-(16)O isotope exchange (PIE) technique. Arrhenius activation energies range from 140 kJ mol(-1) for x = 0 to 86 kJ mol(-1) for x = 0.5. Extrapolating the temperature dependence to the intermediate temperature range, 500-600 °C, indicates that the rate of oxygen exchange, in air, increases with increasing iron mole fraction, but saturates at the highest iron mole fraction for the given series. The observed behavior is concomitant with corresponding increases in both electronic and ionic conductivity with increasing x in SrTi(1-x)Fe(x)O(3-δ). Including literature data of related perovskite-type oxides Ba(0.5)Sr(0.5)Co(0.8)Fe(0.2)O(3-δ), La(0.6)Sr(0.4)Co(0.2)Fe(0.8)O(3-δ), La(0.6)Sr(0.4)CoO(3-δ), and Sm(0.5)Sr(0.5)CoO(3-δ), a linear relationship is observed in the log-log plot between oxygen exchange rate and oxide ionic conductivity with a slope fairly close to unity, suggesting that it is the magnitude of the oxide ionic conductivity that governs the rate of oxygen exchange in these solids. The distribution of oxygen isotopomers ((16)O(2), (16)O(18)O, (18)O(2)) in the effluent pulse can be interpreted on the basis of a two-step exchange mechanism for the isotopic exchange reaction. Accordingly, the observed power law dependence of the overall surface exchange rate on oxygen partial pressure turns out to be an apparent one, depending on the relative rates of both steps involved in the adopted two-step scheme. Supplementary research is, however, required to elucidate which of the two possible reaction schemes better reflects the actual kinetics of oxygen surface exchange on SrTi(1-x)Fe(x)O(3-δ). PMID:22829205

  3. Characterization of the Fe-Doped Mixed-Valent Tunnel Structure 2 Manganese Oxide KOMS-2

    SciTech Connect

    Hanson J. C.; Shen X.; Morey A.M.; Liu J.; Ding Y.; Cai J.; Durand J.; Wang Q.; Wen W.; Hines W.A.; Bai J.; Frenkel A.I.; Reiff W.; Aindow M.; Suib S.L.

    2011-11-10

    A sol-gel-assisted combustion method was used to prepare Fe-doped manganese oxide octahedral molecular sieve (Fe-KOMS-2) materials with the cryptomelane structure. Characterization of the nanopowder samples over a wide range of Fe-doping levels (0 {le} Fe/Mn {le} 1/2) was carried out using a variety of experimental techniques. For each sample, Cu K{alpha} XRD and ICP-AES were used to index the cryptomelane structure and determine the elemental composition, respectively. A combination of SEM and TEM images revealed that the morphology changes from nanoneedle to nanorod after Fe doping. Furthermore, TGA scans indicated that the thermal stability is also enhanced with the doping. Anomalous XRD demonstrated that the Fe ions replace the Mn ions in the cryptomelane structure, particularly in the (211) planes, and results in a lattice expansion along the c axis, parallel to the tunnels. Reasonable fits to EXAFS data were obtained using a model based on the cryptomelane structure. Moessbauer spectra for selected Fe-KOMS-2 samples indicated that the Fe is present as Fe{sup 3+} in an octahedral environment similar to Mn in the MnO{sub 6} building blocks of KOMS-2. Magnetization measurements detected a small amount of {gamma}-Fe{sub 2}O{sub 3} second phase (e.g., 0.6 wt % for the Fe/Mn = 1/10 sample), the vast majority of the Fe being in the structure as Fe{sup 3+} in the high-spin state.

  4. Theranostic Application of Mixed Gold and Superparamagnetic Iron Oxide Nanoparticle Micelles in Glioblastoma Multiforme

    PubMed Central

    Sun, Lova; Joh, Daniel Y.; Al-Zaki, Ajlan; Stangl, Melissa; Murty, Surya; Davis, James J.; Baumann, Brian C.; Alonso-Basanta, Michelle; Kao, Gary D.; Tsourkas, Andrew; Dorsey, Jay F.

    2016-01-01

    The treatment of glioblastoma multiforme, the most prevalent and lethal form of brain cancer in humans, has been limited in part by poor delivery of drugs through the blood-brain barrier and by unclear delineation of the extent of infiltrating tumor margins. Nanoparticles, which selectively accumulate in tumor tissue due to their leaky vasculature and the enhanced permeability and retention effect, have shown promise as both therapeutic and diagnostic agents for brain tumors. In particular, superparamagnetic iron oxide nanoparticles (SPIONs) have been leveraged as T2-weighted MRI contrast agents for tumor detection and imaging; and gold nanoparticles (AuNP) have been demonstrated as radiosensitizers capable of propagating electron and free radical-induced radiation damage to tumor cells. In this study, we investigated the potential applications of novel gold and SPION-loaded micelles (GSMs) coated by polyethylene glycol-polycaprolactone (PEG-PCL) polymer. By quantifying gh2ax DNA damage foci in glioblastoma cell lines, we tested the radiosensitizing efficacy of these GSMs, and found that GSM administration in conjunction with radiation therapy (RT) led to ~2-fold increase in density of double-stranded DNA breaks. For imaging, we used GSMs as a contrast agent for both computed tomography (CT) and magnetic resonance imaging (MRI) studies of stereotactically implanted GBM tumors in a mouse model, and found that MRI but not CT was sufficiently sensitive to detect and delineate tumor borders after administration and accumulation of GSMs. These results suggest that with further development and testing, GSMs may potentially be integrated into both imaging and treatment of brain tumors, serving a theranostic purpose as both an MRI-based contrast agent and a radiosensitizer. PMID:27305768

  5. Theranostic Application of Mixed Gold and Superparamagnetic Iron Oxide Nanoparticle Micelles in Glioblastoma Multiforme.

    PubMed

    Sun, Lova; Joh, Daniel Y; Al-Zaki, Ajlan; Stangl, Melissa; Murty, Surya; Davis, James J; Baumann, Brian C; Alonso-Basanta, Michelle; Kaol, Gary D; Tsourkas, Andrew; Dorsey, Jay F

    2016-02-01

    The treatment of glioblastoma multiforme, the most prevalent and lethal form of brain cancer in humans, has been limited in part by poor delivery of drugs through the blood-brain barrier and by unclear delineation of the extent of infiltrating tumor margins. Nanoparticles, which selectively accumulate in tumor tissue due to their leaky vasculature and the enhanced permeability and retention effect, have shown promise as both therapeutic and diagnostic agents for brain tumors. In particular, superparamagnetic iron oxide nanoparticles (SPIONs) have been leveraged as T2-weighted MRI contrast agents for tumor detection and imaging; and gold nanoparticles (AuNP) have been demonstrated as radiosensitizers capable of propagating electron and free radical-induced radiation damage to tumor cells. In this study, we investigated the potential applications of novel gold and SPION-loaded micelles (GSMs) coated by polyethylene glycol-polycaprolactone (PEG-PCL) polymer. By quantifying gh2ax DNA damage foci in glioblastoma cell lines, we tested the radiosensitizing efficacy of these GSMs, and found that GSM administration in conjunction with radiation therapy (RT) led to ~2-fold increase in density of double-stranded DNA breaks. For imaging, we used GSMs as a contrast agent for both computed tomography (CT) and magnetic resonance imaging (MRI) studies of stereotactically implanted GBM tumors in a mouse model, and found that MRI but not CT was sufficiently sensitive to detect and delineate tumor borders after administration and accumulation of GSMs. These results suggest that with further development and testing, GSMs may potentially be integrated into both imaging and treatment of brain tumors, serving a theranostic purpose as both an MRI-based contrast agent and a radiosensitizer. PMID:27305768

  6. Preparation and activity of Cu-Al mixed oxides via hydrotalcite-like precursors for the oxidation of phenol aqueous solutions

    SciTech Connect

    Alejandre, A.; Medina, F.; Rodriguez, X.; Salagre, P.; Sueiras, J.E.

    1999-12-10

    The authors performed thermogravimetric analysis (TGA), X-ray diffraction (XRD), BET areas, and FT-IR spectroscopy to characterize copper-aluminium mixed-oxide samples with Cu/Al ratios between 0.5 and 3.0. The thermal stability, crystallinity, and purity of the materials depended on the Cu/Al atomic ratio. The FT-IR and TG detected carbonate (mainly) and nitrate as counteranions which interact in the interlayer region. The authors found loosely bound carbonate and nitrate anions and one strongly bound type of carbonate. They used dynamic XRD experiments to study the evolution of phases during calcination. All the samples after calcination showed well-dispersed CuO and/or CuAl{sub 2}O{sub 4} phases. They also tested their catalytic behavior for the oxidation of 5 g/l phenol aqueous solutions using a triphasic tubular reactor working in a trickle-bed regime and air with an oxygen partial pressure of 0.9 MPa at a temperature reaction of 413 K. Phenol conversion decreased continuously over time for the samples calcined at lower temperatures (673 K). This is because of continuous loss of the CuO phase by elution and the formation of a new phase like copper oxalate on the surface of the copper catalysts which also elutes with time XRD shows that samples calcined at higher temperatures (1,073 K) and after HCl treatment (0.1 M) to avoid the CuO phase, have a pure copper aluminate phase. This CuAl{sub 2}O{sub 4} phase reaches steady activity plateaus in the 55--65% range of phenol conversion. The triphasic tubular reactor using trickle-bed regime largely avoids polymer formation as a catalyst-deactivation process.

  7. Effects of asphalt rejuvenator on thermal and mechanical properties on oxidized hot mixed asphalt pavements

    NASA Astrophysics Data System (ADS)

    Farace, Nicholas A.; Buttlar, William G.; Reis, Henrique

    2016-04-01

    The utilization of asphalt rejuvenator, and its effectiveness for restoring thermal and mechanical properties was investigated via Disk-shaped Compact Tension (DC(T)) and acoustic emission (AE) testing for determining mechanical properties and embrittlement temperatures of the mixtures. During the DC(T) testing the fracture energies and peak loads were used to measure the resistance of the rejuvenated asphalt to low temperature cracking. The AE testing monitored the acoustic emission activity while the specimens were cooled from room temperature to -40 °C to estimate the temperature at which thermal cracking began (i.e. the embrittlement temperature). First, a baseline response was obtained by obtaining the mechanical and thermal response of virgin HMA samples and HMA samples that had been exposed to oxidative aging for 36 hours at 135°C. The results showed the virgin samples had much higher peak loads and fracture energies than the 36 hours aged samples. Acoustic Emission showed similar results with the virgin samples having embrittlement temperatures 10 °C cooler than the 36 hours aged specimens. Then, overaged for 36 hours specimens were treated different amounts of rejuvenator (10%, 15%, and 20% by weight of binder content) and left to dwell for increased amount of time periods varying from one to eight weeks. It was observed that the AE results showed an improvement of embrittlement temperature with increasing with the dwell times. The 8 weeks specimens had cooler embrittlement temperatures than the virgin specimens. Finally, the low temperature effects on fracture energy and peak load of the rejuvenated asphalt was investigated. Rejuvenator was applied (10% by weight of binder) to specimens aged 36 hours at 135 °C, and the dwell time was varied from 1 to 4 weeks. The results showed that the peak loads were restored to levels of the virgin specimens, and the fracture energies improved to levels beyond that of the virgin specimens. The results also showed a

  8. Synthesis, characterization, and application of novel microporous mixed metal oxides, and nanostructured layered material-polymer films

    NASA Astrophysics Data System (ADS)

    Jeong, Hae-Kwon

    Zeolites are microporous crystalline aluminosilicates with pores and cavities of molecular dimension. They consist of interconnected aluminum and silicon tetrahedra to build a variety of 3D open framework structures. Due to their structure, stability, and activity, zeolites have been widely used in a broad variety of applications in industry. It is, therefore, of great interest to make new structures with potentially novel properties. In this regard, there has recently been a growing interest in the synthesis of novel mixed metal oxides with octahedral and tetrahedral units owing to the possibility to find unique electronic and optical properties. Hence, these materials can find advanced applications as well as conventional applications, just like zeolites. Research efforts have led to the discovery of several mixed octahedral and tetrahedral metal oxides with novel crystal structures including titanium silicates and cerium silicate. Layered materials with transport paths along the thickness of the layers are of particular interest due to potential usage as selective layers of nanometer scale in nanocomposite membranes. A new layered silicate (we call AMH-3) has been synthesized under hydrothermal conditions. The crystal structure solution via powder X-ray diffraction has revealed its unique layer structure of three dimensional microporosity within layers. Layered materials with porous layers will open up new areas of applications, such as selective nanocomposite separation membranes. Polymer/selective-flake nanocomposite membranes have been fabricated for the first time, which can, in principle, be scaled down to submicrometer structures. A layered aluminophosphate with a porous net layer is used as a selective phase and a polyimide as a continuous phase. The microstructures of the nanocomposite membranes were investigated using various characterization techniques. Nanocomposite membranes with 10 wt% layered aluminophosphate show substantial enhancement in

  9. Self-assembled gold nanoparticle-mixed metal oxide nanocomposites for self-sensitized dye degradation under visible light irradiation.

    PubMed

    Cho, Seungho; Jang, Ji-Wook; Hwang, Sekyu; Lee, Jae Sung; Kim, Sungjee

    2012-12-18

    Gold nanoparticle (Au NP)-mixed metal oxide (MMO) nanocomposite photocatalysts for efficient self-sensitized dye degradations under visible light were prepared by an electrostatically driven self-assembly. Dihydrolipoic acid (DHLA)-capped Au NPs (building block I) were synthesized through a room temperature reaction. Their hydrodynamic size was determined as being around 4.9 nm by dynamic light scattering measurements. MMO nanoplates with lateral dimensions of 100-250 nm (building block II) were prepared by a calcination of zinc aluminum layered double hydroxides at 750 °C for 2 h in air. In a pH 7.0 aqueous solution, the DHLA-capped Au NPs had a negative zeta potential (-22 ± 3 mV); on the other hand, the MMO nanoplates had a positive zeta potential (15 ± 2 mV). Electrostatic self-assembly was achieved by stirring an aqueous solution (pH 7.0) containing DHLA-capped Au NPs and MMO nanoplates at room temperature for 1 h. The self-assembled and sequentially calcined nanocomposites exhibited the superior self-sensitized dye degradation efficiency under visible light to that of ZnO, TiO(2) (P25), or pure MMO nanoplates. The enhanced degradation efficiency could be attributed to strong coupling interactions of ZnO and ZnAl(2)O(4) phases of the MMO and the role of Au as an electron sink and mediator for formations of reactive oxidation species and as a light concentrator. PMID:23186248

  10. Hydrothermal synthesis, structure investigation, and oxide ion conductivity of mixed Si/Ge-based apatite-type phases.

    PubMed

    Li, Henan; Baikie, Tom; Pramana, Stevin S; Shin, J Felix; Keenan, Philip J; Slater, Peter R; Brink, Frank; Hester, James; An, Tao; White, Tim J

    2014-05-19

    Apatite-type oxides ([A(I)4][A(II)6][(BO4)6]O2), particularly those of the rare-earth silicate and germanate systems, are among the more promising materials being considered as alternative solid oxide fuel cell electrolytes. Nonstoichiometric lanthanum silicate and germanate apatites display pure ionic conductivities exceeding those of yttria-stabilized zirconia at moderate temperatures (500-700 °C). In this study, mixed Si/Ge-based apatites were prepared by hydrothermal synthesis under mild conditions rather than the conventional solid-state method at high temperatures. Single-phase and highly crystalline nanosized apatite powders were obtained with the morphology changing across the series from spheres for the Si-based end member to hexagonal rods for the Ge-based end member. Powder X-ray and neutron analysis found all of these apatites to be hexagonal (P63/m). Quantitative X-ray microanalysis established the partial (<15 at%) substitution of La(3+) by Na(+) (introduced from the NaOH hydrothermal reagent), which showed a slight preference to enter the A(I) 4f framework position over the A(II) 6h tunnel site. Moreover, retention of hydroxide (OH(-)) was confirmed by IR spectroscopy and thermogravimetric analysis, and these apatites are best described as oxyhydroxyapatites. To prepare dense pellets for conductivity measurements, both conventional heat treatment and spark plasma sintering methods were compared, with the peculiar features of hydrothermally synthesized apatites and the influence of sodium on the ionic conductivity considered. PMID:24787953

  11. Methane oxidation over mixed-conducting SrFe(Al)O3-delta-SrAl2O4 composite.

    PubMed

    Yaremchenko, A A; Kharton, V V; Valente, A A; Veniaminov, S A; Belyaev, V D; Sobyanin, V A; Marques, F M B

    2007-06-01

    The steady-state CH4 conversion by oxygen permeating through mixed-conducting (SrFe)0.7(SrAl2)0.3Oz composite membranes, comprising strontium-deficient SrFe(Al)O3-delta perovskite and monoclinic SrAl2O4-based phases, occurs via different mechanisms in comparison to the dry methane interaction with the lattice oxygen. The catalytic behavior of powdered (SrFe)0.7(SrAl2)0.3Oz, studied by temperature-programmed reduction in dry CH4 at 523-1073 K, is governed by the level of oxygen nonstoichiometry in the crystal lattice of the perovskite component and is qualitatively similar to that of other perovskite-related ferrites, such as Sr0.7La0.3Fe0.8Al0.2O3-delta. While extensive oxygen release from the ferrite lattice at 700-900 K leads to predominant total oxidation of methane, significant selectivity to synthesis gas formation, with H2/CO ratios close to 2, is observed above 1000 K, when a critical value of oxygen deficiency is achieved. The steady-state oxidation over dense membranes at 1123-1223 K results, however, in prevailing total combustion, particularly due to excessive oxygen chemical potential at the membrane surface. In combination with surface-limited oxygen permeability, mass transport limitations in a porous layer at the membrane permeate side prevent reduction and enable stable operation of (SrFe)0.7(SrAl2)0.3Oz membranes under air/methane gradient. Taking into account the catalytic activity of SrFeO3-delta-based phases for the partial oxidation of methane to synthesis gas and the important role of mass transport-related effects, one promising approach for membrane development is the fabrication of thick layer of porous ferrite-based catalyst at the surface of dense (SrFe)0.7(SrAl2)0.3Oz composite. PMID:17627318

  12. An integrated approach for the verification of fresh mixed oxide fuel (MOX) assemblies at light water reactor MOX recycle reactors

    SciTech Connect

    Menlove, Howard O; Lee, Sang - Yoon

    2009-01-01

    This paper presents an integrated approach for the verification of mixed oxide (MOX) fuel assemblies prior to their being loaded into the reactor. There is a coupling of the verification approach that starts at the fuel fabrication plant and stops with the transfer of the assemblies into the thermal reactor. The key measurement points are at the output of the fuel fabrication plant, the receipt at the reactor site, and the storage in the water pool as fresh fuel. The IAEA currently has the capability to measure the MOX fuel assemblies at the output of the fuel fabrication plants using a passive neutron coincidence counting systems of the passive neutron collar (PNCL) type. Also. at the MOX reactor pool, the underwater coincidence counter (UWCC) has been developed to measure the MOX assemblies in the water. The UWCC measurement requires that the fuel assembly be lifted about two meters up in the storage rack to avoid interference from the fuel that is stored in the rack. This paper presents a new method to verify the MOX fuel assemblies that are in the storage rack without the necessity of moving the fuel. The detector system is called the Underwater MOX Verification System (UMVS). The integration and relationship of the three measurements systems is described.

  13. Mechanical and electrical properties of carbon nanotube/Cu nanocomposites by molecular-level mixing and controlled oxidation process.

    PubMed

    Lim, Byung K; Mo, Chan B; Nam, Dong H; Hong, Soon H

    2010-01-01

    A molecular-level mixing and controlled oxidation process is proposed as a novel fabrication technique for the production of CNT/Cu nanocomposite powders. The fabricated CNT/Cu2O nanocomposite powders showed microstructures with homogeneous dispersion of implanted CNTs in a Cu2O matrix. The CNT/Cu2O nanocomposite powders were reduced to CNT/Cu nanocomposite powders with H2 gas and then the as-prepared CNT/Cu nanocomposite powders were spark plasma sintered to fabricate CNT/Cu nanocomposites. The mechanical properties of the Cu and the CNT/Cu nanocomposites were characterized by tensile testing before and after hot compression. Before hot compression, the CNT/Cu nanocomposites were brittle, but after hot compression both yield strength and elongation were increased, while the yield strength of the Cu was decreased after hot compression. Hot compression enhanced the ductility and strength of the CNT/Cu nanocomposites due to alignment of Cu grains and CNTs. Electrical conductivity was also enhanced due to a reduced scattering of electrons because of the alignment of the CNTs and Cu grains as well as the annealing effects of the Cu matrix. PMID:20352814

  14. MCNP-to-TORT Radiation Transport Calculations in Support of Mixed Oxide Fuels Testing for the Fissile Materials Disposition Program

    SciTech Connect

    Pace, J.V.

    1999-11-01

    The United States (US) Department of Energy Fissile Materials Disposition Program (FMDP) began studies for disposal of surplus weapons-grade plutonium (WG-Pu) as mixed uranium-plutonium oxide (@40X) fuel for commercial light-water reactors(LWRS). As a first step in this program, a test of the utilization of WG-Pu in a LWR environment is being conducted in an I-hole of the Advanced Test Reactor (ATR) at the Idaho National Engineering and Environmental Laboratory (INEEL). Initial radiation transport calculations of the test specimens were made at INEEL using the MCNP Monte Carlo radiation transport code to determine the linear heating rates in the fuel specimens. Unfortunately, the results of the calculations could not show the detailed high and low power-density spots in the specimens. Therefore, INEEL produced an MCNP source at the boundary of a rectangular parallelepiped enclosing the ATR I-hole, and Oak Ridge National Laboratory (ORNL) transformed this boundary source into a discrete -ordinates boundary source for the Three-dimensional Oak Ridge radiation Transport (TORT) code to pinpoint spatial detail. Agreement with average MCNP results were within 5%.

  15. Thermal impact of an eccentric annular flow around a mixed-oxide pin - An in-pile observation

    SciTech Connect

    Lee, M.J.; Strain, R.V.; Lambert, J.D.B.; Feldman, E.E. ); Nomura, S. )

    1989-11-01

    In a typical subassembly of a liquid-metal reactor, slightly unsymmetric coolant flow and temperature distribution around fuel pins is common and inevitable. The geometric location away from the subassembly center and the irradiation-induced rod bowing are among the primary reasons for such occurrences. Studies of the hydrodynamics of the skewed coolant distribution and the associated fuel pin heat transfer are extensive in both computer modeling and laboratory experimental work. In-pile verification of the phenomenon, however, has been rare. High temperature in fuel pins and the perturbation from temperature-monitoring devices discourage such an endeavor. Recent evidence of the sensitive response of the fuel-sodium reaction product (FSRP) to its decomposition temperature, however, might make in-pile verification possible. The clearly demarcated interface of the FSRP would serve as an excellent thermal monitor that reveals the temperature contour within the fuel. This finding from the postirradiation examination (PIE) of mixed-oxide (MOX) pins, is one of the spin-offs of the run-beyond-cladding-breach (RBCB) program jointly sponsored by the U.S. Department of Energy and the Power Reactor and Nuclear Fuel Development Corporation of Japan. The FSRP fuel interface is thus a good benchmark for verifying fuel and coolant temperature distributions. The RBCB experiment and the associated analysis are discussed and conclusions are presented.

  16. Biodiesel synthesis by TiO2-ZnO mixed oxide nanocatalyst catalyzed palm oil transesterification process.

    PubMed

    Madhuvilakku, Rajesh; Piraman, Shakkthivel

    2013-12-01

    Biodiesel is a promising alternating environmentally benign fuel to mineral diesel. For the development of easier transesterification process, stable and active heterogeneous mixed metal oxide of TiO2-ZnO and ZnO nanocatalysts were synthesized and exploited for the palm oil transesterification process. The synthesized catalysts were characterized by XRD, FT-IR, and FE-SEM studies for their structural and morphological characteristics. It was found that TiO2-ZnO nanocatalyst exhibits good catalytic activity and the catalytic performance was greatly depends on (i) catalyst concentration (ii) methanol to oil molar ratio (iii) reaction temperature and (iv) reaction time. A highest 98% of conversion was obtained at the optimum reaction parameters with 200 mg of catalyst loading and the biodiesel was analyzed by TLC and (1)H NMR techniques. The TiO2-ZnO nanocatalyst shows good catalytic performance over the ZnO catalyst, which could be a potential candidate for the large-scale biodiesel production from palm oil at the reduced temperature and time. PMID:24148858

  17. Experience in the reprocessing of mixed-oxide fuels at PNC (Power Reactor and Nuclear Fuel Development Corporation)

    SciTech Connect

    Komatsu, Hisato; Onishi, Moichi; Araya, Sadao; Fukushima, Misao

    1989-01-01

    The Power Reactor and Nuclear Fuel Development Corporation (PNC) in Japan has experience in reprocessing mixed-oxide (MOX) fuels for the advanced thermal reactor (ATR) Fugen at the Tokai Reprocessing Plant (TRP) and for fast breeder reactors (FBRs) at the Chemical Processing Facility (CPF). The TRP was originally designed and constructed as the first reprocessing plant for light water reactor fuels in Japan. It has processed {approximately}400 t of spent fuels since 1977. To utilize recovered plutonium, PNC has developed the prototype ATR Fugen. This reactor has been operated using MOX fuel since 1978. In parallel, utilities are promoting a plutonium thermal project. Several MOX assemblies have already been loaded in a boiling water and a pressurized water reactor. To facilitate the operation of Fugen and promote research and development for the reprocessing of MOX fuels in Japan, PNC obtained a license for reprocessing fuels for Fugen at TRP in 1985. PNC has designed and constructed the CPF at Tokai Works to conduct basic research on the reprocessing of FBR fuels. The Recycle Equipment Test Facility, an engineering scale hot facility, is now being designed for further R and D in this field. It will start hot operation in the mid-1990s.

  18. Los Alamos National Laboratory summary plan to fabricate mixed oxide lead assemblies for the fissile material disposition program

    SciTech Connect

    Buksa, J.J.; Eaton, S.L.; Trellue, H.R.; Chidester, K.; Bowidowicz, M.; Morley, R.A.; Barr, M.

    1997-12-01

    This report summarizes an approach for using existing Los Alamos National Laboratory (Laboratory) mixed oxide (MOX) fuel-fabrication and plutonium processing capabilities to expedite and assure progress in the MOX/Reactor Plutonium Disposition Program. Lead Assembly MOX fabrication is required to provide prototypic fuel for testing in support of fuel qualification and licensing requirements. It is also required to provide a bridge for the full utilization of the European fabrication experience. In part, this bridge helps establish, for the first time since the early 1980s, a US experience base for meeting the safety, licensing, safeguards, security, and materials control and accountability requirements of the Department of Energy and Nuclear Regulatory Commission. In addition, a link is needed between the current research and development program and the production of disposition mission fuel. This link would also help provide a knowledge base for US regulators. Early MOX fabrication and irradiation testing in commercial nuclear reactors would provide a positive demonstration to Russia (and to potential vendors, designers, fabricators, and utilities) that the US has serious intent to proceed with plutonium disposition. This report summarizes an approach to fabricating lead assembly MOX fuel using the existing MOX fuel-fabrication infrastructure at the Laboratory.

  19. Mixed-metal molecular complexes: Single-molecule nanomagnets and bioinorganic models of the water oxidizing complex of photosystem II

    NASA Astrophysics Data System (ADS)

    Mishra, Abhudaya

    2006-12-01

    The current burgeoning research in high nuclearity manganese-containing carboxylate clusters is primarily due to their relevance in areas as diverse as magnetic materials and bioinorganic chemistry. In the former, the ability of single molecules to retain, below a critical temperature (T B), their magnetization vector, resulting in the observation of bulk magnetization in the absence of a field and without long-range ordering of the spins, has termed such molecules as Single-Molecule Magnets (SMMs), or molecular nanomagnets. These molecules display superparamagnet like slow magnetization relaxation arising from the combination of a large molecular spin, S, and a large and negative magnetoanisotropy, D. Traditionally, these nanomagnets have been Mn containing species. An out of the box approach towards synthesizing SMMs is engineering mixed-metal Mn-containing compounds. An attractive choice towards this end is the use of Lanthanides (Ln), which possess both a high spin, S, and a large D. A family of related MnIII8Ce IV SMMs has been synthesized. However, the Ce ion of these complexes is diamagnetic (CeIV). Thus, further investigation has led to the isolation of a family of MnIII11Ln III4 complexes in which all but the Ln = Eu complex function as single-molecule nanomagnets. The mixed-metal synthetic effort has been extended to include actinides with the successful isolation of a Mn IV10ThIV6 complex, albeit this homovalent complex is not a SMM. In the bioinorganic research, the Water Oxidizing Complex (WOC) in Photosystem II (PS II) catalyzes the oxidation of H2O to O2 in green plants, algae and cyanobacteria. Recent crystal structures of the WOC confirm it to be a Mn4CaOx cluster with primarily carboxylate ligation. To date, various multinuclear Mn complexes have been synthesized as putative models of the WOC. On the contrary, there have been no synthetic MnCa(Sr) mixed-metal complexes. Thus, in this bioinorganic modeling research of the WOC, various synthetic

  20. Atomic-Resolution Visualization of Distinctive Chemical Mixing Behavior of Ni, Co and Mn with Li in Layered Lithium Transition-Metal Oxide Cathode Materials

    SciTech Connect

    Yan, Pengfei; Zheng, Jianming; Lv, Dongping; Wei, Yi; Zheng, Jiaxin; Wang, Zhiguo; Kuppan, Saravanan; Yu, Jianguo; Luo, Langli; Edwards, Danny J.; Olszta, Matthew J.; Amine, Khalil; Liu, Jun; Xiao, Jie; Pan, Feng; Chen, Guoying; Zhang, Jiguang; Wang, Chong M.

