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 Acid Oxidation

    SciTech Connect

    Pierce, R.A.

    1999-10-26

    Several non-thermal processes have been developed to destroy organic waste compounds using chemicals with high oxidation potentials. These efforts have focused on developing technologies that work at low temperatures, relative to incineration, to overcome many of the regulatory issues associated with obtaining permits for waste incinerators. One such technique with great flexibility is mixed acid oxidation. Mixed acid oxidation, developed at the Savannah River Site, uses a mixture of an oxidant (nitric acid) and a carrier acid (phosphoric acid). The carrier acid acts as a non-volatile holding medium for the somewhat volatile oxidant. The combination of acids allows appreciable amounts of the concentrated oxidant to remain in the carrier acid well above the oxidant''s normal boiling point.

  3. Mixed oxide fuel development

    SciTech Connect

    Leggett, R.D.; Omberg, R.P.

    1987-05-08

    This paper describes the success of the ongoing mixed-oxide fuel development program in the United States aimed at qualifying an economical fuel system for liquid metal cooled reactors. This development has been the cornerstone of the US program for the past 20 years and has proceeded in a deliberate and highly disciplined fashion with high emphasis on fuel reliability and operational safety as major features of an economical fuel system. The program progresses from feature testing in EBR-II to qualifying full size components in FFTF under fully prototypic conditions to establish a basis for extending allowable lifetimes. The development program started with the one year (300 EFPD) core, which is the FFTF driver fuel, continued with the demonstration of a two year (600 EFPD) core and is presently evaluating a three year (900 EFPD) fuel system. All three of these systems, consistent with other LMR fuel programs around the world, use fuel pellets gas bonded to a cladding tube that is assembled into a bundle and fitted into a wrapper tube or duct for ease of insertion into a core. The materials of construction progressed from austenitic CW 316 SS to lower swelling austenitic D9 to non swelling ferritic/martensitic HT9. 6 figs., 2 tabs.

  4. 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.

  5. 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.

  6. 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.

  7. 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.

  8. 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.

  9. 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)...

  10. 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...

  11. 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...

  12. 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...

  13. 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...

  14. 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...

  15. 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)...

  16. 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...

  17. 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)...

  18. 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...

  19. 40 CFR 721.10006 - 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 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...

  20. 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...

  1. 40 CFR 721.5548 - 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 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)...

  2. 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)...

  3. 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...

  4. 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...

  5. 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...

  6. 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.

  7. 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).

  8. 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.

  9. 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)

  10. Formation of alumina-ceria mixed oxide in model systems

    NASA Astrophysics Data System (ADS)

    Skála, Tomáš; Tsud, Nataliya; Prince, Kevin C.; Matolín, Vladimír

    2011-02-01

    Interaction of aluminium with cerium oxide was studied by photoelectron spectroscopy of Al/CeO2(1 1 1) and CeO2/Al(1 1 1) model systems. It was found in both cases that metallic aluminium was immediately oxidized, CeO2 was partially reduced and a mixed oxide with cerium present as Ce3+ was formed. The compound is probably cerium aluminate CeAlO3 mixed with Al2O3 or Ce2O3. In both cases the intermixing was limited by the diffusion of aluminium into ceria. The excess of deposited material above this limit formed AlOx and CeO2 overlayers on the top of the mixed oxide + aluminate/CeO2 and mixed oxide + aluminate/Al films, respectively.

  11. 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.

  12. Analysis of monoclonal antibody oxidation by simple mixed mode chromatography.

    PubMed

    Pavon, Jorge Alexander; Li, Xiaojuan; Chico, Steven; Kishnani, Umesh; Soundararajan, Soundara; Cheung, Jason; Li, Huijuan; Richardson, Daisy; Shameem, Mohammed; Yang, Xiaoyu

    2016-01-29

    Analysis of oxidation of monoclonal antibodies (mAbs) in most cases relies on peptide mapping and LC-MS, which is time consuming and labor-intensive. A robust chromatography based method that is able to resolve and quantitate mAb oxidation variants due to oxidized methionine or tryptophan is highly desired. Here we developed a novel mixed mode chromatography method using the unique property of Sepax Zenix SEC-300MK column to analyze mAb oxidation levels. The separation of oxidized species relied upon the mixed mode of size exclusion and hydrophobic interaction between the resin and antibodies. The chromatography was performed in a regular SEC mobile phase, PBS, containing NaCl at a concentration (0-2.4M) specific for individual antibodies. This method was able to resolve and quantitate the oxidized antibodies as prepeaks, of either methionine-oxidized species induced by the common oxidants TBHP, tryptophan-oxidized species triggered by AAPH, or oxidized species by UV photo-irradiation. The prepeaks were further characterized by SEC-MALLS as monomers and confirmed by LC-MS as oxidized antibody variants with a mass increase of 16 or 32Da. This method has been successfully applied to monitor multiple monoclonal antibodies of IgG1, IgG2, and IgG4 subclasses. PMID:26774436

  13. 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.

  14. 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.

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

    NASA Astrophysics Data System (ADS)

    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

    2013-11-01

    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.

  16. 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.

  17. Interfacial mixing during annealing of zinc oxide nanoparticle junctions

    NASA Astrophysics Data System (ADS)

    Hu, Ming; Giapis, Konstantinos P.; Poulikakos, Dimos

    2011-05-01

    The process of forming a junction between crystalline zinc oxide (ZnO) nanoparticles during pulsed thermal annealing in liquid tetradecane is studied using molecular dynamics simulation. Pairs of equal and unequal size particles are considered with emphasis on neck growth and atom mixing. The contact area and interface width of the junction are found to increase with heat pulse power albeit at different rates. The results suggest that it is possible to increase the junction area without significant mixing of atoms across the junction interface by tailoring the heat pulse power.

  18. Enhanced arsenic removal using mixed metal oxide impregnated chitosan beads.

    PubMed

    Yamani, Jamila S; Miller, Sarah M; Spaulding, Matthew L; Zimmerman, Julie B

    2012-09-15

    Mixed metal oxide impregnated chitosan beads (MICB) containing nanocrystalline Al₂O₃ and nanocrystalline TiO₂ were successfully developed. This adsorbent exploits the high capacity of Al₂O₃ for arsenate and the photocatalytic activity of TiO₂ to oxidize arsenite to arsenate, resulting in a removal capacity higher than that of either metal oxide alone. The composition of the beads was optimized for maximum arsenite removal in the presence of UV light. The mechanism of removal was investigated and a mode of action was proposed wherein TiO₂ oxidizes arsenite to arsenate which is then removed from solution by Al₂O₃. Pseudo-second order kinetics were used to validate the proposed mechanism. MICB is a more efficient and effective adsorbent for arsenic than TiO₂-impregnated chitosan beads (TICB), previously reported on, yet maintains a desirable life cycle, free of complex synthesis processes, toxic materials, and energy inputs. PMID:22743162

  19. 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.

  20. 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.

  1. 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

  2. 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...

  3. 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...

  4. 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...

  5. 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...

  6. 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...

  7. 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). 721.10574 Section 721.10574 Protection of Environment... reaction products with mixed metal oxides (generic). (a) Chemical substance and significant new uses... reaction products with mixed metal oxides (PMN P-09-48) is subject to reporting under this section for...

  8. 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). 721.10574 Section 721.10574 Protection of Environment... reaction products with mixed metal oxides (generic). (a) Chemical substance and significant new uses... reaction products with mixed metal oxides (PMN P-09-48) is subject to reporting under this section for...

  9. 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...

  10. 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...

  11. 40 CFR 721.10147 - Acrylate derivative of alkoxysilylalkane ester and mixed metal oxides (generic).

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 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...

  12. 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... 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...

  13. 40 CFR 721.10147 - Acrylate derivative of alkoxysilylalkane ester and mixed metal oxides (generic).

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 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...

  14. 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.

  15. Nanoparticle cerium oxide and mixed cerium oxides for improved fuel cell lifetime

    NASA Astrophysics Data System (ADS)

    Stewart, Stephen Michael

    While there is a rich body of literature concerning of properties of bulk cerium oxide and cerium cations in solution, the discussion has been inappropriately applied to nanoscale cerium oxide resulting in many unexpected or unexplained results. In particular, there is very limited understanding about the properties of cerium oxide and its potential use as a radical scavenger, and how the catalytic properties of cerium oxide change as the particle size approaches the nanoscale. For example, the involvement of Ce+4 and Ce+3 cations in reactions such as hydrogen peroxide decomposition have been investigated for both cerium cations and bulk cerium oxide. However, while both are assumed to decompose hydrogen peroxide through the same mechanism, whereby Ce+4 is involved in peroxide decomposition while Ce +3 is involved in radical scavenging, there has been very little done to address how the selectivity and activity of these reactions are affected by changing the majority cation population, as cerium cations in solution are predominantly in the +3 oxidation state while cerium cations are predominantly in the +4 oxidation state in cerium oxide. This matter is further complicated in cerium oxide nanoparticles where the surface concentration of Ce +3 cations is increased due to particle curvature effects. Due to the potential of controlling the surface cerium oxidation state using particle size and using this control to change the catalytic properties, this project investigated the effect of particle size and composition and the activity and selectivity of cerium oxide nanoparticles, and has served to expand the understanding of the properties of pure and mixed nanoparticle cerium oxide. This work explains the metric developed for measuring the catalytic properties of pure and mixed cerium oxide nanoparticles, which is also good at predicting the immediate and long-term behavior of nanoparticles in hydrogen fuel cells. This work also directly demonstrates praseodymium

  16. 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.

  17. 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.

  18. 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.

  19. 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...

  20. 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...

  1. 40 CFR 721.10148 - Acryloxy alkanoic alkane derivative with mixed metal oxides (generic).

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 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...

  2. Iron-tellurium-selenium mixed oxide catalysts for the selective oxidation of propylene to acrolein

    SciTech Connect

    Patel, B.M.; Price, G.L. )

    1990-05-01

    This paper reports on iron-tellurium-selenium mixed oxide catalysts prepared by coprecipitation from aqueous solution investigated for the propylene to acrolein reaction in the temperature range 543-773 K. Infrared spectroscopy, electron dispersive X-ray analysis, X-ray diffraction, and isotopic tracer techniques have also been employed to characterize this catalytic system. Properties of the Fe-Te-Se mixed oxide catalysts have been compared with Fe-Te mixed oxides in an effort to deduce the functionality of Se. The selenium in the Fe-Te-Se-O catalyst has been found to be the hydrocarbon activating site. The activation energies for the acrolein and carbon dioxide formation are 71 and 54 kJ/mol, respectively. Reactions carried out with {sup 18}O{sub 2} have shown lattice oxygen to be primarily responsible for the formation of both acrolein and carbon dioxide. The initial and rate-determining step for acrolein formation is hydrogen abstraction as determined by an isotope effect associated with the C{sub 3}D{sub 6} reaction. No isotope effect is observed for carbon dioxide formation from C{sub 3}D{sub 6} suggesting that CO{sub 2} is formed by parallel, not consecutive, oxidation of propylene.

  3. 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

  4. 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.

  5. Diffusion-controlled creep in mixed-conducting oxides

    SciTech Connect

    Routbort, J.L.; Goretta, K.C.; Cook, R.E.; Wolfenstine, J.; Armstrong, T.R.; Clauss, C.; Dominguez-Rodriguez, A.

    1996-06-01

    Steady-state creep rate of the mixed conducting oxides La{sub 1-x}Sr{sub x}MnO{sub 3} (x=0.1, 0.15, 0.25) and La{sub 0.7}Ca{sub 0.3}MnO{sub 3} has been investigated between 1150 and 1300 C. Creep parameters and TEM indicate that deformation is controlled by lattice diffusion of one of the cations. Dependence of creep rate on Sr concentration, combined with a point-defect model, confirms this hypothesis; however the oxygen partial pressure dependence of creep (from 10{sup -1} to 2x10{sup 4} Pa) cannot be accounted for within the framework of a simple point-defect model.

  6. The mechanism of the oxidation of propene to acrolein over antimony - Tin mixed oxide catalysts

    SciTech Connect

    Ono, Takehiko ); Hillig, K.W. II; Kuczkowski, R.L. )

    1990-05-01

    The oxidation of propenes such as {sup 13}CH{sub 2}{double bond}CH-CH{sub 3}, CH{sub 2}{double bond}CH-CD{sub 3}, cis-CHD{double bond}CD-CH{sub 3}, and CH{sub 2}{double bond}CH-CH{sub 3} was studied over Sb{sub 6}O{sub 13}, SnO{sub 2}, and Sb-Sn mixed oxide catalysts. The results with {sup 13}CH{sub 2}{double bond}CH-CH{sub 3} and CH{sub 2}{double bond}CH-CD{sub 3} were consistent with a {pi}-allyl intermediate. The isotope effect for allylic hydrogen abstraction was 1/0.55 (k{sub H}/k{sub D}) over the Sb-Sn oxide catalysts, indicating that this is the slowest step in the formation of acrolein as with other catalyst systems. The oxidation of CHD{double bond}CH-CH{sub 3} did not exhibit a marked isotope effect for the second hydrogen abstraction. This is inconsistent with a fast {pi}-allyl to {sigma}-allyl equilibration process or the irreversible {pi}-allyl to {sigma}-allyl conversion observed over other metal oxide catalysts. The absence of an isotope effect is similar to oxidations over rhodium. The roles of Sn and Sb ions in the oxidation are also discussed.

  7. Selective extraction of metals from mixed oxide matrixes using choline-based ionic liquids.

    PubMed

    Abbott, Andrew P; Capper, Glen; Davies, David L; Rasheed, Raymond K; Shikotra, Pragna

    2005-09-19

    The solubility of a range of metal oxides in a eutectic mixture of urea/choline chloride is quantified, and it is shown that the dissolved metals can be reclaimed from a mixed metal oxide matrix using electrodeposition. PMID:16156600

  8. 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.

  9. Rational synthesis of multifunctional mixed metal oxides by hydrothermal techniques

    NASA Astrophysics Data System (ADS)

    Stampler, Evan Scott

    Low temperature (<350°C) and pressure (<20 atm) hydrothermal methods have been developed for the synthesis of bismuth copper oxide chalcogenides, hexagonal rare-earth manganites, and silver delafossites with mixed cations on the B-site. These materials are of particular interest because they combine multiple functional properties, such as transparency and conductivity, or magnetism and ferroelectricity, in a single-phase material, thus enabling innovative technological applications. Phase-pure products were achieved by the appropriate combination of starting reagents, pH, and reaction temperature to control the solubility of the reactants. Phase-pure BiCuOS and BiCuOSe have been synthesized in high yield by a single-step hydrothermal reaction at low temperature (250°C) and pressure (< 20 atm). A reaction temperature of 250°C was sufficiently high to solubilize both Bi2O3 ([Bi3+] ≈ 10 -3 M) and Cu2O ([Cu+] ≈ 10-4 M) and stabilize monovalent copper species in solution, yet remains low enough to prevent the oxidation of sulfide and selenide. BiCuOS (Eg = 1.09 eV) and BiCuOSe (Eg = 0.75 eV) have smaller band gaps compared to the p-type transparent conductor LaCuOS (Eg = 3.1 eV) but have significantly higher room temperature conductivities (sigma ≈ 0.08 S cm-1 and 3.3 S cm-1, respectively). The high molar solubility of Mn2O3 ([Mn 3+] ≈ 10-3 M) and the slightly amphoteric character of the late rare-earth sesquioxides were exploited in the hydrothermal synthesis of rare-earth manganites, LnMnO3 (Ln=Ho-Lu and Y). While alkaline conditions were necessary for the solubilization of manganese, a reaction temperature approximately 50°C above the transition temperature of the respective rare-earth trihydroxide (100-300°C) accelerated the transition to the more reactive and soluble rare-earth oxide hydroxide and the subsequent reaction to yield the LnMnO3 phase. The high solubility of Ag2O, [Ag+] ≈ 10 -2.5 M, enabled the synthesis of two new silver delafossite

  10. 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...

  11. Fabrication of non-fertile and evolutionary mixed oxide fuels

    SciTech Connect

    Ramsey, K.B.; Chidester, D.M.

    1996-10-01

    Non-fertile and evolutionary mixed oxide (EMOX) fuels for light water reactors have been fabricated using the solid-state reaction method. Specifically, the non-fertile fuel form fabricated for this study was a PuO{sub 2}-ZrO{sub 2}-CaO-Er{sub 2}O{sub 3}composition. Weapons-grade plutonium served as the source of PuO{sub 2}. The non-fertile fuel offers the key advantage of the {open_quotes}deep burn{close_quotes} capability for a once-through cycle. The non-fertile fuel achieves this performance through the absence of uranium, which breeds plutonium, in the fuel composition. An EMOX fuel form with a composition of PuO{sub 2}-UO{sub 2}-ZrO{sub 2}-CaO was also fabricated using weapons-grade plutonium and depleted uranium. The EMOX fuel concept allows for greater plutonium destruction as compared to standard MOX fuel and provides a licensing path forward towards eventual implementation of non-fertile fuels in light water reactors. This paper summarizes the ongoing activities and past accomplishments for the fabrication of non-fertile and EMOX fuel pellets. 2 figs.

  12. 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}.

  13. 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.

  14. 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.

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

    DOE PAGES

    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

  16. General synthesis of multi-shelled mixed metal oxide hollow spheres with superior lithium storage properties.

    PubMed

    Zhang, Genqiang; Lou, Xiong Wen David

    2014-08-18

    Complex hollow structures of transition metal oxides, especially mixed metal oxides, could be promising for different applications such as lithium ion batteries. However, it remains a great challenge to fabricate well-defined hollow spheres with multiple shells for mixed transition metal oxides. Herein, we have developed a new "penetration-solidification-annealing" strategy which can realize the synthesis of various mixed metal oxide multi-shelled hollow spheres. Importantly, it is found that multi-shelled hollow spheres possess impressive lithium storage properties with both high specific capacity and excellent cycling stability. Specifically, the carbon-coated CoMn2O4 triple-shelled hollow spheres exhibit a specific capacity of 726.7 mA h g(-1) and a nearly 100 % capacity retention after 200 cycles. The present general strategy could represent a milestone in design and synthesis of mixed metal oxide complex hollow spheres and their promising uses in different areas.

  17. General synthesis of multi-shelled mixed metal oxide hollow spheres with superior lithium storage properties.

    PubMed

    Zhang, Genqiang; Lou, Xiong Wen David

    2014-08-18

    Complex hollow structures of transition metal oxides, especially mixed metal oxides, could be promising for different applications such as lithium ion batteries. However, it remains a great challenge to fabricate well-defined hollow spheres with multiple shells for mixed transition metal oxides. Herein, we have developed a new "penetration-solidification-annealing" strategy which can realize the synthesis of various mixed metal oxide multi-shelled hollow spheres. Importantly, it is found that multi-shelled hollow spheres possess impressive lithium storage properties with both high specific capacity and excellent cycling stability. Specifically, the carbon-coated CoMn2O4 triple-shelled hollow spheres exhibit a specific capacity of 726.7 mA h g(-1) and a nearly 100 % capacity retention after 200 cycles. The present general strategy could represent a milestone in design and synthesis of mixed metal oxide complex hollow spheres and their promising uses in different areas. PMID:24962932

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

    DOE PAGES

    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.

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

    DOEpatents

    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.

  20. 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.

  1. Leaching of pyrite by acidophilic heterotrophic iron-oxidizing bacteria in pure and mixed cultures

    SciTech Connect

    Bacelar-Nicolau, P.; Johnson, D.B.

    1999-02-01

    Seven strains of heterotrophic iron-oxidizing acidophilic bacteria were examined to determine their abilities to promote oxidative dissolution of pyrite (FeS{sub 2}) when they were grown in pure cultures and in mixed cultures with sulfur-oxidizing Thiobacillus spp. Only one of the isolates (strain T-24) oxidized pyrite when it was grown in pyrite-basal salts medium. However, when pyrite-containing cultures were supplemented with 0.02% (wt/vol) yeast extract, most of the isolates oxidized pyrite, and one (strain T-24) promoted rates of mineral dissolution similar to the rates observed with the iron-oxidizing autotroph Thiobacillus ferroxidans. Pyrite oxidation by another isolate (strain T-21) occurred in cultures containing between 0.005 and 0.05% (wt/vol) yeast extract but was completely inhibited in cultures containing 0.5% yeast extract. Ferrous iron was also needed for mineral dissolution by the iron-oxidizing heterotrophs, indicating that these organisms oxidize pyrite via the indirect mechanism. Mixed cultures of three isolates (strains T-21, T-232, and T-24) and the sulfur-oxidizing autotroph Thiobacillus thiooxidans promoted pyrite dissolution; since neither strains T-21 and T-23 nor T. thiooxidans could oxidize this mineral in yeast extract-free media, this was a novel example of bacterial synergism. Mixed cultures of strains T-21 and T-23 and the sulfur-oxidizing mixotroph Thiobacillus acidophilus also oxidized pyrite but to a lesser extent than did mixed cultures containing T. thiooxidans. Pyrite leaching by strain T -23 grown in an organic compound-rich medium and incubated either shaken or unshaken was also assessed. The potential environmental significance of iron-oxidizing heterotrophs in accelerating pyrite oxidation is discussed.

  2. 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.

  3. 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.

  4. 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.

  5. 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

  6. 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.

  7. Efficient powder blending in support of plutonium conversion for mixed oxide fuel

    SciTech Connect

    Dennison, D.K.; Brucker, J.P.; Martinez, H.E.

    1999-06-07

    This paper describes a unique system that is used to mix and blend multiple batches of plutonium oxide powder of various consistencies into an equivalent number of identical and homogeneously mixed batches. This system is being designed and built to support the Advanced Recovery and Integrated Extraction System (ARIES) at the Los Alamos TA-55 Plutonium Facility. The ARIES program demonstrates dismantlement of nuclear pits, retrieval of the plutonium components, and conversion of the plutonium into an oxide for eventual use in mixed oxide (MOX) fuel for nuclear reactors. The purpose of this powder blending work is to assure that ARIES oxide is converted into an unclassified homogeneous mixture and that consistent feed material is available for MOX fuel assembly. This blending system is being assembled in a selected glovebox a TA-55 using an LANL designed split/combine apparatus, a commercial Turbula blending unit, and several additional supporting hardware components.

  8. 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.

  9. Direct chemical oxidation of hazardous and mixed wastes

    SciTech Connect

    Cooper, J.F.; Wang, F.; Farmer, J.

    1995-04-11

    Direct Chemical Oxidation (DCO) refers to the use of continuously-regenerated peroxydisulfate (with possible hydrogen peroxide supplements) to effect total destruction of organic wastes in aqueous media. The process does not involve toxic catalysts or the cogeneration of secondary wastes. Peroxydisulfate (S{sub 2}O{sub 8}{sup -2}) is one the strongest known chemical oxidants. It is routinely used in laboratory total carbon analyzers--uncatalyzed at 100{degrees}C, or catalyzed by UV, platinum or dissolved transition metal ions--and detects by oxidative destruction to 0.01 ppm levels. We report: (1) development of a waste treatment approach grounded in industrial electrolysis practice and in reaction rate data for Pt-initiated S{sub 2}O{sub 8}{sup -2} oxidation at 100{degrees}C; (2) tests of an electrochemical cell generating 1.5 N peroxydisulfate solutions; (3) lower-limit rate data for destruction of surrogates for chemical warfare agents and compounds with functional groups resisting oxidation; and (4) destruction of a Dowex{reg_sign} ion exchange resin, such as used in nuclear processing. This technique is particularly suited for applications in analytical laboratories or in manufacturing industries where the waste generation is low in volume, highly toxic or fugitive, or changing. The process may be tailored for destruction of very small to bulk quantities of chemical warfare agents.

  10. 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

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

    DOE PAGES

    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

  12. 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.

  13. 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

  14. 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.

  15. 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.

  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. 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.

  18. Effect of standing transverse acoustic oscillations on fuel-oxidant mixing in cylindrical combustion chambers

    NASA Technical Reports Server (NTRS)

    Mickelsen, William R

    1957-01-01

    Vapor fuel-oxidant mixing is analyzed for standing transverse acoustic fields simulating those existing in screeching or screaming combustors. The additional mixing due to the acoustic field is shown to be a function of sound pressure and frequency, stream velocity, and turbulence. The effects of these parameters are shown graphically for a realistic range of combustor conditions. The fuel-oxidant ratio at various combustor stations is shown to have a cyclic fluctuation which is in phase with the pressure fluctuations. Possible mechanisms contributing to screech and scream are discussed.

  19. 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.

  20. 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.

  1. 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.

  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. Screening study of mixed transition-metal oxides for use as cathodes in thermal batteries

    SciTech Connect

    Guidotti, R.A.; Reinhardt, F.W.

    1996-05-01

    Over 100 candidates were examined, including commercial materials and many that were synthesized in house. The mixed oxides were based on Ti, V, Nb, Cr, Mo, W, Mn, Fe, Co, Ni, and Cu doped with other transition metals. A number of individual (single-metal) oxides were included for comparison. The candidates were tested in single cells with Li(Si) anodes and separators based on LiCl-KCl eutectic. Screening was done under constant-current conditions at current densities of 125 me/cm{sup 2} and, to a lesser extent, 50 me/cm{sup 2} at 500 C. Relative performance and limitations of the oxide cathodes are discussed.

  4. Synthesis and catalytic properties of mesoporous, bifunctional, gallium-niobium mixed oxides.

    PubMed

    Deshmane, Chinmay A; Jasinski, Jacek B; Ratnasamy, Paul; Carreon, Moises A

    2010-09-14

    Thermally stable mesoporous Ga-Nb mixed oxides, active in both acid-catalysed and redox reactions have been synthesized via self-assembly hydrothermal assisted approach. Methyl oleate, a major component of biodiesels, undergoes double bond and skeletal isomerisation as well as dehydrogenation over these novel mesophases.

  5. 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.

  6. 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.

