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Sample records for mixed actinide oxides

  1. Flammability Analysis For Actinide Oxides Packaged In 9975 Shipping Containers

    Energy Technology Data Exchange (ETDEWEB)

    Laurinat, James E.; Askew, Neal M.; Hensel, Steve J.

    2013-03-21

    Packaging options are evaluated for compliance with safety requirements for shipment of mixed actinide oxides packaged in a 9975 Primary Containment Vessel (PCV). Radiolytic gas generation rates, PCV internal gas pressures, and shipping windows (times to reach unacceptable gas compositions or pressures after closure of the PCV) are calculated for shipment of a 9975 PCV containing a plastic bottle filled with plutonium and uranium oxides with a selected isotopic composition. G-values for radiolytic hydrogen generation from adsorbed moisture are estimated from the results of gas generation tests for plutonium oxide and uranium oxide doped with curium-244. The radiolytic generation of hydrogen from the plastic bottle is calculated using a geometric model for alpha particle deposition in the bottle wall. The temperature of the PCV during shipment is estimated from the results of finite element heat transfer analyses.

  2. Electronic structure and ionicity of actinide oxides from first principles

    DEFF Research Database (Denmark)

    Petit, Leon; Svane, Axel; Szotek, Z.

    2010-01-01

    The ground-state electronic structures of the actinide oxides AO, A2O3, and AO2 (A=U, Np, Pu, Am, Cm, Bk, and Cf) are determined from first-principles calculations, using the self-interaction corrected local spin-density approximation. Emphasis is put on the degree of f-electron localization, which...... in the actinide dioxides is discussed, and it is found that the dioxide is the most stable oxide for the actinides from Np onward. Our study reveals a strong link between preferred oxidation number and degree of localization which is confirmed by comparing to the ground-state configurations of the corresponding...

  3. Fusion Techniques for the Oxidation of Refractory Actinide Oxides

    Energy Technology Data Exchange (ETDEWEB)

    Rudisill, T.S.

    1999-04-15

    Small-scale experiments were performed to demonstrate the feasibility of fusing refractory actinide oxides with a series of materials commonly used to decompose minerals, glasses, and other refractories as a pretreatment to dissolution and subsequent recovery operations. In these experiments, 1-2 g of plutonium or neptunium oxide (PuO2 or NpO2) were calcined at 900 degrees Celsius, mixed and heated with the fusing reagent(s), and dissolved. For refractory PuO2, the most effective material tested was a lithium carbonate (Li2CO3)/sodium tetraborate (Na2B4O7) mixture which aided in the recovery of 90 percent of the plutonium. The fused product was identified as a lithium plutonate (Li3PuO4) by x-ray diffraction. The use of a Li2CO3/Na2B4O7 mixture to solubilize high-fired NpO2 was not as effective as demonstrated for refractory PuO2. In a small-scale experiment, 25 percent of the NpO2 was oxidized to a neptunium (VI) species that dissolved in nitric acid. The remaining neptunium was then easily recovered from the residue by fusing with sodium peroxide (Na2O2). Approximately 70 percent of the neptunium dissolved in water to yield a basic solution of neptunium (VII). The remainder was recovered as a neptunium (VI) solution by dissolving the residue in 8M nitric acid. In subsequent experiments with Na2O2, the ratio of neptunium (VII) to (VI) was shown to be a function of the fusion temperature, with higher temperatures (greater than approximately 400 degrees C) favoring the formation of neptunium (VII). The fusion of an actual plutonium-containing residue with Na2O2 and subsequent dissolution was performed to demonstrate the feasibility of a pretreatment process on a larger scale. Sodium peroxide was chosen due

  4. Hydrothermal decomposition of actinide(IV oxalates: a new aqueous route towards reactive actinide oxide nanocrystals

    Directory of Open Access Journals (Sweden)

    Walter Olaf

    2016-01-01

    Full Text Available The hydrothermal decomposition of actinide(IV oxalates (An= Th, U, Pu at temperatures between 95 and 250 °C is shown to lead to the production of highly crystalline, reactive actinide oxide nanocrystals (NCs. This aqueous process proved to be quantitative, reproducible and fast (depending on temperature. The NCs obtained were characterised by X-ray diffraction and TEM showing their size to be smaller than 15 nm. Attempts to extend this general approach towards transition metal or lanthanide oxalates failed in the 95–250 °C temperature range. The hydrothermal decomposition of actinide oxalates is therefore a clean, flexible and powerful approach towards NCs of AnO2 with possible scale-up potential.

  5. Fluoride-conversion synthesis of homogeneous actinide oxide solid solutions

    Energy Technology Data Exchange (ETDEWEB)

    Silva, G W Chinthaka M [ORNL; Hunn, John D [ORNL; Yeamans, Charles B. [University of California, Berkeley; Cerefice, Gary S. [University of Nevada, Las Vegas; Czerwinski, Ken R. [University of Nevada, Las Vegas

    2011-01-01

    Here, a novel route to synthesize (U, Th)O2 solid solutions at a relatively low temperature of 1100 C is demonstrated. First, the separate actinide oxides reacted with ammonium bifluoride to form ammonium actinide fluorides at room temperature. Subsequently, this mixture was converted to the actinide oxide solid solution using a two-phased heat treatment, first at 610 C in static air, then at 1100 C in flowing argon. Solid solutions obeying Vegard s Law were synthesized for ThO2 content from 10 to 90 wt%. Microscopy showed that the (U, Th)O2 solid solutions synthesized with this method to have considerably high crystallinity and homogeneity, suggesting the suitability of material thus synthesized for sintering into nuclear fuel pellets at low temperatures.

  6. Positron Spectroscopy of Hydrothermally Grown Actinide Oxides

    Science.gov (United States)

    2014-03-27

    In this method, the powdered material is placed in a solution which contains extremely powerful mineralizers , such as cesium fluoride for actinide...environmentally triggered background counts and it subtends a very small solid angle with respect to the detector. Thus, the benefit of the lead sheet outweighs...low electron density. This is mainly a property of their atomic makeup , though the microstructure of the paper is porous as well. In addition, a

  7. Gas Generation from Actinide Oxide Materials

    Energy Technology Data Exchange (ETDEWEB)

    George Bailey; Elizabeth Bluhm; John Lyman; Richard Mason; Mark Paffett; Gary Polansky; G. D. Roberson; Martin Sherman; Kirk Veirs; Laura Worl

    2000-12-01

    This document captures relevant work performed in support of stabilization, packaging, and long term storage of plutonium metals and oxides. It concentrates on the issue of gas generation with specific emphasis on gas pressure and composition. Even more specifically, it summarizes the basis for asserting that materials loaded into a 3013 container according to the requirements of the 3013 Standard (DOE-STD-3013-2000) cannot exceed the container design pressure within the time frames or environmental conditions of either storage or transportation. Presently, materials stabilized and packaged according to the 3013 Standard are to be transported in certified packages (the certification process for the 9975 and the SAFKEG has yet to be completed) that do not rely on the containment capabilities of the 3013 container. Even though no reliance is placed on that container, this document shows that it is highly likely that the containment function will be maintained not only in storage but also during transportation, including hypothetical accident conditions. Further, this document, by summarizing materials-related data on gas generation, can point those involved in preparing Safety Analysis Reports for Packages (SARPs) to additional information needed to assess the ability of the primary containment vessel to contain the contents and any reaction products that might reasonably be produced by the contents.

  8. Stabilization of actinides and lanthanides in unusually high oxidation states

    Energy Technology Data Exchange (ETDEWEB)

    Eller, P.G.; Penneman, R.A.

    1986-01-01

    Chemical environments can be chosen which stabilize actinides and lanthanides in unusually high or low oxidation states and in unusual coordination. In many cases, one can rationalize the observed species as resulting from strong charge/size influences provided by specific sites in host lattices (e.g., Tb(IV) in BaTbO/sub 3/ or Am(IV) in polytungstate anions). In other cases, the unusual species can be considered from an acid-base viewpoint (e.g., U(III) in AsF/sub 5//HF solution or Pu(VII) in Li/sub 5/PuO/sub 6/). In still other cases, an interplay of steric and redox effects can lead to interesting comparisons (e.g., instability of double fluoride salts of Pu(V) and Pu(VI) relative to U, Np, and Am analogues). Generalized ways to rationalize compounds containing actinides and lanthanides in unusual valences (particularly high valences), including the above and numerous other examples, will form the focus of this paper. Recently developed methods for synthesizing high valent f-element fluorides using superoxidizers and superacids at low temperatures will also be described. 65 refs., 8 figs., 9 tabs.

  9. Actinide Oxidation State and O/M Ratio in Hypostoichiometric Uranium-Plutonium-Americium U0.750Pu0.246Am0.004O2-x Mixed Oxides.

    Science.gov (United States)

    Vauchy, Romain; Belin, Renaud C; Robisson, Anne-Charlotte; Lebreton, Florent; Aufore, Laurence; Scheinost, Andreas C; Martin, Philippe M

    2016-03-07

    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.

  10. Synthesis of actinide nitrides, phosphides, sulfides and oxides

    Science.gov (United States)

    Van Der Sluys, William G.; Burns, Carol J.; Smith, David C.

    1992-01-01

    A process of preparing an actinide compound of the formula An.sub.x Z.sub.y wherein An is an actinide metal atom selected from the group consisting of thorium, uranium, plutonium, neptunium, and americium, x is selected from the group consisting of one, two or three, Z is a main group element atom selected from the group consisting of nitrogen, phosphorus, oxygen and sulfur and y is selected from the group consisting of one, two, three or four, by admixing an actinide organometallic precursor wherein said actinide is selected from the group consisting of thorium, uranium, plutonium, neptunium, and americium, a suitable solvent and a protic Lewis base selected from the group consisting of ammonia, phosphine, hydrogen sulfide and water, at temperatures and for time sufficient to form an intermediate actinide complex, heating said intermediate actinide complex at temperatures and for time sufficient to form the actinide compound, and a process of depositing a thin film of such an actinide compound, e.g., uranium mononitride, by subliming an actinide organometallic precursor, e.g., a uranium amide precursor, in the presence of an effectgive amount of a protic Lewis base, e.g., ammonia, within a reactor at temperatures and for time sufficient to form a thin film of the actinide compound, are disclosed.

  11. Partial oxidation of methane over bimetallic copper- and nickel-actinide oxides (Th, U)

    Energy Technology Data Exchange (ETDEWEB)

    Ferreira, Ana C.; Goncalves, A.P.; Gasche, T. Almeida [Instituto Tecnologico e Nuclear, Unidade de Ciencias Quimicas e Radiofarmaceuticas, Estrada Nacional 10, 2686-953 Sacavem (Portugal); Ferraria, A.M.; Rego, A.M. Botelho do [Universidade Tecnica de Lisboa, IST, Centro de Quimica-Fisica Molecular and IN, Av. Rovisco Pais, 1049-001 Lisboa (Portugal); Correia, M.R.; Bola, A. Margarida [I3N-Universidade de Aveiro, Department Fisica, Aveiro (Portugal); Branco, J.B., E-mail: jbranco@itn.p [Instituto Tecnologico e Nuclear, Unidade de Ciencias Quimicas e Radiofarmaceuticas, Estrada Nacional 10, 2686-953 Sacavem (Portugal)

    2010-05-14

    The study of partial oxidation of methane (POM) over bimetallic nickel- or copper-actinide oxides was undertaken. Binary intermetallic compounds of the type AnNi{sub 2} (An = Th, U) and ThCu{sub 2} were used as precursors and the products (2NiO.UO{sub 3}, 2NiO.ThO{sub 2} and 2CuO.ThO{sub 2}) characterized by means of X-ray diffraction, X-ray photoelectron spectroscopy, Raman spectroscopy and temperature-programmed reduction. The catalysts were active and selective for the conversion of methane to H{sub 2} and CO and stable for a period of time of {approx}18 h on stream. The nickel catalysts were more active and selective than the copper catalyst and, under the same conditions, show a catalytic behaviour comparable to that of a platinum commercial catalyst, 5 wt% Pt/Al{sub 2}O{sub 3}. The catalytic activity increases when uranium replaces thorium and the selectivity of this type of materials is clearly different from that of single metal oxides and/or mechanical mixtures. The good catalytic behaviour of the bimetallic copper- and nickel-actinide oxides was attributed to an unusual interaction between copper or nickel oxide and the actinide oxide phase as showed by H{sub 2}-TPR, XPS and Raman analysis of the catalysts before and after reaction.

  12. Oxidative dissolution of actinide oxides in H 2O 2 containing aqueous solution - A preliminary study

    Science.gov (United States)

    Pehrman, Reijo; Amme, Marcus; Roth, Olivia; Ekeroth, Ella; Jonsson, Mats

    2010-02-01

    Oxidative dissolution of spent nuclear fuel is an important issue in the safety assessment of a future geological repository for spent nuclear fuel. Although UO 2 constitutes, in terms of mass, the majority of the spent fuel material, its main radiotoxicity is (after extended storage times) contained in actinides with half lives shorter than that of 238-uranium, such as isotopes of Np and Pu. Relatively little information is available on the dissolution behavior of Np and Pu in comparable environments. This work investigates the oxidative dissolution of NpO 2 and PuO 2 in non-complexing aqueous solutions containing H 2O 2 and compares their behavior with that of UO 2. We have found that oxidative dissolution takes place for all three actinides in the presence of H 2O 2. Based on the obtained dissolution rates, we would not expect the dissolution of the actinides to be congruent. Instead, in a system without complexing agent, the release rates of Np and Pu are expected to be lower than the U release rate.

  13. Application of chemical structure and bonding of actinide oxide materials for forensic science

    Energy Technology Data Exchange (ETDEWEB)

    Wilkerson, Marianne Perry [Los Alamos National Laboratory

    2010-01-01

    We are interested in applying our understanding of actinide chemical structure and bonding to broaden the suite of analytical tools available for nuclear forensic analyses. Uranium- and plutonium-oxide systems form under a variety of conditions, and these chemical species exhibit some of the most complex behavior of metal oxide systems known. No less intriguing is the ability of AnO{sub 2} (An: U, Pu) to form non-stoichiometric species described as AnO{sub 2+x}. Environmental studies have shown the value of utilizing the chemical signatures of these actinide oxide materials to understand transport following release into the environment. Chemical speciation of actinide-oxide samples may also provide clues as to the age, source, or process history of the material. The scientific challenge is to identify, measure and understand those aspects of speciation of actinide analytes that carry information about material origin and history most relevant to forensics. Here, we will describe our efforts in material synthesis and analytical methods development that we will use to provide the fundamental science to characterize actinide oxide molecular structures for forensic science. Structural properties and initial results to measure structural variability of uranium oxide samples using synchrotron-based X-ray Absorption Fine Structure will be discussed.

  14. A first principles investigation of the electronic structure of actinide oxides

    DEFF Research Database (Denmark)

    Petit, Leon; Svane, Axel; Szotek, Zdzislawa

    2010-01-01

    The ground state electronic structures of the actinide oxides AO, A2O3 and AO2 (A=U, Np, Pu, Am, Cm, Bk, Cf) are determined from first-principles calculations using the selfinteraction corrected local spin-density approximation. Our study reveals a strong link between preferred oxidation number...

  15. MICROBIAL TRANSFORMATIONS OF TRU AND MIXED WASTES: ACTINIDE SPECIATION AND WASTE VOLUME REDUCTION

    Energy Technology Data Exchange (ETDEWEB)

    Francis, A.J.; Dodge, C.J.

    2006-06-01

    The overall goals of this research project are to determine the mechanism of microbial dissolution and stabilization of actinides in Department of Energy’s (DOE) TRU wastes, contaminated sludges, soils, and sediments. This includes (i) investigations on the fundamental aspects of microbially catalyzed radionuclide and metal transformations (oxidation/reduction reactions, dissolution, precipitation, chelation); (ii) understanding of the microbiological processes that control speciation and alter the chemical forms of complex inorganic/organic contaminant mixtures; and (iii) development of new and improved microbially catalyzed processes resulting in immobilization of metals and radionuclides in the waste with concomitant waste volume reduction.

  16. MICROBIAL TRANSFORMATIONS OF TRU AND MIXED WASTES: ACTINIDE SPECIATION AND WASTE VOLUME REDUCTION

    Energy Technology Data Exchange (ETDEWEB)

    Francis, A.J.; Dodge, C.J.

    2006-06-01

    The overall goals of this research project are to determine the mechanism of microbial dissolution and stabilization of actinides in Department of Energy's (DOE) TRU wastes, contaminated sludges, soils, and sediments. This includes (1) investigations on the fundamental aspects of microbially catalyzed radionuclide and metal transformations (oxidation/reduction reactions, dissolution, precipitation, chelation); (2) understanding of the microbiological processes that control speciation and alter the chemical forms of complex inorganic/organic contaminant mixtures; and (3) development of new and improved microbially catalyzed processes resulting in immobilization of metals and radionuclides in the waste with concomitant waste volume reduction.

  17. MICROBIAL TRANSFORMATIONS OF TRU AND MIXED WASTES: ACTINIDE SPECIATION AND WASTE VOLUME REDUCTION.

    Energy Technology Data Exchange (ETDEWEB)

    FRANCIS, A.J.; DODGE, C.J.

    2006-11-16

    The overall goals of this research project are to determine the mechanism of microbial dissolution and stabilization of actinides in Department of Energy's (DOE) TRU wastes, contaminated sludges, soils, and sediments. This includes (1) investigations on the fundamental aspects of microbially catalyzed radionuclide and metal transformations (oxidation/reduction reactions, dissolution, precipitation, chelation); (2) understanding of the microbiological processes that control speciation and alter the chemical forms of complex inorganic/organic contaminant mixtures; and (3) development of new and improved microbially catalyzed processes resulting in immobilization of metals and radionuclides in the waste with concomitant waste volume reduction.

  18. Microbial Transformation of TRU and Mixed Waste: Actinide Speciation and Waste Volume

    Energy Technology Data Exchange (ETDEWEB)

    Halada, Gary P

    2008-04-10

    In order to understand the susceptibility of transuranic and mixed waste to microbial degradation (as well as any mechanism which depends upon either complexation and/or redox of metal ions), it is essential to understand the association of metal ions with organic ligands present in mixed wastes. These ligands have been found in our previous EMSP study to limit electron transfer reactions and strongly affect transport and the eventual fate of radionuclides in the environment. As transuranic waste (and especially mixed waste) will be retained in burial sites and in legacy containment for (potentially) many years while awaiting treatment and removal (or remaining in place under stewardship agreements at government subsurface waste sites), it is also essential to understand the aging of mixed wastes and its implications for remediation and fate of radionuclides. Mixed waste containing actinides and organic materials are especially complex and require extensive study. The EMSP program described in this report is part of a joint program with the Environmental Sciences Department at Brookhaven National Laboratory. The Stony Brook University portion of this award has focused on the association of uranium (U(VI)) and transuranic analogs (Ce(III) and Eu(III)) with cellulosic materials and related compounds, with development of implications for microbial transformation of mixed wastes. The elucidation of the chemical nature of mixed waste is essential for the formulation of remediation and encapsulation technologies, for understanding the fate of contaminant exposed to the environment, and for development of meaningful models for contaminant storage and recovery.

  19. A many-body potential approach to modelling the thermomechanical properties of actinide oxides.

    Science.gov (United States)

    Cooper, M W D; Rushton, M J D; Grimes, R W

    2014-03-12

    A many-body potential model for the description of actinide oxide systems, which is robust at high temperatures, is reported for the first time. The embedded atom method is used to describe many-body interactions ensuring good reproduction of a range of thermophysical properties (lattice parameter, bulk modulus, enthalpy and specific heat) between 300 and 3000 K for AmO2, CeO2, CmO2, NpO2, ThO2, PuO2 and UO2. Additionally, the model predicts a melting point for UO2 between 3000 and 3100 K, in close agreement with experiment. Oxygen-oxygen interactions are fixed across the actinide oxide series because it facilitates the modelling of oxide solid solutions. The new potential is also used to predict the energies of Schottky and Frenkel pair disorder processes.

  20. LIBS Spectral Data for a Mixed Actinide Fuel Pellet Containing Uranium, Plutonium, Neptunium and Americium

    Energy Technology Data Exchange (ETDEWEB)

    Judge, Elizabeth J. [Los Alamos National Laboratory; Berg, John M. [Los Alamos National Laboratory; Le, Loan A. [Los Alamos National Laboratory; Lopez, Leon N. [Los Alamos National Laboratory; Barefield, James E. [Los Alamos National Laboratory

    2012-06-18

    Laser-induced breakdown spectroscopy (LIBS) was used to analyze a mixed actinide fuel pellet containing 75% UO{sub 2}/20% PuO{sub 2}/3% AmO{sub 2}/2% NpO{sub 2}. The preliminary data shown here is the first report of LIBS analysis of a mixed actinide fuel pellet, to the authors knowledge. The LIBS spectral data was acquired in a plutonium facility at Los Alamos National Laboratory where the sample was contained within a glove box. The initial installation of the glove box was not intended for complete ultraviolet (UV), visible (VIS) and near infrared (NIR) transmission, therefore the LIBS spectrum is truncated in the UV and NIR regions due to the optical transmission of the window port and filters that were installed. The optical collection of the emission from the LIBS plasma will be optimized in the future. However, the preliminary LIBS data acquired is worth reporting due to the uniqueness of the sample and spectral data. The analysis of several actinides in the presence of each other is an important feature of this analysis since traditional methods must chemically separate uranium, plutonium, neptunium, and americium prior to analysis. Due to the historic nature of the sample fuel pellet analyzed, the provided sample composition of 75% UO{sub 2}/20% PuO{sub 2}/3% AmO{sub 2}/2% NpO{sub 2} cannot be confirm without further analytical processing. Uranium, plutonium, and americium emission lines were abundant and easily assigned while neptunium was more difficult to identify. There may be several reasons for this observation, other than knowing the exact sample composition of the fuel pellet. First, the atomic emission wavelength resources for neptunium are limited and such techniques as hollow cathode discharge lamp have different dynamics than the plasma used in LIBS which results in different emission spectra. Secondly, due to the complex sample of four actinide elements, which all have very dense electronic energy levels, there may be reactions and

  1. Influence of microorganisms on the oxidation state distribution of multivalent actinides under anoxic conditions

    Energy Technology Data Exchange (ETDEWEB)

    Reed, Donald Timothy [Los Alamos National Laboratory; Borkowski, Marian [Los Alamos National Laboratory; Lucchini, Jean - Francois [Los Alamos National Laboratory; Ams, David [Los Alamos National Laboratory; Richmann, M. K. [Los Alamos National Laboratory; Khaing, H. [Los Alamos National Laboratory; Swanson, J. S. [Los Alamos National Laboratory

    2010-12-10

    The fate and potential mobility of multivalent actinides in the subsurface is receiving increased attention as the DOE looks to cleanup the many legacy nuclear waste sites and associated subsurface contamination. Plutonium, uranium and neptunium are the near-surface multivalent contaminants of concern and are also key contaminants for the deep geologic disposal of nuclear waste. Their mobility is highly dependent on their redox distribution at their contamination source as well as along their potential migration pathways. This redox distribution is often controlled, especially in the near-surface where organic/inorganic contaminants often coexist, by the direct and indirect effects of microbial activity. Under anoxic conditions, indirect and direct bioreduction mechanisms exist that promote the prevalence of lower-valent species for multivalent actinides. Oxidation-state-specific biosorption is also an important consideration for long-term migration and can influence oxidation state distribution. Results of ongoing studies to explore and establish the oxidation-state specific interactions of soil bacteria (metal reducers and sulfate reducers) as well as halo-tolerant bacteria and Archaea for uranium, neptunium and plutonium will be presented. Enzymatic reduction is a key process in the bioreduction of plutonium and uranium, but co-enzymatic processes predominate in neptunium systems. Strong sorptive interactions can occur for most actinide oxidation states but are likely a factor in the stabilization of lower-valent species when more than one oxidation state can persist under anaerobic microbiologically-active conditions. These results for microbiologically active systems are interpreted in the context of their overall importance in defining the potential migration of multivalent actinides in the subsurface.

  2. A Screened Hybrid DFT Study of Actinide Oxides, Nitrides, and Carbides

    Energy Technology Data Exchange (ETDEWEB)

    Wen, Xiaodong; Martin, Richard L.; Scuseria, Gustavo E.; Rudin, Sven P.; Batista, Enrique R.

    2013-06-27

    A systematic study of the structural, electronic, and magnetic properties of actinide oxides, nitrides, and carbides (AnX1–2 with X = C, N, O) is performed using the Heyd–Scuseria–Ernzerhof (HSE) hybrid functional. Our computed results show that the screened hybrid HSE functional gives a good description of the electronic and structural properties of actinide dioxides (strongly correlated insulators) when compared with available experimental data. However, there are still some problems reproducing the electronic properties of actinide nitrides and carbides (strongly correlated metals). In addition, in order to compare with the results by HSE, the structures, electronic, and magnetic properties of these actinide compounds are also investigated in the PBE and PBE+U approximation. Interestingly, the density of states of UN obtained with PBE compares well with the experimental photoemission spectra, in contrast to the hybrid approximation. This is presumably related to the need of additional screening in the Hartree–Fock exchange term of the metallic phases.

  3. Trivalent Actinide Uptake by Iron (Hydr)oxides.

    Science.gov (United States)

    Finck, Nicolas; Nedel, Sorin; Dideriksen, Knud; Schlegel, Michel L

    2016-10-04

    The retention of Am(III) by coprecipitation with or adsorption onto preformed magnetite was investigated by X-ray diffraction (XRD), solution chemistry, and X-ray absorption spectroscopy (XAS). In the coprecipitation experiment, XAS data indicated the presence of seven O atoms at 2.44(1) Å, and can be explained by an Am incorporation at Fe structural sites at the magnetite surface. Next-nearest Fe were detected at distances suggesting that Am and Fe polyhedra share corners in geometries ranging from bent to close to linear Am-O-Fe bonds. After aging for two years, the coordination number and the distance to the first O shell significantly decreased, and atomic shells were detected at higher distances. These data suggest a structural reorganization and an increase in structural order around sorbed Am. Upon contact with preformed Fe3O4, Am(III) forms surface complexes with cosorbed Fe at the surface of magnetite, a possible consequence of the high concentration of dissolved Fe. In a separate experiment, chloride green rust (GR) was synthesized in the presence of Am(III), and subsequently converted to Fe(OH)2(s) intermixed with magnetite. XAS data indicated that the actinide is successively located first at octahedral brucite-like sites in the GR precursor, then in Fe(OH)2(s), an environment markedly distinct from that of Am(III) in Fe3O4. The findings indicate that the magnetite formation pathway dictates the magnitude of Am(III) incorporation within this solid.

  4. Microstructure and thermophysical characterization of mixed oxide fuels

    Energy Technology Data Exchange (ETDEWEB)

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

    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.

  5. Criticality investigations for the fixed bed nuclear reactor using thorium fuel mixed with plutonium or minor actinides

    Energy Technology Data Exchange (ETDEWEB)

    Sahin, Suemer [Beykoz Lojistik Meslek Yueksekokulu, Beykoz, Istanbul (Turkey)], E-mail: sumer@gazi.edu.tr; Sahin, Haci Mehmet; Acir, Adem [Beykoz Lojistik Meslek Yueksekokulu, Istanbul (Turkey); Al-Kusayer, Tawfik Ahmed [King Saud University, College of Engineering, P.O. Box 800, Riyadh 11421 (Saudi Arabia)

    2009-08-15

    Prospective fuels for a new reactor type, the so called fixed bed nuclear reactor (FBNR) are investigated with respect to reactor criticality. These are (1) low enriched uranium (LEU); (2) weapon grade plutonium + ThO{sub 2}; (3) reactor grade plutonium + ThO{sub 2}; and (4) minor actinides in the spent fuel of light water reactors (LWRs) + ThO{sub 2}. Reactor grade plutonium and minor actinides are considered as highly radio-active and radio-toxic nuclear waste products so that one can expect that they will have negative fuel costs. The criticality calculations are conducted with SCALE5.1 using S{sub 8}-P{sub 3} approximation in 238 neutron energy groups with 90 groups in thermal energy region. The study has shown that the reactor criticality has lower values with uranium fuel and increases passing to minor actinides, reactor grade plutonium and weapon grade plutonium. Using LEU, an enrichment grade of 9% has resulted with k{sub eff} = 1.2744. Mixed fuel with weapon grade plutonium made of 20% PuO{sub 2} + 80% ThO{sub 2} yields k{sub eff} = 1.2864. Whereas a mixed fuel with reactor grade plutonium made of 35% PuO{sub 2} + 65% ThO{sub 2} brings it to k{sub eff} = 1.267. Even the very hazardous nuclear waste of LWRs, namely minor actinides turn out to be high quality nuclear fuel due to the excellent neutron economy of FBNR. A relatively high reactor criticality of k{sub eff} = 1.2673 is achieved by 50% MAO{sub 2} + 50% ThO{sub 2}. The hazardous actinide nuclear waste products can be transmuted and utilized as fuel in situ. A further output of the study is the possibility of using thorium as breeding material in combination with these new alternative fuels.

  6. Thermal conductivities of minor actinide oxides for advanced fuel

    Energy Technology Data Exchange (ETDEWEB)

    Tsuyoshi Nishi; Akinori Itoh; Masahide Takano; Mitsuo Akabori; Yasuo Arai; Kazuo Minato [Nuclear Science and Engineering Directorate, Japan Atomic Energy Agency, Tokai-mura, Ibaraki 319-1195 (Japan)

    2008-07-01

    The thermal diffusivities of americium oxide and neptunium dioxide were determined by a laser flash method. It was found that the thermal diffusivities of AmO{sub 2-x} and NpO{sub 2} decreased with increasing temperature. It was also found that the decrease in O/Am ratio during the thermal diffusivity measurements under vacuum resulted in a slight decrease in thermal diffusivity of AmO{sub 2-x}. The thermal conductivities of AmO{sub 2-x} and NpO{sub 2} were evaluated from the measured thermal diffusivities, heat capacities and bulk densities. The thermal conductivity of AmO{sub 2-x} was smaller than those of the literature values of UO{sub 2} and PuO{sub 2}. On the other hand, the thermal conductivity of NpO{sub 2} from 873 to 1473 K lay between those of UO{sub 2} and PuO{sub 2}. The thermal conductivities of AmO{sub 2-x} and NpO{sub 2} decreased with increasing temperature in the temperature range investigated. This temperature dependence of thermal conductivities showed a similar tendency as those of UO{sub 2}, PuO{sub 2} and (U{sub 0.8}Pu{sub 0.2})O{sub 2-x}. (authors)

  7. Research in actinide chemistry

    Energy Technology Data Exchange (ETDEWEB)

    Choppin, G.R.

    1993-01-01

    This research studies the behavior of the actinide elements in aqueous solution. The high radioactivity of the transuranium actinides limits the concentrations which can be studied and, consequently, limits the experimental techniques. However, oxidation state analogs (trivalent lanthanides, tetravalent thorium, and hexavalent uranium) do not suffer from these limitations. Behavior of actinides in the environment are a major USDOE concern, whether in connection with long-term releases from a repository, releases from stored defense wastes or accidental releases in reprocessing, etc. Principal goal of our research was expand the thermodynamic data base on complexation of actinides by natural ligands (e.g., OH[sup [minus

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

    Energy Technology Data Exchange (ETDEWEB)

    Morreale, A. C.; Ball, M. R.; Novog, D. R.; Luxat, J. C. [Dept. of Engineering Physics, McMaster Univ., 1280 Main St. W, Hamilton, ON (Canada)

    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)

  9. Electronic, structural, and thermodynamic properties of mixed actinide dioxides (U, Pu, Am) O2 from hybrid density functional theory

    Science.gov (United States)

    Ma, Li; Ray, Asok K.

    2010-03-01

    As a continuation of our studies of pure actinide metals using hybrid density functional theory,footnotetextR. Atta-Fynn and A. K. Ray, Europhysics Letters, 85, 27008-p1- p6 (2009); Chemical Physics Letters, 482, 223-227 (2009). we present here a systematic study of the electronic and geometric structure properties of mixed actinide dioxides, U0.5Pu0.5O2, U0.5Am0.5O2, Pu0.5Am0.5 O2 and U0.8Pu0.2O2. The fraction of exact Hartree-Fock exchange used was 40%. To investigate the effect of spin-orbit coupling on the ground state electronic and geometric structure properties, computations have been carried out at two theoretical levels, one at the scalar-relativistic level with no spin-orbit coupling and one at the fully relativistic level with spin-orbit coupling. Thermodynamic properties have been calculated by a coupling of first-principles calculation and lattice dynamics.

  10. Charged defects during alpha-irradiation of actinide oxides as revealed by Raman and luminescence spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Mohun, R.; Desgranges, L.; Léchelle, J. [CEA/DEN/DEC/SESC, Centre de Cadarache, 13108 Saint-Paul-lez-Durance (France); Simon, P.; Guimbretière, G.; Canizarès, A.; Duval, F. [CNRS, UPR 3079 CEMHTI, et Université d’Orléans, 1D avenue de la Recherche Scientifique, 45071 Orléans (France); Jegou, C.; Magnin, M. [CEA/DEN/DTCD, Centre de Marcoule, BP 17171, 30207 Bagnols sur Cèze (France); Clavier, N.; Dacheux, N. [ICSM, UMR 5257 CEA/CNRS/UM2/ENSCM, Site de Marcoule, BP 17171, 30207 Bagnols sur Cèze (France); Valot, C. [CEA/DEN/DTEC/SECA/LCC, BP 17171, 30207 Bagnols sur Cèze (France); Vauchy, R. [CEA/DEN/DEC/SPUA, Centre de Cadarache, 13108 Saint-Paul-lez-Durance (France)

    2016-05-01

    We have recently evidenced an original Raman signature of alpha irradiation-induced defects in UO{sub 2}. In this study, we aim to determine whether the same signature also exists in different actinide oxides, namely ThO{sub 2} and PuO{sub 2}. Sintered UO{sub 2} and ThO{sub 2} were initially irradiated with 21 MeV He{sup 2+} ions using a cyclotron device and were subjected to an in situ luminescence experiment followed by Raman analysis. In addition, a PuO{sub 2} sample which had accumulated self-irradiation damage due to alpha particles was investigated only by Raman measurement. Results obtained for the initially white ThO{sub 2} showed that a blue color appeared in the irradiated areas as well as luminescence signals during irradiation. However, Raman spectroscopic analysis showed the absence of Raman signature in ThO{sub 2}. In contrast, the irradiated UO{sub 2} and PuO{sub 2} confirmed the presence of the Raman signature but no luminescence peaks were observed. The proposed mechanism involves electronic defects in ThO{sub 2}, while a coupling between electronic defects and phonons is required to explain the Raman spectra for UO{sub 2} and PuO{sub 2}.

  11. Experimental findings on actinide recovery utilizing oxidation by peroxydisulfate followed by ion exchange: Fuel cycle research & development

    Energy Technology Data Exchange (ETDEWEB)

    Hobbs, D. T. [Savannah River Site (SRS), Aiken, SC (United States). Savannah River National Lab. (SRNL); Shehee, T. C. [Savannah River Site (SRS), Aiken, SC (United States). Savannah River National Lab. (SRNL)

    2015-08-31

    Our research seeks to determine if inorganic ion-exchange materials can be exploited to provide effective minor actinide (Am, Cm) separation from lanthanides. Previous work has established that a number of inorganic and UMOF ion-exchange materials exhibit varying affinities for actinides and lanthanides, which may be exploited for effective separations. During FY15, experimental work focused on investigating methods to oxidize americium in dilute nitric and perchloric acid with subsequent ion-exchange performance measurements of ion exchangers with the oxidized americium in dilute nitric acid. Ion-exchange materials tested included a variety of alkali titanates. Americium oxidation testing sought to determine the influence that other redox active components may have on the oxidation of AmIII. Experimental findings indicated that CeIII, NpV, and RuII are oxidized by peroxydisulfate, but there are no indications that the presence of CeIII, NpV, and RuII affected the rate or extent of americium oxidation at the concentrations of peroxydisulfate being used.

  12. Experimental findings on actinide recovery utilizing oxidation by peroxydisulfate followed by ion exchange: Fuel cycle research & development

    Energy Technology Data Exchange (ETDEWEB)

    Hobbs, D. T. [Savannah River Site (SRS), Aiken, SC (United States). Savannah River National Lab. (SRNL); Shehee, T. C. [Savannah River Site (SRS), Aiken, SC (United States). Savannah River National Lab. (SRNL)

    2015-08-31

    Our research seeks to determine if inorganic ion-exchange materials can be exploited to provide effective minor actinide (Am, Cm) separation from lanthanides. Previous work has established that a number of inorganic and UMOF ion-exchange materials exhibit varying affinities for actinides and lanthanides, which may be exploited for effective separations. During FY15, experimental work focused on investigating methods to oxidize americium in dilute nitric and perchloric acid with subsequent ion-exchange performance measurements of ion exchangers with the oxidized americium in dilute nitric acid. Ion-exchange materials tested included a variety of alkali titanates. Americium oxidation testing sought to determine the influence that other redox active components may have on the oxidation of AmIII. Experimental findings indicated that CeIII, NpV, and RuII are oxidized by peroxydisulfate, but there are no indications that the presence of CeIII, NpV, and RuII affected the rate or extent of americium oxidation at the concentrations of peroxydisulfate being used.

  13. Crystal growth methods dedicated to low solubility actinide oxalates

    Energy Technology Data Exchange (ETDEWEB)

    Tamain, C., E-mail: christelle.tamain@cea.fr [CEA, Nuclear Energy Division, Marcoule, RadioChemistry & Processes Department, F-30207 Bagnols sur Cèze (France); Arab-Chapelet, B. [CEA, Nuclear Energy Division, Marcoule, RadioChemistry & Processes Department, F-30207 Bagnols sur Cèze (France); Rivenet, M. [University Lille Nord de France, Unité de Catalyse et de Chimie du Solide, UCCS UMR CNRS 8181, ENSCL-USTL, B.P. 90108, F-59652 Villeneuve d’Ascq Cedex (France); Grandjean, S. [CEA, Nuclear Energy Division, Marcoule, RadioChemistry & Processes Department, F-30207 Bagnols sur Cèze (France); Abraham, F. [University Lille Nord de France, Unité de Catalyse et de Chimie du Solide, UCCS UMR CNRS 8181, ENSCL-USTL, B.P. 90108, F-59652 Villeneuve d’Ascq Cedex (France)

    2016-04-15

    Two novel crystal growth syntheses dedicated to low solubility actinide-oxalate systems and adapted to glove box handling are described. These methods based on the use of precursors of either actinide metal or oxalic acid have been optimized on lanthanide systems (analogue of actinides(III)) and then assessed on real actinide systems. They allow the synthesis of several actinide oxalate single crystals, Am{sub 2}(C{sub 2}O{sub 4}){sub 3}(H{sub 2}O){sub 3}·xH{sub 2}O, Th(C{sub 2}O{sub 4}){sub 2}·6H{sub 2}O, M{sub 2+x}[Pu{sup IV}{sub 2−x}Pu{sup III}{sub x}(C{sub 2}O{sub 4}){sub 5}]·nH{sub 2}O and M{sub 1−x}[Pu{sup III}{sub 1−x}Pu{sup IV}{sub x}(C{sub 2}O{sub 4}){sub 2}·H{sub 2}O]·nH{sub 2}O. It is the first time that these well-known compounds are formed by crystal growth methods, thus enabling direct structural studies on transuranic element systems and acquisition of basic data beyond deductions from isomorphic (or not) lanthanide compounds. Characterizations by X-ray diffraction, UV–visible solid spectroscopy, demonstrate the potentialities of these two crystal growth methods to obtain oxalate compounds. - Graphical abstract: Two new single crystal growth methods dedicated to actinide oxalate compounds. - Highlights: • Use of diester as oxalate precursor for crystal growth of actinide oxalates. • Use of actinide oxide as precursor for crystal growth of actinide oxalates. • Crystal growth of Pu(III) and Am(III) oxalates. • Crystal growth of mixed Pu(III)/Pu(IV) oxalates.

  14. Controlling Actinide Hydration in Mixed Solvent Systems: Towards Tunable Solvent Systems to Close the Fuel Cycle

    Energy Technology Data Exchange (ETDEWEB)

    Clark, Sue B. [Washington State Univ., Pullman, WA (United States). Dept. of Chemistry

    2016-10-31

    The goal of this project has been to define the extent of hydration the f-elements and other cations in mixed solvent electrolyte systems. Methanol-water and other mixed solvent systems have been studied, where the solvent dielectric constant was varied systematically. Thermodynamic and spectroscopic studies provide details concerning the energetics of complexation and other reactions of these cations. This information has also been used to advance new understanding of the behavior of these cations in a variety of systems, ranging from environmental studies, chromatographic approaches, and ionization processes for mass spectrometry.

  15. Actinides-1981

    Energy Technology Data Exchange (ETDEWEB)

    1981-09-01

    Abstracts of 134 papers which were presented at the Actinides-1981 conference are presented. Approximately half of these papers deal with electronic structure of the actinides. Others deal with solid state chemistry, nuclear physic, thermodynamic properties, solution chemistry, and applied chemistry.

  16. DISSOLUTION OF METAL OXIDES AND SEPARATION OF URANIUM FROM LANTHANIDES AND ACTINIDES IN SUPERCRITICAL CARBON DIOXIDE

    Energy Technology Data Exchange (ETDEWEB)

    Donna L. Quach; Bruce J. Mincher; Chien M. Wai

    2013-10-01

    This paper investigates the feasibility of extracting and separating uranium from lanthanides and other actinides by using supercritical fluid carbon dioxide (sc-CO2) as a solvent modified with tri-n-butylphosphate (TBP) for the development of a counter current stripping technique, which would be a more efficient and environmentally benign technology for spent nuclear fuel reprocessing compared to traditional solvent extraction. Several actinides (U, Pu, and Np) and europium were extracted in sc-CO2 modified with TBP over a range of nitric acid concentrations and then the actinides were exposed to reducing and complexing agents to suppress their extractability. According to this study, uranium/europium and uranium/plutonium extraction and separation in sc-CO2 modified with TBP is successful at nitric acid concentrations of less than 6 M and at nitric acid concentrations of less than 3 M with acetohydroxamic acid or oxalic acid, respectively. A scheme for recycling uranium from spent nuclear fuel by using sc-CO2 and counter current stripping columns is presented.

  17. Properties of TRPO-HNO3 complex used for direct dissolution of lanthanide and actinide oxides in supercritical fluid CO2

    Institute of Scientific and Technical Information of China (English)

    2007-01-01

    The mixed trialkylphosphine oxide-nitric acid (TRPO-HNO3) complex prepared by contacting pure TRPO with concentrated HNO3 may be used as additives for direct dissolution of lanthanide and actinide oxides in the supercritical fluid carbon dioxide (SCF-CO2). Properties of the TRPO-HNO3 complex have been studied. Experimental results show when the initial HNO3/TRPO volume ratio is varied from 1:7 to 5:1, the concentration of HNO3 in the TRPO-HNO3 complex changes from 2.12 to 6.16 mol/L, the [HNO3]/[TRPO] ratio of the TRPO-HNO3 complex changes from 0.93 to 3.38, and the content of H2O in the TRPO-HNO3 complex changes from 0.97% to 2.70%. All of the density, viscosity and surface tension of the TRPO-HNO3 complex change with the concentration of HNO3 in the complex. The protons of HNO3 and H2O in the complex undergo rapid exchange to exhibit a singlet resonance peak in NMR spectra with D2O insert. When the TRPO-HNO3 complex dissolves in a low dielectric constant solvent, small droplets of HNO3 appear which can be detected by NMR.

  18. Effect of oxidation state and ionic strength on sorption of actinides (Th, U, Np, Am) to geologic media [Abstract and References Only

    Energy Technology Data Exchange (ETDEWEB)

    Dittrich, Timothy M. [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Richmann, Michael K. [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Reed, Donald T. [Los Alamos National Lab. (LANL), Los Alamos, NM (United States)

    2015-10-30

    The degree of conservatism in the estimated sorption partition coefficients (Kds) used in a performance assessment model is being evaluated based on a complementary batch and column method. The main focus of this work is to investigate the role of ionic strength, solution chemistry, and oxidation state (III-VI) in actinide sorption to dolomite rock. Based on redox conditions and solution chemistry expected at the WIPP, possible actinide species include Pu(III), Pu(IV), U(IV), U(VI), Np(IV), Np(V), Am(III), and Th(IV).

  19. Preparation of uniform mixed metal oxide and superconductive oxides

    Energy Technology Data Exchange (ETDEWEB)

    Barder, T.J.

    1991-04-30

    This paper describes a method for producing a uniform mixed metal oxide. It includes dissolving metals as their salts of a carboxylic acid in an aliphatic alcohol in the substantial absence of water, the metals are in the same proportions as in the corresponding mixed metal oxide; co-precipitating the metals as their oxalates by mixing the alcohol solution with oxalic acid; separating the co-precipitated metal oxalates and calcining the oxalates in air or oxygen above about 500{degrees} C to convert the oxalates to the corresponding metal oxides.