    2015-07-06

    Capacity and voltage fading of layer structured cathode based on lithium transition metal oxide is closely related to the lattice position and migration behavior of the transition metal ions. However, it is scarcely clear about the behavior of each of these transition metal ions. We report direct atomic resolution visualization of interatomic layer mixing of transition metal (Ni, Co, Mn) and lithium ions in layer structured oxide cathodes for lithium ion batteries. Using chemical imaging with aberration corrected scanning transmission electron microscope (STEM) and DFT calculations, we discovered that in the layered cathodes, Mn and Co tend to reside almost exclusively at the lattice site of transition metal (TM) layer in the structure or little interlayer mixing with Li. In contrast, Ni shows high degree of interlayer mixing with Li. The fraction of Ni ions reside in the Li layer followed a near linear dependence on total Ni concentration before reaching saturation. The observed distinctively different behavior of Ni with respect to Co and Mn provides new insights on both capacity and voltage fade in this class of cathode materials based on lithium and TM oxides, therefore providing scientific basis for selective tailoring of oxide cathode materials for enhanced performance.

  1. Impact of the cation distribution homogeneity on the americium oxidation state in the U0.54Pu0.45Am0.01O2-x mixed oxide

    NASA Astrophysics Data System (ADS)

    Vauchy, Romain; Robisson, Anne-Charlotte; Martin, Philippe M.; Belin, Renaud C.; Aufore, Laurence; Scheinost, Andreas C.; Hodaj, Fiqiri

    2015-01-01

    The impact of the cation distribution homogeneity of the U0.54Pu0.45Am0.01O2-x mixed oxide on the americium oxidation state was studied by coupling X-ray diffraction (XRD), electron probe micro analysis (EPMA) and X-ray absorption spectroscopy (XAS). Oxygen-hypostoichiometric Am-bearing uranium-plutonium mixed oxide pellets were fabricated by two different co-milling based processes in order to obtain different cation distribution homogeneities. The americium was generated from β- decay of 241Pu. The XRD analysis of the obtained compounds did not reveal any structural difference between the samples. EPMA, however, revealed a high homogeneity in the cation distribution for one sample, and substantial heterogeneity of the U-Pu (so Am) distribution for the other. The difference in cation distribution was linked to a difference in Am chemistry as investigated by XAS, with Am being present at mixed +III/+IV oxidation state in the heterogeneous compound, whereas only Am(IV) was observed in the homogeneous compound. Previously reported discrepancies on Am oxidation states can hence be explained by cation distribution homogeneity effects.

  2. Mixed N-Heterocyclic Carbene-Bis(oxazolinyl)borato Rhodium and Iridium Complexes in Photochemical and Thermal Oxidative Addition Reactions

    SciTech Connect

    Xu, Songchen; Manna, Kuntal; Ellern, Arkady; Sadow, Aaron D

    2014-12-08

    In order to facilitate oxidative addition chemistry of fac-coordinated rhodium(I) and iridium(I) compounds, carbene–bis(oxazolinyl)phenylborate proligands have been synthesized and reacted with organometallic precursors. Two proligands, PhB(OxMe2)2(ImtBuH) (H[1]; OxMe2 = 4,4-dimethyl-2-oxazoline; ImtBuH = 1-tert-butylimidazole) and PhB(OxMe2)2(ImMesH) (H[2]; ImMesH = 1-mesitylimidazole), are deprotonated with potassium benzyl to generate K[1] and K[2], and these potassium compounds serve as reagents for the synthesis of a series of rhodium and iridium complexes. Cyclooctadiene and dicarbonyl compounds {PhB(OxMe2)2ImtBu}Rh(η4-C8H12) (3), {PhB(OxMe2)2ImMes}Rh(η4-C8H12) (4), {PhB(OxMe2)2ImMes}Rh(CO)2 (5), {PhB(OxMe2)2ImMes}Ir(η4-C8H12) (6), and {PhB(OxMe2)2ImMes}Ir(CO)2 (7) are synthesized along with ToMM(η4-C8H12) (M = Rh (8); M = Ir (9); ToM = tris(4,4-dimethyl-2-oxazolinyl)phenylborate). The spectroscopic and structural properties and reactivity of this series of compounds show electronic and steric effects of substituents on the imidazole (tert-butyl vs mesityl), effects of replacing an oxazoline in ToM with a carbene donor, and the influence of the donor ligand (CO vs C8H12). The reactions of K[2] and [M(μ-Cl)(η2-C8H14)2]2 (M = Rh, Ir) provide {κ4-PhB(OxMe2)2ImMes'CH2}Rh(μ-H)(μ-Cl)Rh(η2-C8H14)2 (10) and {PhB(OxMe2)2ImMes}IrH(η3-C8H13) (11). In the former compound, a spontaneous oxidative addition of a mesityl ortho-methyl to give a mixed-valent dirhodium species is observed, while the iridium compound forms a monometallic allyl hydride. Photochemical reactions of dicarbonyl compounds 5 and 7 result in C–H bond oxidative addition providing the compounds {κ4-PhB(OxMe2)2ImMes'CH2}RhH(CO) (12) and {PhB(OxMe2)2ImMes}IrH(Ph)CO (13). In 12, oxidative addition results in cyclometalation of the mesityl ortho-methyl similar to 10, whereas the iridium compound reacts with the benzene solvent to give a rare crystallographically characterized cis

  3. Probing Oxide-Ion Mobility in the Mixed Ionic-Electronic Conductor La2NiO4+δ by Solid-State (17)O MAS NMR Spectroscopy.

    PubMed

    Halat, David M; Dervişoğlu, Rıza; Kim, Gunwoo; Dunstan, Matthew T; Blanc, Frédéric; Middlemiss, Derek S; Grey, Clare P

    2016-09-14

    While solid-state NMR spectroscopic techniques have helped clarify the local structure and dynamics of ionic conductors, similar studies of mixed ionic-electronic conductors (MIECs) have been hampered by the paramagnetic behavior of these systems. Here we report high-resolution (17)O (I = 5/2) solid-state NMR spectra of the mixed-conducting solid oxide fuel cell (SOFC) cathode material La2NiO4+δ, a paramagnetic transition-metal oxide. Three distinct oxygen environments (equatorial, axial, and interstitial) can be assigned on the basis of hyperfine (Fermi contact) shifts and quadrupolar nutation behavior, aided by results from periodic DFT calculations. Distinct structural distortions among the axial sites, arising from the nonstoichiometric incorporation of interstitial oxygen, can be resolved by advanced magic angle turning and phase-adjusted sideband separation (MATPASS) NMR experiments. Finally, variable-temperature spectra reveal the onset of rapid interstitial oxide motion and exchange with axial sites at ∼130 °C, associated with the reported orthorhombic-to-tetragonal phase transition of La2NiO4+δ. From the variable-temperature spectra, we develop a model of oxide-ion dynamics on the spectral time scale that accounts for motional differences of all distinct oxygen sites. Though we treat La2NiO4+δ as a model system for a combined paramagnetic (17)O NMR and DFT methodology, the approach presented herein should prove applicable to MIECs and other functionally important paramagnetic oxides. PMID:27538437

  4. Novel synthesis of manganese and vanadium mixed oxide (V{sub 2}O{sub 5}/OMS-2) as an efficient and selective catalyst for the oxidation of alcohols in liquid phase

    SciTech Connect

    Mahdavi, Vahid Soleimani, Shima

    2014-03-01

    Graphical abstract: Oxidation of various alcohols is studied in the liquid phase over new composite mixed oxide (V{sub 2}O{sub 5}/OMS-2) catalyst using tert-butyl hydroperoxide (TBHP). The activity of V{sub 2}O{sub 5}/OMS-2 samples was considerably increased with respect to OMS-2 catalyst and these samples are found to be suitable for the selective oxidation of alcohols. - Highlights: • V{sub 2}O{sub 5}/K-OMS-2 with different V/Mn molar ratios prepared by the impregnation method. • Oxidation of alcohols was studied in the liquid phase over V{sub 2}O{sub 5}/K-OMS-2 catalyst. • V{sub 2}O{sub 5}/K-OMS-2 catalyst had excellent activity for alcohol oxidation. • Benzyl alcohol oxidation using excess TBHP followed a pseudo-first order kinetic. • The selected catalyst was reused without significant loss of activity. - Abstract: This work reports the synthesis and characterization of mixed oxide vanadium–manganese V{sub 2}O{sub 5}/K-OMS-2 at various V/Mn molar ratios and prepared by the impregnation method. Characterization of these new composite materials was made by elemental analysis, BET, XRD, FT-IR, SEM and TEM techniques. Results of these analyses showed that vanadium impregnated samples contained mixed phases of cryptomelane and crystalline V{sub 2}O{sub 5} species. Oxidation of various alcohols was studied in the liquid phase over the V{sub 2}O{sub 5}/K-OMS-2 catalyst using tert-butyl hydroperoxide (TBHP) and H{sub 2}O{sub 2} as the oxidant. Activity of the V{sub 2}O{sub 5}/K-OMS-2 samples was increased considerably with respect to K-OMS-2 catalyst due to the interaction of manganese oxide and V{sub 2}O{sub 5}. The kinetic of benzyl alcohol oxidation using excess TBHP over V{sub 2}O{sub 5}/K-OMS-2 catalyst was investigated at different temperatures and a pseudo-first order reaction was determined with respect to benzyl alcohol. The effects of reaction time, oxidant/alcohol molar ratio, reaction temperature, solvents, catalyst recycling potential and

  5. A SCALE 5.0 Reactor Physics Assessment using the Module TRITON against Mixed Oxide (MOX) OECD/NEA Benchmarks

    SciTech Connect

    Saccheri, J.G.B.; Diamond, D.J.

    2006-07-01

    Reactor physics numerical benchmarks have been performed at the Brookhaven National Laboratory (BNL) with the software package SCALE 5.0 and its TRITON module to assess their capability to predict neutronics parameters for mixed oxide (MOX) fuels. The results of such calculations are herein presented. Specifically, BNL results for neutron multiplication factors (kINF), neutron fluxes and fuel burnup have been added to published OECD/NEA benchmarks for MOX fuels and particular emphasis has been given to the impact of cross-section libraries and their energy structure on the results. Among the OECD/NEA published benchmarks two have been considered here: the first one models a fuel pin surrounded by moderator, in which two different MOX fuels can be introduced, and for each one of them kINF and neutron fluxes as a function of burnup are calculated. The second one includes both a fuel pin case and a macro-cell case (a heterogeneous 30 by 30 configuration of fuel pins), for which the void coefficient is determined by calculating kINF at zero burnup as a function of moderation. The calculations are repeated for several combinations of MOX and uranium oxide fuels using several different cross-section libraries. The final results have been compared with each other. This study shows that SCALE 5.0 (with TRITON) overall performs in line with the other codes in the benchmark, but the results are dependent on the energy group structure of the cross section libraries used. For instance, when fissile plutonium is increased in the fuel, TRITON results become slightly divergent with burnup (with respect to the other codes in the benchmark) and if the standard 44-group library provided with SCALE 5.0 is used void coefficient calculations become inadequate for very low void (below 10% of the operating value of moderator density). Moreover, the prediction capabilities of the code are shown to be dependent on the MOX fuel enrichment and the MOX isotopic composition. (authors)

  6. Sol-gel route to synthesis of microporous ceramic membranes: Thermal stability of TiO[sub 2]-ZrO[sub 2] mixed oxides

    SciTech Connect

    Qunyin Xu; Anderson, M.A. . Water Chemistry Program)

    1993-08-01

    In this paper concerning the synthesis of microporous ceramic membranes, the authors focus on the preparation and thermal stability of unsupported microporous TiO[sub 2]-ZrO[sub 2] mixed-oxide membranes. It has been observed that, by adding up to 20% ZrO[sub 2] into TiO[sub 2] or up to 10% TiO[sub 2] into ZrO[sub 2], these microporous membranes display improved thermal stability. They can be fired up to 500 C for 0.5 h without closing micropores. However, membranes containing almost equal percentages of each component have lost microporous features and have low surface areas and low porosities. A phase diagram of a two-component TiO[sub 2]-ZrO[sub 2] mixed-oxide membrane has been prepared based on DTA and X-ray diffraction data in order to better understand the microstructure changes upon firing.

  7. Oxygen self-diffusion in polycrystalline uranium-plutonium mixed oxide U0.55Pu0.45O2

    NASA Astrophysics Data System (ADS)

    Vauchy, Romain; Robisson, Anne-Charlotte; Bienvenu, Philippe; Roure, Ingrid; Hodaj, Fiqiri; Garcia, Philippe

    2015-12-01

    Atomic transport properties in uranium-plutonium mixed oxides U1-yPuyO2 are of essential concern because they impact numerous aspects of their physicochemical behavior at all stages of the fuel cycle. In this paper, we report oxygen tracer diffusion coefficients in homogeneous U0.55Pu0.45O2 mixed oxide. The study is based on tracer diffusion coefficient measurements obtained using Secondary Ion Mass Spectrometry (SIMS) following diffusion annealing involving gas-solid 18O/16O isotopic exchange. As for other fundamental material properties governed by the nature and behavior of point defects, we show that a careful study of tracer diffusion coefficients as a function of oxygen partial pressure and temperature is liable to provide insight into prevailing diffusion mechanisms. Under the conditions studied in this work, it appears that oxygen diffusion is vacancy mediated.

  8. Direct conversion of bio-ethanol to isobutene on nanosized Zn(x)Zr(y)O(z) mixed oxides with balanced acid-base sites.

    PubMed

    Sun, Junming; Zhu, Kake; Gao, Feng; Wang, Chongmin; Liu, Jun; Peden, Charles H F; Wang, Yong

    2011-07-27

    We report the design and synthesis of nanosized Zn(x)Zr(y)O(z) mixed oxides for direct and high-yield conversion of bio-ethanol to isobutene (~83%). ZnO is addded to ZrO(2) to selectively passivate zirconia's strong Lewis acidic sites and weaken Brönsted acidic sites, while simultaneously introducing basicity. As a result, the undesired reactions of bio-ethanol dehydration and acetone polymerization/coking are suppressed. Instead, a surface basic site-catalyzed ethanol dehydrogenation to acetaldehyde, acetaldehyde to acetone conversion via a complex pathway including aldol-condensation/dehydrogenation, and a Brönsted acidic site-catalyzed acetone-to-isobutene reaction pathway dominates on the nanosized Zn(x)Zr(y)O(z) mixed oxide catalyst, leading to a highly selective process for direct conversion of bio-ethanol to isobutene. PMID:21682296

  9. ZIRCONIA-BASED MIXED POTENTIAL CARBON MONOXIDE/HYDROCARBON SENSORS WITH LANTHANUM MAGNESIUM OXIDE, AND TERBIUM-DOPED YTTRIUM STABILIZED ZIRCONIA ELECTRODES

    SciTech Connect

    E. L. BROSHA; R. MUKUNDAN; ET AL

    2000-10-01

    We have investigated the performance of dual metal oxide electrode mixed potential sensors in an engine-out, dynamometer environment. Sensors were fabricated by sputtering thin films of LaMnO{sub 3} and Tb-doped YSZ onto YSZ electrolyte. Au gauze held onto the metal oxide thin films with Au ink was used for current collection. The exhaust gas from a 4.8L, V8 engine operated in open loop, steady-state mode around stoichiometry at 1500 RPM and 50 Nm. The sensor showed a stable EMF response (with no hysteresis) to varying concentrations of total exhaust gas HC content. The sensor response was measured at 620 and 670 C and shows temperature behavior characteristic of mixed potential-type sensors. The results of these engine-dynamometer tests are encouraging; however, the limitations associated with Au current collection present the biggest impediment to automotive use.

  10. Direct Conversion of Bio-ethanol to Isobutene on Nanosized ZnxZryOz Mixed Oxides with Balanced Acid–Base Sites

    SciTech Connect

    Sun, Junming; Zhu, Kake; Gao, Feng; Wang, Chong M.; Liu, Jun; Peden, Charles HF; Wang, Yong

    2011-06-17

    Bio-mass conversion has attracted increasing research interests to produce bio-fuels with bio-ethanol being a major product. Development of advanced processes to further upgrade bio-ethanol to other value added fuels or chemicals are pivotal to improving the economics of biomass conversion and deversifying the utilization of biomass resources. In this paper, for the first time, we report the direct conversion of bio-ethanol to isobutene with high yield (~83%) on a multifunctional ZnxZryOz mixed oxide with a dedicated balance of surface acid-base properties. This work illustrates the significance of rational design of a multifunctional mixed oxide catalyst for one step bio-ethanol conversion to a value-added intermediate, isobutene, for chemical and fuel production. This work was supported by the US Department of Energy Basic Energy Sciences' Chemical Sciences, Geosciences & Biosciences Division. Pacific Northwest National Laboratory is operated by Battelle for the US Department of Energy.

  11. MCNP-to-TORT radiation transport calculations in support of mixed oxide fuels testing for the Fissile Materials Disposition Program

    SciTech Connect

    Pace, J.V. III

    1998-04-01

    The US (US) Department of Energy Fissile Materials Disposition Program has begun studies for disposal of surplus weapons-grade plutonium (WG-Pu) as mixed uranium plutonium oxide (MOX) fuel for commercial light water reactors (LWRs). Currently MOX fuel is used commercially in a number of foreign countries, but is not in the US. Most of the experience is with reactor grade plutonium (RG-Pu) in MOX fuel. Therefore, to use WG-Pu in MOX fuel, one must demonstrate that the experience with RG-Pu is relevant. As a first step in this program, the utilization of WG-Pu in a LWR environment must be demonstrated. To accomplish this, a test is to be conducted to investigate some of the unresolved issues. The initial tests will be made in an I-hole of the Advanced Test Reactor (ATR) at the Idaho National Engineering and Environmental Laboratory (INEEL). Initial radiation transport calculations of the test specimens were made at INEEL using the MCNP Monte Carlo radiation transport code. These calculations were made to determine the linear heating rates in the fuel specimens. Unfortunately, the results of the calculations could not show the detailed high and low power density spots in the specimens. However, a discrete ordinates radiation transport code could pinpoint these spatial details. Therefore, INEEL was tasked with producing a MCNP source at the boundary of a rectangular parallelepiped enclosing the ATR I-hole, and Oak Ridge National Laboratory was tasked with transforming this boundary source into a discrete ordinates boundary source for the Three-dimensional Oak Ridge radiation Transport (TORT) code. Thus, the TORT results not only complemented, but also were in agreement with the MCNP results.

  12. Transport of graphene oxide in saturated porous media: effect of cation composition in mixed Na-Ca electrolyte systems.

    PubMed

    Fan, W; Jiang, X H; Yang, W; Geng, Z; Huo, M X; Liu, Z M; Zhou, H

    2015-04-01

    The influence of cation composition in mixed Na-Ca electrolyte systems on the transport of graphene oxide particles in saturated porous media was studied. Column experiments were conducted to elucidate the transport behavior of GO by varied molar ratios of Ca2+/Na+ but of constant ionic strength (IS). The results show that retention of GO in sand column is strongly dependent on IS in the presence of Ca2+, featuring serious deposition rates (Rd) at the higher IS of 10 mM. The maximum Rd was 48.22% at 1 mM and 98.53% at 10 mM. However, there was no obvious difference in GO retention in solutions that only contained Na+ when the IS increased from 1 to 10 mM, and the Rd was 35.17% and 38.21% respectively. The molar ratio of Ca2+/Na+ in solution was much more influential in altering the particle retention behavior at the higher IS of 10 mM, compared with little influence at 1 mM. It was supposed that compression of diffuse double layers mainly controlled GO deposition under lower IS, while charge neutrality and metal (Ca2+) bridging played a significant role at the higher IS. A numerical advection-dispersion-retention model considering the combined processes of Langmuirian dynamics blocking and depth-dependent straining was successfully developed to simulate the transport process of GO through the sand column. Derjaguin-Landau-Verwey-Overbeek (DLVO) interaction energy calculations were also performed to better understand the mechanisms of GO mobility. Coupling analysis of breakthrough experiments, DLVO theory and numerical modeling in this work provides insight into the mechanisms of GO transport in saturated porous media and is useful for reliable prediction of nanoparticle penetration through the vadose zone. PMID:25577737

  13. Angular-resolution and material-characterization measurements for a dual-particle imaging system with mixed-oxide fuel

    NASA Astrophysics Data System (ADS)

    Poitrasson-Rivière, Alexis; Polack, J. Kyle; Hamel, Michael C.; Klemm, Dietrich D.; Ito, Kai; McSpaden, Alexander T.; Flaska, Marek; Clarke, Shaun D.; Pozzi, Sara A.; Tomanin, Alice; Peerani, Paolo

    2015-10-01

    A dual-particle imaging (DPI) system, capable of simultaneously imaging fast neutrons and gamma rays, has been operated in the presence of mixed-oxide (MOX) fuel to assess the system's angular resolution and material-characterization capabilities. The detection principle is based on the scattering physics of neutrons (elastic scattering) and gamma rays (Compton scattering) in organic and inorganic scintillators. The detection system is designed as a combination of a two-plane Compton camera and a neutron-scatter camera. The front plane consists of EJ-309 liquid scintillators and the back plane consists of interleaved EJ-309 and NaI(Tl) scintillators. MCNPX-PoliMi was used to optimize the geometry of the system and the resulting prototype was built and tested using a Cf-252 source as an SNM surrogate. A software package was developed to acquire and process data in real time. The software was used for a measurement campaign to assess the angular resolution of the imaging system with MOX samples. Measurements of two MOX canisters of similar isotopics and intensity were performed for 6 different canister separations (from 5° to 30°, corresponding to distances of 21 cm and 131 cm, respectively). The measurements yielded a minimum separation of 20° at 2.5 m (86-cm separation) required to see 2 separate hot spots. Additionally, the results displayed good agreement with MCNPX-PoliMi simulations. These results indicate an angular resolution between 15° and 20°, given the 5° step. Coupled with its large field of view, and its capability to differentiate between spontaneous fission and (α,n) sources, the DPI system shows its potential for nuclear-nonproliferation applications.

  14. Hafnia-rich mixed oxide ceramics of the system HfO2-ZrO2-TiO2 for heaters and heat exchangers in electrothermal thrusters: The effects of titania on selected electrical and mechanical properties of Hafnia-rich mixed oxides in the system Hafnia-Zirconia-Titania, volume 1

    NASA Technical Reports Server (NTRS)

    Staszak, Paul Russell; Wirtz, G. P.; Berg, M.; Brown, S. D.

    1988-01-01

    A study of the effects of titania on selected properties of hafnia-rich mixed oxides in the system hafnia-zirconia-titania (HZT) was made in the region 5 to 20 mol percent titania. The studied properties included electrical conductivity, thermal expansion, and fracture strength and toughness. The effects of titania on the properties were studied for the reduced state as well as the oxidized state of the sintered mixed oxides. X-ray analysis showed that the materials were not always single phase. The oxidized compositions went from being monoclinic solid solutions at low titania additions to having three phases (two monoclinic and a titanate phase) at high additions of titania. The reduced compositions showed an increasing cubic phase presence mixed with the monoclinic phase as titania was added. The electrical conductivity increased with temperature at approximately 0.1 mhos/cm at 1700 C for all compositions. The thermal expansion coefficient decreased with increasing titania as did the monoclinic to tetragonal transformation temperature. The fracture strength of the oxidized bars tended to decrease with the addition of titania owing to the presence of the second phase titania. The fracture strength of the reduced bars exhibited a minimum corresponding to a two-phase region of monoclinic and cubic phases. When the second phases were suppressed, the titania tended to increase the fracture strength slightly in both the oxidized and reduced states. The fracture toughness followed similar trends.

  15. Lanthanum-promoted copper-based hydrotalcites derived mixed oxides for NO{sub x} adsorption, soot combustion and simultaneous NO{sub x}-soot removal

    SciTech Connect

    Wang, Zhongpeng; Yan, Xiaotong; Bi, Xinlin; Wang, Liguo; Zhang, Zhaoliang; Jiang, Zheng; Xiao, Tiancun; Umar, Ahmad; Wang, Qiang

    2014-03-01

    Graphical abstract: - Highlights: • The addition of La in Cu-based oxides increased the types of active oxygen. • NO{sub x} adsorption, soot oxidation and simultaneous NO{sub x}-soot removal were enhanced. • The possible catalytic mechanism was studied via in situ FTIR analysis. • Soot oxidation was promoted by the NO{sub 2} intermediate. - Abstract: La-promoted Cu-based hydrotalcites derived mixed oxides were prepared and their catalytic activities for NO{sub x} adsorption, soot oxidation, and simultaneous NO{sub x}-soot removal were investigated. The catalysts were characterized by XRD, DTG, BET, FTIR, H2-TPR, TPD and TPO techniques. The oxides catalysts exhibited mesoporous properties with specific surface area of 45–160 m{sup 2}/g. The incorporation of La and Cu decreased the amount of basic sites due to the large decrease in surface areas. Under O{sub 2} atmosphere, La incorporation is dominant for soot oxidation activity, while Cu favors high selectivity to CO{sub 2} formation. A synergetic effect between La and Cu for catalyzed soot oxidation lies in the improved redox property and suitable basicity. The presence of NO in O{sub 2} significantly promoted soot oxidation on the catalysts with the ignition temperature decreased to about 300 °C. In O{sub 2}/NO atmosphere, NO{sub 2} acts as an intermediate which oxidizes soot to CO{sub 2} at a lower temperature with itself reduced to NO or N{sub 2}, contributing to the high catalytic performance in simultaneous removal of NO{sub x} and soot.

  16. Mixed-valence iron minerals on Venus: Fe(2+)-Fe(3+) oxides and oxy-silicates formed by surface-atmosphere interactions

    NASA Technical Reports Server (NTRS)

    Burns, Roger G.; Straub, Darcy W.

    1992-01-01

    Inferences from these investigations are that Fe(3+)-bearing minerals such as hematite magnesioferrite, acmite, and epidote are thermodynamically unstable, and that magnetite is the predominant mixed-valence iron oxide mineral on venus. Recently, the Fe(2+)-Fe(3+) silicate mineral laihunite was proposed to be a reaction product of olivine with the venusian atmosphere. This possibility is discussed further here. We suggest that other mixed-valence Fe(2+)-Fe(3+)-Oz-OH(-) silicates could also result from surface-atmosphere interactions on Venus. Topics discussed include the following: (1) conversion of hematite to magnetite; (2) stability of laihunite; (3) the possible existence of oxy-amphiboles and oxy-micas on Venus; and (4) other mixed-valence Fe(2+)-Fe(3+) silicates likely to exist on Venus.

  17. High catalytic activity of Au/CeOx/TiO2(110) controlled by the nature of the mixed-metal oxide at the nanometer level

    PubMed Central

    Park, Joon B.; Graciani, Jesus; Evans, Jaime; Stacchiola, Dario; Ma, Shuguo; Liu, Ping; Nambu, Akira; Sanz, Javier Fernández; Hrbek, Jan; Rodriguez, José A.

    2009-01-01

    Mixed-metal oxides play a very important role in many areas of chemistry, physics, materials science, and geochemistry. Recently, there has been a strong interest in understanding phenomena associated with the deposition of oxide nanoparticles on the surface of a second (host) oxide. Here, scanning tunneling microscopy, photoemission, and density-functional calculations are used to study the behavior of ceria nanoparticles deposited on a TiO2(110) surface. The titania substrate imposes nontypical coordination modes on the ceria nanoparticles. In the CeOx/TiO2(110) systems, the Ce cations adopt an structural geometry and an oxidation state (+3) that are quite different from those seen in bulk ceria or for ceria nanoparticles deposited on metal substrates. The increase in the stability of the Ce3+ oxidation state leads to an enhancement in the chemical and catalytic activity of the ceria nanoparticles. The codeposition of ceria and gold nanoparticles on a TiO2(110) substrate generates catalysts with an extremely high activity for the production of hydrogen through the water–gas shift reaction (H2O + CO → H2 + CO2) or for the oxidation of carbon monoxide (2CO + O2 → 2CO2). The enhanced stability of the Ce3+ state is an example of structural promotion in catalysis described here on the atomic level. The exploration of mixed-metal oxides at the nanometer level may open avenues for optimizing catalysts through stabilization of unconventional surface structures with special chemical activity. PMID:19276120

  18. Experimental and molecular dynamics study of thermo-physical and transport properties of ThO2-5wt.%CeO2 mixed oxides

    NASA Astrophysics Data System (ADS)

    Somayajulu, P. S.; Ghosh, P. S.; Banerjee, J.; Babu, K. L. N. C.; Danny, K. M.; Mandal, B. P.; Mahata, T.; Sengupta, P.; Sali, S. K.; Arya, A.