  7. Electrospun mixed oxide photocatalysts to decompose dyes in water

    NASA Astrophysics Data System (ADS)

    Divya, Sherlyn

    In this work, four catalysts have been studied for their photocatalytic efficiency by testing each with methylene blue dye solution. Three catalysts were synthesized by the electrospinning method and then compared with the fourth commercially available catalyst for their photocatalytic activity. The basic metal oxide studied was titanium dioxide. Nanocomposite mats of pure titania, copper doped titania and copper doped degussa P25 titania, were synthesized using the electrospinning method. The pure titania and copper doped titania nanocomposites possessed the anatase phase which was obtained by annealing the as-spun nanocomposites at 4500C. All the catalysts were analyzed for their photocatalytic activity both under ultra-violet light and under visible light. The aim of this work was to synthesize titania photocatalysts, demonstrate their photocatalytic activity with methylene blue solution under UV-light and visible light and compare their activities with the commercial titanium dioxide (degussa P25). It is important to synthesize visible light active photocatalysts as these could be activated under a wide spectrum of natural sunlight unlike the degussa titanium dioxide. Doping was incorporated in order to narrow the band gap energy of the photocatalyst for achieving higher efficiency especially under visible light irradiation. The morphology and size of the synthesized photocatalysts were studied by characterizing them with Scanning Electron Microscopy, Energy Dispersive X-Ray Spectroscopy, Transmission Electron Microscopy and X-Ray Diffraction. The photocatalytic activity tests were carried out using UV-Vis Spectroscopy. It was found that the electrospun pure titania and copper doped titania fibers were activated under the visible light spectrum unlike the degussa titanium dioxide. The copper doped titania provided to be the most efficient photocatalyst under visible light radiation and the importance of this finding can be extended for treating industrial

  8. Role of mixing on microwave-enhanced advanced oxidation process in treating sewage sludge.

    PubMed

    Kenge, Anju A; Liao, Ping H; Lo, Kwang V

    2008-10-01

    The microwave enhanced advanced oxidation process (MW/H2O2-AOP) was used for the release of nutrients and the disintegration of suspended solids from both anaerobic sludge and aerobic sludge. The purpose of this study was to determine the effects of mixing on the performance of the process, in terms of soluble ammonia, orthophosphate and soluble chemical oxygen demands. Experiments were conducted on sludge samples with various total solids concentrations (1.1-3.7%) and hydrogen peroxide dosage (1% per 1% of total solids) at 80 degrees C of microwave temperature and five minutes of heating time. The results indicated that mixing affected solids disintegration and nutrient solubilization of sewage sludge, regardless of the sludge used, anaerobic or aerobic. However, the effects of mixing on the MW/H2O2-AOP were dependent on the total solids concentration of the sludge. A paired t-test was performed on data for aerobic sludge: at 2.9% of total solids (TS), the difference for solubilization of nutrients and solids disintegration was statistically significant at a 95% confidence level between mixing and non-mixing samples. At a lower TS of 1.7% only soluble chemical oxygen demand showed significant difference between mixing and non-mixing. The results suggest that, for sludge with higher solids content, the MW/H2O2-AOP can be more effective if a mixing device is implemented.

  9. Bimetallic bonding and mixed oxide formation in the Ga-Pd-CeO2 system

    NASA Astrophysics Data System (ADS)

    Skála, Tomáš; Tsud, Nataliya; Prince, Kevin C.; Matolín, Vladimír

    2011-08-01

    The interaction of gallium and palladium with 2 nm CeO2(111) layers grown on Cu(111) was studied by core level photoelectron spectroscopy and resonant valence band spectroscopy. Palladium alone interacted weakly with ceria layers. Gallium deposited on cerium dioxide formed a mixed Ga2O3-Ce2O3 oxide of 1:1 stoichiometry (cerium gallate CeGaO3), with both metals in the M3+ oxidation state. Increasing Ga coverages led to the formation of lower oxidation states, i.e., Ga1+ in Ga2O oxide and metallic Ga0. Palladium deposited onto this complex system interacted with gallium leading to a breakage of Ga-ceria bonds, a decrease of the oxidation state of gallium, and formation of a Ga-Pd intermetallic alloy in which all components (CeO2, CeGaO3, Ga2O, Ga-Pd, and Pd) are in equilibrium.

  10. The Chemical Capacitance as a Fingerprint of Defect Chemistry in Mixed Conducting Oxides.

    PubMed

    Fleig, Juergen; Schmid, Alexander; Rupp, Ghislain M; Slouka, Christoph; Navickas, Edvinas; Andrejs, Lukas; Hutter, Herbert; Volgger, Lukas; Nenning, Andreas

    2016-01-01

    The oxygen stoichiometry of mixed conducting oxides depends on the oxygen chemical potential and thus on the oxygen partial pressure in the gas phase. Also voltages may change the local oxygen stoichiometry and the amount to which such changes take place is quantified by the chemical capacitance of the sample. Impedance spectroscopy can be used to probe this chemical capacitance. Impedance measurements on different oxides ((La,Sr)FeO3-δ = LSF, Sr(Ti,Fe)O3-δ = STF, and Pb(Zr,Ti)O3 = PZT) are presented, and demonstrate how the chemical capacitance may affect impedance spectra in different types of electrochemical cells. A quantitative analysis of the spectra is based on generalized equivalent circuits developed for mixed conducting oxides by J. Jamnik and J. Maier. It is discussed how defect chemical information can be deduced from the chemical capacitance. PMID:27640378

  11. The Chemical Capacitance as a Fingerprint of Defect Chemistry in Mixed Conducting Oxides.

    PubMed

    Fleig, Juergen; Schmid, Alexander; Rupp, Ghislain M; Slouka, Christoph; Navickas, Edvinas; Andrejs, Lukas; Hutter, Herbert; Volgger, Lukas; Nenning, Andreas

    2016-01-01

    The oxygen stoichiometry of mixed conducting oxides depends on the oxygen chemical potential and thus on the oxygen partial pressure in the gas phase. Also voltages may change the local oxygen stoichiometry and the amount to which such changes take place is quantified by the chemical capacitance of the sample. Impedance spectroscopy can be used to probe this chemical capacitance. Impedance measurements on different oxides ((La,Sr)FeO3-δ = LSF, Sr(Ti,Fe)O3-δ = STF, and Pb(Zr,Ti)O3 = PZT) are presented, and demonstrate how the chemical capacitance may affect impedance spectra in different types of electrochemical cells. A quantitative analysis of the spectra is based on generalized equivalent circuits developed for mixed conducting oxides by J. Jamnik and J. Maier. It is discussed how defect chemical information can be deduced from the chemical capacitance.

  12. 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

  13. 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.

  14. 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.

  15. Photo-oxidation of organic compounds in liquid low-level mixed wastes at the INEL

    SciTech Connect

    Gering, K.L.; Schwendiman, G.L.

    1996-08-01

    A bench-scale oxidation apparatus is implemented to study the effectiveness of using an artificial ultraviolet source, a 175-watt medium pressure mercury vapor lamp, to enhance the destruction of organic contaminants in water with chemical oxidants. The waste streams used in this study are samples or surrogates of mixed wastes at the Idaho National Engineering Laboratory. The contaminants that are investigated include methylene chloride, 1,1,1-trichlorethane, 1, 1-dichlororethane, acetone, 2-propanol, and ethylenediamine tetraacetic acid. We focus on H{sub 2}O{sub 2}-based oxidizers for our treatment scheme, which include the UV/H{sub 2}O{sub 2} system, the dark Fenton system (H{sub 2}O{sub 2}/Fe{sup 2+}), and the photo- assisted Fenton system (UV/H{sub 2}O{sub 2}/Fe{sup 3+}) is used in particular. Variables include concentration of the chemical oxidizer, concentration of the organic contaminant, and the elapsed reaction time. Results indicate that the photo-assisted Fenton system provides the best overall performance of the oxidizing systems listed above, where decreases in concentrations of methylene chloride, 1,1,1- trichloroethane, 1,1-dichlororethane, 2-propanol, and ethylenediamine tetraacetic acid were seen. However, UV-oxidation treatment provided no measurable benefit for a mixed waste containing acetone in the presence of 2-propanol.

  16. 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.

  17. 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

  18. 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.

  19. 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.

  20. 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.

  1. 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.

  2. 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.

  3. Thermal Processing and Microwave Processing of Mixed-Oxide Thin Films

    NASA Astrophysics Data System (ADS)

    Gadre, Mandar

    2011-12-01

    Amorphous oxide semiconductors are promising new materials for various optoelectronic applications. In this study, improved electrical and optical properties upon thermal and microwave processing of mixed-oxide semiconductors are reported. First, arsenic-doped silicon was used as a model system to understand susceptor-assisted microwave annealing. Mixed oxide semiconductor films of indium zinc oxide (IZO) and indium gallium zinc oxide (IGZO) were deposited by room-temperature RF sputtering on flexible polymer substrates. Thermal annealing in different environments---air, vacuum and oxygen was done. Electrical and optical characterization was carried out before and after annealing. The degree of reversal in the degradation in electrical properties of the thin films upon annealing in oxygen was assessed by subjecting samples to subsequent vacuum anneals. To further increase the conductivity of the IGZO films, Ag layers of various thicknesses were embedded between two IGZO layers. Optical performance of the multilayer structures was improved by susceptor-assisted microwave annealing and furnace-annealing in oxygen environment without compromising on their electrical conductivity. The post-processing of the films in different environments was used to develop an understanding of mechanisms of carrier generation, transport and optical absorption. This study establishes IGZO as a viable transparent conductor, which can be deposited at room-temperature and processed by thermal and microwave annealing to improve electrical and optical performance for applications in flexible electronics and optoelectronics.

  4. 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.

  5. An XPS, TEM, and TPD study of the oxidation and ammoxidation of propene using mixed Fe-Sb oxide catalysts

    SciTech Connect

    Allen, M.D.; Poulston, S.; Bowker, M.

    1996-09-15

    Two mixed Fe-Sb oxide catalysts were investigated for the selective oxidation of propene to acrolein and the ammoxidation of propene in the presence of ammonia to acrylonitrile. The techniques used were chiefly X-ray photoelectron spectroscopy (XPS), temperature deprogrammed desorption (TPD), X-ray diffraction, and transmission electron microscopy. After propene dosing TPD experiments were carried out in the absence of gas phase oxygen utilising lattice oxygen for oxidation. The samples contained a 1:1 and 2:1 atomic ratio of Sb:Fe (referred to as SbFe and Sb2Fe, respectively). XPS data indicate that the surface has an antimony oxide enriched selvedge which favours the selective ammoxidation of propene. The Sb enriched surface of SbFe was found to be highly reducible in low pressures of ammonia, yielding a metallic antimony overlayer. Subsequent thermal desorption of this metal coating revealed a surface with an increased iron (III) oxide content which was not so easily reduced and found to be of a lower selectivity to partial ammoxidation products. The Sb2Fe sample was more stable towards reduction. 28 refs., 14 figs., 1 tab.

  6. 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.

  7. 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

  8. Wet Chemical Oxidation and Stabilization of Mixed and Low Level Organic Wastes

    SciTech Connect

    Pierce, R.A.; Livingston, R.R.; Burge, D.A.; Ramsey, W.G.

    1998-03-01

    Mixed acid oxidation is a non-incineration process capable of destroying organic compounds, including papers, plastics, resins, and oils, at moderate temperatures and pressures. The technology, developed at the Savannah River Site, uses a mixture of an oxidant (nitric acid) and a carrier acid (phosphoric acid). The carrier acid acts as a holding medium which allows appreciable amounts of the oxidant to be retained in solution at atmospheric pressure and at the temperatures needed for oxidation. The phosphoric acid also provides the raw materials for making a final waste which contains the metal contaminants from the waste stream. Savannah River has designed, built, and started up a 40-liter pilot reaction vessel to demonstrate the process and its sub-systems on a larger scale than earlier testing. The unit has been demonstrated and has provided important data on the operation of the oxidation and acid recovery systems. Specific results will be presented on oxidation conditions, acid recovery efficiency, chloride removal, metal retention, and process monitoring. Additional studies have been conducted with a smaller vessel in a radioactive hood. Testing with plutonium-bearing waste simulants was performed to make preliminary predictions about the behavior of plutonium in the process. Samples of the remaining phosphoric acid from these tests has been converted to two separate final forms for analysis. Results will be presented on plutonium fractionation during the oxidation process and waste form stability.

  9. 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.

  10. Selectivity of layered double hydroxides and their derivative mixed metal oxides as sorbents of hydrogen sulfide.

    PubMed

    Othman, Mohamed A; Zahid, Waleed M; Abasaeed, Ahmed E

    2013-06-15

    In the context of finding high efficient sorbent materials for removing hydrogen sulfide (H2S) from air stream, a screening study was performed to find the best combination of metals for the synthesis of layered double hydroxides (LDHs) and their derivative mixed metal oxides. Based on selectivity of 998 natural mineral species of sulfur-containing compounds, Cu(2+), Ni(2+) and Zn(2+) were selected as divalent metals, and Fe(3+), Al(3+) and Cr(3+) as trivalent metals to synthesis the LDHs sorbents. 10 LDHs materials and their calcined mixed metal oxides, Ni(0.66)Al(0.34), Cu(0.35)Ni(0.32)Al(0.33), Zn(0.66)Al(0.34), Cu(0.36)Zn(0.32)Al(0.32), Ni(0.64)Fe(0.36), Cu(0.35)Ni(0.31)Fe(0.34), Ni(0.66)Cr(0.34), Cu(0.35)Ni(0.31)Cr(0.34), Zn(0.66)Cr(0.34), Cu(0.33)Zn(0.32)Cr(0.35) were synthesized, characterized chemically and physically, and then tested using breakthrough test to determine their sulfur uptake. Ni(0.64)Fe(0.36) mixed metal oxides was found to have the best uptake of hydrogen sulfide (136 mg H₂S/g). Regeneration of spent Ni(0.64)Fe(0.36) mixed metal oxides was studied using two different mixture solutions, NaCl/NaOH and acetate-buffer/NaCl/NaOH. The latter mixture successfully desorbed the sulfur from the Ni0.64Fe0.36 sorbent for 2 cycles of regeneration/sorption.

  11. 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.

  12. Simulated physical inventory verification exercise at a mixed-oxide fuel fabrication facility

    SciTech Connect

    Reilly, D.; Augustson, R.

    1985-01-01

    A physical inventory verification (PIV) was simulated at a mixed-oxide fuel fabrication facility. Safeguards inspectors from the International Atomic Energy Agency (IAEA) conducted the PIV exercise to test inspection procedures under ''realistic but relaxed'' conditions. Nondestructive assay instrumentation was used to verify the plutonium content of samples covering the range of material types from input powders to final fuel assemblies. This paper describes the activities included in the exercise and discusses the results obtained. 5 refs., 1 fig., 6 tabs.

  13. Mineral and iron oxidation at low temperatures by pure and mixed cultures of acidophilic microorganisms.

    PubMed

    Dopson, Mark; Halinen, Anna-Kaisa; Rahunen, Nelli; Ozkaya, Bestamin; Sahinkaya, Erkan; Kaksonen, Anna H; Lindström, E Börje; Puhakka, Jaakko A

    2007-08-01

    An enrichment culture from a boreal sulfide mine environment containing a low-grade polymetallic ore was tested in column bioreactors for simulation of low temperature heap leaching. PCR-denaturing gradient gel electrophoresis and 16S rRNA gene sequencing revealed the enrichment culture contained an Acidithiobacillus ferrooxidans strain with high 16S rRNA gene similarity to the psychrotolerant strain SS3 and a mesophilic Leptospirillum ferrooxidans strain. As the mixed culture contained a strain that was within a clade with SS3, we used the SS3 pure culture to compare leaching rates with the At. ferrooxidans type strain in stirred tank reactors for mineral sulfide dissolution at various temperatures. The psychrotolerant strain SS3 catalyzed pyrite, pyrite/arsenopyrite, and chalcopyrite concentrate leaching. The rates were lower at 5 degrees C than at 30 degrees C, despite that all the available iron was in the oxidized form in the presence of At. ferrooxidans SS3. This suggests that although efficient At. ferrooxidans SS3 mediated biological oxidation of ferrous iron occurred, chemical oxidation of the sulfide minerals by ferric iron was rate limiting. In the column reactors, the leaching rates were much less affected by low temperatures than in the stirred tank reactors. A factor for the relatively high rates of mineral oxidation at 7 degrees C is that ferric iron remained in the soluble phase whereas, at 21 degrees C the ferric iron precipitated. Temperature gradient analysis of ferrous iron oxidation by this enrichment culture demonstrated two temperature optima for ferrous iron oxidation and that the mixed culture was capable of ferrous iron oxidation at 5 degrees C.

  14. 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.

  15. 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.

  16. 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.

  17. OH-initiated heterogeneous oxidation of internally-mixed squalane and secondary organic aerosol.

    PubMed

    Kolesar, Katheryn R; Buffaloe, Gina; Wilson, Kevin R; Cappa, Christopher D

    2014-03-18

    Recent work has established that secondary organic aerosol (SOA) can exist as an amorphous solid, leading to various suggestions that the addition of SOA coatings to existing particles will decrease the reactivity of those particles toward common atmospheric oxidants. Experimental evidence suggests that O3 is unable to physically diffuse through an exterior semisolid or solid layer thus inhibiting reaction with the core. The extent to which this suppression in reactivity occurs for OH has not been established, nor has this been demonstrated specifically for SOA. Here, measurements of the influence of adding a coating of α-pinene+O3 SOA onto squalane particles on the OH-initiated heterogeneous oxidation rate are reported. The chemical composition of the oxidized internally mixed particles was monitored online using a vacuum ultraviolet-aerosol mass spectrometer. Variations in the squalane oxidation rate with particle composition were quantified by measurement of the effective uptake coefficient, γeff, which is the loss rate of a species relative to the oxidant-particle collision rate. Instead of decreasing, the measured γeff increased continuously as the SOA coating thickness increased, by a factor of ∼2 for a SOA coating thickness of 42 nm (corresponding to ca. two-thirds of the particle mass). These results indicate that heterogeneous oxidation of ambient aerosol by OH radicals is not inhibited by SOA coatings, and further that condensed phase chemical pathways and rates in organic particles depend importantly on composition.

  18. 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.

  19. Oxidative potential of smoke from burning wood and mixed biomass fuels.

    PubMed

    Kurmi, O P; Dunster, C; Ayres, J G; Kelly, F J

    2013-10-01

    More than half the world's population still rely on burning biomass fuels to heat and light their homes and cook food. Household air pollution, a common component of which is inhalable particulate matter (PM), emitted from biomass burning is associated with increased vulnerability to respiratory infection and an enhanced risk of developing chronic obstructive pulmonary disease. In the light of an emerging hypothesis linking chronic PM exposure during childhood and increased vulnerability to respiratory diseases in adulthood, in a chain of events involving oxidative stress, reduced immunity and subsequent infection, the aim of this study was to characterise the oxidative potential (OP) of PM collected during the burning of wood and mixed biomass, whilst cooking food in the Kathmandu Valley, Nepal. Our assessments were based on the capacity of the particles to deplete the physiologically relevant antioxidants from a validated, synthetic respiratory tract lining fluid (RTLF). Incubation of mixed biomass and wood smoke particles suspensions with the synthetic RTLF for 4 h resulted in a mean loss of ascorbate of 64.76 ± 16.83% and 83.37 ± 14.12% at 50 μg/ml, respectively. Reduced glutathione was depleted by 49.29 ± 15.22% in mixed biomass and 65.33 ± 13.01% in wood smoke particles under the same conditions. Co-incubation with the transition metal chelator diethylenetriaminepentaacetate did not inhibit the rate of ascorbate oxidation, indicating a negligible contribution by redox-active metals in these samples. The capacity of biomass smoke particles to elicit oxidative stress certainly has the potential to contribute towards negative health impacts associated with traditional domestic fuels in the developing world. PMID:23926954

  20. Kinetic study of the oxidation of n-butane on vanadium oxide supported on Al/Mg mixed oxide

    SciTech Connect

    Dejoz, A.; Vazquez, I.; Nieto, J.M.L.; Melo, F.

    1997-07-01

    The reaction kinetics of the oxidative dehydrogenation (ODH) of n-butane over vanadia supported on a heat-treated Mg/Al hydrotalcite (37.3 wt % of V{sub 2}O{sub 5}) was investigated by both linear and nonlinear regression techniques. A reaction network including the formation of butenes (1-, 2-cis-, and 2-trans-butene), butadiene, and carbon oxides by parallel and consecutive reactions, at low and high n-butane conversions, has been proposed. Langmuir-Hinshelwood (LH) models can be used as suitable models which allows reproduction of the global kinetic behavior, although differences between oxydehydrogenation and deep oxidation reactions have been observed. Thus, the formation of oxydehydrogenation products can be described by a LH equation considering a dissociative adsorption of oxygen while the formation of carbon oxides is described by a LH equation with a nondissociative adsorption of oxygen. Two different mechanisms operate on the catalyst: (i) a redox mechanism responsible of the formation of olefins and diolefins and associated to vanadium species, which is initiated by a hydrogen abstraction; (ii) a radical mechanism responsible of the formation of carbon oxides from n-butane and butenes and associated to vanadium-free sites of the support. On the other hand, the selectivity to oxydehydrogenation products increases with the reaction temperature. This catalytic performance can be explained taking into account the low reducibility of V{sup 5+}-sites and the higher apparent activation energies of the oxydehydrogenation reactions with respect to deep oxidation reactions.

  1. 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.

  2. Argonne National Laboratory`s photo-oxidation organic mixed waste treatment system - installation and startup testing

    SciTech Connect

    Shearer, T.L.; Nelson, R.A.; Torres, T.; Conner, C.; Wygmans, D.

    1997-09-01

    This paper describes the installation and startup testing of the Argonne National Laboratory (ANL-E) Photo-Oxidation Organic Mixed Waste Treatment System. This system will treat organic mixed (i.e., radioactive and hazardous) waste by oxidizing the organics to carbon dioxide and inorganic salts in an aqueous media. The residue will be treated in the existing radwaste evaporators. The system is installed in the Waste Management Facility at the ANL-E site in Argonne, Illinois. 1 fig.

  3. 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

  4. 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.

  5. Novel mixed-oxide ceramic for neutron multiplication and tritium generation

    NASA Astrophysics Data System (ADS)

    Sathiyamoorthy, Dakshinamoorthy; Ghanwat, S. J.; Tripathi, B. M.; Danani, Chandan

    2011-10-01

    Beryllium and lithium titanate (Li 2TiO 3), have limited use in blankets due to the swelling of beryllium and low thermal conductivity of Li 2TiO 3. A novel mixed oxide composite of beryllium oxide and lithium titanate (BeO-Li 2TiO 3) is proposed, which utilizes the high thermal conductivity of BeO and its favourable neutronics. Li 2TiO 3 was prepared using two different routes, one employing a solid-state reaction and the other through sol-gel route. The sintered BeO-Li 2TiO 3 is found to have no intermediate products and its thermal conductivity decreased from 36 to 14 W/m/K with the increase in temperature from 127 °C to 927 °C. The coefficient of thermal expansion (CTE) of BeO-Li 2TiO 3 is less than that of Li 2TiO 3. Thermodynamic calculations show that tritium cannot be trapped in BeO unless beryllium monotrioxide (BeOT) is formed. The merits of BeO are compared with beryllium metal and neutronic calculations on tritium production in this novel mixed oxide are also presented.

  6. 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.

  7. 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

  8. 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

  9. 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.

  10. 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.

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

    DOE PAGES

    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. Impact of conversion to mixed-oxide fuels on reactor structural components

    SciTech Connect

    Yahr, G.T.

    1997-04-01

    The use of mixed-oxide (MOX) fuel to replace conventional uranium fuel in commercial light-water power reactors will result in an increase in the neutron flux. The impact of the higher flux on the structural integrity of reactor structural components must be evaluated. This report briefly reviews the effects of radiation on the mechanical properties of metals. Aging degradation studies and reactor operating experience provide a basis for determining the areas where conversion to MOX fuels has the potential to impact the structural integrity of reactor components.

  13. 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.

  14. Defects and transport in mixed oxides. Progress report, October 1, 1993--December 20, 1994

    SciTech Connect

    Dieckmann, R.

    1994-12-20

    The PI of this research program came to Cornell University from Hannover (Germany) in July 1987. Beginning in Fall 1987 a new research group and a new research facilities were built up at Cornell. The program {open_quotes}Defects and Transport in Mixed Oxides{close_quotes} was started in July 1988. The last progress report for this program was written on September 30, 1993 and submitted to DOE with the last renewal proposal. Significant progress has been made in the areas of: (i) the nonstoichiometry of quasi-binary spinels, (ii) the cation tracer diffusion in oxide solid solutions of the type (Fe,Me){sub 3{minus}{delta}}O{sub 4}, (iii) the Monte-Carlo simulation of the cation diffusion in spinel solid solutions, (iv) interdiffusion measurements in the spinel solution (Fe,Mn){sub 3{minus}{delta}}O{sub 4}, and (v) defect-related properties of Co{sub 1{minus}{delta}}O.

  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. 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.

  17. 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.

  18. 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.

  19. 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.

  20. 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.

  1. Titanium-based mixed oxides from a series of titanium(IV) citrate complexes

    SciTech Connect

    Deng Yuanfu; Zhang Hualin; Hong Qiming; Weng Weizheng; Wan Huilin; Zhou Zhaohui

    2007-11-15

    The isostructural hexaaquatransition-metal/titanium citrate complexes (NH{sub 4}){sub 2}[M(H{sub 2}O){sub 6}][Ti(H{sub 2}cit){sub 3}]{sub 2}.6H{sub 2}O [M(II)=Mn 1, Fe 2, Co 3, Ni 4, Cu 5, and Zn 6] (H{sub 4}cit=citric acid), which were synthesized by reacting titanium(IV) citrate with divalent metal salts in the 1.0-3.5 pH range, adopt hydrogen-bonded chain motifs. The crystal structures feature three bidentate citrate anions that chelate to the titanium atom through their negatively charged {alpha}-alkoxy and {alpha}-carboxy oxygen atoms; the chelation is consistent with the large downfield shifts of {sup 13}C NMR for carbon atoms for complex 6. The thermal decomposition of the complexes furnishes mixed metal oxides. The main-group magnesium analog when heated at 600 deg. C yielded MgTi{sub 2}O{sub 5} that is of the pseudobrookite type; the particle size is approximately 30 nm. - Graphical abstract: A series of heterobimetallic titanium citrate complexes with novel dodecameric water clusters were isolated and used as molecular precursors in an attempt to the preparations of mixed oxides MTi{sub 2}O{sub 5}.

  2. 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.

  3. 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

  4. A versatile sol-gel synthesis route to metal-silicon mixed oxide nanocomposites that contain metal oxides as the major phase

    SciTech Connect

    Clapsaddle, B J; Sprehn, D W; Gash, A E; Satcher, J H; Simpson, R L

    2003-12-08

    The general synthesis of metal-silicon mixed oxide nanocomposite materials, including a variety of both main group and transition metals, in which the metal oxide is the major component is described. In a typical synthesis, the metal oxide precursor, MCl{sub x}{times}{sub y}H{sub 2}O (x=3-6, y=0-7), was mixed with the silica precursor, tetramethylorthosilicate (TMOS), in ethanol and gelled using an organic epoxide. The successful preparation of homogeneous, monolithic materials depended on the oxidation state of the metal as well as the epoxide chosen for gelation. The composition of the resulting materials was varied from M/Si=1-5 (mol/mol) by adjusting the amount of TMOS added to the initial metal oxide precursor solution. Supercritical processing of the gels in CO{sub 2} resulted in monolithic, porous aerogel nanocomposite materials with surface areas ranging from 100 - 800 m{sup 2}/g. The bulk materials are composed of metal oxide/silica particles that vary in size from 5 - 20 nm depending on the epoxide used for gelation. Metal oxide and silica dispersion throughout the bulk material is extremely uniform on the nanoscale. The versatility and control of the synthesis method will be discussed as well as the properties of the resulting metal-silicon mixed oxide nanocomposite materials.