  20. 3 and 4 oxidation state element solubilities in borosilicate glasses. Implement to actinides in nuclear glasses; Solubilite des elements aux degres d'oxydation (3) et (4) dans les verres de borosilicate. Application aux actinides dans les verres nucleaires

    Energy Technology Data Exchange (ETDEWEB)

    Cachia, J.N

    2005-12-15

    In order to ensure optimal radionuclides containment, the knowledge of the actinide loading limits in nuclear waste glasses and also the comprehension of the solubilization mechanisms of these elements are essential. A first part of this manuscript deals with the study of the differences in solubility of the tri and tetravalent elements (actinides and surrogates) particularly in function of the melting temperature. The results obtained indicate that trivalent elements (La, Gd, Nd, Am, Cm) exhibit a higher solubility than tetravalent elements (Hf, Th, Pu). Consequently, it was planned to reduce plutonium at the oxidation state (III), the later being essentially tetravalent in borosilicate glasses. An innovating reduction process of multi-valent elements (cerium, plutonium) using silicon nitride has been developed in a second part of this work. Reduced plutonium-bearing glasses synthesized by Si{sub 3}N{sub 4} addition made it possible to double the plutonium solubility from 2 to 4 wt% at 1200 deg C. A structural approach to investigate the differences between tri and tetravalent elements was finally undertaken. These investigations were carried out by X-rays Absorption Spectroscopy (EXAFS) and NMR. Trivalent rare earth and actinide elements seem to behave as network modifiers while tetravalent elements rather present true intermediaries' behaviour. (author)

  1. Actinide-Transition Metal heteronuclear Ions and Their Oxides: {IrUO}+ as an Analogue to Uranyl

    Energy Technology Data Exchange (ETDEWEB)

    Gibson, John K [ORNL

    2006-01-01

    Recent theoretical calculations have shown that Ir should behave as a chemical analogue to N, with the result that IrUO{sup +}, like known NUO{sup +}, is predicted to be a stable species isoelectronic with UO{sub 2}{sup 2+}, the uranyl dication. The target heterometallic analogue to uranyl has now been prepared by direct laser desorption/ionization of a U/Ir alloy, and by oxidation of UIr{sup +} with N{sub 2}O and C{sub 2}H{sub 4}O. Properties of UIr{sup +}, UPt{sup +}, and UAu{sup +} bimetallic ions have been studied. They demonstrate direct actinide-transition metal bonding, and support the concept of autogenic isolobality.

  2. Mixed iron-manganese oxide nanoparticles

    NARCIS (Netherlands)

    Lai, Jriuan; Shafi, Kurikka V.P.M.; Ulman, Abraham; Loos, Katja; Yang, Nan-Loh; Cui, Min-Hui; Vogt, Thomas; Estournès, Claude; Locke, Dave C.

    2004-01-01

    Designing nanoparticles for practical applications requires knowledge and control of how their desired properties relate to their composition and structure. Here, we present a detailed systematic study of mixed iron-manganese oxide nanoparticles, showing that ultrasonication provides the high-energy

  3. Understanding the Chemistry of Uncommon Americium Oxidation States for Application to Actinide/Lanthanide Separations

    Energy Technology Data Exchange (ETDEWEB)

    Leigh Martin; Bruce J. Mincher; Nicholas C. Schmitt

    2007-09-01

    A spectroscopic study of the stability of Am(V) and Am(VI) produced by oxidizing Am(III) with sodium bismuthate is presented, varying the initial americium concentration, temperature and length of the oxidation was seen to have profound effects on the resultant solutions.

  4. Influence of dose distribution on risk of lung cancer occurrence after actinide oxide inhalation; Influence de la distribution de dose sur le risque d'apparition de cancers pulmonaires apres inhalation d'oxydes d'actinides

    Energy Technology Data Exchange (ETDEWEB)

    Fritsch, P.; Dudoignon, N.; Guillet, K.; Rateau, G.; Delforge, J. [Lab. de Radiotoxicologie, CEA/DSV/DRR/SRCA, Bruyeres le Chatel (France)

    2002-07-01

    The aim of this work was to estimate risk of lung tumour occurrence after inhalation of actinide oxides from published studies and rat studies in progress. For the same delivered dose, the risk increases when homogeneity of irradiation increases, i.e., the number of particles deposited after inhalation increases (small particles and (or) low specific alpha activity). The dose-effect relationships reported appear linear up to a few gray, depending on the aerosol considered, and then the slope decreases. This slope, which corresponds with the risk, can vary over one order of magnitude de ending on the aerosol used. An effective threshold at about 1 Gy was not observed for the most homogeneous dose distributions. A dosimetric and biological approach is proposed to provide a more realistic risk estimate. (author)

  5. Selective propene oxidation on mixed metal oxide catalysts

    CERN Document Server

    James, D W

    2002-01-01

    Selective catalytic oxidation processes represent a large segment of the modern chemical industry and a major application of these is the selective partial oxidation of propene to produce acrolein. Mixed metal oxide catalysts are particularly effective in promoting this reaction, and the two primary candidates for the industrial process are based on iron antimonate and bismuth molybdate. Some debate exists in the literature regarding the operation of these materials and the roles of their catalytic components. In particular, iron antimonate catalysts containing excess antimony are known to be highly selective towards acrolein, and a variety of proposals for the enhanced selectivity of such materials have been given. The aim of this work was to provide a direct comparison between the behaviour of bismuth molybdate and iron antimonate catalysts, with additional emphasis being placed on the component single oxide phases of the latter. Studies were also extended to other antimonate-based catalysts, including coba...

  6. Heterogeneous catalysis of mixed oxides perovskite and heteropoly catalysts

    CERN Document Server

    Misono, M

    2014-01-01

    Mixed oxides are the most widely used catalyst materials for industrial catalytic processes. The principal objective of this book is to describe systematically the mixed oxide catalysts, from their fundamentals through their practical applications.  After describing concisely general items concerning mixed oxide and mixed oxide catalysts, two important mixed oxide catalyst materials, namely, heteropolyacids and perovskites, are taken as typical examples and discussed in detail. These two materials have several advantages: 1. They are, respectively, typical examples of salts of oxoacids an

  7. Critical experiments with mixed oxide fuel

    Energy Technology Data Exchange (ETDEWEB)

    Harris, D.R. [Rensselaer Polytechnic Institute, Troy, NY (United States)

    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.

  8. effects of mixed of mixed of mixed alkaline earth oxides in potash ...

    African Journals Online (AJOL)

    eobe

    The aim of this work is to investigate the effects of mixed alkaline earth oxide. The aim of this ... been studied. As for the method used, raw materials were collected, batch calculations were made, and the batches ... This research work therefore ...

  9. Subsurface interactions of actinide species and microorganisms : implications for the bioremediation of actinide-organic mixtures.

    Energy Technology Data Exchange (ETDEWEB)

    Banaszak, J.E.; Reed, D.T.; Rittmann, B.E.

    1999-02-12

    By reviewing how microorganisms interact with actinides in subsurface environments, we assess how bioremediation controls the fate of actinides. Actinides often are co-contaminants with strong organic chelators, chlorinated solvents, and fuel hydrocarbons. Bioremediation can immobilize the actinides, biodegrade the co-contaminants, or both. Actinides at the IV oxidation state are the least soluble, and microorganisms accelerate precipitation by altering the actinide's oxidation state or its speciation. We describe how microorganisms directly oxidize or reduce actinides and how microbiological reactions that biodegrade strong organic chelators, alter the pH, and consume or produce precipitating anions strongly affect actinide speciation and, therefore, mobility. We explain why inhibition caused by chemical or radiolytic toxicities uniquely affects microbial reactions. Due to the complex interactions of the microbiological and chemical phenomena, mathematical modeling is an essential tool for research on and application of bioremediation involving co-contamination with actinides. We describe the development of mathematical models that link microbiological and geochemical reactions. Throughout, we identify the key research needs.

  10. Characterization of the sorption behavior of trivalent actinides on zirconium(IV) oxide

    Energy Technology Data Exchange (ETDEWEB)

    Eibl, Manuel; Huittinen, Nina [Helmholtz-Zentrum Dresden-Rossendorf e.V., Dresden (Germany). Surface Processes; Virtanen, S.; Merilaeinen, S.; Lehto, J. [Helsinki Univ. (Finland); Rabung, T. [Karlsruhe Institute of Technology (KIT), Karlsruhe (Germany). Inst. for Nuclear Waste Disposal

    2017-06-01

    The uptake of trivalent Eu and Cm on zirconium(IV) oxide was investigated in batch sorption and TRLFS studies, respectively. Sorption of Eu{sup 3+} was found to start at a pH-value of 4. Based on TRLFS results, sorption of Cm{sup 3+} was assigned to occur through innersphere complex formation at the zirconia surface. A deconvolution of the TRLFS emission spectra gave three different sorption species with strong red-shifts of the peak positions (600.3 nm, 604.3 nm and 608.2 nm) compared to similar systems.

  11. Internal contamination by actinides after wounding: a robust rodent model for assessment of local and distant actinide retention.

    Science.gov (United States)

    Griffiths, N M; Wilk, J C; Abram, M C; Renault, D; Chau, Q; Helfer, N; Guichet, C; Van der Meeren, A

    2012-08-01

    Internal contamination by actinides following wounding may occur in nuclear fuel industry workers or subsequent to terrorist activities, causing dissemination of radioactive elements. Contamination by alpha particle emitting actinides can result in pathological effects, either local or distant from the site of entry. The objective of the present study was to develop a robust experimental approach in the rat for short- and long- term actinide contamination following wounding by incision of the skin and muscles of the hind limb. Anesthetized rats were contaminated with Mixed OXide (MOX, uranium, plutonium oxides containing 7.1% plutonium) or plutonium nitrate (Pu nitrate) following wounding by deep incision of the hind leg. Actinide excretion and tissue levels were measured as well as histological changes from 2 h to 3 mo. Humid swabs were used for rapid evaluation of contamination levels and proved to be an initial guide for contamination levels. Although the activity transferred from wound to blood is higher after contamination with a moderately soluble form of plutonium (nitrate), at 7 d most of the MOX (98%) or Pu nitrate (87%) was retained at the wound site. Rapid actinide retention in liver and bone was observed within 24 h, which increased up to 3 mo. After MOX contamination, a more rapid initial urinary excretion of americium was observed compared with plutonium. At 3 mo, around 95% of activity remained at the wound site, and excretion of Pu and Am was extremely low. This experimental approach could be applied to other situations involving contamination following wounding including rupture of the dermal, vascular, and muscle barriers.

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

    Energy Technology Data Exchange (ETDEWEB)

    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.

  13. Gas-phase energies of actinide oxides -- an assessment of neutral and cationic monoxides and dioxides from thorium to curium

    Energy Technology Data Exchange (ETDEWEB)

    Marcalo, Joaquim; Gibson, John K.

    2009-08-10

    An assessment of the gas-phase energetics of neutral and singly and doubly charged cationic actinide monoxides and dioxides of thorium, protactinium, uranium, neptunium, plutonium, americium, and curium is presented. A consistent set of metal-oxygen bond dissociation enthalpies, ionization energies, and enthalpies of formation, including new or revised values, is proposed, mainly based on recent experimental data and on correlations with the electronic energetics of the atoms or cations and with condensed-phase thermochemistry.

  14. Experimental studies of actinides in molten salts

    Energy Technology Data Exchange (ETDEWEB)

    Reavis, J.G.

    1985-06-01

    This review stresses techniques used in studies of molten salts containing multigram amounts of actinides exhibiting intense alpha activity but little or no penetrating gamma radiation. The preponderance of studies have used halides because oxygen-containing actinide compounds (other than oxides) are generally unstable at high temperatures. Topics discussed here include special enclosures, materials problems, preparation and purification of actinide elements and compounds, and measurements of various properties of the molten volts. Property measurements discussed are phase relationships, vapor pressure, density, viscosity, absorption spectra, electromotive force, and conductance. 188 refs., 17 figs., 6 tabs.

  15. 256-pixel microcalorimeter array for high-resolution γ-ray spectroscopy of mixed-actinide materials

    Energy Technology Data Exchange (ETDEWEB)

    Winkler, R., E-mail: rwinkler@lanl.gov [Los Alamos National Laboratory, Los Alamos, NM (United States); Hoover, A.S.; Rabin, M.W. [Los Alamos National Laboratory, Los Alamos, NM (United States); Bennett, D.A.; Doriese, W.B.; Fowler, J.W.; Hays-Wehle, J.; Horansky, R.D.; Reintsema, C.D.; Schmidt, D.R.; Vale, L.R.; Ullom, J.N. [National Institute of Standards and Technology, Boulder, CO (United States)

    2015-01-11

    The application of cryogenic microcalorimeter detectors to γ-ray spectroscopy allows for measurements with unprecedented energy resolution. These detectors are ideally suited for γ-ray spectroscopy applications for which the measurement quality is limited by the spectral overlap of many closely spaced transitions using conventional detector technologies. The non-destructive analysis of mixed-isotope Pu materials is one such application where the precision can be potentially improved utilizing microcalorimeter detectors compared to current state-of-the-art high-purity Ge detectors (HPGe). The LANL-NIST γ-ray spectrometer, a 256-pixel microcalorimeter array based on transition-edge sensors (TESs), was recently commissioned and used to collect data on a variety of Pu isotopic standards to characterize the instrument performance. These measurements represent the first time the simultaneous readout of all 256 pixels for measurements of mixed-isotope Pu materials has been achieved. The LANL-NIST γ-ray spectrometer has demonstrated an average pixel resolution of 55 eV full-width-at-half-maximum at 100 keV, nearly an order of magnitude better than HPGe detectors. Some challenges of the analysis of many-channel ultra-high resolution data and the techniques used to produce quality spectra for isotopic analysis will be presented. The LANL-NIST γ-ray spectrometer has also demonstrated stable operation and obtained high resolution measurements at total array event rates beyond 1 kHz. For a total event rate of 1.25 kHz, approximately 5.6 cps/pixel, a 72.2 eV average FWHM for the 103 keV photopeak of {sup 153}Gd was achieved.

  16. Overview of actinide chemistry in the WIPP

    Energy Technology Data Exchange (ETDEWEB)

    Borkowski, Marian [Los Alamos National Laboratory; Lucchini, Jean - Francois [Los Alamos National Laboratory; Richmann, Michael K [Los Alamos National Laboratory; Reed, Donald T [Los Alamos National Laboratory; Khaing, Hnin [Los Alamos National Laboratory; Swanson, Juliet [Los Alamos National Laboratory

    2009-01-01

    The year 2009 celebrates 10 years of safe operations at the Waste Isolation Pilot Plant (WIPP), the only nuclear waste repository designated to dispose defense-related transuranic (TRU) waste in the United States. Many elements contributed to the success of this one-of-the-kind facility. One of the most important of these is the chemistry of the actinides under WIPP repository conditions. A reliable understanding of the potential release of actinides from the site to the accessible environment is important to the WIPP performance assessment (PA). The environmental chemistry of the major actinides disposed at the WIPP continues to be investigated as part of the ongoing recertification efforts of the WIPP project. This presentation provides an overview of the actinide chemistry for the WIPP repository conditions. The WIPP is a salt-based repository; therefore, the inflow of brine into the repository is minimized, due to the natural tendency of excavated salt to re-seal. Reducing anoxic conditions are expected in WIPP because of microbial activity and metal corrosion processes that consume the oxygen initially present. Should brine be introduced through an intrusion scenario, these same processes will re-establish reducing conditions. In the case of an intrusion scenario involving brine, the solubilization of actinides in brine is considered as a potential source of release to the accessible environment. The following key factors establish the concentrations of dissolved actinides under subsurface conditions: (1) Redox chemistry - The solubility of reduced actinides (III and IV oxidation states) is known to be significantly lower than the oxidized forms (V and/or VI oxidation states). In this context, the reducing conditions in the WIPP and the strong coupling of the chemistry for reduced metals and microbiological processes with actinides are important. (2) Complexation - For the anoxic, reducing and mildly basic brine systems in the WIPP, the most important

  17. The effects of actinide based fuels on incremental cross sections in a Candu reactor

    Energy Technology Data Exchange (ETDEWEB)

    Morreale, A.C.; Ball, M.R.; Novog, D.R.; Luxat, J.C., E-mail: morreaac@mcmaster.ca, E-mail: ballmr@mcmaster.ca, E-mail: novog@mcmaster.ca, E-mail: luxatj@mcmaster.ca [Department of Engineering Physics, McMaster University, Ontario (Canada)

    2011-07-01

    The reprocessing of spent fuel such as the extraction of actinide materials for use in mixed oxide fuels is a key component of reducing the end waste from nuclear power plant operations. Using recycled spent fuels in current reactors is becoming a popular option to help close the fuel cycle. In order to ensure safe and consistent operations in existing facilities, the properties of these fuels must be compatible with current reactor designs. This paper examines the features of actinide mixed oxide fuel, TRUMOX, in a CANDU reactor. Specifically, the effect of this fuel design on the incremental cross sections related to the use of adjuster rods is investigated. The actinide concentrations studied in this work were based on extraction from thirty year cooled spent fuel and mixed with natural uranium to yield a MOX fuel of 4.75% actinide by weight. The incremental cross sections were calculated using the DRAGON neutron transport code. The results for the actinide fuel were compared to those for standard natural uranium fuel and for a slightly enriched (1% U-235) fuel designed to reduce void reactivity. Adjuster reactivity effect calculations and void reactivity simulations were also performed. The impact of the adjuster on reactivity decreased by as much as 56% with TRUMOX fuel while the CVR was reduced by 71% due to the addition of central burnable poison. The incremental cross sections were largely affected by the use of the TRUMOX fuel primarily due to its increased level of fissile material (five times that of NU). The largest effects are in the thermal neutron group where the Σ{sub T} value is increased by 46.7%, the Σ{sub ny)} values increased by 13.0% and 9.9%. The value associated with thermal fission, υΣ{sub f}, increased by 496.6% over regular natural uranium which is expected due to the much higher reactivity of the fuel. (author)

  18. Enhanced disinfection efficiency of mechanically mixed oxidants with free chlorine.

    Science.gov (United States)

    Son, Hyunju; Cho, Min; Kim, Jaeeun; Oh, Byungtaek; Chung, Hyenmi; Yoon, Jeyong

    2005-02-01

    To the best of our knowledge, this study is the first investigation to be performed into the potential benefits of mechanically mixed disinfectants in controlling bacterial inactivation. The purpose of this study was to evaluate the disinfection efficiency of mechanically mixed oxidants with identical oxidant concentrations, which were made by adding small amounts of subsidiary oxidants, namely ozone (O3), chlorine dioxide (ClO2), hydrogen peroxide (H2O2) and chlorite (ClO2(-)), to free available chlorine (Cl2), using Bacillus subtilis spores as the indicator microorganisms. The mechanically mixed oxidants containing Cl2/O3, Cl2/ClO2 and Cl2/ClO2(-) showed enhanced efficiencies (of up to 52%) in comparison with Cl2 alone, whereas no significant difference was observed between the mixed oxidant, Cl2/H2O2, and Cl2 alone. This enhanced disinfection efficiency can be explained by the synergistic effect of the mixed oxidant itself and the effect of intermediates such as ClO2(-)/ClO2, which are generated from the reaction between an excess of Cl2 and a small amount of O3/ClO2(-). Overall, this study suggests that mechanically mixed oxidants incorporating excess chlorine can constitute a new and moderately efficient method of disinfection.

  19. Sol-Gel/Hydrothermal Synthesis of Mixed Metal Oxide

    African Journals Online (AJOL)

    Mixed metal oxides of titanium and zinc nanocomposites were prepared through sol-gel method under hydrothermal ... the production of TiO -ZnO nanoparticles use. 2 either titanium ... involved using titanium sulphate and thioacetamide for ...

  20. Advanced Aqueous Separation Systems for Actinide Partitioning

    Energy Technology Data Exchange (ETDEWEB)

    Nash, Kenneth L.; Clark, Sue; Meier, G Patrick; Alexandratos, Spiro; Paine, Robert; Hancock, Robert; Ensor, Dale

    2012-03-21

    One of the most challenging aspects of advanced processing of spent nuclear fuel is the need to isolate transuranium elements from fission product lanthanides. This project expanded the scope of earlier investigations of americium (Am) partitioning from the lanthanides with the synthesis of new separations materials and a centralized focus on radiochemical characterization of the separation systems that could be developed based on these new materials. The primary objective of this program was to explore alternative materials for actinide separations and to link the design of new reagents for actinide separations to characterizations based on actinide chemistry. In the predominant trivalent oxidation state, the chemistry of lanthanides overlaps substantially with that of the trivalent actinides and their mutual separation is quite challenging.

  1. Advances in computational actinide chemistry in China

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Dongqi; Wu, Jingyi; Chai, Zhifang [Chinese Academy of Sciences, Beijing (China). Multidisciplinary Initiative Center; Su, Jing [Chinese Academy of Sciences, Shanghai (China). Div. of Nuclear Materials Science and Engineering; Li, Jun [Tsinghua Univ., Beijing (China). Dept. of Chemistry and Laboratory of Organic Optoelectronics and Molecular Engineering

    2014-04-01

    The advances in computational actinide chemistry made in China are reviewed. Several areas relevant to chemistry of actinides in gas, liquid, and solid phases have been explored. However, we limit the scope to selected contributions in the chemistry of molecular actinide systems in gas and liquid phases. These studies may be classified into two categories: treatment of relativistic effects, which cover the development of two- and four-component Hamiltonians and the optimization of relativistic pseudopotentials, and the applications of theoretical methods in actinide chemistry. The applications include (1) the electronic structures of actinocene, noble gas complexes, An-C multiple bonding compounds, uranyl and its isoelectronic species, fluorides and oxides, molecular systems with metal-metal bonding in their isolated forms (U{sub 2}, Pu{sub 2}) and in fullerene (U{sub 2} rate at C{sub 60}), and the excited states of actinide complexes; (2) chemical reactions, including oxidation, hydrolysis of UF{sub 6}, ligand exchange, reactivities of thorium oxo and sulfido metallocenes, CO{sub 2}/CS{sub 2} functionalization promoted by trivalent uranium complex; and (3) migration of actinides in the environment. A future outlook is discussed. (orig.)

  2. Actinide cation-cation complexes

    Energy Technology Data Exchange (ETDEWEB)

    Stoyer, Nancy Jane [Univ. of California, Berkeley, CA (United States)

    1994-12-01

    The +5 oxidation state of U, Np, Pu, and Am is a linear dioxo cation (AnO2+) with a formal charge of +1. These cations form complexes with a variety of other cations, including actinide cations. Other oxidation states of actinides do not form these cation-cation complexes with any cation other than AnO2+; therefore, cation-cation complexes indicate something unique about AnO2+ cations compared to actinide cations in general. The first cation-cation complex, NpO2+•UO22+, was reported by Sullivan, Hindman, and Zielen in 1961. Of the four actinides that form AnO2+ species, the cation-cation complexes of NpO2+ have been studied most extensively while the other actinides have not. The only PuO2+ cation-cation complexes that have been studied are with Fe3+ and Cr3+ and neither one has had its equilibrium constant measured. Actinides have small molar absorptivities and cation-cation complexes have small equilibrium constants; therefore, to overcome these obstacles a sensitive technique is required. Spectroscopic techniques are used most often to study cation-cation complexes. Laser-Induced Photacoustic Spectroscopy equilibrium constants for the complexes NpO2+•UO22+, NpO2+•Th4+, PuO2+•UO22+, and PuO2+•Th4+ at an ionic strength of 6 M using LIPAS are 2.4 ± 0.2, 1.8 ± 0.9, 2.2 ± 1.5, and ~0.8 M-1.

  3. Optical and electrical studies of cerium mixed oxides

    Science.gov (United States)

    Sherly, T. R.; Raveendran, R.

    2014-10-01

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

  4. Optical and electrical studies of cerium mixed oxides

    Energy Technology Data Exchange (ETDEWEB)

    Sherly, T. R., E-mail: trsherly@gmail.com [Post Graduate Department of Physics, Sanathana Dharma College, Alappuzha, Kerala (India); Raveendran, R. [Nanoscience Research Laboratory, Sree Narayana College, Kollam, Kerala 691001 (India)

    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.

  5. Sol-gel chemistry applied to the synthesis of polymetallic oxides including actinides reactivity and structure from solution to solid state; Synthese par voie douce d'oxydes polymetalliques incluant des actinides: reactivite et structure de la solution au solide

    Energy Technology Data Exchange (ETDEWEB)

    Lemonnier, St

    2006-02-15

    Minor actinides transmutation is studied at present in order to reduce the radiotoxicity of nuclear waste and the assessment of its technical feasibility requires specific designed materials. When considering americium, yttria stabilized zirconia (Am{sup III} YII Zriv)Or{sub x} is among the ceramic phases that one which presents the required physico-chemical properties. An innovative synthesis of this mixed oxide by sol-gel process is reported in this manuscript. The main aim of this work is to adjust the reactivity of the different metallic cations in aqueous media using complexing agent, in order to initiate a favourable interaction for a homogeneous elements repartition in the forming solid phase. The originality of the settled synthesis lies on an in-situ formation of a stable and monodisperse nano-particles dispersion in the presence of acetylacetone. The main reaction mechanisms have been identified: the sol stabilisation results from an original interaction between the three compounds (Zrly, trivalent cations and acetylacetone). The sol corresponds to a structured system at the nanometer scale for which zirconium and trivalent cations are homogeneously dispersed, preliminary to the sol-gel transition. Furthermore, preliminary studies were carried out with a view to developing materials. They have demonstrated that numerous innovative and potential applications can be developed by taking advantage of the direct and controlled formation of the sol and by adapting the sol-gel transition. The most illustrating result is the preparation of a sintered pellet with the composition Am0,13Zro,73Yo,0901,89 using this approach. (author)

  6. Sigma Team for Advanced Actinide Recycle FY2015 Accomplishments and Directions

    Energy Technology Data Exchange (ETDEWEB)

    Moyer, Bruce A. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)

    2015-09-30

    The Sigma Team for Minor Actinide Recycle (STAAR) has made notable progress in FY 2015 toward the overarching goal to develop more efficient separation methods for actinides in support of the United States Department of Energy (USDOE) objective of sustainable fuel cycles. Research in STAAR has been emphasizing the separation of americium and other minor actinides (MAs) to enable closed nuclear fuel recycle options, mainly within the paradigm of aqueous reprocessing of used oxide nuclear fuel dissolved in nitric acid. Its major scientific challenge concerns achieving selectivity for trivalent actinides vs lanthanides. Not only is this challenge yielding to research advances, but technology concepts such as ALSEP (Actinide Lanthanide Separation) are maturing toward demonstration readiness. Efforts are organized in five task areas: 1) combining bifunctional neutral extractants with an acidic extractant to form a single process solvent, developing a process flowsheet, and demonstrating it at bench scale; 2) oxidation of Am(III) to Am(VI) and subsequent separation with other multivalent actinides; 3) developing an effective soft-donor solvent system for An(III) selective extraction using mixed N,O-donor or all-N donor extractants such as triazinyl pyridine compounds; 4) testing of inorganic and hybrid-type ion exchange materials for MA separations; and 5) computer-aided molecular design to identify altogether new extractants and complexants and theory-based experimental data interpretation. Within these tasks, two strategies are employed, one involving oxidation of americium to its pentavalent or hexavalent state and one that seeks to selectively complex trivalent americium either in the aqueous phase or the solvent phase. Solvent extraction represents the primary separation method employed, though ion exchange and crystallization play an important role. Highlights of accomplishments include: Confirmation of the first-ever electrolytic oxidation of Am(III) in a

  7. PREFACE: Actinides 2009

    Science.gov (United States)

    Rao, Linfeng; Tobin, James G.; Shuh, David K.

    2010-07-01

    This volume of IOP Conference Series: Materials Science and Engineering consists of 98 papers that were presented at Actinides 2009, the 8th International Conference on Actinide Science held on 12-17 July 2009 in San Francisco, California, USA. This conference was jointly organized by Lawrence Livermore National Laboratory and Lawrence Berkeley National Laboratory. The Actinides conference series started in Baden-Baden, Germany (1975) and this first conference was followed by meetings at Asilomar, CA, USA (1981), Aix-en-Provence, France (1985), Tashkent, USSR (1989), Santa Fe, NM, USA (1993), Baden-Baden, Germany (1997), Hayama, Japan (2001), and Manchester, UK (2005). The Actinides conference series provides a regular venue for the most recent research results on the chemistry, physics, and technology of the actinides and heaviest elements. Actinides 2009 provided a forum spanning a diverse range of scientific topics, including fundamental materials science, chemistry, physics, environmental science, and nuclear fuels. Of particular importance was a focus on the key roles that basic actinide chemistry and physics research play in advancing the worldwide renaissance of nuclear energy. Editors Linfeng Rao Lawrence Berkeley National Laboratory (lrao@lbl.gov) James G Tobin Lawrence Livermore National Laboratory (tobin1@llnl.gov) David K Shuh Lawrence Berkeley National Laboratory (dkshuh@lbl.gov)

  8. Study on Properties of TBP-HNO3 Complex Used for Direct Dissolution of Lanthanide and Actinide Oxides in Supercritical Fluid CO2

    Institute of Scientific and Technical Information of China (English)

    DUAN Wu-Hua; ZHU Li-Yang; JING Shan; ZHU Yong-Jun; CHEN Jing

    2007-01-01

    The tri-n-butyl phosphate-nitric acid (TBP-HNO3) complex prepared by contacting the pure TBP with the concentrated HNO3 can be used for direct dissolution of lanthanide and actinide oxides in the supercritical fluid carbon dioxide (SCF-CO2). Properties of the TBP-HNO3 complex have been studied. Experimental results showed that when the initial HNO3/TBP volume ratio was varied from 1 : 7 to 5 : 1, the concentration of HNO3 in the TBP-HNO3 complex changed from 1.95 to 5.89 mol/L, the [HNO3]/[TBP] ratio of the TBP-HNO3 complex changed from 0.61 to 2.22, and the content of H2O in the TBP-HNO3 complex changed from 2.02% to 4.19%. All of the density, viscosity and surface tension of the TBP-HNO3 complex changed with the concentration of HNO3 in the complex, and were higher than those of the pure TBP. The protons of HNO3 and H2O in the complex underwent rapid exchange to exhibit a singlet resonance peak in nuclear magnetic resonance spectra. When the TBP-HNO3 complex was dissolved in a low dielectric constant solvent, small droplets of HNO3 were formed that can be detected by NMR.

  9. Chemistry of actinides; Chimie des actinides

    Energy Technology Data Exchange (ETDEWEB)

    Vitorge, P. [CEA/Saclay, Dept. d' Entreposage et de Stockage des Dechets (DESD), 91 - Gif-sur-Yvette (France)

    1999-07-01

    This article gives the basic data of the actinides chemistry, describes then qualitatively the main parts of the fuel cycle and concludes with quantitative data. The theoretical recalls give qualitative notions to explain the chemical reactivity of actinides and to understand thus the values of the thermodynamic data which allow quantitative anticipations at equilibrium. The Thermodynamic Data Base (TDB) of the NEA-OECD and the CEA in France have recently estimated some of them in using and developing methodologies whose some are presented here. Some current problems of actinides chemistry are described: analysis of the possibilities to (1)improve the reprocessing of long-lived actinides (2)anticipate their behaviour in the environment in order to compare the impact of the different options of the wastes management. The Pourbaix diagrams summarize the chemistry in solution; the author has added information on the solubility, the influence of the ionic strength and of the complexes formation in bicarbonate/carbonate (HCO{sub 3}{sup -}/CO{sub 3}{sup 2-}) media. The discussion on the choice of the equilibrium constants allows to point out the particular points, the dubiousness and the data which have to be proved. (O.M.)

  10. Structural organization and spectroscopy of peptide-actinide(IV) complexes; Organisation structurale et spectroscopie de peptides susceptibles de complexer les actinides(IV)

    Energy Technology Data Exchange (ETDEWEB)

    Dahou, S.

    2010-11-05

    The contamination of living organisms by actinide elements is at the origin of both radiological and chemical toxicity that may lead to severe dysfunction. Most of the data available on the actinide interaction with biological systems are macroscopic physiological measurements and are lacking a molecular description of the systems. Because of the intricacy of these systems, classical biochemical methods are difficult to implement. Our strategy consisted in designing simplified biomimetic peptides, and describing the corresponding intramolecular interactions with actinides. A carboxylic pentapeptide of the form DDPDD has been at the starting point of this work in order to further assess the influence of the peptide sequence on the topology of the complexes.To do so, various linear (Asp/Ala permutations, peptoids) and cyclic analogues have been synthesized. Furthermore, in order to include the hydroxamic function (with a high affinity for Fe(III)) in the peptide, both desferrioxamine and acetohydroxamic acid have been investigated. However because of difficulties in synthesis, we have not been able to test these peptides. Three actinide cations have been considered at oxidation state +IV (Th, Np, Pu) and compared to Fe(III), often considered as a biological surrogate of Pu(IV). The spatial arrangement of the peptide around the cation has been probed by spectrophotometry and X-ray Absorption Spectroscopy. The spectroscopic data and EXAFS data adjustment lead us to rationalize the topology of the complexes as a function of the peptide sequence: mix hydroxy polynuclear species for linear and cyclic peptides, mononuclear for the desferrioxamine complexes. Furthermore, significant differences have appeared between Fe(III) and actinide(IV), related to differences of reactivity in aqueous medium. (author)

  11. Actinide partitioning and transmutation program. Progress report, July 1--September 30, 1977

    Energy Technology Data Exchange (ETDEWEB)

    Tedder, D.W.; Blomeke, J.O. (comps.)

    1978-02-01

    In Purex process modifications, two cold runs with mixer-settlers were made on the extraction and stripping of ruthenium and zirconium without the presence of uranium. Efforts in actinide recovery from solids were directed toward the determination of dissolution parameters in various reagents for /sup 241/Am and /sup 239/Pu oxide mixtures, /sup 233/U oxide, /sup 237/Np oxide, /sup 244/Cm oxide, /sup 232/Th oxide, and PuO/sub 2/. Studies in americium-curium recovery with OPIX (oxalate precipitation and ion exchange), Talspeak, and cation exchange chromatography focused on the feasibility of forming oxalate precipitates in continuous systems, the effects of zirconium on Talspeak, and methods for removing solvent degradation products of the Talspeak system. In studies of americium-curium recovery using bidentate extractants, additional distribution coefficients for actinides and other key elements between reduced synthetic LWR waste solution and 30 percent dihexyl-N, N-diethyl-carbamylmethylene phosphonate in diisopropylbenzene were measured. Studies in the americium-curium recovery using inorganic ion exchange media to determine the pH dependence of lanthanide ion affinity for niobate, titanate, and zirconate ion exchange materials have been completed. A modified flowsheet for the extraction of uranium, neptunium, plutonium, americium, and curium from high-level liquid waste is presented. Evaluation of methods for measuring actinides from incinerator ash is continuing. A preliminary evaluation of methods for treatment of salt waste and waste waters was completed. In thermal reactor transmutation studies, waste actinides from an LWR lattice containing mixed uranium-plutonium assemblies were recycled in separate target assemblies. (LK)

  12. Selective oxidation of isobutane on V–Mo–O mixed oxide catalysts

    Directory of Open Access Journals (Sweden)

    GHEORGHITA MITRAN

    2008-01-01

    Full Text Available Four V–Mo–O mixed metal oxides were prepared, characterized and tested for the selective oxidation of isobutane in the temperature range 350–550 °C, at atmospheric pressure. Isobutane was mainly oxidized to iso-butene and carbon oxides. The systems with low vanadium contents showed low activities but high isobutene selectivities, while the systems with high vanadium contents showed high activities with high carbon oxides selectivities. The effects of temperature, contact time and the molar ratio iso-butane to oxygen on the conversion of isobutane and the selectivity of the oxidation were studied.

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

    Energy Technology Data Exchange (ETDEWEB)

    Prellberg, J.W.; Thornton, L.M.; Cheuvront, D.A. [Vulcan Peroxidation Systems, Inc., Tucson, AZ (United States)] [and others

    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.

  14. Heterogeneous Partial (ammOxidation and Oxidative Dehydrogenation Catalysis on Mixed Metal Oxides

    Directory of Open Access Journals (Sweden)

    Jacques C. Védrine

    2016-01-01

    Full Text Available This paper presents an overview of heterogeneous partial (ammoxidation and oxidative dehydrogenation (ODH of hydrocarbons. The review has been voluntarily restricted to metal oxide-type catalysts, as the partial oxidation field is very broad and the number of catalysts is quite high. The main factors of solid catalysts for such reactions, designated by Grasselli as the “seven pillars”, and playing a determining role in catalytic properties, are considered to be, namely: isolation of active sites (known to be composed of ensembles of atoms, Me–O bond strength, crystalline structure, redox features, phase cooperation, multi-functionality and the nature of the surface oxygen species. Other important features and physical and chemical properties of solid catalysts, more or less related to the seven pillars, are also emphasized, including reaction sensitivity to metal oxide structure, epitaxial contact between an active phase and a second phase or its support, synergy effect between several phases, acid-base aspects, electron transfer ability, catalyst preparation and activation and reaction atmospheres, etc. Some examples are presented to illustrate the importance of these key factors. They include light alkanes (C1–C4 oxidation, ethane oxidation to ethylene and acetic acid on MoVTe(SbNb-O and Nb doped NiO, propene oxidation to acrolein on BiMoCoFe-O systems, propane (ammoxidation to (acrylonitrile acrylic acid on MoVTe(SbNb-O mixed oxides, butane oxidation to maleic anhydride on VPO: (VO2P2O7-based catalyst, and isobutyric acid ODH to methacrylic acid on Fe hydroxyl phosphates. It is shown that active sites are composed of ensembles of atoms whose size and chemical composition depend on the reactants to be transformed (their chemical and size features and the reaction mechanism, often of Mars and van Krevelen type. An important aspect is the fact that surface composition and surface crystalline structure vary with reaction on stream until

  15. Subsurface Biogeochemistry of Actinides

    Energy Technology Data Exchange (ETDEWEB)

    Kersting, Annie B. [Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States). Univ. Relations and Science Education; Zavarin, Mavrik [Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States). Glenn T. Seaborg Inst.

    2016-06-29

    A major scientific challenge in environmental sciences is to identify the dominant processes controlling actinide transport in the environment. It is estimated that currently, over 2200 metric tons of plutonium (Pu) have been deposited in the subsurface worldwide, a number that increases yearly with additional spent nuclear fuel (Ewing et al., 2010). Plutonium has been shown to migrate on the scale of kilometers, giving way to a critical concern that the fundamental biogeochemical processes that control its behavior in the subsurface are not well understood (Kersting et al., 1999; Novikov et al., 2006; Santschi et al., 2002). Neptunium (Np) is less prevalent in the environment; however, it is predicted to be a significant long-term dose contributor in high-level nuclear waste. Our focus on Np chemistry in this Science Plan is intended to help formulate a better understanding of Pu redox transformations in the environment and clarify the differences between the two long-lived actinides. The research approach of our Science Plan combines (1) Fundamental Mechanistic Studies that identify and quantify biogeochemical processes that control actinide behavior in solution and on solids, (2) Field Integration Studies that investigate the transport characteristics of Pu and test our conceptual understanding of actinide transport, and (3) Actinide Research Capabilities that allow us to achieve the objectives of this Scientific Focus Area (SFA and provide new opportunities for advancing actinide environmental chemistry. These three Research Thrusts form the basis of our SFA Science Program (Figure 1).

  16. Research in actinide chemistry. Progress report, 1990--1993

    Energy Technology Data Exchange (ETDEWEB)

    Choppin, G.R.

    1993-04-01

    This research studies the behavior of the actinide elements in aqueous solution. The high radioactivity of the transuranium actinides limits the concentrations which can be studied and, consequently, limits the experimental techniques. However, oxidation state analogs (trivalent lanthanides, tetravalent thorium, and hexavalent uranium) do not suffer from these limitations. Behavior of actinides in the environment are a major USDOE concern, whether in connection with long-term releases from a repository, releases from stored defense wastes or accidental releases in reprocessing, etc. Principal goal of our research was expand the thermodynamic data base on complexation of actinides by natural ligands (e.g., OH{sup {minus}}, CO{sub 3}{sup 2{minus}}, PO{sub 4}{sup 3{minus}}, humates). The research undertakes fundamental studies of actinide complexes which can increase understanding of the environmental behavior of these elements.

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

    Energy Technology Data Exchange (ETDEWEB)

    Chen, Senniang [Iowa State Univ., Ames, IA (United States)

    2010-05-15

    The work in this dissertation presents the synthesis of two mixed metal oxides for biofuel applications and NMR characterization of silica materials. In the chapter 2, high catalytic efficiency of calcium silicate is synthesized for transesterfication of soybean oil to biodisels. Chapter 3 describes the synthesis of a new Rh based catalyst on mesoporous manganese oxides. The new catalyst is found to have higher activity and selectivity towards ethanol. Chapter 4 demonstrates the applications of solid-state Si NMR in the silica materials.

  18. Development of advanced mixed oxide fuels for plutonium management

    Energy Technology Data Exchange (ETDEWEB)

    Eaton, S.; Beard, C.; Buksa, J.; Butt, D.; Chidester, K.; Havrilla, G.; Ramsey, K.

    1997-06-01

    A number of advanced Mixed Oxide (MOX) fuel forms are currently being investigated at Los Alamos National Laboratory that have the potential to be effective plutonium management tools. Evolutionary Mixed Oxide (EMOX) fuel is a slight perturbation on standard MOX fuel, but achieves greater plutonium destruction rates by employing a fractional nonfertile component. A pure nonfertile fuel is also being studied. Initial calculations show that the fuel can be utilized in existing light water reactors and tailored to address different plutonium management goals (i.e., stabilization or reduction of plutonium inventories residing in spent nuclear fuel). In parallel, experiments are being performed to determine the feasibility of fabrication of such fuels. Initial EMOX pellets have successfully been fabricated using weapons-grade plutonium.

  19. Structure Characterization of Semiconducting Tin and Tungsten Mixed Oxides

    Science.gov (United States)

    Solis, J. L.; Frantti, J.; Lantto, V.; Häggström, L.; Wikner, M.

    Mixed-oxide powders of tin and tungsten were made by heating various mixtures of SnO and WO3 powders, corresponding to the nominal formula SnxWO3+x with x between 0.5 and 2.0, in an argon atmosphere at 600°C for 15 hours. The α-SnWO4 phase was the result of heating of an equi-molar mixture of SnO and WO3 powders. In addition to 119Sn Mössbauer experiments, X-ray diffraction and Raman spectroscopy were used to study the phase structures of the mixed-oxide powders. Mössbauer spectra from all samples show a small peak at ∽0mm/s from phase(s) like rutile SnO2, and a larger peak doublet centred at ∽3.4mm/s from the α-SnWO4 phase, where tin is in the form Sn4+ and Sn2+, respectively. Another peak doublet centred at ∽3.0mm/s was needed to obtain reasonable fits for samples with x≥1.3. This doublet originates from an undocumented phase where tin is also in the divalent form Sn2+. 119Sn Mössbauer spectroscopy made it possible to reveal the relative amounts of the two valence states of tin in the mixed-oxide structures. Raman spectroscopy as the other probe for ``local'' structures was insensitive to reveal the changes in the phase structures between different mixed-oxide samples up to x=1.72, but an extra peak at ∽890cm-1 in the Raman spectrum from the sample with x=2.0 indicates also the presence of the undocumented phase.

  20. Comparative Study of f-Element Electronic Structure across a Series of Multimetallic Actinide, Lanthanide-Actinide and Lanthanum-Actinide Complexes Possessing Redox-Active Bridging Ligands

    Energy Technology Data Exchange (ETDEWEB)

    Schelter, Eric J.; Wu, Ruilian; Veauthier, Jacqueline M.; Bauer, Eric D.; Booth, Corwin H.; Thomson, Robert K.; Graves, Christopher R.; John, Kevin D.; Scott, Brian L.; Thompson, Joe D.; Morris, David E.; Kiplinger, Jaqueline L.

    2010-02-24

    A comparative examination of the electronic interactions across a series of trimetallic actinide and mixed lanthanide-actinide and lanthanum-actinide complexes is presented. Using reduced, radical terpyridyl ligands as conduits in a bridging framework to promote intramolecular metal-metal communication, studies containing structural, electrochemical, and X-ray absorption spectroscopy are presented for (C{sub 5}Me{sub 5}){sub 2}An[-N=C(Bn)(tpy-M{l_brace}C{sub 5}Me4R{r_brace}{sub 2})]{sub 2} (where An = Th{sup IV}, U{sup IV}; Bn = CH{sub 2}C{sub 6}H{sub 5}; M = La{sup III}, Sm{sup III}, Yb{sup III}, U{sup III}; R = H, Me, Et) to reveal effects dependent on the identities of the metal ions and R-groups. The electrochemical results show differences in redox energetics at the peripheral 'M' site between complexes and significant wave splitting of the metal- and ligand-based processes indicating substantial electronic interactions between multiple redox sites across the actinide-containing bridge. Most striking is the appearance of strong electronic coupling for the trimetallic Yb{sup III}-U{sup IV}-Yb{sup III}, Sm{sup III}-U{sup IV}-Sm{sup III}, and La{sup III}-U{sup IV}-La{sup III} complexes, [8]{sup -}, [9b]{sup -} and [10b]{sup -}, respectively, whose calculated comproportionation constant K{sub c} is slightly larger than that reported for the benchmark Creutz-Taube ion. X-ray absorption studies for monometallic metallocene complexes of U{sup III}, U{sup IV}, and U{sup V} reveal small but detectable energy differences in the 'white-line' feature of the uranium L{sub III}-edges consistent with these variations in nominal oxidation state. The sum of this data provides evidence of 5f/6d-orbital participation in bonding and electronic delocalization in these multimetallic f-element complexes. An improved, high-yielding synthesis of 4{prime}-cyano-2,2{prime}:6{prime},2{double_prime}-terpyridine is also reported.