    2015-12-01

    We have determined the thermo-physical (elastic modulus, specific heat, thermal expansion and thermal conductivity) and transport (ionic conductivity) properties of ThO2-5wt.%CeO2 mixed oxide (MOX) using a combined experimental and theoretical methodology. The specific heat, ionic conductivity and elastic properties of ThO2-5wt.%CeO2 pellets prepared by conventional powder metallurgy (POP) and coated agglomerate pelletization (CAP) routes (sintered in both air and Ar-8%H2 atmosphere) are compared with respect to homogeneity (CeO2 distribution in ThO2 matrix), microstructure, porosity and oxygen to metal ratio. The effects of inhomogeneity and pore distribution on thermal expansion and thermal conductivity of the mixed-oxide pellets are identified. Molecular dynamics (MD) simulations using the Coulomb-Buckingham-Morse-many-body model based interatomic potentials are used to predict elastic properties in the temperature range between 300 and 2000 K and thermodynamic properties, viz., enthalpy increment and specific heats of ThO2. Finally, the thermal expansion coefficient and thermal conductivity of ThO2 and (Th,Ce)O2 mixed-oxides obtained from MD are compared with available experimental results.

  19. Highly ordered mesoporous TiO2-Fe2O3 mixed oxide synthesized by sol-gel pathway: an efficient and reusable heterogeneous catalyst for dehalogenation reaction.

    PubMed

    Patra, Astam K; Dutta, Arghya; Bhaumik, Asim

    2012-09-26

    Highly ordered two-dimensional (2D) hexagonal TiO(2)-Fe(2)O(3) mixed-oxide material MFT-1, which is composed of very tiny nanoparticles, is synthesized using sodium dodecylsulfate (SDS) as a structure-directing agent. Interestingly, synthesis of an ordered mesophase was not possible using SDS as a template for mesoporous pure Fe(2)O(3) or TiO(2) phases. This mesoporous iron-titanium mixed-oxide material has been characterized by powder X-ray diffraction (XRD), field-emission scanning electron microscopy (FESEM), high-resolution transmission electron microscopy (HRTEM), N(2) sorption, ultraviolet-visible light diffuse reflectance spectroscopy (UV-vis DRS) studies. N(2) sorption analysis revealed high surface areas (126-385 m(2) g(-1)) and narrow pore size distributions (3.1-3.4 nm) for different samples. UV-vis DRS spectra and wide-angle powder XRD patterns indicate that the material is composed of α-Fe(2)O(3) and anatase TiO(2) phases. This TiO(2)-Fe(2)O(3) mixed-oxide material can act as a very efficient and reusable catalyst in the dehalogenation of aromatic chloride-, bromide-, and iodide-tolerating -F, -CN, -CH(3), -OCH(3) and -NO(2) functional groups in the aromatic ring using 2-propanol as the dispersion medium. PMID:22939382

  20. Mixed hemimicelles solid-phase extraction of cephalosporins in biological samples with ionic liquid-coated magnetic graphene oxide nanoparticles coupled with high-performance liquid chromatographic analysis.

    PubMed

    Wu, Jianrong; Zhao, Hongyan; Xiao, Deli; Chuong, Pham-Huy; He, Jia; He, Hua

    2016-07-01

    A novel mixed hemimicelles solid phase extraction based on magnetic graphene oxide (Fe3O4/GO) and ionic liquid (IL) was developed for the simultaneous extraction and determination of trace cephalosporins in spiked human urine. The high surface area and excellent adsorption capacity of the graphene oxide after modification with1-hexadecyl-3-methylmidazoliumbromide(C16mimBr) were utilized adequately in the solid phase extraction(SPE) process. A comprehensive study of the parameters affecting the extraction recovery, such as the zeta-potential of magnetic graphene oxide, amounts of magnetic graphene oxide and surfactant, pH of solution, ionic strength, extraction time, and desorption condition were optimized. A comparative study on the use of different surfacant-coated Fe3O4/GO NPs as sorbents was presented. Good linearity (R(2)>0.9987) for all calibration curves was obtained. The LODs were ranged between 0.6 and 1.9ng mL(-1) for the cephalosporins and the LOQs were 1.5 to 5.5, respectively. Satisfactory recoveries(84.3% to 101.7%)and low relative standard deviations from 1.7% to 6.3% in biological matrices were achieved. The mixed hemimicelles magnetic SPE (MSPE) method based on ILs and Fe3O4/GO NPs magnetic separation has ever been successfully used for pretreatment of complex biological samples. PMID:27266334

  1. Dual-mode T1 and T2 magnetic resonance imaging contrast agent based on ultrasmall mixed gadolinium-dysprosium oxide nanoparticles: synthesis, characterization, and in vivo application.

    PubMed

    Tegafaw, Tirusew; Xu, Wenlong; Ahmad, Md Wasi; Baeck, Jong Su; Chang, Yongmin; Bae, Ji Eun; Chae, Kwon Seok; Kim, Tae Jeong; Lee, Gang Ho

    2015-09-11

    A new type of dual-mode T1 and T2 magnetic resonance imaging (MRI) contrast agent based on mixed lanthanide oxide nanoparticles was synthesized. Gd(3+) ((8)S7/2) plays an important role in T1 MRI contrast agents because of its large electron spin magnetic moment resulting from its seven unpaired 4f-electrons, and Dy(3+) ((6)H15/2) has the potential to be used in T2 MRI contrast agents because of its very large total electron magnetic moment: among lanthanide oxide nanoparticles, Dy2O3 nanoparticles have the largest magnetic moments at room temperature. Using these properties of Gd(3+) and Dy(3+) and their oxide nanoparticles, ultrasmall mixed gadolinium-dysprosium oxide (GDO) nanoparticles were synthesized and their potential to act as a dual-mode T1 and T2 MRI contrast agent was investigated in vitro and in vivo. The D-glucuronic acid coated GDO nanoparticles (davg = 1.0 nm) showed large r1 and r2 values (r2/r1 ≈ 6.6) and as a result clear dose-dependent contrast enhancements in R1 and R2 map images. Finally, the dual-mode imaging capability of the nanoparticles was confirmed by obtaining in vivo T1 and T2 MR images. PMID:26291827

  2. Adriamycin-induced oxidative stress is prevented by mixed hydro-alcoholic extract of Nigella sativa and Curcuma longa in rat kidney

    PubMed Central

    Mohebbati, Reza; Shafei, Mohammad Naser; Soukhtanloo, Mohammad; Mohammadian Roshan, Noema; Khajavi Rad, Abolfazl; Anaeigoudari, Akbar; Hosseinian, Sara; Karimi, Sareh; Beheshti, Farimah

    2016-01-01

    Objective: Inflammation and oxidative stress is considered to have a crucial role in induction of nephropathy. Curcuma longa (C. longa) and Nigella sativa (N. sativa) have anti-inflammatory and antioxidant effects. This study was designed to investigate the effect of mixed hydro-alcoholic extract of N.sativa and C. longa on the oxidative stress induced by Adriamycin (ADR) in rat kidney. Materials and Methods: The animals were divided into 6 groups: control (CO), ADR, Adriamycin+ Vitamin C (ADR+VIT C), C. longa extract+ Adriamycin (C.LE+ADR), N. sativa extract+ Adriamycin (N.SE+ADR) and C. longa extract+ N. sativa extract + Adriamycin (N.S+C.L+ADR). ADR (5mg/kg) was injected intravenously, whereas VITC (100mg/kg) and extract of C. longa (1000mg/kg) and N. sativa (200mg/kg) were administrated orally. Finally, the renal tissue, urine and blood samples were collected and submitted to measure of redox markers, osmolarity and renal index. Results: The renal content of total thiol and superoxide dismutase (SOD) activity significantly decreased and Malondialdehyde (MDA) concentration increased in Adriamycin group compared to control group. The renal content of total thiol and SOD activity significantly enhanced and MDA concentration reduced in treated-mixed extract of C. longa and N. sativa along with ADR group compared to ADR group. The mixed extract did not restore increased renal index percentage induced by ADR. There also was no significant difference in urine and serum osmolarity between the groups. Conclusion: hydro-alcoholic extracts of N.sativa and C.longa led to an improvement in ADR-induced oxidative stress and mixed administration of the extracts enhanced the aforementioned therapeutic effect. PMID:27247925

  3. Mixed-ligand chelate extraction of lanthanides with 1-phenyl-3-methyl-4-(trifluoroacetyl)-5-pyrazolone and some phosphine oxide compounds

    SciTech Connect

    Umetani, S.; Freiser, H.

    1987-09-23

    Mixed-ligand chelate extraction of lanthanides (Ln) such as La, Pr, Eu, Ho, and Yb into chloroform with 1-phenyl-3-methyl-4-(trifluoroacetyl)-5-pyrazolone (HPMTFP) and with one of three phosphine oxide compounds is studied. The phosphine oxide compounds employed in the present work are tri-n-octylphosphine oxide (TOPO), n-octylphenyl(N,N-diisobutylcarbamoylmethyl)phosphine oxide (CMPO), and methylenebis(diphenylphosphine oxide) (MBDPO). Lanthanide ions are found to be extracted from a 0.1 M sodium perchlorate medium as Ln(PMTFP)/sub 3/(TOPO)/sub 2/ and Ln(PMTFP)/sub 3/(CMPO), respectively. In the extraction of lanthanides with the mixture of HPMTFP and MBDPO, the extracted species are found to be Ln(PMTFP)/sub 3/(MBDPO) or Ln(PMTFP)/sub 2/(ClO/sub 4/)(MBDPO)/sub 2/ in the absence or presence of sodium perchlorate, respectively. The extraction constants of these systems do not increase monotonically with atomic number but have a maximum at Eu or Ho. 11 references, 4 tables.

  4. Redox cycle stability of mixed oxides used for hydrogen generation in the cyclic water gas shift process

    SciTech Connect

    Datta, Pradyot

    2013-10-15

    Graphical abstract: - Highlights: • Fe{sub 2}O{sub 3} modified with CaO, SiO{sub 2} and Al{sub 2}O{sub 3} was studied in cyclic water gas shift reactor. • For the first time stability of such oxides were tested for 100 redox cycles. • Optimally added oxides significantly improved the activity and the stability of Fe{sub 2}O{sub 3}. • Increased stability was attributed to the impediment of neck formation. - Abstract: Repeated cycles of the reduction of Fe{sub 3}O{sub 4} with reductive gas, e.g. hydrogen and subsequent oxidation of the reduced iron material with water vapor can be harnessed as a process for the production of pure hydrogen. The redox behavior of iron oxide modified with various amounts of SiO{sub 2}, CaO and Al{sub 2}O{sub 3} was investigated in the present study. The total amount of the additional metal oxides was always below 15 wt%. The samples were prepared by co-precipitation using urea hydrolysis method. The influence of various metal oxides on the hydrogen production capacity and the material stability was studied in detail in terms of temperature-programmed reduction (TPR), X-ray diffraction (XRD), scanning electron microscopy (SEM) and BET analysis. Furthermore, the activity and the stability of the samples were tested in repeated reduction with diluted H{sub 2} and re-oxidation cycles with H{sub 2}O. The results indicate that combination of several oxides as promoter increases the stability of the iron oxide material by mitigating the sintering process. The positive influence of the oxides in stabilizing the iron oxide material is attributed to the impediment of neck formation responsible for sintering.

  5. Adsorption of propane, isopropyl, and hydrogen on cluster models of the M1 phase of Mo-V-Te-Nb-O mixed metal oxide catalyst

    SciTech Connect

    Govindasamy, Agalya; Muthukumar, Kaliappan; Yu, Junjun; Xu, Ye; Guliants, Vadim V.

    2010-01-01

    The Mo-V-Te-Nb-O mixed metal oxide catalyst possessing the M1 phase structure is uniquely capable of directly converting propane into acrylonitrile. However, the mechanism of this complex eight-electron transformation, which includes a series of oxidative H-abstraction and N-insertion steps, remains poorly understood. We have conducted a density functional theory study of cluster models of the proposed active and selective site for propane ammoxidation, including the adsorption of propane, isopropyl (CH{sub 3}CHCH{sub 3}), and H which are involved in the first step of this transformation, that is, the methylene C-H bond scission in propane, on these active site models. Among the surface oxygen species, the telluryl oxo (Te=O) is found to be the most nucleophilic. Whereas the adsorption of propane is weak regardless of the MO{sub x} species involved, isopropyl and H adsorption exhibits strong preference in the order of Te=O > V=O > bridging oxygens > empty Mo apical site, suggesting the importance of TeO{sub x} species for H abstraction. The adsorption energies of isopropyl and H and consequently the reaction energy of the initial dehydrogenation of propane are strongly dependent on the number of ab planes included in the cluster, which points to the need to employ multilayer cluster models to correctly capture the energetics of surface chemistry on this mixed metal oxide catalyst.

  6. Multi-functional porous mix-valent manganese oxide nano-materials and ruthenium/titanium dioxide for magnetic, electronic, and catalytic applications

    NASA Astrophysics Data System (ADS)

    Shen, Xiongfei

    This thesis contains two parts: (1) development of porous mixed-valent manganese oxide octahedral molecular sieve (OMS) nano-materials with controlled tunnel structures and muilt-functionalities and (2) application of H 2 adsorption for metal particle size evaluation on TiO2 supported Ru Fischer-Tropsch catalysts. Manganese oxide OMS with different nano-scale tunnel sizes may result in various microporosities for different selective catalysis and separation applications. A hydrothermal method was developed to synthesize manganese oxide nano-materials with controlled nano-scale tunnel sizes by hydrothermal treatments of layered structure manganese oxides under different pH conditions. Manganese oxides with increasing tunnel sizes of 2.3 A x 2.3 A (1x1 tunnel structure), 4.6 A x 6.9 A (2x3 tunnel structure), and 4.6 A x 9.2 A (2x4 tunnel structure) were synthesized with increasing pH value from 1.0, 7.0, to 13.0, respectively. Phase transformation mechanism of layered precursors to tunnel structures was obtained by characterization of the materials during synthesis using in situ synchrotron X-ray diffraction. The obtained phase transformation mechanism was used for synthesis of better materials such as new lxl/1x2 tunnel structures and controlled BET surface areas. Most manganese oxide OMS materials show paramagnetism at temperatures from 100 to 350 K. A new method was established to measure the average oxidation state (AOS) of mix-valent manganese in OMS materials by describing their paramagnetic behavior using the Curie-Weiss law. Measurement results show a maximum 7% deviation error compared to the reference titration method for 10 different samples. Magnetism of OMS was further explored by doping Fe into KOMS-2 (a 2x2 tunnel structure manganese oxide) to create high temperature ferromagnetism. The possession of both semiconducting and high temperature ferromagnetism in the Fe-doped KOMS-2 created a highly promising new group of functional materials for

  7. Mechanism of selenite removal by a mixed adsorbent based on Fe-Mn hydrous oxides studied using X-ray absorption spectroscopy.

    PubMed

    Chubar, Natalia; Gerda, Vasyl; Szlachta, Małgorzata

    2014-11-18

    Selenium cycling in the environment is greatly controlled by various minerals, including Mn and Fe hydrous oxides. At the same time, such hydrous oxides are the main inorganic ion exchangers suitable (on the basis of their chemical nature) to sorb (toxic) anions, separating them from water solutions. The mechanism of selenite adsorption by the new mixed adsorbent composed of a few (amorphous and crystalline) phases [maghemite, MnCO3, and X-ray amorphous Fe(III) and Mn(III) hydrous oxides] was studied by extended X-ray absorption fine structure (EXAFS) spectroscopy [supported by Fourier transform infrared (FTIR) and X-ray diffraction (XRD) data]. The complexity of the porous adsorbent, especially the presence of the amorphous phases of Fe(III) and Mn(III) hydrous oxides, is the main reason for its high selenite removal performance demonstrated by batch and column adsorption studies shown in the previous work. Selenite was bound to the material via inner-sphere complexation (via oxygen) to the adsorption sites of the amorphous Fe(III) and Mn(III) oxides. This anion was attracted via bidentate binuclear corner-sharing coordination between SeO3(2-) trigonal pyramids and both FeO6 and MnO6 octahedra; however, the adsorption sites of Fe(III) hydrous oxides played a leading role in selenite removal. The contribution of the adsorption sites of Mn(III) oxide increased as the pH decreased from 8 to 6. Because most minerals have a complex structure (they are seldom based on individual substances) of various crystallinity, this work is equally relevant to environmental science and environmental technology because it shows how various solid phases control cycling of chemical elements in the environment. PMID:25325790

  8. Nanoscale Control Over Interfacial Properties in Mixed Reverse Micelles Formulated by Using Sodium 1,4-bis-2-ethylhexylsulfosuccinate and Tri-n-octyl Phosphine Oxide Surfactants.

    PubMed

    Odella, Emmanuel; Falcone, R Darío; Silber, Juana J; Correa, N Mariano

    2016-08-01

    The interfacial properties of pure reverse micelles (RMs) are a consequence of the magnitude and nature of noncovalent interactions between confined water and the surfactant polar head. Addition of a second surfactant to form mixed RMs is expected to influence these interactions and thus affect these properties at the nanoscale level. Herein, pure and mixed RMs stabilized by sodium 1,4-bis-2-ethylhexylsulfosuccinate and tri-n-octyl phosphine oxide (TOPO) surfactants in n-heptane were formulated and studied by varying both the water content and the TOPO mole fraction. The microenvironment generated was sensed by following the solvatochromic behavior of the 1-methyl-8-oxyquinolinium betaine probe and (31) P NMR spectroscopy. The results reveal unique properties of mixed RMs and we give experimental evidence that free water can be detected in the polar core of the mixed RMs at very low water content. We anticipate that these findings will have an impact on the use of such media as nanoreactors for many types of chemical reactions, such as enzymatic reactions and nanoparticle synthesis. PMID:27128745

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

    SciTech Connect

    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.

  10. Mixed results with mixed disulfides.

    PubMed

    Brigelius-Flohé, Regina

    2016-04-01

    A period of research with Helmut Sies in the 1980s is recalled. Our experiments aimed at an in-depth understanding of metabolic changes due to oxidative challenges under near-physiological conditions, i.e. perfused organs. A major focus were alterations of the glutathione and the NADPH/NADP(+) system by different kinds of oxidants, in particular formation of glutathione mixed disulfides with proteins. To analyze mixed disulfides, a test was adapted which is widely used until today. The observations in perfused rat livers let us believe that glutathione-6-phosphate dehydrogenase (G6PDH), i.a. might be activated by glutathionylation. Although we did not succeed to verify this hypothesis for the special case of G6PDH, the regulation of enzyme/protein activities by glutathionylation today is an accepted posttranslational mechanism in redox biology in general. Our early experimental approaches are discussed in the context of present knowledge. PMID:27095221

  11. Decay Heat Calculations for PWR and BWR Assemblies Fueled with Uranium and Plutonium Mixed Oxide Fuel using SCALE

    SciTech Connect

    Ade, Brian J; Gauld, Ian C

    2011-10-01

    In currently operating commercial nuclear power plants (NPP), there are two main types of nuclear fuel, low enriched uranium (LEU) fuel, and mixed-oxide uranium-plutonium (MOX) fuel. The LEU fuel is made of pure uranium dioxide (UO{sub 2} or UOX) and has been the fuel of choice in commercial light water reactors (LWRs) for a number of years. Naturally occurring uranium contains a mixture of different uranium isotopes, primarily, {sup 235}U and {sup 238}U. {sup 235}U is a fissile isotope, and will readily undergo a fission reaction upon interaction with a thermal neutron. {sup 235}U has an isotopic concentration of 0.71% in naturally occurring uranium. For most reactors to maintain a fission chain reaction, the natural isotopic concentration of {sup 235}U must be increased (enriched) to a level greater than 0.71%. Modern nuclear reactor fuel assemblies contain a number of fuel pins potentially having different {sup 235}U enrichments varying from {approx}2.0% to {approx}5% enriched in {sup 235}U. Currently in the United States (US), all commercial nuclear power plants use UO{sub 2} fuel. In the rest of the world, UO{sub 2} fuel is still commonly used, but MOX fuel is also used in a number of reactors. MOX fuel contains a mixture of both UO{sub 2} and PuO{sub 2}. Because the plutonium provides the fissile content of the fuel, the uranium used in MOX is either natural or depleted uranium. PuO{sub 2} is added to effectively replace the fissile content of {sup 235}U so that the level of fissile content is sufficiently high to maintain the chain reaction in an LWR. Both reactor-grade and weapons-grade plutonium contains a number of fissile and non-fissile plutonium isotopes, with the fraction of fissile and non-fissile plutonium isotopes being dependent on the source of the plutonium. While only RG plutonium is currently used in MOX, there is the possibility that WG plutonium from dismantled weapons will be used to make MOX for use in US reactors. Reactor-grade plutonium

  12. Atmosphere-ocean energy and nitrous oxide exchange and mixed layer dynamics in the Caribbean Sea and neighboring Atlantic Ocean

    NASA Astrophysics Data System (ADS)

    Hernandez Figueroa, Jose Luis

    2000-12-01

    The air-sea fluxes of energy and nitrous oxide (N2O) in oceanic waters of the Caribbean Sea and neighboring Atlantic Ocean (10°N-24°N, 48°W-88°W) were studied. These fluxes were estimated using parameterization formulas and five gas exchange turbulent models applied to 1980-1995 COADS data. The region was divided in four subregions that exhibit different patterns of wind speed (W) and sea surface temperature ( Ts), the main parameters controlling regional heat fluxes. Monthly averages on latitude bands of 2° width and time spectral analysis were obtained for Ts, air surface temperature (Ta), W, relative humidity (RH), cloud cover ( C) and sea level pressure (P). The spatial and temporal behavior of these climate parameters reveals that oceanic regions mainly have annual variation, while coastal areas show biannual variation. The spatial distribution of Ts revealed that the Caribbean Sea is warmer than the Atlantic Ocean with a consistent difference of about 0.5°C-0.75°C throughout the year. Winds affect Ts at coastal areas inducing upwelling in the central (CC) and eastern Caribbean (EC) subregions. The southern part (11°N-13°N) of these subregions is cooler (~0.5°C) than the rest of the Caribbean from January to March. The temperature difference between those latitudes and higher latitudes (24°N) increases up to about 1°C in July when wind speed strengthens. This strengthening is associated to the meridional gradient of P. During July at CC, the highest gradient (0.58 mb/°lat) simultaneously occurs with the highest wind speeds. At low latitudes (11°N-15°N), C presents a maximum during June, simultaneously with a minimum in the solar heat flux. Thermal stability (dTs = Ts-Ta ) is of significant importance in the sea-atmosphere energy exchange. Over the region, a high correlation coefficient (-0.92) was found between net heat flux and dTs. This parameter also controls the mixed layer depth, except in February and July when wind effects become

  13. New insight into self-irradiation effects on local and long-range structure of uranium-americium mixed oxides (through XAS and XRD).

    PubMed

    Lebreton, Florent; Martin, Philippe M; Horlait, Denis; Bès, René; Scheinost, Andreas C; Rossberg, Andre; Delahaye, Thibaud; Blanchart, Philippe

    2014-09-15

    Uranium-americium mixed oxides could be used as transmutation targets to lower Am inventory in spent nuclear fuels. Due to (241)Am activity, these materials are subjected to α-self-irradiation which provokes crystallographic disorder. Previous studies on U-Am mixed oxides gave first insight into α-radiation tolerance of these compounds, but have never been carried out for more than a year, whereas these compounds might be stored up to a few years between fabrication and irradiation. In this work, we study effects of self-irradiation on the structure of U(1-x)Am(x)O(2±δ) solid solutions (x = 0.15 and 0.20) aged 3 to 4 years. Especially, X-ray diffraction and X-ray absorption spectroscopy are combined to observe these effects from both long-range and local perspectives. Results show that the fluorite-type structure of U-Am mixed oxides withstands (241)Am α-irradiation without major damage. Despite the increase of interatomic distances and crystallographic disorder observed during the first months of storage, the present results show that a steady state is then reached. Thus, no detrimental factors have been identified in this study in terms of structural damage for several-year storage of U(1-x)Am(x)O(2±δ) pellets before irradiation. Furthermore, comparison between long-range and local evolution suggests that α-self-irradiation-induced defects are mainly located in low-ordered domains. Based on literature data and present results, the steady state appears related to the equilibrium between radioinduced defect formation and material self-healing. PMID:25162209

  14. Exchange bias and antiferromagnetic interfacial exchange coupling in the mixed-spin oxide Li2/7Ni5/7O

    NASA Astrophysics Data System (ADS)

    Shi, C. X.; Ren, W. J.; Liu, W.; Zhang, Z. D.

    2014-01-01

    We present a detailed study on magnetic properties of mixed spin oxide Li2/7Ni5/7O, where small ferromagnetic (FM) clusters (with averaged diameter of ˜18 Å) immersed with an antiferromagnetic (AFM) host. The exchange bias (EB) with shifts of the hysteresis loop along both the field and magnetization axes is found, which is due to the interfacial interaction between the FM clusters and the AFM host. An AFM interfacial exchange coupling is deduced from the exchange interactions between Ni ions. The type and strength of this interfacial exchange interaction are discussed in terms of the EB at low temperature.

  15. E-beam and UV induced fabrication of CeO2, Eu2O3 and their mixed oxides with UO2

    NASA Astrophysics Data System (ADS)

    Pavelková, Tereza; Vaněček, Vojtěch; Jakubec, Ivo; Čuba, Václav

    2016-07-01

    CeO2, Eu2O3 and mixed oxides of CeO2-UO2, Eu2O3-UO2 were fabricated. The preparative method was based on the irradiation of aqueous solutions containing cerium/europium (and uranyl) nitrates and ammonium formate. In the course of irradiation, the solid phase (precursor) was precipitated. The composition of irradiated solutions significantly affected the properties of precursor formed in the course of the irradiation. However, subsequent heat treatment of (amorphous) precursors at temperatures ≤650 °C invariably resulted in the formation of powder oxides with well-developed nanocrystals with linear crystallite size 13-27 nm and specific surface area 10-46 m2 g-1. The applicability of both ionizing (e-beam) and non-ionizing (UV) radiation was studied.

  16. Optical and structural properties of sol gel made Ce/Ti/Zr mixed oxide thin films as transparent counter electrode for electrochromic devices

    NASA Astrophysics Data System (ADS)

    Ghodsi, F. E.; Tepehan, F. Z.; Tepehan, G. G.

    2008-09-01

    Ce/Ti/Zr mixed oxide thin films were prepared using sol-gel process with mole ratios from 45/5 to 5/45 of Ti/Zr and 50 of Ce and deposited by dip coating technique. Optical, electrochromic, and structural properties of such films were investigated. The thickness, refractive index, and extinction coefficient of the films were calculated through transmission and reflection measurement by an nkd spectrophotometer. The surface morphology and structural behaviors of the films were characterized by atomic force microscopy and X-ray diffraction. Cyclic voltammetry measurements also were used to study electrochromic properties of these films. The best counter electrode Ce/Ti/Zr oxide thin film is achieved for the sample with a mole ratio of 40/10 of Ti/Zr. The ratio between anodic and cathodic charge is about 0.95 for this sample with a surface roughness of 1.8 nm.

  17. Determination of strychnine, brucine, strychnine N-oxide, and brucine N-oxide in plasma samples after the oral administration of processed semen strychni extract by high-performance liquid chromatography with ultrasound-assisted mixed cloud point extraction.

    PubMed

    Guo, Jun; Meng, Hua; Li, Huang Huang; Wang, Qiao Feng

    2016-07-01

    A sensitive and efficient mixed cloud point extraction combined with high-performance liquid chromatography was developed for the simultaneous separation and determination of four alkaloids (strychnine, strychnine N-oxide, brucine, and brucine N-oxide) in plasma after the oral administration of processed semen strychni extract. Tergitol TMN-6 and cetyl-trimethyl ammonium bromide were chosen as the mixed surfactants, and ultrasound was employed to enhance the extraction efficiency. Some important parameters affecting the mixed cloud point extraction efficiency, such as the content of Tergitol TMN-6 and cetyl-trimethyl ammonium bromide, pH, salt effect, extraction temperature, and ultrasound time were studied and optimized. Under optimum conditions, the linear range of four alkaloids was from 1.0 to 1000 ng/mL. All correlation coefficients of the calibration curves were higher than 0.9993. The intraday and interday precision were below 8.65% and the limits of detection for the four alkaloids were less than 1.0 ng/mL (S/N = 3). PMID:27125604

  18. Size- and shape-controlled synthesis and catalytic performance of iron-aluminum mixed oxide nanoparticles for NOX and SO₂ removal with hydrogen peroxide.