  5. Study of sodium dodecyl sulfate-poly(propylene oxide) methacrylate mixed micelles.

    PubMed

    Bastiat, Guillaume; Grassl, Bruno; Khoukh, Abdel; François, Jeanne

    2004-07-01

    Sodium dodecyl sulfate (SDS)-poly(propylene oxide) methacrylate (PPOMA) (of molecular weight M(w) = 434 g x mol(-1)) mixtures have been studied using conductimetry, static light scattering, fluorescence spectroscopy, and 1H NMR. It has been shown that SDS and PPOMA form mixed micelles, and SDS and PPOMA aggregation numbers, N(ag SDS) and N(ag PPOMA), have been determined. Total aggregation numbers of the micelles (N(ag SDS) + N(ag PPOMA)) and those of SDS decrease upon increasing the weight ratio R = PPOMA/SDS. Localization of PPOMA inside the mixed micelles is considered (i) using 1H NMR to localize the methacrylate function at the hydrophobic core-water interface and (ii) by studying the SDS-PPO micellar system (whose M(w) = 400 g x mol(-1)). Both methods have indicated that the PPO chain of the macromonomer is localized at the SDS micelle surface. Models based on the theorical prediction of the critical micellar concentration of mixed micelles and structural model of swollen micelles are used to confirm the particular structure proposed for the SDS-PPOMA system, i.e., the micelle hydrophobic core is primarily composed of the C12 chains of the sodium dodecyl sulfate, the hydrophobic core-water interface is made up of the SDS polar heads as well as methacrylate functions of the PPOMA, the PPO chains of the macromonomer are adsorbed preferentially on the surface, i.e., on the polar heads of the SDS.

  6. 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.

  7. 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.

  8. 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.

  9. 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

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

    PubMed

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

    2014-01-01

    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.

  11. 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

  12. Mixed transition-metal oxides: design, synthesis, and energy-related applications.

    PubMed

    Yuan, Changzhou; Wu, Hao Bin; Xie, Yi; Lou, Xiong Wen David

    2014-02-01

    A promising family of mixed transition-metal oxides (MTMOs) (designated as Ax B3-x O4 ; A, B=Co, Ni, Zn, Mn, Fe, etc.) with stoichiometric or even non-stoichiometric compositions, typically in a spinel structure, has recently attracted increasing research interest worldwide. Benefiting from their remarkable electrochemical properties, these MTMOs will play significant roles for low-cost and environmentally friendly energy storage/conversion technologies. In this Review, we summarize recent research advances in the rational design and efficient synthesis of MTMOs with controlled shapes, sizes, compositions, and micro-/nanostructures, along with their applications as electrode materials for lithium-ion batteries and electrochemical capacitors, and efficient electrocatalysts for the oxygen reduction reaction in metal-air batteries and fuel cells. Some future trends and prospects to further develop advanced MTMOs for next-generation electrochemical energy storage/conversion systems are also presented.

  13. 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.

  14. A simple model for neutron radiography of uranium-plutonium mixed oxide fuel pins

    NASA Astrophysics Data System (ADS)

    Panakkal, J. P.; Ghosh, J. K.

    1988-04-01

    Neutron radiography has been used for monitoring plutonium enrichment in uranium-plutonium mixed oxide fuel pellets inside welded nuclear fuel pins by correlating the optical density of radiographs at the centre of the pellets and plutonium enrichment. Optical density data corresponding to different thickness of the pellets starting from the centre towards the periphery was generated by microdensitometer scanning of neutron radiographs of the experimental fuel pins. An attempt has been made to correlate the optical density at points corresponding to different thickness segments of the pellets and thermal neutron interaction probability (product of the total macroscopic neutron cross section and the distance traversed by the neutrons). Based on the experimental data generated, a simple model for transmission of neutrons through nuclear fuel pins has been evolved. Using this model, it is possible to predict the optical density of plutonium bearing fuel pins containing pellets of different composition or diameter in neutron radiographic investigations.

  15. 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.

  16. 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.

  17. The underwater coincidence counter (UWCC) for plutonium measurements in mixed oxide fuels

    SciTech Connect

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

    1998-12-31

    The use of fresh uranium-plutonium mixed oxide (MOX) fuel in light-water reactors (LWR) is increasing in Europe and Japan and it is necessary to verify the plutonium content in the fuel for international safeguards purposes. The UWCC is a new instrument that has been designed to operate underwater and nondestructively measure the plutonium in unirradiated MOX fuel assemblies. The UWCC can be quickly configured to measure either boiling-water reactor (BWR) or pressurized-water reactor (PWR) fuel assemblies. The plutonium loading per unit length is measured using the UWCC to precisions of less than 1% in a measurement time of 2 to 3 minutes. Initial calibrations of the UWCC were completed on measurements of MOX fuel in Mol, Belgium. The MCNP-REN Monte Carlo simulation code is being benchmarked to the calibration measurements to allow accurate simulations for extended calibrations of the UWCC.

  18. 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.

  19. 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.

  20. 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.

  1. 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.

  2. 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.

  3. Thorium-based mixed oxide fuel in a pressurized water reactor: A feasibility analysis with MCNP

    NASA Astrophysics Data System (ADS)

    Tucker, Lucas Powelson

    This dissertation investigates techniques for spent fuel monitoring, and assesses the feasibility of using a thorium-based mixed oxide fuel in a conventional pressurized water reactor for plutonium disposition. Both non-paralyzing and paralyzing dead-time calculations were performed for the Portable Spectroscopic Fast Neutron Probe (N-Probe), which can be used for spent fuel interrogation. Also, a Canberra 3He neutron detector's dead-time was estimated using a combination of subcritical assembly measurements and MCNP simulations. Next, a multitude of fission products were identified as candidates for burnup and spent fuel analysis of irradiated mixed oxide fuel. The best isotopes for these applications were identified by investigating half-life, photon energy, fission yield, branching ratios, production modes, thermal neutron absorption cross section and fuel matrix diffusivity. 132I and 97Nb were identified as good candidates for MOX fuel on-line burnup analysis. In the second, and most important, part of this work, the feasibility of utilizing ThMOX fuel in a pressurized water reactor (PWR) was first examined under steady-state, beginning of life conditions. Using a three-dimensional MCNP model of a Westinghouse-type 17x17 PWR, several fuel compositions and configurations of a one-third ThMOX core were compared to a 100% UO2 core. A blanket-type arrangement of 5.5 wt% PuO2 was determined to be the best candidate for further analysis. Next, the safety of the ThMOX configuration was evaluated through three cycles of burnup at several using the following metrics: axial and radial nuclear hot channel factors, moderator and fuel temperature coefficients, delayed neutron fraction, and shutdown margin. Additionally, the performance of the ThMOX configuration was assessed by tracking cycle length, plutonium destroyed, and fission product poison concentration.

  4. 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

  5. Highly efficient electrochemical responses on single crystalline ruthenium-vanadium mixed metal oxide nanowires.

    PubMed

    Chun, Sung Hee; Choi, Hyun-A; Kang, Minkyung; Koh, Moonjee; Lee, Nam-Suk; Lee, Sang Cheol; Lee, Minyung; Lee, Youngmi; Lee, Chongmok; Kim, Myung Hwa

    2013-09-11

    Highly efficient single crystalline ruthenium-vanadium mixed metal oxide (Ru1-xVxO2, 0≤x≤1) nanowires were prepared on a SiO2 substrate and a commercial Au microelectrode for the first time through a vapor-phase transport process by adjusting the mixing ratios of RuO2 and VO2 precursors. Single crystalline Ru1-xVxO2 nanowires show homogeneous solid-solution characteristics as well as the distinct feature of having remarkably narrow dimensional distributions. The electrochemical observations of a Ru1-xVxO2 (x=0.28 and 0.66)-decorated Au microelectrode using cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) demonstrate favorable charge-transfer kinetics of [Fe(CN)6]3-/4- and Ru(NH3)6(3+/2+) couples compared to that of a bare Au microelectrode. The catalytic activity of Ru1-xVxO2 for oxygen and H2O2 reduction at neutral pH increases as the fraction of vanadium increases within our experimental conditions, which might be useful in the area of biofuel cells and biosensors.

  6. Mixed fuel strategy for carbon deposition mitigation in solid oxide fuel cells at intermediate temperatures.

    PubMed

    Su, Chao; Chen, Yubo; Wang, Wei; Ran, Ran; Shao, Zongping; Diniz da Costa, João C; Liu, Shaomin

    2014-06-17

    In this study, we propose and experimentally verified that methane and formic acid mixed fuel can be employed to sustain solid oxide fuel cells (SOFCs) to deliver high power outputs at intermediate temperatures and simultaneously reduce the coke formation over the anode catalyst. In this SOFC system, methane itself was one part of the fuel, but it also played as the carrier gas to deliver the formic acid to reach the anode chamber. On the other hand, the products from the thermal decomposition of formic acid helped to reduce the carbon deposition from methane cracking. In order to clarify the reaction pathways for carbon formation and elimination occurring in the anode chamber during the SOFC operation, O2-TPO and SEM analysis were carried out together with the theoretical calculation. Electrochemical tests demonstrated that stable and high power output at an intermediate temperature range was well-maintained with a peak power density of 1061 mW cm(-2) at 750 °C. With the synergic functions provided by the mixed fuel, the SOFC was running for 3 days without any sign of cell performance decay. In sharp contrast, fuelled by pure methane and tested at similar conditions, the SOFC immediately failed after running for only 30 min due to significant carbon deposition. This work opens a new way for SOFC to conquer the annoying problem of carbon deposition just by properly selecting the fuel components to realize their synergic effects.

  7. 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).

  8. Mixed fuel strategy for carbon deposition mitigation in solid oxide fuel cells at intermediate temperatures.

    PubMed

    Su, Chao; Chen, Yubo; Wang, Wei; Ran, Ran; Shao, Zongping; Diniz da Costa, João C; Liu, Shaomin

    2014-06-17

    In this study, we propose and experimentally verified that methane and formic acid mixed fuel can be employed to sustain solid oxide fuel cells (SOFCs) to deliver high power outputs at intermediate temperatures and simultaneously reduce the coke formation over the anode catalyst. In this SOFC system, methane itself was one part of the fuel, but it also played as the carrier gas to deliver the formic acid to reach the anode chamber. On the other hand, the products from the thermal decomposition of formic acid helped to reduce the carbon deposition from methane cracking. In order to clarify the reaction pathways for carbon formation and elimination occurring in the anode chamber during the SOFC operation, O2-TPO and SEM analysis were carried out together with the theoretical calculation. Electrochemical tests demonstrated that stable and high power output at an intermediate temperature range was well-maintained with a peak power density of 1061 mW cm(-2) at 750 °C. With the synergic functions provided by the mixed fuel, the SOFC was running for 3 days without any sign of cell performance decay. In sharp contrast, fuelled by pure methane and tested at similar conditions, the SOFC immediately failed after running for only 30 min due to significant carbon deposition. This work opens a new way for SOFC to conquer the annoying problem of carbon deposition just by properly selecting the fuel components to realize their synergic effects. PMID:24856957

  9. 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.

  10. 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.

  11. 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.

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

    DOE PAGES

    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

  13. 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

  14. 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.

  15. Vapor phase hydrogenation of furfural over nickel mixed metal oxide catalysts derived from layered double hydroxides

    DOE PAGES

    Sulmonetti, Taylor P.; Pang, Simon H.; Claure, Micaela Taborga; Lee, Sungsik; Cullen, David A.; Agrawal, Pradeep K.; Jones, Christopher W.

    2016-03-09

    The hydrogenation of furfural is investigated over various reduced nickel mixed metal oxides derived from layered double hydroxides (LDHs) containing Ni-Mg-Al and Ni-Co-Al. Upon reduction, relatively large Ni(0) domains develop in the Ni-Mg-Al catalysts, whereas in the Ni-Co-Al catalysts smaller metal particles of Ni(0) and Co(0), potentially as alloys, are formed, as evidenced by XAS, XPS, STEM and EELS. All the reduced Ni catalysts display similar selectivities towards major hydrogenation products (furfuryl alcohol and tetrahydrofurfuryl alcohol), though the side products varied with the catalyst composition. The 1.1Ni-0.8Co-Al catalyst showed the greatest activity per titrated site when compared to the othermore » catalysts, with promising activity compared to related catalysts in the literature. In conclusion, the use of base metal catalysts for hydrogenation of furanic compounds may be a promising alternative to the well-studied precious metal catalysts for making biomass-derived chemicals if catalyst selectivity can be improved in future work by alloying or tuning metal-oxide support interactions.« less

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

    PubMed

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

    2012-07-01

    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(NO(3))(2)·6H(2)O, Zn(NO(3))(2), and Fe(NO(3))(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.

  17. 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.

  18. 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.

  19. 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

  20. 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.

  1. Arsenic removal using hydrous nanostructure iron(III)-titanium(IV) binary mixed oxide from aqueous solution.

    PubMed

    Gupta, Kaushik; Ghosh, Uday Chand

    2009-01-30

    The synthetic bimetal iron(III)-titanium(IV) oxide (NHITO) used was characterized as hydrous and nanostructured mixed oxide, respectively, by the Föurier transform infra red (FTIR), X-ray diffraction (XRD) pattern and the transmission electron microscopic (TEM) image analyses. Removal of As(III) and As(V) using the NHITO was studied at pH 7.0 (+/-0.1) with variation of contact time, solute concentration and temperature. The kinetic sorption data, in general, for As(III) described the pseudo-first order while that for As(V) described the pseudo-second order equation. The Langmuir isotherm described the equilibrium data (303 (+/-1.6)K) of fit was well with the Langmuir model. The Langmuir capacity (q(m), mg g(-1)) value of the material is 85.0 (+/-4.0) and 14.0 (+/-0.5), respectively, for the reduced and oxidized species. The sorption reactions on NHITO were found to be endothermic and spontaneous, and took place with increasing entropy. The energy (kJ mol(-1)) of sorption for As(III) and As(V) estimated, respectively, is 9.09 (+/-0.01) and 13.51 (+/-0.04). The sorption percentage reduction of As(V) was significant while that of As(III) was insignificant in presence of phosphate and sulfate. The fixed bed NHITO column (5.1 cm x 1.0 cm) sorption tests gave 3.0, 0.7 and 4.5L treated water (As content < or = 0.01 mg L(-1)) from separate As(III) and As(V) spiked (0.35+/-0.02 mg L(-1)) natural water samples and from high arsenic (0.11+/-0.01 mg L(-1)) ground water, respectively when inflow rate was (0.06 L h(-1)).

  2. Reduction of mixed Mn-Zr oxides: in situ XPS and XRD studies.

    PubMed

    Bulavchenko, O A; Vinokurov, Z S; Afonasenko, T N; Tsyrul'nikov, P G; Tsybulya, S V; Saraev, A A; Kaichev, V V

    2015-09-21

    A series of mixed Mn-Zr oxides with different molar ratios Mn/Zr (0.1-9) have been prepared by coprecipitation of manganese and zirconium nitrates and characterized by X-ray diffraction (XRD) and BET methods. It has been found that at concentrations of Mn below 30 at%, the samples are single-phase solid solutions (MnxZr1-xO2-δ) based on a ZrO2 structure. X-ray photoelectron spectroscopy (XPS) measurements showed that manganese in these solutions exists mainly in the Mn(4+) state on the surface. An increase in Mn content mostly leads to an increase in the number of Mn cations in the structure of solid solutions; however, a part of the manganese cations form Mn2O3 and Mn3O4 in the crystalline and amorphous states. The reduction of these oxides with hydrogen was studied by a temperature-programmed reduction technique, in situ XRD, and near ambient pressure XPS in the temperature range from 100 to 650 °C. It was shown that the reduction of the solid solutions MnxZr1-xO2-δ proceeds via two stages. During the first stage, at temperatures between 100 and 500 °C, the Mn cations incorporated into the solid solutions MnxZr1-xO2-δ undergo partial reduction. During the second stage, at temperatures between 500 and 700 °C, Mn cations segregate on the surface of the solid solution. In the samples with more than 30 at% Mn, the reduction of manganese oxides was observed: Mn2O3 → Mn3O4 → MnO.

  3. 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...

  4. Photocatalytic degradation of 2,4-dichlorophenol with MgAlTi mixed oxides catalysts obtained from layered double hydroxides.

    PubMed

    Mendoza-Damián, G; Tzompantzi, F; Mantilla, A; Barrera, A; Lartundo-Rojas, L

    2013-12-15

    MgAl and MgAlTi mixed oxides were obtained from the thermal treatment of LDH materials synthesized by the sol-gel method; these materials were characterized by N2 physisorption, XRD, UV-vis, XPS, EDS-SEM and TEM techniques. According to the results, Ti was incorporated in the LDH layer when content in the material was low. The MgAl and MgAlTi mixed oxides were evaluated in the photo-degradation of 2,4-dichlorophenol (2,4-DCP) in the presence of UV light. A superior efficiency in the photo-degradation of 2,4-DCP, in comparison with the Degussa P-25 TiO2 reference catalyst was observed, reaching a total decomposition of the 2,4-DCP molecule in less than 60 min. According to the results, Ti was incorporated in the LDH layer when the content in the material was low. The MgAl and MgAlTi mixed oxides were evaluated in the photo-degradation of 2,4-dichlorophenol (2,4-DCP) in the presence of UV light. A superior efficiency in the photo-degradation of 2,4-DCP with the MgAl and MgAlTi mixed oxides, in comparison with the Degussa P-25 TiO2 reference catalyst was observed, reaching a total decomposition of the 2,4-DCP molecule in less than 60 min.

  5. 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.

  6. Novel cerium-tungsten mixed oxide catalyst for the selective catalytic reduction of NO(x) with NH3.

    PubMed

    Shan, Wenpo; Liu, Fudong; He, Hong; Shi, Xiaoyan; Zhang, Changbin

    2011-07-28

    A novel Ce-W mixed oxide catalyst prepared by homogeneous precipitation method presented nearly 100% NO(x) conversion in a wide temperature range from 250 to 425 °C for the selective catalytic reduction of NO(x) with NH(3) under an extremely high GHSV of 500,000 h(-1).

  7. General synthesis of vanadium-based mixed metal oxides hollow nanofibers for high performance lithium-ion batteries

    NASA Astrophysics Data System (ADS)

    Xiang, Juan; Yu, Xin-Yao; Paik, Ungyu

    2016-10-01

    Hollow nanostructured mixed metal oxides have recently been intensively investigated as electrode materials for energy storage and conversion due to their remarkable electrochemical properties. Although great efforts have been made, the synthesis of hollow nanostructured vanadium-based mixed metal oxides especially those with one dimensional structure is rarely reported. Vanadium-based mixed metal oxides are promising electrode materials for lithium-ion batteries with high capacity and good rate capability. Here, we develop a facile and general method for the synthesis of one dimensional MxV2O8 (M = Co, Ni, Fe) tubular structure through a simple single-spinneret electrospinning technique followed by a calcination process. As a demonstration, Co3V2O8 hollow nanofibers are evaluated as anode materials for lithium-ion batteries. As expected, benefiting from their unique one dimensional tubular structure, the as-synthesized Co3V2O8 exhibits excellent electrochemical properties for lithium storage. To be specific, it can deliver a high specific capacity of 900 mAh g-1 at 5 A g-1, and long cycling stability up to 2000 cycles. The present work makes a significant contribution to the design and synthesis of mixed metal oxides with one dimensional tubular structure, as well as their potential applications in electrochemical energy storage.

  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. 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)

  10. 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.

  11. 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

  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. 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.

  14. Mixed-phase oxide catalyst based on Mn-mullite (Sm, Gd)Mn2O5 for NO oxidation in diesel exhaust.

    PubMed

    Wang, Weichao; McCool, Geoffrey; Kapur, Neeti; Yuan, Guang; Shan, Bin; Nguyen, Matt; Graham, Uschi M; Davis, Burtron H; Jacobs, Gary; Cho, Kyeongjae; Hao, Xianghong

    2012-08-17

    Oxidation of nitric oxide (NO) for subsequent efficient reduction in selective catalytic reduction or lean NO(x) trap devices continues to be a challenge in diesel engines because of the low efficiency and high cost of the currently used platinum (Pt)-based catalysts. We show that mixed-phase oxide materials based on Mn-mullite (Sm, Gd)Mn(2)O(5) are an efficient substitute for the current commercial Pt-based catalysts. Under laboratory-simulated diesel exhaust conditions, this mixed-phase oxide material was superior to Pt in terms of cost, thermal durability, and catalytic activity for NO oxidation. This oxide material is active at temperatures as low as 120°C with conversion maxima of ~45% higher than that achieved with Pt. Density functional theory and diffuse reflectance infrared Fourier transform spectroscopy provide insights into the NO-to-NO(2) reaction mechanism on catalytically active Mn-Mn sites via the intermediate nitrate species.

  15. 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.

  16. 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

  17. 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.

  18. 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

  19. Basic properties of the mixed oxides obtained by thermal decomposition of hydrotalcites containing different metallic compositions

    SciTech Connect

    Valente, J.S.; Figueras, F.; Gravelle, M.; Kumbhar, P.; Lopez, J.; Besse, J.P.

    2000-01-25

    Carbonated layered double hydroxides (LDHs) containing Al, Fe, or Cr in a Mg(OH){sub 2} matrix or Al dissolved in hydroxides of Mg, Cu, Ni, Co, or Zn are used as precursors of basic catalysts. Decarbonation is studied by thermal analysis. The average basic strength, evaluated by the decarbonation temperature, is related to the partial charge of oxygen in the LDHs obtained from the Sanderson theory of electronegativity. The enthalpy of adsorption of CO{sub 2} on the resulting mixed oxides is measured by calorimetry. A homogeneous surface is generally observed for CO{sub 2} adsorption, with initial heats of adsorption close to those reported for MgO. The number of sites determined by this method is proportional to the rate constants for {beta}-isophorone isomerization, suggesting that both techniques measure surface properties. The layered structure in which OH{sup {minus}} is the compensating anion can be re-formed by hydration. This process does not appreciably change the adsorption of CO{sub 2}; thus, oxygens and hydroxyls show similar basic strengths in this case.

  20. 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

  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. 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.

  3. 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.

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

    DOE PAGES

    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

  5. 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.

  6. 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.

  7. 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

  8. 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.

  9. 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.

  10. Remote-controlled NDA (nondestructive assay) systems for process areas in a MOX (mixed oxide) facility

    SciTech Connect

    Miller, M.C.; Menlove, H.O.; Augustson, R.H.; Ohtani, T.; Seya, M.; Takahashi, S.; Abedin-Zadeh, R.

    1989-01-01

    Nondestructive assay (NDA) systems have been designed and installed in the process area of an automated mixed-oxide (MOX) fuel fabrication facility. These instruments employ neutron coincidence counting methods to measure the spontaneous-fission rate of plutonium in the powders, pellets, and fuel pins in the process area. The spontaneous fission rate and the plutonium isotopic ratios determine the mass of plutonium in the sample. Measurements can be either attended or unattended. The fuel-pin assay system (FPAS) resides above the robotic conveyor system and measures the plutonium content in fuel-pin trays containing up to 24 pins (/approximately/1 kg of plutonium). The material accountancy glove-box (MAGB) counters consist of two slab detectors mounted on the sides of the glove box to measure samples of powder or pellets as they are brought to the load cell. Samples measured by the MAGB counters may contain up to 18 kg of MOX. This paper describes the design and performance of four systems: the fuel-pin assay system and three separate MAGB systems. The paper also discusses the role of Monte Carlo transport techniques in the detector design and subsequent instrument calibration. 5 refs., 11 figs., 6 tabs.

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

    DOE PAGES

    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. 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

  13. 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.

  14. 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

  15. Melting behavior of (Th,U)O2 and (Th,Pu)O2 mixed oxides

    NASA Astrophysics Data System (ADS)

    Ghosh, P. S.; Kuganathan, N.; Galvin, C. O. T.; Arya, A.; Dey, G. K.; Dutta, B. K.; Grimes, R. W.

    2016-10-01

    The melting behaviors of pure ThO2, UO2 and PuO2 as well as (Th,U)O2 and (Th,Pu)O2 mixed oxides (MOX) have been studied using molecular dynamics (MD) simulations. The MD calculated melting temperatures (MT) of ThO2, UO2 and PuO2 using two-phase simulations, lie between 3650-3675 K, 3050-3075 K and 2800-2825 K, respectively, which match well with experiments. Variation of enthalpy increments and density with temperature, for solid and liquid phases of ThO2, PuO2 as well as the ThO2 rich part of (Th,U)O2 and (Th,Pu)O2 MOX are also reported. The MD calculated MT of (Th,U)O2 and (Th,Pu)O2 MOX show good agreement with the ideal solidus line in the high thoria section of the phase diagram, and evidence for a minima is identified around 5 atom% of ThO2 in the phase diagram of (Th,Pu)O2 MOX.

  16. 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.

  17. 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.

  18. 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.

  19. 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.

  20. 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.

  1. 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.

  2. 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.

  3. Characterization of mixed Ti/Al oxide thin films prepared by ion-beam-induced CVD

    NASA Astrophysics Data System (ADS)

    Capitán, M. J.; Stabel, A.; Sánchez-López, J. C.; Justo, A.; González-Elipe, A. R.; Lefebvre, S.; Fernández, A.

    2000-07-01

    The ion-beam-induced chemical vapor deposition (IBICVD) method has been used for the preparation of TiO 2, Al 2O 3 and mixed oxide Al nTi mO x amorphous films on silica substrates. Also, a double-layer Al 2O 3/TiO 2 film has been prepared. The reflectivity (low angle X-ray diffraction) technique, together with transmission electron microscopy (TEM) and UV-Vis absorption spectroscopy, have been used to get information about thickness, roughness and electronic density of the films. It has been found that the films are homogeneous and flat being the Al 2O 3 layers less dense than the TiO 2 layers. In particular, Al nTi mO x films can be prepared with variable composition and refraction index. The values obtained for electronic density by X-ray reflectivity have been correlated with the compaction degree of the films as stated from TEM and UV-Vis absorption spectroscopy studies.

  4. Decommissioning of a mixed oxide fuel fabrication plant at Winfrith Technolgy Centre

    SciTech Connect

    Pengelly, M.G.A.

    1994-01-01

    The Alpha Materials Laboratory (Building A52) at Winfrith contained a mixed oxide fuel fabrication plant which had a capability of producing 10 te/yr of pelleted/compacted fuel and was in operation from 1962 until 1980, when the requirement for this type of fuel in the UK diminished, and the plant became surplus to requirements. A program to develop decommissioning techniques for plutonium plants was started in 1983, addressing the following aspects of alpha plant decommissioning: (1) Re-usable containment systems, (2) Strippable coating technology, (3) Mobile air filtration plant, (4) Size reduction primarily using cold cutting, (5) techniques, (6) Waste packing, and (7) Alpha plant decommissioning methodology. The technology developed has been used to safely and efficiently decommission radioactive plant and equipment including Pu contaminated glove boxes. (63 glove boxes to date) The technology has been widely adopted in the United Kingdom and elsewhere. This paper outlines the general strategies adopted and techniques used for glove box decommissioning in building A52.