  1. Mixed metal oxide crystalline powders and method for the synthesis thereof

    Energy Technology Data Exchange (ETDEWEB)

    Joyce, I.H.; Blonski, R.P.; Maloney, J.J.; Welch, J.J.; Pipoly, R.A.; Byrne, C.J.

    1993-07-20

    A method is described for the solid state synthesis of mixed metal oxide crystalline powders comprising the steps of: preparing a raw material mixture containing at least two different metal cations; adding a template material to said mixture and blending it therewith; initiating formation of a mixed metal oxide by calcination of said mixture and said template material, whereby particles of the mixed metal oxides are formed in powder form; and thereafter recovering said mixed metal oxide particles.

  2. Selective oxidation of benzylic alcohols using copper-manganese mixed oxide nanoparticles as catalyst

    Directory of Open Access Journals (Sweden)

    Roushown Ali

    2015-07-01

    Full Text Available The catalytic activity of copper-manganese (CuMn2 mixed oxide nanoparticles (Cu/Mn = 1:2 has been studied for the selective oxidation of benzylic alcohols to the corresponding aldehydes using molecular oxygen as an oxidizing agent. The CuMn2 mixed oxide showed excellent catalytic activity for the oxidation of benzylic alcohols to the corresponding aldehydes with high selectivity (>99%. The complete conversion (100% of all the benzylic alcohols to the corresponding aldehydes is achieved within a short reaction period at 102 °C. The catalytic performance is obtained to be dependent on the electronic and steric effects of the substituents present on the phenyl ring. Electron withdrawing and bulky groups attached to the phenyl ring required longer reaction time for a complete conversion of the benzylic alcohols.

  3. An emergency bioassay method for actinides in urine.

    Science.gov (United States)

    Dai, Xiongxin; Kramer-Tremblay, Sheila

    2011-08-01

    A rapid bioassay method has been developed for the sequential measurements of actinides in human urine samples. The method involves actinide separation from a urine matrix by co-precipitation with hydrous titanium oxide (HTiO), followed by anion exchange and extraction chromatography column purification, and final counting by alpha spectrometry after cerium fluoride micro-precipitation. The minimal detectable activities for the method were determined to be 20 mBq L(-1) or less for plutonium, uranium, americium and curium isotopes, with an 8-h sample turn-around time. Spike tests showed that this method would meet the requirements for actinide bioassay following a radiation emergency.

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

    Science.gov (United States)

    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...

  5. 40 CFR 721.5315 - Nickel, cobalt mixed metal oxide (generic).

    Science.gov (United States)

    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 the...

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

    Science.gov (United States)

    Marrs, Michael

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

  7. Direct chemical oxidation of mixed or toxic wastes

    Energy Technology Data Exchange (ETDEWEB)

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

    1999-05-01

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

  8. Thin extractive membrane for monitoring actinides in aqueous streams.

    Science.gov (United States)

    Chavan, Vivek; Paul, Sumana; Pandey, Ashok K; Kalsi, P C; Goswami, A

    2013-09-15

    Alpha spectrometry and solid state nuclear track detectors (SSNTDs) are used for monitoring ultra-trace amount of alpha emitting actinides in different aqueous streams. However, these techniques have limitations i.e. alpha spectrometry requires a preconcentration step and SSNTDs are not chemically selective. Therefore, a thin polymer inclusion membrane (PIM) supported on silanized glass was developed for preconcentraion and determination of ultra-trace concentration of actinides by α-spectrometry and SSNTDs. PIMs were formed by spin coating on hydrophobic glass slide or solvent casting to form thin and self-supported membranes, respectively. Sorption experiments indicated that uptakes of actinides in the PIM were highly dependent on acidity of solution i.e. Am(III) sorbed up to 0.1 molL(-1) HNO₃, U(VI) up to 0.5 molL(-1) HNO₃ and Pu(IV) from HNO₃ concentration as high as 4 molL(-1). A scheme was developed for selective sorption of target actinide in the PIM by adjusting acidity and oxidation state of actinide. The actinides sorbed in PIMs were quantified by alpha spectrometry and SSNTDs. For SSNTDs, neutron induced fission-fragment tracks and α-particle tracks were registered in Garware polyester and CR-39 for quantifications of natural uranium and α-emitting actinides ((241)Am/(239)Pu/(233)U), respectively. Finally, the membranes were tested to quantify Pu in 4 molL(-1) HNO3 solutions and synthetic urine samples.

  9. Mixed protonic and electronic conductors hybrid oxide synaptic transistors

    Science.gov (United States)

    Fu, Yang Ming; Zhu, Li Qiang; Wen, Juan; Xiao, Hui; Liu, Rui

    2017-05-01

    Mixed ionic and electronic conductor hybrid devices have attracted widespread attention in the field of brain-inspired neuromorphic systems. Here, mixed protonic and electronic conductor (MPEC) hybrid indium-tungsten-oxide (IWO) synaptic transistors gated by nanogranular phosphorosilicate glass (PSG) based electrolytes were obtained. Unique field-configurable proton self-modulation behaviors were observed on the MPEC hybrid transistor with extremely strong interfacial electric-double-layer effects. Temporally coupled synaptic plasticities were demonstrated on the MPEC hybrid IWO synaptic transistor, including depolarization/hyperpolarization, synaptic facilitation and depression, facilitation-stead/depression-stead behaviors, spiking rate dependent plasticity, and high-pass/low-pass synaptic filtering behaviors. MPEC hybrid synaptic transistors may find potential applications in neuron-inspired platforms.

  10. Synthesis and characterization of mixed melilite-type oxides

    Science.gov (United States)

    Granata, V.; Ubaldini, A.; Fittipaldi, R.; Rocco, L.; Pace, S.; Vecchione, A.

    2017-01-01

    The melilite-type oxides are potential targets for exploring interesting magnetic and electronic properties as well as multiferroicity and magnetoelectric effects. Polycrystalline samples of Ba2Cu1-xMnxGe2O7 have been synthesized by solid state reaction method. The morphology and chemical composition of the samples have been investigated by scanning electron microscopy (SEM) and energy dispersive spectroscopy (EDS). By using powder X-ray diffraction, the phase composition of the synthesized compounds and the evolution of their crystallographic axes as a function of the doping have been systematically studied. The synthesis of the polycrystalline compounds reported in this work is a prerequisite for the growth of high quality single crystals of mixed melilite-type oxides essential for the investigations of the complex magnetic phase diagram of these non-centrosymmetric systems.

  11. Ceria doped mixed metal oxide nanoparticles as oxidation catalysts: Synthesis and their characterization

    Directory of Open Access Journals (Sweden)

    S.S.P. Sultana

    2015-11-01

    Full Text Available Mixed metal nanoparticles (NPs have attracted significant attention as catalysts for various organic transformations. In this study, we have demonstrated the preparation of nickel–manganese mixed metal oxide NPs doped with X% nano cerium oxide (X = 1, 3, 5 mol% by a facile co-precipitation technique using surfactant and surfactant free methodologies. The as-synthesized materials were calcined at different temperatures (300 °C, 400 °C, and 500 °C, and were characterized using various spectroscopic techniques, including, FTIR and XRD. SEM analysis, TEM analysis and TGA were employed to evaluate the structural properties of the as-prepared catalyst. These were evaluated for their catalytic behaviour towards the conversion of benzyl alcohol to benzaldehyde, which was used as a model reaction with molecular oxygen as oxidant. Furthermore, the effect of the variation of the percentage of nano ceria doping and the calcination temperature on the performance of as-prepared mixed metal catalysts was also evaluated. The kinetic studies of the reactions performed employing gas chromatographic technique have revealed that the mixed metal oxide catalyst doped with 5% nano ceria displayed excellent catalytc activity, among various catalysts synthesized.

  12. Design of unique pins for irradiation of higher actinides in a fast reactor

    Energy Technology Data Exchange (ETDEWEB)

    Basmajian, J.A.; Birney, K.R.; Weber, E.T.; Adair, H.L.; Quinby, T.C.; Raman, S.; Butler, J.K.; Bateman, B.C.; Swanson, K.M.

    1982-03-01

    The actinides produced by transmutation reactions in nuclear reactor fuels are a significant factor in nuclear fuel burnup, transportation and reprocessing. Irradiation testing is a primary source of data of this type. A segmented pin design was developed which provides for incorporation of multiple specimens of actinide oxides for irradiation in the UK's Prototype Fast Reactor (PFR) at Dounreay Scotland. Results from irradiation of these pins will extend the basic neutronic and material irradiation behavior data for key actinide isotopes.

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

    Science.gov (United States)

    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.

  14. Device for Detecting Actinides, Method for Detecting Actinides

    Energy Technology Data Exchange (ETDEWEB)

    Stevens, Fred J.; Wilkins-Stevens, Priscilla

    1998-10-29

    A heavy metal detector is provided comprising a first molecule and a second molecule, whereby the first and second molecules interact in a predetermined manner; a first region on the first molecule adapted to interact with an actinide; and a second region on the second molecule adapted to interact with the actinide, whereby the interactions of the actinide with the regions effect the predetermined manner of interaction between the molecules.

  15. Fundamental thermodynamics of actinide-bearing mineral waste forms. 1998 annual progress report

    Energy Technology Data Exchange (ETDEWEB)

    Williamson, M.A. [Los Alamos National Lab., NM (US); Ebbinghaus, B.B.

    1998-06-01

    'The end of the Cold War raised the need for the technical community to be concerned with the disposition of excess nuclear weapon material. The plutonium will either be converted into mixed-oxide fuel for use in nuclear reactors or immobilized in glass or ceramic waste forms and placed in a repository. The stability and behavior of plutonium in the ceramic materials as well as the phase behavior and stability of the ceramic material in the environment is not well established. In order to provide technically sound solutions to these issues, thermodynamic data are essential in developing an understanding of the chemistry and phase equilibria of the actinide-bearing mineral waste form materials proposed as immobilization matrices. Mineral materials of interest include zircon, zirconolite, and pyrochlore. High temperature solution calorimetry is one of the most powerful techniques, sometimes the only technique, for providing the fundamental thermodynamic data needed to establish optimum material fabrication parameters, and more importantly, understand and predict the behavior of the mineral materials in the environment. The purpose of this project is to experimentally determine the enthalpy of formation of actinide orthosilicates, the enthalpy of formation of actinide substituted zircon, zirconolite and pyrochlore, and develop an understanding of the bonding characteristics and stability of these materials. This report summarizes work after eight months of a three year project.'

  16. Fundamental Thermodynamics of Actinide-Bearing Mineral Waste Forms - Final Report

    Energy Technology Data Exchange (ETDEWEB)

    Williamson, Mark A.; Ebbinghaus, Bartley B.; Navrotsky, Alexandra

    2001-03-01

    The end of the Cold War raised the need for the technical community to be concerned with the disposition of excess nuclear weapon material. The plutonium will either be converted into mixed-oxide fuel for use in nuclear reactors or immobilized in glass or ceramic waste forms and placed in a repository. The stability and behavior of plutonium in the ceramic materials as well as the phase behavior and stability of the ceramic material in the environment is not well established. In order to provide technically sound solutions to these issues, thermodynamic data are essential in developing an understanding of the chemistry and phase equilibria of the actinide-bearing mineral waste form materials proposed as immobilization matrices. Mineral materials of interest include zircon, zirconolite, and pyrochlore. High temperature solution calorimetry is one of the most powerful techniques, sometimes the only technique, for providing the fundamental thermodynamic data needed to establish optimum material fabrication parameters, and more importantly understand and predict the behavior of the mineral materials in the environment. The purpose of this project is to experimentally determine the enthalpy of formation of actinide orthosilicates, the enthalpies of formation of actinide substituted zirconolite and pyrochlore, and develop an understanding of the bonding characteristics and stabilities of these materials.

  17. Structure and Catalytic Behavior of CuO-ZrO-CeO2 Mixed Oxides

    Institute of Scientific and Technical Information of China (English)

    王恩过; 陈诵英

    2002-01-01

    The effect of doping CuO on the structure and properties of zirconia-ceria mixed oxide was studied. The results show that addition of CuO decreases the reduction temperature of ceria, and stabilizes the cubic structure of mixed oxides, and enhances catalytic activity of CuO-ZrO-CeO2 mixed oxides for CO oxidation. Increasing ceria content in the mixed oxides can enhance the catalytic activity, but some impurities such as sulfate make catalytic activity falling. There is little effect of calcination temperature on catalytic activities, implying that these catalysts are effective with good thermal stability.

  18. Mass transport in mixed conducting perovskite related oxides

    CERN Document Server

    Shaw, C K M

    2001-01-01

    mechanical and chemical stability of LSCN under practical operating temperatures have been measured and related to long term stability in typical SOFC assemblies. The phase stability and the effect of preparation conditions under different atmospheres on La sub 2 Ni sub 1 sub - sub x Co sub x O sub 4 sub + subdelta compounds were examined using high temperature X-ray diffraction. Fast oxygen uptake at low temperatures was observed in these studies indicating rapid oxygen diffusion, which was confirmed by isotope exchange investigations. The oxygen diffusion and surface exchange data obtained from IEDP-SIMS measurements of La sub 2 Ni sub 0 sub . sub 8 Co sub 0 sub . sub 2 O sub 4 sub + subdelta have enabled suppositions to be made regarding the reduction process and aided further interpretation of the defect model for these oxides. Mixed ionic electronic conducting oxides of the perovskite structure have attracted great interest in the field of solid oxide electrochemical devices. Their ability to allow poten...

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

    Science.gov (United States)

    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

  20. Perovskite-type Mixed Oxides Catalyst for Complete Oxidation of Acetone

    Institute of Scientific and Technical Information of China (English)

    DUAN; ZhiYing

    2001-01-01

    The catalytic oxidation of VOCs (volatile organic compounds) is an attractive subject in the field of environmental protection now. Furthermore, most countries have made out regulations m controlling the maximum content of VOCs in some places. Presently, the leading way of domestic and foreign means to eliminate VOCs is to completely oxidize VOCs into carbon dioxide and water in presence of noble metal catalyst. But noble metal is expensive for lack of resource[2]. So it is insistent to research a low-cost catalyst for removal of VOCs. In this work, we have used some base metals (such as La, Sr, Ce, Ni, Cu) to synthesize mixed oxides catalyst supported on γ-A12O3. We have investigated the catalytic properties in the complete oxidation of acetone over the catalyst prepared and achieved an exciting result.……

  1. Perovskite-type Mixed Oxides Catalyst for Complete Oxidation of Acetone

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    @@ The catalytic oxidation of VOCs (volatile organic compounds) is an attractive subject in the field of environmental protection now. Furthermore, most countries have made out regulations m controlling the maximum content of VOCs in some places. Presently, the leading way of domestic and foreign means to eliminate VOCs is to completely oxidize VOCs into carbon dioxide and water in presence of noble metal catalyst. But noble metal is expensive for lack of resource[2]. So it is insistent to research a low-cost catalyst for removal of VOCs. In this work, we have used some base metals (such as La, Sr, Ce, Ni, Cu) to synthesize mixed oxides catalyst supported on γ-A12O3. We have investigated the catalytic properties in the complete oxidation of acetone over the catalyst prepared and achieved an exciting result.

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

    Science.gov (United States)

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

    2006-09-01

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

  3. Actinide (III) solubility in WIPP Brine: data summary and recommendations

    Energy Technology Data Exchange (ETDEWEB)

    Borkowski, Marian; Lucchini, Jean-Francois; Richmann, Michael K.; Reed, Donald T.

    2009-09-01

    The solubility of actinides in the +3 oxidation state is an important input into the Waste Isolation Pilot Plant (WIPP) performance assessment (PA) models that calculate potential actinide release from the WIPP repository. In this context, the solubility of neodymium(III) was determined as a function of pH, carbonate concentration, and WIPP brine composition. Additionally, we conducted a literature review on the solubility of +3 actinides under WIPP-related conditions. Neodymium(III) was used as a redox-invariant analog for the +3 oxidation state of americium and plutonium, which is the oxidation state that accounts for over 90% of the potential release from the WIPP through the dissolved brine release (DBR) mechanism, based on current WIPP performance assessment assumptions. These solubility data extend past studies to brine compositions that are more WIPP-relevant and cover a broader range of experimental conditions than past studies.

  4. Soft X-ray scanning transmission X-ray microscopy (STXM) of actinide particles.

    Science.gov (United States)

    Nilsson, Hans J; Tyliszczak, Tolek; Wilson, Richard E; Werme, Lars; Shuh, David K

    2005-09-01

    A descriptive account is given of our most recent research on the actinide dioxides with the Advanced Light Source Molecular Environmental Science (ALS-MES) Beamline 11.0.2 soft X-ray scanning transmission X-ray microscope (STXM) at the Lawrence Berkeley National Laboratory (LBNL). The ALS-MES STXM permits near-edge X-ray absorption fine structure (NEXAFS) and imaging with 30-nm spatial resolution. The first STXM spectromicroscopy NEXAFS spectra at the actinide 4d5/2 edges of the imaged transuranic particles, NpO2 and PuO2, have been obtained. Radiation damage induced by the STXM was observed in the investigation of a mixed oxidation state particle (Np(V,VI)) and was minimized during collection of the actual spectra at the 4d5/2 edge of the Np(V,VI) solid. A plutonium elemental map was obtained from an irregular PuO2 particle with the dimensions of 650 x 650 nm. The Pu 4d5/2 NEXAFS spectra were collected at several different locations from the PuO2 particle and were identical. A representative oxygen K-edge spectrum from UO2 was collected and resembles the oxygen K-edge from the bulk material. The unique and current performance of the ALS-MES STXM at extremely low energies (ca. 100 eV) that may permit the successful measurement of the actinide 5d edge is documented. Finally, the potential of STXM as a tool for actinide investigations is briefly discussed.

  5. Characterization of manganese-gallium mixed oxide powders

    Energy Technology Data Exchange (ETDEWEB)

    Sanchez Escribano, V.; Fernandez Lopez, E.; Sanchez Huidobro, P. [Universidad de Salamanca, Dept. de Quimica Inorganica (Spain); Panizza, M.; Resini, C.; Busca, G. [UNiversita di Genova, Dipt. di Ingegneria Chimica e di Processo, Genova (Italy); Resini, C. [Istituto Nazionale di Fisica della Materia, INFM (Spain); Gallardo- Amores, J.M. [Universidad Complutense, Dept. de Quimica Inorganica, Lab. Complutense de Altas Presiones, Madrid (Spain)

    2003-12-01

    Mn-Ga mixed oxides have been prepared by coprecipitation of the corresponding oxo-hydroxides as powders and have been characterized in relation to their structural and optical properties. The materials have been characterized by XRD, TG-DTA, skeletal IR and UV-visible-NIR spectroscopies. Large solubility of Mn in the diaspore type {alpha}-GaOOH oxo-hydroxide has been found. The spinel related structures of hausmannite Mn{sub 3}O{sub 4} and of {beta}-gallia present large reciprocal solubilities at least in a metastable form. At high temperature also bixbyite-type {alpha}-Mn{sub O3} solid solutions containing up to 20% at. Ga have been observed. (authors)

  6. Yttrium bismuth titanate pyrochlore mixed oxides for photocatalytic hydrogen production

    Energy Technology Data Exchange (ETDEWEB)

    Merka, Oliver

    2012-10-18

    In this work, the sol-gel synthesis of new non-stoichiometric pyrochlore titanates and their application in photocatalytic hydrogen production is reported. Visible light response is achieved by introducing bismuth on the A site or by doping the B site by transition metal cations featuring partially filled d orbitals. This work clearly focusses on atomic scale structural changes induced by the systematical introduction of non-stoichiometry in pyrochlore mixed oxides and the resulting influence on the activity in photocatalytic hydrogen production. The materials were characterized in detail regarding their optical properties and their atomic structure. The pyrochlore structure tolerates tremendous stoichiometry variations. The non-stoichiometry in A{sub 2}O{sub 3} rich compositions is compensated by distortions in the cationic sub-lattice for the smaller Y{sup 3+} cation and by evolution of a secondary phase for the larger Bi{sup 3+} cation on the A site. For TiO{sub 2} rich compositions, the non-stoichiometry leads to a special vacancy formation in the A and optionally O' sites. It is shown that pyrochlore mixed oxides in the yttrium bismuth titanate system represent very active and promising materials for photocatalytic hydrogen production, if precisely and carefully tuned. Whereas Y{sub 2}Ti{sub 2}O{sub 7} yields stable hydrogen production rates over time, the bismuth richer compounds of YBiTi{sub 2}O{sub 7} and Bi{sub 2}Ti{sub 2}O{sub 7} are found to be not stable under irradiation. This drawback is overcome by applying a special co-catalyst system consisting of a precious metal core and a Cr{sub 2}O{sub 3} shell on the photocatalysts.

  7. Calculational Benchmark Problems for VVER-1000 Mixed Oxide Fuel Cycle

    Energy Technology Data Exchange (ETDEWEB)

    Emmett, M.B.

    2000-03-17

    Standard problems were created to test the ability of American and Russian computational methods and data regarding the analysis of the storage and handling of Russian pressurized water reactor (VVER) mixed oxide fuel. Criticality safety and radiation shielding problems were analyzed. Analysis of American and Russian multiplication factors for fresh fuel storage for low-enriched uranium (UOX), weapons- (MOX-W) and reactor-grade (MOX-R) MOX differ by less than 2% for all variations of water density. For shielding calculations for fresh fuel, the ORNL results for the neutron source differ from the Russian results by less than 1% for UOX and MOX-R and by approximately 3% for MOX-W. For shielding calculations for fresh fuel assemblies, neutron dose rates at the surface of the assemblies differ from the Russian results by 5% to 9%; the level of agreement for gamma dose varies depending on the type of fuel, with UOX differing by the largest amount. The use of different gamma group structures and instantaneous versus asymptotic decay assumptions also complicate the comparison. For the calculation of dose rates from spent fuel in a shipping cask, the neutron source for UOX after 3-year cooling is within 1% and for MOX-W within 5% of one of the Russian results while the MOX-R difference is the largest at over 10%. These studies are a portion of the documentation required by the Russian nuclear regulatory authority, GAN, in order to certify Russian programs and data as being acceptably accurate for the analysis of mixed oxide fuels.

  8. Applications of Metal/Mixed Metal Oxides as Photocatalyst: (A Review

    Directory of Open Access Journals (Sweden)

    Avnish Kumar Arora

    2016-08-01

    Full Text Available Metal oxides/ Mixed metal oxides have wide applications as catalyst, Adsorbents, Superconductors, semiconductors, ceramics, antifungal agents and also have spacious applications in medicines. This review article is focused on their applications as photocatalyst in various organic reactions.

  9. Analysis of the Gas Core Actinide Transmutation Reactor (GCATR)

    Science.gov (United States)

    Clement, J. D.; Rust, J. H.

    1977-01-01

    Design power plant studies were carried out for two applications of the plasma core reactor: (1) As a breeder reactor, (2) As a reactor able to transmute actinides effectively. In addition to the above applications the reactor produced electrical power with a high efficiency. A reactor subsystem was designed for each of the two applications. For the breeder reactor, neutronics calculations were carried out for a U-233 plasma core with a molten salt breeding blanket. A reactor was designed with a low critical mass (less than a few hundred kilograms U-233) and a breeding ratio of 1.01. The plasma core actinide transmutation reactor was designed to transmute the nuclear waste from conventional LWR's. The spent fuel is reprocessed during which 100% of Np, Am, Cm, and higher actinides are separated from the other components. These actinides are then manufactured as oxides into zirconium clad fuel rods and charged as fuel assemblies in the reflector region of the plasma core actinide transmutation reactor. In the equilibrium cycle, about 7% of the actinides are directly fissioned away, while about 31% are removed by reprocessing.

  10. Methane combustion over lanthanum-based perovskite mixed oxides

    Energy Technology Data Exchange (ETDEWEB)

    Arandiyan, Hamidreza [New South Wales Univ., Sydney (Australia). School of Chemical Engineering

    2015-11-01

    This book presents current research into the catalytic combustion of methane using perovskite-type oxides (ABO{sub 3}). Catalytic combustion has been developed as a method of promoting efficient combustion with minimum pollutant formation as compared to conventional catalytic combustion. Recent theoretical and experimental studies have recommended that noble metals supported on (ABO{sub 3}) with well-ordered porous networks show promising redox properties. Three-dimensionally ordered macroporous (3DOM) materials with interpenetrated and regular mesoporous systems have recently triggered enormous research activity due to their high surface areas, large pore volumes, uniform pore sizes, low cost, environmental benignity, and good chemical stability. These are all highly relevant in terms of the utilization of natural gas in light of recent catalytic innovations and technological advances. The book is of interest to all researchers active in utilization of natural gas with novel catalysts. The research covered comes from the most important industries and research centers in the field. The book serves not only as a text for researcher into catalytic combustion of methane, 3DOM perovskite mixed oxide, but also explores the field of green technologies by experts in academia and industry. This book will appeal to those interested in research on the environmental impact of combustion, materials and catalysis.

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

    Science.gov (United States)

    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.

  12. Melting behavior of mixed U–Pu oxides under oxidizing conditions

    Energy Technology Data Exchange (ETDEWEB)

    Strach, Michal [CEA, DEN, DTEC, SECA, LCC, Cadarache F-13108, Saint-Paul-Lez-Durance (France); IM2NP, UMR CNRS 7334 – Aix Marseille University, Case 251, Avenue Escadrille Normandie Niemen, 13397 Marseille Cedex 20 (France); Manara, Dario [European Commission, Joint Research Centre, Institute for Transuranium Elements, P.O. Box 2340, 76125 Karlsruhe (Germany); Belin, Renaud C. [CEA, DEN, DTEC, SECA, LCC, Cadarache F-13108, Saint-Paul-Lez-Durance (France); Rogez, Jacques [IM2NP, UMR CNRS 7334 – Aix Marseille University, Case 251, Avenue Escadrille Normandie Niemen, 13397 Marseille Cedex 20 (France)

    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)O{sub 2} 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.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2011-05-01

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

  14. Advanced Aqueous Separation Systems for Actinide Partitioning

    Energy Technology Data Exchange (ETDEWEB)

    Nash, Ken [Washington State Univ., Pullman, WA (United States); Martin, Leigh [Idaho National Lab. (INL), Idaho Falls, ID (United States); Lumetta, Gregg [Pacific Northwest National Lab. (PNNL), Richland, WA (United States)

    2015-04-02

    One of the most challenging aspects of advanced processing of used nuclear fuel is the separation of transplutonium actinides from fission product lanthanides. This separation is essential if actinide transmutation options are to be pursued in advanced fuel cycles, as lanthanides compete with actinides for neutrons in both thermal and fast reactors, thus limiting efficiency. The separation is difficult because the chemistry of Am3+ and Cm3+ is nearly identical to that of the trivalent lanthanides (Ln3+). The prior literature teaches that two approaches offer the greatest probability of devising a successful group separation process based on aqueous processes: 1) the application of complexing agents containing ligand donor atoms that are softer than oxygen (N, S, Cl-) or 2) changing the oxidation state of Am to the IV, V, or VI state to increase the essential differences between Am and lanthanide chemistry (an approach utilized in the PUREX process to selectively remove Pu4+ and UO22+ from fission products). The latter approach offers the additional benefit of enabling a separation of Am from Cm, as Cm(III) is resistant to oxidation and so can easily be made to follow the lanthanides. The fundamental limitations of these approaches are that 1) the soft(er) donor atoms that interact more strongly with actinide cations than lanthanides form substantially weaker bonds than oxygen atoms, thus necessitating modification of extraction conditions for adequate phase transfer efficiency, 2) soft donor reagents have been seen to suffer slow phase transfer kinetics and hydro-/radiolytic stability limitations and 3) the upper oxidation states of Am are all moderately strong oxidants, hence of only transient stability in media representative of conventional aqueous separations systems. There are examples in the literature of both approaches having been described. However, it is not clear at present that any extant process is sufficiently robust for application at the scale

  15. Selective oxidation of propane to acrylic acid over mixed metal oxide catalysts

    Institute of Scientific and Technical Information of China (English)

    Wei Zheng; Zhenxing Yu; Ping Zhang; Yuhang Zhang; Hongying Fu; Xiaoli Zhang; Qiquan Sun; Xinguo Hu

    2008-01-01

    The effects of metal atomic ratio, water content, oxygen content, and calcination temperature on the catalytic perfor-mances of MoVTeNbO mixed oxide catalyst system for the selective oxidation of propane to acrylic acid have been investigated and discussed. Among the catalysts studied, it was found that the MoVTeNbO catalyst calcined at a temperature of 600 ℃ showed the best performance in terms of propane conversion and selectivity for acrylic acid under an atmosphere of nitrogen. An effective MoVTeNbO oxide catalyst for propane selective oxidation to acrylic acid was obtained with a combination of a preferred metal atomic ratio (Mo1 V0.31Te0.23Nb0.12). The optimum reaction condition for the selective oxidation of propane was the molar ratio of C3H81 :O2 : H2O : N1 = 4.4 : 12.8 : 15.3 : 36.9. Under such conditions, the conversion of propane and the maximum yield of acrylic acid reached about 50% and 21%, respectively.

  16. Different Abilities of Eight Mixed Cultures of Methane-oxidizing Bacteria to Degrade TCE

    DEFF Research Database (Denmark)

    Broholm, Kim; Christensen, Thomas Højlund; Jensen, Bjørn K.

    1993-01-01

    The ability of eight mixed cultures of methane-oxidizing bacteria to degrade trichloroethylene (TCE) was examined in laboratory batch experiments. This is one of the first reported works studying TCE degradation by mixed cultures of methane-oxidizing bacteria at 10°C, a common temperature for soils...

  17. 76 FR 65544 - Standard Format and Content of License Applications for Mixed Oxide Fuel Fabrication Facilities

    Science.gov (United States)

    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...

  18. Solubility of actinides and surrogates in nuclear glasses; Solubilite des actinides et de leurs simulants dans les verres nucleaires. Limites d'incorporation et comprehension des mecanismes

    Energy Technology Data Exchange (ETDEWEB)

    Lopez, Ch

    2003-07-01

    The nuclear wastes are currently incorporated in borosilicate glass matrices. The resulting glass must be perfectly homogeneous. The work discussed here is a study of actinide (thorium and plutonium) solubility in borosilicate glass, undertaken to assess the extent of actinide solubility in the glass and to understand the mechanisms controlling actinide solubilization. Glass specimens containing; actinide surrogates were used to prepare and optimize the fabrication of radioactive glass samples. These preliminary studies revealed that actinide Surrogates solubility in the glass was enhanced by controlling the processing temperature, the dissolution kinetic of the surrogate precursors, the glass composition and the oxidizing versus reducing conditions. The actinide solubility was investigated in the borosilicate glass. The evolution of thorium solubility in borosilicate glass was determined for temperatures ranging from 1200 deg C to 1400 deg C.Borosilicate glass specimens containing plutonium were fabricated. The experimental result showed that the plutonium solubility limit ranged from 1 to 2.5 wt% PuO{sub 2} at 1200 deg C. A structural approach based on the determination of the local structure around actinides and their surrogates by EXAFS spectroscopy was used to determine their structural role in the glass and the nature of their bonding with the vitreous network. This approach revealed a correlation between the length of these bonds and the solubility of the actinides and their surrogates. (author)

  19. Co-Al Mixed Oxides Prepared via LDH Route Using Microwaves or Ultrasound: Application for Catalytic Toluene Total Oxidation

    Directory of Open Access Journals (Sweden)

    Eric Genty

    2015-05-01

    Full Text Available Co6Al2HT hydrotalcite-like compounds were synthesized by three different methods: co-precipitation, microwaves-assisted and ultrasound-assisted methods. The mixed oxides obtained after calcination were studied by several techniques: XRD, TEM, H2-TPR and XPS. They were also tested as catalysts in the reaction of total oxidation of toluene. The physico-chemical studies revealed a modification of the structural characteristics (surface area, morphology as well as of the reducibility of the formed mixed oxides. The solid prepared by microwaves-assisted synthesis was the most active. Furthermore, a relationship between the ratio of Co2+ on the surface, the reducibility of the Co-Al mixed oxide and the T50 in toluene oxidation was demonstrated. This suggests a Mars Van Krevelen mechanism for toluene total oxidation on these catalysts.

  20. Novel mesoporous mixed Nb-M (M = V, Mo, and Sb) oxides for oxidative dehydrogenation of propane.

    Science.gov (United States)

    Yuan, Li; Bhatt, Salil; Beaucage, Gregory; Guliants, Vadim V; Mamedov, Sergey; Soman, Rajiv S

    2005-12-15

    Novel thermally stable mesoporous mixed metal Nb-M (M = V, Mo and Sb) oxides were synthesized in the presence of a nonionic Pluronic P123 surfactant. These oxides displayed promising pore structures and chemical compositions for selective oxidative functionalization of propane: high surface areas (up to 200 m2/g), large pore sizes (5-14 nm), and high pore volumes (up to 0.46 cm3/g). The oxidative dehydrogenation of propane to propylene over mesoporous mixed metal Nb-M oxides employed as a probe reaction suggested that the M component was dispersed as the molecular surface species and also formed a solid solution with NbOx in the inorganic walls of these mesoporous mixed metal oxides.

  1. Atomistic Calculations of the Effect of Minor Actinides on Thermodynamic and Kinetic Properties of UO{sub 2{+-}x}

    Energy Technology Data Exchange (ETDEWEB)

    Deo, Chaitanya; Adnersson, Davis; Battaile, Corbett; uberuaga, Blas

    2012-10-30

    The team will examine how the incorporation of actinide species important for mixed oxide (MOX) and other advanced fuel designs impacts thermodynamic quantities of the host UO{sub 2} nuclear fuel and how Pu, Np, Cm and Am influence oxygen mobility. In many cases, the experimental data is either insufficient or missing. For example, in the case of pure NpO2, there is essentially no experimental data on the hyperstoichiometric form it is not even known if hyperstoichiometry NpO{sub 2{+-}x} is stable. The team will employ atomistic modeling tools to calculate these quantities

  2. Preparation of Mixed Perovskite Oxides for Blue-Green Lasers

    Science.gov (United States)

    1984-02-01

    higher for oxide or fluoride . 𔃽. A high radiative lifetime and high fluorescent quantum yield for Ce or the rare earth are desirable. 3 + 4...for all of our single crystal -4- preparations are lanthanum oxide (La„0 ), aluminum oxide (Al^O^) , scandium oxide (Sc„0-.) , and cerium oxide (Ce...crystal material is highly important. Ideally, oxides should be grown in O2, fluorides in ?„, and so forth in order to prevent defects such as

  3. Characterisation of Fe-Cr-Al mixed oxides

    Energy Technology Data Exchange (ETDEWEB)

    Gallardo Amores, J.M. [Universidad Complutense de Madrid (Spain). Dept. de Quimica Inorg.; Sanchez Escribano, V. [Departamento de Quimica Inorganica, Universidad, Salamanca (Spain); Busca, G. [Istituto di Chimica, Facolta di Ingegneria, Universita, P.le J.F. Kennedy, I-16129, Genova (Italy)

    1999-08-16

    Several samples of iron chromium aluminium mixed oxides with different composition have been prepared by coprecipitation at controlled pH starting from the corresponding nitrate salts and following dried at 393 K and calcination at 673 K for 3 h and 1173 K for 3 h. The powders have been characterised by XRD, FT-IR and DR UV-Vis spectroscopies, DTA-TG thermal analyses and measurements of BET surface area. It has been found alumina is soluble into {alpha}-FeCrO{sub 3} phase up to near 20%. These samples are stable at 1243 K with a relative high specific surface area. The {gamma},{theta}{yields}{alpha} phase transition is shifted towards higher temperatures by increasing Al content, being not detectable when {alpha}-FeCrO{sub 3} phase is the main phase. Surface chromates species are identified by the different techniques used and their amount seem to depend directly on the specific surface area of each sample. (orig.) 36 refs.

  4. Sol-gel derived oxides and mixed oxides catalysts with narrow mesoporous distribution

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    A novel sol-gel process for preparing oxides and mixed oxides sols from precipitation and peptization process is reported in this article. Inorganic salts are used as raw materials in this study. It is found that the amount of acid has great influence on the stability and particle diameter distribution of the precursor sols. Ultrasonic treatment is used to prepare alumina sol at room temperature. The result of 27Al NMR shows that there exist Al137+ species in the sol. By controlling the sol particles with narrow particle diameter distribution, alumina, titania and silica-alumina (SA) materials with narrow mesoporous distribution are formed by regular packing of sol particles during gelation without using any templates. The results also show that the structure and particle diameter distribution of precursor sol determine the final materials' texture.

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

    Directory of Open Access Journals (Sweden)

    Muhammad B. Haider

    2012-02-01

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

  6. Catalytic wet air oxidation with Ni- and Fe-doped mixed oxides derived from hydrotalcites.

    Science.gov (United States)

    Ovejero, G; Rodríguez, A; Vallet, A; Gómez, P; García, J

    2011-01-01

    Catalytic wet air oxidation of Basic Yellow 11 (BY11), a basic dye, was studied in a batch reactor. Layered double hydroxides with the hydrotalcite-like structure containing nickel or iron cations have been prepared by coprecipitation and subsequently calcined leading to Ni- and Fe-doped mixed oxides, respectively. Compared with the results in the wet air oxidation of BY11, these catalysts showed high activity for total organic carbon (TOC), toxicity and dye removal at 120 degrees C and 50 bars after 120 min. It has been demonstrated that the activity depended strongly on the presence of catalyst. The results show that catalysts containing nickel provide a higher extent of oxidation of the dye whereas the reaction carried out with the iron catalyst is faster. The Ni and Fe dispersion determined from the TPR results was higher for the catalysts with a lower Ni or Fe content and decreased for higher Ni or Fe contents. On the basis of activity and selectivity, the Ni containing catalyst with the medium (3%) Ni content was found to be the best catalyst. Finally, a relationship between metal content of the catalyst and reaction rate has been established.

  7. Actinide transmutation in nuclear reactors

    Energy Technology Data Exchange (ETDEWEB)

    Bultman, J.H.

    1995-01-17

    An optimization method is developed to maximize the burning capability of the ALMR while complying with all constraints imposed on the design for reliability and safety. This method leads to a maximal transuranics enrichment, which is being limited by constraints on reactivity. The enrichment can be raised by using the neutrons less efficiently by increasing leakage from the fuel. With the developed optimization method, a metallic and an oxide fueled ALMR were optimized. Both reactors perform equally well considering the burning of transuranics. However, metallic fuel has a much higher heat conductivity coefficient, which in general leads to better safety characteristics. In search of a more effective waste transmuter, a modified Molten Salt Reactor was designed. A MSR operates on a liquid fuel salt which makes continuous refueling possible, eliminating the issue of the burnup reactivity loss. Also, a prompt negative reactivity feedback is possible for an overmoderated reactor design, even when the Doppler coefficient is positive, due to the fuel expansion with fuel temperature increase. Furthermore, the molten salt fuel can be reprocessed based on a reduction process which is not sensitive to the short-lived spontaneously fissioning actinides. (orig./HP).

  8. Oxidative stabilization of mixed mayonnaises made with linseed oil and saturated medium-chain triglyceride oil

    DEFF Research Database (Denmark)

    Raudsepp, Piret; Brüggemann, Dagmar A.; Lenferink, Aufried;

    2014-01-01

    Mayonnaises, made with either saturated medium chain triglyceride (MCT) oil or unsaturated purified linseed oil (LSO), were mixed. Raman confocal microspectrometry demonstrated that lipid droplets in mixed mayonnaise remained intact containing either MCT oil or LSO. Peroxide formation during stor...... simply diluting unsaturated triglycerides with saturated triglycerides is causing the oxidative stabilization observed for mixed mayonnaise and mixed oil mayonnaise. © 2013 Elsevier Ltd. All rights reserved.......Mayonnaises, made with either saturated medium chain triglyceride (MCT) oil or unsaturated purified linseed oil (LSO), were mixed. Raman confocal microspectrometry demonstrated that lipid droplets in mixed mayonnaise remained intact containing either MCT oil or LSO. Peroxide formation during...... storage was lower in mixed mayonnaise compared to LSO mayonnaise, while in mixed oil mayonnaise the level of peroxides was constantly low. Mixed oil mayonnaise had a lower rate of oxygen consumption than mixed mayonnaise, LSO mayonnaise having the highest rate. The decay of water-soluble nitroxyl radicals...

  9. Effect of spectral characterization of gaseous fuel reactors on transmutation and burning of actinides

    Energy Technology Data Exchange (ETDEWEB)

    Fung, C.; Anghaie, S. [Florida Univ., Wilmington, NC (United States)

    2007-07-01

    Gaseous Core Reactors (GCR) are fueled with stable uranium compounds in a reflected cavity. The spectral characteristics of neutrons in GCR systems could shift from one end of the spectrum to the other end by changing design parameters such as reflector material and thickness, uranium enrichment, and the average operational temperature and pressure. The rate of actinide generation, transmutation, and burnup is highly influenced by the average neutron energy in reactor core. In particular, the production rate and isotopic mix of plutonium are highly dependent on the neutron spectrum in the reactor. Other actinides of primary interest to this work are neptunium-237 and americium-241 due to their pivotal impact on high-level nuclear waste disposal. In all cavity reactors including GCR's, the reflector material and thickness are the most important design parameters in determining the core spectrum. The increase in the gaseous fuel pressure and enrichment results in relative shift of neutron population toward energies greater than 2 eV. Reflector materials considered in this study are beryllium oxide, lithium hydride, lithium deuteride, zirconium carbide, graphite, lead, and tungsten. Results of the study suggest that the beryllium oxide and tungsten reflected GCR systems set the lower (softest) and upper (hardest) limits of neutron spectra, respectively. The inventory of actinides with half-lives greater than 1000 years can be minimized by increasing neutron flux level in the reactor core. The higher the neutron flux, the lower the inventory of these actinides. The majority of the GCR designs maintained a flux level on the order of 10{sup 15} cm{sup -2}*s{sup -1} while the PWR flux is one order of magnitude lower. The inventory of the feeder isotopes to Np{sup 237} including U{sup 237}, Pu{sup 241}, and Am{sup 241} decreases with relative shift of neutron spectrum toward higher energies. This is due to increased resonance absorption in these isotopes due to higher

  10. Effect of Sr on the properties of Ce–Zr–La mixed oxides

    Directory of Open Access Journals (Sweden)

    RICHUAN RAO

    2006-03-01

    Full Text Available Ce–Zr–La–Sr mixed oxides, with different Sr contents, were prepared by the sol–gel method. In a flow-system microreactor, the reduction properties and the oxygen storage capacity (OSC of the Ce–Zr–La–Sr mixed oxides were investigated by a temperature programmed reduction (TPR and a pulse technique. It was shown that the properties of the Ce–Zr–La mixed oxides depend on the Sr content and that the optimum Sr content in the Ce–Zr–La–Sr mixed oxide is 3 mol%. The Ce–Zr–La–Sr mixed oxides doped with 3 mol% Sr (Ce0.52Zr0.4La0.05Sr0.03O1.945 has the largest specific surface area and better reduction properties and oxygen storage capacity in comparison to the other investigated samples. The XRD results of the Ce–Zr–La–Sr mixed oxides showed that their X-ray diffraction patterns are well in agreement with that of fluorite-type CeO2 with Sr ions incorporated into the Ce–Zr–La mixed oxide structures. With increasing calcination temperature, the intensity of the X-ray diffraction peaks increased, but no new peaks were observed. All of these indicate that the synthesized samples had good thermal stability.

  11. Thermally unstable complexants: Stability of lanthanide/actinide complexes, thermal instability of the ligands, and applications in actinide separations

    Energy Technology Data Exchange (ETDEWEB)

    Nash, K.L.; Rickert, P.G.

    1991-01-01

    Water soluble complexing agents are commonly used in separations to enhance the selectivity of both ion exchange and solvent extraction processes. Applications of this type in the treatment of nuclear wastes using conventional complexing agents have found mixed success due to the nature of the complexants. In addition, the residual solutions containing these species have led to potentially serious complications in waste storage. To overcome some of the limitations of carboxylic acid and aminopolycarboxylate ligands, we have initiated a program to investigate the complexing ability, thermal/oxidative instability, and separation potential of a group of water soluble organophosphorus compounds which we call Thermally Unstable Complexants, or simply TUCS. Complexants of this type appear to be superior to conventional analogues in a number of respects. In this report, we will summarize our research to date on the actinide/lanthanide complexes with a series of substituted methanediphosphonic acids, the kinetics of their oxidative decomposition, and a few applications which have been developed for their use. 17 refs., 5 figs., 3 tab.

  12. Moessbauer spectroscopy with actinide elements

    Energy Technology Data Exchange (ETDEWEB)

    Potzel, W.; Moser, J.; Asch, L.; Kalvius, G.M. (Technische Univ. Muenchen, Garching (Germany, F.R.)

    1983-01-01

    Although formally equivalent to the lanthanide (4f) elements, the light actinides show a much more varied behaviour due to the larger spatial extent and ionizability of the 5f electrons. The application of Moessbauer spectroscopy for the determination of electronic properties of the actinides is outlined. Emphasis is put on high pressure Moessbauer experiments using the 60 keV transition in /sup 237/Np to study questions of delocalization of 5f electrons.