    PubMed

    Ding, Jie; Zhong, Qin; Zhang, Shule; Cai, Wei

    2015-01-01

    A novel, simple, reproducible and low-cost strategy is introduced for the size- and shape-controlled synthesis of iron-aluminum mixed oxide nanoparticles (NIAO(x/y)). The as-synthesized NIAO(x/y) catalyze decomposition of H2O2 yielding highly reactive hydroxyl radicals (OH) for NOX and SO2 removal. 100% SO2 removal is achieved. NIAO(x/y) with Fe/Al molar ratio of 7/3 (NIAO(7/3)) shows the highest NOX removal of nearly 80% at >170°C, whereas much lower NOX removal (<63%) is obtained for NIAO(3/7). The melting of aluminum oxides in NIAO(7/3) promotes the formation of lamellar products, thus improving the specific surface areas and mesoporous distribution, benefiting the production of OH radicals. Furthermore, the NIAO(7/3) leads to the minor increase of points of zero charges (PZC), apparent enhancement of FeOH content and high oxidizing ability of Fe(III), further improving the production of OH radicals. However, the NIAO(3/7) results in the formation of aluminum surface-enriched spherical particles, thus decreasing the surface atomic ratio of iron oxides, decreasing OH radical production. More importantly, the generation of FeOAl causes the decline of active sites. Finally, the catalytic decomposition of H2O2 on NIAO(x/y) is proposed. And the well catalytic stability of NIAO(7/3) is obtained for evaluation of 30 h. PMID:25464305

  19. Photo-induced low temperature synthesis of nanocrystalline UO2, ThO2 and mixed UO2-ThO2 oxides

    NASA Astrophysics Data System (ADS)

    Pavelková, Tereza; Čuba, Václav; Šebesta, Ferdinand

    2013-11-01

    Photochemically induced preparation of nanocrystalline uranium and/or thorium oxides is based on UV radiation induced formation of amorphous solid precursor in aqueous solutions containing uranium and/or thorium nitrate and ammonium formate. Subsequent heat treatment under various atmospheres leads to formation of nanocrystalline UO2, ThO2 or UO2-ThO2 solid solution at minimum temperatures in the interval 300-550 °C. The materials consist of nanoparticles from 3 to 15 nm in diameter and with narrow size distribution. The initial solutions contain soluble salts of respective metals and OH radical scavenger (ammonium formate) satisfying the "CHON principle". Solutions may be used without further adjustment (e.g. saturation by inert gases or adjusting pH). Photo-induced precipitation proceeds at room temperature and does not require strict control of reaction conditions (pH, temperature). Due to negligible amounts of carbon in solid precursor formed from any solution, it is possible to prepare crystalline nanomaterials containing U(IV) oxide from solid precursors directly via heat treatment in Ar + H2 atmosphere without pre-calcination in air. Mild heat treatment (450-550 °C) results in formation of oxides with well-developed nanocrystals. In the case of mixed oxides, high level of interaction of both components was observed, resulting in the formation of solid solution U0.56Th0.44O2 at 300 °C or higher.

  20. Lung injury in guinea pigs caused by multiple exposures to submicron zinc oxide mixed with sulfur dioxide in a humidified furnace

    SciTech Connect

    Conner, M.W.; Lam, H.F.; Rogers, A.E.; Fitzgerald, S.; Amdur, M.O.

    1985-01-01

    Sulfur dioxide, water vapor, and ultrafine particles rich in oxides of zinc and other surface-deposited trace elements are important products of coal combustion. In order to study the toxicity of zinc oxide generated under conditions simulating combustion, guinea pigs were exposed in a nose-only apparatus for 3 h on 6 consecutive days to 6 mg/mT of submicron zinc oxide particles (count median diameter of 0.05 m, sigma/sub g/ 2.0), which were generated in a humid furnace and mixed with 1 ppm sulfur dioxide. The exposures caused increases in lung weight and (TH)thymidine labeling index of terminal bronchiolar cell nuclei and inflammation of the proximal portion of the alveolar duct. The lung weights and labeling index had returned to normal and inflammatory changes had nearly resolved by 72 h after the last exposure. Total lung capacity, functional residual volume, alveolar volume, and diffusing capacity for carbon monoxide were decreased following exposure and had not returned to normal by 72 h after the last exposure. Large airways were not affected by the repeated exposures, as indicated by normal morphology of trachea and bronchi, unchanged secretory cell concentration, and unaltered epithelial permeability to horseradish peroxidase. These results are essentially identical to changes the authors reported in guinea pigs exposed to zinc oxide alone, suggesting that surface-deposited sulfur compounds, which are important determinants of the response to a single exposure to these ultrafine particles, become less important as exposure progresses.

  1. Improvement on the catalytic performance of Mg-Zr mixed oxides for furfural-acetone aldol condensation by supporting on mesoporous carbons.

    PubMed

    Faba, Laura; Díaz, Eva; Ordóñez, Salvador

    2013-03-01

    A new procedure for improving the performance of the most common catalysts used in aqueous-phase aldol condensation (Mg-Zr mixed oxides) reactions is presented. This reaction is of interest for upgrading carbohydrate feedstocks. The procedure involves supporting Mg-Zr oxides on non-microporous carbonaceous materials, such as carbon nanofibers (CNFs) or high-surface-area graphites (HSAGs), using either incipient wetness or coprecipitation procedures. The use of HSAGs together with the coprecipitation method provides the best performance. Results obtained for the cross-condensation of acetone and furfural at 323 K reveal that the catalyst performance is greatly improved compared to the bulk oxides (96.5 % conversion vs. 81.4 % with the bulk oxide; 87.8 % selectivity for C13 and C8 adducts vs. 76.2 % with the bulk oxide). This difference is even more prominent in terms of rates per catalytically active basic site (four and seven times greater for C8 and C13 adducts, respectively). The improved performance is explained in terms of a more appropriate basic site distribution and by greater interaction of the reactants with the carbon surface. In addition, deactivation behavior of the catalyst is improved by tuning the morphology of the carbonaceous support. An important enhancement of the catalytic stability can be obtained selecting a HSAG with an appropriate pore diameter. With HSAG100 the activity decreased by less than 20 % between successive reaction cycles and the selectivity for the condensation products remained almost unaltered. The decrease is greater than 80 % for the bulk oxides tested at these conditions, with important increases in the selectivity for by-product formation. PMID:23362138

  2. Method for making fine and ultrafine spherical particles of zirconium titanate and other mixed metal oxide systems

    DOEpatents

    Hu, Michael Z.

    2006-05-23

    Disclosed is a method for making amorphous spherical particles of zirconium titanate and crystalline spherical particles of zirconium titanate comprising the steps of mixing an aqueous solution of zirconium salt and an aqueous solution of titanium salt into a mixed solution having equal moles of zirconium and titanium and having a total salt concentration in the range from 0.01 M to about 0.5 M. A stearic dispersant and an organic solvent is added to the mixed salt solution, subjecting the zirconium salt and the titanium salt in the mixed solution to a coprecipitation reaction forming a solution containing amorphous spherical particles of zirconium titanate wherein the volume ratio of the organic solvent to aqueous part is in the range from 1 to 5. The solution of amorphous spherical particles is incubated in an oven at a temperature .ltoreq.100.degree. C. for a period of time .ltoreq.24 hours converting the amorphous particles to fine or ultrafine crystalline spherical particles of zirconium titanate.

  3. Influence of anodization parameters on the volume expansion of anodic aluminum oxide formed in mixed solution of phosphoric and oxalic acids

    NASA Astrophysics Data System (ADS)

    Kao, Tzung-Ta; Chang, Yao-Chung

    2014-01-01

    The growth of anodic alumina oxide was conducted in the mixed solution of phosphoric and oxalic acids. The influence of anodizing voltage, electrolyte temperature, and concentration of phosphoric and oxalic acids on the volume expansion of anodic aluminum oxide has been investigated. Either anodizing parameter is chosen to its full extent of range that allows the anodization process to be conducted without electric breakdown and to explore the highest possible volume expansion factor. The volume expansion factors were found to vary between 1.25 and 1.9 depending on the anodizing parameters. The variation is explained in connection with electric field, ion transport number, temperature effect, concentration, and activity of acids. The formation of anodic porous alumina at anodizing voltage 160 V in 1.1 M phosphoric acid mixed with 0.14 M oxalic acid at 2 °C showed the peak volume expansion factor of 1.9 and the corresponding moderate growth rate of 168 nm/min.

  4. Synthesis, Characterization, and Catalytic Activity of Sulfided Silico-Alumino-Titanate (Si-Al-Ti) Mixed Oxides Xerogels Supported Ni-Mo Catalyst

    SciTech Connect

    Al-Adwani, H.A.; Anthony, R.G.; Gardner, T.J.; Thammachote, N.

    1999-02-24

    Layered semicrystalline silico-alumino-titanate (Si-Al-Ti) mixed oxides were synthesized by a modified sol-gel method with hydrothermal synthesis temperatures less than 200 C and autogenic pressure. The solid products are semicrystalline materials with a surface area of 136-367 m{sup 2}/g and a monomodal pore size distribution with an average pore diameter of 3.6-4.7 nrn. The catalytic activity for pyrene hydrogenation in a batch reactor at 300 C and 500 psig was determined for sulfided Ni-Mo supported on the Si-Al-Ti mixed oxide. The activity was a function of the support composition the heat treatment before and after loading the active metals, the addition of organic templates, and different methods of metal loading. The most active sulfided Ni-Mo/Si-Al-Ti catalyst has an activity in the same range as the commercial catalyst, Shell 324, but the metal loading is 37% less than the commercial catalyst.

  5. Comparative XRPD and XAS study of the impact of the synthesis process on the electronic and structural environments of uranium–americium mixed oxides

    SciTech Connect

    Prieur, D.; Lebreton, F.; Somers, J.; Delahaye, T.

    2015-10-15

    Uranium–americium mixed oxides are potential compounds to reduce americium inventory in nuclear waste via a partitioning and transmutation strategy. A thorough assessment of the oxygen-to-metal ratio is paramount in such materials as it determines the important underlying electronic structure and phase relations, affecting both thermal conductivity of the material and its interaction with the cladding and coolant. In 2011, various XAS experiments on U{sub 1−x}Am{sub x}O{sub 2±δ} samples prepared by different synthesis methods have reported contradictory results on the charge distribution of U and Am. This work alleviates this discrepancy. The XAS results confirm that, independently of the synthesis process, the reductive sintering of U{sub 1−x}Am{sub x}O{sub 2±δ} leads to the formation of similar fluorite solid solution indicating the presence of Am{sup +III} and U{sup +V} in equimolar proportions. - Graphical abstract: Formation of (U{sup IV/V},Am{sup III})O{sup 2} solid solution by sol–gel and by powder metallurgy. - Highlights: • Uranium–americium mixed oxides were synthesized by sol–gel and powder metallurgy. • Fluorite solid solutions with similar local environment have been obtained. • U{sup V} and Am{sup III} are formed in equimolar proportions.

  6. The investigation of Ni-Al and Co-Al based layered double hydroxides and their derived mixed oxides thin films deposited by pulsed laser deposition

    NASA Astrophysics Data System (ADS)

    Birjega, R.; Matei, A.; Filipescu, M.; Stokker-Cheregi, F.; Luculescu, C.; Colceag, D.; Zavoianu, R.; Pavel, O. D.; Dinescu, M.

    2013-08-01

    Layered Double Hydroxides (LDHs) are host-guest materials consisting of positively charged metal/hydroxides sheets with intercalated anions and water molecules. LDHs can be described by the generic formula [[ṡmHO and their structure is formed by layers containing divalent cations (M2+: Mg, Zn, Ni, Co,…) and trivalent cations (M3+: Al, Ga, Cr,…) with an octahedral coordination. LDH films with well-oriented structure and controlled thickness are needed for numerous applications like sensors, protective coatings, catalysts, components for optoelectronics etc. In this work, we report on the deposition of Ni-Al and Co-Al based LDHs and their derived mixed oxides by pulsed laser deposition as a new approach to fabricate oriented LDHs or highly dispersed metallic mixed oxides. The influence of the laser characteristics, such as wavelength and fluence, on the films properties was studied. The films investigation techniques were X-Ray Diffraction, Atomic Force Microscopy, Scanning Electron Microscopy combined with energy dispersive X-ray analysis, and Secondary Ions Mass Spectrometry.

  7. Pyrocarbons prepared by carbonisation of polymers adsorbed or synthesised on a surface of silica and mixed oxides

    NASA Astrophysics Data System (ADS)

    Gun'ko, V. M.; Skubiszewska-Zi ęba, J.; Leboda, R.; Voronin, E. F.; Zarko, V. I.; Levitskaya, S. I.; Brei, V. V.; Guzenko, N. V.; Kazakova, O. A.; Seledets, O.; Janusz, W.; Chibowski, S.

    2004-04-01

    Initial oxides fumed silica, alumina/silica and titania/silica and silica gel and hybrid adsorbents with pyrocarbon formed on these oxide substrates by carbonisation of immobilised (adsorbed or synthesised) polymers such as starch, methyl cellulose, polyvinylpyrrolidone, polystyrene, and polybutylvinyl ether were studied by adsorption, AFM, TEM, and FTIR methods. Polymer/oxide materials were investigated by nitrogen and Pb(II) adsorption, FTIR, and potentiometric titration methods. Analysis of nitrogen adsorption-desorption isotherms by different methods, FTIR spectra, AFM and TEM images of the initial and hybrid adsorbents reveals that the morphology of the substrates significantly changes on carbonisation of oxygen-containing polymers because of hydrothermal treatment of them by water eliminated as a product of pyrolysis. Contribution of own microporosity of pyrocarbon deposits formed on carbonisation of immobilised polymers is greater (dependent on reaction conditions) than that on pyrolysis of low-molecular compounds at the same oxide substrates. Pyrocarbon particles formed on silica gel are larger than those formed on fumed oxides and larger than those formed on silica gel on pyrolysis of low-molecular compounds.

  8. High-temperature mixed oxidation of nitride-bonded silicon carbide in oxidizing gas mixtures containing 2% Cl{sub 2}

    SciTech Connect

    Park, C.; McNallan, M.J.

    1995-04-01

    Nitride-bonded silicon carbide ceramics have lower processing costs than many other SiC-based ceramics and adequate properties for use as high-temperature heat exchangers in oxidizing environments. Silicon nitride has much better resistance to attack by chlorine at temperatures above 900 C than silicon carbide. When nitride bonded silicon carbide ceramics are exposed to gas mixtures containing 2% Cl{sub 2} and small amounts of oxygen in this temperature range, the SiC is selectively chlorinated, leaving behind a porous matrix of silicon nitride. The rate of corrosion is controlled by a combination of interfacial kinetics at the surfaces of the SiC grains and transport of volatile species through the silicon nitride skeleton. In more oxidizing environments, the rate of chlorination is suppressed by the formation of a protective SiO{sub 2} film. In more oxidizing environments at temperatures in excess of 1,200 C, the formation of volatile chloride reaction products at the interface between the SiC and the passivating SiO{sub 2} layer causes bubbles to form in the SiO{sub 2}, which accelerates the oxidation.

  9. Stabilization of {alpha}-SiAlONs using a rare-earth mixed oxide (RE{sub 2}O{sub 3}) as sintering additive

    SciTech Connect

    Santos, C.; Silva, O.M.M.; Silva, C.R.M.

    2005-07-12

    {alpha}-SiAlONs are commonly produced by liquid phase sintering of Si{sub 3}N{sub 4} with AlN and Y{sub 2}O{sub 3} as additives. The formation of the {alpha}-SiAlONs using a mixed oxide (RE{sub 2}O{sub 3}), containing yttria and rare-earth oxides, as an alternative additive was investigated. Dense {alpha}-SiAlONs were obtained by gas-pressure sintering, starting from {alpha}-Si{sub 3}N{sub 4} and AlN-Y{sub 2}O{sub 3} or AlN-RE{sub 2}O{sub 3} as additives. The mixed oxide powder RE{sub 2}O{sub 3} was characterized by means of high-resolution synchrotron X-ray diffraction and compared to Y{sub 2}O{sub 3}. The X-ray diffraction analysis of the mixed oxide shows a pattern indicating a true solid solution formation. The Rietveld refinement of the crystal structure of the sintered {alpha}-SiAlON using AlN-RE{sub 2}O{sub 3} as additive revealed a similar crystal structure to the {alpha}-SiAlON using AlN-RE{sub 2}O{sub 3} as additive. The comparison of the microstructures of the both {alpha}-SiAlONs produced using pure Y{sub 2}O{sub 3} or RE{sub 2}O{sub 3}, revealed similar grain sizes of about 4.5 {mu}m with aspect ratios of about 5. Both materials show also similar mechanical properties, with hardness of 18.5 GPa and fracture toughness of 5 MPa m{sup 1/2}. It could be, thus, demonstrated that pure Y{sub 2}O{sub 3} can be substituted by the rare-earth solid solution, RE{sub 2}O{sub 3}, in the formation of {alpha}-SiAlONs, presenting similar microstructural and mechanical properties.

  10. Redox preparation of mixed-valence cobalt manganese oxide nanostructured materials: highly efficient noble metal-free electrocatalysts for sensing hydrogen peroxide

    NASA Astrophysics Data System (ADS)

    Kuo, Cheng-Chi; Lan, Wen-Jie; Chen, Chun-Hu

    2013-12-01

    High-performance hydrogen peroxide sensors provide valuable signals of biological interactions, disorders, and developing of diseases. Low-cost metal oxides are promising alternatives but suffer from low conductivity and sensing activity. Multi-component metal oxides are excellent candidates to accomplish these challenges, but the composition inhomogeneity is difficult to manage with conventional material preparation. We demonstrated redox preparation strategies to successfully synthesize highly homogeneous, noble metal-free H2O2 sensors of spinel nanostructured cobalt manganese oxides with enhanced conductivity, multiple mixed-valence features, and efficient H2O2 sensing activities. The designed redox reactions accompanied with material nucleation/formation are the key factors for compositional homogeneity. High conductivity (1.5 × 10-2 S cm-1) and H2O2 sensing activity (12 times higher than commercial Co3O4) were achieved due to the homogeneous multiple mixed-valence systems of Co(ii)/(iii) and Mn(iii)/(iv). A wide linear detection range (from 0.1 to 25 mM) with a detection limit of 15 μM was observed. Manganese species assist the formation of large surface area nanostructures, enhancing the H2O2 reduction activities, and inhibit the sensing interference. The material controls of hierarchical nanostructures, elemental compositions, porosity, and electrochemical performances are highly associated with the reaction temperatures. The temperature-dependent properties and nanostructure formation mechanisms based on a reaction rate competition are proposed.High-performance hydrogen peroxide sensors provide valuable signals of biological interactions, disorders, and developing of diseases. Low-cost metal oxides are promising alternatives but suffer from low conductivity and sensing activity. Multi-component metal oxides are excellent candidates to accomplish these challenges, but the composition inhomogeneity is difficult to manage with conventional material

  11. Methanol suppression of trichloroethylene degradation by Methylosinus trichosporium (OB3b) and methane-oxidizing mixed cultures

    SciTech Connect

    Eng, W.; Palumbo, A.V.; Strandberg, G.W.; Sriharan, S.

    1991-12-31

    The effect of methanol on trichloroethylene (TCE) degradation by mixed and pure methylotrophic cultures was examined in batch culture experiments. Methanol was found to relieve growth inhibition of Methylosinus trichosporium (OB3b) at high (14 mg/L) TCE concentrations. Degradation of TCE was determined by both radiolabeling and gas chromatography techniques. When cultures were grown on methanol over 10 to 14 d with 0.3 mg/L TCE, OB3b degraded 16.89 {+-} 0.82% (mean {+-} SD) of the TCE, and a mixed culture (DT type II) degraded 4.55 {+-} 0.11%. Mixed culture (JS type I) degraded 4.34 {+-} 0.06% of the TCE. When grown on methane with 0.3 mg/L TCE, 32.93 {+-} 2.01% of the TCE was degraded by OB3b, whereas the JS culture degraded 24.3 {+-} 1.38% of the TCE, and the DT culture degraded 34.3 {+-} 2.97% of the TCE. The addition of methanol to cultures grown on methane reduced TCE degradation to 16.21 {+-} 1.17% for OB3b and to 5.08 {+-} 0.56% for JS. Although methanol reduces the toxicity of TCE to the cultures, biodegradation of TCE cannot be sustained in methanol-grown cultures. Since high TCE concentrations appear to inhibit methane uptake and growth, we suggest the primary toxicity of TCE is directed towards the methane monooxygenase.

  12. Magnetism of iron oxide based core-shell nanoparticles from interface mixing with enhanced spin-orbit coupling

    NASA Astrophysics Data System (ADS)

    Skoropata, E.; Desautels, R. D.; Chi, C.-C.; Ouyang, H.; Freeland, J. W.; van Lierop, J.

    2014-01-01

    We show that the magnetism of core-shell nanoparticles (made of maghemite, γ-Fe2O3, cores and transition-metal and metal-oxide shells) is altered substantially by the interface, which is a doped iron-oxide layer formed naturally during the seed-mediated synthesis process, a route used typically to produce core-shell nanoparticles. Characteristics fundamental to useful applications, such as the anisotropy and superparamagnetic blocking temperature, were altered substantially with Cu, CoO, MnO, and NiO shells. To ascertain the origin of this behavior, the prototype γ-Fe2O3/CoO core-shell nanoparticles are described in detail. We show that the magnetism originates essentially from an interfacial doped iron-oxide layer formed via migration of shell ions, e.g., Co2+, into octahedral site vacancies in the surface layers of the γ-Fe2O3 core. For this system, an overall Fe morb/mspin=0.15±0.03 is measured (morb˜0 for the Fe-oxides) and an enhanced Co morb/mspin=0.65±0.03 elucidates the origin of the unexpectedly high overall anisotropy of the nanoparticle. This interfacial layer is responsible for the overall (e.g., bulk) magnetism and provides a perspective on how the magnetism of core-shell nanoparticles manifests from the selected core and shell materials.

  13. RATES OF IRON OXIDATION AND ARSENIC SORPTION DURING GROUND WATER-SURFACE WATER MIXING AT A HAZARDOUS WASTE SITE

    EPA Science Inventory

    The fate of arsenic discharged from contaminated ground water to a pond at a hazardous waste site is controlled, in part, by the rate of ferrous iron oxidation-precipitation and arsenic sorption. Laboratory experiments were conducted using site-derived water to assess the impact...

  14. Actinide Oxidation State and O/M Ratio in Hypostoichiometric Uranium-Plutonium-Americium U0.750Pu0.246Am0.004O2-x Mixed Oxides.

    PubMed

    Vauchy, Romain; Belin, Renaud C; Robisson, Anne-Charlotte; Lebreton, Florent; Aufore, Laurence; Scheinost, Andreas C; Martin, Philippe M

    2016-03-01

    Innovative americium-bearing uranium-plutonium mixed oxides U1-yPuyO2-x are envisioned as nuclear fuel for sodium-cooled fast neutron reactors (SFRs). The oxygen-to-metal (O/M) ratio, directly related to the oxidation state of cations, affects many of the fuel properties. Thus, a thorough knowledge of its variation with the sintering conditions is essential. The aim of this work is to follow the oxidation state of uranium, plutonium, and americium, and so the O/M ratio, in U0.750Pu0.246Am0.004O2-x samples sintered for 4 h at 2023 K in various Ar + 5% H2 + z vpm H2O (z = ∼ 15, ∼ 90, and ∼ 200) gas mixtures. The O/M ratios were determined by gravimetry, XAS, and XRD and evidenced a partial oxidation of the samples at room temperature. Finally, by comparing XANES and EXAFS results to that of a previous study, we demonstrate that the presence of uranium does not influence the interactions between americium and plutonium and that the differences in the O/M ratio between the investigated conditions is controlled by the reduction of plutonium. We also discuss the role of the homogeneity of cation distribution, as determined by EPMA, on the mechanisms involved in the reduction process. PMID:26907589

  15. A method for the estimation of the enthalpy of formation of mixed oxides in Al{sub 2}O{sub 3}-Ln{sub 2}O{sub 3} systems

    SciTech Connect

    Vonka, P.; Leitner, J.

    2009-04-15

    A new method is proposed for the estimation of the enthalpy of formation (DELTA{sub ox}H) of various Al{sub 2}O{sub 3}-Ln{sub 2}O{sub 3} mixed oxides from the constituent binary oxides. Our method is based on Pauling's concept of electronegativity and, in particular, on the relation between the enthalpy of formation of a binary oxide and the difference between the electronegativities of the oxide-forming element and oxygen. This relation is extended to mixed oxides with a simple formula given for the calculation of DELTA{sub ox}H. The parameters of this equation were fitted using published experimental values of DELTA{sub ox}H derived from high-temperature oxide melt solution calorimetry. Using our proposed method, we obtained a standard deviation (sigma) of 4.87 kJ mol{sup -1} for this data set. Taking into account regularities within the lanthanide series, we then estimated the DELTA{sub ox}H values for Al{sub 2}O{sub 3}-Ln{sub 2}O{sub 3} mixed oxides. The values estimated using our method were compared with those obtained by Aronson's and Zhuang's empirical methods, both of which give significantly poorer results. - Graphical abstract: Enthalpy of formation of Ln-Al-O oxides from the constituent binary ones.

  16. Synthesis and characterization of Th{sub 1−x}Ln{sub x}O{sub 2−x/2} mixed-oxides

    SciTech Connect

    Horlait, D.; Clavier, N.

    2012-12-15

    Graphical abstract: Display Omitted Highlights: ► Th{sub 1−x}Ln{sub x}O{sub 2−x/2} (Ln = Nd, Sm, Gd, Dy, Yb) were produced from oxalates precursors. ► The isomorphic thermal conversion of oxalates to oxides were followed by HT-ESEM. ► The stabilization of the ThO{sub 2} fluorite structure up to x = 0.4 was evidenced by XRD. ► Neodymium incorporation limits in solid solutions were determined by XRD and μ-Raman. ► Lanthanide incorporation mechanism in ThO{sub 2} structure was formally determined by μ-Raman. -- Abstract: Several Th{sub 1−x}Ln{sub x}O{sub 2−x/2} mixed-oxides (Ln = Nd, Sm, Gd, Dy, Er or Yb) were prepared from oxalate precursors. Structural and microstructural investigations of both initial precursors and resulting oxides were undertaken by XRD, μ-Raman spectroscopy and SEM, with a particular attention paid to the Th{sub 1−x}Nd{sub x}O{sub 2−x/2} series. For oxides, XRD and μ-Raman agreed well with the stabilization of the Fm3{sup ¯}m structure up to x{sub Nd} = 0.4, thanks to the concomitant creation of oxygen vacancies, as also confirmed by μ-Raman. Then, a structural transition to the Ia3{sup ¯} superstructure occurred. For x{sub Nd} ≥ 0.49, mixed-oxides with an additional hexagonal Nd{sub 2}O{sub 3} phase were prepared. Besides, the unit cell parameter of the Th{sub 1−x}Ln{sub x}O{sub 2−x/2} series followed a quadratic relation versus the x substitution rate as a result of the combination between modifications of cationic radius and cation coordination, and the decrease of O-O repulsion linked to the presence of oxygen vacancies.

  17. Influence of Adsorption Site and Wavelength on the Photodesorption of NO from the (Fe,Cr) 3 O 4 (111) Mixed Oxide Surface

    SciTech Connect

    Henderson, M. A.

    2014-09-11

    The photochemical properties of nitric oxide on a mixed oxide single crystal surface was examined in ultrahigh vacuum (UHV) using temperature programmed desorption (TPD), photon stimulated desorption (PSD) and low energy electron diffraction (LEED). The mixed oxide was a 75% Fe and 25% Cr corundum (0001) oxide film prepared on an α-Al2O3(0001) crystal, however its surface became terminated with a magnetite-like (111) structure after sputter/anneal cleaning, leading to a surface designated of (Fe,Cr)3O4(111). TPD of NO from the (Fe,Cr)3O4(111) surface revealed three chemisorbed states at 220, ~315 and 370 K assigned to NO binding at Fe3+, Cr3+ and Fe2+ sites, respectively. No significant thermal chemistry of NO was detected. NO photodesorption, the primary photochemical pathway in UHV, was sensitive to the adsorption site, with rates at the three adsorption sites following the trend: Fe3+ > Fe2+ > Cr3+. Multiexponential rate behavior seen in the overall NO PSD spectra was linked directly to site heterogeneity being manifested as a convolution of the individual NO photodesorption rates at the three types of surface sites. The photodesorption rate with UV light (365 nm) was ~10 times greater than that in the visible, but the per-photon rates across the visible spectrum (from 460 to 630 nm) were independent of the wavelength, which is suggestive of localized photon absorption at the adsorption site. Results in this study demonstrate that the adsorption site plays a critical role in determining photochemical rates on complex oxide surfaces. This work was supported by the US Department of Energy, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences & Biosciences. Pacific Northwest National Laboratory (PNNL) is a multi-program national laboratory operated for DOE by Battelle. The research was performed using EMSL, a national scientific user facility sponsored by the Department of Energy's Office of Biological and Environmental Research and located

  18. QUALIFICATION OF THE SAVANNAH RIVER SITE 252CF SHUFFLER FOR RECEIPT VERIFICATION MEASUREMENTS OF MIXED U-PU OXIDES STORED IN 9975 SHIPPING CONTAINERS

    SciTech Connect

    Dubose, F.