  5. 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.

  6. Superior Dielectric Performance of Engineering Thermoplastic as a Result of In situ Embedding of Nanoscale Mixed-Phase Molybdenum Oxide

    NASA Astrophysics Data System (ADS)

    Qureshi, Nilam; Shinde, Manish; Ratheesh, R.; Bhalerao, Anand; Kale, Bharat; Mulik, Uttam; Amalnerkar, Dinesh P.

    2015-07-01

    To facilitate in situ generation of single and mixed-phase molybdenum oxide on the nanoscale in a network of polyphenylene sulfide (PPS), a novel polymer-inorganic solid-state reaction is proposed. Ammonium molybdate was homogeneously mixed with PPS in 1:1 molar ratio and heated at 285°C for different times (6 h, 24 h, or 48 h) under ambient conditions. The products were characterized by x-ray diffractometry, field emission scanning electron microscopy, and transmission electron microscopy. Structural investigations revealed the co-existence of mix-phased molybdenum oxide, i.e. dominant orthorhombic α-MoO3, and minor monoclinic Mo8O23 phases, within the modified PPS matrix. The resulting molybdenum oxide nanostructures had rod and sheet-like morphology in the PPS matrix. Dielectric measurements on pellets prepared from the resulting nanocomposites revealed improvement of the dielectric properties compared with values reported for pure PPS. The resulting nano-composites may exhibit properties synergistically derived from those of their components (molybdenum oxide and PPS), i.e. lower dielectric constant and loss tangent, enabling application as relatively high-temperature capacitors.

  7. 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

  8. 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.

  9. A small-angle neutron scattering study of sodium dodecyl sulfate-poly(propylene oxide) methacrylate mixed micelles.

    PubMed

    Bastiat, Guillaume; Grassl, Bruno; Borisov, Oleg; Lapp, Alain; François, Jeanne

    2006-03-15

    Mixed micelle of protonated or deuterated sodium dodecyl sulfate (SDS and SDSd25, respectively) and poly(propylene oxide) methacrylate (PPOMA) are studied by small-angle neutron scattering (SANS). In all the cases the scattering curves exhibit a peak whose position changes with the composition of the system. The main parameters which characterize mixed micelles, i.e., aggregation numbers of SDS and PPOMA, geometrical dimensions of the micelles and degree of ionisation are evaluated from the analysis of the SANS curves. The position q(max) of the correlation peak can be related to the average aggregation numbers of SDS-PPOMA and SDSd25-PPOMA mixed micelles. It is found that the aggregation number of SDS decreases upon increasing the weight ratio PPOMA/SDS (or SDSd25). The isotopic combination, which uses the "contrast effect" between the two micellar systems, has allowed us to determine the mixed micelle composition. Finally, the SANS curves were adjusted using the RMSA for the structure factor S(q) of charged spherical particles and the form factor P(q) of spherical core-shell particle. This analysis confirms the particular core-shell structure of the SDS-PPOMA mixed micelle, i.e., a SDS "core" micelle surrounded by the shell formed by PPOMA macromonomers. The structural parameters of mixed micelles obtained from the analysis of the SANS data are in good agreement with those determined previously by conductimetry and fluorescence studies.

  10. Synthesis of metastable rare-earth-iron mixed oxide with the hexagonal crystal structure

    SciTech Connect

    Nishimura, Tatsuya; Hosokawa, Saburo; Masuda, Yuichi; Wada, Kenji; Inoue, Masashi

    2013-01-15

    Rare-earth-iron mixed oxides with the rare earth/iron ratio=1 have either orthorhombic (o-REFeO{sub 3}) or hexagonal (h-REFeO{sub 3}) structure. h-REFeO{sub 3} is a metastable phase and the synthesis of h-REFeO{sub 3} is usually difficult. In this work, the crystallization process of the precursors obtained by co-precipitation and Pechini methods was investigated in detail to synthesize h-REFeO{sub 3}. It was found that the crystallization from amorphous to hexagonal phase and the phase transition from hexagonal to orthorhombic phase occurred at a similar temperature range for rare earth elements with small ionic radii (Er-Lu, Y). For both co-precipitation and Pechini methods, single-phase h-REFeO{sub 3} was obtained by shortening the heating time during calcination process. The hexagonal-to-orthorhombic phase transition took place by a nucleation growth mechanism and vermicular morphology of the thus-formed orthorhombic phase was observed. The hexagonal YbFeO{sub 3} had higher catalytic activity for C{sub 3}H{sub 8} combustion than orthorhombic YbFeO{sub 3}. - Graphical abstract: Although the synthesis of metastable hexagonal REFeO{sub 3} by the conventional method is difficult, we found that this phase is obtained by shortening the heating time of the precursor prepared by co-precipitation method. Highlights: Black-Right-Pointing-Pointer Synthesis of metastable REFeO{sub 3} with hexagonal structure by the co-precipitation method. Black-Right-Pointing-Pointer Hexagonal REFeO{sub 3} is obtained for the rare earth elements with small ionic radii. Black-Right-Pointing-Pointer Hexagonal-to-orthorhombic transformation of REFeO{sub 3}. Black-Right-Pointing-Pointer Catalytic activity of hexagonal REFeO{sub 3} for C{sub 3}H{sub 8} combustion.

  11. 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.

  12. Lithium Storage in Microstructures of Amorphous Mixed-Valence Vanadium Oxide as Anode Materials.

    PubMed

    Zhao, Di; Zheng, Lirong; Xiao, Ying; Wang, Xia; Cao, Minhua

    2015-07-01

    Constructing three-dimensional (3 D) nanostructures with excellent structural stability is an important approach for realizing high-rate capability and a high capacity of the electrode materials in lithium-ion batteries (LIBs). Herein, we report the synthesis of hydrangea-like amorphous mixed-valence VOx microspheres (a-VOx MSs) through a facile solvothermal method followed by controlled calcination. The resultant hydrangea-like a-VOx MSs are composed of intercrossed nanosheets and, thus, construct a 3 D network structure. Upon evaluation as an anode material for LIBs, the a-VOx MSs show excellent lithium-storage performance in terms of high capacity, good rate capability, and long-term stability upon extended cycling. Specifically, they exhibit very stable cycling behavior with a highly reversible capacity of 1050 mA h g(-1) at a rate of 0.1 A g(-1) after 140 cycles. They also show excellent rate capability, with a capacity of 390 mA h g(-1) at a rate as high as 10 A g(-1) . Detailed investigations on the morphological and structural changes of the a-VOx MSs upon cycling demonstrated that the a-VOx MSs went through modification of the local VO coordinations accompanied with the formation of a higher oxidation state of V, but still with an amorphous state throughout the whole discharge/charge process. Moreover, the a-VOx MSs can buffer huge volumetric changes during the insertion/extraction process, and at the same time they remain intact even after 200 cycles of the charge/discharge process. Thus, these microspheres may be a promising anode material for LIBs.

  13. 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)

  14. 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.

  15. Measurement of isoprene and its oxidation products in a mixed deciduous forest - first results of the ECHO-campaign

    NASA Astrophysics Data System (ADS)

    Schaub, A.; Komenda, M.; Koppmann, R.

    2003-04-01

    Biogenic hydrocarbons contribute significantly to the budget of reactive trace gases in the atmosphere. Isoprene which is emitted from almost every plant is the most abundant of the biogenic VOC. Most of the ambient measurements of isoprene and its oxidation products methacrolein (MACR) and methyl vinyl ketone (MVK) have been carried out only for short periods of several days to weeks. Therefore, the knowledge of long term changes in isoprene emission and photooxidation are scarce. One objective of the ECHO-project (Emission and Chemical transformation of biogenic volatile organic compounds) is to investigate the isoprene chemistry in a mixed deciduous forest and the exchange processes between the forest and the PBL. Here we describe measurements of isoprene and its oxidation products measured with an online GC-FID system between June and November 2002 in a mixed beech oak forest. The results show a diurnal cycle of isoprene mixing ratios being dependent on temperature and light intensity. The mixing ratios were in the range of 0.02 - 3 ppb with a mean daytime maximum of 500 ppt. In October the daytime isoprene mixing ratio decreased to 50 ppt indicating senescence of leaves. For MVK and MACR a diurnal cycle was found with mean daytime maximum values of 60 ppt and 80 ppt, respectively. In June and July 2002 the maximum daytime ratio between MVK and MACR was < 1, in August this ratio increased to 1.6. This surprising result, which pointed towards a strong influence of NOx on the isoprene oxidation pathways, was further investigated in simulation experiments (see contribution by Komenda et al) and model studies (see contribution by Karl and Dorn).

  16. Acyloxylation of 1,4-Dioxanes and 1,4-Dithianes Catalyzed by a Copper-Iron Mixed Oxide.

    PubMed

    García-Cabeza, Ana Leticia; Marín-Barrios, Rubén; Moreno-Dorado, F Javier; Ortega, María J; Vidal, Hilario; Gatica, José M; Massanet, Guillermo M; Guerra, Francisco M

    2015-07-01

    The use of a copper-iron mixed oxide as a heterogeneous catalyst for the efficient synthesis of α-acyloxy-1,4-dioxanes and 1,4-dithianes employing t-butyl peroxyesters is reported. The preparation and characterization of the catalyst are described. The effect of the heteroatoms and a plausible mechanism are discussed. The method is operationally simple and involves low-cost starting materials affording products in good to excellent yields.

  17. 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.

  18. A hexanuclear mixed-valence oxovanadium(IV,V) complex as a highly efficient alkane oxidation catalyst.

    PubMed

    Sutradhar, Manas; Kirillova, Marina V; Guedes da Silva, M Fátima C; Martins, Luísa M D R S; Pombeiro, Armando J L

    2012-11-01

    The new hexanuclear mixed-valence vanadium complex [V(3)O(3)(OEt)(ashz)(2)(μ-OEt)](2) (1) with an N,O-donor ligand is reported. It acts as a highly efficient catalyst toward alkane oxidations by aqueous H(2)O(2). Remarkably, high turnover numbers up to 25000 with product yields of up to 27% (based on alkane) stand for one of the most active systems for such reactions.

  19. Effect of structure and composition on epoxidation of hexene catalyzed by microporous and mesoporous Ti-Si mixed oxides

    SciTech Connect

    Liu, Z.; Crumbaugh, G.M.; Davis, R.J.

    1996-03-01

    A series of microporous titania-silica mixed oxides were characterized and tested as catalysts for the liquid-phase epoxidation of 1-hexene with t-butyl hydroperoxide. Results from {sup 29}Si MAS NMR spectroscopy verified results from earlier characterization studies that indicated cohydrolysis of alkoxide precursors produced well-mixed oxide samples. The catalytic activity of the samples for hexene epoxidation at 353 K increased with increasing silica content. Since the fraction of tetrahedral Ti atoms in the samples also increased with silica content, the active site for the reaction is proposed to be a tetrahedrally coordinated Ti atom in a silica matrix. Polar solvents like water, acetone, and methanol inhibited the epoxidation reaction. To investigate the effect of pore size on activity, mesoporous Ti-Si mixed oxides analogous to MCM-41 were synthesized. The mesoporous samples were the most active and selective catalysts for epoxidation with TBHP, presumably due to the ease of access of the reactants to the active Ti sites. Results from EXAFS and UV reflectance spectroscopy indicated that Ti atoms in the mesoporous mixed oxides are tetrahedrally coordinated to oxygen atoms with the same Ti-O bond distance as TS-1. However, the activities of mesoporous samples are orders of magnitude lower than that of TS-1 for hexene epoxidation with aqueous hydrogen peroxide. Lower hydrophobicity of a silica mesopore (2-4 nm) compared to a TS-1 micropore (0.6 nm) may account for the difference in activity observed in reactions with aqueous hydrogen peroxide. 26 refs., 5 figs., 5 tabs.

  20. 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.

  1. 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.

  2. Calibration Tools for Measurement of Highly Enriched Uranium in Oxide and Mixed Uranium-Plutonium Oxide with a Passive-Active Neutron Drum Shuffler

    SciTech Connect

    Mount, M; O'Connell, W; Cochran, C; Rinard, P

    2003-06-13

    Lawrence Livermore National Laboratory (LLNL) has completed an extensive effort to calibrate the LLNL passive-active neutron drum (PAN) shuffler (Canberra Model JCC-92) for accountability measurement of highly enriched uranium (HEU) oxide and HEU in mixed uranium-plutonium (U-Pu) oxide. Earlier papers described the PAN shuffler calibration over a range of item properties by standards measurements and an extensive series of detailed simulation calculations. With a single normalization factor, the simulations agree with the HEU oxide standards measurements to within {+-}1.2% at one standard deviation. Measurement errors on mixed U-Pu oxide samples are in the {+-}2% to {+-}10% range, or {+-}20 g for the smaller items. The purpose of this paper is to facilitate transfer of the LLNL procedure and calibration algorithms to external users who possess an identical, or equivalent, PAN shuffler. Steps include (1) measurement of HEU standards or working reference materials (WRMs); (2) MCNP simulation calculations for the standards or WRMs and a range of possible masses in the same containers; (3) a normalization of the calibration algorithms using the standard or WRM measurements to account for differences in the {sup 252}Cf source strength, the delayed-neutron nuclear data, effects of the irradiation protocol, and detector efficiency; and (4) a verification of the simulation series trends against like LLNL results. Tools include EXCEL/Visual Basic programs which pre- and post-process the simulations, control the normalization, and embody the calibration algorithms.

  3. 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

  4. Direct formation of iron oxide/MCM-41 nanocomposites via single or mixed n-alkyltrimethylammonium bromide surfactants.

    PubMed

    Khalil, Kamal M S; Khalaf, Mai M; Mohran, Hossnia S; Elsamahy, Ahmed A

    2012-02-15

    Iron oxide/MCM-41 nanocomposites, Fe(2)O(3)/MCM-41, containing 5%, 10%, and 20% (w/w) iron oxide, were prepared via a direct nonhydrothermal method at room temperature. The preparations were preformed by using iron(III) nitrate, tetra-ethoxysilane (TEOS), and cetyltrimethylammonium bromide (CTAB) mixed or unmixed with dodecyltrimethylammonium bromide (DTAB). The produced materials were dried and calcined at 550 °C for 3 h. Test materials were characterized by thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), Fourier transform infrared spectroscopy (FTIR), N(2) gas adsorption/desorption isotherms, small angle and wide angle X-ray diffraction (XRD). Results indicate that mixing of CTAB with DTAB does not harm the formation of blank MCM-41 structure. For the composite Fe(2)O(3)/MCM-41 materials, results showed formation of more stable MCM-41 structure with higher surface area and improved porosity in the presence of mixed (CTAB+DTAB) than in the presence of single (CTAB) surfactants for up to 10% Fe(2)O(3)/MCM-41 (w/w). This was explained in terms of the effect DTAB on contraction of the template micellar size to compensate for the expected size expansion upon the addition of ionic iron(III) nitrate precursor. Highly dispersed Fe(2)O(3) nanoparticles were formed in all cases even with the highest iron oxide percentage. Formation of the nanocomposites was postulated to be determined by fast nucleation and slow growth of iron oxide species, which facilitated formation of well dispersed iron oxide nanoparticles inside and on the wall of the MCM-41 material.

  5. 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.

  6. 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.

  7. Effects of calcination temperature and acid-base properties on mixed potential ammonia sensors modified by metal oxides.

    PubMed

    Satsuma, Atsushi; Katagiri, Makoto; Kakimoto, Shiro; Sugaya, Satoshi; Shimizu, Kenichi

    2011-01-01

    Mixed potential sensors were fabriated using yttria-stabilized zirconia (YSZ) as a solid electrolyte and a mixture of Au and various metal oxides as a sensing electrode. The effects of calcination temperature ranging from 600 to 1,000 °C and acid-base properties of the metal oxides on the sensing properties were examined. The selective sensing of ammonia was achieved by modification of the sensing electrode using MoO(3), Bi(2)O(3) and V(2)O(5), while the use of WO(3,) Nb(2)O(5) and MgO was not effective. The melting points of the former group were below 820 °C, while those of the latter group were higher than 1,000 °C. Among the former group, the selective sensing of ammonia was strongly dependent on the calcination temperature, which was optimum around melting point of the corresponding metal oxides. The good spreading of the metal oxides on the electrode is suggested to be one of the important factors. In the former group, the relative response of ammonia to propene was in the order of MoO(3) > Bi(2)O(3) > V(2)O(5), which agreed well with the acidity of the metal oxides. The importance of the acidic properties of metal oxides for ammonia sensing was clarified.

  8. Effects of Calcination Temperature and Acid-Base Properties on Mixed Potential Ammonia Sensors Modified by Metal Oxides

    PubMed Central

    Satsuma, Atsushi; Katagiri, Makoto; Kakimoto, Shiro; Sugaya, Satoshi; Shimizu, Kenichi

    2011-01-01

    Mixed potential sensors were fabriated using yttria-stabilized zirconia (YSZ) as a solid electrolyte and a mixture of Au and various metal oxides as a sensing electrode. The effects of calcination temperature ranging from 600 to 1,000 °C and acid-base properties of the metal oxides on the sensing properties were examined. The selective sensing of ammonia was achieved by modification of the sensing electrode using MoO3, Bi2O3 and V2O5, while the use of WO3, Nb2O5 and MgO was not effective. The melting points of the former group were below 820 °C, while those of the latter group were higher than 1,000 °C. Among the former group, the selective sensing of ammonia was strongly dependent on the calcination temperature, which was optimum around melting point of the corresponding metal oxides. The good spreading of the metal oxides on the electrode is suggested to be one of the important factors. In the former group, the relative response of ammonia to propene was in the order of MoO3 > Bi2O3 > V2O5, which agreed well with the acidity of the metal oxides. The importance of the acidic properties of metal oxides for ammonia sensing was clarified. PMID:22319402

  9. Synthesis of alumina powder by the urea-glycine-nitrate combustion process: a mixed fuel approach to nanoscale metal oxides

    NASA Astrophysics Data System (ADS)

    Sharma, Amit; Rani, Amita; Singh, Ajay; Modi, O. P.; Gupta, Gaurav K.

    2014-03-01

    Main objective of present work is to study the efficiency of mixed fuel towards solution combustion synthesis of alumina powder, which otherwise prepared by single fuel and study of properties of final product with mixed fuel approach. Two different fuels, glycine and urea, along with aluminium nitrates have been used to prepare nanophase alumina powder. Different fuel to oxidizer ratios and different percentage combination of two fuels were used to prepare six samples. In all samples, nanoscale particle size obtained. Parameter which continuously changes the results of various characterisations is percentage combination of two fuels. In case where percentage of urea is higher than glycine reaction takes place with high exothermicity and hence crystallinity in product phase, whereas glycine promotes amorphous character. With mixed fuel approach, crystallinity can be enhanced easily, by calcinations of powder product at low temperature, because due to mixed urea and glycine, there is already some fraction of crystallinity observed. Overall mixed fuel approach has ability to produce nanophase alumina powder with wide range of particles size.

  10. 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.

  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. 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

  13. Properties of cerium-zirconium mixed oxides partially substituted by neodymium: Comparison with Zr-Ce-Pr-O ternary oxides

    SciTech Connect

    Mikulova, Jana; Rossignol, Sylvie . E-mail: Sylvie.rossignol@univ-poitiers.fr; Gerard, Francois; Mesnard, Danielle; Kappenstein, Charles; Duprez, Daniel

    2006-08-15

    CeO{sub 2} doped with praseodymium, neodymium and/or zirconium atoms were prepared by coprecipitation and by the sol-gel method. Structural properties were investigated by in situ XRD and Raman spectroscopy while oxygen storage capacity (OSC) was measured by transient CO oxidation. All the compounds, except pure Nd{sub 2}O{sub 3}, have a fluorite-type structure as well as a Raman band at 560 cm{sup -1} characteristic of the oxygen vacancies involving non-stoichiometric oxides. The lattice parameter under hydrogen, being dependent on the temperature, revealed two reduction mechanisms: one at a low temperature at the surface and another at a high temperature in the bulk. Ce-Nd binary oxides show a strong tendency towards crystallite aggregation, which reduces accessibility to gases and OSC properties. Zirconium improves the thermal resistance to sintering of both Ce-Nd and Ce-Pr oxides. The Zr-Ce-Pr-O followed by Zr-Ce-Nd-O compounds displaying high oxygen mobility at a low temperature, appear to be very promising for practical applications such as OSC materials. - Graphical abstract: Variation of oxygen vacancies under hydrogen on ternary oxides.

  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. 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.

  16. Monte-Carlo Code (MCNP) Modeling of the Advanced Test Reactor Applicable to the Mixed Oxide (MOX) Test Irradiation

    SciTech Connect

    G. S. Chang; R. C. Pederson

    2005-07-01

    Mixed oxide (MOX) test capsules prepared with weapons-derived plutonium have been irradiated to a burnup of 50 GWd/t. The MOX fuel was fabricated at Los Alamos National Laboratory by a master-mix process and has been irradiated in the Advanced Test Reactor (ATR) at the Idaho National Laboratory (INL). Previous withdrawals of the same fuel have occurred at 9, 21, 30, and 40 GWd/t. Oak Ridge National Laboratory (ORNL) manages this test series for the Department of Energy’s Fissile Materials Disposition Program (FMDP). The fuel burnup analyses presented in this study were performed using MCWO, a welldeveloped tool that couples the Monte Carlo transport code MCNP with the isotope depletion and buildup code ORIGEN-2. MCWO analysis yields time-dependent and neutron-spectrum-dependent minor actinide and Pu concentrations for the ATR small I-irradiation test position. The purpose of this report is to validate both the Weapons-Grade Mixed Oxide (WG-MOX) test assembly model and the new fuel burnup analysis methodology by comparing the computed results against the neutron monitor measurements.

  17. 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

  18. A novel approach for analyzing electrochemical properties of mixed conducting solid oxide fuel cell anode materials by impedance spectroscopy.

    PubMed

    Nenning, A; Opitz, A K; Huber, T M; Fleig, J

    2014-10-28

    For application of acceptor-doped mixed conducting oxides as solid oxide fuel cell (SOFC) anodes, high electrochemical surface activity as well as acceptable electronic and ionic conductivity are crucial. In a reducing atmosphere, particularly the electronic conductivity of acceptor-doped oxides can become rather low and the resulting complex interplay of electrochemical reactions and charge transport processes makes a mechanistic interpretation of impedance measurements very complicated. In order to determine all relevant resistive and capacitive contributions of mixed conducting electrodes in a reducing atmosphere, a novel electrode design and impedance-based analysis technique is therefore introduced. Two interdigitating metallic current collectors are placed in a microelectrode, which allows in-plane measurements within the electrode as well as electrochemical measurements versus a counter electrode. Equivalent circuit models for quantifying the spectra of both measurement modes are developed and applied to simultaneously fit both spectra, using the same parameter set. In this manner, the electronic and ionic conductivity of the material as well as the area-specific resistance of the surface reaction and the chemical capacitance can be determined on a single microelectrode in a H2-H2O atmosphere. The applicability of this new tool was demonstrated in SrTi0.7Fe0.3O(3-δ) (STFO) thin film microelectrodes, deposited on single-crystalline yttria-stabilized zirconia (YSZ) substrates. All materials parameters that contribute to the polarization resistance of STFO electrodes in a reducing atmosphere could thus be quantified.

  19. 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

  20. Surface kinetics modeling of silicon and silicon oxide plasma etching. III. Modeling of silicon oxide etching in fluorocarbon chemistry using translating mixed-layer representation

    SciTech Connect

    Kwon, Ohseung; Bai Bo; Sawin, Herbert H.

    2006-09-15

    Silicon oxide etching was modeled using a translating mixed-layer model, a novel surface kinetic modeling technique, and the model showed good agreement with measured data. Carbon and fluorine were identified as the primary contributors to deposition and etching, respectively. Atomic fluorine flux is a major factor that determines the etching behavior. With a chemistry having a small amount of atomic fluorine (such as the C{sub 4}F{sub 8} chemistry), etching yield shows stronger dependence on the composition change in the gas flux.

  1. 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

  2. Observations of reactive nitrogen oxide fluxes by eddy covariance above two mid-latitude North American mixed hardwood forests

    NASA Astrophysics Data System (ADS)

    Geddes, J. A.; Murphy, J. G.

    2013-10-01

    Significant knowledge gaps persist in the understanding of forest-atmosphere exchange of reactive nitrogen oxides, partly due to a lack of direct observations. Chemical transport models require representations of dry deposition over a variety of land surface types, and the role of canopy exchange of NOx (= NO + NO2) is highly uncertain. Biosphere-atmosphere exchange of NOx and NOy (= NOx + HNO3 + PANs + RONO2 + pNO3- + ...) was measured by eddy covariance above a mixed hardwood forest in central Ontario (HFWR), and a mixed hardwood forest in northern lower Michigan (PROPHET) during the summers of 2011 and 2012 respectively. NOx and NOy mixing ratios were measured by a custom built two-channel analyzer based on chemiluminescence, with selective NO2 conversion via LED photolysis and NOy conversion via a hot molybdenum converter. Consideration of interferences from water and O3, and random uncertainty of the calculated fluxes are discussed. NOy flux observations were predominantly of deposition at both locations. The magnitude of deposition scaled with NOy mixing ratios, resulting in campaign-average deposition velocities close to 0.6 cm s-1 at both locations. A~period of highly polluted conditions (NOy concentrations up to 18 ppb) showed distinctly different flux characteristics than the rest of the campaign. Integrated daily average NOy flux was 0.14 mg (N) m-2 day-1 and 0.34 mg (N) m-2 day-1 at HFWR and PROPHET respectively. Concurrent wet deposition measurements were used to estimate the contributions of dry deposition to total reactive nitrogen oxide inputs, found to be 22% and 40% at HFWR and PROPHET, respectively.

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

    NASA Astrophysics Data System (ADS)

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

    2014-04-01

    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.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. Electronic supplementary information (ESI) available: Image of microbial fuel cells, ID/IG ratio, simulation of the reaction equation, antibacterial experiment of Escherichia coli and Staphylococcus

  4. 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.

  5. 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.

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

    PubMed

    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.

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

    PubMed

    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. PMID:26026564

  8. 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.

  9. 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.

  10. 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.