  13. Efficient room temperature oxidation of cyclohexane over highly active hetero-mixed WO3/V2O5 oxide catalyst

    CSIR Research Space (South Africa)

    Makgwane, PR

    2014-09-01

    Full Text Available An efficient room temperature catalyzed oxidation of cyclohexane to cyclohexanone (K) and cyclohexanol (A) was achieved over hetero-mixed tungsten–vanadia (WO(sub3)/V(sub2)O(sub5)) using H(sub2)O(sub2) oxidant. WO(sub3)/V(sub2)O(sub5) exhibited high...

  14. Catalytic performance for methane combustion of supported Mn-Ce mixed oxides

    Institute of Scientific and Technical Information of China (English)

    SHI Limin; CHU Wei; QU Fenfen; HU Jinyan; LI Minmin

    2008-01-01

    A series of supported Mn-Ce mixed oxide catalysts were prepared by the impregnation method and used for the oxidation of methane. The catalysts were characterized by N2 adsorption (BET), X-ray diffraction (XRD), laser Raman spectrum (LRS), and temperature programmed reduction (TPR) techniques. The XRD and LRS results confirmed the high dispersion of active components or formation of solid solution between manganese and cerium oxides in the bulk and on the surface of mixed oxide catalysts. The reducibility was remarka-bly promoted by the stronger synergistic interaction between the two oxides from H2-TPR measurements. As expected, all the experimental mixed oxide catalysts showed excellent activity for methane combustion at low temperature. Especially, for the catalyst with Mn-Ce ratio 3:7, methane conversion reached 92% at a temperature as low as 470 ℃.

  15. Selection of actinide chemical analogues for WIPP tests

    Energy Technology Data Exchange (ETDEWEB)

    Villarreal, R.; Spall, D.

    1995-07-05

    The Department of Energy must demonstrate the effectiveness of the Waste Isolation Pilot Plant (WIPP) as a permanent repository for the disposal of transuranic (TRU) waste. Performance assessments of the WIPP require that estimates of the transportability and outcome of the radionuclides (actinides) be determined from disposal rooms that may become either partially or completely filled with brine. Federal regulations limit the amount of radioactivity that may be unintentionally released to the accessible environment by any mechanism during the post closure phase up to 10,000 years. Thermodynamic models have been developed to predict the concentrations of actinides in the WIPP disposal rooms under various situations and chemical conditions. These models are based on empirical and theoretical projections of the chemistry that might be present in and around the disposal room zone for both near and long-term periods. The actinides that are known to be present in the TRU wastes (and are included in the model) are Th, U, Np, Pu, and Am. Knowledge of the chemistry that might occur in the disposal rooms when the waste comes in contact with brine is important in understanding the range of oxidation states that might be present under different conditions. There is a need to establish the mechanisms and resultant rate of transport, migration, or effective retardation of actinides beyond the disposal rooms to the boundary of the accessible environment. The influence of the bulk salt rock, clay sediments and other geologic matrices on the transport behavior of actinides must be determined to establish the overall performance and capability of the WIPP in isolating waste from the environment. Tests to determine the capabilities of the WIPP geologic formations in retarding actinide species in several projected oxidation states would provide a means to demonstrate the effectiveness of the WIPP in retaining TRU wastes.

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

    Energy Technology Data Exchange (ETDEWEB)

    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.

  17. Ce-Fe-O mixed oxide as oxygen carrier for the direct partial oxidation of methane to syngas

    Institute of Scientific and Technical Information of China (English)

    魏永刚; 王华; 李孔斋

    2010-01-01

    The Ce-Fe-O mixed oxide with a ratio of Ce/Fe=7:3, which was prepared by coprecipitation method and employed as oxygen carrier, for direct partial oxidation of methane to syngas in the absence of gaseous oxygen was explored. The mixed oxide was characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM), and the catalytic performances were studied in a fixed-bed quartz reactor and a thermogravimetric reactor, respectively. Approximately 99.4% H2 se...

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

    Energy Technology Data Exchange (ETDEWEB)

    Bacelar-Nicolau, P.; Johnson, D.B. [Univ. of Wales, Bangor (United Kingdom). School of Biological Sciences

    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.

  19. Nanoparticles of TiAlZr mixed oxides as supports of hydrodesulfurization catalysts: Synthesis and characterization

    Energy Technology Data Exchange (ETDEWEB)

    Kraleva, E., E-mail: ekraleva@gmail.com [Institute of Biodiversity and Ecosystems Research, Bulgarian Academy of Sciences, Sofia, Gagarin st.2 (Bulgaria); Spojakina, A. [Institute of Catalysis, Bulgarian Academy of Sciences, 1113 Sofia (Bulgaria); Saladino, M.L. [Dipartimento di Chimica ' S. Cannizzaro' , Universita di Palermo and INSTM-Udr Palermo, Parco d' Orleans II Viale delle Scienze pad 17, I-90128 Palermo,Italy (Italy); Caponetti, E. [Dipartimento di Chimica ' S. Cannizzaro' , Universita di Palermo and INSTM-Udr Palermo, Parco d' Orleans II Viale delle Scienze pad 17, I-90128 Palermo,Italy (Italy); Centro Grandi Apparecchiature - UniNetLab, Universita di Palermo, Via F. Marini 14, I-90128 Palermo (Italy); Nasillo, G. [Centro Grandi Apparecchiature - UniNetLab, Universita di Palermo, Via F. Marini 14, I-90128 Palermo (Italy); Jiratova, K. [Institute of Chemical Process Fundamentals, 16502 Prague 6 (Czech Republic)

    2012-02-05

    Highlights: Black-Right-Pointing-Pointer Preparation of ternary mixed oxide by sol-gel method. Black-Right-Pointing-Pointer Catalytic properties of the three-mixed oxides. Black-Right-Pointing-Pointer Heteropolyacid H{sub 3}PMo{sub 12}O{sub 40} and its cobalt salt Co{sub 1.5}PMo{sub 12}O{sub 40} that of active components in catalytic systems for thiophene hydrodesulfurization (HDS). - Abstract: TiAlZr mixed oxides, synthesized using sol-gel method, were characterized and used as supports of hydrodesulfurization catalysts (12 wt% Mo) prepared by impregnation either with molybdenum heteropolyacid H{sub 3}PMo{sub 12}O{sub 40} or its cobalt salt Co{sub 1.5}PMo{sub 12}O{sub 40}. Structure, morphology and textural properties of oxides and catalysts were characterized using X-ray powder diffraction (XRD), Raman spectroscopy, Nitrogen adsorption porosimetry, TEM-EDS, temperature-programmed desorption (TPD) and temperature-programmed reduction (TPR) techniques. Activity of the catalytic systems was tested in thiophene hydrodesulfurization (HDS). No formation of a new oxide phase was revealed in the synthesized mixed materials. However the effect of separated oxides on the structure of ternary oxides was observed. Maximum in HDS activity of Mo containing samples was determined by optimum content of alumina in the mixed oxides. Incorporation of cobalt into the heteropolyacid increased the HDS activity about two times and masked the effect of the support composition.

  20. Ethanol steam reforming over Mg-Al mixed-oxide catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Coleman, L.J.; Hudgins, R.R.; Silveston, P.L.; Croiset, E. [Waterloo Univ., ON (Canada). Dept. of Chemical Engineering

    2007-07-01

    Eight magnesium-aluminium (Mg-Al) mixed oxides and magnesium oxide (MgO) and aluminium oxide (Al{sub 2}O{sub 3}) were studied in order to identify the most effective Mg-Al mixed oxide for hydrogen production via ethanol steam reforming. Co-precipitated precursors were calcinated to prepare the Mg-Al mixed oxides. Activity and selectivity of the mixed oxides for ethanol steam reforming were evaluated at 773 and 923 K. Results showed that all catalysts performed poorly during the steam reforming reaction, and produced low rates of hydrogen, carbon monoxide (CO) and carbon dioxide (CO{sub 2}). Catalysts with an MgAl{sub 2}O{sub 4} spinel crystal structure gave the best performance at both reaction temperatures. However, carbon deposits were discovered on all catalysts for reactions performed at 923 K. Co-precipitation resulted in more effective contact between the Mg and Al in the form of Mg-Al LDO and MgAL{sub 2}O{sub 3}. The absence of pure oxides suggested that Mg and Al were chemically coupled in the mixed oxide catalysts. Results of the study showed that the catalyst with an atomic ratio of 0.66 Mg1Al2 was the most active and achieved the highest rates of production for hydrogen. 14 refs., 3 tabs., 1 fig.

  1. Study on Catalysts with Rhodium Loading on Different Cerium-Zirconium Mixed Oxides

    Institute of Scientific and Technical Information of China (English)

    2006-01-01

    The catalysts with Rh loading on different cerium-zirconium mixed oxides were characterized by BET, H2-TPR and OSC. The effects of different cerium-zirconium mixed oxides on catalytic performance and thermal stability of Rh loaded catalyst were studied. The results show that: (1) Rh can enhance cerium-zirconium mixed oxides OSC and catalytic reaction rates; (2) cerium-zirconium mixed oxides with high Ce contents and low Zr contents are more favorable to the stability of catalysts. Moreover, the contents of CeO2 have important effect on catalysts characteristics, and the addition of some rare earth components, such as La, Pr and Nd also have some influences.

  2. Flotation of cobalt bearing minerals from a mixed copper-cobalt oxidized ore

    OpenAIRE

    2012-01-01

    M.Tech. (Extraction Metallurgy) The techniques for the flotation of mixed copper and cobalt bearing oxide ores using the sulphidization method in order to recover the oxidized copper and cobalt bearing minerals have been well documented by previous researchers. These processes have been successfully implemented in many of the metallurgical plant operations in the Democratic Republic of Congo (DRC). The mixed copper and cobalt oxidised ores from this region present significant chal-lenges t...

  3. Study on Mg/Fe Mixed Oxides Derived from Hydrotalite as De—SOx Catalyst

    Institute of Scientific and Technical Information of China (English)

    GuangLanZHUO; YinFeiCHEN; 等

    2002-01-01

    A novel class of desulfurization agent derived from hydrotalcite has been developed and its activity for SOx uptake have been investigated. The results showed that the Mg/Fe mixed oxide having high SOx uptake ability at a broad reaction temperature (e.g.673K-973K). The Mg/Fe ratio of the mixed oxide strongly affect the desulfurization role of the material and it can be used repeatly without much loss of SOx uptake ability.

  4. Study on Mg/Fe Mixed Oxides Derived from Hydrotalcite as De-SOx Catalyst

    Institute of Scientific and Technical Information of China (English)

    2002-01-01

    A novel class of desulfurization agent derived from hydrotalcite has been developed and its activity for Sox uptake have been investigated. The results showed that the Mg/Fe mixed oxide having high Sox uptake ability at a broad reaction temperature (e.g. 673K ~ 973K). The Mg/Fe ratio of the mixed oxide strongly affect the desulfurization role of the material and it can be used repeatly without much loss of Sox uptake ability.

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

    Energy Technology Data Exchange (ETDEWEB)

    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.

  6. Conversion of Russian weapon-grade plutonium into oxide for mixed oxide (MOX) fuel fabrication

    Energy Technology Data Exchange (ETDEWEB)

    Glagovski, E.; Zakharkin, B. [A.A. Bochvar All-Russian Research Institute of Inorganic Materials, Russian Research Center, Moscow (Russian Federation); Kolotilov, Y. [Specialized State Design Institute, GSPI, Moscow (Russian Federation); Glagolenko, Y.; Skobtsov, A. [Mayak Production Association, Ozyorsk (Russian Federation); Zygmunt, S.; Mason, C.; Hahn, W.; Durrer, R. [Los Alamos National Lab., Nuclear Materials and Technology Div. NMT, Los Alamos, N.M. (United States); Thomas, S. [National Nuclear Security Administration, Washington DC (United States); Sicard, B.; Brossard, P.; Herlet, N. [CEA Marcoule 30 (France); Fraize, G.; Villa, A. [Cogema, 78 - Saint Quentin en Yvelines (France)

    2001-07-01

    Progress has been made in the Russian Federation towards the conversion of Russian weapons-grade plutonium (W-Pu) into plutonium oxide (PuO{sub 2}) suitable for further manufacture into mixed oxide (MOX) fuels. This program is funded both by French Commissariat at the Atomic Energy (CEA) and the US National Nuclear Security Administration (NNSA). The French program was started in the frame of the two cooperation agreements signed between Russian Federation and France in November 1992 concerning dismantling of nuclear weapons and the use of their nuclear materials for civilian purposes. The US program was started in 1998 in response to US proliferation concerns and the acknowledged international need to decrease available W-Pu. Russia has selected both the conversion process and the manufacturing site. This paper discusses the present state of development towards fulfilling this mission: the demonstration plant designed to process small amounts of Pu and validate all process stages and the industrial plant that will process up to 5 metric tons of Pu per year. (author)

  7. Titanium oxide modification with oxides of mixed cobalt valence for photo catalysis

    Energy Technology Data Exchange (ETDEWEB)

    Alanis O, R.; Jimenez B, J., E-mail: jaime.jimenez@inin.gob.m [ININ, Departamento de Quimica, Carretera Mexico-Toluca s/n, 52750 Ocoyoacac, Estado de Mexico (Mexico)

    2010-07-01

    In the present work, heterogenous photo catalysis, a technique often used for organic compound degradation toxic in water, was used. The photo catalyst most often used in this technique is TiO{sub 2}, which due to its physical and chemical properties, can degrade a great number of organic compounds. In addition, in recent years it has been verified that the doping of semiconductors with metals or metallic oxides increases the photo catalytic activity of these semiconductors, which is why it was proposed for doping by the impregnating method using commercial TiO{sub 2} synthesized by the Degussa company (TiO{sub 2} Degussa P25) with and oxide of mixed cobalt valence (Co{sub 3}O{sub 4}) synthesized using the sol-gel method. The synthesized photo catalyst TiO{sub 2}/Co{sub 3}O{sub 4} was characterized by the techniques of X-ray diffraction, scanning electronic microscopy, Raman spectroscopy and finally, photo catalytic tests by means of the degradation of methylene blue. (Author)

  8. 33rd Actinide Separations Conference

    Energy Technology Data Exchange (ETDEWEB)

    McDonald, L M; Wilk, P A

    2009-05-04

    Welcome to the 33rd Actinide Separations Conference hosted this year by the Lawrence Livermore National Laboratory. This annual conference is centered on the idea of networking and communication with scientists from throughout the United States, Britain, France and Japan who have expertise in nuclear material processing. This conference forum provides an excellent opportunity for bringing together experts in the fields of chemistry, nuclear and chemical engineering, and actinide processing to present and discuss experiences, research results, testing and application of actinide separation processes. The exchange of information that will take place between you, and other subject matter experts from around the nation and across the international boundaries, is a critical tool to assist in solving both national and international problems associated with the processing of nuclear materials used for both defense and energy purposes, as well as for the safe disposition of excess nuclear material. Granlibakken is a dedicated conference facility and training campus that is set up to provide the venue that supports communication between scientists and engineers attending the 33rd Actinide Separations Conference. We believe that you will find that Granlibakken and the Lake Tahoe views provide an atmosphere that is stimulating for fruitful discussions between participants from both government and private industry. We thank the Lawrence Livermore National Laboratory and the United States Department of Energy for their support of this conference. We especially thank you, the participants and subject matter experts, for your involvement in the 33rd Actinide Separations Conference.

  9. Authigenic iron oxide formation in the estuarine mixing zone of the Yangtze River

    Science.gov (United States)

    Fan, D. J.; Neuser, R. D.; Sun, X. G.; Yang, Z. S.; Guo, Z. G.; Zhai, S. K.

    2008-02-01

    Estuaries are elementary geochemical fronts where river water and seawater mix. Within this mixing zone, iron and other non-conservative elements can undergo complex reactions to form new solid phases. In order to understand authigenic iron oxide formation in the Yangtze River Estuary, two onsite water-mixing sets of experiments were conducted, one by mixing variable amounts of unfiltered Yangtze River water with filtered East China Sea water of different salinity (set 1), the other by mixing variable amounts of filtered Yangtze River water with filtered East China Sea water of different salinity (set 2). In set 2, the minerals newly formed in the course of mixing were investigated by means of a scanning electron microscope fitted with an energy-dispersive X-ray analytical system. It was found that ferrihydrite and lepidocrocite were formed in these mixing experiments, coexisting in nearly equal amounts. These iron oxides appear as aggregated particles with a large grain-size range of several microns to more than 100 μm. The electrolytic properties of seawater played an important role in the formation of these authigenic iron oxides. Kaolinite and organic aggregates were also found in the experimentally mixed pre-filtered waters. Amounts of newly formed suspended matter (set 2) were one to three orders of magnitude lower than those of total suspended matter (TSM) (set 1). This implies that newly formed minerals represent only a very small proportion of TSM in the estuarine mixing zone of the Yangtze River.

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

    Energy Technology Data Exchange (ETDEWEB)

    Henych, Jiří, E-mail: henych@iic.cas.cz [Department of Material Chemistry, Institute of Inorganic Chemistry AS CR v.v.i., 25068 Řež (Czech Republic); Štengl, Václav; Slušná, Michaela; Matys Grygar, Tomáš [Department of Material Chemistry, Institute of Inorganic Chemistry AS CR v.v.i., 25068 Řež (Czech Republic); Janoš, Pavel; Kuráň, Pavel; Štastný, Martin [Faculty of the Environment, J.E. Purkyně University, Králova Výšina 7, 400 96 Ústí nad Labem (Czech Republic)

    2015-07-30

    Highlights: • Ti–Fe mixed oxides were synthesized via low-temperature one-pot method. • Mixed oxides were used for degradation of parathion methyl. • Pure reference oxide samples showed no degradation ability. • Mixed oxides reached 70% degree of conversion of parathion methyl. - Abstract: 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.

  11. Calculation of cohesive energy of actinide metals

    Institute of Scientific and Technical Information of China (English)

    钱存富; 陈秀芳; 余瑞璜; 耿平; 段占强

    1997-01-01

    According to empirical electron theory of solids and molecules (EET), an equation for calculating the cohesive energy of actinide metals is given, the cohesive energy of 9 actinide metals with known crystal structure is calculated, which is identical with the experimental values on the whole, and the cohesive energy of 6 actinide metals with unknown crystal structure is forecast.

  12. Control of differential strain during heating and cooling of mixed conducting metal oxide membranes

    Science.gov (United States)

    Carolan, Michael Francis

    2007-12-25

    Method of operating an oxygen-permeable mixed conducting membrane having an oxidant feed side and a permeate side, which method comprises controlling the differential strain between the oxidant feed side and the permeate side by varying either or both of the oxygen partial pressure and the total gas pressure on either or both of the oxidant feed side and the permeate side of the membrane while changing the temperature of the membrane from a first temperature to a second temperature.

  13. Actinides and Life's Origins.

    Science.gov (United States)

    Adam, Zachary

    2007-12-01

    There are growing indications that life began in a radioactive beach environment. A geologic framework for the origin or support of life in a Hadean heavy mineral placer beach has been developed, based on the unique chemical properties of the lower-electronic actinides, which act as nuclear fissile and fertile fuels, radiolytic energy sources, oligomer catalysts, and coordinating ions (along with mineralogically associated lanthanides) for prototypical prebiotic homonuclear and dinuclear metalloenzymes. A four-factor nuclear reactor model was constructed to estimate how much uranium would have been required to initiate a sustainable fission reaction within a placer beach sand 4.3 billion years ago. It was calculated that about 1-8 weight percent of the sand would have to have been uraninite, depending on the weight percent, uranium enrichment, and quantity of neutron poisons present within the remaining placer minerals. Radiolysis experiments were conducted with various solvents with the use of uraniumand thorium-rich minerals (metatorbernite and monazite, respectively) as proxies for radioactive beach sand in contact with different carbon, hydrogen, oxygen, and nitrogen reactants. Radiation bombardment ranged in duration of exposure from 3 weeks to 6 months. Low levels of acetonitrile (estimated to be on the order of parts per billion in concentration) were conclusively identified in 2 setups and tentatively indicated in a 3(rd) by gas chromatography/mass spectrometry. These low levels have been interpreted within the context of a Hadean placer beach prebiotic framework to demonstrate the promise of investigating natural nuclear reactors as power production sites that might have assisted the origins of life on young rocky planets with a sufficiently differentiated crust/mantle structure. Future investigations are recommended to better quantify the complex relationships between energy release, radioactive grain size, fissionability, reactant phase, phosphorus

  14. Actinides and Life's Origins

    Science.gov (United States)

    Adam, Zachary

    2007-12-01

    There are growing indications that life began in a radioactive beach environment. A geologic framework for the origin or support of life in a Hadean heavy mineral placer beach has been developed, based on the unique chemical properties of the lower-electronic actinides, which act as nuclear fissile and fertile fuels, radiolytic energy sources, oligomer catalysts, and coordinating ions (along with mineralogically associated lanthanides) for prototypical prebiotic homonuclear and dinuclear metalloenzymes. A four-factor nuclear reactor model was constructed to estimate how much uranium would have been required to initiate a sustainable fission reaction within a placer beach sand 4.3 billion years ago. It was calculated that about 1-8 weight percent of the sand would have to have been uraninite, depending on the weight percent, uranium enrichment, and quantity of neutron poisons present within the remaining placer minerals. Radiolysis experiments were conducted with various solvents with the use of uranium- and thorium-rich minerals (metatorbernite and monazite, respectively) as proxies for radioactive beach sand in contact with different carbon, hydrogen, oxygen, and nitrogen reactants. Radiation bombardment ranged in duration of exposure from 3 weeks to 6 months. Low levels of acetonitrile (estimated to be on the order of parts per billion in concentration) were conclusively identified in 2 setups and tentatively indicated in a 3rd by gas chromatography/mass spectrometry. These low levels have been interpreted within the context of a Hadean placer beach prebiotic framework to demonstrate the promise of investigating natural nuclear reactors as power production sites that might have assisted the origins of life on young rocky planets with a sufficiently differentiated crust/mantle structure. Future investigations are recommended to better quantify the complex relationships between energy release, radioactive grain size, fissionability, reactant phase, phosphorus

  15. Preliminary considerations concerning actinide solubilities

    Energy Technology Data Exchange (ETDEWEB)

    Newton, T.W.; Bayhurst, B.P.; Daniels, W.R.; Erdal, B.R.; Ogard, A.E.

    1980-01-01

    Work at the Los Alamos Scientific Laboratory on the fundamental solution chemistry of the actinides has thus far been confined to preliminary considerations of the problems involved in developing an understanding of the precipitation and dissolution behavior of actinide compounds under environmental conditions. Attempts have been made to calculate solubility as a function of Eh and pH using the appropriate thermodynamic data; results have been presented in terms of contour maps showing lines of constant solubility as a function of Eh and pH. Possible methods of control of the redox potential of rock-groundwater systems by the use of Eh buffers (redox couples) is presented.

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

    Energy Technology Data Exchange (ETDEWEB)

    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.

  17. Actinide partitioning-transmutation program final report. IV. Miscellaneous aspects. [Transport; fuel fabrication; decay; policy; economics

    Energy Technology Data Exchange (ETDEWEB)

    Alexander, C.W.; Croff, A.G.

    1980-09-01

    This report discusses seven aspects of actinide partitioning-transmutation (P-T) which are important in any complete evaluation of this waste treatment option but which do not fall within other major topical areas concerning P-T. The so-called miscellaneous aspects considered are (1) the conceptual design of a shipping cask for highly neutron-active fresh and spent P-T fuels, (2) the possible impacts of P-T on mixed-oxide fuel fabrication, (3) alternatives for handling the existing and to-be-produced spent fuel and/or wastes until implementation of P-T, (4) the decay and dose characteristics of P-T and standard reactor fuels, (5) the implications of P-T on currently existing nuclear policy in the United States, (6) the summary costs of P-T, and (7) methods for comparing the risks, costs, and benefits of P-T.

  18. Mixed conductivity in terbia-stabilized bismuth oxide

    NARCIS (Netherlands)

    Vinke, I.C.; Boukamp, B.A.; Vries, de K.J.; Burggraaf, A.J.

    1992-01-01

    The mixed conducting solid solution 0.75Bi2O3−0.25Tb4O7 (BT40) was studied by impedance techniques using ionically blocking electrodes. These measurements confirmed the p-type electronic conductivity suggested in literature. In air at temperatures between 600 and 900 K the ionic transference number

  19. Actinide Solubility and Speciation in the WIPP

    Energy Technology Data Exchange (ETDEWEB)

    Reed, Donald T. [Los Alamos National Laboratory

    2015-11-02

    The presentation begins with the role and need for nuclear repositories (overall concept, international updates (Sweden, Finland, France, China), US approach and current status), then moves on to the WIPP TRU repository concept (design, current status--safety incidents of February 5 and 14, 2014, path forward), and finally considers the WIPP safety case: dissolved actinide concentrations (overall approach, oxidation state distribution and redox control, solubility of actinides, colloidal contribution and microbial effects). The following conclusions are set forth: (1) International programs are moving forward, but at a very slow and somewhat sporadic pace. (2) In the United States, the Salt repository concept, from the perspective of the long-term safety case, remains a viable option for nuclear waste management despite the current operational issues/concerns. (3) Current model/PA prediction (WIPP example) are built on redundant conservatisms. These conservatisms are being addressed in the ongoing and future research to fill existing data gaps--redox control of plutonium by Fe(0, II), thorium (analog) solubility studies in simulated brine, contribution of intrinsic and biocolloids to the mobile concentration, and clarification of microbial ecology and effects.

  20. Evaluation of actinide biosorption by microorganisms

    Energy Technology Data Exchange (ETDEWEB)

    Happel, A.M.

    1996-06-01

    Conventional methods for removing metals from aqueous solutions include chemical precipitation, chemical oxidation or reduction, ion exchange, reverse osmosis, electrochemical treatment and evaporation. The removal of radionuclides from aqueous waste streams has largely relied on ion exchange methods which can be prohibitively costly given increasingly stringent regulatory effluent limits. The use of microbial cells as biosorbants for heavy metals offers a potential alternative to existing methods for decontamination or recovery of heavy metals from a variety of industrial waste streams and contaminated ground waters. The toxicity and the extreme and variable conditions present in many radionuclide containing waste streams may preclude the use of living microorganisms and favor the use of non-living biomass for the removal of actinides from these waste streams. In the work presented here, we have examined the biosorption of uranium by non-living, non-metabolizing microbial biomass thus avoiding the problems associated with living systems. We are investigating biosorption with the long term goal of developing microbial technologies for the remediation of actinides.

  1. New cubic structure compounds as actinide host phases

    Energy Technology Data Exchange (ETDEWEB)

    Stefanovsky, S V [SIA Radon, 7th Rostovskii lane 2/14, Moscow 119121 (Russian Federation); Yudintsev, S V; Livshits, T S, E-mail: profstef@mtu-net.ru [Institute of Geology of Ore Deposits, Petrography, Mineralogy and Geochemistry RAS, Staromonetny lane 35, Moscow 119017 (Russian Federation)

    2010-03-15

    more promising actinide hosts are ferrites with garnet structure. The matrices containing sometime complex fluorite structure oxide as an extra phase have leach and radiation resistance similar to the other well-known actinide waste forms.

  2. Molecular and electronic structure of actinide hexa-cyanoferrates; Structure moleculaire et electronique des hexacyanoferrates d'actinides

    Energy Technology Data Exchange (ETDEWEB)

    Bonhoure, I

    2001-07-01

    The goal of this work is to improve our knowledge on the actinide-ligand bond properties. To this end, the hexacyanoferrate entities have been used as pre-organized ligand. We have synthesized, using mild chemistry, the following series of complexes: An{sup IV}[Fe{sup II}(CN){sub 6}].xH{sub 2}O (An = Th, U, Np, Pu); Am{sup III}[Fe{sup III}(CN){sub 6}].xH{sub 2}O; Pu {sup III}[Co{sup III}(CN){sub 6}].xH{sub 2}O and K(H?)An{sup III}[Fe{sup II}(CN){sub 6}].xH{sub 2}O (An = Pu, Am). The metal oxidation states have been obtained thanks to the {nu}{sub CN}, stretching vibration and to the actinide L{sub III} absorption edge studies. As Prussian Blue, the An{sup IV}[Fe{sup II}(CN){sub 6}].xH{sub 2}O (An = Np, Pu) are class II of Robin and Day compounds. X-ray Diffraction has shown besides that these complexes crystallize in the P6{sub 3}/m space group, as the isomorphic LaKFe(CN){sub 6}.4H{sub 2}O complex used as structural model. The EXAFS oscillations at the iron K edge and at the An L{sub III} edge allowed to determine the An-N, An-O, Fe-C and Fe-N distances. The display of the multiple scattering paths for both edges explains the actinide contribution absence at the iron edge, whereas the iron signature is present at the actinide edge. We have shown that the actinide coordination sphere in actinides hexa-cyanoferrates is comparable to the one of lanthanides. However, the actinides typical behavior towards the lanthanides is brought to the fore by the An{sup IV} versus Ln{sup III} ions presence in this family of complexes. Contrarily to the 4f electrons, the 5f electrons influence the electronic properties of the compounds of this family. However, the gap between the An-N and Ln-N distances towards the corresponding metals ionic radii do not show any covalence bond evolution between the actinide and lanthanide series. (author)

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

    Energy Technology Data Exchange (ETDEWEB)

    Prasankumar, T.; Jose, Sujin P., E-mail: sujamystica@yahoo.com [School of Physics, Madurai Kamaraj University, Madurai-625021, Tamil Nadu (India); Ilangovan, R.; Venkatesh, K. S. [Department of Nanoscience and Technology, Alagappa University, Karaikudi-630003, Tamil Nadu (India)

    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.

  4. Environmental research on actinide elements

    Energy Technology Data Exchange (ETDEWEB)

    Pinder, J.E. III; Alberts, J.J.; McLeod, K.W.; Schreckhise, R.G. (eds.)

    1987-08-01

    The papers synthesize the results of research sponsored by DOE's Office of Health and Environmental Research on the behavior of transuranic and actinide elements in the environment. Separate abstracts have been prepared for the 21 individual papers. (ACR)

  5. Nuclear fuel cycle-oriented actinides separation in China

    Energy Technology Data Exchange (ETDEWEB)

    Chen, Jing; He, Xihong; Wang, Jianchen [Tsinghua Univ., Beijing (China). Inst. of Nuclear and New Energy Technology

    2014-04-01

    In the last decades, the separation of actinides was widely and continuously studied in China. A few kinds of salt-free reductants to adjust Pu and Np valences have been investigated. N,N-dimethylhydroxylamine is a good reductant with high reduction rate constants for the co-reduction of Pu(IV) and Np(VI), and monomethylhydrazine is a simple compound for the individual reduction of Np(VI). Advanced PUREX based on Organic Reductants (APOR) was proposed. Trialkylphosphine oxide (TRPO) with a single functional group was found to possess strong affinity to tri-, tetra- and hexa-valent actinides. TRPO process has been first explored in China for actinides partitioning from high level waste and the good partitioning performance was demonstrated by the hot test. High extraction selectivity for trivalent actinides over lanthanides by dialkyldithiophosphinic acids was originally found in China. A separation process based on purified Cyanex 301 for the separation of Am from lanthanides was presented and successfully tested in a battery of miniature centrifugal contactors. (orig.)

  6. Solvent-Free Selective Oxidation of Toluene with O2 Catalyzed by Metal Cation Modified LDHs and Mixed Oxides

    Directory of Open Access Journals (Sweden)

    Xiaoli Wang

    2016-01-01

    Full Text Available A series of metal cation modified layered-double hydroxides (LDHs and mixed oxides were prepared and used to be the selective oxidation of toluene with O2. The results revealed that the modified LDHs exhibited much higher catalytic performance than their parent LDH and the modified mixed oxides. Moreover, the metal cations were also found to play important roles in the catalytic performance and stabilities of modified catalysts. Under the optimal reaction conditions, the highest toluene conversion reached 8.7% with 97.5% of the selectivity to benzyldehyde; moreover, the catalytic performance remained after nine catalytic runs. In addition, the reaction probably involved a free-radical mechanism.

  7. Oxidative stabilization of mixed mayonnaises made with linseed oil and saturated medium-chain triglyceride oil.

    Science.gov (United States)

    Raudsepp, Piret; Brüggemann, Dagmar A; Lenferink, Aufried; Otto, Cees; Andersen, Mogens L

    2014-01-01

    Mayonnaises, made with either saturated medium chain triglyceride (MCT) oil or unsaturated purified linseed oil (LSO), were mixed. Raman confocal microspectrometry demonstrated that lipid droplets in mixed mayonnaise remained intact containing either MCT oil or LSO. Peroxide formation during storage was lower in mixed mayonnaise compared to LSO mayonnaise, while in mixed oil mayonnaise the level of peroxides was constantly low. Mixed oil mayonnaise had a lower rate of oxygen consumption than mixed mayonnaise, LSO mayonnaise having the highest rate. The decay of water-soluble nitroxyl radicals showed radicals are formed in the aqueous phase with the same rate independent of the lipids. This was also reflected in decay of α-tocopherol during storage being similar in MCT and LSO mayonnaises, but being stable in mixed oil mayonnaise and mixed mayonnaise. Results suggest that other effects than simply diluting unsaturated triglycerides with saturated triglycerides is causing the oxidative stabilization observed for mixed mayonnaise and mixed oil mayonnaise. Copyright © 2013 Elsevier Ltd. All rights reserved.

  8. Minimization of actinide waste by multi-recycling of thoriated fuels in the EPR reactor

    Science.gov (United States)

    Rose, S. J.; Wilson, J. N.; Capellan, N.; David, S.; Guillemin, P.; Ivanov, E.; Méplan, O.; Nuttin, A.; Siem, S.

    2012-02-01

    The multi-recycling of innovative uranium/thorium oxide fuels for use in the European Pressurized water Reactor (EPR) has been investigated. If increasing quantities of 238U, the fertile isotope in standard UO2 fuel, are replaced by 232Th, then a greater yield of new fissile material (233U) is produced during the cycle than would otherwise be the case. This leads to economies of natural uranium of around 45% if the uranium in the spent fuel is multi-recycled. In addition we show that minor actinide and plutonium waste inventories are reduced and hence waste radio-toxicities and decay heats are up to a factor of 20 lower after 103 years. Two innovative fuel types named S90 and S20, ThO2 mixed with 90% and 20% enriched UO2 respectively, are compared as an alternative to standard uranium oxide (UOX) and uranium/plutonium mixed oxide (MOX) fuels at the longest EPR fuel discharge burn-ups of 65 GWd/t. Fissile and waste inventories are examined, waste radio-toxicities and decay heats are extracted and safety feedback coefficients are calculated.

  9. Minimization of actinide waste by multi-recycling of thoriated fuels in the EPR reactor

    Directory of Open Access Journals (Sweden)

    Nuttin A.

    2012-02-01

    Full Text Available The multi-recycling of innovative uranium/thorium oxide fuels for use in the European Pressurized water Reactor (EPR has been investigated. If increasing quantities of 238U, the fertile isotope in standard UO2 fuel, are replaced by 232Th, then a greater yield of new fissile material (233U is produced during the cycle than would otherwise be the case. This leads to economies of natural uranium of around 45% if the uranium in the spent fuel is multi-recycled. In addition we show that minor actinide and plutonium waste inventories are reduced and hence waste radio-toxicities and decay heats are up to a factor of 20 lower after 103 years. Two innovative fuel types named S90 and S20, ThO2 mixed with 90% and 20% enriched UO2 respectively, are compared as an alternative to standard uranium oxide (UOX and uranium/plutonium mixed oxide (MOX fuels at the longest EPR fuel discharge burn-ups of 65 GWd/t. Fissile and waste inventories are examined, waste radio-toxicities and decay heats are extracted and safety feedback coefficients are calculated.

  10. Active oxygen by Ce–Pr mixed oxide nanoparticles outperform diesel soot combustion Pt catalysts

    OpenAIRE

    Guillén Hurtado, Noelia; Garcia-Garcia, Avelina; Bueno López, Agustín

    2015-01-01

    A Ce0.5Pr0.5O2 mixed oxide has been prepared with the highest surface area and smallest particle size ever reported (125 m2/g and 7 nm, respectively), also being the most active diesel soot combustion catalyst ever tested under realistic conditions if catalysts forming highly volatile species are ruled out. This Ce–Pr mixed oxide is even more active than a reference platinum-based commercial catalyst. This study provides an example of the efficient participation of oxygen species released by ...

  11. Visibly transparent and radiopaque inorganic organic composites from flame-made mixed-oxide fillers

    Energy Technology Data Exchange (ETDEWEB)

    Maedler, Lutz [University of California, Los Angeles, Department of Chemical Engineering (United States)], E-mail: lutz@seas.ucla.edu; Krumeich, Frank [Laboratory of Inorganic Chemistry, Department of Chemistry and Applied Biosciences (Switzerland); Burtscher, Peter; Moszner, Norbert [Ivoclar Vivadent AG (Liechtenstein)

    2006-08-15

    Radiopaque composites have been produced from flame-made ytterbium/silica mixed oxide within a crosslinked methacrylate resin matrix. The refractive index of the filler powder increased with ytterbium oxide loading. A high transparency was achieved for a matching refractive index of the filler powder and the polymer in comparison to commercial materials with 52 wt% ceramic filling. It was demonstrated that powder homogeneity with regard to particle morphology and distribution of the individual metal atoms is essential to obtain a highly transparent composite. In contrast, segregation of crystalline single-oxide phases drastically decreased the composite transparency despite similar specific surface areas, refractive indices and overall composition. The superior physical strength, transparency and radiopacity compared to composites made from conventional silica based-fillers makes the flame-made mixed-oxide fillers especially attractive for dental restoration materials.

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

    Science.gov (United States)

    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.

  13. Visibly transparent & radiopaque inorganic organic composites from flame-made mixed-oxide fillers

    Science.gov (United States)

    Mädler, Lutz; Krumeich, Frank; Burtscher, Peter; Moszner, Norbert

    2006-08-01

    Radiopaque composites have been produced from flame-made ytterbium/silica mixed oxide within a crosslinked methacrylate resin matrix. The refractive index of the filler powder increased with ytterbium oxide loading. A high transparency was achieved for a matching refractive index of the filler powder and the polymer in comparison to commercial materials with 52 wt% ceramic filling. It was demonstrated that powder homogeneity with regard to particle morphology and distribution of the individual metal atoms is essential to obtain a highly transparent composite. In contrast, segregation of crystalline single-oxide phases drastically decreased the composite transparency despite similar specific surface areas, refractive indices and overall composition. The superior physical strength, transparency and radiopacity compared to composites made from conventional silica based-fillers makes the flame-made mixed-oxide fillers especially attractive for dental restoration materials.

  14. Characterization of Actinides in Simulated Alkaline Tank Waste Sludges and Leachates

    Energy Technology Data Exchange (ETDEWEB)

    Nash, Kenneth L.; Jensen, Mark P.; Rao, Linfeng

    2003-06-01

    Treatment of underground tanks at Hanford with concentrated alkali to improve removal of waste-limiting components of sludges has proven less efficacious for Al and Cr removal than had been hoped. Hence, more aggressive treatments of sludges, including contact with oxidants targeting Cr(III), have been tested in a limited number of samples and found to enhance Cr removal. Unfortunately, treatments of sludge samples with oxidative alkaline leachates produce conditions under which normally insoluble actinide ions (e.g., Am3+, Pu4+, Np4+) can no longer be reliably assumed to remain in the sludge phase. Few experimental or meaningful theoretical studies of actinide chemistry in strongly alkaline, strongly oxidizing solutions have been completed. Extrapolation of acid phase thermodynamic data to these radically different conditions provides little reliable guidance for predicting actinide speciation in highly salted alkaline solutions. In this project, we are investigating the fundamental chemistry of actinides in sludge simulants and supernatants under representative oxidative leaching conditions. We are also examining the potential impact of acidic leaching with concurrent secondary separations to enhance Al removal. Our objective is to provide adequate insight into actinide behavior under these conditions to enable prudent decision making as tank waste treatment protocols develop. We expect to identify those components of sludges that are likely to be problematic in the application of oxidative leaching protocols.

  15. Ni–Ta–O mixed oxide catalysts for the low temperature oxidative dehydrogenation of ethane to ethylene

    KAUST Repository

    Zhu, Haibo

    2015-09-01

    The "wet" sol-gel and "dry" solid-state methods were used to prepare Ni-Ta-O mixed oxide catalysts. The resulting Ni-Ta oxides exhibit high activity and selectivity for the low temperature oxidative dehydrogenation of ethane to ethylene. The Ta/(Ni + Ta) atomic ratios (varying from 0 to 0.11 in "wet" sol-gel method, and from 0 to 0.20 in "dry" solid-state method) as well as the preparation methods used in the synthesis, play important roles in controlling catalyst structure, activity, selectivity and stability in the oxidative dehydrogenation of ethane. Electron microscopy characterizations (TEM, EELS mapping, and HAADF-STEM) clearly demonstrate that the Ta atoms are inserted into NiO crystal lattice, resulting in the formation of a new Ni-Ta oxide solid solution. More Ta atoms are found to be located at the lattice sites of crystal surface in sol-gel catalyst. While, a small amount of thin layer of Ta2O5 clusters are detected in solid-state catalyst. Further characterization by XRD, N2 adsorption, SEM, H2-TPR, XPS, and Raman techniques reveal different properties of these two Ni-Ta oxides. Due to the different properties of the Ni-Ta oxide catalysts prepared by two distinct approaches, they exhibit different catalytic behaviors in the ethane oxidative dehydrogenation reaction at low temperature. Thus, the catalytic performance of Ni-Ta-O mixed oxide catalysts can be systematically modified and tuned by selecting a suitable synthesis method, and then varying the Ta content. ©2015 Elsevier Inc. All rights reserved.

  16. Magnetic behavior of Mg-Al-Zn-Fe mixed oxides from precursors layered double hydroxide

    Energy Technology Data Exchange (ETDEWEB)

    Oliva, M.I., E-mail: marcosivanoliva@gmail.com [Facultad de Matematica, Astronomia y Fisica, Universidad Nacional de Cordoba, M. Allende y H. de la Torre Ciudad Universitaria, 5000 Cordoba (Argentina); IFFAM AF (CONICET - FaMAF UNC), M. Allende y H. de la Torre Ciudad Universitaria, 5000 Cordoba (Argentina); Heredia, A. [CITeQ - Facultad R. Cordoba, Universidad Tecnologica Nacional Maestro Lopez esq. Cruz Roja Argentina, CP 5016 Cordoba (Argentina); Zandalazini, C.I. [Centro Laser de Ciencias Moleculares. INFIQC-FCQ-Grupo de Ciencia de Materiales-FaMAF-Universidad Nacional de Cordoba, Ciudad Universitaria, CP5000 Cordoba, Argentina CONICET (Argentina); Crivello, M. [CITeQ - Facultad R. Cordoba, Universidad Tecnologica Nacional Maestro Lopez esq. Cruz Roja Argentina, CP 5016 Cordoba (Argentina); Corchero, E. [Facultad de Matematica, Astronomia y Fisica, Universidad Nacional de Cordoba, M. Allende y H. de la Torre Ciudad Universitaria, 5000 Cordoba (Argentina)

    2012-08-15

    Mixed oxides of Mg-Al-Zn-Fe were obtained by calcination of layered double hydroxides (LDH) prepared by coprecipitation reaction with hydrothermal treatment. The structural characterization of precursors and oxides was carried out by X rays diffraction, showing increases of ZnO phase with the increase of the zinc content. Magnetic behavior was studied by vibrating sample magnetometer (VSM) and by a superconducting quantum interference device (SQUID) showing both paramagnetic and super paramagnetic behavior depending on both particles size and composition.

  17. CHARACTERIZATION OF ACTINIDES IN SIMULATED ALKALINE TANK WASTE SLUDGES AND LEACHATES

    Energy Technology Data Exchange (ETDEWEB)

    Nash, Kenneth L.

    2008-11-20

    In this project, both the fundamental chemistry of actinides in alkaline solutions (relevant to those present in Hanford-style waste storage tanks), and their dissolution from sludge simulants (and interactions with supernatants) have been investigated under representative sludge leaching procedures. The leaching protocols were designed to go beyond conventional alkaline sludge leaching limits, including the application of acidic leachants, oxidants and complexing agents. The simulant leaching studies confirm in most cases the basic premise that actinides will remain in the sludge during leaching with 2-3 M NaOH caustic leach solutions. However, they also confirm significant chances for increased mobility of actinides under oxidative leaching conditions. Thermodynamic data generated improves the general level of experiemental information available to predict actinide speciation in leach solutions. Additional information indicates that improved Al removal can be achieved with even dilute acid leaching and that acidic Al(NO3)3 solutions can be decontaminated of co-mobilized actinides using conventional separations methods. Both complexing agents and acidic leaching solutions have significant potential to improve the effectiveness of conventional alkaline leaching protocols. The prime objective of this program was to provide adequate insight into actinide behavior under these conditions to enable prudent decision making as tank waste treatment protocols develop.

  18. One-electron physics of the actinides

    Science.gov (United States)

    Toropova, A.; Marianetti, C. A.; Haule, K.; Kotliar, G.