    2011-05-26

    To extend their ability to perform accountability and verification measurements of {sup 235}U in a U-Pu oxide matrix, the K-Area Material Storage facility commissioned the development and construction of a Passive/Active {sup 252}Cf Shuffler. A series of {sup 252}Cf, PuO{sub 2}, and U-Pu oxide standards, in addition to a single U{sub 3}O{sub 8} standard, were measured to characterize and calibrate the shuffler. Accompanying these measurements were simulations using MCNP5/MCNPX, aimed at isolating the neutron countrate contributions for each of the isotopes present. Two calibration methods for determining the {sup 235}U content in mixed UPu oxide were then developed, yielding comparable results. The first determines the {sup 235}U mass by estimating the {sup 239}Pu/{sup 235}U ratio-dependent contributions from the primary delayed neutron contributors. The second defines an average linear response based on the {sup 235}U and {sup 239}Pu mass contents. In each case, it was observed that self-shielding due to {sup 235}U mass has a large influence on the observed rates, requiring bounds on the applicable limits of each calibration method.

  19. The formation of volatile corrosion products during the mixed oxidation-chlorination of cobalt at 650 C

    NASA Technical Reports Server (NTRS)

    Jacobson, N. S.; Mcnallan, M. J.; Lee, Y. Y.

    1986-01-01

    The reaction of cobalt with 1 pct Cl2 in 1, 10, and 50 pct O2/Ar atmospheres has been studied at 650 C with thermogravimetry and mass spectrometry. The principal vapor species appear to be CoCl2 and CoCl3. In all cases, CoCl2(s) forms at the oxide/metal interface and equilibration of the volatile chlorides with Co3O4 does not occur in the early stages of the reaction. In the 1 pct Cl2 1 pct O2-Ar case, continuous volatilization occurs. In the 1 pct Cl2-10 pct O2-Ar and 1 pct CL2-50 pct O2-Ar cases, volatilization occurs only in the first few minutes of reaction. Afterwards, the reaction is predominantly oxidation.

  20. Nano SnO 2-Al 2O 3 mixed oxide and SnO 2-Al 2O 3-carbon composite oxides as new and novel electrodes for supercapacitor applications

    NASA Astrophysics Data System (ADS)

    Jayalakshmi, M.; Venugopal, N.; Raja, K. Phani; Rao, M. Mohan

    New nano-materials like SnO 2-Al 2O 3 and SnO 2-Al 2O 3-carbon were synthesized by a single step hydrothermal method in searching for novel mixed oxides with high electrochemical double layer capacitance. A SnO 2-Al 2O 3-carbon sample was calcined at 600 °C and tested for its performance. The source of carbon was tetrapropyl ammonium hydroxide. The capacitive behavior of SnO 2 was compared to the performance of SnO 2-Al 2O 3, SnO 2-Al 2O 3-carbon and calcined SnO 2-Al 2O 3-carbon using the techniques of cyclic voltammetry, double potential step, chronopotentiometry and E-log I polarization. In 0.1 M NaCl solutions, SnO 2-Al 2O 3 gave the best performance with a value of 119 Fg -1 and cycled 1000 times. The nano-material mixed oxides were characterized by TEM, XRD, ICP-AES and SEM-EDAX.

  1. Kinetic and stoichiometric characterization of anoxic sulfide oxidation by SO-NR mixed cultures from anoxic biotrickling filters.

    PubMed

    Mora, Mabel; Fernández, Maikel; Gómez, José Manuel; Cantero, Domingo; Lafuente, Javier; Gamisans, Xavier; Gabriel, David

    2015-01-01

    Monitoring the biological activity in biotrickling filters is difficult since it implies estimating biomass concentration and its growth yield, which can hardly be measured in immobilized biomass systems. In this study, the characterization of a sulfide-oxidizing nitrate-reducing biomass obtained from an anoxic biotrickling filter was performed through the application of respirometric and titrimetric techniques. Previously, the biomass was maintained in a continuous stirred tank reactor under steady-state conditions resulting in a growth yield of 0.328 ± 0.045 g VSS/g S. To properly assess biological activity in respirometric tests, abiotic assays were conducted to characterize the stripping of CO2 and sulfide. The global mass transfer coefficient for both processes was estimated. Subsequently, different respirometric tests were performed: (1) to solve the stoichiometry related to the autotrophic denitrification of sulfide using either nitrate or nitrite as electron acceptors, (2) to evaluate the inhibition caused by nitrite and sulfide on sulfide oxidation, and (3) to propose, calibrate, and validate a kinetic model considering both electron acceptors in the overall anoxic biodesulfurization process. The kinetic model considered a Haldane-type equation to describe sulfide and nitrite inhibitions, a non-competitive inhibition to reflect the effect of sulfide on the elemental sulfur oxidation besides single-step denitrification since no nitrite was produced during the biological assays. PMID:24705508

  2. Mixed-phase Pd-Pt bimetallic alloy on graphene oxide with high activity for electrocatalytic applications

    NASA Astrophysics Data System (ADS)

    Khan, Majid; Yousaf, Ammar Bin; Chen, Mingming; Wei, Chengsha; Wu, Xibo; Huang, Ningdong; Qi, Zeming; Li, Liangbin

    2015-05-01

    Bimetallic PdPt alloy nanoparticles on graphene oxide (GO) have been prepared by a simple and facile chemical route, in which the reduction of metal precursors is carried out using CO as a reductant. Structural and morphological characterizations of GO/PdPt composites are performed using X-ray diffraction, X-ray photoelectron spectroscopy analysis and transmission electron microscopy. It is found that PdPt bimetallic nanoparticles are successfully synthesized and uniformly attached on the graphene sheets. The electrocatalytic and electrochemical properties of GO/PdPt composites including methanol oxidation reaction (MOR), oxygen reduction reaction (ORR) and methanol tolerant oxygen reduction reaction (MTORR) are studied in HClO4 aqueous solution. A significant improvement in the electrocatalytic activities is observed by increasing the atomic ratio of Pt in PdPt bimetallic alloys compared to the freestanding Pd nanoparticles on GO. The prepared GO/PdPt composites with an (Pd:Pt) atomic ratio of 40:60 exhibits higher methanol oxidation activity, higher specific ORR activity and better tolerance to CO poisoning. The results can be attributed to the collective effects of the PdPt nanoparticles and the enhanced electron transfer of graphene.

  3. A novel preparation of three-dimensionally ordered macroporous M/Ti (M=Zr or Ta) mixed oxide nanoparticles with enhanced photocatalytic activity.

    PubMed

    Wang, Changhua; Geng, Aifang; Guo, Yihang; Jiang, Shujuan; Qu, Xuesong; Li, Li

    2006-09-01

    Three-dimensionally ordered macroporous (3 DOM) M/Ti (M=Zr or Ta) mixed oxides were prepared by cohydrolysis of a mixture of Zr(n-OC(4)H(9))(4)/TTIP or TaCl(5)/TTIP (TTIP=titanium isopropoxide) combined with a polystyrene (PS) latex sphere templating technique. The resulting products exhibited homogeneous wall compositions, namely, Zr or Ta was uniformly dispersed into the TiO(2) framework with the loading levels of 5, 10, and 20 mol% for Zr and 2.5, 5.0, and 7.5 mol% for Ta, respectively. The estimated macropore diameter, wall thickness, and particle size of the products ranged from 280 to 290 nm, from 30 to 50 nm, and from 10 to 12 nm, respectively. The products showed only anatase phase structure although their starting solitary metal oxides exhibited suitable crystalline structures under the same preparation conditions. Raman scattering spectroscopy showed that the crystal structure of titania had a slight interference due to the incorporation of Zr or Ta, and UV-vis diffuse reflectance spectroscopy (DRS) showed the narrower band gap of the products compared with that of pure anatase TiO(2). The products exhibited mesoporous wall structures, and their BET surface areas were higher than those of the corresponding pure 3 DOM metal oxides. The UV-light photocatalytic activity of the products was assessed by monitoring the photodegradation of two organic molecules including 4-nitrophenol (4-NP) and rhodamine B (RB). Both the photocatalytic reactions confirmed that the presence of the second metal oxide in the titania framework resulted in enhanced photocatalytic activity compared with the pure titania framework. PMID:16777130

  4. Solar-Driven H2 O2 Generation From H2 O and O2 Using Earth-Abundant Mixed-Metal Oxide@Carbon Nitride Photocatalysts.

    PubMed

    Wang, Ruirui; Pan, Kecheng; Han, Dandan; Jiang, Jingjing; Xiang, Chengxiang; Huang, Zhuangqun; Zhang, Lu; Xiang, Xu

    2016-09-01

    Light-driven generation of H2 O2 only from water and molecular oxygen could be an ideal pathway for clean production of solar fuels. In this work, a mixed metal oxide/graphitic-C3 N4 (MMO@C3 N4 ) composite was synthesized as a dual-functional photocatalyst for both water oxidation and oxygen reduction to generate H2 O2 . The MMO was derived from a NiFe-layered double hydroxide (LDH) precursor for obtaining a high dispersion of metal oxides on the surface of the C3 N4 matrix. The C3 N4 is in the graphitic phase and the main crystalline phase in MMO is cubic NiO. The XPS analyses revealed the doping of Fe(3+) in the dominant NiO phase and the existence of surface defects in the C3 N4 matrix. The formation and decomposition kinetics of H2 O2 on the MMO@C3 N4 and the control samples, including bare MMO, C3 N4 matrix, Ni- or Fe-loaded C3 N4 and a simple mixture of MMO and C3 N4 , were investigated. The MMO@C3 N4 composite produced 63 μmol L(-1) of H2 O2 in 90 min in acidic solution (pH 3) and exhibited a significantly higher rate of production for H2 O2 relative to the control samples. The positive shift of the valence band in the composite and the enhanced water oxidation catalysis by incorporating the MMO improved the light-induced hole collection relative to the bare C3 N4 and resulted in the enhanced H2 O2 formation. The positively shifted conduction band in the composite also improved the selectivity of the two-electron reduction of molecular oxygen to H2 O2 . PMID:27484581

  5. Comparative study of structural, optical and impedance measurements on V{sub 2}O{sub 5} and V-Ce mixed oxide thin films

    SciTech Connect

    Malini, D. Rachel; Sanjeeviraja, C.

    2015-06-24

    Vanadium pentoxide (V{sub 2}O{sub 5}) and Vanadium-Cerium mixed oxide thin films at different molar ratios of V{sub 2}O{sub 5} and CeO{sub 2} have been deposited at 200 W rf power by rf planar magnetron sputtering in pure argon atmosphere. The structural and optical properties were studied by taking X-ray diffraction and transmittance and absorption spectra respectively. The amorphous thin films show an increase in transmittance and optical bandgap with increase in CeO{sub 2} content in as-prepared thin films. The impedance measurements for as-deposited thin films show an increase in electrical conductivity with increase in CeO{sub 2} material.

  6. Significant Promotion Effect of Mo Additive on a Novel Ce-Zr Mixed Oxide Catalyst for the Selective Catalytic Reduction of NO(x) with NH3.

    PubMed

    Ding, Shipeng; Liu, Fudong; Shi, Xiaoyan; Liu, Kuo; Lian, Zhihua; Xie, Lijuan; He, Hong

    2015-05-13

    A novel Mo-promoted Ce-Zr mixed oxide catalyst prepared by a homogeneous precipitation method was used for the selective catalytic reduction (SCR) of NO(x) with NH3. The optimal catalyst showed high NH3-SCR activity, SO2/H2O durability, and thermal stability under test conditions. The addition of Mo inhibited growth of the CeO2 particle size, improved the redox ability, and increased the amount of surface acidity, especially the Lewis acidity, all of which were favorable for the excellent NH3-SCR performance. It is believed that the catalyst is promising for the removal of NO(x) from diesel engine exhaust. PMID:25894854

  7. Comparative XRPD and XAS study of the impact of the synthesis process on the electronic and structural environments of uranium-americium mixed oxides

    NASA Astrophysics Data System (ADS)

    Prieur, D.; Lebreton, F.; Martin, P. M.; Caisso, M.; Butzbach, R.; Somers, J.; Delahaye, T.

    2015-10-01

    Uranium-americium mixed oxides are potential compounds to reduce americium inventory in nuclear waste via a partitioning and transmutation strategy. A thorough assessment of the oxygen-to-metal ratio is paramount in such materials as it determines the important underlying electronic structure and phase relations, affecting both thermal conductivity of the material and its interaction with the cladding and coolant. In 2011, various XAS experiments on U1-xAmxO2±δ samples prepared by different synthesis methods have reported contradictory results on the charge distribution of U and Am. This work alleviates this discrepancy. The XAS results confirm that, independently of the synthesis process, the reductive sintering of U1-xAmxO2±δ leads to the formation of similar fluorite solid solution indicating the presence of Am+III and U+V in equimolar proportions.

  8. Effects of sintering and mixed oxide growth on the interface cracking of air-plasma-sprayed thermal barrier coating system at high temperature

    NASA Astrophysics Data System (ADS)

    Lv, Bowen; Xie, Hua; Xu, Rong; Fan, Xueling; Zhang, Weixu; Wang, T. J.

    2016-01-01

    Sintering and mixed oxide (MO) growth significantly affect the thermal and mechanical properties of thermal barrier coating system (TBCs) in gas turbine at high temperature. In this work, we numerically analyzed the effects of sintering and MO growth on the interface cracking of TBCs. A thermal-elasto-viscoplastic constitutive model was introduced, in which the effect of sintering was studied using a spherical shell model. Based on the same spherical shell model and our previous experimental observations, we theoretically derived the evolution of relative density and applied this constitutive model to the sintering of ceramic coating. The numerical results showed that viscosity, initial porosity of ceramic and the growth rate of MO had significant effects on interface cracking. In contrast, the influence of initial pore size of ceramic coating was neglectable. Suggestions were also made for the choice of material during TBCs design.

  9. A density functional theory guide to high quality modification of mixed metal oxides used for photocatalytic water splitting

    NASA Astrophysics Data System (ADS)

    Mayfield, Cedric Leon

    Phase stability and charge transport of pristine and transition metal alloyed bismuth titanate (Bi2Ti2O7, a.k.a. BTO), a photocatalytic water splitter, has been studied using the generalized gradient approximated density functional theory (GGA-DFT). The primary goals of this work were to predict the effective conditions for pure phase synthesis of the modified ternary multi-metal oxide and to determine the most suitable modifications for enhancing its photocatalytic properties. To understand the details of phase stability and photoconduction, we have derived the formation enthalpies, defect formation energies, electronic structures, spectral absorptions and polaron activation energies for pristine and transition metal doped bismuth titanate (Bi2Ti2O7, a.k.a. BTO). Implantation of the localized 3d electrons is a primary band engineering technique for extending the spectral absorptions of metal oxides into the visible range. However, localized states typically increase charge trapping that reduces crucial photocurrent for the photocatalytic process. Therefore one objective here is to understand the extent to which localization plays a role in electron transfer and which mode of conduction, band or polaron hopping, is dominantly effected. As predicting the effective conditions for pure phase stability and modeling electron transport of multi metal oxide materials is still in development as a whole, we have benchmarked our methods by reproducing relative quantities of world class metal oxide photocatalyst, rutile TiO2 and monoclinic scheelite BiVO4. In recognition of our methods, our results have been used to enhance H2 production of a facile hydrothermal synthesized Fe-doped BTO. Furthermore, we demonstrate with results for Cr- and Mn-doped BTO how experimental characterization can also be enhanced. For each transition metal ion (M = Cr, Mn, and Fe), pure phase stability has a unique association with the presence or absence of O defects. Band modifications vary with

  10. Interaction of iron-copper mixed metal oxide oxygen carriers with simulated synthesis gas derived from steam gasification of coal

    SciTech Connect

    Siriwardane, Ranjani V.; Ksepko, Ewelina; Tian, Hanging

    2013-01-01

    The objective of this work was to prepare supported bimetallic Fe–Cu oxygen carriers and to evaluate their performance for the chemical-looping combustion (CLC) process with simulated synthesis gas derived from steam gasification of coal/air. Ten-cycle CLC tests were conducted with Fe–Cu oxygen carriers in an atmospheric thermogravimetric analyzer utilizing simulated synthesis gas derived from the steam gasification of Polish Janina coal and Illinois #6 coal as fuel. The effect of temperature on reaction rates, chemical stability, and oxygen transport capacity were determined. Fractional reduction, fractional oxidation, and global rates of reactions were calculated from the thermogravimetric analysis (TGA) data. The supports greatly affected reaction performance. Data showed that reaction rates and oxygen capacities were stable during the 10-cycle TGA tests for most Fe–Cu/support oxygen carriers. Bimetallic Fe–Cu/support oxygen carriers showed higher reduction rates than Fe-support oxygen carriers. The carriers containing higher Cu content showed better stabilities and better reduction rates. An increase in temperature from 800 °C to 900 °C did not have a significant effect on either the oxygen capacity or the reduction rates with synthesis gas derived from Janina coal. Oxidation reaction was significantly faster than reduction reaction for all supported Fe–Cu oxygen carriers. Carriers with higher Cu content had lower oxidation rates. Ten-cycle TGA data indicated that these oxygen carriers had stable performances at 800–900 °C and might be successfully used up to 900 °C for coal CLC reaction in the presence of steam.

  11. Experiment Safety Assurance Package for Mixed Oxide Fuel Irradiation in an Average Power Position (I-24) in the Advanced Test Reactor

    SciTech Connect

    J. M . Ryskamp; R. C. Howard; R. C. Pedersen; S. T. Khericha

    1998-10-01

    The Fissile Material Disposition Program Light Water Reactor Mixed Oxide Fuel Irradiation Test Project Plan details a series of test irradiations designed to investigate the use of weapons-grade plutonium in MOX fuel for light water reactors (LWR) (Cowell 1996a, Cowell 1997a, Thoms 1997a). Commercial MOX fuel has been successfully used in overseas reactors for many years; however, weapons-derived test fuel contains small amounts of gallium (about 2 parts per million). A concern exists that the gallium may migrate out of the fuel and into the clad, inducing embrittlement. For preliminary out-of-pile experiments, Wilson (1997) states that intermetallic compound formation is the principal interaction mechanism between zircaloy cladding and gallium. This interaction is very limited by the low mass of gallium, so problems are not expected with the zircaloy cladding, but an in-pile experiment is needed to confirm the out-of-pile experiments. Ryskamp (1998) provides an overview of this experiment and its documentation. The purpose of this Experiment Safety Assurance Package (ESAP) is to demonstrate the safe irradiation and handling of the mixed uranium and plutonium oxide (MOX) Fuel Average Power Test (APT) experiment as required by Advanced Test Reactor (ATR) Technical Safety Requirement (TSR) 3.9.1 (LMITCO 1998). This ESAP addresses the specific operation of the MOX Fuel APT experiment with respect to the operating envelope for irradiation established by the Upgraded Final Safety Analysis Report (UFSAR) Lockheed Martin Idaho Technologies Company (LMITCO 1997a). Experiment handling activities are discussed herein.

  12. Fabrication, Inspection, and Test Plan for the Advanced Test Reactor (ATR) High-Power Mixed-Oxide (MOX) Fuel Irradiation Project

    SciTech Connect

    Wachs, G. W.

    1998-09-01

    The Department of Energy (DOE) Fissile Disposition Program (FMDP) has announced that reactor irradiation of Mixed-Oxide (MOX) fuel is one of the preferred alternatives for disposal of surplus weapons-usable plutonium (Pu). MOX fuel has been utilized domestically in test reactors and on an experimental basis in a number of Commercial Light Water Reactors (CLWRs). Most of this experience has been with Pu derived from spent low enriched uranium (LEU) fuel, known as reactor grade (RG) Pu. The High-Power MOX fuel test will be irradiated in the Advanced Test Reactor (ATR) to provide preliminary data to demonstrate that the unique properties of surplus weapons-derived or weapons-grade (WG) plutonium (Pu) do not compromise the applicability of this MOX experience base. The purpose of the high-power experiment, in conjunction with the currently ongoing average-power experiment at the ATR, is to contribute new information concerning the response of WG plutonium under more severe irradiation conditions typical of the peak power locations in commercial reactors. In addition, the high-power test will contribute experience with irradiation of gallium-containing fuel to the database required for resolution of generic CLWR fuel design issues. The distinction between "high-power" and "average-power" relates to the position within the nominal CLWR core. The high-power test project is subject to a number of requirements, as discussed in the Fissile Materials Disposition Program Light Water Reactor Mixed Oxide Fuel Irradiation High-Power Test Project Plan (ORNL/MD/LTR-125).

  13. High specific surface area nickel mixed oxide powders LaNiO{sub 3} (perovskite) and NiCo{sub 2}O{sub 4} (spinel) via sol-gel type routes for oxygen electrocatalysis in alkaline media

    SciTech Connect

    El Baydi, M.; Chartier, P.; Koenig, J.F.; Poillerat, G.; Tiwari, S.K. |; Singh, R.N.; Rehspringer, J.L.

    1995-04-01

    A novel sol-gel process of preparation of oxide electrocatalysts is investigated to prepare Ni-containing mixed oxides LaNiO{sub 3} and NiCo{sub 2}O{sub 4} at moderate temperatures. High surface area (20-55 m{sup 2} g{sup {minus}1}) powders and high roughness electrodes (30-1500) were obtained. Apparent and real electrocatalytical activity are compared and discussed.

  14. A La-doped Mg-Al mixed metal oxide supported copper catalyst with enhanced catalytic performance in transfer dehydrogenation of 1-decanol.

    PubMed

    Zhang, Ming; Zhao, Yajie; Liu, Qian; Yang, Lan; Fan, Guoli; Li, Feng

    2016-01-21

    In the present work, a La-doped Mg-Al mixed metal oxide supported copper catalyst (Cu/La-MgAlO) was synthesized through a layered double hydroxide precursor route. The materials were characterized by powder X-ray diffraction, transmission electron microscopy, CO2-temperature programmed desorption, Fourier transform infrared spectra of CO2 absorption, and X-ray photoelectron spectroscopy. The results revealed that the introduction of a trace amount of La could significantly improve the surface basicity of the Cu/La-MgAlO catalyst, especially strong Lewis basicity. Compared with the undoped supported Cu catalyst, Cu/La-MgAlO exhibited much higher activity and selectivity in the liquid-phase transfer dehydrogenation of 1-decanol with a 1-decanal yield up to 89%. The excellent catalytic efficiency was mainly ascribed to the surface cooperation between the Lewis basic sites and the adjacent Cu(0)/Cu(+) species. That is, basic sites, especially strong-strength basic sites, held the key to the abstraction of protons from the hydroxyl group in 1-decanol, while the adjacent Cu(0) and Cu(+) species were responsible for the hydrogen transfer and the adsorption of styrene in the transfer dehydrogenation and hydrogenation reactions, respectively. This study provides a new method for designing cost-effective supported copper-based catalysts highly efficient for the transfer dehydrogenation of primary aliphatic alcohols by modifying the surface basicity of metal oxide supports. PMID:26659760

  15. Demonstration of omnivorous non-thermal mixed waste treatment: Direct chemical oxidation using peroxydisulfate. Progress report SF2-3-MW-35, October--December 1995

    SciTech Connect

    Cooper, J.F.; Wang, F.; Krueger, R.; King, K.; Shell, T.; Farmer, J.C.; Adamson, M.

    1996-01-27

    Direct Chemical Oxidation is an emerging ``omnivorous`` waste destruction technique which uses one of the strongest known oxidants (ammonium peroxydisulfate) to convert organic solids or liquids to carbon dioxide and their mineral constituents. The process operates at ambient pressure and at moderate temperatures (80--100 C) where organic destruction is rapid without catalysts. The byproduct (ammonium sulfate) is benign and may be recycled using commercial electrolysis equipment. The authors have constructed and initially tested a bench-scale facility (batch prereactor and plug-flow reactor) which allows treatability tests on any solid or liquid organic waste surrogate, with off-gas analysis by mass spectroscopy. Shake-down tests of the plug flow reactor on model chemical ethylene glycol confirmed earlier predictive models. Pre-reactor tests on water-immiscible substances confirmed destruction of cotton rags (cellulose), kerosene, tributyl phosphate and triethylamine. The process is intended to provide an all-aqueous, ambient pressure destruction technique for difficult materials not suitable or fully accepted for conventional incineration. Such wastes include solid and liquid mixed wastes containing incinerator chars, halogenated and nitrogenated wastes, oils and greases, and chemical or biological warfare agents.

  16. Mixed Brownian alignment and Néel rotations in superparamagnetic iron oxide nanoparticle suspensions driven by an ac field

    PubMed Central

    Shah, Saqlain A.; Reeves, Daniel B.; Ferguson, R. Matthew; Weaver, John B.

    2015-01-01

    Superparamagnetic iron oxide nanoparticles with highly nonlinear magnetic behavior are attractive for biomedical applications like magnetic particle imaging and magnetic fluid hyperthermia. Such particles display interesting magnetic properties in alternating magnetic fields and here we document experiments that show differences between the magnetization dynamics of certain particles in frozen and melted states. This effect goes beyond the small temperature difference (ΔT ~ 20 °C) and we show the dynamics to be a mixture of Brownian alignment of the particles and Néel rotation of their moments occurring in liquid particle suspensions. These phenomena can be modeled in a stochastic differential equation approach by postulating log-normal distributions and partial Brownian alignment of an effective anisotropy axis. We emphasize that precise particle-specific characterization through experiments and nonlinear simulations is necessary to predict dynamics in solution and optimize their behavior for emerging biomedical applications including magnetic particle imaging. PMID:26504371

  17. Mixed-oxide formation during preparation of alumina-supported zirconia and titania: an EXAFS and DFT study

    NASA Astrophysics Data System (ADS)

    Leito, A. A.; Souza, K. R.; Eon Faro, J. G., Jr.; Rocha, A. B.; Capaz, R. B.

    2004-03-01

    Alumina-supported zirconia and titania catalysts were prepared and characterized. EXAFS measurements for zirconia/alumina indicate that the supported phase consists of Zr^+4 species that do not have Zr as a second neighbors, hexacoordinated to oxide anions, suggesting that these ions occupy octahedral positions in the defective spinel structure of the γ-alumina support. This conclusion is confirmed by DFT calculations of model unit cells of ZrAl_4O8 that indicate that the octahedral Zr are energetically favorable. Moreover, excellent agreement between experimental and simulated EXAFS spectra are obtained. Similar calculations for TiAl_4O8 indicate that Ti in octahedral and tetrahedral sites have similar energetics, but the electronic band gap is very sensitive to the Ti position.

  18. The effect of sterilisation on a poly(dimethylsiloxane)/poly(hexamethylene oxide) mixed macrodiol-based polyurethane elastomer.

    PubMed

    Simmons, Anne; Hyvarinen, Jari; Poole-Warren, Laura

    2006-09-01

    The effect of various forms of sterilisation on a novel thermoplastic polyurethane elastomer synthesised using poly(hexamethylene oxide) (PHMO) and poly(dimethylsiloxane) (PDMS) macrodiols has been studied. The five sterilisation methods investigated were ethylene oxide (EtO) (single and multiple cycles), gas plasma, steam, vapour phase liquid chemical and gamma-irradiation (single and multiple cycles). Following sterilisation, scanning electron microscopy (SEM) and attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR) were used to assess changes in the surface chemical structure and morphology, and gel permeation chromatography (GPC) and tensile testing were used to examine changes in bulk characteristics. Biostability was assessed using subcutaneous implantation of strained samples in sheep for 6 weeks. The results showed that the properties of the commercially available control material, Pellethane 2363-80A, were significantly affected by exposure to gamma-irradiation, steam and multiple cycles of EtO with aging and implantation compounding the effect. Exposure to a gas plasma sterilisation process resulted in significant degradation in both polyurethanes. A vapour phase liquid chemical sterilisation process caused minimal adverse effects. Sterilisation of the PDMS-based polyurethane using EtO, gamma-irradiation and autoclaving resulted in no significant changes in properties. The material's biostability was also unaffected by exposure to each of these sterilisation processes followed by short-term implantation suggesting that this material is a potential candidate for use in a wide range of implantable medical devices sterilised using commercially available processes. Further biostability studies should be performed to assess the longer-term in vivo biostability of the PDMS-based material sterilised using autoclaving and gamma-irradiation. PMID:16690122

  19. Mixed-function oxidase enzyme activity and oxidative stress in lake trout (Salvelinus namaycush) exposed to 3,3{prime},4,4{prime}5-pentachlorobiphenyl (PCB-126)

    SciTech Connect

    Palace, V.P.; Klaverkamp, J.F.; Lockhart, W.L. |; Metner, D.A.; Muir, D.C.G.; Brown, S.B.

    1996-06-01

    Juvenile lake trout were intraperitoneally injected with corn oil containing nominal concentrations of 0, 0.6, 6.3, or 25 {micro}g [{sup 14}C]-3,3{prime},4,4{prime},5-pentachlorobiphenyl (PCB-126) per gram of body weight. The PCB-126 accumulated in liver in a dose-dependent manner to a sustained concentration by 6 weeks and remained elevated for the 30-week experimental period. Mixed-function oxidase (MFO) enzyme activity was elevated in the two highest dose groups relative to the control group, but not in the low-dose group throughout the 30 weeks. Oxidative stress, measured by the thiobarbituric acid reactive substances test, was correlated with ethoxyresorufin O-deethylase and was elevated in liver of the two highest PCB dose groups but not the low-dose group. The activities of the enzymatic antioxidants superoxide dismutase, catalase, and glutathione peroxidase were unaffected by PCB-126 exposure. The nonenzymatic antioxidants superoxide dismutase, catalase, and glutathione peroxidase were unaffected by PCB-126 exposure. The nonenzymatic antioxidant tocopherol was depleted to approximately 75% of the control concentration in liver of all three PCB-dosed groups. Hepatic ascorbic acid levels were not different in any of the treatment groups. Retinol was depleted by greater than an order of magnitude in liver of the two highest dose groups but not in the los-dose group. This study demonstrates a correlation between hepatic MFO activity and oxidative stress in PCB-exposed lake trout. Tocopherol and retinol may be important mediators of oxidative stress but additional study is required to confirm the antioxidant activity of retinol.