  11. Structure and electronic properties of MoVO type mixed-metal oxides - a combined view by experiment and theory.

    PubMed

    Chiu, Cheng-Chau; Vogt, Thomas; Zhao, Lili; Genest, Alexander; Rösch, Notker

    2015-08-21

    In this review we address recent efforts from experimental and theoretical side to study MoVO-type mixed metal oxides (MMOs) and their properties. We illustrate how structures of MMOs have been evaluated using a large variety of experimental techniques, such as electron microscopy, neutron diffraction, and X-ray diffraction. Furthermore, we discuss the current view on structure-catalysis correlations, derived from recent experiments. In a second part, we examine useful tools of theoretical chemistry for exploring MoVO-type systems. We discuss the need for using hybrid DFT methods and we analyze how, in the context of MMOs studies, semi-local DFT approximations can encounter problems due to a notable self-interaction error when describing oxidic species and reactions on them. In addition, we discuss various aspects of the model that are important when attempting to map complex MMO systems. PMID:26126874

  12. Oxidation of hydrogen sulfide by mixed cultures of Thiobacillus denitrificans and heterotrophs

    SciTech Connect

    Sublette, K.L.; Sylvester, N.D.

    1987-04-01

    A process for the microbial desulfurization of natural gas based on the oxidation of H/sub 2/S(g) by Thiobacillus denitrificans has been previously proposed. The proposed process could be greatly simplified if aseptic operation of the reactor was not required. Accordingly, the authors report here a study of the effects of heterotrophic contaminants on H/sub 2/S(g) oxidation by T. denitrificans.

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

    NASA Astrophysics Data System (ADS)

    Fan, Guoli; Wang, Hui; Xiang, Xu; Li, Feng

    2013-01-01

    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.

  14. 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.

  15. 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.

  16. Investigating the Composition and Conductance Distributions on Highly GeSi Mixed Quantum Dots and Inside Oxidation Problem

    NASA Astrophysics Data System (ADS)

    Ye, F. F.; Ma, Y. J.; Lv, Y.; Jiang, Z. M.; Yang, X. J.

    2015-12-01

    With the help of a nanoscale trench, the composition and conductance distributions of single GeSi quantum dots (QDs) are obtained by conductive atomic force microscopy combined with selective chemical etching. However, the obtained composition and current distributions are unwonted and inconsistent on the QDs grown at 680 °C. With a series of confirmatory experiments, it is suggested that a thick oxide layer is formed and remains on the QDs' surface after etching. Though this selective chemical etching has already been widely applied to investigate the composition distribution of GeSi nanostructures, the oxidation problem has not been concerned yet. Our results indicate that the oxidation problem could not be ignored on highly GeSi mixed QDs. After removing the oxide layer, the composition and conductance distributions as well as their correlation are obtained. The results suggest that QDs' current distribution is mainly determined by the topographic shape, while the absolute current values are influenced by the Ge/Si contents.

  17. 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

  18. Depletion analysis of mixed-oxide fuel pins in light water reactors and the Advanced Test Reactor

    SciTech Connect

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

    2000-03-01

    An experiment containing weapons-grade mixed-oxide (WG-MOX) fuel has been designed and is being irradiated in the Advanced Test Reactor (ATR) at the Idaho National Engineering and Environmental Laboratory (INEEL). The ability to accurately predict fuel pin performance is an essential requirement for the MOX fuel test assembly design. Detailed radial fission power and temperature profile effects and fission gas release in the fuel pin are a function of the fuel pin's temperature, fission power, and fission product ad actinide concentration profiles. In addition, the burnup-dependent profile analyses in irradiated fuel pins is important for fuel performance analysis to support the potential licensing of the MOX fuel made from WG-plutonium and depleted uranium for use in US reactors. The MCNP Coupling With ORIGEN2 burnup calculation code (MCWO) can analyze the detailed burnup profiles of WG-MOX and reactor-grade mixed-oxide (RG-MOX) fuel pins. The validated code MCWO can provide the best-estimate neutronic characteristics of fuel burnup performance analysis. Applying this capability with a new minicell method allows calculation of detailed nuclide concentration and power distributions within the MOX pins as a function of burnup. This methodology was applied to MOX fuel in a commercial pressurized water reactor and in an experiment currently being irradiated in the ATR. The prediction of nuclide concentration profiles and power distributions in irradiated MOX plus via this new methodology can provide insights into MOX fuel performance.

  19. Observations of reactive nitrogen oxide fluxes by eddy covariance above two midlatitude North American mixed hardwood forests

    NASA Astrophysics Data System (ADS)

    Geddes, J. A.; Murphy, J. G.

    2014-03-01

    Significant knowledge gaps persist in the understanding of forest-atmosphere exchange of reactive nitrogen oxides, partly due to a lack of direct observations. Chemical transport models require representations of dry deposition over a variety of land surface types, and the role of canopy exchange of NOx (= NO + NO2) is highly uncertain. Biosphere-atmosphere exchange of NOx and NOy (= NOx + HNO3 + PANs + RONO2 + pNO3- + ...) was measured by eddy covariance above a mixed hardwood forest in central Ontario (Haliburton Forest and Wildlife Reserve, or HFWR), and a mixed hardwood forest in northern lower Michigan (Program for Research on Oxidants: Photochemistry, Emissions and Transport, or PROPHET) during the summers of 2011 and 2012 respectively. NOx and NOy mixing ratios were measured by a custom-built two-channel analyser based on chemiluminescence, with selective NO2 conversion via LED photolysis and NOy conversion via a hot molybdenum converter. Consideration of interferences from water vapour and O3, and random uncertainty of the calculated fluxes are discussed. NOy flux observations were predominantly of deposition at both locations. In general, the magnitude of deposition scaled with NOy mixing ratios. Average midday (12:00-16:00) deposition velocities at HFWR and PROPHET were 0.20 ± 0.25 and 0.67 ± 1.24 cm s-1 respectively. Average nighttime (00:00-04:00) deposition velocities were 0.09 ± 0.25 cm s-1 and 0.08 ± 0.16 cm s-1 respectively. At HFWR, a period of highly polluted conditions (NOy concentrations up to 18 ppb) showed distinctly different flux characteristics than the rest of the campaign. Integrated daily average NOy flux was -0.14 mg (N) m-2 day-1 and -0.34 mg (N) m-2 day-1 (net deposition) at HFWR and PROPHET respectively. Concurrent wet deposition measurements were used to estimate the contributions of dry deposition to total reactive nitrogen oxide inputs, found to be 22 and 40% at HFWR and PROPHET respectively.

  20. 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

  1. Defects and transport in mixed oxides. Progress report, [December 22, 1992--September 30,1993

    SciTech Connect

    Dieckmann, R.

    1993-09-30

    Progress has been made in: nonstoichiometry of rock salt structure oxide solid solutions; cation tracer diffusion in oxide solid solutions of the types (Co,Mn){sub 3-{delta}}O{sub 4} and (Co,Fe){sub 1-{Delta}}O; electrical conductivity in solid solution (Co,Fe){sub 1-{Delta}}O; Monte-Carlo simulation of the cation diffusion in spinel solid solutions; thermodynamic modelling of the ternary phase diagram of the system Co-Fe-Mn-O and the boundary systems Co-Fe-O and Fe-Mn-O at 1200 C; and interdiffusion in spinel solid solutions.

  2. 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…

  3. Synthesis of coral-like tantalum oxide films via anodization in mixed organic-inorganic electrolytes.

    PubMed

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

    2013-01-01

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

  4. The thermovoltaic effect in zinc oxide inhomogeneously doped with mixed-valence impurities

    NASA Astrophysics Data System (ADS)

    Pronin, I. A.; Averin, I. A.; Bozhinov, A. S.; Georgieva, A. Ts.; Dimitrov, D. Ts.; Karmanov, A. A.; Moshnikov, V. A.; Papazova, K. I.; Terukov, E. I.; Yakushova, N. D.

    2015-10-01

    The thermovoltaic effect has been for the first time observed in zinc oxide. The samples had the form of ZnO/ZnO-Me sandwich structures (Me = Cu, Fe) formed by the sol-gel method. An electromotive force of 1-10 mV appeared in the temperature range of 200-300°C.

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

    PubMed Central

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

    2013-01-01

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

  6. A mixed solution-processed gate dielectric for zinc-tin oxide thin-film transistor and its MIS capacitance

    PubMed Central

    Kim, Hunho; Kwack, Young-Jin; Yun, Eui-Jung; Choi, Woon-Seop

    2016-01-01

    Solution-processed gate dielectrics were fabricated with the combined ZrO2 and Al2O3 (ZAO) in the form of mixed and stacked types for oxide thin film transistors (TFTs). ZAO thin films prepared with double coatings for solid gate dielectrics were characterized by analytical tools. For the first time, the capacitance of the oxide semiconductor was extracted from the capacitance-voltage properties of the zinc-tin oxide (ZTO) TFTs with the combined ZAO dielectrics by using the proposed metal-insulator-semiconductor (MIS) structure model. The capacitance evolution of the semiconductor from the TFT model structure described well the threshold voltage shift observed in the ZTO TFT with the ZAO (1:2) gate dielectric. The electrical properties of the ZTO TFT with a ZAO (1:2) gate dielectric showed low voltage driving with a field effect mobility of 37.01 cm2/Vs, a threshold voltage of 2.00 V, an on-to-off current ratio of 1.46 × 105, and a subthreshold slope of 0.10 V/dec. PMID:27641430

  7. Chemical thermodynamics of Cs and Te fission product interactions in irradiated LMFBR mixed-oxide fuel pins

    NASA Astrophysics Data System (ADS)

    Adamson, M. G.; Aitken, E. A.; Lindemer, T. B.

    1985-02-01

    A combination of fuel chemistry modelling and equilibrium thermodynamic calculations has been used to predict the atom ratios of Cs and Te fission products (Cs:Te) that find their way into the fuel-cladding interface region of irradiated stainless steel-clad mixed-oxide fast breeder reactor fuel pins. It has been concluded that the ratio of condensed, chemically-associated Cs and Te in the interface region,Čs:Te, which in turn determines the Te activity, is controlled by an equilibrium reaction between Cs 2Te and the oxide fuel, and that the value of Čs:Te is, depending on fuel 0:M, either equal to or slightly less than 2:1. Since Cs and Te fission products are both implicated as causative agents in FCCI (fission product-assisted inner surface attack of stainless steel cladding) and in FPLME (fission product-assisted liquid metal embrittlement of AISI-Type 316), the observed out-of-pile Cs:Te thresholds for FCCI (4˜:1) and FPLME (2˜:1) have been rationalized in terms of Cs:Te thermochemistry and phase equilibria. Also described in the paper is an updated chemical evolution model for reactive/volatile fission product behavior in irradiated oxide pins.

  8. A mixed solution-processed gate dielectric for zinc-tin oxide thin-film transistor and its MIS capacitance.

    PubMed

    Kim, Hunho; Kwack, Young-Jin; Yun, Eui-Jung; Choi, Woon-Seop

    2016-01-01

    Solution-processed gate dielectrics were fabricated with the combined ZrO2 and Al2O3 (ZAO) in the form of mixed and stacked types for oxide thin film transistors (TFTs). ZAO thin films prepared with double coatings for solid gate dielectrics were characterized by analytical tools. For the first time, the capacitance of the oxide semiconductor was extracted from the capacitance-voltage properties of the zinc-tin oxide (ZTO) TFTs with the combined ZAO dielectrics by using the proposed metal-insulator-semiconductor (MIS) structure model. The capacitance evolution of the semiconductor from the TFT model structure described well the threshold voltage shift observed in the ZTO TFT with the ZAO (1:2) gate dielectric. The electrical properties of the ZTO TFT with a ZAO (1:2) gate dielectric showed low voltage driving with a field effect mobility of 37.01 cm(2)/Vs, a threshold voltage of 2.00 V, an on-to-off current ratio of 1.46 × 10(5), and a subthreshold slope of 0.10 V/dec. PMID:27641430

  9. A mixed solution-processed gate dielectric for zinc-tin oxide thin-film transistor and its MIS capacitance

    NASA Astrophysics Data System (ADS)

    Kim, Hunho; Kwack, Young-Jin; Yun, Eui-Jung; Choi, Woon-Seop

    2016-09-01

    Solution-processed gate dielectrics were fabricated with the combined ZrO2 and Al2O3 (ZAO) in the form of mixed and stacked types for oxide thin film transistors (TFTs). ZAO thin films prepared with double coatings for solid gate dielectrics were characterized by analytical tools. For the first time, the capacitance of the oxide semiconductor was extracted from the capacitance-voltage properties of the zinc-tin oxide (ZTO) TFTs with the combined ZAO dielectrics by using the proposed metal-insulator-semiconductor (MIS) structure model. The capacitance evolution of the semiconductor from the TFT model structure described well the threshold voltage shift observed in the ZTO TFT with the ZAO (1:2) gate dielectric. The electrical properties of the ZTO TFT with a ZAO (1:2) gate dielectric showed low voltage driving with a field effect mobility of 37.01 cm2/Vs, a threshold voltage of 2.00 V, an on-to-off current ratio of 1.46 × 105, and a subthreshold slope of 0.10 V/dec.

  10. 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.

  11. 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.

  12. Calibration of the Lawrence Livermore National Laboratory Passive-Active Neutron Drum Shuffler for Measurement of Highly Enriched Uranium in Mixed Oxide

    SciTech Connect

    Mount, M; O'Connell, W; Cochran, C; Rinard, P; Dearborn, D; Endres, E

    2002-05-23

    As a follow-on to the Lawrence Livermore National Laboratory (LLNL) effort to calibrate the LLNL passive-active neutron drum (PAN) shuffler for measurement of highly enriched uranium (HEU) oxide, a method has been developed to extend the use of the PAN shuffler to the measurement of HEU in mixed uranium-plutonium (U-Pu) oxide. This method uses the current LLNL HEU oxide calibration algorithms, appropriately corrected for the mixed U-Pu oxide assay time, and recently developed PuO{sub 2} calibration algorithms to yield the mass of {sup 235}U present via differences between the expected count rate for the PuO{sub 2} and the measured count rate of the mixed U-Pu oxide. This paper describes the LLNL effort to use PAN shuffler measurements of units of certified reference material (CRM) 149 [uranium (93% Enriched) Oxide - U{sub 3}O{sub 8} Standard for Neutron Counting Measurements] and CRM 146 [Uranium Isotopic Standard for Gamma Spectrometry Measurements] and a selected set of LLNL PuO{sub 2}-bearing containers in consort with Monte Carlo simulations of the PAN shuffler response to each to (1) establish and validate a correction to the HEU calibration algorithm for the mixed U-Pu oxide assay time, (2) develop a PuO{sub 2} calibration algorithm that includes the effect of PuO{sub 2} density (2.4 g/cm{sup 3} to 4.8 g/cm{sup 3}) and container size (8.57 cm to 9.88 cm inside diameter and 9.60 cm to 13.29 cm inside height) on the PAN shuffler response, and (3) develop and validate the method for establishing the mass of {sup 235}U present in an unknown of mixed U-Pu oxide.

  13. 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.

  14. Preparation and Mixed Conductivity of Mn-DOPED Bi-Sr-Fe-BASED Perovskite Type Oxides

    NASA Astrophysics Data System (ADS)

    Baek, Doohyun; Takamura, Hitoshi

    2013-07-01

    Bi0.7Sr0.3FeO3-δ (BSF) with perovskite structure and Mn-doped BSFs were prepared by solid-state reaction and their mixed conductivities were discussed based on results of electrical conductivity and oxygen permeation measurement through membranes of those compounds. BSF showed only 2 S/cm at 800 °C suggesting that its charge unbalance is likely to be compensated by generation of oxygen vacancies. However, Mn-doping caused the increase of electrical conductivity and the decrease of oxygen permeation rate, that is, the extent of charge compensation by electron holes increased through Mn-doping.

  15. 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

  16. 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

  17. 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.

  18. Synthesis of multifunctional nanostructured zinc-iron mixed oxide photocatalyst by a simple solution-combustion technique.

    PubMed

    Pradhan, Gajendra Kumar; Martha, Satyabadi; Parida, K M

    2012-02-01

    A series of nanostructure zinc-iron mixed oxide photocatalysts have been fabricated by solution-combustion method using urea as the fuel, and nitrate salts of both iron and zinc as the metal source. Different characterization tools, such as X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), diffuse reflectance UV-visible spectra (DRUV-vis), electron microscopy, and photoelectrochemical measurement were employed to establish the structural, electronic, and optical properties of the material. Electron microscopy confirmed the nanostructure of the photocatalyst. The synthesized photocatalysts were examined towards photodegradation of 4-chloro-2-nitro phenol (CNP), rhodamine 6G (R6G), and photocatalytic hydrogen production under visible light (λ ≥ 400 nm). The photocatalyst having zinc to iron ratio of 50:50 showed best photocatalytic activity among all the synthesized photocatalysts.

  19. 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.

  20. Novel Mn-Ce-Ti mixed-oxide catalyst for the selective catalytic reduction of NOx with NH₃.

    PubMed

    Liu, Zhiming; Zhu, Junzhi; Li, Junhua; Ma, Lingling; Woo, Seong Ihl

    2014-08-27

    Mn-Ce-Ti mixed-oxide catalyst prepared by the hydrothermal method was investigated for the selective catalytic reduction (SCR) of NOx with NH3 in the presence of oxygen. It was found that the environmentally benign Mn-Ce-Ti catalyst exhibited excellent NH3-SCR activity and strong resistance against H2O and SO2 with a broad operation temperature window, which is very competitive for the practical application in controlling the NOx emission from diesel engines. On the basis of the catalyst characterization, the dual redox cycles (Mn(4+) + Ce(3+) ↔ Mn(3+) + Ce(4+), Mn(4+) + Ti(3+) ↔ Mn(3+) + Ti(4+)) and the amorphous structure play key roles for the high catalytic deNOx performance. Diffuse reflectance infrared Fourier transform spectroscopy studies showed that the synergetic effect between Mn and Ce contributes to the formation of reactive intermediate species, thus promoting the NH3-SCR to proceed.

  1. 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.

  2. 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.

  3. 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.

  4. Evaluation of mixed valent iron oxides as reactive adsorbents for arsenic removal.

    PubMed

    Mishra, Dhananjay; Farrell, James

    2005-12-15

    The objective of this research was to determine if Fe(II)-bearing iron oxides generate ferric hydroxides at sufficient rates for removing low levels of arsenic in packed-bed reactors, while at the same time avoiding excessive oxide production that contributes to bed clogging in oxygenated waters. Column experiments were performed to determine the effectiveness of three media for arsenic removal over a range in empty bed contact times, influent arsenic concentrations, dissolved oxygen (DO) levels, and solution pH values. Corrosion rates of the media as a function of the water composition were determined using batch and electrochemical methods. Rates of arsenic removal were first order in the As(V) concentration and were greater for media with higher corrosion rates. As(V) removal increased with increasing DO levels primarily due to faster oxidation of the Fe2+ released by media corrosion. To obtain measurable amounts of arsenic removal in 15 mM NaCl electrolyte solutions containing 50 microg/L As(V), the rate of Fe2+ released by the media needed to be at least 15 times greater than the As(V) feed rate into the column. In waters containing 30 mg/L of silica and 50 microg/L of As(V), measurable amounts of arsenic removal were obtained only for Fe2+ release rates that were at least 200 times greater than the As(V) feed rate. Although all columns showed losses in hydraulic conductivity overthe course of 90 days of operation, the conductivity values remained high, and the losses could be reversed by backwashing the media. The reaction products produced by the media in domestic tap water had average As-to-Fe ratios that were approximately 25% higher than those for a commercially available adsorbent.

  5. 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

  6. 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

  7. Rational design of mixed ionic and electronic conducting perovskite oxides for solid oxide fuel cell anode materials: A case study for doped SrTiO3

    SciTech Connect

    Suthirakun, Suwit; Xiao, Guoliang; Ammal, Salai Cheettu; Chen, Fanglin; zur Loye, Hans-Conrad; Heyden, Andreas

    2014-01-01

    The effect of p- and n-type dopants on ionic and electronic conductivity of SrTiO3 based perovskites were investigated both computationally and experimentally. Specifically, we performed density functional theory (DFT) calculations of Na- and La-doped SrTiO3 and Na- and Nb-doped SrTiO3 systems. Constrained ab initio thermodynamic calculations were used to evaluate the phase stability and reducibility of doped SrTiO3 under both oxidizing and reducing synthesis conditions, as well as under anodic solid oxide fuel cell (SOFC) conditions. The density of states (DOS) of these materials was analyzed to study the effects of p- and n-doping on the electronic conductivity. Furthermore, Na- and La-doped SrTiO3 and Na- and Nb-doped SrTiO3 samples were experimentally prepared and the conductivity was measured to confirm our computational predictions. The experimental observations are in very good agreement with the theoretical predictions that doping n-doped SrTiO3 with small amounts of p-type dopants promotes both the ionic and electronic conductivity of the material. This doping strategy is valid independent of p- and n-doping site and permits the synthesis of perovskite based mixed ionic/electronic conductors.

  8. 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

  9. 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.

  10. 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.

  11. In situ atomic force microscopy imaging of electrodeposition of mixed layers of copper/cuprous oxide

    SciTech Connect

    Bonnefont, A.; Kostecki, R.; McLarnon, F.; Arrayet, J.C.; Servant, L.; Argoul, F.

    1999-11-01

    In situ atomic force microscopy (AFM) was applied to the dynamic characterization of the growth of mixed Cu/Cu{sub 2}O layers obtained by galvanostatic electrodeposition from alkaline Cu(II) lactate solutions. The correlation of the cathode potential profile with the average topographic profiles computed from the AFM images provided evidence for two transitions in the deposit growth during which the average growth velocity underwent rapid accelerations, the first one corresponding to zero interfacial concentration (Sand's time) and the second one to the emergence of the oscillations by a smooth transition. Despite its temporal resolution, the AFM technique could not capture the details of a single oscillation, but it proved to be quite adequate for tracking the general evolution of the electrode surface.

  12. 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

  13. Mixed Pro- and Anti-Oxidative Effects of Pomegranate Polyphenols in Cultured Cells

    PubMed Central

    Danesi, Francesca; Kroon, Paul A.; Saha, Shikha; de Biase, Dario; D’Antuono, Luigi Filippo; Bordoni, Alessandra

    2014-01-01

    In recent years, the number of scientific papers concerning pomegranate (Punica granatum L.) and its health properties has increased greatly, and there is great potential for the use of bioactive-rich pomegranate extracts as ingredients in functional foods and nutraceuticals. To translate this potential into effective strategies it is essential to further elucidate the mechanisms of the reported bioactivity. In this study HepG2 cells were supplemented with a pomegranate fruit extract or with the corresponding amount of pure punicalagin, and then subjected to an exogenous oxidative stress. Overall, upon the oxidative stress the gene expression and activity of the main antioxidant enzymes appeared reduced in supplemented cells, which were more prone to the detrimental effects than unsupplemented ones. No differences were detected between cells supplemented with the pomegranate juice or the pure punicalagin. Although further studies are needed due to the gaps existing between in vitro and in vivo studies, our results suggest caution in the administration of high concentrations of nutraceutical molecules, particularly when they are administered in concentrated form. PMID:25350111

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

    NASA Astrophysics Data System (ADS)

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

    1999-04-01

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

  15. 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}.

  16. Removal of hazardous chlorinated VOCs over Mn-Cu mixed oxide based catalyst.

    PubMed

    Vu, Van Hinh; Belkouch, Jamal; Ould-Dris, Aïssa; Taouk, Bechara

    2009-09-30

    MnCuO(x)/TiO(2) supported catalyst was synthesized by the incipient wetness impregnation method. The catalyst was then tested for the oxidation of chlorobenzene (CB) used as a Cl-VOC model. The results showed that MnCuO(x)/TiO(2) is very active for CB oxidation since a total conversion (exclusively into H(2)O, CO(2) and Cl(2)) was reached at 350 degrees C without formation of any other harmful organic compounds and no catalyst deactivation was observed. This performance was attributed to the formation Mn(1.6)Cu(1.4)O(4) spinel phase. However, at lower temperatures, some deactivation occurred before a steady-state is reached. At 300 degrees C, the CB conversion decreased and stabilised at 75% after 5h and a small amount of HCl and traces of CO were detected. The reason why HCl was not detected at temperatures higher than 350 degrees C was explained by Deacon reaction. SEM/EDS analysis revealed the presence of chlorine uniformly dispersed on the catalyst surface. The formation of chlorinated compound (MnCuO(x-a)Cl(2a)/TiO(2)), which is presumed to be responsible of the catalyst partial deactivation, was confirmed by other analysis experiments (TG/DTA, TPR). The catalyst regeneration under air at 350 degrees C allowed the system to recover the initial activity in spite of the fact that the chlorine was not completely removed from the catalyst. PMID:19411136

  17. 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.

  18. 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

  19. 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.

  20. 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

  1. 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.

  2. 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

  3. 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.

  4. Mixed titanium, silicon, and aluminum oxide nanostructures as novel adsorbent for removal of rhodamine 6G and methylene blue as cationic dyes from aqueous solution.

    PubMed

    Pal, Umapada; Sandoval, Alberto; Madrid, Sergio Isaac Uribe; Corro, Grisel; Sharma, Vivek; Mohanty, Paritosh

    2016-11-01

    Mixed oxide nanoparticles containing Ti, Si, and Al of 8-15 nm size range were synthesized using a combined sol-gel - hydrothermal method. Effects of composition on the structure, morphology, and optical properties of the nanoparticles were studied using X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), microRaman spectroscopy, and diffuse reflectance spectroscopy (DRS). Dye removal abilities of the nanoparticles from aqueous solutions were tested for different cationic dyes. While all the mixed oxide nanoparticles revealed high and fast adsorption of cationic dyes, the particles containing Ti and Si turned out to be the best. The adsorption kinetics and equilibrium adsorption behavior of the adsorbate - adsorbent systems could be well described by pseudo-second-order kinetics and Langmuir isotherm model, respectively. Estimated thermodynamic parameters revealed the adsorption process is spontaneous, driven mainly by the electrostatic force between the cationic dye molecules and negative charge at nanoparticle surface. Highest dye adsorption capacity (162.96 mg MB/g) of the mixed oxide nanostructures containing Ti and Si is associated to their high specific surface area, and the presence of surface Si-O(δ-) groups, in addition to the hydroxyl groups of amorphous titania. Mixed oxide nanoparticles containing 75% Ti and 25% Si seen to be the most efficient adsorbents for removing cationic dye molecules from wastewater.

  5. Mixed titanium, silicon, and aluminum oxide nanostructures as novel adsorbent for removal of rhodamine 6G and methylene blue as cationic dyes from aqueous solution.