    2007-10-01

    We present a detailed analysis of the one-electron physics of the actinides. Various linear muffin-tin orbital basis sets are analyzed in order to determine a robust bare Hamiltonian for the actinides. The hybridization between f and spd states is compared with the f-f hopping in order to understand the Anderson-like and Hubbard-like contributions to itineracy in the actinides. We show that both contributions decrease strongly as one moves from the light actinides to the heavy actinides, while the Anderson-like contribution dominates in all cases. A real-space analysis of the band structure shows that nearest-neighbor hopping dominates the physics in these materials. Finally, we discuss the implications of our results to the delocalization transition as a function of atomic number across the actinide series.

  19. NMR studies of actinide dioxides

    Energy Technology Data Exchange (ETDEWEB)

    Tokunaga, Y. [Advanced Science Research Center, Japan Atomic Energy Agency, Tokai, Ibaraki 319-1195 (Japan)], E-mail: tokunaga.yo@jaea.go.jp; Sakai, H.; Fujimoto, T.; Kambe, S.; Walstedt, R.E.; Ikushima, K.; Yasuoka, H. [Advanced Science Research Center, Japan Atomic Energy Agency, Tokai, Ibaraki 319-1195 (Japan); Aoki, D.; Homma, Y. [Institute for Materials Research, Tohoku University, Oarai, Ibaraki 311-1313 (Japan); Haga, Y.; Matsuda, T.D.; Ikeda, S.; Yamamoto, E.; Nakamura, A. [Advanced Science Research Center, Japan Atomic Energy Agency, Tokai, Ibaraki 319-1195 (Japan); Shiokawa, Y. [Institute for Materials Research, Tohoku University, Oarai, Ibaraki 311-1313 (Japan); Nakajima, K.; Arai, Y. [Department of Nuclear Energy System, Japan Atomic Energy Agency, Tokai, Ibaraki 319-1195 (Japan); Onuki, Y. [Advanced Science Research Center, Japan Atomic Energy Agency, Tokai, Ibaraki 319-1195 (Japan); Department of Physics, Osaka University, Toyonaka, Osaka 560-0043 (Japan)

    2007-10-11

    {sup 17}O NMR measurements have been performed on a series of the actinide dioxides, UO{sub 2}, NpO{sub 2} and PuO{sub 2}. Although the {sup 17}O NMR spectra in these materials are similar at higher temperatures, the low-temperature spectra present are significantly different. In UO{sub 2} we have observed a wide spectrum, forming a rectangular shape below T{sub N}=30 K. In NpO{sub 2}, on the other hand, the spectra broaden rather gradually and exhibit a two-peak structure below T{sub 0}=26 K. In PuO{sub 2}, neither spectrum broadening nor splitting has been observed. We show that these NMR spectra clearly indicate the different nature of the low-temperature magnetic ground states in these actinide compounds.

  20. Moessbauer spectroscopy of actinide intermetallics

    Energy Technology Data Exchange (ETDEWEB)

    Kalvius, G.M.; Potzel, W.; Moser, J.; Litterst, F.J.; Asch, L.; Zaenkert, J.; Potzel, U.; Kratzer, A.; Wunsch, M. (Technische Univ. Muenchen, Garching (Germany, F.R.). Fakultaet fuer Physik); Gal, J.

    1985-04-01

    Due to their wider radical extent the 5f electrons may form bands of different width and hybridization in metallic compounds of the light actinides. This leads to a broad spectrum of magnetic properties ranging from the localized magnetism of the lanthanides to the itinerant electron magnetism often found in transition metal compounds. Also, the influence of the crystalline electric field tends to be more pronounced than in rare earth compounds, but is usually not as dominant as in the 3d series. Magnetic structures and the question of 5f electron delocalization will be reviewed with respect to actinide Moessbauer data and new results will be presented. In particular the influence of applying external pressure will be discussed.

  1. Mossbauer spectroscopy of actinide intermetallics

    Energy Technology Data Exchange (ETDEWEB)

    Kalvius, G.M.; Potzel, W.; Moser, J.; Litterst, F.J.; Asch, L.; Zankert, J.; Potzel, U.; Kratzer, A.; Wunsch, M.; Gal, J.

    1984-09-01

    Due to their wider radial extend the 5f electrons may form bands of different width and hybridization in metallic compounds of the light actinides. This leads to a broad spectrum of magnetic properties ranging from the localized magnetism of the lanthanides to the itinerant electron magnetism often found in transition metal compounds. Also, the influence of the crystalline electric field tends to be more pronounced than in rare earth compounds, but is usually not as dominant as in the 3d series. Magnetic structures and the question of 5f electron delocalization are reviewed with respet to actinide Moessbauer data and new results are presented. In particular the influence of applying external pressure is discussed. 60 references, 24 figures.

  2. 78 FR 9431 - Shaw AREVA MOX Services, LLC (Mixed Oxide Fuel Fabrication Facility); Order Approving Indirect...

    Science.gov (United States)

    2013-02-08

    ... COMMISSION [NRC-2011-0081; Docket No. 70-3098; Construction Authorization No. CAMOX-001] Shaw AREVA MOX... Construction Authorization I Shaw AREVA MOX Services, LLC (MOX Services) holds Construction ] Authorization (CA) CAMOX-001 for construction of a Mixed Oxide (MOX) Fuel Fabrication Facility (MFFF) at the...

  3. 76 FR 22735 - Shaw AREVA MOX Services, Mixed Oxide Fuel Fabrication Facility; License Amendment Request, Notice...

    Science.gov (United States)

    2011-04-22

    ... From the Federal Register Online via the Government Publishing Office NUCLEAR REGULATORY COMMISSION Shaw AREVA MOX Services, Mixed Oxide Fuel Fabrication Facility; License Amendment Request, Notice.... Introduction The NRC has received, by letter dated February 8, 2011, an amendment request from Shaw AREVA...

  4. Nickel/magnesium-lanthanum mixed oxide catalyst in the Kumada-coupling.

    Science.gov (United States)

    Kiss, Arpád; Hell, Zoltán; Bálint, Mária

    2010-01-21

    A new, heterogeneous, magnesium-lanthanum mixed oxide solid base-supported nickel(ii) catalyst was developed. The catalyst was used successfully in the Kumada coupling of aryl halides, especially aryl bromides. The optimal reaction conditions of the coupling were determined.

  5. A study of oxygen transport in mixed conducting oxides using isotopic exchange and conductivity relaxation

    NARCIS (Netherlands)

    Otter, den Matthijs Willem

    2000-01-01

    Mixed conducting oxygen ion conductors can be applied as membranes for the separation of oxygen from air, as electrodes for both oxygen pumps and solid oxide fuel cells. In these applications, oxygen molecules dissociate on the surface of the material. The atomic oxygen species pick up two electrons

  6. Transport processes in mixed conducting oxides: combining time domain experiments and frequency domain analysis

    NARCIS (Netherlands)

    Boukamp, Bernard A.; Otter, den Matthijs W.; Bouwmeester, Henny J.M.

    2004-01-01

    The conductivity relaxation (CR) method is often used for measuring the surface transfer rate, Ktr, and the bulk diffusion coefficient, $$\\tilde{D},$$ for oxygen transport in mixed conducting oxides (MIECs). The time domain analysis of the obtained CR response is rather complex and is based on lsquo

  7. Electrospun mixed oxide photocatalysts to decompose dyes in water

    Science.gov (United States)

    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. Superconducting Hg-Based Mixed Oxides and Oxyfluorides

    Science.gov (United States)

    Antipov, E. V.

    2000-09-01

    Syntheses under high pressure and under controlled mercury and oxygen partial pressures of different members of the HgBa2Can-1CunO2n+2+δ series have been developed. There are two main parameters influencing Tc in this family: width of a perovskite slab (n) and concentration (δ) of the extra oxygen located in the Hg layer. The increase of Tc with n occurs until the third member, while after that it decreases. All the members of the series exhibit similar cupola shaped dependencies of Tc vs. δ. Strongly overdoped high members of the series with n = 3-5 were prepared only using high pressure technique and BaO2 as an internal oxidizer. Neutron powder diffraction experiments were carried out for monophase oxygenated HgBa2CuO4F4+δ and fluorinated HgBa2CuO4Fδ samples with different extra oxygen or fluorine content and Tc values. Fluorinated series also exhibits the cupola -like behavior for the Tc vs. δ dependence. NPD showed twice the amount of extra fluorine in comparison with those for the oxygenated Hg-1201 phases with close Tc's. The exchange of the extra oxygen by double amount of fluorine causes shortening of the apical Cu-O distances, while the in-plane ones, as well as Tc, do not vary. The influence of the external pressure on the structure and Tc of Hg-1201 strongly depends on the doping level. The increase of the extra oxygen content on going from underdoped to overdoped state results in the larger compression of the apical Cu-O and Ba-OHg distances while the HgO2 dumbbell as well as the distance between Ba and O from the (CuO2) layers becomes practically pressure independent. These results together with the data for fluorinated materials allow to elucidate the crucial structural features responsible for the Tc variation under high pressure.

  9. Partial oxidation of methane to syngas in a mixed-conducting oxygen permeable membrane reactor

    Institute of Scientific and Technical Information of China (English)

    2000-01-01

    Mixed-conducting oxygen permeable membranes represent a class of novel ceramic membranes, which exhibit mixed oxygen ionic and electronic conductivities. At high temperatures, oxygen can permeate through the membrane from the high to low oxygen pressure side under an oxygen concentration gradient. Theoretically, the permselectivity of oxygen is 100%. Recently, a novel mixed-conducting membrane--Ba0.5Sr0.5Co0.8Fe0.2O3-δ has been developed, which shows extremely high oxygen permeability and promising stability. Furthermore, the reactor made with such membranes was successfully applied to the partial oxidation of methane to syngas reaction using air as the oxygen source, which realized the coupling of the separation of oxygen from air and the partial oxidation of membrane reaction in one process. At 850℃, methane conversion >88%, CO selectivity >97% and oxygen permeation rate of about 7.8 mL/(cm2.min) were obtained.

  10. Influence of vanadium oxidation states on the performance of V-Mg-Al mixed-oxide catalysts for the oxidative dehydrogenation of propane

    Energy Technology Data Exchange (ETDEWEB)

    Schacht, L. [IPN, Escuela Superior de Fisica y Matematicas, Departamento de Ciencia de Materiales, Av. IPN s/n, Edificio 9, Col. Lindavista, 07738 Mexico D. F. (Mexico); Navarrete, J.; Schacht, P.; Ramirez, M. A., E-mail: pschacha@imp.m [Instituto Mexicano del Petroleo, Programa de Ingenieria Molecular, Eje Central Lazaro Cardenas No. 152, 07730 Mexico D. F. (Mexico)

    2010-07-01

    V-Mg-Al mixed-oxide catalysts for oxidative dehydrogenation of propane were prepared by thermal decomposition of Mg-Al-layered double hydroxides with vanadium interlayer doping. The obtained catalysts were tested for the oxidative dehydrogenation of propane, obtaining good results in catalytic activity (conversion 16.55 % and selectivity 99.97 %) Results indicated that catalytic performance of these materials depends on how vanadium is integrated in the layered structure, which is determined by the Mg/Al ratio. Vanadium interlayer doping modifies the oxidation state of vanadium and consequently catalytic properties. Surface properties were studied by X-ray photoelectron spectroscopic and diffuse reflectance, UV-visible spectroscopy, and temperature programmed reduction. The analyses provided information about the oxidation state, before and after the reaction. From these results, it is suggested that selectivity to propylene and catalytic activity depend mainly of vanadium oxidation state. (Author)

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

    Science.gov (United States)

    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.

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

    Energy Technology Data Exchange (ETDEWEB)

    Perdomo, Camilo [Estado Sólido y Catálisis Ambiental (ESCA), Departamento de Química, Facultad de Ciencias, Universidad Nacional de Colombia, Carrera 30 45-03, Bogotá (Colombia); Pérez, Alejandro [Grupo de Investigación Fitoquímica (GIFUJ), Departamento de Química, Facultad de Ciencias, Pontificia Universidad Javeriana, Carrera 7 No. 43-82, Bogotá D.C (Colombia); Molina, Rafael [Estado Sólido y Catálisis Ambiental (ESCA), Departamento de Química, Facultad de Ciencias, Universidad Nacional de Colombia, Carrera 30 45-03, Bogotá (Colombia); Moreno, Sonia, E-mail: smorenog@unal.edu.co [Estado Sólido y Catálisis Ambiental (ESCA), Departamento de Química, Facultad de Ciencias, Universidad Nacional de Colombia, Carrera 30 45-03, Bogotá (Colombia)

    2016-10-15

    Highlights: • Ce addition to the catalysts improves the availability of oxygen in the materials. • Mixed oxide with Co and Cu exhibits the best oxygen transport properties. • Co presence improves O{sub 2} mobility in the catalysts. • The presence of Cu in the solids improves redox properties. - Abstract: 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, {sup 18}O{sub 2} isotopic exchange and O{sub 2}-H{sub 2} 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.

  13. Fabrication of uranium–americium mixed oxide pellet from microsphere precursors: Application of CRMP process

    Energy Technology Data Exchange (ETDEWEB)

    Remy, E. [Radiochemistry and Processes Department, CEA, Nuclear Energy Division, F-30207 Bagnols-sur-Cèze (France); Picart, S., E-mail: sebastien.picart@cea.fr [Radiochemistry and Processes Department, CEA, Nuclear Energy Division, F-30207 Bagnols-sur-Cèze (France); Delahaye, T. [Fuel Cycle Technology Department, CEA, Nuclear Energy Division, F-30207 Bagnols-sur-Cèze (France); Jobelin, I. [Radiochemistry and Processes Department, CEA, Nuclear Energy Division, F-30207 Bagnols-sur-Cèze (France); Lebreton, F.; Horlait, D. [Fuel Cycle Technology Department, CEA, Nuclear Energy Division, F-30207 Bagnols-sur-Cèze (France); Bisel, I. [Radiochemistry and Processes Department, CEA, Nuclear Energy Division, F-30207 Bagnols-sur-Cèze (France); Blanchart, P. [Heterogeneous Materials Research Group, Centre Européen de la Céramique, F-87068 Limoges (France); Ayral, A. [Institut Européen des Membranes, CNRS-ENSCM-UM2, CC47, University Montpellier 2, F-34095 Montpellier cedex 5 (France)

    2014-10-15

    Highlights: • Dust free process for (U,Am)O{sub 2} transmutation target fabrication. • Synthesis of U{sub 0.9}Am{sub 0.1}O{sub 2} mixed oxide microspheres from ion exchange resin. • Fabrication of dense U{sub 0.9}Am{sub 0.1}O{sub 2} pellet with 95% TD from mixed oxide microspheres. - Abstract: 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 U{sub 0.9}Am{sub 0.1}O{sub 2±δ} is described as well as its characterisation. The use of this free-flowing precursor allows the pressing and sintering of one pellet of U{sub 0.9}Am{sub 0.1}O{sub 2±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.

  14. Control of the optical properties of silicon and chromium mixed oxides deposited by reactive magnetron sputtering

    Energy Technology Data Exchange (ETDEWEB)

    Vergara, L., E-mail: vergara@icmm.csic.e [Instituto de Ciencia de Materiales de Madrid, Consejo Superior de Investigaciones Cientificas, Cantoblanco, 28049 Madrid (Spain); Galindo, R. Escobar [Instituto de Ciencia de Materiales de Madrid, Consejo Superior de Investigaciones Cientificas, Cantoblanco, 28049 Madrid (Spain); Centro de Microanalisis de Materiales, Universidad Autonoma de Madrid, Cantoblanco, 28049 Madrid (Spain); Martinez, R. [AIN, Centro de Ingenieria Avanzada de Superficies, 31191 Cordovilla, Pamplona (Spain); Sanchez, O. [Instituto de Ciencia de Materiales de Madrid, Consejo Superior de Investigaciones Cientificas, Cantoblanco, 28049 Madrid (Spain); Palacio, C. [Departamento de Fisica Aplicada, Universidad Autonoma de Madrid, Cantoblanco, 28049 Madrid (Spain); Albella, J.M. [Instituto de Ciencia de Materiales de Madrid, Consejo Superior de Investigaciones Cientificas, Cantoblanco, 28049 Madrid (Spain)

    2011-03-31

    The development of mixed-oxide thin films allows obtaining materials with better properties than those of the different binary oxides, which makes them suitable for a great number of applications in different fields, such as tribology, optics or microelectronics. In this paper we investigate the deposition of mixed chromium and silicon oxides deposited by reactive magnetron sputtering with a view to use them as optical coatings with an adjustable refractive index. These films have been characterized by means of Rutherford backscattering spectrometry, Auger electron spectroscopy, X-ray diffraction, scanning electron microscopy, Fourier-transform infrared spectroscopy and spectroscopic ellipsometry so as to determine how the deposition conditions influence the characteristics of the material. We have found that the deposition parameter whose influence determines the properties of the films to a greater extent is the amount of oxygen in the reactive sputtering gas.

  15. Porous microspheres of manganese-cerium mixed oxides by a polyvinylpyrrolidone assisted solvothermal method

    Science.gov (United States)

    Schmit, F.; Bois, L.; Chiriac, R.; Toche, F.; Chassagneux, F.; Descorme, C.; Besson, M.; Khrouz, L.

    2017-04-01

    Mixed cerium manganese oxides were synthesized using a polyvinylpyrrolidone (PVP) assisted solvothermal method. Materials obtained after calcination at 400 °C were characterized by X-ray diffraction, scanning and transmission electron microscopies, electron paramagnetic resonance (EPR), Raman spectroscopy, thermal analysis and nitrogen adsorption/desorption isotherms. The influence of the synthesis parameters on the oxide structure, such as the Mn:Ce ratio or the amount of PVP, was discussed. Micrometric spheres of mixed Mn-Ce oxides, resulting from the aggregation of 100 nm porous snowflakes, were successfully synthesized. These snowflakes were formed from the aggregation of smaller oriented crystallites (size 4 nm). The hydrothermal stability of these materials was also investigated.

  16. Pyrometallurgical processes for recovery of actinide elements

    Energy Technology Data Exchange (ETDEWEB)

    Battles, J.E.; Laidler, J.J.; McPheeters, C.C.; Miller, W.E.

    1994-01-01

    A metallic fuel alloy, nominally U-20-Pu-lOZr, is the key element of the Integral Fast Reactor (IFR) fuel cycle. Metallic fuel permits the use of an innovative, simple pyrometallurgical process, known as pyroprocessing, (the subject of this report), which features fused salt electrorefining of the spent fuel. Electrorefining separates the actinide elements from fission products, without producing a separate stream of plutonium. The plutonium-bearing product is contaminated with higher actinides and with a minor amount of rare earth fission products, making it diversion resistant while still suitable as a fuel material in the fast spectrum of the IFR core. The engineering-scale demonstration of this process will be conducted in the refurbished EBR-II Fuel Cycle Facility, which has entered the start-up phase. An additional pyrometallurgical process is under development for extracting transuranic (TRU) elements from Light Water Reactor (LWR) spent fuel in a form suitable for use as a feed to the IFR fuel cycle. Four candidate extraction processes have been investigated and shown to be chemically feasible. The main steps in each process are oxide reduction with calcium or lithium, regeneration of the reductant and recycle of the salt, and separation of the TRU product from the bulk uranium. Two processes, referred to as the lithium and salt transport (calcium reductant) processes, have been selected for engineering-scale demonstration, which is expected to start in late 1993. An integral part of pyroprocessing development is the treatment and packaging of high-level waste materials arising from the operations, along with the qualification of these waste forms for disposal in a geologic repository.

  17. Synergy of FexCe1-xO2 mixed oxides for N2O decomposition

    NARCIS (Netherlands)

    Perez-Alonso, FJ; Melian Cabrera, Ignacio; Granados, ML; Kapteijn, F; Fierro, JLG

    2006-01-01

    Fe-Ce mixed oxides prepared by coprecipitation showed considerable synergy in N2O decomposition when compared with pure metal oxide counterparts. The mixed system also displayed higher stability in reaction at high temperature. Through characterisation by XRD, XPS and TPR, the activity-stability

  18. Synergy of FexCe1−xO2 mixed oxides for N2O decomposition

    NARCIS (Netherlands)

    Perez-Alonso, F.J.; Melián-Cabrera, I.; López Granados, M.; Kapteijn, F.; Fierro, J.L.G.

    2006-01-01

    Fe–Ce mixed oxides prepared by coprecipitation showed considerable synergy in N2O decomposition when compared with pure metal oxide counterparts. The mixed system also displayed higher stability in reaction at high temperature. Through characterisation by XRD, XPS and TPR, the activity–stability

  19. Synergy of FexCe1−xO2 mixed oxides for N2O decomposition

    NARCIS (Netherlands)

    Perez-Alonso, F.J.; Melián-Cabrera, I.; López Granados, M.; Kapteijn, F.; Fierro, J.L.G.

    2006-01-01

    Fe–Ce mixed oxides prepared by coprecipitation showed considerable synergy in N2O decomposition when compared with pure metal oxide counterparts. The mixed system also displayed higher stability in reaction at high temperature. Through characterisation by XRD, XPS and TPR, the activity–stability imp

  20. Synergy of FexCe1-xO2 mixed oxides for N2O decomposition

    NARCIS (Netherlands)

    Perez-Alonso, FJ; Melian Cabrera, Ignacio; Granados, ML; Kapteijn, F; Fierro, JLG

    2006-01-01

    Fe-Ce mixed oxides prepared by coprecipitation showed considerable synergy in N2O decomposition when compared with pure metal oxide counterparts. The mixed system also displayed higher stability in reaction at high temperature. Through characterisation by XRD, XPS and TPR, the activity-stability imp

  1. Recovery of minor actinides from irradiated superfact fuels

    Energy Technology Data Exchange (ETDEWEB)

    Apoltolidis, C.; Glatz, J.P.; Molinet, R.; Nicholl, A.; Pagliosa, G.; Romer, K.; Bokelund, H.; Koch, L. [European Commission, JRC, Institute fuer Transuranium Elements, Karlsruhe (Germany)

    1995-12-31

    It could be demonstrated that the reprocessing of fast reactor oxide fuels containing up to 45 % MA (Np and Am), irradiated in the PHENIX reactor in the frame of a transmutation study, is possible. The fuels were dissolved under PUREX type conditions in order to determine their behaviour in the head-end step of the reprocessing process. For one of the fuels containing 20 % Am and 20 % Np before irradiation, an almost complete partitioning of actinides from the dissolver solution could be achieved. Chromatographic extraction was used for the separation of the main bulk elements U, Pu and Np, whereas centrifugal extractors were used to separate the minor actinides from the remaining high level liquid wastes (HLLW). For the relevant radio-toxic isotopes a high recovery rate from the irradiation targets was reached. Those elements are thus available for new fuel fabrication. (authors) 12 refs.

  2. MINOR ACTINIDE SEPARATIONS USING ION EXCHANGERS OR IONIC LIQUIDS

    Energy Technology Data Exchange (ETDEWEB)

    Hobbs, D.; Visser, A.; Bridges, N.

    2011-09-20

    This project seeks to determine if (1) inorganic-based ion exchange materials or (2) electrochemical methods in ionic liquids can be exploited to provide effective Am and Cm separations. Specifically, we seek to understand the fundamental structural and chemical factors responsible for the selectivity of inorganic-based ion-exchange materials for actinide and lanthanide ions. Furthermore, we seek to determine whether ionic liquids can serve as the electrolyte that would enable formation of higher oxidation states of Am and other actinides. Experiments indicated that pH, presence of complexants and Am oxidation state exhibit significant influence on the uptake of actinides and lanthanides by layered sodium titanate and hybrid zirconium and tin phosphonate ion exchangers. The affinity of the ion exchangers increased with increasing pH. Greater selectivity among Ln(III) ions with sodium titanate materials occurs at a pH close to the isoelectric potential of the ion exchanger. The addition of DTPA decreased uptake of Am and Ln, whereas the addition of TPEN generally increases uptake of Am and Ln ions by sodium titanate. Testing confirmed two different methods for producing Am(IV) by oxidation of Am(III) in ionic liquids (ILs). Experimental results suggest that the unique coordination environment of ionic liquids inhibits the direct electrochemical oxidation of Am(III). The non-coordinating environment increases the oxidation potential to a higher value, while making it difficult to remove the inner coordination of water. Both confirmed cases of Am(IV) were from the in-situ formation of strong chemical oxidizers.

  3. Features of the Thermodynamics of Trivalent Lanthanide/Actinide Distribution Reactions by Tri-n-Octylphosphine Oxide and Bis(2-EthylHexyl) Phosphoric Acid

    Energy Technology Data Exchange (ETDEWEB)

    Travis S. Grimes; Peter R. Zalupski

    2014-11-01

    A new methodology has been developed to study the thermochemical features of the biphasic transfer reactions of trisnitrato complexes of lanthanides and americium by a mono-functional solvating ligand (tri-n-octyl phosphine oxide - TOPO). Stability constants for successive nitrato complexes (M(NO3)x3-x (aq) where M is Eu3+, Am3+ or Cm3+) were determined to assist in the calculation of the extraction constant, Kex, for the metal ions under study. Enthalpies of extraction (?Hextr) for the lanthanide series (excluding Pm3+) and Am3+ by TOPO have been measured using isothermal titration calorimetry. The observed ?Hextr were found to be constant at ~29 kJ mol-1across the series from La3+-Er3+, with a slight decrease observed from Tm3+-Lu3+. These heats were found to be consistent with enthalpies determined using van ’t Hoff analysis of temperature dependent extraction studies. A complete set of thermodynamic parameters (?G, ?H, ?S) was calculated for Eu(NO3)3, Am(NO3)3 and Cm(NO3)3 extraction by TOPO and Am3+ and Cm3+ extraction by bis(2-ethylhexyl) phosphoric acid (HDEHP). A discussion comparing the energetics of these systems is offered. The measured biphasic extraction heats for the transplutonium elements, ?Hextr, presented in these studies are the first ever direct measurements offered using two-phase calorimetric techniques.

  4. Modern x-ray spectral methods in the study of the electronic structure of actinide compounds: Uranium oxide UO2 as an example

    Directory of Open Access Journals (Sweden)

    Teterin Yury A.

    2004-01-01

    Full Text Available Fine X-ray photo electron spectral (XPS structure of uranium dioxide UO2 in the binding energy (BE range 0-~č40 eV was associated mostly with the electrons of the outer (OVMO (0-15 eV BE and inner (IVMO (15-40 eV BE valence molecular orbitals formed from the incompletely U5f,6d,7s and O2p and completely filled U6p and O2s shells of neighboring uranium and oxygen ions. It agrees with the relativistic calculation results of the electronic structure for the UO812–(Oh cluster reflecting uranium close environment in UO2, and was confirmed by the X-ray (conversion electron, non-resonance and resonance O4,5(U emission, near O4,5(U edge absorption, resonance photoelectron, Auger spectroscopy data. The fine OVMO and IVMO related XPS structure was established to yield conclusions on the degree of participation of the U6p,5f electrons in the chemical bond, uranium close environment structure and interatomic distances in oxides. Total contribution of the IVMO electrons to the covalent part of the chemical bond can be comparable with that of the OVMO electrons. It has to be noted that the IVMO formation can take place in compounds of any elements from the periodic table. It is a novel scientific fact in solid-state chemistry and physics.

  5. Paving the way for the synthesis of a series of divalent actinide complexes: a theoretical perspective.

    Science.gov (United States)

    Wu, Q-Y; Lan, J-H; Wang, C-Z; Cheng, Z-P; Chai, Z-F; Gibson, J K; Shi, W-Q

    2016-02-21

    Recently, the +2 formal oxidation state in soluble molecular complexes for lanthanides (La-Nd, Sm-Lu) and actinides (Th and U) has been discovered [W. J. Evans, et al., J. Am. Chem. Soc., 2011, 133, 15914; J. Am. Chem. Soc., 2012, 134, 8420; J. Am. Chem. Soc., 2013, 135, 13310; Chem. Sci., 2015, 6, 517]. To explore the nature of the bonding and stabilities of the low-valent actinide complexes, a series of divalent actinide species, [AnCp'3](-) (An[double bond, length as m-dash]Th-Am, Cp' = [η(5)-C5H4(SiMe3)](-)) have been investigated in THF solution using scalar relativistic density functional theory. The electronic structures and electron affinity properties were systematically studied to identify the interactions between the +2 actinide ions and Cp' ligands. The ground state electron configurations for the [AnCp'3](-) species are [ThCp'3](-) 6d(2), [PaCp'3](-) 5f(2)6d(1), [UCp'3](-) 5f(3)6d(1), [NpCp'3](-) 5f(5), [PuCp'3](-) 5f(6), and [AmCp'3](-) 5f(7), respectively, according to the MO analysis. The total bonding energy decreases from the Th- to the Am-complex and the electrostatic interactions mainly dominate the bonding between the actinide atom and ligands. The electron affinity analysis suggests that the reduction reaction of AnCp'3→ [AnCp'3](-) should become increasingly facile across the actinide series from Th to Am, in accord with the known An(iii/ii) reduction potentials. This work expands the knowledge on the low oxidation state chemistry of actinides, and further motivates and guides the synthesis of related low oxidation state compounds of 5f elements.

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

    Energy Technology Data Exchange (ETDEWEB)

    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.

  7. Chemical properties of the heavier actinides and transactinides

    Energy Technology Data Exchange (ETDEWEB)

    Hulet, E.K.

    1981-01-01

    The chemical properties of each of the elements 99 (Es) through 105 are reviewed and their properties correlated with the electronic structure expected for 5f and 6d elements. A major feature of the heavier actinides, which differentiates them from the comparable lanthanides, is the increasing stability of the divalent oxidation state with increasing atomic number. The divalent oxidation state first becomes observable in the anhydrous halides of californium and increases in stability through the series to nobelium, where this valency becomes predominant in aqueous solution. In comparison with the analogous 4f electrons, the 5f electrons in the latter part of the series are more tightly bound. Thus, there is a lowering of the 5f energy levels with respect to the Fermi level as the atomic number increases. The metallic state of the heavier actinides has not been investigated except from the viewpoint of the relative volatility among members of the series. In aqueous solutions, ions of these elements behave as a normal trivalent actinides and lanthanides (except for nobelium). Their ionic radii decrease with increasing nuclear charge which is moderated because of increased screening of the outer 6p electrons by the 5f electrons. The actinide series of elements is completed with the element lawrencium (Lr) in which the electronic configuration is 5f/sup 14/7s/sup 2/7p. From Mendeleev's periodicity and Dirac-Fock calculations, the next group of elements is expected to be a d-transition series corresponding to the elements Hf through Hg. The chemical properties of elements 104 and 105 only have been studied and they indeed appear to show the properties expected of eka-Hf and eka-Ta. However, their nuclear lifetimes are so short and so few atoms can be produced that a rich variety of chemical information is probably unobtainable.

  8. Determination of mechanism for soot oxidation with NO on potassium supported Mg-Al hydrotalcite mixed oxides

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Y.; Su, Q.; Gao, X. [Institute of Internal Combustion Engine, Dalian University of Technology, Dalian (China); Li, Q.; Wang, Z.; Zhang, Z. [School of Chemistry and Chemical Engineering, University of Jinan, Jinan (China)

    2011-11-15

    Soot oxidation with NO (in the absence of gas phase O{sub 2}) on potassium-supported Mg-Al hydrotalcite mixed oxides (K/MgAlO) was studied using a temperature-programmed reaction and in situ FTIR techniques. Nitrite and the ketene group were identified as the reaction intermediates and thus a nitrite-ketene mechanism was proposed in which surface active oxygen on K sites of K/MgAlO is transferred to soot by NO through nitrites. In the absence of gas phase O{sub 2}, soot oxidation with NO at lower temperatures (below 450 C) is limited by the amount of active oxygen on the K sites. This kind of active oxygen is not reusable but can be replenished in the presence of gas phase O{sub 2}. (Copyright copyright 2011 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  9. Oxidative dehydrogenation of isobutane over supported V–Mo mixed oxides

    Directory of Open Access Journals (Sweden)

    IOAN-CEZAR MARCU

    2010-08-01

    Full Text Available Vanadium–molybdenum oxides supported on Al2O3, CeO2 and TiO2 were prepared by a “wet” impregnation method, characterized using XRD, N2 adsorption, UV–Vis spectroscopy, electrical conductivity measurements and tested in the oxidative dehydrogenation of isobutane. The catalytic performance in the oxidative dehydrogenation of isobutane at 400–550 °C depended on the nature of support and on the content of VMoO species on the support. The catalysts supported on alumina were more active and selective than those supported on ceria and titania.

  10. Selective oxidation of benzene and cyclohexane using amorphous microporous mixed oxides; Selektive Oxidation von Benzol und Cyclohexan mit amorphen mikroporoesen Mischoxiden

    Energy Technology Data Exchange (ETDEWEB)

    Stoeckmann, M.

    2000-07-01

    Phenol was to be produced by direct oxidation of benzene with environment-friendly oxidants like hydrogen peroxide, oxygen, or ozone. Catalysts were amorphous microporous mixed oxides whose properties can be selected directly in the sol-gel synthesis process. Apart from benzene, also cyclohexane was oxidized with ozone using AMM catalysts in order to get more information on the potential of ozone as oxidant in heterogeneously catalyzed reactions. [German] Ziel dieser Arbeit war die Herstellung von Phenol durch die Direktoxidation von Benzol mit umweltfreundlichen Oxidationsmitteln wie Wasserstoffperoxid, Sauerstoff oder Ozon. Als Katalysatoren dienten amorphe mikroporoese Mischoxide, da deren Eigenschaften direkt in der Synthese durch den Sol-Gel-Prozess gezielt eingestellt werden koennen. Neben Benzol wurde auch Cyclohexan mit Ozon unter der Verwendung von AMM-Katalysatoren oxidiert, um das Potential von Ozon als Oxiationsmittel in heterogen katalysierten Reaktionen naeher zu untersuchen. (orig.)

  11. Soft chemical control of the crystal and magnetic structure of a layered mixed valent manganite oxide sulfide

    Directory of Open Access Journals (Sweden)

    Jack N. Blandy

    2015-04-01

    Full Text Available Oxidative deintercalation of copper ions from the sulfide layers of the layered mixed-valent manganite oxide sulfide Sr2MnO2Cu1.5S2 results in control of the copper-vacancy modulated superstructure and the ordered arrangement of magnetic moments carried by the manganese ions. This soft chemistry enables control of the structures and properties of these complex materials which complement mixed-valent perovskite and perovskite-related transition metal oxides.

  12. Hybrid Co-deposition of Mixed-Valent Molybdenum-Germanium Oxides (MoxGeyOz): A Route to Tunable Optical Transmission (Postprint)

    Science.gov (United States)

    2015-08-05

    ultraviolet– visible -near-infrared optical spectrophotometry ( UV –Vis–NIR). Structural properties of the as-deposited MoxGeyOz films, including roughness...photoelectron spectroscopy . 15. SUBJECT TERMS Magnetron sputtering, Ellipsometry, X-ray photoelectron spectroscopy , Mixed oxides, Germanium oxide...photoelectron spectroscopy Mixed oxides Germanium oxide Molybdenum oxide Thin film Optical characterizationMixed-valent oxides of molybdenum and germanium

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

    Science.gov (United States)

    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.

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

    Science.gov (United States)

    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 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.

  15. Prompt fission neutron spectrum of actinides

    Energy Technology Data Exchange (ETDEWEB)

    Capote, R. [International Atomic Energy Agency, Vienna (Austria); Chen, Y. -J. [China Institute of Atomic Energy, Beijing (China); Hambsch, F. J. [European Commission, Joint Research Centre - IRRM, Geel (Belgium); Jurado, B. [CENBG, CNRS/IN2P3, Gradignan (France); Kornilov, N. [Ohio Univ., Athens, OH (United States); Lestone, J. P. [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Litaize, O. [CEA, DEN, DER, SPRC, Saint-Paul-Lez-Durance (France); Morillon, B. [CEA, DAM, DIF, Arpajon (France); Neudecker, D. [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Oberstedt, S. [European Commission, Joint Research Centre - IRRM, Geel (Belgium); Ohsawa, T. [Kinki Univ., Osaka-fu (Japan); Otuka, N. [International Atomic Energy Agency, Vienna (Austria); Pronyaev, V. G. [Institute of Physics and Power Engineering, Obninsk (Russian Federation); Saxena, A. [Bhabha Atomic Research Centre, Mumbai (India); Schmidt, K. H. [CENBG, CNRS/IN2P3, Gradignan (France); Serot, O. [CEA, DEN, DER, SPRC, Saint-Paul-Lez-Durance (France); Shcherbakov, O. A. [Petersburg Nuclear Physics Institute of NRC " Kurchatov Institute" , Gatchina (Russian Federation); Shu, N. -C. [China Institute of Atomic Energy, Beijing (China); Smith, D. L. [Argonne National Lab. (ANL), Argonne, IL (United States); Talou, P. [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Trkov, A. [International Atomic Energy Agency, Vienna (Austria); Tudora, A. C. [Univ. of Bucharest, Magurele (Romania); Vogt, R. [Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States); Univ. of California, Davis, CA (United States); Vorobyev, A. S. [Petersburg Nuclear Physics Institute of NRC " Kurchatov Institute" , Gatchina (Russian Federation)

    2016-01-06

    Here, the energy spectrum of prompt neutron emitted in fission (PFNS) plays a very important role in nuclear science and technology. A Coordinated Research Project (CRP) "Evaluation of Prompt Fission Neutron Spectra of Actinides" was established by the IAEA Nuclear Data Section in 2009, with the major goal to produce new PFNS evaluations with uncertainties for actinide nuclei.

  16. Calculated Atomic Volumes of the Actinide Metals

    DEFF Research Database (Denmark)

    Skriver, H.; Andersen, O. K.; Johansson, B.

    1979-01-01

    The equilibrium atomic volume is calculated for the actinide metals. It is possible to account for the localization of the 5f electrons taking place in americium.......The equilibrium atomic volume is calculated for the actinide metals. It is possible to account for the localization of the 5f electrons taking place in americium....

  17. Selection of mixed conducting oxides for oxidative dehydrogenation of propane with pulse experiments

    NARCIS (Netherlands)

    Crapanzano, Salvatore; Babich, Igor V.; Lefferts, Leon

    2011-01-01

    In this study, propane pulse experiments at 550 °C are used as a method to select suitable oxides for further operation of catalytic dense membrane reactor (CDMR) for oxidative dehydrogenation of propane. Ba0.5Sr0.5Co0.8Fe0.2O3−δ (BSCF), La2NiO4+δ (LN) and PrBaCo2O5+δ (PBC) powders were used as mode

  18. Catalytic Organic Transformations Mediated by Actinide Complexes

    Directory of Open Access Journals (Sweden)

    Isabell S. R. Karmel

    2015-10-01

    Full Text Available This review article presents the development of organoactinides and actinide coordination complexes as catalysts for homogeneous organic transformations. This chapter introduces the basic principles of actinide catalysis and deals with the historic development of actinide complexes in catalytic processes. The application of organoactinides in homogeneous catalysis is exemplified in the hydroelementation reactions, such as the hydroamination, hydrosilylation, hydroalkoxylation and hydrothiolation of alkynes. Additionally, the use of actinide coordination complexes for the catalytic polymerization of α-olefins and the ring opening polymerization of cyclic esters is presented. The last part of this review article highlights novel catalytic transformations mediated by actinide compounds and gives an outlook to the further potential of this field.

  19. Actinide ion sensor for pyroprocess monitoring

    Science.gov (United States)

    Jue, Jan-fong; Li, Shelly X.

    2014-06-03

    An apparatus for real-time, in-situ monitoring of actinide ion concentrations which comprises a working electrode, a reference electrode, a container, a working electrolyte, a separator, a reference electrolyte, and a voltmeter. The container holds the working electrolyte. The voltmeter is electrically connected to the working electrode and the reference electrode and measures the voltage between those electrodes. The working electrode contacts the working electrolyte. The working electrolyte comprises an actinide ion of interest. The reference electrode contacts the reference electrolyte. The reference electrolyte is separated from the working electrolyte by the separator. The separator contacts both the working electrolyte and the reference electrolyte. The separator is ionically conductive to the actinide ion of interest. The reference electrolyte comprises a known concentration of the actinide ion of interest. The separator comprises a beta double prime alumina exchanged with the actinide ion of interest.

  20. Reaction pathways for catalytic gas-phase oxidation of glycerol over mixed metal oxides

    Energy Technology Data Exchange (ETDEWEB)

    Suprun, W.; Glaeser, R.; Papp, H. [Leipzig Univ. (Germany). Inst. of Chemical Technology

    2011-07-01

    Glycerol as a main by-product from bio-diesel manufacture is a cheap raw material with large potential for chemical or biochemical transformations to value-added C3-chemicals. One possible way of glycerol utilization involves its catalytic oxidation to acrylic acid as an alternative to petrochemical routes. However, this catalytic conversion exhibits various problems such as harsh reaction conditions, severe catalyst coking and large amounts of undesired by-products. In this study, the reaction pathways for gas-phase conversion of glycerol over transition metal oxides (Mo, V und W) supported on TiO{sub 2} and SiO{sub 2} were investigated by two methods: (i) steady state experiments of glycerol oxidation and possible reactions intermediates, i.e., acrolein, 3-hydroxy propionaldehyde and acetaldehyde, and (ii) temperature-programmed surface reaction (TPSR) studies of glycerol conversion in the presence and in the absence of gas-phase oxygen. It is shown that the supported W-, V and Mo-oxides possess an ability to catalyze the oxidation of glycerol to acrylic acid. These investigations allowed us to gain a deeper insight into the reaction mechanism. Thus, based on the obtained results, three possible reactions pathways for the selective oxidation of glycerol to acrylic acid on the transition metal-containing catalysts are proposed. The major pathways in presence of molecular oxygen are a fast successive destructive oxidation of glycerol to CO{sub x} and the dehydration of glycerol to acrolein which is a rate-limiting step. (orig.)

  1. Electronic structure and spectroscopic properties of mixed sodium actinide oxides Na2AnO4 (An = U, Np, Pu, Am)

    Science.gov (United States)

    Kovács, Attila

    2017-03-01

    Multireference relativistic post-HF and DFT calculations have been performed on four Na2AnO4 (An = U, Np, Pu, Am) molecules. Beyond the electronic characteristics of the ground and excited electronic states, the molecular geometries and vibrational frequencies have been determined.

  2. XPS study of surface absorbed oxygen of ABO3 mixed oxides

    Institute of Scientific and Technical Information of China (English)

    ZHAO Xin; YANG Qiuhua; CUI Jinjin

    2008-01-01

    Perovskite-type complex oxides ABO3 (A=Sr, La;B=Mn, Fe, Co) were prepared by citric acid method. The degradation of water-solubilized dyes was carried out using the mixed oxides as photocatalyst. The surface absorbed oxygen was analyzed using X-ray photoelectron spectroscopy (XPS). The results indicated that there was a relationship between the photocatalytic activity and the content of the surface absorbed oxygen. The higher the content of the surface absorbed oxygen was, the better the performance of the photocatalyst.

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

    Energy Technology Data Exchange (ETDEWEB)

    Shi, Fa-Nian, E-mail: fshi@ua.pt [School of Science, Shenyang University of Technology, 110870 Shenyang (China); Department of Chemistry, CICECO, University of Aveiro, 3810-193 Aveiro (Portugal); Rosa Silva, Ana [Department of Chemistry, CICECO, University of Aveiro, 3810-193 Aveiro (Portugal); Bian, Liang [Key Laboratory of Functional Materials and Devices for Special Environments, Chinese Academy of Sciences, Urumqi 830011, Xinjiang (China)

    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.

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

    Energy Technology Data Exchange (ETDEWEB)

    Marchand, M., E-mail: mickael.marchand@cea.fr [Commissariat à l’Energie Atomique et aux énergies alternatives, CEA, CADARACHE, DEN, DEC, SPUA/Laboratoire des Combustibles Uranium, 13108 Saint Paul-lez-Durance Cedex (France); Fiquet, O., E-mail: olivier.fiquet@cea.fr [Commissariat à l’Energie Atomique et aux énergies alternatives, CEA, CADARACHE, DEN, DEC, SPUA/Laboratoire des Combustibles Uranium, 13108 Saint Paul-lez-Durance Cedex (France); Brothier, M. [Commissariat à l’Energie Atomique et aux énergies alternatives, CEA, CADARACHE, DEN, DEC, SPUA/Laboratoire des Combustibles Uranium, 13108 Saint Paul-lez-Durance Cedex (France)

    2013-06-15

    Highlights: ► Experimental study of uranium carbides and graphite powder oxidations. ► Single rate limiting step identification by extensive kinetic analysis. ► Pseudo-steady-state validation during chemical conversion. ► Combination of TGA, TDA, XRD and gas phase chromatography results. -- Abstract: The oxidation of a mixed uranium dicarbide and graphite powder has been investigated by simultaneous thermal gravimetric (TGA) and differential thermal (DTA) analyses coupled with gas phase chromatography. For isothermal oxidation conditions with temperatures below 330 °C, only the UC{sub 2} chemical phase is progressively oxidised into U{sub 3}O{sub 8} oxides. Parabolic weight gain curves as a function of oxidation over time were obtained. A detailed kinetic study is proposed to establish a pseudo-steady-state during the oxidation process. Using an experimental method based on the sudden temperature increases, a single rate-limiting step has been validated and then modelled by a 3D diffusion law. An apparent activation energy calculated from the Arrhenius representation has been evaluated at −35 kJ/mol, thus describing the diffusion of oxygen through the oxide layer.