  20. Enhanced ionic oxygen flow through mixed ionic-electronic conducting membranes: Directional dependence, composite construction and the partial oxidation of methane

    NASA Astrophysics Data System (ADS)

    Gerdes, Kirk R.

    Mixed Ionic-Electronic Conducting (MIEC) membranes transport ions and electrons in a crystalline matrix. Ionic transport occurs through MIEC materials in the presence of an applied ionic potential gradient. MIEC membranes form a special class of ionic conductors with primary applications as membrane separators, sensors, and components in solid oxide fuel cells. Current efforts focus on separation of oxygen from air for supply to high temperature reactions. One such reaction is the methane partial oxidation to synthesis gas (CO and H2). Certain MIEC membrane characteristics are required for a methane partial oxidation reactor: (1) the cost of the material must be economical on a tube cost per mol oxygen transported basis; (2) the membrane must be stable in steep oxygen partial pressure gradients and in the presence of reducing gases; (3) the membrane must be stable at temperatures exceeding 800°C without fracturing due to thermal stress. Two mechanisms govern the transport of oxygen through MIEC membranes: surface exchange at the MIEC/gas surface and ionic transport through the MIEC bulk. Most MIEC membranes conduct oxygen with a mixed transport mechanism, i.e., both surface exchange and bulk diffusion affect the total transport. We investigate the relative importance of bulk diffusion versus surface exchange in MIEC tubular and disk membranes made of La0.5Sr0.5Fe 0.8Ga0.2O3-delta. We propose a proof based on the currently accepted transport model for the directional dependence of ionic flow through a tubular MIEC. We qualitatively confirm directional dependence using a novel experimental system. Further, we propose a model for ionic flow in a composite membrane system consisting of a dense, tubular LSFG substrate with a thin, dense layer of SrCox Fe1-xO3-delta applied to the surface(s). Comparisons are made between the performance of the monolithic membrane tube and the layered composite membrane tube. A layered composite tubular membrane is constructed and tested

  1. Long-term in vivo biostability of poly(dimethylsiloxane)/poly(hexamethylene oxide) mixed macrodiol-based polyurethane elastomers.

    PubMed

    Simmons, Anne; Hyvarinen, Jari; Odell, Ross A; Martin, Darren J; Gunatillake, Pathiraja A; Noble, Kathryn R; Poole-Warren, Laura A

    2004-09-01

    The long-term biostability of a novel thermoplastic polyurethane elastomer (Elast-Eon 2 80A) synthesized using poly(hexamethylene oxide) (PHMO) and poly(dimethylsiloxane) (PDMS) macrodiols has been studied using an in vivo ovine model. The material's biostability was compared with that of three commercially available control materials, Pellethane 2363-80A, Pellethane 2363-55D and Bionate 55D, after subcutaneous implantation of strained compression moulded flat sheet dumbbells in sheep for periods ranging from 3 to 24 months. Scanning electron microscopy, attenuated total reflectance-Fourier transform infrared spectroscopy, and X-ray photoelectron spectroscopy were used to assess changes in the surface chemical structure and morphology of the materials. Gel permeation chromatography, differential scanning calorimetry and tensile testing were used to examine changes in bulk characteristics of the materials. The results showed that the biostability of the soft flexible PDMS-based test polyurethane was significantly better than the control material of similar softness, Pellethane 80A, and as good as or better than both of the harder commercially available negative control polyurethanes, Pellethane 55D and Bionate 55D. Changes observed in the surface of the Pellethane materials were consistent with oxidation of the aliphatic polyether soft segment and hydrolysis of the urethane bonds joining hard to soft segment with degradation in Pellethane 80A significantly more severe than that observed in Pellethane 55D. Very minor changes were seen on the surfaces of the Elast-Eon 2 80A and Bionate 55D materials. There was a general trend of molecular weight decreasing with time across all polymers and the molecular weights of all materials decreased at a similar relative rate. The polydispersity ratio, Mw/Mn, increased with time for all materials. Tensile tests indicated that UTS increased in Elast-Eon 2 80A and Bionate 55D following implantation under strained conditions

  2. Mixed-function oxygenases, oxidative stress, and chromosomal damage measured in lesser scaup wintering on the Indiana Harbor Canal

    USGS Publications Warehouse

    Custer, T.W.; Custer, Christine M.; Hines, R.K.; Sparks, D.W.; Melancon, M.J.; Hoffman, D.J.; Bickham, J.W.; Wickliffe, J.K.

    2000-01-01

    During the winter of 1993-1994, male lesser scaup (Aythya affinis) were collected on the heavily polluted Indiana Harbor Canal, East Chicago, Indiana, and examined for several bioindicators of chemical exposure. Livers were analyzed for activities of three cytochrome P450-associated monooxygenases and four measures of oxidative stress. Blood and spleen were analyzed by flow cytometry for chromosomal damage. In a concurrent study, scaup tissues were analyzed for organic and inorganic contaminants. Ethoxyresorufin-O-dealkylase (EROD) activity in livers of scaup collected in January 1994 was significantly higher than in livers of scaup collected in March 1994 or in livers of reference birds. Three hepatic monooxygenase activities were each significantly correlated with polycyclic aromatic hydrocarbon (PAH) concentrations in scaup carcasses. Thiobarbituric acid (TBA) activity in scaup livers was positively correlated with iron, boron, and lead concentrations in livers and polychlorinated biphenyl concentrations in carcasses. TBA activity was negatively correlated with protein-bound thiol activity and mercury concentrations in livers. The coefficient of variation of DNA content in scaup blood cells was correlated with PAH concentrations in scaup carcasses. This is the first field study with birds to demonstrate a correlation between liver monooxygenase activity and carcass PAH concentrations and to show a direct correlation between PAH concentrations in tissues and somatic chromosomal damage in blood.

  3. Mixed-function oxygenases, oxidative stress, and chromosomal damage measured in lesser scaup wintering on the Indiana Harbor Canal

    USGS Publications Warehouse

    Custer, T.W.; Custer, Christine M.; Hines, R.K.; Sparks, D.W.; Melancon, M.J.; Hoffman, D.J.; Bickham, J.W.; Wickliffe, J.K.

    2000-01-01

    During the winter of 1993-1994, male lesser scaup (Aythya alfinis) were collected on the heavily polluted Indiana Harbor Canal, East Chicago, Indiana, and examined for several bioindicators of chemical exposure. Livers were analyzed for activities of three cytochrome P450-associated monooxygenases and four measures of oxidative stress. Blood and spleen were analyzed by flow cytometry for chromosomal damage. In a concurrent study, scaup tissues were analyzed for organic and inorganic contaminants. Ethoxyresomfm-O-dealkylase (EROD) activity in livers of scaup collected in January 1994 was significantly higher than in livers of scaup collected in March 1994 or in livers of reference birds. Three hepatic monooxygenase activities were each significantly correlated with polycyclic aromatic hydrocarbon (PAH) concentrations in scaup carcasses. Thiobarbituric acid (TBA) activity in scaup livers was positively correlated with iron, boron, and lead concentrations in livers and polychlorinated biphenyl concentrations in carcasses. TBA activity was negatively correlated with protein-bound thiol activity and mercury concentrations in livers. The coefficient of variation of DNA content in scaup blood cells was correlated with PAH concentrations in scaup carcasses. This is the first field study with birds to demonstrate a correlation between liver monooxygenase activity and carcass PAH concentrations and to show a direct correlation between PAH concentrations in tissues and somatic chromosomal damage in blood.

  4. Mixed-function oxygenases, oxidative stress, and chromosomal damage measured in lesser scaup wintering on the Indiana Harbor Canal.

    PubMed

    Custer, T W; Custer, C M; Hines, R K; Sparks, D W; Melancon, M J; Hoffman, D J; Bickham, J W; Wickliffe, J K

    2000-05-01

    During the winter of 1993-1994, male lesser scaup (Aythya affinis) were collected on the heavily polluted Indiana Harbor Canal, East Chicago, Indiana, and examined for several bioindicators of chemical exposure. Livers were analyzed for activities of three cytochrome P450-associated monooxygenases and four measures of oxidative stress. Blood and spleen were analyzed by flow cytometry for chromosomal damage. In a concurrent study, scaup tissues were analyzed for organic and inorganic contaminants. Ethoxyresorufin-O-dealkylase (EROD) activity in livers of scaup collected in January 1994 was significantly higher than in livers of scaup collected in March 1994 or in livers of reference birds. Three hepatic monooxygenase activities were each significantly correlated with polycyclic aromatic hydrocarbon (PAH) concentrations in scaup carcasses. Thiobarbituric acid (TBA) activity in scaup livers was positively correlated with iron, boron, and lead concentrations in livers and polychlorinated biphenyl concentrations in carcasses. TBA activity was negatively correlated with protein-bound thiol activity and mercury concentrations in livers. The coefficient of variation of DNA content in scaup blood cells was correlated with PAH concentrations in scaup carcasses. This is the first field study with birds to demonstrate a correlation between liver monooxygenase activity and carcass PAH concentrations and to show a direct correlation between PAH concentrations in tissues and somatic chromosomal damage in blood. PMID:10787104

  5. Reverse micelles directed synthesis of TiO{sub 2}-CeO{sub 2} mixed oxides and investigation of their crystal structure and morphology

    SciTech Connect

    Matejova, Lenka; Vales, Vaclav; Fajgar, Radek; Matej, Zdenek; Holy, Vaclav; Solcova, Olga

    2013-02-15

    The synthesis of TiO{sub 2}-CeO{sub 2} mixed oxides based on the sol-gel process controlled within reverse micelles of non-ionic surfactant Triton X-114 in cyclohexane is reported. The crystallization, phase composition, trends in nanoparticles growth and porous structure properties are studied as a function of Ti:Ce molar composition and annealing temperature by in-situ X-ray diffraction, Raman spectroscopy and physisorption. The brannerite-type CeTi{sub 2}O{sub 6} crystallizes as a single crystalline phase at Ti:Ce molar composition of 70:30 and in the mixture with cubic CeO{sub 2} and anatase TiO{sub 2} for composition 50:50. At Ti:Ce molar ratios 90:10 and 30:70 the mixtures of TiO{sub 2} anatase, rutile and cubic CeO{sub 2} appear. In these mixtures TiO{sub 2} rutile is formed at higher temperatures than conventionally. Additionally, the amount of a present amorphous phase in individual mixtures was estimated from diffraction data. The porous structure morphology depends both on molar composition and annealing temperature. This is correlated with the presence of carbon impurities of different character. - Graphical abstract: The phase composition of Ti90--Ce10 and Ti50--Ce50 oxide mixtures as a function of annealing temperature. The amount of the amorphous phase was estimated and attributed to TiO{sub 2}. Highlights: Black-Right-Pointing-Pointer Ti/Ce oxides were prepared using reverse micelles of Triton X-114. Black-Right-Pointing-Pointer Crystallization of TiO{sub 2}, CeO{sub 2} or CeTi{sub 2}O{sub 6} depends on Ti:Ce molar ratio. Black-Right-Pointing-Pointer Amorphous phase attributed to TiO{sub 2} was identified. Black-Right-Pointing-Pointer Metal oxides surface area is influenced by the character of present carbon impurities.

  6. Local structure and charge distribution in mixed uranium-americium oxides: effects of oxygen potential and Am content.

    PubMed

    Prieur, Damien; Martin, Philippe M; Jankowiak, Aurélien; Gavilan, Elisabeth; Scheinost, Andreas C; Herlet, Nathalie; Dehaudt, Philippe; Blanchart, Philippe

    2011-12-19

    Partitioning and transmutation (P&T) of minor actinides (MA) is currently studied to reduce the nuclear waste inventory. In this context, the fabrication of MA bearing materials is of great interest to achieve an effective recycling of these highly radioactive elements. To ensure the in-pile behavior, nuclear oxide fuels have to respect several criteria including preservation of the fluorite structure and defined oxygen to metal ratio (O/M). In the case of Am bearing materials, such as U(1-y)Am(y)O(2±x) (y = 0.10, 0.15, 0.20), the O/M determination is quite challenging using conventional methods (TGA, XRD) because of the particular thermodynamic properties of Am. Despite the lack of experimental data in the U-Am-O system, thermodynamical models are currently developed to effectively assess the O/M ratio. In this work, the O/M ratios were calculated for various oxygen potentials using the cation molar fraction determined by XAS measurements. These results are an important addition to the experimental data available for the U-Am-O system. Moreover, XRD and XAS indicated that the fabrication of fluorite U(1-y)Am(y)O(2±x) solid solution was achieved for all Am content and oxygen potentials investigated. On the basis of the molar fraction, a description of the solid solution was proposed depending on the considered sintering conditions. Finally, the occurrence of an unexpected charge compensation mechanism was pointed out. PMID:22087707

  7. Performance of Thorium-Based Mixed Oxide Fuels for the Consumption of Plutonium and Minor Actinides in Current and Advanced Reactors

    SciTech Connect

    Weaver, Kevan Dean; Herring, James Stephen

    2002-06-01

    A renewed interest in thorium-based fuels has arisen lately based on the need for proliferation resistance, longer fuel cycles, higher burnup and improved wasteform characteristics. Recent studies have been directed toward homogeneously mixed, heterogeneously mixed, and seed-and-blanket thorium-uranium fuel cycles that rely on "in situ" use of the bred-in U-233. However, due to the higher initial enrichment required to achieve acceptable burnups, these fuels are encountering economic constraints. Thorium can nevertheless play a large role in the nuclear fuel cycle; particularly in the reduction of plutonium. While uranium-based mixedoxide (MOX) fuel will decrease the amount of plutonium, the reduction is limited due to the breeding of more plutonium (and higher actinides) from the U-238. Here we present calculational results and a comparison of the potential burnup of a thorium-based and uranium-based mixed oxide fuel in a light water reactor (LWR). Although the uranium-based fuels outperformed the thorium-based fuels in achievable burnup, a depletion comparison of the initially charged plutonium (both reactor and weapons grade) showed that the thorium-based fuels outperformed the uranium-based fuels by more that a factor of 2; where more than 70% of the total plutonium in the thorium-based fuel is consumed during the cycle. This is significant considering that the achievable burnup of the thorium-based fuels were 1.4 to 4.6 times less than the uranium-based fuels. Furthermore, use of a thorium-based fuel could also be used as a strategy for reducing the amount of long-lived nuclides (including the minor actinides), and thus the radiotoxicity in spent nuclear fuel. Although the breeding of U-233 is a concern, the presence of U-232 and its daughter products can aid in making this fuel self-protecting, and/or enough U-238 can be added to denature the fissile uranium. From these calculations, it appears that thorium-based fuel for plutonium incineration is superior as

  8. FABRICATION AND CHARACTERIZATION OF BOROSILICATE GLASSES CONTAINING ALPHA-RADIONUCLIDES AND SILVER FROM CONVERSION AND MIXED-OXIDE FACILITIES PROPOSED FOR RUSSIA

    SciTech Connect

    Aloy, A; Trofimenko, V; Uspensky, A; Jardine, L

    2005-10-25

    Liquid and solid radioactive wastes are formed during conversion of plutonium metal to oxide and during fabrication of weapons-grade plutonium into mixed-oxide (MOX) fuel. In Russia, these wastes are to be processed for disposition by immobilization in either borosilicate glass or cement matrices depending upon the waste stream-specific radionuclide contents. Vitrification is planned for the liquid high-level waste raffinate stream containing the bulk of the Am-241 produced from Pu-241 decay. Previous work on the Russian MOX Fuel Fabrication Facility (R-MFFF) by the Public Joint Stock Corporation (TVEL) [1] showed that this waste stream may contain significant amounts of silver derived from the electrochemical dissolution of PuO2 using a Ag(II) catalyst. The work reported here further investigated silver solubility limits, which, if exceeded in a production glass melter, allow discrete silver grains to form in the glass and also deposit over time on the bottom of a joule-heated ceramic melter. In melters with immersed electrodes, such as the Russian EP-100 for phosphate glasses or the US Duratek DP-100 type melters for borosilicate glasses that are being considered for use at the Siberian Chemical Combine (SCC) Tomsk site, the undissolved silver could cause a short circuit and an unacceptable production melter failure. The silver solubility limit of 3.85 wt% Ag{sub 2}O in liquid, alpha-bearing wastes determined in this work will guide the production scale use of borosilicate glass compositions, and effectively increase the capacity of the ceramic melters and reduce the total volume of solidified vitrified wastes at SCC Tomsk that require storage prior to geologic disposal.

  9. Mixed Valent Gold Oxides: Syntheses, Structures, and Properties of Rb 5Au 3O 2, Rb 7Au 5O 2, and Cs 7Au 5O 2

    NASA Astrophysics Data System (ADS)

    Mudring, Anja-Verena; Nuss, Jürgen; Wedig, Ulrich; Jansen, Martin

    2000-11-01

    The title compounds Rb5Au3O2, Rb7Au5O2, and Cs7Au5O2 are the first examples of mixed valent phases containing gold in the oxidation states +1 and -1. Their crystal structures (Rb5Au3O2, Pbam, a=736.4(1) pm, b=1430.8(2) pm, c=567.9(1) pm, Z=2, R(F)=0.053, 647 reflections; Rb7Au5O2, Immm, a=567.1(2) pm, b=930.1(1) pm, C=1659.4(3) pm, Z=2, R(F)=0.066, 409 reflections; Cs7Au5O2, Immm, a=599.4(1) pm, b=960.6(3) pm, c=1720.8(12) pm, Z=2, R(F)=0.039, 386 reflections) are characterized by the combination of distinctive structural features of gold(I) oxides and aurides: for Au(+1) a typical linear coordination by oxygen is found and the surroundings of Au(-1) bear a close resemblance to the binary 1:1 aurides. In consequence the overall structures of Rb5Au3O2 and M7Au5O2 can be described as intergrowths of M3AuO2 and MAu (M=Rb, Cs), constituting members of a homologous series [MAu]n[M3AuO2] with n=2 and 4, respectively. The crystal chemical evidence for the valence states assumed, also confirmed by Mößbauer spectroscopy, is supported by various band structure calculations (Hartee-Fock and density functional) clearly indicating the coexistence of two different oxidation states. The compounds have been synthesized by reacting binary aurides MAu and alkali monoxides M2O (M=Rb, Cs) with elemental gold in the required stochiometric amounts. Hereby, a further astonishing parallel to the chemistry of halogens is revealed. Like these, gold disproportionates upon interaction with bases.

  10. Neutronics Benchmarks for the Utilization of Mixed-Oxide Fuel: Joint U.S./Russian Progress Report for Fiscal Year 1997

    SciTech Connect

    Akkurt, H

    2001-01-11

    In 1967, a series of critical experiments were conducted at the Westinghouse Reactor Evaluation Center (WREC) using mixed-oxide (MOX) PuO{sub 2}-UO{sub 2} and/or UO{sub 2} fuels in various lattices and configurations . These experiments were performed under the joint sponsorship of the Empire State Atomic Development Associates (ESADA) plutonium program and Westinghouse . The purpose of these experiments was to develop experimental data to validate analytical methods used in the design of a plutonium-bearing replacement fuel for water reactors. Three different fuels were used during the experimental program: two MOX fuels and a low-enriched UO{sub 2} fuel. The MOX fuels were distinguished by their {sup 240}Pu content: 8 wt% {sup 240}Pu and 24 wt% {sup 240}Pu. Both MOX fuels contained 2.0 wt % PuO{sub 2} in natural UO{sub 2} . The UO{sub 2} fuel with 2.72 wt % enrichment was used for comparison with the plutonium data and for use in multiregion experiments.

  11. Criticality Safety Scoping Study for the Transport of Weapons-Grade Mixed-Oxide Fuel Using the MO-1 Shipping Package

    SciTech Connect

    Dunn, M.E.; Fox, P.B.

    1999-05-01

    This report provides the criticality safety information needed for obtaining certification of the shipment of mixed-oxide (MOX) fuel using the MO-1 [USA/9069/B()F] shipping package. Specifically, this report addresses the shipment of non-weapons-grade MOX fuel as certified under Certificate of Compliance 9069, Revision 10. The report further addresses the shipment of weapons-grade MOX fuel using a possible Westinghouse fuel design. Criticality safety analysis information is provided to demonstrate that the requirements of 10 CFR S 71.55 and 71.59 are satisfied for the MO-1 package. Using NUREG/CR-5661 as a guide, a transport index (TI) for criticality control is determined for the shipment of non-weapons-grade MOX fuel as specified in Certificate of Compliance 9069, Revision 10. A TI for criticality control is also determined for the shipment of weapons-grade MOX fuel. Since the possible weapons-grade fuel design is preliminary in nature, this report is considered to be a scoping evaluation and is not intended as a substitute for the final criticality safety analysis of the MO-1 shipping package. However, the criticality safety evaluation information that is presented in this report does demonstrate the feasibility of obtaining certification for the transport of weapons-grade MOX lead test fuel using the MO-1 shipping package.

  12. Reduction of interpore distance of anodized aluminum oxide nano pattern by mixed H3PO4:H2SO4 electrolyte.

    PubMed

    Song, Kwang Min; Park, Joonmo; Ryu, Sang-Wan

    2007-11-01

    A self-formed and ordered anodized aluminum oxide (AAO) nano pattern has generated considerable interest in both scientific research and commercial application. However, the interpore distance obtainable by AAO is limited by 40-500 nm depending on electrolyte and anodizing voltage. It's believed that below-30 nm AAO pattern is a key technology in the fabrication semiconductor nano structures with enhanced quantum confinement effect, so we worked on the reduction of interpore distance of AAO with a novel electrolyte. AAO nano patterns were fabricated with mixed H2SO4 and H3PO4 as an electrolyte for various voltages and temperatures. The interpore distance and pore diameter of AAO were decreased with reduced anodizing voltage. As a result, an AAO nano pattern with the interpore distance of 27 nm and the pore diameter of 7 nm was obtained. This is the smallest pattern, as long as we know, reported till now with AAO technique. The fabricated AAO pattern could be utilized for uniform and high density quantum dots with increased quantum effect. PMID:18047152

  13. Mixed-valence metal oxide nanoparticles as electrochemical half-cells: substituting the Ag/AgCl of reference electrodes by CeO(2-x) nanoparticles.

    PubMed

    Nagarale, Rajaram K; Hoss, Udo; Heller, Adam

    2012-12-26

    Cations of mixed valence at surfaces of metal oxide nanoparticles constitute electrochemical half-cells, with potentials intermediate between those of the dissolved cations and those in the solid. When only cations at surfaces of the particles are electrochemically active, the ratio of electrochemically active/all cations is ~0.1 for 15 nm diameter CeO(2-x) particles. CeO(2-x) nanoparticle-loaded hydrogel films on printed carbon and on sputtered gold constitute reference electrodes having a redox potential similar to that of Ag/AgCl in physiological (0.14 M) saline solutions. In vitro the characteristics of potentially subcutaneously implantable glucose monitoring sensors made with CeO(2-x) nanoparticle reference electrodes are undistinguishable from those of sensors made with Ag/AgCl reference electrodes. Cerium is 900 times more abundant than silver, and commercially produced CeO(2-x) nanoparticle solutions are available at prices well below those of the Ag/AgCl pastes used in the annual manufacture of ~10(9) reference electrodes of glucose monitoring strips for diabetes management. PMID:23171288

  14. An investigation of composite electrolytes by mixing polyethylene oxide- and polytetramethylene glycol-based waterborne polyurethane with the addition of LiClO{sub 4}/propylene carbonate

    SciTech Connect

    Wen, T.C.; Chang, J.S.; Cheng, T.T.

    1998-10-01

    Various composite electrolytes (CE) were prepared by mixing polytetramethylene glycol-based waterborne polyurethane [WPU(PTMG)], polyethylene oxide (PEO), and LiClO{sub 4}/propylene carbonate (PC). The conductivity of these CEs was investigated using ac impedance. Differential scanning calorimetry (DSC) and polarizing microscopy (PM) were employed for material characterization. The temperature dependence of the conductivity follows the Arrhenius law for samples with a LiClO{sub 4}/PC content larger than 30%, while for samples with LiClO{sub 4}/PC content approximating 8%, it shows linear segments separated by a transition zone between 25 and 65 C. According to the ac and DSC results, the conductivity is increased, and the melting temperature is decreased by increasing the LiClO{sub 4}/PC content. PM results indicate that the increase in PEO ratio increases the crystallinity of the PEO-WPU(PTMG) films. When LiClO{sub 4}/PC is added, the increase in PEO ratio results in an increase in conductivity. The CE comprising 33% PEO, 17% WPU(PTMG), and 50% LiClO{sub 4}/PC exhibits conductivities as high as Ca. {approximately}10{sup {minus}2} S/cm at 85 C and 5 {times} 10{sup {minus}3} S/cm at 15 C.

  15. GEP-based method to formulate adhesion strength and hardness of Nb PVD coated on Ti-6Al-7Nb aimed at developing mixed oxide nanotubular arrays.

    PubMed

    Rafieerad, A R; Bushroa, A R; Nasiri-Tabrizi, B; Fallahpour, A; Vadivelu, J; Musa, S N; Kaboli, S H A

    2016-08-01

    PVD process as a thin film coating method is highly applicable for both metallic and ceramic materials, which is faced with the necessity of choosing the correct parameters to achieve optimal results. In the present study, a GEP-based model for the first time was proposed as a safe and accurate method to predict the adhesion strength and hardness of the Nb PVD coated aimed at growing the mixed oxide nanotubular arrays on Ti67. Here, the training and testing analysis were executed for both adhesion strength and hardness. The optimum parameter combination for the scratch adhesion strength and micro hardness was determined by the maximum mean S/N ratio, which was 350W, 20 sccm, and a DC bias of 90V. Results showed that the values calculated in the training and testing in GEP model were very close to the actual experiments designed by Taguchi. The as-sputtered Nb coating with highest adhesion strength and microhardness was electrochemically anodized at 20V for 4h. From the FESEM images and EDS results of the annealed sample, a thick layer of bone-like apatite was formed on the sample surface after soaking in SBF for 10 days, which can be connected to the development of a highly ordered nanotube arrays. This novel approach provides an outline for the future design of nanostructured coatings for a wide range of applications. PMID:26874249

  16. Development of quality control data base ``DANTE'' and relational analysis between fission gas release behavior and plutonium homogeneity in mixed oxide fuel by DANTE

    NASA Astrophysics Data System (ADS)

    Takahashi, K.; Kamimura, K.; Yamaguchi, T.; Masuda, S.

    1988-04-01

    The PNC Plutonium Fabrication Facility (PPFF) of Tokai Works of the "Power Reactor and Nuclear Fuel Development Corporation" (PNC) has produced several types of mixed oxide fuels which have been used as the fuels for the Advanced Thermal Reactor FUGEN, and the Experimental Fast Reactor JOYO. Accumulated production of MOX fuel is about 58000 pins as of December, 1986. PPFF production technique is so reliable that no failure of driver fuel pins has been found in the FUGEN and JOYO. This is based on the adequate process control and quality control. In this paper the outline of quality control method applied to MOX fuels in our facility will be reviewed. The discussion is done mainly on the viewpoint of the software system including data gathering, data analysis and data storage, etc. The code system, Data Analysing Technology for Engineers, DANTE, has been developed for this purpose. The DANTE code system is consisted of real time system having relational data base. It is possible to refer the data base relationally and to make tables and figures of the analyzed results on real time by using the DANTE code system. The DANTE code system contributes to quality assurance in the MOX Fuel production facility by evaluating overall data which come from each process such as production and inspection processes.

  17. TRU decontamination of high-level Purex waste by solvent extraction using a mixed octyl(phenyl)-N,N-diisobutyl-carbamoylmethylphosphine oxide/TBP/NPH (TRUEX) solvent

    SciTech Connect

    Horwitz, E.P.; Kalina, D.G.; Diamond, H.; Kaplan, L.; Vandegrift, G.F.; Leonard, R.A.; Steindler, M.J.; Schulz, W.W.

    1984-01-01

    The TRUEX (transuranium extraction) process was tested on a simulated high-level dissolved sludge waste (DSW). A batch counter-current extraction mode was used for seven extraction and three scrub stages. One additional extraction stage and two scrub stages and all strip stages were performed by batch extraction. The TRUEX solvent consisted of 0.20 M octyl(phenyl)-N,N-diisobutylcarbamoyl-methylphosphine oxide-1.4 M TBP in Conoco (C/sub 12/-C/sub 14/). The feed solution was 1.0 M in HNO/sub 3/, 0.3 M in H/sub 2/C/sub 2/O/sub 4/ and contained mixed (stable) fission products, U, Np, Pu, and Am, and a number of inert constituents, e.g., Fe and Al. The test showed that the process is capable of reducing the TRU concentration in the DSW by a factor of 4 x 10/sup 4/ (to <100 nCi/g of disposed form) and reducing the quantity of TRU waste by two orders of magnitude.