    PubMed

    Pal, Umapada; Sandoval, Alberto; Madrid, Sergio Isaac Uribe; Corro, Grisel; Sharma, Vivek; Mohanty, Paritosh

    2016-11-01

    Mixed oxide nanoparticles containing Ti, Si, and Al of 8-15 nm size range were synthesized using a combined sol-gel - hydrothermal method. Effects of composition on the structure, morphology, and optical properties of the nanoparticles were studied using X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), microRaman spectroscopy, and diffuse reflectance spectroscopy (DRS). Dye removal abilities of the nanoparticles from aqueous solutions were tested for different cationic dyes. While all the mixed oxide nanoparticles revealed high and fast adsorption of cationic dyes, the particles containing Ti and Si turned out to be the best. The adsorption kinetics and equilibrium adsorption behavior of the adsorbate - adsorbent systems could be well described by pseudo-second-order kinetics and Langmuir isotherm model, respectively. Estimated thermodynamic parameters revealed the adsorption process is spontaneous, driven mainly by the electrostatic force between the cationic dye molecules and negative charge at nanoparticle surface. Highest dye adsorption capacity (162.96 mg MB/g) of the mixed oxide nanostructures containing Ti and Si is associated to their high specific surface area, and the presence of surface Si-O(δ-) groups, in addition to the hydroxyl groups of amorphous titania. Mixed oxide nanoparticles containing 75% Ti and 25% Si seen to be the most efficient adsorbents for removing cationic dye molecules from wastewater. PMID:27529381

  6. 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.

  7. 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

  8. 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

  9. Fe(II)Ti(IV)O3 mixed oxide monolayer at rutile TiO2(011): Structures and reactivities

    NASA Astrophysics Data System (ADS)

    Wen, Zhan-Hui; Halpegamage, Sandamali; Gong, Xue-Qing; Batzill, Matthias

    2016-11-01

    Mixed-metal oxide monolayer grown at an oxide support is of great potential in applications like heterogeneous catalysis. In this work, the experimentally obtained ordered mixed FeTiO3 oxide monolayer supported by rutile TiO2(011) surface has been carefully studied with density functional theory calculations. The genetic algorithm based optimization scheme has been employed to improve the searching capacity for possible structures, and a well ordered mixed Fe(II)Ti(IV)O3 monolayer oxide structure much more stable than the one proposed previously has been successfully located. The new surface structure consists of uniformly distributed Ti and Fe cations in the ratio of 2:1. The simulated Scanning Tunneling Microscopy image based on this model is well consistent with the experimental one. Our calculations have shown that the O vacancy formation energy is rather high at the surface. We have also studied the adsorption of O2 and CO at the exposed Fe sites on the surface as well as their reactions. The adsorption energies of O2 are generally higher than those of CO. The catalytic cycle of CO oxidation following an Eley-Rideal type mechanism has been located for CO to react with surface adsorbed O2 and O.

  10. Cholesterol oxidase catalyzed oxidation of cholesterol in mixed lipid monolayers: effects of surface pressure and phospholipid composition on catalytic activity.

    PubMed

    Grönberg, L; Slotte, J P

    1990-04-01

    The catalytic activity of cholesterol oxidase from Streptomyces sp. in mixed monolayers of 1-palmitoyl-2-oleoylphosphatidylcholine (POPC), N-oleoylsphingomyelin (O-SPM), and cholesterol (CHL) has been determined at lateral surface pressures between 10 and 30 mN/m. The highest cholesterol oxidase activity (determined at 37 degrees C) was observed at surface pressures around 20 mN/m in a POPC/CHL monolayer (50:50 mol %). Above and below this surface pressure, the enzyme activity decreased markedly. A similar optimal activity vs surface pressure relationship was observed also for an O-SPM/CHL monolayer (50:50 mol %). The activity of cholesterol oxidase toward cholesterol in the O-SPM/CHL monolayer was, however, less than in the corresponding POPC mixed monolayer. The surface activity of cholesterol oxidase decreased markedly when the temperature was lowered to 20 degrees C, and hardly any enzyme activity was observed in an O-SPM/CHL monolayer at 25 mN/m or above. With a monolayer containing POPC/O-SPM/CHL (42:18:40 mol %), maximal cholesterol oxidase activity was observed at the lowest surface pressure tested (i.e., 10 mN/m), and the catalytic activity decreased markedly with increasing lateral surface pressures in the monolayer. The results of this study show (i) that the activity of cholesterol oxidase in general is highly dependent on the lateral surface pressure in the substrate membranes and (ii) that sphingomyelin, by interacting tightly with cholesterol, can prevent or restrain the accessibility of cholesterol for oxidation by cholesterol oxidase.

  11. 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

  12. 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

  13. 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

  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. 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.

  16. 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.

  17. Overall and local distortion effects on the metal-nonmetal transitions of mixed valent perovskite type manganese oxides

    NASA Astrophysics Data System (ADS)

    Kwon, Young-Uk; Chi, Eun-Ok; Kang, Jae-Kyoung; Hur, Nam Hwi

    1997-09-01

    The metal-nonmetal (MN) transition data of mixed valent manganese oxide perovskites A1-xAx'MnO3 (A: trivalent lanthanide metals, A': divalent metals, 0.20.906 and σ≲σ=232t-202 (pm). Large t and small σ are favorable for high TMN. TMN data of A0.7Ba0.15Sr0.15MnO3 (A=La, Pr, Nd, Sm), A0.7Ba0.15Ca0.15MnO3 (A=La, Pr, Nd, Sm), (La0.7Ca0.3)x(Gd0.7Ba0.3)1-xMnO3 (x=0.1, 0.3, 0.5, 0.7, 0.9), and (Nd0.7Ca0.3)x (Gd0.7Ba0.3)1-xMnO3 (x=0.25, 0.3, 0.5, 0.55, 0.7, 0.75) newly synthesized are reported.

  18. Optical and chemical properties of mixed-valent rhenium oxide films synthesized by reactive DC magnetron sputtering

    NASA Astrophysics Data System (ADS)

    Murphy, Neil R.; Gallagher, Regina C.; Sun, Lirong; Jones, John G.; Grant, John T.

    2015-07-01

    Mixed-valent rhenium oxide thin films were deposited using reactive magnetron sputtering employing a metallic rhenium target within an oxygen-argon environment. The oxygen and argon flow rates were systematically varied, while the extinction coefficient, k, of the deposited layers was monitored using in situ spectroscopic ellipsometry. In situ monitoring was used to identify absorption features specific to ReO3, namely, the minimization of k brought on by the gap between interband absorption features in the UV at 310 nm and the onset of free electron absorption at wavelengths above 540 nm. Based on these results, oxygen flow ratios of 50% and 60% were shown to produce films having optical properties characteristic of ReO3, and thus, were selected for detailed ex situ characterization. Chemical analysis via X-ray photoelectron spectroscopy confirmed that all films consisted largely of ReO3, but had some contributions from Re2O3, ReO2 and Re2O7. Additional monitoring of the chemistry, as a function of environmental exposure time, indicated a correlation between structural instability and the presence of Re2O3 and Re2O7 in the films.

  19. Computer modeling of the local structure, mixing properties, and stability of solid solutions of alkaline-earth metal oxides

    SciTech Connect

    Urusov, V. S. Petrova, T. G. Eremin, N. N.

    2008-11-15

    A technique for the computer modeling of disordered binary oxide solid solutions MO-M'O in a wide composition range has been developed. The method of atomistic pair potentials was used for 4 x 4 x 4 supercells. The parameters of the potentials are optimized using the structural and elastic properties of pure components MgO, CaO, SrO, and BaO. The temperature dependences of the heat capacity and entropy are calculated for pure components. The excess mixing properties (enthalpy, volume, bulk modulus, vibrational entropy) are found for different compositions of Mg{sub x}Ca{sub (1-x)}O, Ca{sub x}Sr{sub (1-x)}O, and Sr{sub x}Ba{sub (1-x)}O solid solutions. Temperature and composition dependences of the excess Gibbs energy were constructed, which made it possible to approximately estimate the critical decomposition temperatures and limits of component miscibility. Statistical analysis of lattice distortions in the first and second coordination spheres reveals a detailed picture of the solid-solution local structure.

  20. 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.

  1. Computer modeling of the local structure, mixing properties, and stability of solid solutions of alkaline-earth metal oxides

    NASA Astrophysics Data System (ADS)

    Urusov, V. S.; Petrova, T. G.; Eremin, N. N.

    2008-11-01

    A technique for the computer modeling of disordered binary oxide solid solutions MO- M'O in a wide composition range has been developed. The method of atomistic pair potentials was used for 4 × 4 × 4 supercells. The parameters of the potentials are optimized using the structural and elastic properties of pure components MgO, CaO, SrO, and BaO. The temperature dependences of the heat capacity and entropy are calculated for pure components. The excess mixing properties (enthalpy, volume, bulk modulus, vibrational entropy) are found for different compositions of Mg x Ca(1 - x)O, Ca x Sr(1 - x)O, and Sr x Ba(1 - x)O solid solutions. Temperature and composition dependences of the excess Gibbs energy were constructed, which made it possible to approximately estimate the critical decomposition temperatures and limits of component miscibility. Statistical analysis of lattice distortions in the first and second coordination spheres reveals a detailed picture of the solid-solution local structure.

  2. Charge injection properties of iridium oxide films produced on Ti-6Al-4V alloy substrates by ion-beam mixing techniques

    SciTech Connect

    Williams, J.M. ); Lee, I-S.; Buchanan, R.A. )

    1991-10-01

    The charge injection capabilities of iridium oxide films, as produced on Ti6Al-4V alloy substrates by ion beam mixing techniques, have been investigated. Iridium oxide is a valence change oxide, and therefore has high values of charge injection density upon voltage cycling in electrolytes. Because of this property, iridium oxide films are useful as working elements in neural prostheses. Iridium films of three thicknesses, produced by sputter deposition followed by ion beam mixing, were tested in cyclic voltammetry out to 1000 cycles or more. Two surface preparations, mechanical polishing and an acid passivation treatment, were also used as controls. Surface analysis was primarily by Rutherford backscattering spectrometry. Both the ion- beam mixing and the acid pretreatment increased the lifetimes of films, in comparison with the mechanically polished standards. Reductions in charge injection capability, when they occurred, were attributed to loss of Ir from the films, and there was a close correlation between the charge injection density and the Ir inventory. 13 refs., 5 figs.

  3. 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.

  4. 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.

  5. Surface sites on Pt-CeO2 mixed oxide catalysts probed by CO adsorption: a synchrotron radiation photoelectron spectroscopy study.

    PubMed

    Neitzel, Armin; Lykhach, Yaroslava; Skála, Tomáš; Tsud, Nataliya; Vorokhta, Mykhailo; Mazur, Daniel; Prince, Kevin C; Matolín, Vladimír; Libuda, Jörg

    2014-12-01

    By means of synchrotron radiation photoemission spectroscopy, we have investigated Pt-CeO2 mixed oxide films prepared on CeO2(111)/Cu(111). Using CO molecules as a probe, we associate the corresponding surface species with specific surface sites. This allows us to identify the changes in the composition and morphology of Pt-CeO2 mixed oxide films caused by annealing in an ultrahigh vacuum. Specifically, two peaks in C 1s spectra at 289.4 and 291.2 eV, associated with tridentate and bidentate carbonate species, are formed on the nanostructured stoichiometric CeO2 film. The peak at 290.5-291.0 eV in the C 1s spectra indicates the onset of restructuring, i.e. coarsening, of the Pt-CeO2 film. This peak is associated with a carbonate species formed near an oxygen vacancy. The onset of cerium oxide reduction is indicated by the peak at 287.8-288.0 eV associated with carbonite species formed near Ce(3+) cations. The development of surface species on the Pt-CeO2 mixed oxides suggests that restructuring of the films occurs above 300 K irrespective of Pt loadings. We do not find any adsorbed CO species associated with Pt(4+) or Pt(2+). The onset of Pt(2+) reduction is indicated by the peak at 286.9 eV in the C 1s spectra due to CO adsorption on metallic Pt particles. The thermal stability of Pt(2+) in Pt-CeO2 mixed oxide depends on Pt loading. We find excellent stability of Pt(2+) for 12% Pt content in the CeO2 film, whereas at a Pt concentration of 25% in the CeO2 film, a large fraction of the Pt(2+) is converted into metallic Pt particles above 300 K.

  6. 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

  7. Probing Oxide-Ion Mobility in the Mixed Ionic–Electronic Conductor La2NiO4+δ by Solid-State 17O MAS NMR Spectroscopy

    PubMed Central

    2016-01-01

    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 17O (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 17O NMR and DFT methodology, the approach presented herein should prove applicable to MIECs and other functionally important paramagnetic oxides. PMID:27538437

  8. 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

  9. 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

  10. 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)

  11. Ferrocene functionalized nanoscale mixed-oxides as a potent phosphate adsorbent from the synthetic and real (Persian Gulf) waters.

    PubMed

    Arshadi, M; Zandi, H; Akbari, J; Shameli, A

    2015-07-15

    The application of covalently attached ferrocene groups to the aluminum-silicate nanoparticles (ASNPs) for phosphate (P) removal from the synthetic and real waters has been studied and the prepared nanomaterials were analyzed by XPS, EDS, BET, TEM, chemical analysis (CHN), FTIR, and ICP-AES. The immobilization of the ferrocene on the surface of the inorganic support (mixed oxides) can lead to reduce the drawback of the pristine ferrocene molecules which may have strong tendency to agglomerate into larger particles, resulting in the negative effect on both available active sites and catalyst performance. XPS of Fe ions evidenced that most of the active sites of the nano-adsorbent is in the form of Fe(III) ions at the surface. The heterogeneous Fe(III) ions were effective toward removal of phosphate. The contact time to obtain equilibrium for maximum adsorption of phosphate (100%) was found to be 120 min. The adsorption kinetics of P has been evaluated in terms of pseudo-first- and -second-order kinetics, and the Freundlich and Langmuir isotherm models have also been tested to the equilibrium adsorption results. The adsorption process was spontaneous and endothermic in nature and followed pseudo-second-order kinetic model. FTIR, EDS and XPS results confirmed the formation of Fe-O-P bond on the Si/Al@Fe surface after adsorption of P from aqueous media. The Si/Al@Fe displayed high reusability due to its high removal capacity after 10th adsorption-desorption runs. The proposed adsorbent could also be utilized to adsorb the P ions from the real sample (Persian Gulf water). The high removal capacity of P ions from the real water and the high levels of reusability confirmed the versatility of the heterogenized ferrocene groups on the ASNPs.

  12. Controlling nanotube dimensions: correlation between composition, diameter, and internal energy of single-walled mixed oxide nanotubes.

    PubMed

    Konduri, Suchitra; Mukherjee, Sanjoy; Nair, Sankar

    2007-12-01

    Control over the diameter of nanotubes is of significance in manipulating their properties, which depend on their dimensions in addition to their structure and composition. This aspect has remained a challenge in both carbon and inorganic nanotubes, since there is no obvious aspect of the formation mechanism that allows facile control over nanotube curvature. Here we develop and analyze a quantitative correlation between the composition, diameter, and internal energy of a class of single-walled mixed oxide aluminosilicogermanate (AlSiGeOH) nanotubes. A series of synthetic AlSiGeOH nanotubes with varying Si/Ge ratio are characterized by X-ray photoelectron spectroscopy, vibrational spectroscopy, energy dispersive X-ray spectroscopy, and X-ray diffraction to relate their compositions and diameters. We then study these nanotubes computationally by first parametrizing and validating a suitable interatomic potential model, and then using this potential model to investigate the internal energy of the nanotube as a function of diameter and composition via molecular dynamics simulations. There are minima in the internal energy as a function of diameter which progressively shift to larger nanotube diameters with increasing Ge content. An approximate analytical theory of nanotube diameter control, which contains a small number of physically significant fitted parameters, well describes the computational data by relating the composition and geometry to the strain energy of bending into a nanotube. The predicted composition-dependent shift in the energetically favored diameter follows the experimental trends. We suggest related methods of controlling nanotube energetics and their role in engineering nanotubes of controlled dimensions by liquid-phase chemistry.

  13. 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.

  14. Overall and local distortion effects on the metal{endash}nonmetal transitions of mixed valent perovskite type manganese oxides

    SciTech Connect

    Kwon, Y.; Chi, E.; Kang, J.; Hur, N.H.

    1997-09-01

    The metal{endash}nonmetal (MN) transition data of mixed valent manganese oxide perovskites A{sub 1{minus}x}A{sub x}{sup {prime}}MnO{sub 3} (A: trivalent lanthanide metals, A{sup {prime}}: divalent metals, 0.2{lt}x{lt}0.5) are analyzed in terms of the tolerance factor (t), and the standard deviation ({sigma}) of the A-site cation sizes. The interplay of these two parameters that measure the overall and atomic scale distortions, respectively, determine whether a compound can show a MN transition or not and its transition temperature (T{sub MN}). In order to show a MN transition, a compound should have t{gt}0.906 and {sigma}{approx_lt}{sigma}=232t{minus}202 (pm). Large t and small {sigma} are favorable for high T{sub MN}. T{sub MN} data of A{sub 0.7}Ba{sub 0.15}Sr{sub 0.15}MnO{sub 3} (A=La, Pr, Nd, Sm), A{sub 0.7}Ba{sub 0.15}Ca{sub 0.15}MnO{sub 3} (A=La, Pr, Nd, Sm), (La{sub 0.7}Ca{sub 0.3}){sub x}(Gd{sub 0.7}Ba{sub 0.3}){sub 1{minus}x}MnO{sub 3} (x=0.1, 0.3, 0.5, 0.7, 0.9), and (Nd{sub 0.7}Ca{sub 0.3}){sub x} (Gd{sub 0.7}Ba{sub 0.3}){sub 1{minus}x}MnO{sub 3} (x=0.25, 0.3, 0.5, 0.55, 0.7, 0.75) newly synthesized are reported. {copyright} {ital 1997 American Institute of Physics.}

  15. 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.

  16. 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

  17. 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.

  18. 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.

  19. 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.

  20. 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.

  1. Au-supported Pt-Au mixed atomic monolayer electrocatalyst with ultrahigh specific activity for oxidation of formic acid in acidic solution.

    PubMed

    Huang, Zhao; Liu, Yan; Xie, Fangyun; Fu, Yingchun; He, Yong; Ma, Ming; Xie, Qingji; Yao, Shouzhuo

    2012-12-25

    Au-supported Pt-Au mixed atomic monolayer electrocatalyst was prepared by underpotential deposition of Cu on Au and then redox replacement with noble metal atoms, which shows an ultrahigh Pt-mass (or Pt-area) normalized specific electrocatalytic activity of 102 mA μg(Pt)(-1) (124 mA cm(Pt)(-2)) for oxidation of formic acid in acidic aqueous solution.

  2. 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

  3. 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.

  4. Thermal and sonochemical synthesis of porous (Ce,Zr)O2 mixed oxides from metal β-diketonate precursors and their catalytic activity in wet air oxidation process of formic acid.

    PubMed

    Cau, Camille; Guari, Yannick; Chave, Tony; Larionova, Joulia; Nikitenko, Sergey I

    2014-07-01

    Porous (Ce0.5Zr0.5)O2 solid solutions were prepared by thermolysis (T=285 °C) or sonolysis (20 kHz, I=32 W cm(-2), Pac=0.46 W mL(-1), T=200 °C) of Ce(III) and Zr(IV) acetylacetonates in oleylamine or hexadecylamine under argon followed by heat treatment of the precipitates obtained in air at 450 °C. Transmission Electron Microscopy images of the samples show nanoparticles of ca. 4-6 nm for the two synthetic approaches. The powder X-ray diffraction, scanning electron microscopy, energy dispersive X-ray and μ-Raman spectroscopy of solids obtained after heat treatment indicate the formation of (Ce0.5Zr0.5)O2 solid solutions with a metastable tetragonal crystal structure for the two synthetic routes. The specific surface area of the samples varies between 78 and 149 m(2) g(-1) depending on synthesis conditions. The use of Barrett-Joyner-Halenda and t-plot methods reveal the formation of mixed oxides with a hybrid morphology that combines mesoporosity and microporosity regardless of the method of preparation. Platinum nanoparticles were deposited on the surface of the mixed oxides by sonochemical reduction of Pt(IV). It was found that the materials prepared by sonochemistry exhibit better resistance to dissolution during the deposition process of platinum. X-ray photoelectron spectroscopy analysis shows the presence of Pt(0) and Pt(II) on the surface of mixed oxides. Porous (Ce0.5Zr0.5)O2 mixed oxides loaded with 1.5%wt. platinum exhibit high activity in catalytic wet air oxidation of formic acid at 40 °C.

  5. Synthesis and characterization of TiO{sub 2}--MgO mixed oxides prepared by the sol-gel method

    SciTech Connect

    Lopez, T.; Hernandez, J.; Gomez, R.; Bokhimi, X.; Boldu, J.L.; Munoz, E.; Novaro, O.; Garcia-Ruiz, A.

    1999-08-31

    Titania-magnesia mixed oxides, with magnesia concentrations between 10 and 90 wt%, were prepared by using to sol-gel method with titanium n-butoxide and magnesium ethoxide as precursors. The mixed oxides were characterized with X-ray powder diffraction, BET nitrogen adsorption isotherms, electron spin resonance (ESR), and by testing their catalytic activity for 2-propanol and 2-butanol dehydration. Samples contained periclase, anatase, karooite (MgTi{sub 2}O{sub 5}), geikielite (MgTiO{sub 3}), and qandilite (Mg{sub 2}TiO{sub 4}). The BET specific surface area varied with magnesia concentration; the samples with 50 wt% MgO had the highest area, 211 m{sup 2}/g. Samples had paramagnetic centers that produced complex ESR spectra when many crystalline phases coexisted. For 2-propanol and 2-butanol decomposition, the activity and selectivity patterns of the mixed oxides were substantially different to those observed in pure TiO{sub 2} and pure MgO. This singular behavior should be a result of the structural defects created by the substitution of Mg{sup 2+} ions by Ti{sup 4+} cations in titania lattice, as well as by the interfaces created when several crystalline phases coexisted.

  6. A practical organometallic decorated nano-size SiO2-Al2O3 mixed-oxides for methyl orange removal from aqueous solution

    NASA Astrophysics Data System (ADS)

    Arshadi, M.; Salimi Vahid, F.; Salvacion, J. W. L.; Soleymanzadeh, M.

    2013-09-01

    In this study, the application of a functional ferrocene (ferrocenecarboxaldehyde) firmly heterogenized over a modified nano-size SiO2-Al2O3 mixed-oxides was reported as a novel adsorbent for the removal of methyl orange from aqueous solution. SiO2-Al2O3 mixed-oxides was functionalized with 3-aminopropyl-triethoxysilane (3-APTES) group and ferrocenecarboxaldehyde covalently linked on this organo-functionalized SiO2-Al2O3 mixed-oxides support. The synthesized materials were characterized by FT-IR spectroscopy, UV-vis, CHN elemental analysis, BET, TGA, ICP-MS, TEM, and XPS. The contact time to obtain equilibrium for maximum adsorption was 50 min. XPS of Fe ions evidenced that most of the active sites of the nano-adsorbent is in the form of Fe3+ ions at the surface. The heterogeneous Fe3+ ions were found to be effective adsorbent for the removal of dyes from solution. The adsorption of methyl orange ions has been studied in terms of pseudo-first-order and pseudo-second-order kinetics, and the Freundlich, Langmuir, and Langmuir-Freundlich isotherm models have also been applied to the equilibrium adsorption data. The adsorption process was spontaneous and endothermic in nature and followed pseudo-second-order kinetic model.

  7. 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.

  8. Dual-mode T1 and T2 magnetic resonance imaging contrast agent based on ultrasmall mixed gadolinium-dysprosium oxide nanoparticles: synthesis, characterization, and in vivo application

    NASA Astrophysics Data System (ADS)

    Tegafaw, Tirusew; Xu, Wenlong; Wasi Ahmad, Md; Baeck, Jong Su; Chang, Yongmin; Bae, Ji Eun; Chae, Kwon Seok; Kim, Tae Jeong; Lee, Gang Ho

    2015-09-01

    A new type of dual-mode T1 and T2 magnetic resonance imaging (MRI) contrast agent based on mixed lanthanide oxide nanoparticles was synthesized. Gd3+ (8S7/2) 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 Dy3+ (6H15/2) 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 Gd3+ and Dy3+ 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.

  9. 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.

  10. 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

  11. 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

  12. Structural and spectroscopic properties of high temperature prepared ZrO2-TiO2 mixed oxides

    NASA Astrophysics Data System (ADS)

    Gionco, Chiara; Battiato, Alfio; Vittone, Ettore; Paganini, Maria Cristina; Giamello, Elio

    2013-05-01

    ZrO2-TiO2 mixed oxides of various composition, with the molar fraction of TiO2 ranging from 0.1% to 15%, have been prepared via sol-gel synthesis and then calcined at 1273 K to check both their thermal stability and physicochemical properties. These solids are usually employed in photocatalytic processes and as active phase supports in heterogeneous catalysis. As indicated by X-ray diffraction and Raman spectroscopy, solid solutions based on Ti ions diluted in the ZrO2 matrix are formed in the whole range of Ti molar fraction examined. Materials with low Ti loading (0.1%-1%) are basically constituted by the monoclinic phase of ZrO2 while the tetragonal phase becomes prevalent at 15% of TiO2 molar fraction. The presence of Ti ions modify the electronic structure of the solid as revealed by investigation of the optical properties. The typical band gap transition of ZrO2 undergoes, in fact, a red shift roughly proportional to the Ti loading which reach the remarkable value of 1.6 eV for the sample with 10% of molar Ti concentration. Comparing chemical analysis of the solids with XPS data it has been put into evidence that the titanium ions distribution into the solid is not uniform and the concentration of Ti4+ tend to be higher in subsurface layers than in the crystal bulk. The introduction of titanium ions in the structure increases the reducibility of the solid. Annealing under vacuum at various temperatures causes oxygen depletion with consequent reduction of the solid which shows up mainly in terms of formation of Ti3+ reduced centres which are characterized by a typical EPR signal. Ti3+ defects forms, as also forecast by theoretical modelling of the solid, as their energy is lower than that of other possible reduced defective centers. The reduced solids are able to transfer electrons to adsorbed oxygen molecules in mild condition resulting in the formation of surface superoxide anions (O2•-) which are stabilized on surface Zr4+ or, alternatively, on Ti4+ ions

  13. The effect of oxidant and the non-oxidant alteration of cellular thiol concentration on the formation of protein mixed-disulfides in HEK 293 cells.