  5. Synthesis of mesoporous cerium-zirconium mixed oxides by hydrothermal templating method

    Institute of Scientific and Technical Information of China (English)

    2008-01-01

    Mesoporous cerium-zirconium mixed oxides were prepared by hydrothermal method using cetyl trimethyl ammonium bromide (CTAB) as template.The effects of amount of template,pH value of solution and hydrothermal temperature on mesostructure of samples were systematically investigated.The final products were characterized by XRD,TEM,FT-IR,and BET.The results indicate that all the cerium-zirconium mixed oxides present a meso-structure.At molar ratio of n(CTAB)/n((Ce)+(Zr))=0.15,pH value of 9,and hydrothermal temperature of 120 ℃,the samples obtained possess a specific surface area of 207.9 m2/g with pore diameter of 3.70 nm and pore volume of 0.19 cm3/g.

  6. Sol-gel synthesis and characterization of mesoporous iron-titanium mixed oxide for catalytic application

    Energy Technology Data Exchange (ETDEWEB)

    Parida, K.M., E-mail: paridakulamani@yahoo.com [Colloids and Materials Chemistry Department, Institute of Minerals and Materials Technology, Bhubaneswar 751013, Orissa (India); Pradhan, Gajendra Kumar [Colloids and Materials Chemistry Department, Institute of Minerals and Materials Technology, Bhubaneswar 751013, Orissa (India)

    2010-10-01

    A mixed phase of mesoporous iron-titanium mixed oxide (ITMO) has been successfully synthesized by simple sol-gel technique by taking iron (II) sulphate and Ti-isopropoxide as the precursors and sodium dodecyl sulphate (SDS) as the surfactant. The prepared catalysts were characterized by X-ray diffraction (XRD), fourier transform infrared spectroscopy (FTIR), diffuse reflectance UV-vis spectra (UV-vis DRS), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), atomic absorption spectroscopy (AAS), N{sub 2} adsorption-desorptions isotherm, temperature programmed desorption (TPD) and gas chromatography (GC). Low-angle XRD (LAXRD) as well as surface area analysis confirms the mesoporosity nature of the catalysts. The phase and crystallinity were revealed by XRD study. The crystallinity of the catalysts increased with increase in calcinations temperature. Catalysts screening were performed for oxidation of cyclohexane to cyclohexanol and cyclohexanone.

  7. Direct electrochemical production of Ti-10W alloys from mixed oxide preform precursors

    Energy Technology Data Exchange (ETDEWEB)

    Dring, K. [Imperial College London, Department of Materials, London SW7 2AZ (United Kingdom)]. E-mail: kevin.dring@imperial.ac.uk; Bhagat, R. [Imperial College London, Department of Materials, London SW7 2AZ (United Kingdom); Jackson, M. [Imperial College London, Department of Materials, London SW7 2AZ (United Kingdom); Dashwood, R. [Imperial College London, Department of Materials, London SW7 2AZ (United Kingdom); Inman, D. [Imperial College London, Department of Materials, London SW7 2AZ (United Kingdom)

    2006-08-10

    Ti-W alloys were produced via electrochemical reduction of TiO{sub 2}-WO{sub 3} mixed oxide preforms in a pre-electrolysed, molten calcium chloride electrolyte at 1173 K. Electrolysis voltages of 1500-3200 mV were applied for times ranging from 6 to 24 h across a graphite anode and Grade 2 commercial purity (CP) titanium cathodic current collector, which supported the ceramic precursors. Low-oxygen, homogeneous material was subsequently water washed and characterized to determine the level of residual species remaining from the reduction process, such as Cl and Ca. The microstructure (porosity and microchemistry) of the reduced material and microstructural examination of the mixed oxide feedstock (particle morphology, size and chemistry) were characterized using a field emission gun scanning electron microscope (FEG-SEM) with backscattered electron imaging (BSE) and X-ray energy dispersive spectrometry (X-EDS)

  8. A literature review of actinide-carbonate mineral interactions

    Energy Technology Data Exchange (ETDEWEB)

    Stout, D.L. [Missouri Univ., Columbia, MO (United States). Dept. of Geological Sciences; Carroll, S.A. [Lawrence Livermore National Lab., CA (United States)

    1993-10-01

    Chemical retardation of actinides in groundwater systems is a potentially important mechanism for assessing the performance of the Waste Isolation Pilot Plant (WIPP), a facility intended to demonstrate safe disposal of transuranic waste. Rigorous estimation of chemical retardation during transport through the Culebra Dolomite, a water-bearing unit overlying the WIPP, requires a mechanistic understanding of chemical reactions between dissolved elements and mineral surfaces. This report represents a first step toward this goal by examining the literature for pertinent experimental studies of actinide-carbonate interactions. A summary of existing models is given, along with the types of experiments on which these models are based. Articles pertaining to research into actinide interactions with carbonate minerals are summarized. Select articles involving trace element-carbonate mineral interactions are also reviewed and may serve as templates for future research. A bibliography of related articles is included. Americium(III), and its nonradioactive analog neodymium(III), partition strongly from aqueous solutions into carbonate minerals. Recent thermodynamic, kinetic, and surface studies show that Nd is preferentially removed from solution, forming a Nd-Ca carbonate solid solution. Neptunium(V) is rapidly removed from solution by carbonates. Plutonium incorporation into carbonates is complicated by multiple oxidation states. Little research has been done on the radium(H) and thorium(IV) carbonate systems. Removal of uranyl ion from solution by calcite is limited to monolayer surface coverage.

  9. Coordinated safeguards for materials management in a mixed-oxide fuel facility

    Energy Technology Data Exchange (ETDEWEB)

    Shipley, J.P.; Cobb, D.D.; Dietz, R.J.; Evans, M.L.; Schelonka, E.P.; Smith, D.B.; Walton, R.B.

    1977-02-01

    A coordinated safeguards system is described for safeguarding strategic quantities of special nuclear materials in mixed-oxide recycle fuel fabrication facilities. The safeguards system is compatible with industrial process requirements and combines maximum effectiveness consistent with modest cost and minimal process interference. It is based on unit process accounting using a combination of conventional and state-of-the-art NDA measurement techniques. The effectiveness of the system against single and multiple thefts is evaluated using computer modeling and simulation techniques.

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

    Science.gov (United States)

    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.

  11. Effects of Transition-Metal Mixing on Na Ordering and Kinetics in Layered P 2 Oxides

    Science.gov (United States)

    Zheng, Chen; Radhakrishnan, Balachandran; Chu, Iek-Heng; Wang, Zhenbin; Ong, Shyue Ping

    2017-06-01

    Layered P 2 oxides are promising cathode materials for rechargeable sodium-ion batteries. In this work, we systematically investigate the effects of transition-metal (TM) mixing on Na ordering and kinetics in the NaxCo1 -yMnyO2 model system using density-functional-theory (DFT) calculations. The DFT-predicted 0-K stability diagrams indicate that Co-Mn mixing reduces the energetic differences between Na orderings, which may account for the reduction of the number of phase transformations observed during the cycling of mixed-TM P 2 layered oxides compared to a single TM. Using ab initio molecular-dynamics simulations and nudged elastic-band calculations, we show that the TM composition at the Na(1) (face-sharing) site has a strong influence on the Na site energies, which in turn impacts the kinetics of Na diffusion towards the end of the charge. By employing a site-percolation model, we establish theoretical upper and lower bounds for TM concentrations based on their effect on Na(1) site energies, providing a framework to rationally tune mixed-TM compositions for optimal Na diffusion.

  12. Methodologies For Characterising Mixed Conducting Oxides For Oxygen Membrane And SOFC Cathode Application

    DEFF Research Database (Denmark)

    Hendriksen, Peter Vang; Søgaard, Martin; Plonczak, Pawel

    2012-01-01

    Two methods for detailed characterization of the process of oxygen exchange between the gas phase and a mixed conducting solid oxide are discussed. First, the use of solid electrolyte probes for measuring the change in oxygen activity over the surface of a mixed conductor is presented and advanta......Two methods for detailed characterization of the process of oxygen exchange between the gas phase and a mixed conducting solid oxide are discussed. First, the use of solid electrolyte probes for measuring the change in oxygen activity over the surface of a mixed conductor is presented...... and advantages of the technique discussed. Secondly, the use of thin film model electrodes is treated. Studies of thin films applied by PLD on both sides of a YSZ single crystal are presented for three different film materials; La0.85Sr0.15MnO3, La0.6Sr0.4Fe0.8Co0.2O3 and La0.6Sr0.4CoO3. Variations in electrode...

  13. Catalytic combustion of soot over Ru-doped mixed oxides catalysts

    Institute of Scientific and Technical Information of China (English)

    LF Nascimento; RF Martins; OA Serra

    2014-01-01

    We employed modified substrates as outer heterogeneous catalysts to reduce the soot originating from the incomplete die-sel combustion. Here, we proposed that ceria (CeO2)-based catalysts could lower the temperature at which soot combustion occurred from 610 ºC to values included in the operation range of diesel exhausts (270-400 ºC). Here, we used the sol-gel method to synthesize catalysts based on mixed oxides (ZnO:CeO2) deposited on cordierite substrates, and modified by ruthenium nanoparticles. The presence of ZnO in these mixed oxides produced defects associated with oxygen vacancies, improving thermal stability, redox potential, sulfur resistance, and oxygen storage. We evaluated the morphological and structural properties of the material by X-ray diffraction (XRD), Brumauer-emmett-teller method (BET), temperature programmed reduction (H2-TPR), scanning electron micros-copy (SEM), and transmission electron microscopy (TEM). We investigated how the addition of Ru (0.5 wt.%) affected the catalytic activity of ZnO:CeO2 in terms of soot combustion. Thermogravimetric analysis (TG/DTA) revealed that presence of the catalyst de-creased the soot combustion temperature by 250 ºC, indicating that the oxygen species arose at low temperatures, which was the main reason for the high reactivity of the oxidation reactions. Comparative analysis of soot emission by diffuse reflectance spectroscopy (DRS) showed that the catalyst containing Ru on the mixed oxide-impregnated cordierite samples efficiently oxidized soot in a diesel stationary motor:soot emission decreased 80%.

  14. The ALMR actinide burning system

    Energy Technology Data Exchange (ETDEWEB)

    Quinn, J.E. (General Electric Co., San Jose, CA (United States))

    1993-01-01

    The advanced liquid-metal reactor (ALMR) actinide burning system is being developed under the sponsorship of the US Department of Energy to bring its unique capabilities to fruition for deployment in the early 21st century. The system consists of four major parts: the reactor plant, the metal fuel and its recycle, the processing of light water reactor (LWR) spent fuel to extract the actinides, and the development of a residual waste package. This paper addresses the status and outlook for each of these four major elements. The ALMR is being developed by an industrial group under the leadership of General Electric (GE) in a cost-sharing arrangement with the US Department of Energy. This effort is nearing completion of the advanced conceptual design phase and will enter the preliminary design phase in 1994. The innovative modular reactor design stresses simplicity, economics, reliability, and availability. The design has evolved from GE's PRISM design initiative and has progressed to the final stages of a prelicensing review by the US Nuclear Regulatory Commission (NRC); a safety evaluation report is expected by the end of 1993. All the major issues identified during this review process have been technically resolved. The next design phases will focus on implementation of the basic safety philosophy of passive shutdown to a safe, stable condition, even without scram, and passive decay heat removal. Economic projections to date show that it will be competitive with non- nuclear and advanced LWR nuclear alternatives.

  15. Ionic Interactions in Actinide Tetrahalides

    Science.gov (United States)

    Akdeniz, Z.; Karaman, A.; Tosi, M. P.

    2001-05-01

    We determine a model of the ionic interactions in AX 4 compounds (where A is an atom in the actinide series from Th to Am and X = F, Cl, Br or I) by an analysis of data on the static and dynamic structure of their molecular monomers. The potential energy function that we adopt is taken from earlier work on rare-earth trihalides [Z. Akdeniz, Z. Q q e k and M. P. Tosi, Z. Naturforsch. 55a, 861 (2000)] and in particular allows for the electronic polarizability of the actinide ion. This polarizability quantitatively determines the antisymmetric-bending vibrational mode, but its magnitude remains compatible with a symmetric tetrahedral shape of the molecule at equilibrium. The fluorides have an especially high degree of ionic character, and the interionic-force parameters for each halide of the U, Np, Pu and Am series show regular trends, suggesting that extrapolations to the other transuranic-element halides may usefully be made. The Th compounds show some deviations from these trends, and the interionic-force model that we determine for ThCl4 differs somewhat from that obtained in a previous study. We therefore return on the evaluation of the relative stability of charged oligomers of ThCl4 and ZrCl4 and find confirmation of our earlier results on this problem.

  16. Catalysis of the rare earth containing mixed oxides Ln2CuO4 in phenol hydroxylation

    Institute of Scientific and Technical Information of China (English)

    刘持标; 赵震; 叶兴凯; 吴越

    1997-01-01

    Mixed oxides Ln2CuO4±λ(Ln=La,Pr,Nd,Sm,Gd) with K2NiF4 structure were prepared Their crystal structures were studied with XRD and IR spectra.Meanwhile,the average valence of Cu ions and non stoichiometric oxygen (λ) were determined through chemical analyses.Catalysis of the above-mentioned mixed oxides in the phenol hydroxylation was investigated.Results show that the catalysis of these mixed oxides has close relation with their structures and composition.Substitution of A site atom in Ln2CuO4λ has a great influence on then eatalysis in the phenol hydroxylation.

  17. Surface and bulk aspects of mixed oxide catalytic nanoparticles: oxidation and dehydration of CH(3)OH by polyoxometallates.

    Science.gov (United States)

    Nakka, Lingaiah; Molinari, Julie E; Wachs, Israel E

    2009-10-28

    The molecular structures and surface chemistry of mixed metal oxide heteropolyoxo vanadium tungstate (H(3+x)PW(12-x)V(x)O(40) with x = 0, 1, 2, and 3) Keggin nanoparticles (NPs), where vanadium is incorporated into the primary Keggin structure, and supported VO(x) on tungstophosphoric acid (TPA, H(3)PW(12)O(40)), where vanadium is present on the surface of the Keggin unit, were investigated with solid-state magic angle spinning (51)V NMR, FT-IR, in situ Raman, in situ UV-vis, CH(3)OH temperature-programmed surface reaction (TPSR), and steady-state methanol oxidation. The incorporated VO(x) unit possesses one terminal V horizontal lineO bond, four bridging V-O-W/V bonds, and one long V-O-P bond in the primary Keggin structure, and the supported VO(x) unit possesses a similar coordination in the secondary structure under ambient conditions. The specific redox reaction rate for VO(x) in the Keggin primary structure is comparable to that of bulk V(2)O(5) and the more active supported vanadium oxide catalysts. The specific acidic reaction rate for the WO(x) in the TPA Keggin, however, is orders of magnitude greater than found for bulk WO(3), supported tungsten oxide catalysts, and even the highly acidic WO(3)-ZrO(2) catalyst synthesized by coprecipitation of ammonium metatungstate and ZrO(OH)(2). From CH(3)OH-TPSR and in situ Raman spectroscopy it was found that incorporation of vanadium oxide into the primary Keggin structure is also accompanied by the formation of surface VO(x) species at secondary sites on the Keggin outer surface. Both CH(3)OH-TPSR and steady-state methanol oxidation studies demonstrated that the surface VO(x) species on the Keggin outer surface are significantly less active than the VO(x) species incorporated into the primary Keggin structure. The presence of the less active surface VO(x) sites in the Keggins, thus, decreases the specific reaction rates for both methanol oxidation and methanol dehydration. During methanol oxidation/dehydration (O(2

  18. Sensitivity analysis of minor actinides transmutation to physical and technological parameters

    Directory of Open Access Journals (Sweden)

    Kooyman Timothée

    2015-01-01

    Full Text Available Minor actinides transmutation is one of the three main axis defined by the 2006 French law for management of nuclear waste, along with long-term storage and use of a deep geological repository. Transmutation options for critical systems can be divided in two different approaches: (a homogeneous transmutation, in which minor actinides are mixed with the fuel. This exhibits the drawback of “polluting” the entire fuel cycle with minor actinides and also has an important impact on core reactivity coefficients such as Doppler Effect or sodium void worth for fast reactors when the minor actinides fraction increases above 3 to 5% depending on the core; (b heterogeneous transmutation, in which minor actinides are inserted into transmutation targets which can be located in the center or in the periphery of the core. This presents the advantage of decoupling the management of the minor actinides from the conventional fuel and not impacting the core reactivity coefficients. In both cases, the design and analyses of potential transmutation systems have been carried out in the frame of Gen IV fast reactor using a “perturbation” approach in which nominal power reactor parameters are modified to accommodate the loading of minor actinides. However, when designing such a transmutation strategy, parameters from all steps of the fuel cycle must be taken into account, such as spent fuel heat load, gamma or neutron sources or fabrication feasibility. Considering a multi-recycling strategy of minor actinides, an analysis of relevant estimators necessary to fully analyze a transmutation strategy has been performed in this work and a sensitivity analysis of these estimators to a broad choice of reactors and fuel cycle parameters has been carried out. No threshold or percolation effects were observed. Saturation of transmutation rate with regards to several parameters has been observed, namely the minor actinides volume fraction and the irradiation time

  19. Catalytic wet-oxidation of a mixed liquid waste: COD and AOX abatement.

    Science.gov (United States)

    Goi, D; de Leitenburg, C; Trovarelli, A; Dolcetti, G

    2004-12-01

    A series of catalytic wet oxidation (CWO) reactions, at temperatures of 430-500 K and in a batch bench-top pressure vessel were carried out utilizing a strong wastewater composed of landfill leachate and heavily organic halogen polluted industrial wastewater. A CeO2-SiO2 mixed oxide catalyst with large surface area to assure optimal oxidation performance was prepared. The catalytic process was examined during batch reactions controlling Chemical Oxygen Demand (COD) and Adsorbable Organic Halogen (AOX) parameters, resulting AOX abatement to achieve better effect. Color and pH were also controlled during batch tests. A simple first order-two stage reaction behavior was supposed and verified with the considered parameters. Finally an OUR test was carried out to evaluate biodegradability changes of wastewater as a result of the catalytic reaction.

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

    Science.gov (United States)

    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 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.

  1. Selective oxidations on vanadiumoxide containing amorphous mixed oxides (AMM-V) with tert.-butylhydroperoxide

    Energy Technology Data Exchange (ETDEWEB)

    Deng, Y.; Hunnius, M.; Storck, S.; Maier, W.F. [Max-Planck-Institut fuer Kohlenforschung, Muelheim an der Ruhr (Germany)

    1998-12-31

    The catalytic oxygen transfer properties of vanadium containing zeolites and vanadium based sol-gel catalysts with hydrogen peroxides are well known. The severe problem of vanadium leaching caused by the presence of the by-product water has been addressed. To avoid any interference with homogeneously catalyzed reactions, our study focusses on selective oxidations in a moisture-free medium with tert.-butylhydroperoxide. We have investigated the catalytic properties of amorphous microporous materials based on SiO{sub 2}, TiO{sub 2}, ZrO{sub 2} and Al{sub 2}O{sub 3} as matrix material and studied the effects of surface polarity on the oxidation of 1-octene and cyclohexane. (orig.)

  2. Mixed

    Directory of Open Access Journals (Sweden)

    Pau Baya

    2011-05-01

    Full Text Available Remenat (Catalan (Mixed, "revoltillo" (Scrambled in Spanish, is a dish which, in Catalunya, consists of a beaten egg cooked with vegetables or other ingredients, normally prawns or asparagus. It is delicious. Scrambled refers to the action of mixing the beaten egg with other ingredients in a pan, normally using a wooden spoon Thought is frequently an amalgam of past ideas put through a spinner and rhythmically shaken around like a cocktail until a uniform and dense paste is made. This malleable product, rather like a cake mixture can be deformed pulling it out, rolling it around, adapting its shape to the commands of one’s hands or the tool which is being used on it. In the piece Mixed, the contortion of the wood seeks to reproduce the plasticity of this slow heavy movement. Each piece lays itself on the next piece consecutively like a tongue of incandescent lava slowly advancing but with unstoppable inertia.

  3. Electrochemical oxidation of reverse osmosis concentrate on mixed metal oxide (MMO) titanium coated electrodes.

    Science.gov (United States)

    Bagastyo, Arseto Y; Radjenovic, Jelena; Mu, Yang; Rozendal, René A; Batstone, Damien J; Rabaey, Korneel

    2011-10-15

    Reverse osmosis (RO) membranes have been successfully applied around the world for wastewater reuse applications. However, RO is a physical separation process, and besides the clean water stream (permeate) a reverse osmosis concentrate (ROC) is produced, usually representing 15-25% of the feed water flow and containing the organic and inorganic contaminants at higher concentrations. In this study, electrochemical oxidation was investigated for the treatment of ROC generated during the reclamation of municipal wastewater effluent. Using laboratory-scale two-compartment electrochemical systems, five electrode materials (i.e. titanium coated with IrO2-Ta2O5, RuO2-IrO2, Pt-IrO2, PbO2, and SnO2-Sb) were tested as anodes in batch mode experiments, using ROC from an advanced water treatment plant. The best oxidation performance was observed for Ti/Pt-IrO2 anodes, followed by the Ti/SnO2-Sb and Ti/PbO2 anodes. The effectiveness of the treatment appears to correlate with the formation of oxidants such as active chlorine (i.e. Cl2/HClO/ClO-). As a result, electro-generated chlorine led to the abundant formation of harmful by-products such as trihalomethanes (THMs) and haloacetic acids (HAAs), particularly at Ti/SnO2-Sb and Ti/Pt-IrO2 anodes. The highest concentration of total HAAs (i.e. 2.7 mg L(-1)) was measured for the Ti/SnO2-Sb electrode, after 0.55 Ah L(-1) of supplied specific electrical charge. Irrespective of the used material, electrochemical oxidation of ROC needs to be complemented by a polishing treatment to alleviate the release of halogenated by-products. Copyright © 2011 Elsevier Ltd. All rights reserved.

  4. Surface composition and catalytic activity of La-Fe mixed oxides for methane oxidation

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Fengxiang [School of Chemistry, Beijing Institute of Technology, Liangxiang East Road, Beijing 102488 (China); Li, Zhanping [Analysis Center, Tsinghua University, Beijing 100084 (China); Ma, Hongwei [School of Chemistry, Beijing Institute of Technology, Liangxiang East Road, Beijing 102488 (China); Gao, Zhiming, E-mail: zgao@bit.edu.cn [School of Chemistry, Beijing Institute of Technology, Liangxiang East Road, Beijing 102488 (China)

    2015-10-01

    Graphical abstract: - Highlights: • The sample with La/Fe atomic ratio of 0.94 is single phase perovskite La{sub 0.94}FeO{sub 3−d}. • The excess ironic oxide exists on the surface of the perovskite crystallites. • La{sup 3+} ions are enriched on surface of the oxides even for the La{sub 0.68}Fe sample. - Abstract: Four La-Fe oxide samples with La/Fe atomic ratio y = 1.02 ∼ 0.68 (denoted as LayFe) were prepared by the citrate method. The samples had a decreased specific surface area with the La/Fe atomic ratio decreasing. XRD pattern proved that the sample La{sub 0.94}Fe is single phase perovskite La{sub 0.94}FeO{sub 3−d}. Phase composition of the samples was estimated by the Rietveld refinement method. XPS analyses indicate that La{sup 3+} ions are enriched on surface of crystallites for all the samples, and surface carbonate ions are relatively abundant on the samples La{sub 1.02}Fe and La{sub 0.94}Fe. Catalytic activity for methane oxidation per unit surface area of the samples is in the order of La{sub 0.68}Fe > La{sub 0.76}Fe > La{sub 0.94}Fe > La{sub 1.02}Fe both in the presence and in the absence of gaseous oxygen. A reason for this order would be the higher concentration of Fe{sup 3+} ion on the surface of the samples La{sub 0.68}Fe and La{sub 0.76}Fe.

  5. Decay Heat Calculations for PWR and BWR Assemblies Fueled with Uranium and Plutonium Mixed Oxide Fuel using SCALE

    Energy Technology Data Exchange (ETDEWEB)

    Ade, Brian J [ORNL; Gauld, Ian C [ORNL

    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

  6. Spin and orbital moments in actinide compounds

    DEFF Research Database (Denmark)

    Lebech, B.; Wulff, M.; Lander, G.H.

    1991-01-01

    experiments designed to determine the magnetic moments at the actinide and transition-metal sublattice sites in compounds such as UFe2, NpCo2, and PuFe2 and to separate the spin and orbital components at the actinide sites. The results show, indeed, that the ratio of the orbital to spin moment is reduced......The extended spatial distribution of both the transition-metal 3d electrons and the actinide 5f electrons results in a strong interaction between these electron states when the relevant elements are alloyed. A particular interesting feature of this hybridization, which is predicted by single...

  7. Recovery of actinides from actinide-aluminium alloys by chlorination: Part I

    OpenAIRE

    Cassayre, Laurent; Soucek, Pavel; Mendes, Eric; Malmbeck, Rikard; Nourry, Christophe; Eloirdi, Rachel; Glatz, Jean-Paul

    2011-01-01

    Pyrochemical processes in molten LiCl–KCl are being developed in ITU for recovery of actinides from spent nuclear fuel. The fuel is anodically dissolved to the molten salt electrolyte and actinides are electrochemically reduced on solid aluminium cathodes forming solid actinide–aluminium alloys. A chlorination route is being investigated for recovery of actinides from the alloys. This route consists in three steps: Vacuum distillation for removal of the salt adhered on the electrode, chlorina...

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

    Energy Technology Data Exchange (ETDEWEB)

    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.

  9. Optical and Chemical Properties of Mixed-valent Rhenium Oxide Films Synthesized by Reactive DC Magnetron Sputtering

    Science.gov (United States)

    2015-04-03

    AFRL-RX-WP-JA-2015-0178 OPTICAL AND CHEMICAL PROPERTIES OF MIXED- VALENT RHENIUM OXIDE FILMS SYNTHESIZED BY REACTIVE DC MAGNETRON...To) 06 May 2010 – 16 March 2015 4. TITLE AND SUBTITLE OPTICAL AND CHEMICAL PROPERTIES OF MIXED-VALENT RHENIUM OXIDE FILMS SYNTHESIZED BY REACTIVE ...DC MAGNETRON SPUTTERING (POSTPRINT) 5a. CONTRACT NUMBER In-house 5b. GRANT NUMBER 5c. PROGRAM ELEMENT NUMBER 62102F 6. AUTHOR(S) (see

  10. Nano-vanadium oxide thin films in mixed phase for microbolometer applications

    Energy Technology Data Exchange (ETDEWEB)

    Subrahmanyam, A; Bharat Kumar Reddy, Y [Department of Physics, Indian Institute of Technology Madras, Chennai 600036 (India); Nagendra, C L [LEOS, ISRO, Peenya Industrial Estate, Bangalore 560060 (India)], E-mail: manu@iitm.ac.in

    2008-10-07

    Among the several phases of vanadium oxide, mixed phases of VO{sub 2} and V{sub 2}O{sub 5} are preferred for uncooled micro-bolometers with low noise. The aim of this investigation is to achieve mixed phase VO{sub 2} and V{sub 2}O{sub 5} thin films with nanometre grain sizes and high temperature coefficient of resistance (TCR). Since the phase depends upon the oxygen reactivity, these vanadium oxide thin films are prepared by reactive electron beam evaporation at different oxygen flow rates and substrate temperatures. The mixed phases have been evaluated through x-ray diffraction and x-ray photo emission studies. The temperature dependence of resistance has shown that the films grown at 473 K with 2.8 x 10{sup -5} mbar chamber pressure of oxygen (VO{sub 2} : V{sub 2}O{sub 5} ratio of 36 : 64) have the highest TCR of -3.2 K{sup -1} with a reasonable low resistance (120 {omega}/square)

  11. Selective oxidations of a dithiolate complex produce a mixed sulfonate/thiolate complex.

    Science.gov (United States)

    Chohan, Balwant S; Maroney, Michael J

    2006-03-06

    Oxygenation or peroxidation of a planar, tetracoordinate, low-spin nickel(II) complex of a N2S2-donor ligand, (N,N'-dimethyl-N,N'-bis(2-mecaptoethyl)-1, 3-propanediaminato)nickel(II), proceeds via the formation of a mixed sulfinate/thiolate complex and leads to the production of a novel dimeric complex containing both sulfonate and thiolate ligands. Thus, reaction proceeds via selective oxidation of the sulfinate sulfur atom, leaving the thiolate reduced. The novel sulfonate/thiolate complex has been isolated and characterized by electospray ionization mass spectrometry and single-crystal X-ray diffraction. Crystals form in the monoclinic space group P2(1)/c with cell dimensions a = 8.4647(12) A, b = 12.592(3) A, and c = 12.531(2) A, angles alpha = gamma = 90 degrees and beta = 106.645(11) degrees , and Z = 2. The structure was refined to R = 5.20% and R(w) = 12.86% [I > 2sigma(I)]. The isolation of this mixed sulfonate/thiolate complex from oxidation of a mixed sulfinate/thiolate complex provides experimental evidence for the formation of a sulfonate ligand via a Ni-O-O-SO2R intermediate, as suggested by recent density functional theory calculations.

  12. Reversible optical sensor for the analysis of actinides in solution; Capteur optique reversible pour l'analyse des actinides en solution

    Energy Technology Data Exchange (ETDEWEB)

    Lesage, B.; Picard, S. [CEA Marcoule, Dept. de Radiochimie et Procedes, Service de Chimie des Procedes de Separation, Lab. de Chimie des Actinides, 30 (France); Serein-Spirau, F.; Lereporte, J.P. [Ecole Nationale Superieure de Chimie de Montpellier (ENSCM), CNRS UMR 5076, Lab. Heterochimie Moleculaire et Macromoleculaire, 34 - Montpellier (France)

    2007-07-01

    In this work is presented a concept of reversible optical sensor for actinides. It is composed of a p doped conducing polymer support and of an anion complexing the actinides. The chosen conducing polymer is the thiophene-2,5-di-alkoxy-benzene whose solubility and conductivity are perfectly known. The actinides selective ligand is a lacunar poly-oxo-metallate such as P{sub 2}W{sub 17}O{sub 61}{sup 10-} or SiW{sub 11}O{sub 39}{sup 8-} which are strong anionic complexing agents of actinides at the oxidation state (IV) even in a very acid medium. The sensor is prepared by spin coating of the composite mixture 'polymer + ligand' on a conducing glass electrode and then tested towards its optical and electrochemical answer in presence of uranium (IV). The absorption change due to the formation of cations complexes by poly-oxo-metallate reveals the presence of uranium (IV). After the measurement, the sensor is regenerated by anodic polarization of the support and oxidation of the uranium (IV) into uranium (VI) which weakly interacts with the poly-oxo-metallate and is then released in solution. (O.M.)

  13. Preparation and characterization of Cu-Ce-La mixed oxide as water-gas shift catalyst for fuel cells application

    Institute of Scientific and Technical Information of China (English)

    ZHI Keduan; LIU Quansheng; ZHAO Ruigang; HE Runxia; ZHANG Lifeng

    2008-01-01

    Cu-Ce-La mixed oxides were prepared by three precipitation methods (coprecipitation, homogeneous precipitation, and deposition precipitation) with variable precipitators and characterized using X-ray diffraction, BET, temperature-programmed reduction, and catalytic reaction for the water-gas shift. The Cu-Ce-La mixed oxide prepared by coprecipitation method with NaOH as precipitator presented the highest activity and thermal stability. Copper ion substituted quadrevalent ceria entered CeO2 (111) framework was in favor of activity and thermal stability of catalyst. The crystallinity of fresh catalysts increased with the reduction process. La3+ or Ce4+ substituted copper ion entered the CeO2 framework during reduction process. The coexistence of surface copper oxide (crystalline) and pure bulk crystalline copper oxide both contributed to the high activity and thermal stability of Cu-Ce-La mixes oxide catalyst.

  14. Influence of Gold on Ce-Zr-Co Fluorite-Type Mixed Oxide Catalysts for Ethanol Steam Reforming

    Directory of Open Access Journals (Sweden)

    Véronique Pitchon

    2012-02-01

    Full Text Available The effect of gold presence on carbon monoxide oxidation and ethanol steam reforming catalytic behavior of two Ce-Zr-Co mixed oxides catalysts with a constant Co charge and different Ce/Zr ratios was investigated. The Ce-Zr-Co mixed oxides were obtained by the pseudo sol-gel like method, based on metallic propionates polymerization and thermal decomposition, whereas the gold-supported Ce-Zr-Co mixed oxides catalysts were prepared using the direct anionic exchange. The catalysts were characterized using XRD, TPR, and EDXS-TEM. The presence of Au in doped Ce-Zr-Co oxide catalyst decreases the temperature necessary to reduce the cobalt and the cerium loaded in the catalyst and favors a different reaction pathway, improving the acetaldehyde route by ethanol dehydrogenation, instead of the ethylene route by ethanol dehydration or methane re-adsorption, thus increasing the catalytic activity and selectivity into hydrogen.

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

    Science.gov (United States)

    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.

  16. Feasibility Study of 1/3 Thorium-Plutonium Mixed Oxide Core

    Directory of Open Access Journals (Sweden)

    Cheuk Wah Lau

    2014-01-01

    Full Text Available Thorium-plutonium mixed oxide (Th-MOX fuel has become one of the most promising solutions to reduce a large and increasing plutonium stockpile. Compared with traditional uranium-plutonium mixed oxide (U-MOX fuels, Th-MOX fuel has higher consumption rate of plutonium in LWRs. Besides, thorium based fuels have improved thermomechanical material properties compared with traditional U-MOX fuels. Previous studies on a full Th-MOX core have shown reduced efficiency in reactivity control mechanisms, stronger reactivity feedback, and a significantly lower fraction of delayed neutrons compared with a traditional uranium oxide (UOX core. These problems complicate the implementation of a full Th-MOX core in a similar way as for a traditional U-MOX core. In order to reduce and avoid some of these issues, the introduction of a lower fraction of Th-MOX fuel in the core is proposed. In this study, one-third of the assemblies are Th-MOX fuel, and the rest are traditional UOX fuel. The feasibility study is based on the Swedish Ringhals-3 PWR. The results show that the core characteristics are more similar to a traditional UOX core, and the fraction of delayed neutrons is within acceptable limits. Moreover, the damping of axial xenon oscillations induced by control rod insertions is almost 5 times more effective for the 1/3 Th-MOX core compared with the standard core.

  17. BWR Assembly Optimization for Minor Actinide Recycling

    Energy Technology Data Exchange (ETDEWEB)

    G. Ivan Maldonado; John M. Christenson; J.P. Renier; T.F. Marcille; J. Casal

    2010-03-22

    The Primary objective of the proposed project is to apply and extend the latest advancements in LWR fuel management optimization to the design of advanced boiling water reactor (BWR) fuel assemblies specifically for the recycling of minor actinides (MAs).

  18. Low-temperature synthesis of Mn-based mixed metal oxides with novel fluffy structures as efficient catalysts for selective reduction of nitrogen oxides by ammonia.

    Science.gov (United States)

    Meng, Bo; Zhao, Zongbin; Chen, Yongsheng; Wang, Xuzhen; Li, Yong; Qiu, Jieshan

    2014-10-21

    A series of Mn-based mixed metal oxide catalysts (Co-Mn-O, Fe-Mn-O, Ni-Mn-O) with high surface areas were prepared via low temperature crystal splitting and exhibited extremely high catalytic activity for the low-temperature selective catalytic reduction of nitrogen oxides with ammonia.

  19. Actinides record, power calculations and activity for present isotopes in the spent fuel of a BWR; Historial de actinidos y calculos de potencia y actividad para isotopos presentes en el combustible gastado de un BWR

    Energy Technology Data Exchange (ETDEWEB)

    Enriquez C, P.; Ramirez S, J. R.; Lucatero, M. A., E-mail: pastor.enriquez@inin.gob.mx [ININ, Carretera Mexico-Toluca s/n, 52750 Ocoyoacac, Estado de Mexico (Mexico)

    2012-10-15

    The administration of spent fuel is one of the more important stages of the nuclear fuel cycle, and this has become a problem of supreme importance in countries that possess nuclear reactors. Due to this in this work, the study on the actinides record and present fission products to the discharge of the irradiated fuel in a light water reactor type BWR is shown, to quantify the power and activity that emit to the discharge and during the cooling time. The analysis was realized on a fuel assembly type 10 x 10 with an enrichment average of 3.69 wt % in U-235 and the assembly simulation assumes four cycles of operation of 18 months each one and presents an exposition of 47 G Wd/Tm to the discharge. The module OrigenArp of the Scale 6 code is the computation tool used for the assembly simulation and to obtain the results on the actinides record presents to the fuel discharge. The study covers the following points: a) Obtaining of the plutonium vector used in the fuel production of mixed oxides, and b) Power calculation and activity for present actinides to the discharge. The results presented in this work, correspond at the same time immediate of discharge (0 years) and to a cooling stage in the irradiated fuel pool (5 years). (Author)

  20. Transmutation of actinides in power reactors.

    Science.gov (United States)

    Bergelson, B R; Gerasimov, A S; Tikhomirov, G V

    2005-01-01

    Power reactors can be used for partial short-term transmutation of radwaste. This transmutation is beneficial in terms of subsequent storage conditions for spent fuel in long-term storage facilities. CANDU-type reactors can transmute the main minor actinides from two or three reactors of the VVER-1000 type. A VVER-1000-type reactor can operate in a self-service mode with transmutation of its own actinides.

  1. The Actinide Transition Revisited by Gutzwiller Approximation

    Science.gov (United States)

    Xu, Wenhu; Lanata, Nicola; Yao, Yongxin; Kotliar, Gabriel

    2015-03-01

    We revisit the problem of the actinide transition using the Gutzwiller approximation (GA) in combination with the local density approximation (LDA). In particular, we compute the equilibrium volumes of the actinide series and reproduce the abrupt change of density found experimentally near plutonium as a function of the atomic number. We discuss how this behavior relates with the electron correlations in the 5 f states, the lattice structure, and the spin-orbit interaction. Our results are in good agreement with the experiments.

  2. Predictive Modeling in Actinide Chemistry and Catalysis

    Energy Technology Data Exchange (ETDEWEB)

    Yang, Ping [Los Alamos National Lab. (LANL), Los Alamos, NM (United States)

    2016-05-16

    These are slides from a presentation on predictive modeling in actinide chemistry and catalysis. The following topics are covered in these slides: Structures, bonding, and reactivity (bonding can be quantified by optical probes and theory, and electronic structures and reaction mechanisms of actinide complexes); Magnetic resonance properties (transition metal catalysts with multi-nuclear centers, and NMR/EPR parameters); Moving to more complex systems (surface chemistry of nanomaterials, and interactions of ligands with nanoparticles); Path forward and conclusions.

  3. Lattice effects in the light actinides

    Energy Technology Data Exchange (ETDEWEB)

    Lawson, A.C.; Cort, B.; Roberts, J.A.; Bennett, B.I.; Brun, T.O.; Dreele, R.B. von [Los Alamos National Lab., NM (United States); Richardson, J.W. Jr. [Argonne National Lab., IL (United States)

    1998-12-31

    The light actinides show a variety of lattice effects that do not normally appear in other regions of the periodic table. The article will cover the crystal structures of the light actinides, their atomic volumes, their thermal expansion behavior, and their elastic behavior as reflected in recent thermal vibration measurements made by neutron diffraction. A discussion of the melting points will be given in terms of the thermal vibration measurements. Pressure effects will be only briefly indicated.

  4. Fabrication of pulsed-laser deposited V-W-Nd mixed-oxide films

    Energy Technology Data Exchange (ETDEWEB)

    Iida, Yusuke; Venkatachalam, S.; Kaneko, Yoshikazu [Interdisciplinary Graduate School of Medicine and Engineering, University of Yamanashi, 4-3-11 Takeda, Kofu 400-8511 (Japan); Kanno, Yoshinori [Interdisciplinary Graduate School of Medicine and Engineering, University of Yamanashi, 4-3-11 Takeda, Kofu 400-8511 (Japan)], E-mail: kanno@yamanashi.ac.jp

    2007-11-15

    V-W-Nd mixed-oxide films were prepared by pulse-laser deposition (PLD) technique from the targets sintered at different temperatures. X-ray photoelectron spectroscopy (XPS) data indicate that the films fabricated from the targets sintered at low temperature were composed of various mixed valences. Raman spectroscopy shows that V-W-Nd films were composed of the vanadates as NdVO{sub 4}, and the W{sup 6+} doping supplements the formation of vanadate. Atomic force microscopy (AFM) image of the films fabricated from the target sintered at 923 K reveals the average particle size is estimated around 86 nm. The surface morphology of the films roughness shows a dramatic change at 923-943 K.

  5. Research in actinide chemistry. Progress report, March 1, 1980-February 28, 1981

    Energy Technology Data Exchange (ETDEWEB)

    Choppin, G.R.

    1981-01-01

    Visible spectroscopy, NMR (/sup 1/H/sub 1/, /sup 6/C/sub 13/, /sup 57/La/sub 139/) spectroscopy, potentiometry, and calorimetry were used in lanthanide studies which have allowed much more thorough interpretation of actinide tracer studies. In the last several years, the studies were expanded to include actinides in the IV, V and VI oxidation states. Part of the research during this time was directed to investigation of actinide interaction with naturally occurring polyelectrolytes such as humic and fulvic acids. Since redox reactions seemingly occur in some of these interactions, a study of plutonium and neptunium redox behavior in the presence of organic complexing agents was started. Preliminary data are given for reduction of Np(VI) by various organic acids.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    1994-06-01

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

  7. Application of Ni-Oxide@TiO2 Core-Shell Structures to Photocatalytic Mixed Dye Degradation, CO Oxidation, and Supercapacitors

    OpenAIRE

    Seungwon Lee; Jisuk Lee; Kyusuk Nam; Weon Gyu Shin; Youngku Sohn

    2016-01-01

    Performing diverse application tests on synthesized metal oxides is critical for identifying suitable application areas based on the material performances. In the present study, Ni-oxide@TiO2 core-shell materials were synthesized and applied to photocatalytic mixed dye (methyl orange + rhodamine + methylene blue) degradation under ultraviolet (UV) and visible lights, CO oxidation, and supercapacitors. Their physicochemical properties were examined by field-emission scanning electron microscop...

  8. Catalytic activity of titania zirconia mixed oxide catalyst for dimerization eugenol

    Science.gov (United States)

    Tursiloadi, S.; Kristiani, A.; Jenie, S. N. Aisyiyah; Laksmono, J. A.

    2017-01-01

    Clove oil has been found to possess antibacterial, antifungal, antiviral, antitumor, antioxidant and insecticidal properties. The major compound of clove oil is eugenol about 49-87%. Eugenol as phenolic compounds exhibits antioxidant and antimicrobial activities. The derivative compound of eugenol, dieugenol, show antioxidant potency better than parent eugenol. A series of TiO2-ZrO2 mixed oxides (TZ) with various titanium contents from 0 to 100wt%, prepared by using sol gel method were tested their catalytic activity for dimerization eugenol, Their catalytic activity show that these catalysts resulted a low yield of dimer eugenol, dieugenol, about 2-9 % and the purity is more than 50%.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2016-04-10

    tA highly versatile ethanol conversion process to selectively generate high value compounds is pre-sented here. By changing the reaction temperature, ethanol can be selectively converted to >C2alcohols/oxygenates or phenolic compounds over hydrotalcite derived bi-functional MgO–Al2O3cata-lyst via complex cascade mechanism. Reaction temperature plays a role in whether aldol condensationor the acetone formation is the path taken in changing the product composition. This article containsthe catalytic activity comparison between the mono-functional and physical mixture counterpart to thehydrotalcite derived mixed oxides and the detailed discussion on the reaction mechanisms.

  10. The Applications of Mixed Metal Oxides to Capture the CO2 and Convert to Syn-Gas

    Directory of Open Access Journals (Sweden)

    A. G. Gaikwad

    2015-01-01

    Full Text Available AbstractThe applicationsof different mixed metal oxides were explored for the capture of CO2and convert of CO2 to syn-gas. The several samples of the mixedmetal oxides were prepared by the sol gel, solid-solid fusion, precipitation,molten salt and template methods in order to investigate the performance ofmixed mtal oxides to the CO2 applications. These samples werecalcined for the 3h in air at 900 oC. The mixed metal oxides sampleswere characterized by acidity/ basicity, surface area, XRD pattern, SEM imagesand to capture CO2. The basicity and surface area of the samples of mixedmetal oxides were found to be in the range from 0.7 to 15.7 mmol g-1and 2.24 to 138.76 m2 g-1, respectively. The obtainedresults of prepared mixed metal oxides by different method were compared forthe purpose of searching the efficient materials. The temperature profiles of thecaptured CO2 by the samples of mixed metal oxides were obtained inthe range 100 to 800 oC. The captured CO2 was found to bein the range from 7.36 to 26.93 wt%. The conversions of CO2 bymethane were explored to syn-gas over the mixed metal oxides including the calciumiron lanthanum mixed metal oxides and Pd (5 wt %/Al2O3at 700 oC with the gas hourly space velocities (GHSV 6000 ml h-1g-1 of methane, 6000 ml h-1 g-1 of CO2and 24000 ml h-1 g-1 of helium.