  18. Neutronics Benchmarks for the Utilization of Mixed-Oxide Fuel: Joint U.S./Russian Progress Report for Fiscal Year 1997 Volume 2-Calculations Performed in the United States

    SciTech Connect

    Primm III, RT

    2002-05-29

    This volume of the progress report provides documentation of reactor physics and criticality safety studies conducted in the US during fiscal year 1997 and sponsored by the Fissile Materials Disposition Program of the US Department of Energy. Descriptions of computational and experimental benchmarks for the verification and validation of computer programs for neutron physics analyses are included. All benchmarks include either plutonium, uranium, or mixed uranium and plutonium fuels. Calculated physics parameters are reported for all of the computational benchmarks and for those experimental benchmarks that the US and Russia mutually agreed in November 1996 were applicable to mixed-oxide fuel cycles for light-water reactors.

  19. Surface chemistry of RuO(2)/IrO(2)/TiO(2) mixed-oxide electrodes: secondary ion mass spectrometric study of the changes induced by electrochemical treatment.

    PubMed

    Barison, S; De Battisti, A; Fabrizio, M; Daolio, S; Piccirillo, C

    2000-01-01

    The IrO(2)/RuO(2)/TiO(2) ternary system is well known for its electrocatalytic activity towards oxygen- and chlorine-evolution reactions. Electrochemical processing induces noticeable chemical and morphological modifications on these electrodes, depending on the noble metal oxide content. In this work, cathodic/anodic polarization and the oxygen-evolution reaction were studied in order to evaluate the electrocatalytic activity at various noble metal oxide percentages. The best performing electrode (30 mol% noble metal oxides) was analyzed before and after electrochemical tests by means of secondary ion mass spectrometry (SIMS) in order to determine the chemical composition modification which occurred on the surface and in deeper regions of the mixed-oxide film. PMID:11114026

  20. Fischer-Tropsch Synthesis: Assessment of the Ripening of Cobalt Clusters and Mixing Between Co and Ru Promoter via Oxidation-Reduction-Cycles over Lower Co-Loaded Ru-Co/A12O3 Catalysts

    SciTech Connect

    Jacobs,G.; Sarkar, A.; Ji, Y.; Luo, M.; Dozier, A.; Davis, B.

    2008-01-01

    A 2% Ru-promoted 15% Co/Al2O3 catalyst was tested after reduction and after being subjected to oxidation-reduction cycles. The catalysts were characterized over four oxidation-reduction cycles by XANES/EXAFS, TPR, HRTEM, and EDS elemental mapping. The oxidation-reduction treatments were found to assist in sintering the metallic clusters to a larger size, and to promote mixing on at least the order of the nanoscale. The larger crystallites in closer proximity to the Ru promoter led to a more facile reduction of the cobalt crystallites. In addition, a catalyst exposed to two oxidation-reduction cycles resulted in slightly higher conversion, higher a-value product, slightly lower methane selectivity, and greater stability over a reduced freshly calcined catalyst.

  1. Fully Coupled Modeling of Burnup-Dependent (U1- y , Pu y )O2- x Mixed Oxide Fast Reactor Fuel Performance

    NASA Astrophysics Data System (ADS)

    Liu, Rong; Zhou, Wenzhong; Zhou, Wei

    2016-03-01

    During the fast reactor nuclear fuel fission reaction, fission gases accumulate and form pores with the increase of fuel burnup, which decreases the fuel thermal conductivity, leading to overheating of the fuel element. The diffusion of plutonium and oxygen with high temperature gradient is also one of the important fuel performance concerns as it will affect the fuel material properties, power distribution, and overall performance of the fuel pin. In order to investigate these important issues, the (U1- y Pu y )O2- x fuel pellet is studied by fully coupling thermal transport, deformation, oxygen diffusion, fission gas release and swelling, and plutonium redistribution to evaluate the effects on each other with burnup-dependent models, accounting for the evolution of fuel porosity. The approach was developed using self-defined multiphysics models based on the framework of COMSOL Multiphysics to manage the nonlinearities associated with fast reactor mixed oxide fuel performance analysis. The modeling results showed a consistent fuel performance comparable with the previous results. Burnup degrades the fuel thermal conductivity, resulting in a significant fuel temperature increase. The fission gas release increased rapidly first and then steadily with the burnup increase. The fuel porosity increased dramatically at the beginning of the burnup and then kept constant as the fission gas released to the fuel free volume, causing the fuel temperature to increase. Another important finding is that the deviation from stoichiometry of oxygen affects greatly not only the fuel properties, for example, thermal conductivity, but also the fuel performance, for example, temperature distribution, porosity evolution, grain size growth, fission gas release, deformation, and plutonium redistribution. Special attention needs to be paid to the deviation from stoichiometry of oxygen in fuel fabrication. Plutonium content will also affect the fuel material properties and performance

  2. An improved characterization method for international accountancy measurements of fresh and irradiated mixed oxide (MOX) fuel: helping achieve continual monitoring and safeguards through the fuel cycle

    SciTech Connect

    Evans, Louise G; Croft, Stephen; Swinhoe, Martyn T; Tobin, S. J.; Menlove, H. O.; Schear, M. A.; Worrall, Andrew

    2011-01-13

    Nuclear fuel accountancy measurements are conducted at several points through the nuclear fuel cycle to ensure continuity of knowledge (CofK) of special nuclear material (SNM). Non-destructive assay (NDA) measurements are performed on fresh fuel (prior to irradiation in a reactor) and spent nuclear fuel (SNF) post-irradiation. We have developed a fuel assembly characterization system, based on the novel concept of 'neutron fingerprinting' with multiplicity signatures to ensure detailed CofK of nuclear fuel through the entire fuel cycle. The neutron fingerprint in this case is determined by the measurement of the various correlated neutron signatures, specific to fuel isotopic composition, and therefore offers greater sensitivity to variations in fissile content among fuel assemblies than other techniques such as gross neutron counting. This neutron fingerprint could be measured at the point of fuel dispatch (e.g. from a fuel fabrication plant prior to irradiation, or from a reactor site post-irradiation), monitored during transportation of the fuel assembly, and measured at a subsequent receiving site (e.g. at the reactor site prior to irradiation, or reprocessing facility post-irradiation); this would confirm that no unexpected changes to the fuel composition or amount have taken place during transportation and/ or reactor operations. Changes may indicate an attempt to divert material for example. Here, we present the current state of the practice of fuel measurements for both fresh mixed oxide (MOX) fuel and SNF (both MOX and uranium dioxide). This is presented in the framework of international safeguards perspectives from the US and UK. We also postulate as to how the neutron fingerprinting concept could lead to improved fuel characterization (both fresh MOX and SNF) resulting in: (a) assured CofK of fuel across the nuclear fuel cycle, (b) improved detection of SNM diversion, and (c) greater confidence in safeguards of SNF transportation.

  3. An improved characterization method for international accountancy measurements of fresh and irradiated mixed oxide (MOX) fuel: helping achieve continual monitoring and safeguards through the fuel cycle

    SciTech Connect

    Evans, Louise G; Croft, Stephen; Swinhoe, Martyn T; Tobin, S. J.; Boyer, B. D.; Menlove, H. O.; Schear, M. A.; Worrall, Andrew

    2010-11-24

    Nuclear fuel accountancy measurements are conducted at several points through the nuclear fuel cycle to ensure continuity of knowledge (CofK) of special nuclear material (SNM). Non-destructive assay (NDA) measurements are performed on fresh fuel (prior to irradiation in a reactor) and spent nuclear fuel (SNF) post-irradiation. We have developed a fuel assembly characterization system, based on the novel concept of 'neutron fingerprinting' with multiplicity signatures to ensure detailed CofK of nuclear fuel through the entire fuel cycle. The neutron fingerprint in this case is determined by the measurement of the various correlated neutron signatures, specific to fuel isotopic composition, and therefore offers greater sensitivity to variations in fissile content among fuel assemblies than other techniques such as gross neutron counting. This neutron fingerprint could be measured at the point of fuel dispatch (e.g. from a fuel fabrication plant prior to irradiation, or from a reactor site post-irradiation), monitored during transportation of the fuel assembly, and measured at a subsequent receiving site (e.g. at the reactor site prior to irradiation, or reprocessing facility post-irradiation); this would confirm that no unexpected changes to the fuel composition or amount have taken place during transportation and/or reactor operations. Changes may indicate an attempt to divert material for example. Here, we present the current state of the practice of fuel measurements for both fresh mixed oxide (MOX) fuel and SNF (both MOX and uranium dioxide). This is presented in the framework of international safeguards perspectives from the US and UK. We also postulate as to how the neutron fingerprinting concept could lead to improved fuel characterization (both fresh MOX and SNF) resulting in: (a) assured CofK of fuel across the nuclear fuel cycle, (b) improved detection of SNM diversion, and (c) greater confidence in safeguards of SNF transportation.

  4. Mixing and compaction temperatures for Superpave mixes

    NASA Astrophysics Data System (ADS)

    Yildirim, Yetkin

    According to Superpave mixture design, gyratory specimens are mixed and compacted at equiviscous binder temperatures corresponding to viscosities of 0.17 and 0.28 Pa.s. respectively. These were the values previously used in the Marshal mix design method to determine optimal mixing and compaction temperatures. In order to estimate the appropriate mixing and compaction temperatures for Superpave mixture design, a temperature-viscosity relationship for the binder needs to be developed (ASTM D 2493, Calculation of Mixing and Compaction Temperatures). The current approach is simple and provides reasonable temperatures for unmodified binders. However, some modified binders have exhibited unreasonably high temperatures for mixing and compaction using this technique. These high temperatures can result in construction problems, damage of asphalt, and production of fumes. Heating asphalt binder to very high temperatures during construction oxidizes the binder and separates the polymer from asphalt binder. It is known that polymer modified asphalt binders have many benefits to the roads, such as; increasing rutting resistance, enhancing low temperature cracking resistance, improving traction, better adhesion and cohesion, elevating tensile strength which are directly related to the service life of the pavement. Therefore, oxidation and separation of the polymer from the asphalt binder results in reduction of the service life. ASTM D 2493 was established for unmodified asphalt binders which are Newtonian fluids at high temperatures. For these materials, viscosity does not depend on shear rate. However, most of the modified asphalt binders exhibit a phenomenon known as pseudoplasticity, where viscosity does depend on shear rate. Thus, at the high shear rates occurring during mixing and compaction, it is not necessary to go to very high temperatures. This research was undertaken to determine the shear rate during compaction such that the effect of this parameter could be

  5. Catalysis and the nature of mixed-metal oxides at the nanometer level: special properties of MO(x)/TiO(2)(110) {M= V, W, Ce} surfaces.

    PubMed

    Rodriguez, José A; Stacchiola, Dario

    2010-09-01

    To rationalize structure-reactivity relationships for mixed-metal oxide catalysts, well-defined systems are required. Studies involving the deposition of nanoparticles and clusters of VO(x), CeO(x) and WO(x) on TiO(2)(110) and other well-defined oxide surfaces have shown novel structures that have special chemical properties. Dimers of vanadia and ceria have been found on TiO(2)(110), monomers of vanadia on CeO(2)(111), and (WO(3))(3) clusters on TiO(2)(110). The V[double bond, length as m-dash]O or W[double bond, length as m-dash]O groups present in VO(x)/TiO(2)(110), VO(x)/CeO(2)(111) and WO(x)/TiO(2)(110) surfaces dislay a very high activity for the selective oxidation of alkanes and the dehydrogenation of alcohols. The non-typical coordination modes imposed by TiO(2)(110) on ceria nanoparticles make possible the direct participation of this oxide in catalytic reactions and enhance the dispersion of metals on the titania substrate. Au/CeO(x)/TiO(2)(110) surfaces display an extremely high catalytic activity for CO oxidation and the water-gas shift reaction. In general, the chemical behavior of the MO(x)/TiO(2)(110) {M = V, Ce or W} surfaces reflects their unique structure at the nanometer level. These simple models can provide a conceptual framework for modifying or controlling the chemical properties of mixed-metal oxides and for engineering industrial catalysts. PMID:20571690

  6. Reactive uptake of N2O5 to internally mixed inorganic and organic particles: the role of organic carbon oxidation state and inferred organic phase separations

    NASA Astrophysics Data System (ADS)

    Gaston, C. J.; Thornton, J. A.; Ng, N. L.

    2014-06-01

    We measured N2O5 reactive uptake onto mixed organic/inorganic submicron particles using organic compounds with a variety of oxidation states (using mainly atomic O : C ratios as a proxy) and molecular weights. The organic mass fraction, organic molecular composition, and relative humidity (RH) were varied to assess their effects separately on the N2O5 uptake coefficient, γ(N2O5). At a constant RH, mixtures of organic components having an O : C < 0.5 with ammonium bisulfate significantly suppressed the uptake of N2O5(g) compared to pure ammonium bisulfate, even at small organic mass fractions (e.g., ≤ 15%). The effect of the organic component became less pronounced at higher RH. In general, highly oxygenated organic components (O : C > 0.8) had a smaller or even negligible impact on N2O5(g) uptake at all RHs probed; however, a few exceptions were observed. Notably, γ(N2O5) for mixtures of ammonium bisulfate with polyethylene glycol (PEG), PEG-300 (O : C = 0.56), decreased nearly linearly as the PEG mass fraction increased at constant RH until leveling off at the value measured for pure PEG. The response of γ(N2O5) to increasing PEG mass fraction was similar to that measured on ambient atmospheric particles as a function of organic mass fraction. The effects of the organic mass fraction on γ(N2O5), for mixtures having an O : C < ~0.8, were best described using a standard resistor model of reactive uptake assuming the particles had an RH-dependent inorganic core-organic shell morphology. This model suggests that the N2O5 diffusivity and/or solubility in the organic layer is up to a factor of 20 lower compared to aqueous solution particles, and that the diffusivity, solubility, and reactivity of N2O5 within organic coatings and particles depend upon both RH and the molecular composition of the organic medium. We use these dependencies and ambient measurements of organic aerosol from the global aerosol mass spectrometry (AMS) database to show that the typical

  7. Use of Mixed CH3-/HC(O)CH2CH2-Si(111) Functionality to Control Interfacial Chemical and Electronic Properties During the Atomic-Layer Deposition of Ultrathin Oxides on Si(111).

    PubMed

    O'Leary, Leslie E; Strandwitz, Nicholas C; Roske, Christopher W; Pyo, Suyeon; Brunschwig, Bruce S; Lewis, Nathan S

    2015-02-19

    Silicon surfaces terminated with a mixed monolayer containing both a propyl aldehyde functionality and methyl groups were prepared and used to control the interfacial chemical and electronic properties of Si(111) surfaces during atomic-layer deposition (ALD) of Al2O3 or MnO. Si(111) surfaces functionalized only with the aldehyde moiety exhibited surface recombination velocities, S, of 2500 ± 600 cm s(-1) whereas the mixed CH3-/HC(O)CH2CH2-Si(111) surfaces displayed S = 25 ± 7 cm s(-1). During the ALD growth of either Al2O3 or MnO, both the HC(O)CH2CH2-Si(111) and CH3-/HC(O)CH2CH2-Si(111) surfaces produced increased metal oxide deposition at low cycle number, relative to H-Si(111) or CH3-Si(111) surfaces. As detected by X-ray photoelectron spectroscopy after the ALD process, the CH3- and mixed CH3-/HC(O)CH2CH2- functionalized Si(111) surfaces exhibited less interfacial SiOx than was observed for ALD of metal oxides on H-Si(111) substrates. PMID:26262493

  8. Synthesis of fatty acid methyl ester from the transesterification of high- and low-acid-content crude palm oil (Elaeis guineensis) and karanj oil (Pongamia pinnata) over a calcium-lanthanum-aluminum mixed-oxides catalyst.

    PubMed

    Syamsuddin, Y; Murat, M N; Hameed, B H

    2016-08-01

    The synthesis of fatty acid methyl ester (FAME) from the high- and low-acid-content feedstock of crude palm oil (CPO) and karanj oil (KO) was conducted over CaO-La2O3-Al2O3 mixed-oxide catalyst. Various reaction parameters were investigated using a batch reactor to identify the best reaction condition that results in the highest FAME yield for each type of oil. The transesterification of CPO resulted in a 97.81% FAME yield with the process conditions of 170°C reaction temperature, 15:1 DMC-to-CPO molar ratio, 180min reaction time, and 10wt.% catalyst loading. The transesterification of KO resulted in a 96.77% FAME yield with the conditions of 150°C reaction temperature, 9:1 DMC-to-KO molar ratio, 180min reaction time, and 5wt.% catalyst loading. The properties of both products met the ASTM D6751 and EN 14214 standard requirements. The above results showed that the CaO-La2O3-Al2O3 mixed-oxide catalyst was suitable for high- and low-acid-content vegetable oil. PMID:27136612

  9. Mixed Dementia

    MedlinePlus

    ... bodies , What Is Alzheimer's? NIA-Funded Memory & Aging Project Reveals Mixed Dementia Common Data from the first ... disease. For example, in the Memory and Aging Project study involving long-term cognitive assessments followed by ...

  10. ZnO/MoO 3 mixed oxide nanotube: A highly efficient and stable catalyst for degradation of dye by air under room conditions

    NASA Astrophysics Data System (ADS)

    Huang, Jiguo; Wang, Xiaohong; Li, Sen; Wang, Yu

    2010-10-01

    As a continuation of our work to develop catalysts with high activity for catalytic air wet oxidation process under mild conditions, degradation of wastewater containing 0.3 g/L Safranin-T (ST) by air oxidation over ZnO/MoO 3 nanotube catalyst was studied. It was found the decolorization efficiency and the chemical oxygen demand (COD) removal of ST reached above 98% and 95%, respectively, within 18 min at room temperature and atmospheric pressure. And the organic pollutants were totally mineralized to simple inorganic species such as HCO 3-, Cl - and NO 3-, while the total organic carbon (TOC) decreased 99.3%. The structure and morphology of the catalyst after ten cycling runs showed that the catalyst was stable under such operating condition and the leaching test showed negligible leaching effect. This ZnO/MoO 3 nanotube is proved to be an active and stable heterogeneous catalyst in CWAO of ST under extremely mild conditions.

  11. Pyrochemical processes for the recovery of weapons grade plutonium either as a metal or as PuO{sub 2} for use in mixed oxide reactor fuel pellets

    SciTech Connect

    Colmenares, C.A.; Ebbinghaus, B.B.; Bronson, M.C.

    1995-11-03

    The authors have developed two processes for the recovery of weapons grade Pu, as either Pu metal or PuO{sub 2}, that are strictly pyrochemical and do not produce any liquid waste. Large amounts of Pu metal (up to 4 kg.), in various geometric shapes, have been recovered by a hydride/dehydride/casting process (HYDEC) to produce metal ingots of any desired shape. The three processing steps are carried out in a single compact apparatus. The experimental technique and results obtained will be described. The authors have prepared PuO{sub 2} powders from weapons grade Pu by a process that hydrides the Pu metal followed by the oxidation of the hydride (HYDOX process). Experimental details of the best way to carry out this process will be presented, as well as the characterization of both hydride and oxide powders produced.

  12. Doped palladium containing oxidation catalysts

    DOEpatents

    Mohajeri, Nahid

    2014-02-18

    A supported oxidation catalyst includes a support having a metal oxide or metal salt, and mixed metal particles thereon. The mixed metal particles include first particles including a palladium compound, and second particles including a precious metal group (PMG) metal or PMG metal compound, wherein the PMG metal is not palladium. The oxidation catalyst may also be used as a gas sensor.

  13. Computation Results from a Parametric Study to Determine Bounding Critical Systems of Homogeneously Water-Moderated Mixed Plutonium--Uranium Oxides

    SciTech Connect

    Shimizu, Y.

    2001-01-11

    This report provides computational results of an extensive study to examine the following: (1) infinite media neutron-multiplication factors; (2) material bucklings; (3) bounding infinite media critical concentrations; (4) bounding finite critical dimensions of water-reflected and homogeneously water-moderated one-dimensional systems (i.e., spheres, cylinders of infinite length, and slabs that are infinite in two dimensions) that were comprised of various proportions and densities of plutonium oxides and uranium oxides, each having various isotopic compositions; and (5) sensitivity coefficients of delta k-eff with respect to critical geometry delta dimensions were determined for each of the three geometries that were studied. The study was undertaken to support the development of a standard that is sponsored by the International Standards Organization (ISO) under Technical Committee 85, Nuclear Energy (TC 85)--Subcommittee 5, Nuclear Fuel Technology (SC 5)--Working Group 8, Standardization of Calculations, Procedures and Practices Related to Criticality Safety (WG 8). The designation and title of the ISO TC 85/SC 5/WG 8 standard working draft is WD 14941, ''Nuclear energy--Fissile materials--Nuclear criticality control and safety of plutonium-uranium oxide fuel mixtures outside of reactors.'' Various ISO member participants performed similar computational studies using their indigenous computational codes to provide comparative results for analysis in the development of the standard.

  14. Proton affinity distributions of TiO{sub 2}-SiO{sub 2} and ZrO{sub 2}-SiO{sub 2} mixed oxides and their relationship to catalyst activities for 1-butene isomerization

    SciTech Connect

    Contescu, C.; Popa, V.T.; Schwarz, J.A.

    1995-11-01

    Proton-releasing properties at the oxide/aqueous solution interface were examined as a function of pH for two series of mixed oxide aerogels and their pure oxide components using potentiometric titrimetry. Reports of synthesis, surface characterization, and catalytic activity (1-butene isomerization) have appeared recently for similar preparation batches of titania-silica and zirconia-silica. After deconvolution of potentiometric titration data, the pK spectra of the oxide surfaces were obtained; they reveal the number and strength of various proton donor sites present under {open_quotes}wet{close_quotes} conditions. The activity in 1-butene isomerization measures weak Bronsted sites of the {open_quotes}pseudo-dry{close_quotes} catalyst (reaction at 423 K after drying at 473 K). We find that the activity for 1-butene isomerization is linearly related to the density of a particular type of proton donor site determined from pK spectra. This shows that only a limited number of the total Bronsted sites accessed by potentiometric titrimetry is specifically active for 1-butene isomerization under the conditions used here. The pK range of active sites and the corresponding TOF numbers are 6.3 {le} pK {le} 8.7, (8.2 {plus_minus} 2.1) x 10{sup {minus}3} s{sup {minus}1} for titania-silica and 6.4 {le} pK {le} 6.5, (93 {plus_minus} 24) x 10{sup {minus}3} s{sup {minus}1} for zirconia-silica. In the two catalysts series the catalytic performance varied with either composition (titania-silica) or preparation parameters (zirconia-silica) at constant composition. 51 refs., 9; figs., 2 tabs.

  15. Roles of Fe2+, Fe3+, and Cr3+ Surface Sites in the Oxidation of NO on the (Fe,Cr)3O4(1 1 1) Surface Termination of an α-(Fe,Cr)2O3(0 0 0 1) Mixed Oxide

    SciTech Connect

    Henderson, Michael A.

    2014-10-01

    The oxidation and photooxidation reactions of nitric oxide were explored on a mixed Fe and Cr mixed oxide surface using temperature programmed desorption (TPD). The mixed oxide surface examined initially had a corundum (0001) structure with a nominal cation composition of 75% Fe and 25% Cr, but after sputter/anneal cleaning was transformed into a magnetite-like (111) surface structure enriched with Cr (~40%). TPD studies of nitric oxide on the (Fe,Cr)3O4(111) surface revealed two main desorption states at 220 and 370 K, along with a third minor desorption state at ~310 K. Similarly, O2 TPD occurred in two main TPD states (100 and 230 K) and a minor state (155 K). The more strongly and weakly bound NO and O2 molecules were assigned to adsorption at Fe2+ and Fe3+ sites, respectively, with the minor desorption states assigned to Cr3+ sites. No thermal decomposition or surface chemistry was detected in TPD for adsorbed NO (e.g., no N2 or N2O formation), whereas ~10% of the adsorbed O2 irreversibly dissociated at Fe2+ sites. These dissociated oxygen species did not react with coadsorbed NO, but instead blocked NO adsorption at the Fe2+ sites, but had no effect on NO adsorption at Fe3+ sites. In contrast, NO reacted with preadsorbed O2 molecules to generate an adsorbed nitrate/nitrite species that decomposed in TPD to liberate NO at 425 K, leaving an O atom on the surface. Coadsorption of 15N18O with 16O2 suggests the oxidized species was a nitrate based on the detected level of oxygen scrambling. Preadsorption of O2 was required for nitrate formation as preadsorbed NO blocked both O2 adsorption and the oxidation reaction. Irradiation of adsorbed NO with 460 nm light at 40 K resulted in rapid photodesorption of NO without generation of any new surface species. Irradiation of the coadsorbed NO+O2 system did not promote additional NO oxidation, but limited the extent of thermal NO oxidation (in subsequent TPD) by photodepleting the surface of adsorbed NO. Preheating the NO

  16. Environmentally clean slurry using nano-TiO2-abrasive mixed with oxidizer H2O2 for ruthenium-film chemical mechanical planarization

    NASA Astrophysics Data System (ADS)

    Cui, Hao; Park, Jin-Hyung; Park, Jea-Gun

    2013-10-01

    A colloidal silica-abrasive-based slurry mixed with periodate salts has been used for chemical mechanical planarization (CMP) of ruthenium (Ru) film in semiconductor-chip fabrication. This slurry has serious environmental problems such as generation of toxic RuO4 gas, corrosion, and ionic contamination. We developed an environmentally clean slurry using nano-TiO2 abrasive mixed with hydrogen peroxide (H2O2) for the purpose of Ru-film CMP. Moreover, this slurry is free of corrosion and ionic contamination. The polishing rates of Ru and SiO2 films with this slurry strongly depended on the H2O2 concentration; the Ru-film polishing rate rapidly increased with H2O2 concentration up to 1 wt% and then slightly decreased or saturated, whereas the SiO2-film polishing rate abruptly dropped to ∼50 Å/min. In particular, the adsorbed amount of H2O2 on nano-TiO2 abrasive directly determined the Ru-film polishing rate, indicating a new CMP mechanism of Ru film in the slurry.

  17. Experiment Safety Assurance Package for the 40- to 52-GWd/MT Burnup Phase of Mixed Oxide Fuel Irradiation in Small I-hole Positions in the Advanced Test Reactor

    SciTech Connect

    S. T. Khericha; R. C. Pedersen

    2003-09-01

    This experiment safety assurance package (ESAP) is a revision of the last mixed uranium and plutonium oxide (MOX) ESAP issued in June 2002). The purpose of this revision is to provide a basis to continue irradiation up to 52 GWd/MT burnup [as predicted by MCNP (Monte Carlo N-Particle) transport code The last ESAP provided basis for irradiation, at a linear heat generation rate (LHGR) no greater than 9 kW/ft, of the highest burnup capsule assembly to 50 GWd/MT. This ESAP extends the basis for irradiation, at a LHGR no greater than 5 kW/ft, of the highest burnup capsule assembly from 50 to 52 GWd/MT.

  18. The influence of metal speciation in combustion waste on the efficiency of Cu, Pb, Zn, Cd, Ni and Cr bioleaching in a mixed culture of sulfur-oxidizing and biosurfactant-producing bacteria.

    PubMed

    Karwowska, Ewa; Wojtkowska, Małgorzata; Andrzejewska, Dorota

    2015-12-15

    Metal leachability from ash and combustion slag is related to the physico-chemical properties, including their speciation in the waste. Metals speciation is an important factor that influences the efficiency of metal bioleaching from combustion wastes in a mixed culture of acidophilic and biosurfactant-producing bacteria. It was observed that individual metals tended to occur in different fractions, which reflects their susceptibility to bioleaching. Cr and Ni were readily removed from wastes when present with a high fraction bound to carbonates. Cd and Pb where not effectively bioleached when present in high amounts in a fraction bound to organic matter. The best bioleaching results were obtained for power plant slag, which had a high metal content in the exchangeable, bound to carbonates and bound to Fe and Mg oxides fractions- the metal recovery percentage for Zn, Cu and Ni from this waste exceeded 90%. PMID:26073519

  19. Radionuclide inventories : ORIGEN2.2 isotopic depletion calculation for high burnup low-enriched uranium and weapons-grade mixed-oxide pressurized-water reactor fuel assemblies.

    SciTech Connect

    Gauntt, Randall O.; Ross, Kyle W.; Smith, James Dean; Longmire, Pamela

    2010-04-01

    The Oak Ridge National Laboratory computer code, ORIGEN2.2 (CCC-371, 2002), was used to obtain the elemental composition of irradiated low-enriched uranium (LEU)/mixed-oxide (MOX) pressurized-water reactor fuel assemblies. Described in this report are the input parameters for the ORIGEN2.2 calculations. The rationale for performing the ORIGEN2.2 calculation was to generate inventories to be used to populate MELCOR radionuclide classes. Therefore the ORIGEN2.2 output was subsequently manipulated. The procedures performed in this data reduction process are also described herein. A listing of the ORIGEN2.2 input deck for two-cycle MOX is provided in the appendix. The final output from this data reduction process was three tables containing the radionuclide inventories for LEU/MOX in elemental form. Masses, thermal powers, and activities were reported for each category.