    PubMed

    Gilge, Jasen Lee; Fisher, Michael; Chai, Yuh-Cherng

    2008-01-01

    Cellular molecules possess various mechanisms in responding to oxidant stress. In terms of protein responses, protein S-glutathionylation is a unique post-translational modification of protein reactive cysteines forming disulfides with glutathione molecules. This modification has been proposed to play roles in antioxidant, regulatory and signaling in cells under oxidant stress. Recently, the increased level of protein S-glutathionylation has been linked with the development of diseases. In this report, specific S-glutathionylated proteins were demonstrated in human embryonic kidney 293 cells treated with two different oxidative reagents: diamide and hydrogen peroxide. Diamide is a chemical oxidizing agent whereas hydrogen peroxide is a physiological oxidant. Under the experimental conditions, these two oxidants decreased glutathione concentration without toxicity. S-glutathionylated proteins were detected by immunoblotting and glutathione concentrations were determined by high performance liquid chromatography. We further show the effect of alteration of the cellular thiol pool on the amount of protein S-glutathionylation in oxidant-treated cells. Cellular thiol concentrations were altered either by a specific way using buthionine sulfoximine, a specific inhibitor of glutathione biosynthesis or by a non-specific way, incubating cells in cystine-methionine deficient media. Cells only treated with either buthionine sulfoximine or cystine-methionine deficient media did not induce protein S-glutathionylation, even though both conditions decreased 65% of cellular glutathione. Moreover, the amount of protein S-glutathionylation under both conditions in the presence of oxidants was not altered when compared to the amount observed in regular media with oxidants present. Protein S-glutathionylation is a dynamic reaction which depends on the rate of adding and removing glutathione. Phenylarsine oxide, which specifically forms a covalent adduct with vicinal thiols, was used

  14. Solid state reactions of nanocrystalline Ce{sub 0.5}Yb{sub 0.5}O{sub 1.75} mixed oxide with high surface area silica in oxidizing and reducing atmosphere

    SciTech Connect

    Malecka, Malgorzata A.; Kepinski, Leszek

    2012-08-15

    The interaction of nanocrystalline Ce{sub 0.5}Yb{sub 0.5}O{sub 1.75} mixed oxide with a high surface amorphous silica support in an oxidizing and reducing atmosphere was studied by XRD, HRTEM, SAED, SEM and BET techniques. The Ce{sub 0.5}Yb{sub 0.5}O{sub 1.75}-SiO{sub 2} system shows very high structural and size stability in the oxidizing atmosphere up to 1000 Degree-Sign C, but in hydrogen spreading of the oxide onto silica occurs at temperatures above 800 Degree-Sign C. In the oxidizing atmosphere stability of the mixed oxide is limited by extraction of ytterbium from the oxide driven by a tendency to form ytterbium silicates. A new polymorph of Yb silicate, isomorphic with y-Y{sub 2}Si{sub 2}O{sub 7} (yttrialite), has been identified in the samples containing the mixed Ce-Yb oxide. The absence of y-Yb{sub 2}Si{sub 2}O{sub 7} silicate in the Yb{sub 2}O{sub 3}-SiO{sub 2} samples treated in similar conditions indicates that Ce{sup 4+} ions are needed to stabilize the structure. - Graphical abstract: Structure evolution of nano-Ce{sub 0.5}Yb{sub 0.5}O{sub 1.75}-SiO{sub 2} in air and in H{sub 2}. Highlights: Black-Right-Pointing-Pointer Nano-Ce{sub 0.50}Yb{sub 0.50}O{sub 1.75} on SiO{sub 2} is stable in air up to 1000 Degree-Sign C but spreads in hydrogen at 800 Degree-Sign C. Black-Right-Pointing-Pointer Formation of Yb silicates determines the stability of Ce{sub 0.50}Yb{sub 0.50}O{sub 1.75} at high temperatures. Black-Right-Pointing-Pointer New, y-Yb{sub 2}Si{sub 2}O{sub 7} silicate (yttrialite type) forms in Ce{sub 0.5}Yb{sub 0.5}O{sub 1.75}-SiO{sub 2} in H{sub 2} at 1100 Degree-Sign C.

  15. 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.

  16. 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.

  17. Amperometric biosensors based on carbon paste electrodes modified with nanostructured mixed-valence manganese oxides and glucose oxidase.

    PubMed

    Cui, Xiaoli; Liu, Guodong; Lin, Yuehe

    2005-06-01

    Nanostructured, multivalent, manganese-oxide octahedral molecular sieves (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 subnanometer 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. With glucose oxidase (GOx) as an enzyme model, amperometric glucose biosensors are constructed by bulk modification of carbon paste electrodes with GOx 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 mmol/L and 1.75 mmol/L, and detection limits (S/N = 3) of 0.1 mmol/L and 0.05 mmol/L 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.

  18. 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.

  19. 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

  20. 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

  1. Photochemically deposited nano-Ag/sol-gel TiO2-In2O3 mixed oxide mesoporous-assembled nanocrystals for photocatalytic dye degradation.

    PubMed

    Sreethawong, Thammanoon; Ngamsinlapasathian, Supachai; Yoshikawa, Susumu

    2014-05-01

    This work focused on the improvement of the photocatalytic activity for Congo Red (CR) azo dye degradation of mesoporous-assembled 0.95 TiO2-0.05 In2O3 mixed oxide photocatalyst (with a TiO2-to-In2O3 molar ratio of 0.95:0.05) by loading with Ag nanoparticles. The mesoporous-assembled 0.95TiO2-0.05In2O3 mixed oxide photocatalyst was synthesized by a hydrolytic sol-gel method with the aid of a structure-directing surfactant, prior to loading with various Ag contents (0.5-2 wt.%) by a photochemical deposition method. The optimum Ag loading content was found to be 1.5 wt.%, exhibiting a great increase in photocatalytic CR dye degradation activity. The 1.5 wt.% Ag-loaded 0.95TiO2-0.05In2O3 mixed oxide photocatalyst was further applied for the CR dye degradation in the presence of water hardness. Different types (Ca2+ and Ca2+ -Mg2+ mixture) and concentrations (200 and 500 mg/l) of water hardness were investigated. The results showed that the water hardness reduced the photocatalytic CR dye degradation activity, particularly for the extremely hard water with 500 mg/l of Ca2+ -Mg2+ mixture. The adjustment of initial solution pH of the CR dye-containing hard water to an appropriate value was found to improve the photocatalytic CR dye degradation activity under the identical reaction conditions.

  2. Mixed-metal MIL-100(Sc,M) (M=Al, Cr, Fe) for Lewis acid catalysis and tandem C-C bond formation and alcohol oxidation.

    PubMed

    Mitchell, Laura; Williamson, Patrick; Ehrlichová, Barbora; Anderson, Amanda E; Seymour, Valerie R; Ashbrook, Sharon E; Acerbi, Nadia; Daniels, Luke M; Walton, Richard I; Clarke, Matthew L; Wright, Paul A

    2014-12-15

    The trivalent metal cations Al(3+) , Cr(3+) , and Fe(3+) were each introduced, together with Sc(3+) , into MIL-100(Sc,M) solid solutions (M=Al, Cr, Fe) by direct synthesis. The substitution has been confirmed by powder X-ray diffraction (PXRD) and solid-state NMR, UV/Vis, and X-ray absorption (XAS) spectroscopy. Mixed Sc/Fe MIL-100 samples were prepared in which part of the Fe is present as α-Fe2 O3 nanoparticles within the mesoporous cages of the MOF, as shown by XAS, TGA, and PXRD. The catalytic activity of the mixed-metal catalysts in Lewis acid catalysed Friedel-Crafts additions increases with the amount of Sc present, with the attenuating effect of the second metal decreasing in the order Al>Fe>Cr. Mixed-metal Sc,Fe materials give acceptable activity: 40 % Fe incorporation only results in a 20 % decrease in activity over the same reaction time and pure product can still be obtained and filtered off after extended reaction times. Supported α-Fe2 O3 nanoparticles were also active Lewis acid species, although less active than Sc(3+) in trimer sites. The incorporation of Fe(3+) into MIL-100(Sc) imparts activity for oxidation catalysis and tandem catalytic processes (Lewis acid+oxidation) that make use of both catalytically active framework Sc(3+) and Fe(3+) . A procedure for using these mixed-metal heterogeneous catalysts has been developed for making ketones from (hetero)aromatics and a hemiacetal.

  3. Poly(ethylene glycol) and hydroxy functionalized alkane phosphate mixed self-assembled monolayers to control nonspecific adsorption of proteins on titanium oxide surfaces.

    PubMed

    Bozzini, Sabrina; Petrini, Paola; Tanzi, Maria Cristina; Zürcher, Stefan; Tosatti, Samuele

    2010-05-01

    The spontaneous formation of alkane phosphate self-assembled monolayers (SAMs) on titanium oxide was chosen as a tool to tailor the surface physicochemical properties in terms of nonspecific adsorption of proteins. For this aim, poly(ethylene glycol)-modified (PEG) alkane phosphate was codeposited with OH-terminated alkane phosphates. X-ray photoelectron spectroscopy and ellipsometry of the resulting mixed SAMs indicate that the PEG density can be controlled by varying the mole fraction of PEG-terminated phosphates in the solutions used during the deposition process, leading to surfaces with different degrees of protein resistance.

  4. Analysis of optical density data generated from neutron radiographs of uranium-plutonium mixed oxide fuel pellets inside sealed nuclear fuel pins

    NASA Astrophysics Data System (ADS)

    Panakkal, J. P.; Ghosh, J. K.; Roy, P. R.

    1986-03-01

    A quantitative analysis of neutron radiographs of welded nuclear fuel pins containing uranium-plutonium mixed oxide fuel pellets has been carried out to obtain a simple model for the transmission of neutrons through fuel pins during neutron radiography. The optical density data obtained by detailed microdensitometer scanning across the image of pellets of varying plutonium enrichment has been correlated to the product of the macroscopic neutron cross section and the distance traversed by the neutrons. Based on the experimental data, a simple model which can be applied to fuel pins of different dimensions and plutonium enrichment has been derived.

  5. 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.

  6. Improved low temperature NH3-SCR performance of FeMnTiO(x) mixed oxide with CTAB-assisted synthesis.

    PubMed

    Wu, Shiguo; Yao, Xiaojiang; Zhang, Lei; Cao, Yuan; Zou, Weixin; Li, Lulu; Ma, Kaili; Tang, Changjin; Gao, Fei; Dong, Lin

    2015-02-25

    FeMnTiOx mixed oxide is prepared by the CTAB-assisted co-precipitation method, and the transformation of anatase into rutile is inhibited by CTAB to some extent. The catalyst obtained in the present work shows nearly 100% NO conversion at 100-350 °C, more than 80% N2 selectivity at 75-200 °C, and excellent H2O durability for the selective catalytic reduction of NO by NH3 with a space velocity of 30,000 mL g(-1) h(-1).

  7. 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.

  8. 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).

  9. 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.

  10. Determination of intermediates and mechanism for soot combustion with NOx/O₂ on potassium-supported Mg-Al hydrotalcite mixed oxides by in situ FTIR.

    PubMed

    Zhang, Zhaoliang; Zhang, Yexin; Su, Qingyun; Wang, Zhongpeng; Li, Qian; Gao, Xiyan

    2010-11-01

    The soot combustion with NO(x) and/or O(2) on potassium-supported Mg-Al hydrotalcite mixed oxides under tight contact condition was studied using temperature-programmed oxidation (TPO), isothermal reaction and in situ FTIR techniques. The presence of NO(x) in O(2) favors the soot combustion at lower temperatures (<300 °C). However, a little suppression was observed at higher temperatures (>300 °C), which was accompanied by a substantial NO(x) reduction. The ketene (C═C═O) and isocyanate (NCO(-)) species were determined as the reaction intermediates. In NO(x) + O(2), NO(2) directly interacts with the free carbon sites (C═C*) through two parallel reactions: (1) NO(2) + C═C* → C═C═O + NO; (2) NO(2) + C═C* → NCO(-) + CO(2). The two reactions can proceed easily, which accounts for the promotion effect of NO(x) on soot combustion at lower temperatures. The further oxidation of NCO(-) by NO(2) or O(2) is responsible for the simultaneous reduction of NO(x). However, the reactions between NO(2) and C═C* are limited by the amount of free carbon sites, which can be provided by the oxidation of soot by O(2) at higher temperatures. The interaction of NO(x) and catalyst results in the formation of nitrates and nitrites, which poisoned the active K sites.

  11. 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.

  12. 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

  13. 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

  14. Measurements of substrate oxidation using (13)CO 2-breath testing reveals shifts in fuel mix during starvation.

    PubMed

    McCue, Marshall D; Pollock, Erik D

    2013-12-01

    Most fasting animals are believed to sequentially switch from predominantly utilizing one metabolic substrate to another from carbohydrates, to lipids, then to proteins. The timing of these physiological transitions has been estimated using measures of substrate oxidation including changes in respiratory exchange ratios, blood metabolites, nitrogen excretion, or enzyme activities in tissues. Here, we demonstrate how (13)CO2-breath testing can be used to partition among the oxidation of distinct nutrient pools in the body (i.e., carbohydrates, lipids, and proteins) that have become artificially enriched in (13)C. Seventy-two Swiss Webster mice were raised to adulthood on diets supplemented with (13)C-1-L-leucine, (13)C-1-palmitic acid, (13)C-1-D-glucose, or no tracer. Mice were then fasted for 72 h during which [Formula: see text], [Formula: see text], δ(13)C of exhaled CO2, body temperature, body mass, and blood metabolites (i.e., glucose, ketone bodies, and triacylglycerols) were measured. The fasting mice exhibited reductions in body mass (29 %), body temperature (3.3 °C), minimum observed metabolic rates (24 %), and respiratory exchange ratio (0.18), as well as significant changes in blood metabolites; but these responses were not particularly indicative of changes in oxidative fuel mixture. Measurements of endogenous nutrient oxidation by way of (13)CO2-breath testing revealed a decrease in the rate of oxidation of carbohydrates from 61 to 10 % of the total energy expenditure during the first 6 h without food. This response was mirrored by a coincidental increase in rate of endogenous lipid oxidation from 18 to 64 %. A transient peak in carbohydrate oxidation occurred between 8 and 14 h, presumably during increased glycogen mobilization. A well-defined period of protein sparing between 8 and 12 h was observed where endogenous protein oxidation accounted for as little as 8 % of the total energy expenditure. Thereafter, protein oxidation continually

  15. Method for making fine and ultrafine spherical particles of zirconium titanate and other mixed metal oxide systems

    SciTech Connect

    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.

  16. Structure and photoluminescence studies of CeO2·CuAlO2 mixed metal oxide fabricated by co-precipitation method

    NASA Astrophysics Data System (ADS)

    Subhan, Md Abdus; Ahmed, Tanzir; Awal, M. R.; Kim, B. Moon

    2015-01-01

    A novel mixed metal oxide, CeO2·CuAlO2 was fabricated by co-precipitation method in aqueous medium. CeO2·CuAlO2 was characterized by XRD, SEM, EDS, TEM, FTIR and PL spectra. The optical properties of the nanoparticles were studied by photoluminescence (PL) spectra. PL spectra at different excitations were recorded. The composite showed emission in UV, visible and NIR region depending on the excitation wavelength. The special spectral feature observed for this composite is that it showed six emission bands at 364, 409, 434, 448, 465 and 481 nm when excited at 298 nm. The green and red emissions observed at 512 and 669 nm are originated from cubic CeO2 phase when excited at 450 nm. The PL spectra were found to be dependent on excitation wavelength violating Kasha's rule. The X-ray diffraction reveals a cubic CeO2 phase and hexagonal CuAlO2 phase. EDS spectra revealed the presence of cerium (Ce), copper (Cu), aluminum (Al) and oxygen (O) elements. The particle size of the CeO2·CuAlO2 mixed oxide was estimated using Scherrer's formula, which was found to be in the range of 17.2-34.2 nm. The TEM image showed particles are almost uniform size of approximately 15-50 nm with spherical morphology.

  17. Structure and photoluminescence studies of CeO2·CuAlO2 mixed metal oxide fabricated by co-precipitation method.

    PubMed

    Subhan, Md Abdus; Ahmed, Tanzir; Awal, M R; Kim, B Moon

    2015-01-25

    A novel mixed metal oxide, CeO2·CuAlO2 was fabricated by co-precipitation method in aqueous medium. CeO2·CuAlO2 was characterized by XRD, SEM, EDS, TEM, FTIR and PL spectra. The optical properties of the nanoparticles were studied by photoluminescence (PL) spectra. PL spectra at different excitations were recorded. The composite showed emission in UV, visible and NIR region depending on the excitation wavelength. The special spectral feature observed for this composite is that it showed six emission bands at 364, 409, 434, 448, 465 and 481 nm when excited at 298 nm. The green and red emissions observed at 512 and 669 nm are originated from cubic CeO2 phase when excited at 450 nm. The PL spectra were found to be dependent on excitation wavelength violating Kasha's rule. The X-ray diffraction reveals a cubic CeO2 phase and hexagonal CuAlO2 phase. EDS spectra revealed the presence of cerium (Ce), copper (Cu), aluminum (Al) and oxygen (O) elements. The particle size of the CeO2·CuAlO2 mixed oxide was estimated using Scherrer's formula, which was found to be in the range of 17.2-34.2 nm. The TEM image showed particles are almost uniform size of approximately 15-50 nm with spherical morphology. PMID:25113734

  18. 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.

  19. 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.

  20. 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.

  1. Study of multiphasic molybdate-based catalysts. II. Synergy effect between bismuth molybdates and mixed iron and cobalt molybdates in mild oxidation of propene

    SciTech Connect

    Millet, J.M.M.; Ponceblanc, H.; Coudurier, G.; Vedrine, J.C. ); Herrmann, J.M. )

    1993-08-01

    Results are reported concerning the synergy effect observed in the oxidation of propene to acrolein over bismuth and mixed iron and cobalt molybdates. The pure bismuth, iron, and cobalt molybdates and mixed cobalt and iron molybdates (solid solutions) have been prepared and individually tested as catalysts. Mechanical mixtures of these phases have been prepared and tested as catalysts. All the catalysts have been characterized before and after the catalytic reaction by several techniques such as ESR, XPS, EDX-STEM, TEM, XRD, and Moessbauer and UV spectroscopies. The synergy effect observed is tentatively explained as due to the deposition on the large bismuth molybdate particles of smaller mixed iron and cobalt molybdate particles with spreading of the bismuth molybdate over the latter particles. It is proposed that the Fe[sub x]Co[sub 1-x]MoO[sub 4] phase plays the role of the fast electron conducting material which enhances the electron mobility and the efficiency of the redox mechanism, the active and selective phase being the overlying bismuth molybdate compounds. 27 refs., 5 figs., 7 tabs.

  2. Chemical composition and oxidative status of tissues from Iberian pigs as affected by diets: extensive feeding v. oleic acid- and tocopherol-enriched mixed diets.

    PubMed

    Ventanas, S; Tejeda, J F; Estévez, M

    2008-04-01

    The present work was intended to analyse the chemical composition and oxidative stability of the muscle biceps femoris and adipose tissues from Iberian pigs fed different finishing diets: free-range feeding on grass and acorns in a 'Montanera' traditional system (MON), fed in confinement with a mixed diet containing high-oleic sunflower oil (115 g/kg of diet) and supplemented with 250 mg/kg α-tocopherol (HOVE), and fed in confinement with a tocopherol-non-supplemented control mixed diet (CON). Muscles from MON pigs contained significantly (P < 0.05) higher amounts of intramuscular fat than those from HOVE and CON pigs. Muscles from MON and HOVE pigs had significantly higher levels of α-tocopherol than muscles from CON pigs whereas free-range feeding provided significantly higher levels of γ-tocopherol to muscles from MON pigs than the experimental diets did to CON and HOVE pigs. Adipose tissues from MON and HOVE pigs contained significantly lower proportions of saturated fatty acids and significantly higher levels of oleic acid and monounsaturated fatty acids than those from CON pigs. Tissues from MON pigs contained significantly smaller levels of polyunsaturated fatty acids than those from CON and HOVE pigs. To a higher extent, feeding background affected the fatty acid composition of polar lipids from the muscle biceps femoris than that of neutral lipids. Tissues from MON pigs contained significantly smaller ω-6/ω-3 values than those from pigs fed mixed diets. Compared to tissues from CON pigs, those from MON and HOVE pigs exhibited a higher oxidative stability as a likely result of a most favourable fatty acid composition and the presence of higher tocopherol levels.

  3. Effect of the rare earth in the perovskite-type mixed oxides AMnO{sub 3} (A=Y, La, Pr, Sm, Dy) as catalysts in methanol oxidation

    SciTech Connect

    Levasseur, B.; Kaliaguine, S.

    2008-11-15

    The effect of the rare earth in the perovskite-type mixed oxides AMnO{sub 3} (A=Y, La, Pr, Sm, Dy) on catalytic properties in methanol oxidation was investigated in this work. The perovskites were prepared by reactive grinding in order to enhance the specific surface area in comparison with other classical synthesis procedures. These catalysts were characterized by N{sub 2} adsorption, X-ray diffraction, H{sub 2} temperature-programmed reduction (TPR-H{sub 2}), O{sub 2}-, CH{sub 3}OH- and CO{sub 2}-temperature-programmed desorption (TPD). The activity of the five catalysts under study in the methanol oxidation reaction was evaluated. The behaviour of the {alpha}-O{sub 2} from the surface of the perovskite was strongly related to the nature of the A-site cation and particularly to its electronegativity but also to its density. Concerning the {beta}-O{sub 2} from the bulk, the rare earth only induces an indirect effect notably due to structural modifications. As suggested in a previous study, the activity in methanol oxidation was directly linked with the surface oxygen density. Under an excess of {alpha}-oxygen, the reaction intermediate was found to be a monodentate carbonate that decomposes into CO{sub 2}. The stability of monodentate carbonates was also found to be related to the electronegativity of the rare earth during both CH{sub 3}OH- and CO{sub 2}-temperature-programmed desorption. However, as soon as a lack of {alpha}-oxygen was observed in the structure, the dominant reaction intermediate was a bidentate carbonate that induces a consumption of anion vacancies in spite of the production of CO{sub 2}. Nevertheless, the accumulation of these carbonates leads to a decrease in the oxidation rate since their desorption requires high temperatures. - Graphical abstract: Perovskite-type mixed oxides AMnO{sub 3} (with A=Y, La, Pr, Sm, Dy) with high specific surface area were prepared by reactive grinding. The influence of the rare earth on the two kinds of oxygen

  4. 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...

  5. 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.

  6. 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

  7. 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.

  8. 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

  9. The mixed glass former effect in 0.35sodium oxide + 0.65[(x)boron trioxide + (1-x)phosphorus pentoxide] glasses

    NASA Astrophysics Data System (ADS)

    Christensen, Randilynn Beth

    Energy storage is a growing concern in an ever increasingly battery driven society. Development of safer, smaller, and longer lasting batteries is in demand. Ion conducting glasses are an important type of solid electrolyte that could be used to answer this need. Unfortunately, many known ion conducting glasses, such as binary lithium oxide glasses with conductivities in the 10-7--10-8 S/cm range, are not conductive enough for practical use. In order for ion conducting glasses to be used as a commercial solid electrolyte, a method of increasing the glasses' ionic conductivity must be found. While alkali mixed glass former glasses, such as Bi2O3+B2O3+LiO2 and Li2S+SiS2+GeS2, have shown increases in the alkali ion conductivity up to two orders of magnitude, the cause of this increase is unclear. This phenomena has become known as the Mixed Glass Former Effect (MGFE) and is defined by a non-linear, non-additive change in ionic conductivity. Although the MGFE has been observed in the literature, it has not been observed in all mixed glass former (MGF) glasses and has also been seen as a negative or positive effect. In this talk, I will review our comprehensive study of the physical properties, structure, and the effect of composition on MGF sodium borophosphate glasses. It is our hypothesis that changes in the short range order structures, caused by the mixing of the boron and phosphate networks, are responsible for the MGFE. I will show a strong correlation between physical properties and structural changes with changing glass former composition.

  10. 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.

  11. 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.

  12. 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.

  13. 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

  14. 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

  15. Catalytic properties of Fe/sub 2/O/sub 3//Sb/sub 2/O/sub 4/ mixed oxides--1. Mechanism of propene oxidation

    SciTech Connect

    Aso, I.; Furukawa, S.; Yamazoe, N.; Seiyama, T.

    1980-07-01

    On a catalyst containing a 1:1 antimony-iron ratio (Sb/Fe) and consisting entirely of FeSbO/sub 4/, and on a catalyst containing a 2:1 antimony-iron ratio (2Sb/Fe) and consisting of FeSbO/sub 4/ and Sb/sub 2/O/sub 4/, the acrolein yields from propylene oxidation at 400/sup 0/C were similar, but Sb/Fe was also active in the deep oxidation of propylene to carbon dioxide, i.e., 2Sb/Fe had a much higher acrolein selectivity. The rate constants for acrolein formation, i.e., catalyst reduction, and for catalyst reoxidation were determined. Catalyst reduction with propylene showed initial rapid acrolein (and CO/sub 2/) formation until the surface oxygen was consumed, and then much slower formation of acrolein, 1,5-hexadiene, and CO/sub 2/, which was identical for both catalysts and corresponded to bulk reduction. The initial rapid acrolein formation was first order in propylene and second order in surface oxygen. Acrolein formation apparently proceeds via an allyl intermediate whose attack of surface oxygen (i.e., the second surface reaction step) is rate-controlling. The presence of Sb/sub 2/O/sub 4/ in 2Sb/Fe apparently modifies the catalyst surface structure to provide oxygen for the selectiive acrolein formation.

  16. Laser-induced evaporation, reactivity and deposition of ZrO 2, CeO 2, V 2O 5 and mixed Ce-V oxides

    NASA Astrophysics Data System (ADS)

    Flamini, C.; Ciccioli, A.; Traverso, P.; Gnecco, F.; Giardini Guidoni, A.; Mele, A.

    2000-12-01

    It has been found that pulsed laser ablation has good potentiality for the deposition of ZrO2, CeO2, V2O5 and mixed Ce-V oxides which are very important materials for their application in optics and electrochromic devices. Laser induced compositional changes of thin films in the ablation and deposition processes of these materials have been explored. The effect of the oxygen gas pressure on the thin film composition has been examined. The congruency of the process has been treated on the basis of a thermal mechanism of evaporation-decomposition of the compounds. An attempt to model the processes by means of a thermodynamic approach is reported.

  17. Micellar copolymerization of associative polymers: study of the effect of acrylamide on sodium dodecyl sulfate-poly(propylene oxide) methacrylate mixed micelles.

    PubMed

    Bastiat, Guillaume; Grassl, Bruno; François, Jeanne

    2005-09-15

    Mixed micelles of sodium dodecyl sulfate (SDS) and poly(propylene oxide) methacrylate (PPOMA) have been studied in the presence of acrylamide using conductimetry, fluorescence spectroscopy, and small-angle neutron scattering (SANS) under the following conditions: (i) the SDS-acrylamide binary system in water; (ii) the SDS-acrylamide-PPOMA ternary system in water. The addition of acrylamide in SDS solutions perturbs the micellization of the surfactant by decreasing the aggregation number of the micelles and increasing their ionization degree. The variations of the various micellar parameters versus the weight ratio R=PPOMA/SDS are different in the presence of acrylamide or in pure water. These differences are much more pronounced for the lower than for the higher PPOMA concentrations. There is competition between acrylamide and PPOMA and at higher PPOMA concentration, acrylamide tends to be released from SDS micelles and is completely replaced by PPOMA.

  18. 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.

  19. 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.