  11. Silica-based composite and mixed-oxide nanoparticles from atmospheric pressure flame synthesis

    Science.gov (United States)

    Akurati, Kranthi K.; Dittmann, Rainer; Vital, Andri; Klotz, Ulrich; Hug, Paul; Graule, Thomas; Winterer, Markus

    2006-08-01

    Binary TiO2/SiO2 and SnO2/SiO2 nanoparticles have been synthesized by feeding evaporated precursor mixtures into an atmospheric pressure diffusion flame. Particles with controlled Si:Ti and Si:Sn ratios were produced at various flow rates of oxygen and the resulting powders were characterized by BET (Brunauer-Emmett-Teller) surface area analysis, XRD, TEM and Raman spectroscopy. In the Si-O-Ti system, mixed oxide composite particles exhibiting anatase segregation formed when the Si:Ti ratio exceeded 9.8:1, while at lower concentrations only mixed oxide single phase particles were found. Arrangement of the species and phases within the particles correspond to an intermediate equilibrium state at elevated temperature. This can be explained by rapid quenching of the particles in the flame and is in accordance with liquid phase solubility data of Ti in SiO2. In contrast, only composite particles formed in the Sn-O-Si system, with SnO2 nanoparticles predominantly found adhering to the surface of SiO2 substrate nanoparticles. Differences in the arrangement of phases and constituents within the particles were observed at constant precursor mixture concentration and the size of the resultant segregated phase was influenced by varying the flow rate of the oxidant. The above effect is due to the variation of the residence time and quenching rate experienced by the binary oxide nanoparticles when varying the oxygen flow rate and shows the flexibility of diffusion flame aerosol reactors.

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

    Science.gov (United States)

    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.

  13. Sorption Speciation of Lanthanides/Actinides on Minerals by TRLFS, EXAFS and DFT Studies: A Review

    Directory of Open Access Journals (Sweden)

    Xiaoli Tan

    2010-11-01

    Full Text Available Lanthanides/actinides sorption speciation on minerals and oxides by means of time resolved laser fluorescence spectroscopy (TRLFS, extended X-ray absorption fine structure spectroscopy (EXAFS and density functional theory (DFT is reviewed in the field of nuclear disposal safety research. The theoretical aspects of the methods are concisely presented. Examples of recent research results of lanthanide/actinide speciation and local atomic structures using TRLFS, EXAFS and DFT are discussed. The interaction of lanthanides/actinides with oxides and minerals as well as their uptake are also of common interest in radionuclide chemistry. Especially the sorption and inclusion of radionuclides into several minerals lead to an improvement in knowledge of minor components in solids. In the solid-liquid interface, the speciation and local atomic structures of Eu(III, Cm(III, U(VI, and Np(IV/VI in several natural and synthetic minerals and oxides are also reviewed and discussed. The review is important to understand the physicochemical behavior of lanthanides/actinides at a molecular level in the natural environment.

  14. Pyrochlore as nuclear waste form. Actinide uptake and chemical stability

    Energy Technology Data Exchange (ETDEWEB)

    Finkeldei, Sarah Charlotte

    2015-07-01

    Radioactive waste is generated by many different technical and scientific applications. For the past decades, different waste disposal strategies have been considered. Several questions on the waste disposal strategy remain unanswered, particularly regarding the long-term radiotoxicity of minor actinides (Am, Cm, Np), plutonium and uranium. These radionuclides mainly arise from high level nuclear waste (HLW), specific waste streams or dismantled nuclear weapons. Although many countries have opted for the direct disposal of spent fuel, from a scientific and technical point of view it is imperative to pursue alternative waste management strategies. Apart from the vitrification, especially for trivalent actinides and Pu, crystalline ceramic waste forms are considered. In contrast to glasses, crystalline waste forms, which are chemically and physically highly stable, allow the retention of radionuclides on well-defined lattice positions within the crystal structure. Besides polyphase ceramics such as SYNROC, single phase ceramics are considered as tailor made host phases to embed a specific radionuclide or a specific group. Among oxidic single phase ceramics pyrochlores are known to have a high potential for this application. This work examines ZrO{sub 2} based pyrochlores as potential nuclear waste forms, which are known to show a high aqueous stability and a high tolerance towards radiation damage. This work contributes to (1) understand the phase stability field of pyrochlore and consequences of non-stoichiometry which leads to pyrochlores with mixed cationic sites. Mixed cationic occupancies are likely to occur in actinide-bearing pyrochlores. (2) The structural uptake of radionuclides themselves was studied. (3) The chemical stability and the effect of phase transition from pyrochlore to defect fluorite were probed. This phase transition is important, as it is the result of radiation damage in ZrO{sub 2} based pyrochlores. ZrO{sub 2} - Nd{sub 2}O{sub 3} pellets

  15. Structural characterization of mixed uranium-plutonium co-precipitates and oxides synthesized by oxalic co-conversion route

    Energy Technology Data Exchange (ETDEWEB)

    Arab-Chapelet, B.; De Bruycker, F.; Picart, S.; Leturcq, G.; Grandjean, S. [Laboratoire de Chimie des Actinides, CEA Valrho, bat 399, BP17171, 30207 Bagnols sur Ceze cedex (France)

    2008-07-01

    In this study, mixed uranium(IV)-plutonium(III) oxalate co-precipitates with Pu/(U+Pu) molar ratio equal to 29 and 45% were synthesized and characterized by X-ray powder diffraction (XRD) and Scanning Electron Microscopy (SEM). The thermal conversion step of these co-precipitates into oxide was carried out under argon flow up to 700 deg. C leading to mixed oxides. The structural investigation on these oxides indicates the formation of (U,Pu)O{sub 2} fluorite-type solid solution characterized by a very homogeneous distribution of plutonium and uranium, a controlled oxygen stoichiometry and well-defined morphology of particles. (authors)

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

    Energy Technology Data Exchange (ETDEWEB)

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

    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

  17. Methane oxidation over Fe-, Co-, Ni- and V-containing mixed conductors

    Energy Technology Data Exchange (ETDEWEB)

    Kharton, V.V.; Yaremchenko, A.A.; Tsipis, E.V.; Shaula, A.L.; Frade, J.R. [Department of Ceramics and Glass Engineering, CICECO, University of Aveiro, 3810-193 Aveiro (Portugal); Valente, A.A.; Rocha, J. [Department of Chemistry, CICECO, University of Aveiro, 3810-193 Aveiro (Portugal); Sobyanin, V.A.; Belyaev, V.D.; Semin, G.L.; Veniaminov, S.A. [Boreskov Institute of Catalysis SB RAS, 5 pr. Akademika Lavrentieva, Novosibirsk 630090 (Russian Federation)

    2005-02-28

    The catalytic oxidation of methane over mixed conducting ceramics, including perovskite-type SrFe{sub 0.7}Al{sub 0.3}O{sub 3-{delta}} and La{sub 0.3}Sr{sub 0.7}Co{sub 0.8}Ga{sub 0.2}O{sub 3-{delta}}, dual-phase composite (SrCo){sub 0.5}(Sr{sub 2}Fe{sub 3}){sub 0.5}O{sub 4.75+}/-{sub {delta}}, La{sub 2}Ni{sub 0.9}Co{sub 0.1}O{sub 4+{delta}} with K{sub 2}NiF{sub 4}-type structure and zircon-type CeVO{sub 4+{delta}}, is primarily governed by bonding energy between oxygen and transition metal cations, which leads to general correlations between the catalytic activity, oxygen desorption, oxygen ionic transport, thermal expansion, and, often, phase stability. The steady-state conversion of dry CH{sub 4} either by oxygen permeating through dense oxide ceramics in a membrane reactor or by atmospheric O{sub 2} (methane/air ratio of 30:70) in a fixed bed reactor with membrane material as catalyst results in high CO{sub 2} selectivity, increasing when the oxygen permeability of mixed conductors increases. The prevailing mechanism of total methane combustion makes it necessary to incorporate reforming catalysts in the membrane reactors for natural gas conversion to Synthesis gas (syngas). Dominant CO{sub 2} formation is also observed for the oxidation of CH{sub 4} pulses supplied in helium flow over the mixed conductor powders, except for SrFe{sub 0.7}Al{sub 0.3}O{sub 3-{delta}} yielding synthesis gas with the H{sub 2}/CO ratio close to 2, characteristic of the partial oxidation process. For a model reactor comprising one disk-shaped membrane and a catalyst both made of SrFe{sub 0.7}Al{sub 0.3}O{sub 3-{delta}}, the methane conversion and CO selectivity at 1223 K achieved 65% and 48%, respectively.

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

    Science.gov (United States)

    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.

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

    Directory of Open Access Journals (Sweden)

    B. Seok

    2013-08-01

    Full Text Available 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.

  20. A magnetic route to measure the average oxidation state of mixed-valent manganese in manganese oxide octahedral molecular sieves (OMS).

    Science.gov (United States)

    Shen, Xiong-Fei; Ding, Yun-Shuang; Liu, Jia; Han, Zhao-Hui; Budnick, Joseph I; Hines, William A; Suib, Steven L

    2005-05-04

    A magnetic route has been applied for measurement of the average oxidation state (AOS) of mixed-valent manganese in manganese oxide octahedral molecular sieves (OMS). The method gives AOS measurement results in good agreement with titration methods. A maximum analysis deviation error of +/-7% is obtained from 10 sample measurements. The magnetic method is able to (1) confirm the presence of mixed-valent manganese and (2) evaluate AOS and the spin states of d electrons of both single oxidation state and mixed-valent state Mn in manganese oxides. In addition, the magnetic method may be extended to (1) determine AOS of Mn in manganese oxide OMS with dopant "diamagnetic" ions, such as reducible V5+ (3d0) ions, which is inappropriate for the titration method due to interference of redox reactions between these dopant ions and titration reagents, such as KMnO4, (2) evaluate the dopant "paramagnetic" ions that are present as clusters or in the OMS framework, and (3) determine AOS of other mixed-valent/single oxidation state ion systems, such as Mo3+(3d3)-Mo4+(3d2) systems and Fe3+ in FeCl3.

  1. Mixed oxides derived from layered double hydroxides as novel catalysts for phenol photodegradation

    Science.gov (United States)

    Puscasu, C. M.; Carja, G.; Mureseanu, M.; Zaharia, C.

    2017-08-01

    The removal of organic pollutants is nowadays a very challenging aspect of the environmental research. There are strong interests to develop novel semiconducting photocatalysts able to efficiently promote advanced oxidation reactions. The development of photocatalysts based on the mixtures of mixed oxides derived from layered double hydroxides (LDHs) - a family of naturally occurring anionic clays - might offer novel environmental-friendly solutions for the cost effective removal of organic pollutants. This work presents ZnO/ZnAl2O4, ZnO/Zn2TiO4 and ZnO/ZnCr2O4 as novel photocatalytic formulations for phenol degradation under UV irradiation. They were obtained by the controlled thermal treatment of the layered double hydroxides matrices (LDHs), as precursors materials, type ZnM-LDH (M = Al3+, Cr3+ or Ti4+). The LDHs were synthesized by the co-precipitation method at a constant pH. Controlled calcination at 650°C gives rise to solutions of mixed metal oxides. The structural and nanoarchitectonics characteristics of the studied catalysts were described by: XRD, SEM/TEM and TG/DTG techniques. Results show that in the photocatalytic process of the phenol degradation from aqueous solutions, ZnO/ZnCr2O4 and ZnO/ZnAl2O4 showed the best performance degrading ∼98% of phenol after 3.5 hs and 5 hs, respectively; while ZnO/Zn2TiO4 has degraded almost 80 % after 7.5 hs of UV irradiation. These results open new opportunities in the development of new cost effective photoresponsive formulations able to facilitate the photo-degradation of the organic pollution as “green” solution for removal of dangerous pollutants.

  2. Hydration of ordinary portland cements made from raw mix containing transition element oxides

    Energy Technology Data Exchange (ETDEWEB)

    Kakali, G.; Tsivilis, S.; Tsialtas, A. [National Technical Univ. of Athens (Greece)

    1998-03-01

    The use of industrial wastes, such as waste tires, waste oil, non-ferrous metal slag, or waste molding sand, as alternative raw materials and fuel in cement plants has been established from an environmental and recycling point of view and is expected to increase in the future. Cement is broadly used, among other hydraulic binders, in the solidification and stabilization of industrial and municipal wastes. This tendency to the use of wastes in the cement industry or the utilization of cement for the handling of wastes has led to the presence of several transition element compounds in the clinker and/or in the hydrated cement. The subject of this paper is the study of the hydration process in cements made from raw mixes containing transition element oxides. The oxides used are ZrO{sub 2}, V{sub 2}O{sub 5}, Ni{sub 2}O{sub 3}, CuO, Co{sub 2}O{sub 3}, MnO, Cr{sub 2}O{sub 3}, TiO{sub 2}, MoO{sub 3}, and ZnO, and their percentage in the raw mixes is 2% w/w. The cement pastes are cured in water for 24 h, 48 h, 7 days and 28 days. Hydration rate and products are studied by means of X-ray diffraction, differential scanning calorimetry, and thermogravimetric analysis. As it is concluded, the added oxides provoke, in general, a retardation of the hydration reactions. The effect is stronger during the first 2 days and becomes negligible at 28 days. The addition of CuO strongly delays the hydration even after 28 days. Its action is related to the formation of Cu(OH){sub 2} during the first days of hydration.

  3. PF-4 actinide disposition strategy

    Energy Technology Data Exchange (ETDEWEB)

    Margevicius, Robert W [Los Alamos National Laboratory

    2010-05-28

    The dwindling amount of Security Category I processing and storage space across the DOE Complex has driven the need for more effective storage of nuclear materials at LANL's Plutonium Facility's (PF-4's) vault. An effort was begun in 2009 to create a strategy, a roadmap, to identify all accountable nuclear material and determine their disposition paths, the PF-4 Actinide Disposition Strategy (PADS). Approximately seventy bins of nuclear materials with similar characteristics - in terms of isotope, chemical form, impurities, disposition location, etc. - were established in a database. The ultimate disposition paths include the material to remain at LANL, disposition to other DOE sites, and disposition to waste. If all the actions described in the document were taken, over half of the containers currently in the PF-4 vault would been eliminated. The actual amount of projected vault space will depend on budget and competing mission requirements, however, clearly a significant portion of the current LANL inventory can be either dispositioned or consolidated.

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

    Science.gov (United States)

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

    2009-05-15

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

  5. Characterization of CeO2-ZrO2 mixed oxides prepared by two different co-precipitation methods

    Institute of Scientific and Technical Information of China (English)

    YUE Mei; CUI Meisheng; ZHANG Na; LONG Zhiqi; HUANG Xiaowei

    2013-01-01

    A series of cerium zirconium mixed oxides were prepared by two co-precipitation methods using magnesium hydrogen carbonate (MHC) and mixed ammonia-ammonia hydrogen carbonate (AAHC) as precipitant respectively.The crystal structure,BET surface area and morphology of the produced cerium zirconium mixed oxides were characterized by X-ray diffraction (XRD),Brumauer-Emmett-Teller (BET) and scanning electron microscopy (SEM) techniques.The reduction-oxidation behavior and oxygen storage capacity (OSC) performance were also studied by temperature programmed reduction (TPR) and oxygen pulse chemical adsorption methods.The XRD results demonstrated that the cerium zirconium mixed oxides obtained by both methods possessed structure of cubic solid solution phase.The fresh surface area calcinated at 600 ℃,aged surface area after 1000 ℃ and OSC at 500 ℃ of cerium zirconium mixed oxides were determined to be 89.337,34.784 m2/g,and 567 μmol O2/g for MHC method and 122.010,46.307 m2/g,and 665 μmol O2/g for AAHC method,respectively.

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

    Energy Technology Data Exchange (ETDEWEB)

    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.

  7. Tuning Oleophobicity of Silicon Oxide Surfaces with Mixed Monolayers of Aliphatic and Fluorinated Alcohols.

    Science.gov (United States)

    Lee, Austin W H; Gates, Byron D

    2016-12-13

    We demonstrate the formation of mixed monolayers derived from a microwave-assisted reaction of alcohols with silicon oxide surfaces in order to tune their surface oleophobicity. This simple, rapid method provides an opportunity to precisely tune the constituents of the monolayers. As a demonstration, we sought fluorinated alcohols and aliphatic alcohols as reagents to form monolayers from two distinct constituents for tuning the surface oleophobicity. The first aspect of this study sought to identify a fluorinated alcohol that formed monolayers with a relatively high surface coverage. It was determined that 1H,1H,2H,2H-perfluoro-1-octanol yielded high quality monolayers with a water contact angle (WCA) value of ∼110° and contact angle values of ∼80° with toluene and hexadecane exhibiting both an excellent hydrophobicity and oleophobicity. Tuning of the oleophobicity of the modified silicon oxide surfaces was achieved by controlling the molar ratio of 1H,1H,2H,2H-perfluoro-1-octanol within the reaction mixtures. Surface oleophobicity progressively decreased with a decrease in the fluorinated alcohol content while the monolayers maintained their hydrophobicity with WCA values of ∼110°. The simple and reliable approach to preparing monolayers of a tuned composition that is described in this article can be utilized to control the fluorocarbon content of the hydrophobic monolayers on silicon oxide surfaces.

  8. Crystal structure of a mixed-valence μ-oxide Sn12 cluster

    Directory of Open Access Journals (Sweden)

    Marina M. Kireenko

    2014-11-01

    Full Text Available The mixed-valence μ-oxide Sn12 cluster, decacarbonyltetra-μ4-oxido-hexa-μ3-oxido-tetrakis[μ-2,2′-(pyridine-2,6-diylbis(1,1-diphenylethanolato]decatin(IIditin(IVdimolybdenum(O(2 Mo—Sn toluene heptasolvate, [Mo2Sn12(C33H27NO24O10(CO10]·7C7H8, has a crystallographically imposed inversion centre. The asymmetric unit also contains three and a half toluene solvent molecules, one of which is disordered about a centre of symmetry. The complex molecule comprises six distinct Sn atom species with four different coordination numbers, namely 3, 4, 5, and 6. The SnII atoms forming the central Sn10O10 core adopt distorted trigonal–pyramidal, square-pyramidal and octahedral coordination geometries provided by the μ-oxide atoms and by the O- and N-donor atoms of two pyridinediethanolate ligands. The terminal SnIV atoms have distorted trigonal–bipyramidal coordination geometries, with a μ4-oxide atom and the N atom of a pyridinediethanolate ligand occupying the axial positions, and the Mo atom of a Mo(CO5 group and the alkoxy O atoms of a ligand forming the equatorial plane. In the crystal, weak intra- and intermolecular C—H...O hydrogen bonds are observed.

  9. TUCS/phosphate mineralization of actinides

    Energy Technology Data Exchange (ETDEWEB)

    Nash, K.L. [Argonne National Lab., IL (United States)

    1997-10-01

    This program has as its objective the development of a new technology that combines cation exchange and mineralization to reduce the concentration of heavy metals (in particular actinides) in groundwaters. The treatment regimen must be compatible with the groundwater and soil, potentially using groundwater/soil components to aid in the immobilization process. The delivery system (probably a water-soluble chelating agent) should first concentrate the radionuclides then release the precipitating anion, which forms thermodynamically stable mineral phases, either with the target metal ions alone or in combination with matrix cations. This approach should generate thermodynamically stable mineral phases resistant to weathering. The chelating agent should decompose spontaneously with time, release the mineralizing agent, and leave a residue that does not interfere with mineral formation. For the actinides, the ideal compound probably will release phosphate, as actinide phosphate mineral phases are among the least soluble species for these metals. The most promising means of delivering the precipitant would be to use a water-soluble, hydrolytically unstable complexant that functions in the initial stages as a cation exchanger to concentrate the metal ions. As it decomposes, the chelating agent releases phosphate to foster formation of crystalline mineral phases. Because it involves only the application of inexpensive reagents, the method of phosphate mineralization promises to be an economical alternative for in situ immobilization of radionuclides (actinides in particular). The method relies on the inherent (thermodynamic) stability of actinide mineral phases.

  10. Final Report on Actinide Glass Scintillators for Fast Neutron Detection

    Energy Technology Data Exchange (ETDEWEB)

    Bliss, Mary; Stave, Jean A.

    2012-10-01

    This is the final report of an experimental investigation of actinide glass scintillators for fast-neutron detection. It covers work performed during FY2012. This supplements a previous report, PNNL-20854 “Initial Characterization of Thorium-loaded Glasses for Fast Neutron Detection” (October 2011). The work in FY2012 was done with funding remaining from FY2011. As noted in PNNL-20854, the glasses tested prior to July 2011 were erroneously identified as scintillators. The decision was then made to start from “scratch” with a literature survey and some test melts with a non-radioactive glass composition that could later be fabricated with select actinides, most likely thorium. The normal stand-in for thorium in radioactive waste glasses is cerium in the same oxidation state. Since cerium in the 3+ state is used as the light emitter in many scintillating glasses, the next most common substitute was used: hafnium. Three hafnium glasses were melted. Two melts were colored amber and a third was clear. It barely scintillated when exposed to alpha particles. The uses and applications for a scintillating fast neutron detector are important enough that the search for such a material should not be totally abandoned. This current effort focused on actinides that have very high neutron capture energy releases but low neutron capture cross sections. This results in very long counting times and poor signal to noise when working with sealed sources. These materials are best for high flux applications and access to neutron generators or reactors would enable better test scenarios. The total energy of the neutron capture reaction is not the only factor to focus on in isotope selection. Many neutron capture reactions result in energetic gamma rays that require large volumes or high densities to detect. If the scintillator is to separate neutrons from gamma rays, the capture reactions should produce heavy particles and few gamma rays. This would improve the detection of a

  11. Effect of different mixing ways in palladium/ceria-zirconia/alumina preparation on partial oxidation of methane

    Institute of Scientific and Technical Information of China (English)

    ZHANG Qingwei; WEN Jing; SHEN Meiqing; WANG Jun

    2008-01-01

    The effect of the mixing ways of Ce0.7Zr0.3O2-Al2O3 mixed oxides on the partial oxidations of methane (POM) was investigated over Pd/Ce0.7Zr0.3O2-Al2O3 catalysts, the mixing ways including salt precursor mixing (ATOM), precipitator mixing (MOL), and powder mechanically mixing (MECH), respectively. The test results indicated that among the three samples, Pd/ATOM had the best catalytic activity,while Pd/MOL had the best stability in the stability test. Both the activity sequences of the fresh and used samples were consistent with the order of Pd dispersion. According to the X-ray diffraction (XRD) and BET characterization, the interaction of Ce4+, Zr4+, and Al3+ in the ATOM mixed oxide was in favor of performing higher catalytic activity and thermal stability. The stability test indicated that Pd/MOL had the highest Pd dispersion and least coke formation on the active sites calculated by the H2-chemisorption and TG results, which was consid-ered to relate to its superior activity of POM to other catalysts.

  12. Electrolytic reduction of mixed (Fe, Ti) oxide using molten calcium chloride electrolyte

    Energy Technology Data Exchange (ETDEWEB)

    Panigrahi, Mrutyunjay, E-mail: mp@mail.tagen.tohoku.ac.jp [Institute of Multidisciplinary Research for Advanced Materials (IMRAM), Tohoku University, 2-1-1 Katahira, Aobaku, Sendai 980-8577 (Japan); Iizuka, Atsushi; Shibata, Etsuro; Nakamura, Takashi [Institute of Multidisciplinary Research for Advanced Materials (IMRAM), Tohoku University, 2-1-1 Katahira, Aobaku, Sendai 980-8577 (Japan)

    2013-02-15

    Highlights: Black-Right-Pointing-Pointer Tan et al. have electrolyzed mixtures of TiO{sub 2} and Fe{sub 2}O{sub 3} to produce alloys containing Fe-Ti intermetallic phases such as FeTi and Fe{sub 2}Ti using the FFC process. However, the produced alloys have a porous structure with many carbon impurities, e.g., titanium carbide (TiC). Most of the carbon contamination could be caused by the presence of carbon particles in the porous alloy structure. They did not mention any obvious ways of excluding carbon and other impurities, and only suggested that the use of mixed oxides with refined structures or using a single phase, namely ilmenite (FeO{center_dot}TiO{sub 2}), were methods of decreasing impurities in the formed alloys. For future industrialization, there is an urgent need for obvious ways of producing purer Fe-Ti alloys with dense structures, rather than porous structures, as these absorb carbon impurities. Black-Right-Pointing-Pointer Finally, we successfully reduced to a highly purified Fe-Ti intermetallic alloy of FeTi and {beta}-Ti (FeTi{sub 4}) phases. FeTi phases of size around 5-10 {mu}m were dispersed in a matrix of the {beta}-Ti (FeTi{sub 4}) phase. The carbon content of the electrolyzed alloy was as low as less than 0.01 mass%. It was suggested that the dense structure of the alloy of FeTi and {beta}-Ti (FeTi{sub 4}) avoided the inclusion of carbon particle impurities, unlike the porous alloy structure. - Abstract: The production of high-purity metals or alloys using effective technologies is critical for future industrialization. With this aim in mind, a fundamental study of electrolysis in molten CaCl{sub 2} electrolytes was conducted to develop a new production process for ferrotitanium (Fe-Ti) intermetallic alloys. Mixed solid oxides of TiO{sub 2} and Fe{sub 2}O{sub 3} were used in a molar ratio of 5.44:1.00. In this composition of Ti and Fe, FeTi and {beta}-Ti containing iron can co-exist in equilibrium. A mixed solid (Fe, Ti) oxide was reduced

  13. Structural and spectroscopic properties of high temperature prepared ZrO₂–TiO₂ mixed oxides

    Energy Technology Data Exchange (ETDEWEB)

    Gionco, Chiara [Dipartimento di Chimica and NIS (Nanostructured Surfaces and Interfaces), Università degli Studi di Torino, Via Giuria 7, 10125 Torino (Italy); Battiato, Alfio; Vittone, Ettore [Dipartimento di Fisica, Università degli Studi di Torino, Via Giuria 1, 10125 Torino (Italy); Paganini, Maria Cristina, E-mail: mariacristina.paganini@unito.it [Dipartimento di Chimica and NIS (Nanostructured Surfaces and Interfaces), Università degli Studi di Torino, Via Giuria 7, 10125 Torino (Italy); Giamello, Elio [Dipartimento di Chimica and NIS (Nanostructured Surfaces and Interfaces), Università degli Studi di Torino, Via Giuria 7, 10125 Torino (Italy)

    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 Zr

  14. Aqueous waste management for minor actinides and lanthanides separation process

    Energy Technology Data Exchange (ETDEWEB)

    Pochon, P.; Boyer, S.; Sans, D

    2004-07-01

    The French strategy of high level radioactive aqueous waste management is an incorporation in glassy fission products containers. Therefore, nitric acid soluble organic reagents needed for minor actinides and lanthanides selective separation from fission product solutions have to be sufficiently removed to reach carbon concentrations compatible with calcinator working. Thus, the ability of reagents to be oxidized under concentration conditions with or without denitration becomes a criteria of selection and have been studied. Further, if not working, other operations like hot hydrogen peroxide oxidation, catalyzed or not, are investigated. Reagents involved in this work are mainly complexing products (N-(2-Hydroxyethyl) Ethylene-diamine-tri-acetic Acid), pH keeping reagents (carboxylic acids like citric, glycolic, tartaric and lactic acid) and alkaline species (Tetramethylammonium hydroxide). Behaviour of acetic acid, which is often the main degradation product, has also been observed. In all cases, reaction products are characterized. (authors)

  15. Nanosecond multi-pulse laser-induced damage mechanisms in pure and mixed oxide thin films

    Energy Technology Data Exchange (ETDEWEB)

    Wagner, Frank R., E-mail: frank.wagner@fresnel.fr; Gouldieff, Céline, E-mail: celine.gouldieff@univ-rennes1.fr; Natoli, Jean-Yves, E-mail: jean-yves.natoli@fresnel.fr; Commandré, Mireille, E-mail: mireille.commandre@fresnel.fr

    2015-10-01

    We report on nanosecond laser-induced damage of pure and mixed oxide thin films deposited by ion beam sputtering. Silica, hafnia and alumina as well as their binary mixtures have been tested in S-on-1 mode at 355 nm and 266 nm using a multiscale approach. The results were analyzed qualitatively to discuss the different fatigue behaviors observed. The absence of a multi-photon absorption step in the 1-on-1 damage thresholds as a function of the band gap indicates defect-mediated damage mechanisms. During the multi-pulse experiments we observed laser-induced defects that cause fatigue effects and preexisting low-density defects, which are insensitive to multiple pulse irradiation. Depending on material and beam size both types of defects (preexisting and light-induced) may contribute equally to the observed damage probability. Comparing the fatigue behavior of the mixtures to their constituting pure oxides, we found that, in general, the fatigue behavior of binary mixtures cannot be interpolated from the behaviors of the pure oxides. - Highlights: • Multi-pulse laser damage can be analyzed plotting damaging shot number vs. fluence. • A fatigue effect was only observed for small laser beams, avoiding worse precursors. • The fatigue behavior of a mixture cannot be interpolated from the pure oxides. • SiO{sub 2} and Al{sub 2}O{sub 3} damage at 266 nm is due to deterministic material modifications. • Hafnia multi-pulse laser damage with small beams is stochastic even at 266 nm.

  16. Hydrothermal Synthesis, Characterization and Catalytic Properties of Nanoporous MoO3/ZrO2 Mixed Oxide

    Institute of Scientific and Technical Information of China (English)

    2006-01-01

    A nanoporous MoO3/ZrO2 mixed oxide was hydrothermally synthesized by hydrolyzing zirconium isopropoxide in the presence of a cationic surfactant, cetyltrimethylammonium bromide(CTAB). The crystal structure and the acidity of the obtained nanoporous MoO3/ZrO2 mixed oxide were determined by means of XRD, N2 adsorption-desorption and NH3-TPD, respectively. The isobutane/butene alkylation over the MoO3/ZrO2 catalyst was carried out in a fixed bed reactor. The results reveal that ZrO2 in MoO3/ZrO2 exists mainly in the tetragonal phase, and the catalyst samples possess large specific surface areas as well as moderate acidity for isobutane/butene alkylation. Compared with samples prepared by impregnation and sol-gel processes, MoO3/ZrO2 mixed oxide samples prepared in this work have a better catalytic activity.

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

    Science.gov (United States)

    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.

  18. Influence of thermal treatments on the basic and catalytic properties of Mg,Al-mixed oxides derived from hydrotalcites

    Directory of Open Access Journals (Sweden)

    R. Bastiani

    2004-06-01

    Full Text Available This work studied the influence of calcination conditions on basic properties and catalytic performance of Mg,Al-mixed oxides derived from a hydrotalcite sample (Al/(Al+Mg=0.20. Various heating rates, calcination atmospheres and lengths of calcination at 723K were evaluated. TPD of CO2 and retroaldolization of diacetone alcohol (DAA were used to determine the basic properties of the mixed oxides. The basic site density determined by TPD of CO2 showed a better correlation with catalytic activity for acetone/citral aldol condensation than the relative basicity obtained from retroaldolization of DAA. Calcination atmosphere was the parameter that influenced most the basic and the catalytic properties of the Mg,Al-mixed oxides, with calcination under dry air being the best choice.

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

    Directory of Open Access Journals (Sweden)

    Amaury Pérez-Verdejo

    2014-08-01

    Full Text Available 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.

  20. Bright blue photoluminescence from a mixed tin and manganese oxide xerogel prepared via sol-hydrothermal-gel process

    Institute of Scientific and Technical Information of China (English)

    Xiang Xia; Cheng Xiao-Feng; He Shao-Bo; Yuan Xiao-Dong; Zheng Wan-Guo; Li Zhi-Jie; Liu Chun-Ming; Zhou Wei-Lie; Zu Xiao-Tao

    2011-01-01

    A new blue photoluminescent material,a mixed tin and manganese oxide xerogel,is prepared via sol-hydrothermalgel process assisted by citric acid.The composition xerogel exhibits strong blue emission at room temperature,with an emission maximum at 434 nm under short (234 nm) or long-wavelength (343 nm) ultraviolet excitation.The photoluminescent excitation spectrum of the mixed tin and manganese oxide xerogel,monitored at an intensity maximum wavelength of 434 nm of the emission,consists of two excitation peaks at 234 nm and 343 nm.With heat treatment temperature increasing from 110 ℃ to 200 ℃,the blue emission intensity increases remarkably,whereas it is almost completely quenched after being treated at 300 ℃.The carbon impurities in the mixed tin and manganese oxide xerogel,confirmed by Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy,should be responsible for the bright blue photoluminescence.

  1. Electronic Structure of the Actinide Metals

    DEFF Research Database (Denmark)

    Johansson, B.; Skriver, Hans Lomholt

    1982-01-01

    Some recent experimental photoelectron spectroscopic results for the actinide metals are reviewed and compared with the theoretical picture of the basic electronic structure that has been developed for the actinides during the last decade. In particular the experimental data confirm the change from...... itinerant to localized 5f electron behaviour calculated to take place between plutonium and americium. From experimental data it is shown that the screening of deep core-holes is due to 5f electrons for the lighter actinide elements and 6d electrons for the heavier elements. A simplified model for the full...... LMTO electronic structure calculations is introduced. In this model the spd and 5f electronic contributions are treated as separable entities. It is shown that the model reproduces quite well the results from the full treatment. The equilibrium volume, cohesive energy and bulk modulus are calculated...

  2. Monazite as a suitable actinide waste form

    Energy Technology Data Exchange (ETDEWEB)

    Schlenz, Hartmut; Heuser, Julia; Schmitz, Stephan; Bosbach, Dirk [Forschungszentrum Juelich GmbH (Germany). Inst. fuer Energie und Klimaforschung (IEK), Nukleare Entsorgung und Reaktorsicherheit (IEK-6); Neumann, Andreas [Forschungszentrum Juelich GmbH (Germany). Inst. fuer Energie und Klimaforschung (IEK), Nukleare Entsorgung und Reaktorsicherheit (IEK-6); RWTH Aachen Univ. (Germany). Inst. for Crystallography

    2013-03-01

    The conditioning of radioactive waste from nuclear power plants and in some countries even of weapons plutonium is an important issue for science and society. Therefore the research on appropriate matrices for the immobilization of fission products and actinides is of great interest. Beyond the widely used borosilicate glasses, ceramics are promising materials for the conditioning of actinides like U, Np, Pu, Am, and Cm. Monazite-type ceramics with general composition LnPO{sub 4} (Ln = La to Gd) and solid solutions of monazite with cheralite or huttonite represent important materials in this field. Monazite appears to be a promising candidate material, especially because of its outstanding properties regarding radiation resistance and chemical durability. This article summarizes the most recent results concerning the characterization of monazite and respective solid solutions and the study of their chemical, thermal, physical and structural properties. The aim is to demonstrate the suitability of monazite as a secure and reliable waste form for actinides. (orig.)

  3. Structure, activity and kinetics of supported molybdenum oxide and mixed molybdenum-vanadium oxide catalysts prepared by flame spray pyrolysis for propane OHD

    DEFF Research Database (Denmark)

    Høj, Martin; Kessler, Thomas; Beato, Pablo

    2013-01-01

    reflectance UV-vis spectroscopy and evaluated as catalysts for the oxidative dehydrogenation (ODH) of propane. The results show that samples with high specific surface areas between 122 and 182 m2/g were obtained, resulting in apparent MoOx and VOx surface densities from 0.7 to 7.7 nm -2 and 1.5 to 1.9 nm-2......, respectively. Raman spectroscopy, UV-vis spectroscopy and XRD confirmed the high dispersion of molybdenum and vanadia species on γ-Al2O3 as the main crystalline phase. Only at the highest loading of 15 wt% Mo, with theoretically more than monolayer coverage, some crystalline molybdenum oxide was observed....... For the mixed molybdenum-vanadium oxide catalysts the surface species were separate molybdenum oxide and vanadium oxide monomers at low loadings of molybdenum, but with increasing molybdenum loading interactions between surface molybdenum and vanadium oxide species were observed with Raman spectroscopy...

  4. Synthesis and Evaluation of new Polyfunctional Molecules for Group Actinide Extraction; Synthese et evaluation de Nouvelles Molecules Polyfonctionnelles pour la Separation Groupee des Actinides

    Energy Technology Data Exchange (ETDEWEB)

    Marie, C.

    2009-10-15

    The aim of this project is to design new extracting molecules for spent nuclear fuel reprocessing. In order to minimize the long-term residual radiotoxicity of the waste, the GANEX process is an option based on homogeneous recycling of actinides. All actinides (U, Np, Pu, Am, Cm), present in a highly acidic aqueous solution, would be extracted together and separated from fission products (especially from lanthanides) using liquid-liquid extraction. In this context, twenty new bi-topic ligands constituted of a nitrogen poly-aromatic unit functionalized by amide groups were synthesized. Liquid-liquid extraction tests with these ligands dissolved alone in the organic phase show that N, N, N', N'-tetra-alkyl-6, 6''(2, 2':6', 2''-terpyridine)-diamides are able to selectively extract actinides at different oxidation states (Np(V et VI), U(VI), Pu(IV), Am(III), Cm(III)) from an aqueous solution 3M HNO{sub 3}. Nevertheless, actinides(III) are poorly extracted. According to crystallographic structures of complexes with Nd(III) and U(VI) determined by X-rays diffraction, these ligands are penta-dentate. In solution (methanol), complexes stoichiometries (1:1) of Nd(III), U(VI) and Pu(IV) were determined by electro-spray ionization mass spectrometry. Stability constants, evaluated by UV-visible spectrophotometry in MeOH/H{sub 2}O solutions, confirm the selectivity of ligands toward actinides(III) with respect to lanthanides(III). Associate to nuclear magnetic resonance experiments and DFT calculations (Density Functional Theory), a better knowledge of their coordination mode was achieved. (author)

  5. Fluorine and chlorine determination in mixed uranium-plutonium oxide fuel and plutonium dioxide

    Energy Technology Data Exchange (ETDEWEB)

    Elinson, S.V.; Zemlyanukhina, N.A.; Pavlova, I.V.; Filatkina, V.P.; Tsvetkova, V.T.

    1981-01-01

    A technique of fluorine and chlorine determination in the mixed uranium-plutonium oxide fuel and plutonium dioxide, based on their simultaneous separation by means of pyrohydrolysis, is developed. Subsequently, fluorine is determined by photometry with alizarincomplexonate of lanthanum or according to the weakening of zirconium colouring with zylenol orange. Chlorine is determined using the photonephelometric method according to the reaction of chloride-ion interaction with silver nitrate or by spectrophotometric method according to the reaction with mercury rhodanide. The lower limit of fluorine determination is -6x10/sup -5/ %, of chlorine- 1x10/sup -4/% in the sample of 1g. The relative mean quadratic deviation of the determination result (Ssub(r)), depends on the character of the material analyzed and at the content of nx10/sup -4/ - nx10/sup -3/ mass % is equal to from 0.05 to 0.32 for fluorine and from 0.11 to 0.35 for chlorine.

  6. Effect of CO2 on the Conversion of Isobutane over Iron, Cerium and Molybdenum Mixed Oxides

    Directory of Open Access Journals (Sweden)

    Daifallah Al-Dhayan

    2016-10-01

    Full Text Available A series of cerium and iron mixed oxide catalysts were prepared by thermal decomposition of Fe1.5PMo12O40 and Ce1.5PMo12O40 heteropolyanions mixture. The prepared catalysts have been characterized and tested for the conversion of isobutane in the presence of CO2. Characterization by XRD showed that besides Fe2O3 and CeO2, α-MoO3 was the main phase formed after thermal treatment. The effect of the support, the reaction temperature, and the presence of H2O in the reactant mixture was investigated. It has been found that the support enhanced both the conversion and isobutene selectivity. As for the reaction temperature and addition of water, it has been found that increasing the temperature increased both the conversion and isobutene selectivity, whereas the presence of water increased the isobutene selectivity but decreased the conversion.

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

    Energy Technology Data Exchange (ETDEWEB)

    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.

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

    Science.gov (United States)

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

    2014-02-03

    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.

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

    Energy Technology Data Exchange (ETDEWEB)

    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.

  10. Thermochemical prediction of chemical form distributions of fission products in LWR mixed oxide fuels

    Energy Technology Data Exchange (ETDEWEB)

    Moriyama, Kouki; Furuya, Hirotaka [Kyushu Univ., Fukuoka (Japan). Faculty of Engineering

    1998-06-01

    Radial distribution of chemical forms of fission products (FPs) in LWR mixed oxide (MOX) fuel pins was theoretically predicted by a thermochemical computer code SOLGASMIX-PV. The amounts of fission products generated in the fuel were calculated by ORIGEN-2 code, and the radial distributions of temperature and oxygen potential were calculated by taking the neutron depression and oxygen redistribution in the fuel into account. A fuel pellet was radially divided into 51 sections and chemical forms of FPs were calculated in each section. The effects of linear heat rating (LHR) and average O/U ratio on radial distribution of chemical form were evaluated. It was found that the radial distribution of chemical forms depends strongly on the LHR and the O/M ratio, and is not proportional to that of burnup. (author)

  11. Mixed Nanostructured Ti-W Oxides Films for Efficient Electrochromic Windows

    Directory of Open Access Journals (Sweden)

    Nguyen Nang Dinh

    2012-01-01

    Full Text Available With the aim to enhance the electrochromic (EC efficiency and electrochemical stability of electrochromic devices (ECD, mixed nanostructured TiO2/WO3 films were prepared by an electrochemical deposition method with the purpose of adding WO3 nanoparticles to porous nanocrystalline doctor-blade TiO2 (nc-TiO2 films. The results of the characterization of electrochromic properties in 1 M LiClO4 + propylene carbonate (LiClO4 + PC of both the nc-TiO2/F-doped tin oxide (FTO and WO3/TiO2/FTO configurations showed the reversible coloration and bleaching of the ECDs. The response time of the ECD coloration of WO3/TiO2/FTO was found to be as small as 2 sec, and its coloration efficiency (CE as high as 35.7 cm2 × C−1. By inserting WO3 nanoparticles into the porous TiO2 structures, WO3/TiO2 heterojunctions were formed in the films, consequently enabling both the CE and electrochemical stability of the working electrodes to be considerably enhanced. Since a large-area WO3/TiO2 can be prepared by the doctor-blade technique followed by the electrochemical deposition process, mixed nanostructured Ti-W oxides electrodes constitute a good candidate for smart window applications, taking advantage of the excellent coloration and stability properties as well as the simple and economical fabrication process involved.

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

    Science.gov (United States)

    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.

  13. Spin–orbit coupling in actinide cations

    DEFF Research Database (Denmark)

    Bagus, Paul S.; Ilton, Eugene S.; Martin, Richard L.

    2012-01-01

    The limiting case of Russell–Saunders coupling, which leads to a maximum spin alignment for the open shell electrons, usually explains the properties of high spin ionic crystals with transition metals. For actinide compounds, the spin–orbit splitting is large enough to cause a significantly reduced...... spin alignment. Novel concepts are used to explain the dependence of the spin alignment on the 5f shell occupation. We present evidence that the XPS of ionic actinide materials may provide direct information about the angular momentum coupling within the 5f shell....

  14. Actinide and fission product separation and transmutation

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    1993-07-01

    The second international information exchange meeting on actinide and fission product separation and transmutation, took place in Argonne National Laboratory in Illinois United States, on 11-13 November 1992. The proceedings are presented in four sessions: Current strategic system of actinide and fission product separation and transmutation, progress in R and D on partitioning processes wet and dry, progress in R and D on transmutation and refinements of neutronic and other data, development of the fuel cycle processes fuel types and targets. (A.L.B.)

  15. Conversion of Syngas-Derived C2+ Mixed Oxygenates to C3-C5 Olefins over ZnxZryOz Mixed Oxides Catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Smith, Colin D.; Lebarbier, Vanessa M.; Flake, Matthew D.; Ramasamy, Karthikeyan K.; Kovarik, Libor; Bowden, Mark E.; Onfroy, Thomas; Dagle, Robert A.

    2016-04-01

    In this study we report on a ZnxZryOz mixed oxide type catalyst capable of converting a syngas-derived C2+ mixed oxygenate feedstock to isobutene-rich olefins. Aqueous model feed comprising of ethanol, acetaldehyde, acetic acid, ethyl acetate, methanol, and propanol was used as representative liquid product derived from a Rh-based mixed oxygenate synthesis catalyst. Greater than 50% carbon yield to C3-C5 mixed olefins was demonstrated when operating at 400-450oC and 1 atm. In order to rationalize formation of the products observed feed components were individually evaluated. Major constituents of the feed mixture (ethanol, acetaldehyde, acetic acid, and ethyl acetate) were found to produce isobutene-rich olefins. C-C coupling was also demonstrated for propanol feedstock - a minor constituent of the mixed oxygenate feed - producing branched C6 olefins, revealing scalability to alcohols higher than ethanol following an analogous reaction pathway. Using ethanol and propanol feed mixtures, cross-coupling reactions produced mixtures of C4, C5, and C6 branched olefins. The presence of H2 in the feed was found to facilitate hydrogenation of the ketone intermediates, thus producing straight chain olefins as byproducts. While activity loss from coking is observed complete catalyst regeneration is achieved by employing mild oxidation. For conversion of the mixed oxygenate feed a Zr/Zn ratio of 2.5 and a reaction temperature of 450oC provides the best balance of stability, activity, and selectivity. X-ray diffraction and scanning transmission electron microscopy analysis reveals the presence of primarily cubic phase ZrO2 and a minor amount of the monoclinic phase, with ZnO being highly dispersed in the lattice. The presence of ZnO appears to stabilize the cubic phase resulting in less monoclinic phase as the ZnO concentration increases. Infrared spectroscopy shows the mixed oxide acid sites are characterized as primarily Lewis type acidity. The direct relationship between

  16. Removal of Hazardous Pollutants from Wastewaters: Applications of TiO2-SiO2 Mixed Oxide Materials

    Directory of Open Access Journals (Sweden)

    Shivatharsiny Rasalingam

    2014-01-01

    Full Text Available 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 application of TiO2-SiO2 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.