  20. The effect of B{sub 2}O{sub 3} addition on the crystallization of amorphous TiO{sub 2}-ZrO{sub 2} mixed oxide

    SciTech Connect

    Mao Dongsen Lu Guanzhong

    2007-02-15

    The effect of B{sub 2}O{sub 3} addition on the crystallization of amorphous TiO{sub 2}-ZrO{sub 2} mixed oxide was investigated by X-ray diffraction (XRD), thermogravimetric and differential thermal analysis (TG/DTA). TiO{sub 2}-ZrO{sub 2} mixed oxide was prepared by co-precipitation method with aqueous ammonia as the precipitation reagent. Boric acid was used as a source of boria, and boria contents varied from 2 to 20 wt%. The results indicate that the addition of small amount of boria (<8 wt%) hinders the crystallization of amorphous TiO{sub 2}-ZrO{sub 2} into a crystalline ZrTiO{sub 4} compound, while a larger amount of boria ({>=}8 wt%) promotes the crystallization process. FT-IR spectroscopy and {sup 11}B MAS NMR results show that tetrahedral borate species predominate at low boria loading, and trigonal borate species increase with increasing boria loading. Thus it is concluded that highly dispersed tetrahedral BO{sub 4} units delay, while a build-up of trigonal BO{sub 3} promote, the crystallization of amorphous TiO{sub 2}-ZrO{sub 2} to form ZrTiO{sub 4} crystals. - Graphical abstract: The addition of small amount of boria (<8 wt%) hinders the crystallization of amorphous TiO{sub 2}-ZrO{sub 2} into a crystalline ZrTiO{sub 4} compound, while the larger amount of boria ({>=}8 wt%) promotes the crystallization process.

  1. Aromatization of hydrocarbons by oxidative dehydrogenation catalyzed by the mixed addenda heteropoly acid H sub 5 PMo sub 10 V sub 2 O sub 40

    SciTech Connect

    Neumann, R. ); Lissle, M. )

    1989-09-15

    The mixed addenda heteropoly acid H{sub 5}PMo{sub 10}V{sub 2}O{sub 40} dissolved in 1,2-dichloroethane with tetraglyme, forming the (tetraglyme){sub 3}-H{sub 5}PMo{sub 10}V{sub 2}O{sub 40} complex, catalyzes the aromatization of cyclic dienes at moderate temperatures in the presence of molecular oxygen. Dehydrogenations of exocyclic dienes such as limonene show that dehydrogenation is preceded by isomerization to their endocyclic isomers. Aromatization takes place by successive one-electron transfers and proton abstractions from the organic substrate to the heteropoly acid the latter being reoxidized by dioxygen coupled with the formation of water.

  2. Dependence of the mixed alkali effect on temperature and total alkali oxide content in y[xLi{sub 2}O.(1-x)Na{sub 2}O].(1-y)B{sub 2}O{sub 3} glasses

    SciTech Connect

    Gao Yong . E-mail: yonggao@uni-muenster.de

    2005-11-15

    The complex conductivity spectra of mixed alkali borate glasses of compositions y [xLi{sub 2}O.(1-x)Na{sub 2}O].(1-y)B{sub 2}O{sub 3} (with x=0.0, 0.2, 0.4, 0.6, 0.8, 1.0; y=0.1, 0.2, 0.3) in a frequency range between 10{sup -2}Hz and 3MHz and at temperatures ranging from 298 to 573K have been studied. For each glass composition the conductivities show a transition from the dc values into a dispersive regime where the conductivity is found to increase continuously with frequency, tending towards a linear frequency dependence at sufficiently low temperatures. Mixed alkali effects (MAEs) in the dc conductivity and activation energy are identified and discussed. It has been for the first time found that the strength of the MAE in the logarithm of the dc conductivity linearly increases with the total alkali oxide content, y, and the reciprocal temperature, 1/T.

  3. Additional studies on mixed uranyl oxide-hydroxide hydrate alteration products of uraninite from the palermo and ruggles granitic pegmatites, grafton county, New Hampshire

    USGS Publications Warehouse

    Foord, E.E.; Korzeb, S.L.; Lichte, F.E.; Fitzpatrick, J.J.

    1997-01-01

    Additional studies on an incompletely characterized secondary uranium "mineral" from the Ruggles and Palermo granitic pegmatites, New Hampshire, referred to as mineral "A" by Frondel (1956), reveal a mixture of schoepite-group minerals and related uranyl oxide-hydroxide hydrated compounds. A composite chemical analysis yielded (in wt.%): PbO 4.85 (EMP), UO3 83.5 (EMP), BaO 0.675 (av. of EMP and ICP), CaO 0.167 (av. of EMP and ICP), K2O 2.455 (av. of EMP and ICP), SrO 0.21 (ICP), ThO2 0.85 (ICP), H2O 6.9, ??99.61. Powder-diffraction X-ray studies indicate a close resemblance in patterns between mineral "A" and several uranyl oxide-hydroxide hydrated minerals, including the schoepite family of minerals and UO2(OH)2. The powder-diffraction data for mineral "A" are most similar to those for synthetic UO2.86??1.5H2O and UO2(OH)2, but other phases are likely present as well. TGA analysis of both mineral "A" and metaschoepite show similar weight-loss and first derivative curves. The dominant losses are at 100??C, with secondary events at 400?? and 600??C. IR spectra show the presence of (OH) and H2O. Uraninite from both pegmatites, analyzed by LAM-ICP-MS, shows the presence of Th, Pb, K and Ca.

  4. Superior performance of Ni–W–Ce mixed-metal oxide catalysts for ethanol steam reforming: Synergistic effects of W- and Ni-dopants

    DOE PAGESBeta

    Liu, Zongyuan; Xu, Wenqian; Yao, Siyu; Johnson-Peck, Aaron C.; Zhao, Fuzhen; Michorczyk, Piotr; Kubacka, Anna; Stach, Eric A.; Fernández-García, Marcos; Senanayake, Sanjaya D.; et al

    2014-11-26

    In this study, the ethanol steam reforming (ESR) reaction was examined over a series of Ni-W-Ce oxide catalysts. The structures of the catalysts were characterized using in-situ techniques including X-ray diffraction, Pair Distribution Function, X-ray absorption fine structure and transmission electron microscopy; while possible surface intermediates for the ESR reaction were investigated by Diffuse Reflectance Infrared Fourier Transform Spectroscopy. In these materials, all the W and part of the Ni were incorporated into the CeO₂ lattice, with the remaining Ni forming highly dispersed nano NiO (< 2 nm) outside the Ni-W-Ce oxide structure. The nano NiO was reduced to Nimore » under ESR conditions. The Ni-W-Ce systeme exhibited a much larger lattice strain than those seen for Ni-Ce and W-Ce. Synergistic effects between Ni and W inside ceria produced a substantial amount of defects and O vacancies that led to high catalytic activity, selectivity and stability (i.e. resistance to coke formation) during ethanol steam reforming.« less

  5. Superior performance of Ni–W–Ce mixed-metal oxide catalysts for ethanol steam reforming: Synergistic effects of W- and Ni-dopants

    SciTech Connect

    Liu, Zongyuan; Xu, Wenqian; Yao, Siyu; Johnson-Peck, Aaron C.; Zhao, Fuzhen; Michorczyk, Piotr; Kubacka, Anna; Stach, Eric A.; Fernández-García, Marcos; Senanayake, Sanjaya D.; Rodriguez, José A.

    2014-11-26

    In this study, the ethanol steam reforming (ESR) reaction was examined over a series of Ni-W-Ce oxide catalysts. The structures of the catalysts were characterized using in-situ techniques including X-ray diffraction, Pair Distribution Function, X-ray absorption fine structure and transmission electron microscopy; while possible surface intermediates for the ESR reaction were investigated by Diffuse Reflectance Infrared Fourier Transform Spectroscopy. In these materials, all the W and part of the Ni were incorporated into the CeO₂ lattice, with the remaining Ni forming highly dispersed nano NiO (< 2 nm) outside the Ni-W-Ce oxide structure. The nano NiO was reduced to Ni under ESR conditions. The Ni-W-Ce systeme exhibited a much larger lattice strain than those seen for Ni-Ce and W-Ce. Synergistic effects between Ni and W inside ceria produced a substantial amount of defects and O vacancies that led to high catalytic activity, selectivity and stability (i.e. resistance to coke formation) during ethanol steam reforming.

  6. Optical Properties of Some Fluorinated Poly(1,3,4-Oxadiazole-Ether)s in Homogeneous and Heterogeneous Media. Changes Induced by SnO2, NiO and SnO2/NiO Mixed-Oxide Nanoparticles.

    PubMed

    Homocianu, Mihaela; Airinei, Anton; Ipate, Alina Mirela; Dorneanu, Petronela Pascariu; Hamciuc, Corneliu

    2016-01-01

    Optical characteristics of some fluorinated poly(1,3,4-oxadiazole-ether)s in presence of SnO2, NiO and SnO2/NiO mixed-oxide nanoparticles (NPs) was investigated. The interactions between polymers and metal oxide NPs were studied by steady-state UV-Vis absorption and fluorescence spectroscopy techniques. The absorption and fluorescence signals of all investigated polymers was modified by presence of both pure and mixed-oxide nanoparticles. The moderate values of Stern-Volmer quenching constant and non-linear trend of Scott plot indicate the less affinity between metal oxide NPs and polymers. The solvation behavior of some fluorinated poly(1,3,4-oxadiazole-ether)s in chloroform-N,N-dimethylformamide and N,N-dimethylformamide-dimethylsulfoxide mixtures was discussed. PMID:26518577

  7. Synthesis, structure, and properties of a mixed-valent triiron complex of tetramethyl reductic acid, an ascorbic acid analogue, and its relationship to a functional non-heme iron oxidation catalyst system.

    PubMed

    Kim, YooJin; Feng, Xudong; Lippard, Stephen J

    2007-07-23

    The purple triiron(II,III,III) complex, [Fe(3)Cl(2)(TMRASQ)(4)(HTMRA)(2)] x C(5)H(12) (1 x C(5)H(12)), where H(2)TMRA is a tetramethyl reductic acid, 4,4,5,5-tetramethyl-2,3-dihydroxy-2-cyclopenten-1-one, and HTMRASQ is the semiquinone form of this ligand, was prepared from (Et(4)N)(2)[Fe(2)OCl(6)] and H(2)TMRA and characterized by X-ray crystallography, Mössbauer spectroscopy, and redox titrations. The physical properties of the complex in solution are consistent with its mixed-valent character, as delineated by a solid-state structure analysis. Assignments of the iron and ligand oxidation states in the crystal were made on the basis of a valence bond sum analysis and the internal ligand geometry. As the first well-characterized iron complex of an ascorbic acid H(2)AA analogue, 1 provides insight into the possible coordination geometry of the family of complexes containing H(2)AA and its analogues. In the presence of air and H(2)TMRA, 1 is able to catalyze the oxidation of cyclohexane to cyclohexanol with remarkable selectivity, but the nature of the true catalyst remains unknown. PMID:17579400

  8. Synthesis, Structure, and Properties of a Mixed-Valent Triiron Complex of Tetramethyl Reductic Acid, an Ascorbic Acid Analog, and its Relationship to a Functional Non-Heme Iron Oxidation Catalyst System

    PubMed Central

    Kim, YooJin; Feng, Xudong; Lippard, Stephen J.

    2011-01-01

    The purple triiron(II,III,III) complex, [Fe3Cl2(TMRASQ)4(HTMRA)2]·C5H12 (1·C5H12), where H2(TMRA) is tetramethyl reductic acid, 4,4,5,5-tetramethyl-2,3-dihydroxy-2-cyclopenten-1-one, and H(TMRASQ) is the semiquinone form of this ligand, was prepared from (Et4N)2[Fe2OCl6] and H2(TMRA) and characterized by X-ray crystallography, Mössbauer spectroscopy, and redox titrations. The physical properties of the complex in solution are consistent with its mixed-valent character, as delineated by a solid-state structure analysis. Assignments of the iron and ligand oxidation states in the crystal were made on the basis of a valence bond sum analysis and the internal ligand geometry. As the first well-characterized iron complex of an ascorbic acid H2(AA) analog, 1 provides insight into the possible coordination geometry of the family of complexes containing H2AA and its analogues. In the presence of air and H2TMRA, 1 is able to catalyze the oxidation of cyclohexane to cyclohexanol with remarkable selectivity, but the nature of the true catalyst remains unknown. PMID:17579400

  9. Mixed-phase p-type silicon oxide containing silicon nanocrystals and its role in thin-film silicon solar cells

    NASA Astrophysics Data System (ADS)

    Cuony, P.; Marending, M.; Alexander, D. T. L.; Boccard, M.; Bugnon, G.; Despeisse, M.; Ballif, C.

    2010-11-01

    Lower absorption, lower refractive index, and tunable resistance are three advantages of amorphous silicon oxide containing nanocrystalline silicon grains (nc-SiOx) compared to microcrystalline silicon (μc-Si), when used as a p-type layer in μc-Si thin-film solar cells. We show that p-nc-SiOx with its particular nanostructure increases μc-Si cell efficiency by reducing reflection and parasitic absorption losses depending on the roughness of the front electrode. Furthermore, we demonstrate that the p-nc-SiOx reduces the detrimental effects of the roughness on the electrical characteristics, and significantly increases μc-Si and Micromorph cell efficiency on substrates until now considered too rough for thin-film silicon solar cells.

  10. Application of modified direct denitration to support the ORNL coupled-end-to-end demonstration in production of mixed oxides suitable for pellet fabrication

    SciTech Connect

    Walker, E.A.; Vedder, R.J.; Felker, L.K.; Marschman, S.C.

    2007-07-01

    The current and future development of the Modified Direct Denitration (MDD) process is in support of Oak Ridge National Laboratory's (ORNL) Coupled End-to-End (CETE) research, development, and demonstration (R and D) of proposed advanced fuel reprocessing and fuel fabrication processes. This work will involve the co-conversion of the U/Pu/Np product streams from the UREX+3 separation flow sheet utilizing the existing MDD glove-box setup and the in-cell co-conversion of the U/Pu/Np/Am/Cm product streams from the UREX+1a flow sheet. Characterization equipment is being procured and installed. Oxide powder studies are being done on calcination/reduction variables, as well as pressing and sintering of pellets to permit metallographic examinations. (authors)

  11. Mixed cerium-platinum oxides: Electronic structure of [CeO]Ptn (n = 1, 2) and [CeO2]Pt complex anions and neutrals

    NASA Astrophysics Data System (ADS)

    Ray, Manisha; Kafader, Jared O.; Topolski, Josey E.; Jarrold, Caroline Chick

    2016-07-01

    The electronic structures of several small Ce-Pt oxide complexes were explored using a combination of anion photoelectron (PE) spectroscopy and density functional theory calculations. Pt and Pt2 both accept electron density from CeO diatomic molecules, in which the cerium atom is in a lower-than-bulk oxidation state (+2 versus bulk +4). Neutral [CeO]Pt and [CeO]Pt2 complexes are therefore ionic, with electronic structures described qualitatively as [CeO+2]Pt-2 and [CeO+]Pt2-, respectively. The associated anions are described qualitatively as [CeO+]Pt-2 and [CeO+]Pt2-2, respectively. In both neutrals and anions, the most stable molecular structures determined by calculations feature a distinct CeO moiety, with the positively charged Ce center pointing toward the electron rich Pt or Pt2 moiety. Spectral simulations based on calculated spectroscopic parameters are in fair agreement with the spectra, validating the computationally determined structures. In contrast, when Pt is coupled with CeO2, which has no Ce-localized electrons that can readily be donated to Pt, the anion is described as [CeO2]Pt-. The molecular structure predicted computationally suggests that it is governed by charge-dipole interactions. The neutral [CeO2]Pt complex lacks charge-dipole stabilizing interactions, and is predicted to be structurally very different from the anion, featuring a single Pt-O-Ce bridge bond. The PE spectra of several of the complexes exhibit evidence of photodissociation with Pt- daughter ion formation. The electronic structures of these complexes are related to local interactions in Pt-ceria catalyst-support systems.

  12. Mixed cerium-platinum oxides: Electronic structure of [CeO]Ptn (n = 1, 2) and [CeO2]Pt complex anions and neutrals.

    PubMed

    Ray, Manisha; Kafader, Jared O; Topolski, Josey E; Jarrold, Caroline Chick

    2016-07-28

    The electronic structures of several small Ce-Pt oxide complexes were explored using a combination of anion photoelectron (PE) spectroscopy and density functional theory calculations. Pt and Pt2 both accept electron density from CeO diatomic molecules, in which the cerium atom is in a lower-than-bulk oxidation state (+2 versus bulk +4). Neutral [CeO]Pt and [CeO]Pt2 complexes are therefore ionic, with electronic structures described qualitatively as [CeO(+2)]Pt(-2) and [CeO(+)]Pt2 (-), respectively. The associated anions are described qualitatively as [CeO(+)]Pt(-2) and [CeO(+)]Pt2 (-2), respectively. In both neutrals and anions, the most stable molecular structures determined by calculations feature a distinct CeO moiety, with the positively charged Ce center pointing toward the electron rich Pt or Pt2 moiety. Spectral simulations based on calculated spectroscopic parameters are in fair agreement with the spectra, validating the computationally determined structures. In contrast, when Pt is coupled with CeO2, which has no Ce-localized electrons that can readily be donated to Pt, the anion is described as [CeO2]Pt(-). The molecular structure predicted computationally suggests that it is governed by charge-dipole interactions. The neutral [CeO2]Pt complex lacks charge-dipole stabilizing interactions, and is predicted to be structurally very different from the anion, featuring a single Pt-O-Ce bridge bond. The PE spectra of several of the complexes exhibit evidence of photodissociation with Pt(-) daughter ion formation. The electronic structures of these complexes are related to local interactions in Pt-ceria catalyst-support systems. PMID:27475371

  13. Synthesis and characterization of homo- and heterobimetallic niobium{sup v} and tantalum{sup v} peroxo-polyaminocarboxylato complexes and their use as single or multiple molecular precursors for Nb-Ta mixed oxides

    SciTech Connect

    Bayot, Daisy . E-mail: devillers@chim.ucl.ac.be

    2005-09-15

    New water-soluble bimetallic peroxo complexes of niobium{sup V} and/or tantalum{sup V} with high-denticity polyaminocarboxylate ligands have been prepared, characterized from the spectroscopic point of view, and used as molecular precursors for Nb-Ta mixed oxides. Four new homobimetallic complexes (gu){sub 3}[Nb{sub 2}(O{sub 2}){sub 4}(dtpaO{sub 3})].3H{sub 2}O 1 (gu){sub 3}[Ta{sub 2}(O{sub 2}){sub 4}(dtpaO{sub 3})].5H{sub 2}O 2 (gu){sub 3}[Nb{sub 2}(O{sub 2}){sub 4}(HtthaO{sub 4})].2H{sub 2}O 4 and (gu){sub 3}[Ta{sub 2}(O{sub 2}){sub 4}(HtthaO{sub 4})].3H{sub 2}O 5 and the corresponding heterometallic complexes (gu){sub 3}[NbTa(O{sub 2}){sub 4}(dtpaO{sub 3})].2.5H{sub 2}O 3 and (gu){sub 3}[NbTa(O{sub 2}){sub 4}(HtthaO{sub 4)}].2H{sub 2}O 6 have been obtained. In these compounds, the in situ oxidation of the nitrogen atoms of the PAC ligands into N-oxide groups has been evidenced by IR spectroscopy and mass spectrometry. The thermal treatment of the homonuclear complexes in air at 700 or 800 deg. C, depending on the Ta content, provided Nb{sub 2}O{sub 5} or Ta{sub 2}O{sub 5} while the heteronuclear compounds led to the solid solution TaNbO{sub 5}. BET and SEM measurements have been carried out and comparison of the morphology of the samples prepared from homo- and heterometallic precursors is discussed.

  14. [Mixed marriages].

    PubMed

    Harmsen, C N

    1998-08-01

    The author examines the extent and characteristics of mixed marriages in the Netherlands. "Nine out of ten married persons born in Turkey or Morocco have a partner who was born in the same country. The majority of married Surinamese also have a partner originating from the same country. Those who spend (a part of) their youth in Indonesia (the former Dutch East Indies), on the other hand, are mostly married to someone born in the Netherlands." (EXCERPT) PMID:12294179

  15. Thermal oxidation process accelerates degradation of the olive oil mixed with sunflower oil and enables its discrimination using synchronous fluorescence spectroscopy and chemometric analysis

    NASA Astrophysics Data System (ADS)

    Mabood, Fazal; Boqué, Ricard; Folcarelli, Rita; Busto, Olga; Al-Harrasi, Ahmed; Hussain, Javid

    2015-05-01

    We have investigated the effect of thermal treatment on the discrimination of pure extra virgin olive oil (EVOO) samples from EVOO samples adulterated with sunflower oil. Two groups of samples were used. One group was analyzed at room temperature (25 °C) and the other group was thermally treated in a thermostatic water bath at 75 °C for 8 h, in contact with air and with light exposure, to favor oxidation. All samples were then measured with synchronous fluorescence spectroscopy. Fluorescence spectra were acquired by varying the excitation wavelength in the region from 250 to 720 nm. In order to optimize the differences between excitation and emission wavelengths, four constant differential wavelengths, i.e., 20 nm, 40 nm, 60 nm and 80 nm, were tried. Partial least-squares discriminant analysis (PLS-DA) was used to discriminate between pure and adulterated oils. It was found that the 20 nm difference was the optimal, at which the discrimination models showed the best results. The best PLS-DA models were those built with the difference spectra (75-25 °C), which were able to discriminate pure from adulterated oils at a 2% level of adulteration. Furthermore, PLS regression models were built to quantify the level of adulteration. Again, the best model was the one built with the difference spectra, with a prediction error of 1.75% of adulteration.

  16. Structure and properties of Y 5Mo 2O 12 and Gd 5Mo 2O 12: Mixed valence oxides with structurally equivalent molybdenum atoms

    NASA Astrophysics Data System (ADS)

    Torardi, C. C.; Fecketter, C.; McCarroll, W. H.; DiSalvo, F. J.

    1985-12-01

    Crystals of Ln5Mo 2O 12 ( Ln = Y, Gd) were grown by electrochemical reduction of alkali-molybdate/rare-earth oxide melts at 1075-1100°C. A single crystal of Y 5Mo 2O 12, used for structure determination, was found to be monoclinic with a = 12.2376(7) Å, b = 5.7177(8) Å, c = 7.4835(5) Å, β = 108.034(5)°, and Z = 2. Although the structure was refined in space group {C2}/{m}, the true space group appears to be {P2 1}/{m}. In Y 5Mo 2O 12, rutile-like sheets of edge-shared MoO 6 chains linked by YO 6 octahedra are interconnected with YO 7 monocapped trigonal prisms. The Mo atoms in the chains have alternating distances of 2.496 and 3.221 Å and in that respect are similar to MoO 2. However, in contrast to metallic MoO 2 both the Y and Gd compounds are n-type semiconductors with room temperature resistivities of the order of 10 3 ohm-cm. Magnetic susceptibility measurements confirm the presence of one unpaired electron per Mo 2 unit. The semiconducting behavior can be explained in terms of an unfavorable bridging oxygen coordination which prevents electron delocalization through metal-oxygen pi bonding as in MoO 2.

  17. Enhanced photocatalytic activity of TiO2-impregnated with MgZnAl mixed oxides obtained from layered double hydroxides for phenol degradation

    NASA Astrophysics Data System (ADS)

    de Almeida, Marciano Fabiano; Bellato, Carlos Roberto; Mounteer, Ann Honor; Ferreira, Sukarno Olavo; Milagres, Jaderson Lopes; Miranda, Liany Divina Lima

    2015-12-01

    A series of TiO2/MgZnAl photocatalysts were successfully synthesized from ternary (Mg, Zn and Al) layered double hydroxides impregnated with TiO2 nanoparticles by the co-precipitation method at variable pH with different Zn2+/Mg2+ molar ratios. The composite photocatalysts were calcined at 500 °C resulting in the incorporation of oxide zinc, in the calcined MgZnAl LDH structure. Synergistic effect between ZnO and TiO2 lead to significant enhancement of TiO2/MgZnAl photocatalytic activity. Composite photocatalysts were characterized by ICP-MS, N2 adsorption-desorption, XRD, SEM, EDS, IR and UV-vis DRS. Phenol in aqueous solution (50 mg/L) was used as a model compound for evaluation of UV-vis (filter cut-off for λ > 300 nm) photocatalytic activity. The most efficient photocatalyst composite was obtained at a 5% Zn2+/Mg2+ molar ratio, in the catalyst identified as TiO2/MgZnAl-5. This composite catalyst had high photocatalytic activity, completely destroying phenol and removing 80% of total organic carbon in solution after 360 min. The TiO2/MgZnAl-5 catalyst remained relatively stable, presenting a 15% decrease in phenol degradation efficiency after five consecutive photocatalytic cycles.

  18. A mix-and-read fluorescence strategy for the switch-on probing of kinase activity based on an aptameric-peptide/graphene-oxide platform.

    PubMed

    Lei, Chunyang; Xu, Xiahong; Zhou, Jiang; Liu, Xin; Nie, Zhou; Qing, Meng; Li, Pei; Huang, Yan; Yao, Shouzhuo

    2014-09-01

    Protein kinase plays a vital role in regulating signal-transduction pathways and its simple and quick detection is highly desirable because traditional kinase assays typically rely on a time-consuming kinase-phosphorylation process (ca. 1 h). Herein, we report a new and rapid fluorescence-based sensing platform for probing the activity of protein kinase that is based on the super-quenching capacity of graphene oxide (GO) nanosheets and specific recognition of the aptameric peptide (FITC-IP20). On the GO/peptide platform, the fluorescence quenching of FITC-IP20 that is adsorbed onto GO can be restored by selective binding of active protein kinase to the aptameric peptide, thereby resulting in the fast switch-on detection of kinase activity (ca. 15 min). The feasibility of this method has been demonstrated by the sensitive measurement of the activity of cAMP-dependent protein kinase (PKA), with a detection limit of 0.053 mU μL(-1). This assay technique was also successfully applied to the detection of kinase activation in cell lysate. PMID:25048161

  19. Thermal oxidation process accelerates degradation of the olive oil mixed with sunflower oil and enables its discrimination using synchronous fluorescence spectroscopy and chemometric analysis.

    PubMed

    Mabood, Fazal; Boqué, Ricard; Folcarelli, Rita; Busto, Olga; Al-Harrasi, Ahmed; Hussain, Javid

    2015-05-15

    We have investigated the effect of thermal treatment on the discrimination of pure extra virgin olive oil (EVOO) samples from EVOO samples adulterated with sunflower oil. Two groups of samples were used. One group was analyzed at room temperature (25°C) and the other group was thermally treated in a thermostatic water bath at 75°C for 8h, in contact with air and with light exposure, to favor oxidation. All samples were then measured with synchronous fluorescence spectroscopy. Fluorescence spectra were acquired by varying the excitation wavelength in the region from 250 to 720nm. In order to optimize the differences between excitation and emission wavelengths, four constant differential wavelengths, i.e., 20nm, 40nm, 60nm and 80nm, were tried. Partial least-squares discriminant analysis (PLS-DA) was used to discriminate between pure and adulterated oils. It was found that the 20nm difference was the optimal, at which the discrimination models showed the best results. The best PLS-DA models were those built with the difference spectra (75-25°C), which were able to discriminate pure from adulterated oils at a 2% level of adulteration. Furthermore, PLS regression models were built to quantify the level of adulteration. Again, the best model was the one built with the difference spectra, with a prediction error of 1.75% of adulteration. PMID:25748285

  20. Microstructure and polarization characteristics of anode supported tubular solid oxide fuel cell with co-precipitated and mechanically mixed Ni-YSZ anodes

    NASA Astrophysics Data System (ADS)

    Shikazono, Naoki; Sakamoto, Yusuke; Yamaguchi, Yu; Kasagi, Nobuhide

    An anode support tubular solid oxide fuel cell (SOFC) is fabricated and the dependence of its polarization resistance on anode microstructural parameters is investigated by means of stereology and concept of contiguity (c-c) theory. Nickel yttria-stabilized zirconia (Ni-YSZ) anode supported cell with YSZ electrolyte, lanthanum-strontium-manganite (LSM)-YSZ composite cathode, and LSM cathode layers is fabricated by dip coating. Submicrometer resolution images of anode microstructure are successfully obtained by low voltage SEM-EDX and quantified by stereological analysis. Cell voltage measurements and impedance spectroscopy are performed at temperatures of 650 and 750 °C with hydrogen and nitrogen mixture gas as a fuel. A quantitative relationship between polarization resistance and microstructural parameters such as circularity, three-phase boundary length, contiguity, etc. is investigated using the concept of contiguity (c-c) theory. The effectiveness of correlating polarization resistance of anode supported tubular SOFC using stereology and c-c theory is evaluated.