  20. 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.

  1. 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

  2. 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.

  3. 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.

  4. Extensive feeding versus oleic acid and tocopherol enriched mixed diets for the production of Iberian dry-cured hams: Effect on chemical composition, oxidative status and sensory traits.

    PubMed

    Ventanas, S; Ventanas, J; Tovar, J; García, C; Estévez, M

    2007-10-01

    The present study aimed to analyse the chemical composition and oxidative status of Iberian dry-cured hams from pigs fed different finishing diets: extensive feeding on acorns and pasture in a "Montanera" traditional system (MON), fed in confinement with a mixed diet containing high-oleic sunflower oil (115g/kg of diet) and supplemented with 250mg/kg α-tocopherol (HOVE), and fed in confinement control mixed diet (CON) without added tocopherol and oleic acid fat. Muscles from MON dry-cured hams contained significantly (p<0.05) higher amounts of intramuscular fat (IMF) than those from HOVE and CON hams. The feeding background affected the tocopherol levels in dry-cured hams as those from MON and HOVE pigs had significantly higher levels of α-tocopherol than those from CON pigs whereas the extensive feeding provided muscles from MON pigs with significantly higher levels of γ-tocopherol than the experimental diets did to CON and HOVE pigs. The HOVE diet significantly increased the levels of oleic acid in Iberian dry-cured hams with these levels being similar to the oleic acid levels found in MON hams and significantly higher than those in CON hams. Compared to dry-cured hams from CON pigs, those from MON and HOVE pigs exhibited a higher oxidative stability as a likely result of a most favourable fatty acid composition and the presence of higher tocopherol levels. The principal component analysis (PCA) successfully discriminated between dry-cured hams from pigs fed different finishing diets.

  5. Macromolecular crowding effect upon in vitro enzyme kinetics: mixed activation-diffusion control of the oxidation of NADH by pyruvate catalyzed by lactate dehydrogenase.

    PubMed

    Balcells, Cristina; Pastor, Isabel; Vilaseca, Eudald; Madurga, Sergio; Cascante, Marta; Mas, Francesc

    2014-04-17

    Enzyme kinetics studies have been usually designed as dilute solution experiments, which differ substantially from in vivo conditions. However, cell cytosol is crowded with a high concentration of molecules having different shapes and sizes. The consequences of such crowding in enzymatic reactions remain unclear. The aim of the present study is to understand the effect of macromolecular crowding produced by dextran of different sizes and at diverse concentrations in the well-known reaction of oxidation of NADH by pyruvate catalyzed by L-lactate dehydrogenase (LDH). Our results indicate that the reaction rate is determined by both the occupied volume and the relative size of dextran obstacles with respect to the enzyme present in the reaction. Moreover, we analyzed the influence of macromolecular crowding on the Michaelis-Menten constants, vmax and Km. The obtained results show that only high concentrations and large sizes of dextran reduce both constants suggesting a mixed activation-diffusion control of this enzymatic reaction due to the dextran crowding action. From our knowledge, this is the first experimental study that depicts mixed activation-diffusion control in an enzymatic reaction due to the effect of crowding.

  6. 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.

  7. Inverse gas chromatography as a technique for the characterization of the performance of Mn/Zr mixed oxides as combustion catalysts.

    PubMed

    Cuervo, Montserrat R; Díaz, Eva; de Rivas, Beatriz; López-Fonseca, Rubén; Ordóñez, Salvador; Gutiérrez-Ortiz, José I

    2009-11-01

    Adsorption of different volatile organic compounds (trichloroethylene, TCE; 1,2-dichloroethane, DCE; n-hexane) over different manganese-zirconia mixed oxides (Mn(x)Zr(1-x)O(2)) - widely used as combustion catalysts - was studied by inverse gas chromatography. Adsorption isotherms (calculated in the Henry region), adsorption enthalpies (DeltaH(ads)), and dispersive (gamma(S)(D)) and specific (I(sp)) components of the surface energy have been determined at infinite dilution for the investigated compounds. Both the adsorption enthalpy and the specificity of the interaction of TCE and DCE over Mn(x)Zr(1-x)O(2) catalysts depend strongly on manganese content. Thus, the adsorption strength of the reactants over the active sites is closely related with both the surface acidity and the accessibility of the lattice oxygen. A great influence of the specific interaction on the catalytic pattern has been also noticed. Since I(sp) depends on the redox properties, it has been proved that the specific interaction is determined by the presence of bulk Mn(3)O(4), which hinders the mobility of the oxygen lattice, and MnO(x), with the contrary effect. Finally, the selectivity to oxidation products has been correlated with both the enthalpy of adsorption and the specific interaction parameter, decreasing the selectivity to HCl with the increase of the enthalpy of adsorption.

  8. 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.

  9. 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

  10. 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

  11. 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.

  12. 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.

  13. 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

  14. 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.

  15. 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.

  16. 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.

  17. Properties of the System for the Mixed Function Oxidation of Kaurene and Kaurene Derivatives in Microsomes of the Immature Seed of Marah macrocarpus

    PubMed Central

    Hasson, Edna P.; West, Charles A.

    1976-01-01

    Cytochrome P-450 and cytochrome b5 at levels of approximately 0.10 and 0.60 nanomole per milligram of microsomal protein were detected by spectral measurements in microsomes prepared from endosperm tissue of immature Marah macrocarpus seeds. TPNH-cytochrome c reductase, DPNH-cytochrome c reductase, andDPNH-cytochrome b5 reductase activities were also present in these microsomes at levels of approximately 0.060, 0.22, and 0.52 unit per milligram of microsomal protein, respectively. (One unit of reductase is the amount of enzyme catalyzing the reduction of 1 micromole of electron acceptor per minute.) Treatments of microsomes with steapsin or trypsin were not effective in solubilizing any of these electron transport components in detectable form. However, treatment of a microsomal suspension in 25% glycerol with 1% sodium deoxycholate led to the release of about 60% of the protein and each of the above hemoproteins and electron transfer activities to the fraction which was not pelleted after centrifugation for 2 hours at 105,000g. Some ent-kaur-16-ene oxidase activity could be detected in the solubilized fraction after removal of the detergent. Cytochrome b5 and DPNH-cytochrome b5 reductase activity were largely separated from one another and from an overlapping mixture of TPNH-cytochrome c reductase and DPNH-cytochrome c reductase when the sodium deoxycholate-solubilized fraction was chromatographed on a DEAE-cellulose column. No cytochrome P-450 or cytochrome P-420 was detected in the column fractions and no ent-kaur-16-ene oxidase activity was detected when the column fractions were tested singly or in combination. The possible participation of these components in the mixed function oxidation of ent-kaur-16-ene and a number of its oxidized derivatives catalyzed by these microsomes is discussed in relation to the model which has been developed to explain the function of analogous components in mixed function oxidase reactions in mammalian liver microsomes. PMID

  18. 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.

  19. 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

  20. 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.

  1. Development of durable mixed-metal oxide sorbents for high-temperature desulfurization of coal gases in moving-bed reactors

    SciTech Connect

    Ayala, R.E.; Jain, S.C.

    1993-06-01

    Mixed-metal oxide sorbents, particularly zinc ferrite and zinc titanate, are being developed for use in hot gas cleanup of coal gas in the integrated gasification combined-cycle (IGCC). For the case of moving-bed systems, the pelletized sorbent moves between the absorber and regenerator as it absorbs H{sub 2}S from coal gas and is regenerated under diluted air. Therefore a mechanically strong and chemically active sorbent is necessary for proper long-term operation of the system. These desired properties depend on the active components in the sorbent, the type and concentration of the binder material, and the sorbent preparation procedure. In the current program, several zinc titanate sorbent formulations have been prepared using a new rounding fabrication procedure, and varying the types of additives/binders (e.g., bentonite and molybdenum) and calcination temperature (1450-1800 {degree}F, 788-982 {degree}C). Comparison with baseline cylindrical formulations was made by measuring attrition resistance, crush strength, thermogravimetric reactivity and bench-scale reactor performance.

  2. Synthesis of hybrid Zn-Al-In mixed metal oxides/carbon nanotubes composite and enhanced visible-light-induced photocatalytic performance

    NASA Astrophysics Data System (ADS)

    Lan, Meng; Fan, Guoli; Sun, Wei; Li, Feng

    2013-10-01

    Hybrid nanocomposite of Zn-Al-In mixed metal oxides (ZnAlIn-MMO) and multi-walled carbon nanotubes (CNTs) was synthesized effectively from composite precursor of ternary Zn-Al-In layered double hydroxide (ZnAlIn-LDH) and 1-pyrenebutyric acid-modified CNTs (P-CNTs). The structural, morphological and optical properties of the materials were characterized by powder X-ray diffraction (XRD), transmission electron microscopy (TEM), low temperature nitrogen adsorption-desorption, Raman spectra, and UV-vis diffuse reflectance spectroscopy. The results indicated that ZnAlIn-LDH nanoparticles could be attached closely onto the surface of the P-CNTs through the interfacial interaction, thus resulting in the formation of the remarkably dispersed ZnAlIn-MMO nanoparticles on the surface of the modified nanotubes after calcination. Compared with pristine ZnAlIn-MMO, as-synthesized hybrid ZnAlIn-MMO/P-CNTs had smaller band gap of about 2.08 eV, characteristic of enhanced visible light absorption. Furthermore, ZnAlIn-MMO/P-CNTs exhibited excellent visible-light-induced photodegradation activity toward methylene blue, which was attributable to the efficient separation and transportation of the photogenerated charge carriers originating from the unique heterostructure of such nanocomposite. The present finding provides an approach to fabricate new types of visible-light-induced heteronanostructured photocatalysts.

  3. Reverse micelles directed synthesis of TiO2-CeO2 mixed oxides and investigation of their crystal structure and morphology

    NASA Astrophysics Data System (ADS)

    Matějová, Lenka; Valeš, Václav; Fajgar, Radek; Matěj, Zdeněk; Holý, Václav; Šolcová, Olga

    2013-02-01

    The synthesis of TiO2-CeO2 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 CeTi2O6 crystallizes as a single crystalline phase at Ti:Ce molar composition of 70:30 and in the mixture with cubic CeO2 and anatase TiO2 for composition 50:50. At Ti:Ce molar ratios 90:10 and 30:70 the mixtures of TiO2 anatase, rutile and cubic CeO2 appear. In these mixtures TiO2 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.

  4. FY 1992 Annual report: Mediated electrochemical oxidation treatment for Rocky Flats combustible low-level mixed waste. Final report to Rocky Flats Plant

    SciTech Connect

    Chiba, Z.; Lewis, P.R.; Kahle, R.W.

    1993-03-01

    The Mediated Electrochemical Oxidation (MEO) process was studied for destroying low-level combustible mixed wastes at Rocky Flats (RFP). Tests were performed with nonradioactive surrogate materials: Trimsol for the contaminated oils, and reagent-grade cellulose for the cellulosic wastes. Extensive testing was carried out on Trimsol in both small laboratory-scale apparatus and on a large-scale system incorporating an industrial-size electrochemical cell. Preliminary tests were also carried out in the small-scale system with cellulose. The following operating and system parameters were studied: use of a silver-nitric acid versus a cobalt-sulfuric acid system, effect of electrolyte temperature, effect of acid concentration, effect of current density, and use of ultrasonic agitation. Destruction and coulombic efficiencies were calculated using data obtained from continuous carbon dioxide monitors and total organic carbon (TOC) analysis of electrolyte samples. For Trimsol, the best performance was achieved with the silver-nitrate system at high acid concentrations, temperatures, and current densities. Destruction efficiencies of 98% or greater and coulombic efficiencies close to 50% were obtained in both small- and large-scale systems. For the cellulose, high destruction efficiencies and reasonable coulombic efficiencies were obtained for both silver-nitrate and cobalt-sulfate systems.

  5. 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.

  6. Study on the mechanism of diametral cladding strain and mixed-oxide fuel element breaching in slow-ramp extended overpower transients

    SciTech Connect

    Tomoyuki Uwaba; Seiichiro Maeda; Tomoyasu Mizuno; Melissa C. Teague

    2012-10-01

    Cladding strain caused by fuel/cladding mechanical interaction (FCMI) was evaluated for mixed-oxide fuel elements subjected to 70–90% slow-ramp extended overpower transient tests in the experimental breeder reactor II. Calculated transient-induced cladding strains were correlated with cumulative damage fractions (CDFs) using cladding strength correlations. In a breached high-smeared density solid fuel element with low strength cladding, cladding thermal creep strain was significantly increased to approximately half the transient-induced cladding strain that was considered to be caused by the tertiary creep when the CDF was close to the breach criterion (=1.0), with the remaining strain due to instantaneous plastic deformation. In low-smeared density annular fuel elements, FCMI load was significantly mitigated and resulted in little cladding strain. The CDFs of the annular fuel elements were lower than 0.01 at the end of the overpower transient, indicating a substantial margin to breach. A substantial margin to breach was also maintained in a high-smeared density fuel element with high strength cladding.

  7. 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.

  8. 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

  9. 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.

  10. Nanostructure Cu-Zn mixed-oxide supported photocatalyst fabricated by impregnation method for the photocatalytic degradation of C.I. Reactive Orange 16 (V3R) in water.

    PubMed

    Habibi, Mohammad Hossein; Karimi, Bahareh

    2014-04-24

    Nanostructure Cu-Zn mixed-oxide (CZMO) have been prepared by an impregnation method using copper nitrate and zinc oxide tetrapod precursors. X-ray powder diffractometry (XRD) and field emission scanning electron microscopy (FESEM) were used to characterize the structural of CZMO. The XRD patterns confirmed metal oxides formation and their good crystallinity. In agreement with XRD results, FESEM images also illustrated nanosized particles with an average nanocrystallite size of 33 nm. The photocatalytic activity of CZMO was studied using the photocatalytic decolorization of C.I. Reactive Orange 16 (V3R) in aqueous environment. The results indicated that the CZMO display good photocatalytic efficiency. The related photocatalytic mechanism was discussed based on the coupling of zinc-copper oxide.

  11. 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.

  12. 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.

  13. Efficient catalytic decomposition of CO2 to CO and O2 over Pd/ mixed-conducting oxide catalyst in an oxygen-permeable membrane reactor.

    PubMed

    Jin, Wanqin; Zhang, Chun; Chang, Xianfeng; Fan, Yiqun; Xing, Weihong; Xu, Nanping

    2008-04-15

    The thermal decomposition of CO2 to CO and O2 is a potential route for the consumption and utilization of CO2. However, this reaction is limited by both the thermodynamic equilibrium and the kinetic barrier. In this study, we reported an innovative catalytic process to decompose CO2 in an oxygen-permeation membrane reactor packed with a mixed-conducting oxide supported noble metal catalyst, or Pd/SrCo0.4Fe0.5Zr0.1O3-delta (Pd/ SCFZ), which is of high activity in the decomposition of CO2 into CO and O2. Pd/SCFZ catalyst was prepared by incipient wetness impregnation of the SCFZ powders with an aqueous solution of PdCl2, and the CO2 sorption/desorption property was examined by in situ Fourier transform infrared spectroscopy and temperature-programmed desorption-mass spectrometry technologies. It was shown that there appeared a typical of bridged carbonyls (Pd-CO) on the surface of the Pd/SCFZ catalyst formed after CO2 decomposition. Both CO2 and CO could be detected in the species desorbed from Pd/SCFZ catalyst, which implied that the Pd/SCFZ catalyst could effectively activate the CO2 molecule. During the catalytic process, furthermore, the activity of the Pd/SCFZ catalyst can self-regenerate by removing the produced lattice oxygen through the dense oxygen-permeable ceramic membrane. At 900 degrees C, this catalytic process attains 100% of CO formation selectivity at 15.8% of CO2 conversions. PMID:18497167

  14. 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

  15. Dietary effects of a mix derived from oregano (Origanum vulgare L.) essential oil and sweet chestnut (Castanea sativa Mill.) wood extract on pig performance, oxidative status and pork quality traits.

    PubMed

    Ranucci, D; Beghelli, D; Trabalza-Marinucci, M; Branciari, R; Forte, C; Olivieri, O; Badillo Pazmay, G V; Cavallucci, C; Acuti, G

    2015-02-01

    The effects of a pre-formulated commercial plant extract mix, composed of equal parts of oregano essential oil and sweet chestnut wood extract, on performance, oxidative status and pork quality traits were evaluated. In two 155-d studies, 60 pigs (mean liveweight: 42.9 kg) were assigned to either a control diet (CTR) or an identical diet supplemented (0.2%) with the plant extract mix (OC). No differences in the growth rate were observed. Glutathione peroxidase and glutathione reductase activities in the OC muscles (Longissimus lumborum) were higher than in CTR muscles. The lipid oxidation of meat was lower in the OC group. In the cooked meat samples, OC animals had the lowest L* and H° values and the highest a* values. The OC meat received higher scores for colour, taste and overall liking in both the blind and the labelled consumer tests. PMID:25454470

  16. Dietary effects of a mix derived from oregano (Origanum vulgare L.) essential oil and sweet chestnut (Castanea sativa Mill.) wood extract on pig performance, oxidative status and pork quality traits.

    PubMed

    Ranucci, D; Beghelli, D; Trabalza-Marinucci, M; Branciari, R; Forte, C; Olivieri, O; Badillo Pazmay, G V; Cavallucci, C; Acuti, G

    2015-02-01

    The effects of a pre-formulated commercial plant extract mix, composed of equal parts of oregano essential oil and sweet chestnut wood extract, on performance, oxidative status and pork quality traits were evaluated. In two 155-d studies, 60 pigs (mean liveweight: 42.9 kg) were assigned to either a control diet (CTR) or an identical diet supplemented (0.2%) with the plant extract mix (OC). No differences in the growth rate were observed. Glutathione peroxidase and glutathione reductase activities in the OC muscles (Longissimus lumborum) were higher than in CTR muscles. The lipid oxidation of meat was lower in the OC group. In the cooked meat samples, OC animals had the lowest L* and H° values and the highest a* values. The OC meat received higher scores for colour, taste and overall liking in both the blind and the labelled consumer tests.

  17. 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

  18. 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

  19. 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.

    2013-12-01

    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 separately assess their effect on the N2O5 uptake coefficient, γ(N2O5). At a constant RH, mixtures of organic components having an O : C < 0.5 with ammonium bisulfate (ABS) significantly suppressed the uptake of N2O 0.8) had a smaller or even negligible impact on N2O5 uptake at all RHs probed; however, a few exceptions were observed. Notably, γ(N2O5) for mixtures of ABS 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 on 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 a 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 impact of organic aerosol

  20. 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.

  1. Electro-Catalytic Activity of RuO2-IrO2-Ta2O5 Mixed Metal Oxide Prepared by Spray Thermal Decomposition for Alkaline Water Electrolysis.

    PubMed

    Hwang, Hyein; Lim, Dongwook; Kim, Taewoo; Lee, Duwon; Shim, Sang Eun; Baeck, Sung-Hyeon

    2016-05-01

    Oxygen evolution reaction for alkaline water electrolysis was studied using various mixed metal oxide catalysts. Mixed metal oxide electrodes consisting of RuO2, IrO2, and Ta2O5 with various ratios on a titanium substrate were prepared by spray thermal decomposition. The crystallinity of the synthesized catalyst was investigated via X-ray diffraction, and the oxidation state of each component was determined using X-ray photoelectron spectroscopy (XPS). Surface morphology was investigated by scanning electron microscopy, and the roughness factor was determined by cyclic voltammetry (CV) in 1 M H2SO4. Electo-catalytic activity for oxygen evolution reaction was measured by cyclic voltammetry (CV) in 1 M KOH at room temperature, and it was found to be strongly dependent.on composition of catalyst. Among all electrodes tested, catalyst with a composition of Ru:Ir:Ta = 1:2:2.5 exhibited the highest current density of 100 mA cm(-2) at 1.67 V, corresponding to an overpotential of 0.44 V. PMID:27483764

  2. The Expression of Type-1 and Type-2 Nitric Oxide Synthase in Selected Tissues of the Gastrointestinal Tract during Mixed Mycotoxicosis

    PubMed Central

    Gajęcka, Magdalena; Stopa, Ewa; Tarasiuk, Michał; Zielonka, Łukasz; Gajęcki, Maciej

    2013-01-01

    The aim of the study was to verify the hypothesis that intoxication with low doses of mycotoxins leads to changes in the mRNA expression levels of nitric oxide synthase-1 and nitric oxide synthase-2 genes in tissues of the gastrointestinal tract and the liver. The experiment involved four groups of immature gilts (with body weight of up to 25 kg) which were orally administered zearalenone in a daily dose of 40 μg/kg BW (group Z, n = 18), deoxynivalenol at 12 μg/kg BW (group D, n = 18), zearalenone and deoxynivalenol (group M, n = 18) or placebo (group C, n = 21) over a period of 42 days. The lowest mRNA expression levels of nitric oxide synthase-1 and nitric oxide synthase-2 genes were noted in the sixth week of the study, in particular in group M. Our results suggest that the presence of low mycotoxin doses in feed slows down the mRNA expression of both nitric oxide synthase isomers, which probably lowers the concentrations of nitric oxide, a common precursor of inflammation. PMID:24284830

  3. Investigation of mixed metal sorbent/catalysts for the simultaneous removal of sulfur and nitrogen oxides. Semiannual report, Apr 1, 1998--Oct 31, 1998

    SciTech Connect

    Dr. Ates Akyurtlu; Dr. Jale F. Akyurtlu

    1998-10-31

    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}. The objective of this research is to conduct kinetic and parametric studies of the selective catalytic reduction of NO{sub x} with NH{sub 3} and CH{sub 4} over alumina-supported cerium oxide and copper oxide-cerium oxide sorbent/catalysts; investigate SO{sub 2} removal at lower temperatures by supported copper oxide-cerium oxide sorbents; and investigate the possibility of elemental sulfur production during regeneration with CO or with CH{sub 4} air mixtures. The sorbents consisting of cerium oxide and copper oxide impregnated on alumina have been prepared and characterized. Their sulfation performance has been investigated in a TGA setup

  4. 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

  5. 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.

  6. 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 ...

  7. 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.

  8. 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.

  9. 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.

  10. Mixed ligand complex via zinc(II)-mediated in situ oxidative heterocyclization of hydrochloride salt of 2-chlorobenzaldehyde hydralazine hydrazone as potential of antihypertensive agent.

    PubMed

    Bakale, Raghavendra P; Naik, Ganesh N; Mangannavar, Chandrashekhar V; Muchchandi, Iranna S; Shcherbakov, I N; Frampton, Chris; Gudasi, Kalagouda B

    2014-02-12

    An unusual tetrahedral mixed ligand Zn(II) complex ZnT(L)Cl, where L = 2-chlorobenzaldehyde hydralazine hydrazone and T = in situ generated 3-(2-chlorophenyl)-1,2,4-triazolo[3,4-a]phthalazine is reported. Structure of the fused triazole has been confirmed by single crystal X-ray diffraction studies. Structure of Co(II), Ni(II), Cu(II) and Zn(II) complexes has been confirmed by spectral and analytical methods. Metal complexes have exhibited better activity in the fructose induced hypertension studies in animal model and are comparable with the standard.

  11. 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

  12. 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.

  13. 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%.

  14. The comparison of calculated transition probabilities with luminescence characteristics of erbium(III) in fluoride glasses and in the mixed yttrium-zirconium oxide crystal

    NASA Astrophysics Data System (ADS)

    Reisfeld, R.; Katz, G.; Jacoboni, C.; De Pape, R.; Drexhage, M. G.; Brown, R. N.; Jørgensen, C. K.

    1983-07-01

    Fluorozirconate glasses containing 2 mole% ErF 3 were prepared by melting the binary fluorides with ammonium bifluoride under an atmosphere of carbon tetrachloride and argon at 850°C. Absorption spectra of these glasses were obtained and the Judd-Ofelt parameters were calculated. Emission spectra and lifetimes of erbium in fluorozirconate glass, in lead-gallium-zinc fluoride glass, and in yttrium-zirconium oxide crystal were measured and compared with the theoretical calculations. Laser emission lines in these materials are deduced from these measurements. It is suggested that materials doped with erbium may serve as light sources for fiber optic waveguides made from the undoped materials.

  15. 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.

  16. 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.

  17. The hazard assessment of nanostructured CeO₂-based mixed oxides on the zebrafish Danio rerio under environmentally relevant UV-A exposure.

    PubMed

    Jemec, Anita; Djinović, Petar; Crnivec, Ilja Gasan Osojnik; Pintar, Albin

    2015-02-15

    The effect of nanomaterials on biota under realistic environmental conditions is an important question. However, there is still a lack of knowledge on how different illumination conditions alter the toxicity of some photocatalytic nanomaterials. We have investigated how environmentally relevant UV-A exposure (intensity 8.50 ± 0.61 W/m(2), exposure dose 9.0J/cm(2)) affected the toxicity of cerium oxide (CeO2)-based nanostructured materials to the early-life stages of zebrafish Danio rerio. Pure cerium oxide (CeO2), copper-cerium (CuO-CeO2) (with a nominal 10, 15 and 20 mol.% CuO content), cerium-zirconium (CeO2-ZrO2) and nickel and cobalt (Ni-Co) deposited over CeO2-ZrO2 were tested. It was found that under both illumination regimes, none of the tested materials affected the normal development or induced mortality of zebrafish early-life stages up to 100mg/L. Only in the case of CuO-CeO2, the growth of larvae was decreased (96 h LOEC values for CuCe10, CuCe15 and CuCe20 were 50, 50 and 10mg/L, respectively). To conclude, CeO2-based nanostructured materials are not severely toxic to zebrafish and environmentally relevant UV-A exposure does not enhance their toxicity.

  18. 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.

  19. The effect of tropical islands on the chemical mixing of biogenics and their oxidation products from the surface layer to the upper troposphere

    NASA Astrophysics Data System (ADS)

    Hornsby, K. E.; Monks, P. S.; Warwick, N. J.; Carver, G. D.; Pyle, J. A.

    2011-12-01

    In recent years much interest has been shown in the composition of the tropical atmosphere from the surface to the tropopause. During June 2008 an extensive measurement campaign (OP3) was conducted from the ground level in the canopy of the tropical rainforest of Borneo concurrently with aircraft flights over coastal areas, a mixture of rainforest and palm plantations on the island. The aim of this campaign was to gain a better understanding of the chemical processes governing the tropical boundary layer and emissions from changing vegetation types. Tropical islands present a set of meteorological conditions that have the potential to loft surface emissions into the upper troposphere which can later have an impact on the upper troposphere/lower stratosphere. The experimental data in conjunction with models has been used to assess the impact of introducing surface biogenic emissions to the upper troposphere on the chemical processing throughout the entire air column. The data show the lifting lifetimes are in the order of 1 to 2 hours and that the islands act in effect as a tropical chimney lifting a significant range of biogenics and NOx. The oxidative impact of the tropical region on global oxidative capacity will be explored.

  20. 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.