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

    Science.gov (United States)

    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.

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

    Science.gov (United States)

    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 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.

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

    Science.gov (United States)

    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.

  20. Actinide Solubility and Speciation in the WIPP [PowerPoint

    Energy Technology Data Exchange (ETDEWEB)

    Reed, Donald T. [Los Alamos National Lab. (LANL), Los Alamos, NM (United States)

    2015-11-02

    The presentation begins with the role and need for nuclear repositories (overall concept, international updates (Sweden, Finland, France, China), US approach and current status), then moves on to the WIPP TRU repository concept (design, current status--safety incidents of February 5 and 14, 2014, path forward), and finally considers the WIPP safety case: dissolved actinide concentrations (overall approach, oxidation state distribution and redox control, solubility of actinides, colloidal contribution and microbial effects). The following conclusions are set forth: (1) International programs are moving forward, but at a very slow and somewhat sporadic pace. (2) In the United States, the Salt repository concept, from the perspective of the long-term safety case, remains a viable option for nuclear waste management despite the current operational issues/concerns. (3) Current model/PA prediction (WIPP example) are built on redundant conservatisms. These conservatisms are being addressed in the ongoing and future research to fill existing data gaps--redox control of plutonium by Fe(0, II), thorium (analog) solubility studies in simulated brine, contribution of intrinsic and biocolloids to the mobile concentration, and clarification of microbial ecology and effects.

  1. Fabrication of nitride fuels for transmutation of minor actinides

    Science.gov (United States)

    Minato, Kazuo; Akabori, Mitsuo; Takano, Masahide; Arai, Yasuo; Nakajima, Kunihisa; Itoh, Akinori; Ogawa, Toru

    2003-07-01

    At the Japan Atomic Energy Research Institute, the concept of the transmutation of minor actinides (MA: Np, Am and Cm) with accelerator-driven systems is being studied. The MA nitride fuel has been chosen as a candidate because of the possible mutual solubility among the actinide mononitrides and excellent thermal properties besides supporting hard neutron spectrum. MA nitrides of NpN, (Np, Pu)N, (Np, U)N, AmN, (Am, Y)N, (Am, Zr)N and (Cm, Pu)N were prepared from the oxides by the carbothermic reduction method. The prepared MA nitrides were examined by X-ray diffraction and the contents of impurities of oxygen and carbon were measured. The fabrication conditions for MA nitrides were improved so as to reduce the impurity contents. For an irradiation test of U-free nitride fuels, pellets of (Pu, Zr)N and PuN + TiN were prepared and a He-bonded fuel pin was fabricated. The irradiation test started in May 2002 and will go on for two years in the Japan Materials Testing Reactor.

  2. Comparison of the redox activities of sol-gel and conventionally prepared Bi-Mo-Ti mixed oxides

    Energy Technology Data Exchange (ETDEWEB)

    Wildberger, M.; Grundwaldt, J.D.; Mallat, T.; Baiker, A. [Lab. of Technical Chemistry, Swiss Federal Inst. of Technology, ETH-Zentrum, Zuerich (Switzerland)

    1998-12-31

    Novel sol-gel Bi-Mo-Ti oxides have been prepared and characterized by XRD, XPS, FT-Raman and HRTEM. The surface Bi{sup 3+} and Mo{sup 6+} species of some xerogels and an aerogel could be reduced and oxidized at room temperature, whereas the conventionally prepared reference materials were not reduced by H{sub 2} below 300 C. The unusual redox properties, under very mild conditions, are likely due to the unique morphology of Bi-Mo-oxides stabilized by titania. During butadiene oxidation to furan at above 400 C to sol-gel mixed oxides restructured considerably and their performance was barely better than that of titania-supported Bi-Mo oxides. (orig.)

  3. Properties of TiO2-SiO2 Mixed Oxides and Photocatalytic Oxidation of Heptane and Sulfur Dioxide

    Institute of Scientific and Technical Information of China (English)

    XIE Chao; XU Zi-li; YANG Qiu-jing; LI Na; WANG De-bao; DU Yao-guo

    2005-01-01

    A series of TiO2-XSiO2[X denotes the molar fraction(%) of silica in the mixed oxides] with different n(Ti)/n(Si) ratios was prepared with ammonia water as a hydrolysis catalyst. The photocatalysts prepared were characterized by XRD, thermal analysis, FTIR, UV-Vis and SPS. The characterization results of FTIR and UV-Vis spectra show that Ti atoms were gradually changed from octahedral coordination to tetrahedral coordination with the addition of silica, which is not beneficial for obtaining strong Brnsted acidity and higher photocatalytic activity. The photocatalytic activity experiments, which were conducted by using heptane(or SO2) as the model reactant, showed that TiO2-SiO2 containing a suitable amount of silica can exhibit much higher photocatalytic activity than pure TiO2. The enhanced photocatalytic activity can be attributed to three following factors: (1) smaller crystalline size; (2) higher thermal stability; (3) the new strong Brnsted acidity.

  4. EBSD and TEM characterization of high burn-up mixed oxide fuel

    Science.gov (United States)

    Teague, Melissa; Gorman, Brian; Miller, Brandon; 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 ∼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 ∼2.5× 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 ∼25 μm 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.

  5. Enrichment and characteristics of mixed methane-oxidizing bacteria from a Chinese coal mine.

    Science.gov (United States)

    Jiang, Hao; Duan, Changhong; Luo, Mingfang; Xing, Xin-Hui

    2016-12-01

    In methane-rich environments, methane-oxidizing bacteria usually occur predominantly among consortia including other types of microorganisms. In this study, artificial coal bed gas and methane gas were used to enrich mixed methanotrophic cultures from the soil of a coal mine in China, respectively. The changes in microbial community structure and function during the enrichment were examined. The microbial diversity was reduced as the enrichment proceeded, while the capacity for methane oxidation was significantly enhanced by the increased abundance of methanotrophs. The proportion of type II methanotrophs increased greatly from 7.84 % in the sampled soil to about 50 % in the enrichment cultures, due to the increase of methane concentration. After the microbial community of the cultures got stable, Methylomonas and Methylocystis became the dominant type I and type II methanotrophs, while Methylophilus was the prevailing methylotroph. The sequences affiliated with pigment-producing strains, Methylomonas rubra, Hydrogenophaga sp. AH-24, and Flavobacterium cucumis, could explain the orange appearance of the cultures. Comparing the two cultures, the multi-carbon sources in the artificial coal bed gas caused more variety of non-methanotrophic bacteria, but did not help to maintain the diversity or to increase the quantity and activity of methanotrophs. The results could help to understand the succession and interaction of microbial community in a methane-driven ecosystem.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2016-05-01

    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 other catalysts, with promising activity compared to related catalysts in the literature. 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.

  7. Water gas shift reaction over Cu catalyst supported by mixed oxide materials for fuel cell application

    Directory of Open Access Journals (Sweden)

    Tepamatr Pannipa

    2016-01-01

    Full Text Available The water gas shift activities of Cu on ceria and Gd doped ceria have been studied for the further enhancement of hydrogen purity [1] after the steam reforming of ethanol. The catalytic properties of commercial catalysts were also studied to compare with the as-prepared catalysts. Copper-containing cerium oxide materials are shown in this work to be suitable for the high temperature. Copper-ceria is a stable high-temperature shift catalyst, unlike iron-chrome catalysts that deactivate severely in CO2-rich gases. We found that 5%Cu/10%GDC(D has much higher activity than other copper ceria based catalysts. The finely dispersed CuO species is favorable to the higher activity, which explained the activity enhancement of this catalyst. The kinetics of the WGS reaction over Cu catalysts supported by mixed oxide materials were measured in the temperature range 200-400 °C. An independence of the CO conversion rate on CO2 and H2 was found.

  8. Mg-Fe-mixed oxides derived from layered double hydroxides: A study of the surface properties

    Directory of Open Access Journals (Sweden)

    Marinković-Nedučin Radmila P.

    2011-01-01

    Full Text Available The influence of surface properties on the selectivity of the synthesized catalysts was studied, considering that their selectivity towards particular hydrocarbons is crucial for their overall activity in the chosen Fischer- -Tropsch reaction. Magnesium- and iron-containing layered double hydroxides (LDH, with the general formula: [Mg1-xFex(OH2](CO3x/2?mH2O, x = = n(Fe/(n(Mg+n(Fe, synthesized with different Mg/Fe ratio and their thermally derived mixed oxides were investigated. Magnesium was chosen because of its basic properties, whereas iron was selected due to its well-known high Fischer-Tropsch activity, redox properties and the ability to form specific active sites in the layered LDH structure required for catalytic application. The thermally less stable multiphase system (synthesized outside the optimal single LDH phase range with additional Fe-phase, having a lower content of surface acid and base active sites, a lower surface area and smaller fraction of smaller mesopores, showed higher selectivity in the Fischer-Tropsch reaction. The results of this study imply that the metastability of derived multiphase oxides structure has a greater influence on the formation of specific catalyst surface sites than other investigated surface properties.

  9. Catalytic propane dehydrogenation over In₂O₃–Ga₂O₃ mixed oxides

    Energy Technology Data Exchange (ETDEWEB)

    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. (Dow); (GIT)

    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.

  10. A solid oxide photoelectrochemical cell with UV light-driven oxygen storage in mixed conducting electrodes

    Science.gov (United States)

    Walch, Gregor; Rotter, Bernhard; Brunauer, Georg Christoph; Esmaeili, Esmaeil; Opitz, Alexander Karl; Kubicek, Markus; Summhammer, Johann; Ponweiser, Karl

    2017-01-01

    A single crystalline SrTiO3 working electrode in a zirconia-based solid oxide electrochemical cell is illuminated by UV light at temperatures of 360–460 °C. In addition to photovoltaic effects, this leads to the build-up of a battery-type voltage up to more than 300 mV. After switching off UV light, this voltage only slowly decays. It is caused by UV-induced oxygen incorporation into the mixed conducting working electrode and thus by changes of the oxygen stoichiometry δ in SrTiO3–δ under UV illumination. These changes of the oxygen content could be followed in time-dependent voltage measurements and also manifest themselves in time-dependent resistance changes during and after UV illumination. Discharge currents measured after UV illumination reveal that a large fraction of the existing oxygen vacancies in SrTiO3 become filled under UV light. Additional measurements on cells with TiO2 thin film electrodes show the broader applicability of this novel approach for transforming light into chemical energy and thus the feasibility of solid oxide photoelectrochemical cells (SOPECs) in general and of a “light-charged oxygen battery” in particular. PMID:28261480

  11. Transparent conductive electrodes of mixed TiO2−x–indium tin oxide for organic photovoltaics

    KAUST Repository

    Lee, Kyu-Sung

    2012-05-22

    A transparent conductive electrode of mixed titanium dioxide (TiO2−x)–indium tin oxide (ITO) with an overall reduction in the use of indium metal is demonstrated. When used in organic photovoltaicdevices based on bulk heterojunction photoactive layer of poly (3-hexylthiophene) and [6,6]-phenyl C61 butyric acid methyl ester, a power conversion efficiency of 3.67% was obtained, a value comparable to devices having sputtered ITO electrode. Surface roughness and optical efficiency are improved when using the mixed TiO2−x–ITO electrode. The consumption of less indium allows for lower fabrication cost of such mixed thin filmelectrode.

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

    Energy Technology Data Exchange (ETDEWEB)

    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.

  13. Application of Ni-Oxide@TiO2 Core-Shell Structures to Photocatalytic Mixed Dye Degradation, CO Oxidation, and Supercapacitors

    Directory of Open Access Journals (Sweden)

    Seungwon Lee

    2016-12-01

    Full Text Available Performing diverse application tests on synthesized metal oxides is critical for identifying suitable application areas based on the material performances. In the present study, Ni-oxide@TiO2 core-shell materials were synthesized and applied to photocatalytic mixed dye (methyl orange + rhodamine + methylene blue degradation under ultraviolet (UV and visible lights, CO oxidation, and supercapacitors. Their physicochemical properties were examined by field-emission scanning electron microscopy, X-ray diffraction analysis, Fourier-transform infrared spectroscopy, and UV-visible absorption spectroscopy. It was shown that their performances were highly dependent on the morphology, thermal treatment procedure, and TiO2 overlayer coating.

  14. Effect of loading content of copper oxides on performance of Mn-Cu mixed oxide catalysts for catalytic combustion of benzene

    Institute of Scientific and Technical Information of China (English)

    CAO Hongyan; LI Xiaoshuang; CHEN Yaoqiang; GONG Maochu; WANG Jianli

    2012-01-01

    A series of Mn-Cu mixed oxide catalysts were prepared by precipitation method.The catalysts were characterized by N2 adsorption-desorption,H2-TPR and XPS.When the loading ratio of manganese oxides to copper oxides was 8:2 or 7:3,the catalysts possessed better catalytic activity,and benzene was converted completely at 558 K.Results of H2-TPR showed that the loading of a small amount of copper oxides decreased the reduction temperature of catalysts.Results of XPS showed that the loading of a small amount of copper oxides increased the proportion of manganese and defective oxygen on the surface of catalysts,and stabilized manganese at higher oxidation state.And the catalyst with the loading ratio 7:3 was a little worse than 8:2,since the interaction between manganese oxides and copper oxides is too strong,copper oxides migrate to the surface of catalysts and manganese oxides in excess are immerged.

  15. ENHANCED CHEMICAL CLEANING OF SRS WASTE TANKS TO IMPROVE ACTINIDE SOLUBILITY

    Energy Technology Data Exchange (ETDEWEB)

    Rudisill, T.; Thompson, M.

    2011-09-20

    Processes for the removal of residual sludge from SRS waste tanks have historically used solutions containing up to 0.9 M oxalic acid to dissolve the remaining material following sludge removal. The selection of this process was based on a comparison of a number of studies performed to evaluate the dissolution of residual sludge. In contrast, the dissolution of the actinide mass, which represents a very small fraction of the waste, has not been extensively studied. The Pu, Np, and Am in the sludge is reported to be present as hydrated and crystalline oxides. To identify aqueous solutions which have the potential to increase the solubility of the actinides, the alkaline and mildly acidic test solutions shown below were selected as candidates for use in a series of solubility experiments. The efficiency of the solutions in solubilizing the actinides was evaluated using a simulated sludge prepared by neutralizing a HNO{sub 3} solution containing Pu, Np, and Am. The hydroxide concentration was adjusted to a 1.2 M excess and the solids were allowed to age for several weeks prior to starting the experiments. The sludge was washed with 0.01 M NaOH to prepare the solids for use. Following the addition of an equal portion of the solids to each test solution, the concentrations of Pu, Np, and Am were measured as a function of time over a 792 h (33 day) period to provide a direct comparison of the efficiency of each solution in solubilizing the actinide elements. Although the composition of the sludge was limited to the hydrated actinide oxides (and did not contain other components of demonstrated importance), the results of the study provides guidance for the selection of solutions which should be evaluated in subsequent tests with a more realistic surrogate sludge and actual tank waste.

  16. Transmuting minor actinides with thermal reactor neutrons

    Directory of Open Access Journals (Sweden)

    Yu. A Kazansky

    2015-11-01

    The final conclusion about the practicability of Americium and Curium transmutation must be drawn by taking into account in the considered scenarios the difference in probability of the environmental release, the difference of biological effect and the transmutation efficiency of minor actinides continuously fed to spent fuel storages by the operating nuclear energy industry.

  17. Actinide valences in xenotime and monazite

    Energy Technology Data Exchange (ETDEWEB)

    Vance, E.R. [Institute of Materials Engineering, Australian Nuclear Science and Technology Organisation, Locked Bag 2001 Kirrawee DC, NSW 2232 (Australia); Zhang, Y., E-mail: yzx@ansto.gov.au [Institute of Materials Engineering, Australian Nuclear Science and Technology Organisation, Locked Bag 2001 Kirrawee DC, NSW 2232 (Australia); McLeod, T.; Davis, J. [Institute of Materials Engineering, Australian Nuclear Science and Technology Organisation, Locked Bag 2001 Kirrawee DC, NSW 2232 (Australia)

    2011-02-28

    Tetravalent U, Np and Pu can be substituted by ceramic methods into the rare earth site of xenotime and monazite in air atmospheres using Ca ions as charge compensators, while no evidence of penta- or hexavalent actinide ions was found. Some Pu{sup 3+} and Np{sup 3+} can be incorporated in xenotime samples fired in a reducing atmosphere.

  18. Actinide and fission product partitioning and transmutation

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    1995-07-01

    The third international information exchange meeting on actinide and fission product partitioning and transmutation, took place in Cadarache France, on 12-14 December 1994. The proceedings are presented in six sessions : an introduction session, the major programmes and international cooperation, the systems studies, the reactors fuels and targets, the chemistry and a last discussions session. (A.L.B.)

  19. Scalar Static Polarizabilities of Lanthanides and Actinides

    CERN Document Server

    Dzuba, V A; Flambaum, V V

    2014-01-01

    We calculate scalar static polarizabilities for lanthanides and actinides, the atoms with open $4f$ or $5f$ subshell. We show that polarizabilities of the low states are approximately the same for all states of given configuration and present a way of calculating them reducing valence space to just two or three valence electrons occupying $6s$ and $5d$ states for lanthanides or $7s$ and $6d$ states for actinides while $4f$ and $5f$ states are considered to be in the core. Configuration interaction technique is used to calculate polarizabilities of lanthanides and actinides for all states of the $4f^n6s^2$ and $4f^{n-1}6s^25d$ configurations of lanthanides and all states of the $5f^{n}7s^2$ and $5f^{n-1}7s^26d$ configurations of actinides. Polarizability of the electron core (including f-orbitals) has been calculated in the RPA approximation.

  20. Actinide measurements by AMS using fluoride matrices

    Energy Technology Data Exchange (ETDEWEB)

    Cornett, R.J., E-mail: Jack.Cornett@uottawa.ca [André E. Lalonde AMS Laboratory, University of Ottawa, 150 Louis Pasteur, Ottawa, ON K1N 6N5 (Canada); Department of Earth Sciences, University of Ottawa, 150 Louis Pasteur, Ottawa, ON K1N 6N5 (Canada); Kazi, Z.H. [André E. Lalonde AMS Laboratory, University of Ottawa, 150 Louis Pasteur, Ottawa, ON K1N 6N5 (Canada); Department of Earth Sciences, University of Ottawa, 150 Louis Pasteur, Ottawa, ON K1N 6N5 (Canada); Zhao, X.-L. [André E. Lalonde AMS Laboratory, University of Ottawa, 150 Louis Pasteur, Ottawa, ON K1N 6N5 (Canada); Department of Physics, University of Ottawa, 150 Louis Pasteur, Ottawa, ON K1N 6N5 (Canada); Chartrand, M.G. [André E. Lalonde AMS Laboratory, University of Ottawa, 150 Louis Pasteur, Ottawa, ON K1N 6N5 (Canada); Department of Earth Sciences, University of Ottawa, 150 Louis Pasteur, Ottawa, ON K1N 6N5 (Canada); Charles, R.J.; Kieser, W.E. [André E. Lalonde AMS Laboratory, University of Ottawa, 150 Louis Pasteur, Ottawa, ON K1N 6N5 (Canada); Department of Physics, University of Ottawa, 150 Louis Pasteur, Ottawa, ON K1N 6N5 (Canada)

    2015-10-15

    Actinides can be measured by alpha spectroscopy (AS), mass spectroscopy or accelerator mass spectrometry (AMS). We tested a simple method to separate Pu and Am isotopes from the sample matrix using a single extraction chromatography column. The actinides in the column eluent were then measured by AS or AMS using a fluoride target matrix. Pu and Am were coprecipitated with NdF{sub 3}. The strongest AMS beams of Pu and Am were produced when there was a large excess of fluoride donor atoms in the target and the NdF{sub 3} precipitates were diluted about 6–8 fold with PbF{sub 2}. The measured concentrations of {sup 239,240}Pu and {sup 241}Am agreed with the concentrations in standards of known activity and with two IAEA certified reference materials. Measurements of {sup 239,240}Pu and {sup 241}Am made at A.E. Lalonde AMS Laboratory agree, within their statistical uncertainty, with independent measurements made using the IsoTrace AMS system. This work demonstrated that fluoride targets can produce reliable beams of actinide anions and that the measurement of actinides using fluorides agree with published values in certified reference materials.

  1. Assessment of SFR fuel pin performance codes under advanced fuel for minor actinide transmutation

    Energy Technology Data Exchange (ETDEWEB)

    Bouineau, V.; Lainet, M.; Chauvin, N.; Pelletier, M. [French Alternative Energies and Atomic Energy Commission - CEA, CEA Cadarache, DEN/DEC/SESC, 13108 Saint Paul lez Durance (France); Di Marcello, V.; Van Uffelen, P.; Walker, C. [European Commission, Joint Research Centre, Institute for Transuranium Elements, Hermann-von-Helmholtz-Platz 1, D- 76344 Eggenstein-Leopoldshafen (Germany)

    2013-07-01

    Americium is a strong contributor to the long term radiotoxicity of high activity nuclear waste. Transmutation by irradiation in nuclear reactors of long-lived nuclides like {sup 241}Am is, therefore, an option for the reduction of radiotoxicity and residual power packages as well as the repository area. In the SUPERFACT Experiment four different oxide fuels containing high and low concentrations of {sup 237}Np and {sup 241}Am, representing the homogeneous and heterogeneous in-pile recycling concepts, were irradiated in the PHENIX reactor. The behavior of advanced fuel materials with minor actinide needs to be fully characterized, understood and modeled in order to optimize the design of this kind of fuel elements and to evaluate its performances. This paper assesses the current predictability of fuel performance codes TRANSURANUS and GERMINAL V2 on the basis of post irradiation examinations of the SUPERFACT experiment for pins with low minor actinide content. Their predictions have been compared to measured data in terms of geometrical changes of fuel and cladding, fission gases behavior and actinide and fission product distributions. The results are in good agreement with the experimental results, although improvements are also pointed out for further studies, especially if larger content of minor actinide will be taken into account in the codes. (authors)

  2. 77 FR 70193 - Shaw Areva MOX Services (Mixed Oxide Fuel Fabrication Facility); Notice of Atomic Safety and...

    Science.gov (United States)

    2012-11-23

    ... From the Federal Register Online via the Government Publishing Office NUCLEAR REGULATORY 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...

  3. Technology, safety and costs of decommissioning a reference small mixed oxide fuel fabrication plant. Volume 1. Main report

    Energy Technology Data Exchange (ETDEWEB)

    Jenkins, C. E.; Murphy, E. S.; Schneider, K J

    1979-01-01

    Detailed technology, safety and cost information are presented for the conceptual decommissioning of a reference small mixed oxide fuel fabrication plant. Alternate methods of decommissioning are described including immediate dismantlement, safe storage for a period of time followed by dismantlement and entombment. Safety analyses, both occupational and public, and cost evaluations were conducted for each mode.

  4. Measurement and modelling of the defect chemistry and transport properties of ceramic oxide mixed ionic and electronic conductors

    NARCIS (Netherlands)

    Dalslet, Bjarke Thomas

    2008-01-01

    The mixed ionic and electronic conducting fluorite and perovskite materials examined in this thesis are all oxide ion conducting materials. The defect chemistry and transport properties of a number of these materials are measured using: 1) a measurement technique using an oxygen pump and an electrol

  5. Measurement and modelling of the defect chemistry and transport properties of ceramic oxide mixed ionic and electronic conductors

    DEFF Research Database (Denmark)

    Dalslet, Bjarke Thomas

    2008-01-01

    The subject of this thesis is ceramic mixed ionic and electronic conductors (MIECs). MIECs have potential uses, such as solid oxygen permeation membranes, as catalysts, and as components in fuel cells. The MIECs examined in this thesis are all oxide ion conducting materials. This thesis describes...

  6. Structure and growth of polymeric niobia-silica mixed-oxide sols for microporous molecular sieving membranes: a SAXS study

    NARCIS (Netherlands)

    Boffa, V.; Castricum, H.L.; Garcia, R.; Schmuhl, R.; Petukhov, A.V.; Blank, D.H.A.; ten Elshof, J.E.

    2009-01-01

    Branched polymeric niobia-silica (NS) mixed-oxide sols with a Nb:Si molar ratio between 0.33 and 0.8 were made by acid-catalyzed sol-gel synthesis and characterized using small-angle X-ray scattering (SAXS) and dynamic light scattering (DLS). The growth rate of NS sols after addition of a niobium al

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

    Science.gov (United States)

    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. Engineering test plan for US/UK higher actinides irradiations tests

    Energy Technology Data Exchange (ETDEWEB)

    Basmajian, J A

    1981-03-01

    The objective of the Higher Actinides Irradiations Program is to verify the neutronic and irradiation performance of americium and curium oxides in a fast reactor. The data obtained from the irradiation will be used to assess the basic neutronics parameters for actinide elements and determine the irradiation potential of the oxides of {sup 241}Am and {sup 244}Cm. This information has application in breeder reactor physics, fuel cycle analysis and assessment of waste management options. The irradiation test program is a cooperative effort wherein the US is supplying the completed irradiation test pins, while the UK will perform the irradiation in their Prototype Fast Reactor (PFR). Postirradiation examination and data analyses will be conducted on a cooperative basis, with some examinations performed in the UK and others in the US. 5 figs., 5 tabs.

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

    Energy Technology Data Exchange (ETDEWEB)

    Ryskamp, J.M.; Sterbentz, J.W.; Chang, G.S. [and others

    1995-09-01

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

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

    Science.gov (United States)

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

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

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

    Energy Technology Data Exchange (ETDEWEB)

    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.

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

    Directory of Open Access Journals (Sweden)

    B. Seok

    2012-12-01

    Full Text Available 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

  13. Adventures in Actinide Chemistry: A Year of Exploring Uranium and Thorium in Los Alamos

    Energy Technology Data Exchange (ETDEWEB)

    Pagano, Justin [Los Alamos National Lab. (LANL), Los Alamos, NM (United States)

    2016-01-08

    The first part of this collection of slides is concerned with considerations when working with actinides. The topics discussed in the document as a whole are the following: Actinide chemistry vs. transition metal chemistry--tools we can use; New synthetic methods to obtain actinide hydrides; Actinide metallacycles: synthesis, structure, and properties; and Reactivity of actinide metallacycles.

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

    Science.gov (United States)

    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. Facilities for preparing actinide or fission product-based targets

    CERN Document Server

    Sors, M

    1999-01-01

    Research and development work is currently in progress in France on the feasibility of transmutation of very long-lived radionuclides such as americium, blended with an inert medium such as magnesium oxide and pelletized for irradiation in a fast neutron reactor. The process is primarily designed to produce ceramics for nuclear reactors, but could also be used to produce targets for accelerators. The Actinide Development Laboratory is part of the ATALANTE complex at Marcoule, where the CEA investigates reprocessing, liquid and solid waste treatment and vitrification processes. The laboratory produces radioactive sources; after use, their constituents are recycled, notably through R and D programs requiring such materials. Recovered americium is purified, characterized and transformed for an experiment known as ECRIX, designed to demonstrate the feasibility of fabricating americium-based ceramics and to determine the reactor transmutation coefficients.

  16. A novel CMPO-functionalized task specific ionic liquid: Synthesis, extraction and spectroscopic investigations of actinide and lanthanide complexes

    NARCIS (Netherlands)

    Mohapatra, P.K.; Kandwal, P.; Iqbal, M.; Huskens, Jurriaan; Murali, M.S.; Verboom, Willem

    2013-01-01

    A novel CMPO (carbamoylmethylphosphine oxide) based task specific ionic liquid (TSIL) with an NTf2− counter anion was synthesized and evaluated for actinide/lanthanide extraction from acidic feed solutions using several room temperature ionic liquids (RTILs). The extraction data were compared with

  17. O/M ratio measurement in pure and mixed oxide fuels - where are we now?

    Energy Technology Data Exchange (ETDEWEB)

    Rubin, J.; Chidester, K.; Thompson, M. [Los Alamos National Lab., NM (United States)

    2001-07-01

    The scale-down in the US and Russian nuclear weapons stockpiles has produced a surplus of weapons grade plutonium and highly enriched uranium. The incorporation into mixed-oxide fuel (MOX) is one of the currently favored routes for surplus weapons-grade plutonium. The use of MOX as a nuclear reactor fuel is well established, particularly in Europe and Japan but not in the US. The primary purpose of this investigation was to evaluate existing analytical techniques for their applicability to O/M (oxygen-to-metal ratio) measurements of MOX derived from excess weapons plutonium. The second objective of this investigation was to bring up-to-date the literature on O/M measurement methods, which has not been undertaken in over 20 years. There are several classification schemes that can be used to organize O/M measurement methods. The most popular schemes are based on (a) whether the analysis is performed in solution (wet chemical) or on solid material (dry), and (b) whether the concentration of major constituents are analyzed directly (direct) or are inferred (indirect). Solid state coulometric titration is currently used extensively in studies of phase equilibria, defect chemistry, thermochemical measurement of oxides, including ferrites. Regardless of which indirect method is used (solid state coulometric titration or thermogravimetry), a primary, direct method will also be required for the establishment of the MO{sub 2} reference state, determination of method bias, and periodic calibration. It was recommended that the following direct method be adapted for this purpose: oxygen measurement by inert gas fusion/carbon reduction, and total U, Pu by controlled potential coulometry. In a table are listed the experimental values of accuracy for about 30 O/M methods. (A.C.)

  18. Studies on carboxylated graphene oxide incorporated polyetherimide mixed matrix ultrafiltration membranes

    Energy Technology Data Exchange (ETDEWEB)

    Kaleekkal, Noel Jacob, E-mail: noeljacob89@gmail.com [Membrane Laboratory, Department of Chemical Engineering, ACT, Anna University, Chennai, 600025 (India); Thanigaivelan, A., E-mail: thanichemstar@gmail.com [Membrane Laboratory, Department of Chemical Engineering, ACT, Anna University, Chennai, 600025 (India); Rana, Dipak, E-mail: rana@uottawa.ca [Department of Chemical and Biological Engineering, University of Ottawa, 161 Louis Pasteur Private, Ottawa, Ontario, K1N 6N5 (Canada); Mohan, D., E-mail: mohantarun@gmail.com [Membrane Laboratory, Department of Chemical Engineering, ACT, Anna University, Chennai, 600025 (India)

    2017-01-15

    In this work the graphene oxide prepared by the modified Hummers’ method was effectively carboxylated. These carboxylated graphene oxide (c-GO) microsheets was characterized by X-ray diffraction analysis, Raman shift, zeta potential, and their morphology was observed using a high resolution scanning/transmission electron microscopy. Polyetherimide mixed matrix membranes (MMMs) were fabricated by the non-solvent induced phase separation technique with varying concentration of this microsheet. The presence of these microsheets on the membrane surface was confirmed by Fourier transform infrared spectroscopy, Raman spectroscopy and could also be confirmed visually by optical images. The membranes were further characterized; they showed a greater water flux, higher porosity, and sufficient thermal stability. Incorporation of these microsheets improved the hydrophilicity of the membrane confirmed by the lower contact angle values, which in turn explained the lower interfacial free energy, the increase in work of adhesion, the higher solid-vapor free energy and the spreading coefficient. Membranes loaded with 0.3 wt% of c-GO showed a flux recovery of 94% and only a small flux decline even after 180 min of filtration of humic acid (HA) solution. The efficiency of these membranes in removal of HA, toxic metal ions was also investigated. The bacterial anti-adhesion property of c-GO in the membranes was also explored using Escherichia coli, as a model bio-foulant. The charge of the microsheets and their unique architecture imparts higher hydrophilicity and greater fouling resistance along with improved permeation flux when incorporated into the polymer matrix. - Highlights: • Novel membranes by incorporating carboxylated GO into polyetherimide matrix. • Modified membranes exhibited greater porosity, flux and high humic acid rejection. • Nanoplatelets improved the flux recovery ratio to >94%. • Liquid phase polymer based retention utilized for toxic heavy metal

  19. Phase relations and ionic transport behaviour in new mixed oxides of ceria–zirconia–gadolinia

    Energy Technology Data Exchange (ETDEWEB)

    Anithakumari, P.; Grover, V., E-mail: vinita@barc.gov.in; Tyagi, A.K.

    2015-10-25

    The present study investigates structure and the phase relations observed in complex oxide systems obtained by substituting Gd{sub 2}O{sub 3} in the mixed oxide (Ce{sub 0.8}Zr{sub 0.2})O{sub 2}. The X-ray diffraction studies performed on this system revealed two single-phasic phase-fields; fluorite-type (F-type) and C-type. The transformation from F-type to C-type structure was observed at 60 mol% Gd{sup 3+} substitution. The Raman spectroscopic studies, however, reveal further fine structural insights wherein the F-type region was observed only up to 30 mol% of Gd{sup 3+} which was followed by the co-existence of C-type ordered region and F-type region. The single-phasic C-type phase-field was observed only beyond 80 mol% Gd{sup 3+}-substitution. The AC impedance analysis revealed minimum in the activation energy and maximum in ionic conductivity values as a function of Gd{sup 3+}-content. An antagonistic interplay of activation energy and pre-exponential factor is explained as the major factor behind this behaviour. The determination of migration and association energies supported the trend observed in the ionic conductivity values as a function of Gd{sup 3+}-content. The activation energies for hopping are in good agreement with migration activation energies thus establishing that the conduction mechanism involved hopping of oxygen ions. - Highlights: • Presence of single-phasic F- and C-type phases was revealed by XRD studies. • Both, inter-anionic repulsions and ionic sizes governed the lattice parameters. • C-type micro domains in F-type region and vice versa observed by Raman spectra. • High conductivity of 30% Gd{sup 3+} doped sample agrees with low association energy. • Similar migration and hopping energies reveal the hopping mechanism for conduction.

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

    Science.gov (United States)

    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

  1. Molten salt oxidation of mixed wastes: Separation of radioactive materials and Resource Conservation and Recovery Act (RCRA) materials

    Energy Technology Data Exchange (ETDEWEB)

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

    1993-12-01

    The Oak Ridge National Laboratory (ORNL) is involved in a program to apply a molten salt oxidation (MSO) process to the treatment of mixed wastes at Oak Ridge and other Department of Energy (DOE) sites. Mixed wastes are defined as those wastes that contain both radioactive components, which are regulated by the atomic energy legislation, and hazardous waste components, which are regulated under the Resource Conservation and Recovery Act (RCRA). A major part of our ORNL program involves the development of separation technologies that are necessary for the complete treatment of mixed wastes. The residues from the MSO treatment of the mixed wastes must be processed further to separate the radioactive components, to concentrate and recycle residues, or to convert the residues into forms acceptable for final disposal. This paper is a review of the MSO requirements for separation technologies, the information now available, and the concepts for our development studies.

  2. Aqueous chemistry of Ce(iv): estimations using actinide analogues.

    Science.gov (United States)

    Marsac, Rémi; Réal, Florent; Banik, Nidhu Lal; Pédrot, Mathieu; Pourret, Olivier; Vallet, Valérie

    2017-10-10

    The prediction of cerium (Ce) aqueous speciation is relevant in many research fields. Indeed, Ce compounds are used for many industrial applications, which may require the control of Ce aqueous chemistry for their synthesis. The aquatic geochemistry of Ce is also of interest. Due to its growing industrial use and its release into the environment, Ce is now considered as an emerging contaminant. Cerium is also used as a proxy of (paleo)redox conditions due to the Ce(iv)/Ce(iii) redox transition. Finally, Ce(iv) is often presented as a relevant analogue of tetravalent actinides (An(iv)). In the present study, quantum chemical calculations were conducted to highlight the similarities between the structures of Ce(iv) and tetravalent actinide (An(iv); An = Th, Pa, U, Np, Pu) aqua-ions, especially Pu(iv). The current knowledge of An(iv) hydrolysis, solubility and colloid formation in water was briefly reviewed but important discrepancies were observed in the available data for Ce(iv). Therefore, new estimations of the hydrolysis constants of Ce(iv) and the solubility of Ce(iv)-(hydr)oxides are proposed, by analogy with Pu(iv). By plotting pH-Eh (Pourbaix) diagrams, we showed that the pH values corresponding to the onset of Ce(iv) species formation (i.e. Ce(iv)-(hydr)oxide or dissolved Ce(iv)) agreed with various experimental results. Although further experimental studies are required to obtain a more accurate thermodynamic database, the present work might yet help to predict more accurately the Ce chemical behavior in aqueous solution.

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

    Energy Technology Data Exchange (ETDEWEB)

    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.

  4. Method of CO and/or CO.sub.2 hydrogenation to higher hydrocarbons using doped mixed-metal oxides

    Energy Technology Data Exchange (ETDEWEB)

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

    2017-03-21

    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 pyrochlore, 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 olefins, paraffins, or mixtures thereof.

  5. JOWOG 22/2 - Actinide Chemical Technology (July 9-13, 2012)

    Energy Technology Data Exchange (ETDEWEB)

    Jackson, Jay M. [Los Alamos National Laboratory; Lopez, Jacquelyn C. [Los Alamos National Laboratory; Wayne, David M. [Los Alamos National Laboratory; Schulte, Louis D. [Los Alamos National Laboratory; Finstad, Casey C. [Los Alamos National Laboratory; Stroud, Mary Ann [Los Alamos National Laboratory; Mulford, Roberta Nancy [Los Alamos National Laboratory; MacDonald, John M. [Los Alamos National Laboratory; Turner, Cameron J. [Los Alamos National Laboratory; Lee, Sonya M. [Los Alamos National Laboratory

    2012-07-05

    The Plutonium Science and Manufacturing Directorate provides world-class, safe, secure, and reliable special nuclear material research, process development, technology demonstration, and manufacturing capabilities that support the nation's defense, energy, and environmental needs. We safely and efficiently process plutonium, uranium, and other actinide materials to meet national program requirements, while expanding the scientific and engineering basis of nuclear weapons-based manufacturing, and while producing the next generation of nuclear engineers and scientists. Actinide Process Chemistry (NCO-2) safely and efficiently processes plutonium and other actinide compounds to meet the nation's nuclear defense program needs. All of our processing activities are done in a world class and highly regulated nuclear facility. NCO-2's plutonium processing activities consist of direct oxide reduction, metal chlorination, americium extraction, and electrorefining. In addition, NCO-2 uses hydrochloric and nitric acid dissolutions for both plutonium processing and reduction of hazardous components in the waste streams. Finally, NCO-2 is a key team member in the processing of plutonium oxide from disassembled pits and the subsequent stabilization of plutonium oxide for safe and stable long-term storage.

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

    Science.gov (United States)

    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.

  7. Low-Frequency Mechanical Spectroscopy of Lanthanum Cobaltite Based Mixed Conducting Oxides

    Directory of Open Access Journals (Sweden)

    Wu Xiu Sheng

    2016-09-01

    Full Text Available The low-frequency mechanical spectra of lanthanum cobaltite based mixed conducting oxides have been measured using a computer-controlled inverted torsion pendulum. The results indicate that the internal friction spectra and shear modulus depend on the Sr doping contents (x. For undoped samples, no internal friction peak is observed. However, for La0.8Sr0.2CoO3‒δ, three internal friction peaks (P2, P3 and P4 are observed. In addition to these peaks, two more peaks (P0 and P1 are observed in La0.6Sr0.4CoO3‒δ. The P0 and P1 peaks show characteristics of a phase transition, while the P2, P3 and P4 peaks are of relaxation-type. Our analysis suggests that the P0 peak is due to a phase separation and the P1 peak is related to the ferromagnetic–paramagnetic phase transition. The P2, P3 and P4 peaks are associated with the motion of domain walls. The formation of this kind of domain structure is a consequence of a transformation from the paraelastic cubic phase to the ferroelastic rhombohedral phase. With partial substitution of Fe for Co, only one peak is observed, which is discussed as a result of different microstructure.

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

    Energy Technology Data Exchange (ETDEWEB)

    J. RUBIN; ET AL

    2000-12-01

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

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

    Energy Technology Data Exchange (ETDEWEB)

    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.

  10. Percolation Theory in Solid Oxide Fuel Cell Composite Electrodes with a Mixed Electronic and Ionic Conductor

    Directory of Open Access Journals (Sweden)

    Meng Ni

    2013-03-01

    Full Text Available Percolation theory is generalized to predict the effective properties of specific solid oxide fuel cell composite electrodes, which consist of a pure ion conducting material (e.g., YSZ or GDC and a mixed electron and ion conducting material (e.g., LSCF, LSCM or CeO2. The investigated properties include the probabilities of an LSCF particle belonging to the electron and ion conducting paths, percolated three-phase-boundary electrochemical reaction sites, which are based on different assumptions, the exposed LSCF surface electrochemical reaction sites and the revised expressions for the inter-particle ionic conductivities among LSCF and YSZ materials. The effects of the microstructure parameters, such as the volume fraction of the LSCF material, the particle size distributions of both the LSCF and YSZ materials (i.e., the mean particle radii and the non-dimensional standard deviations, which represent the particle size distributions and the porosity are studied. Finally, all of the calculated results are presented in non-dimensional forms to provide generality for practical application. Based on these results, the relevant properties can be easily evaluated, and the microstructure parameters and intrinsic properties of each material are specified.

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

    Energy Technology Data Exchange (ETDEWEB)

    Som, S.; Choubey, A. [Department of Applied Physics, Indian School of Mines, Dhanbad, Jharkhand 826004 (India); Sharma, S.K., E-mail: sksharma_ism@yahoo.co.in [Department of Applied Physics, Indian School of Mines, Dhanbad, Jharkhand 826004 (India)

    2012-09-01

    This paper reports the photoluminescence and thermoluminescence properties of gamma ray induced rare earth doped yttrium gadolinium mixed oxide phosphor. The europium (Eu{sup 3+}) was used as rare earth dopant. The phosphor was prepared by chemical co-precipitation method according to the formula (Y{sub 2-x-y}Gd{sub x}) O{sub 3}: Eu{sub y}{sup 3+} (x=0.5; y=0.05). The photoluminescence emission spectrum of the prepared phosphor shows intense peaks in the red region at 615 nm for {sup 5}D{sub 0}{yields}{sup 7}F{sub 2} transitions and the photoluminescence excitation spectra show a broad band located around 220-270 nm for the emission wavelength fixed at 615 nm. The thermoluminescence studies were carried out after irradiating the phosphor by gamma rays in the dose range from 100 Gy to 1 KGy. In the thermoluminescence glow curves, one single peak was observed at about 300 Degree-Sign C of which the intensity increases linearly in the studied dose range of gamma rays. The glow peak was deconvoluted by GlowFit program and the kinetic parameters associated with the deconvoluted peaks were calculated. The kinetic parameters were also calculated by various glow curve shape and heating rate methods.

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

    Science.gov (United States)

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

    2012-09-01

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

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

    Energy Technology Data Exchange (ETDEWEB)

    Pengelly, M.G.A. [AEA Technology, Dorchester (United Kingdom)

    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.

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

    Energy Technology Data Exchange (ETDEWEB)

    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.

  15. Synthesis and Characterization of K-Ta Mixed Oxides for Hydrogen Generation in Photocatalysis

    Directory of Open Access Journals (Sweden)

    Beata Zielińska

    2012-01-01

    Full Text Available K-Ta mixed oxides photocatalysts have been prepared by impregnation followed by calcination. The influence of the reaction temperature (450°C–900°C on the phase formation, crystal morphology, and photocatalytic activity in hydrogen generation of the produced materials was investigated. The detailed analysis has revealed that all products exhibit high crystallinity and irregular structure. Moreover, two different crystal structures of potassium tantalates such as KTaO3 and K2Ta4O11 were obtained. It was also found that the sample composed of KTaO3 and traces of unreacted Ta2O5 (annealed at 600°C exhibits the highest activity in the reaction of photocatalytic hydrogen generation. The crystallographic phases, optical and vibronic properties were examined by X-ray diffraction (XRD and diffuse reflectance (DR UV-vis and resonance Raman spectroscopic methods, respectively. Morphology and chemical composition of the produced samples were studied using a high-resolution transmission electron microscope (HR-TEM and an energy dispersive X-ray spectrometer (EDX as its mode.

  16. Thermally induced growth of ZnO nanocrystals on mixed metal oxide surfaces.

    Science.gov (United States)

    Inayat, Alexandra; Makky, Ayman; Giraldo, Jose; Kuhnt, Andreas; Busse, Corinna; Schwieger, Wilhelm

    2014-06-23

    An in situ method for the growth of ZnO nanocrystals on Zn/Al mixed metal oxide (MMO) surfaces is presented. The key to this method is the thermal treatment of Zn/Al layered double hydroxides (Zn/Al LDHs) in the presence of nitrate anions, which results in partial demixing of the LDH/MMO structure and the subsequent crystallization of ZnO crystals on the surface of the forming MMO layers. In a first experimental series, thermal treatment of Zn/Al LDHs with different fractions of nitrate and carbonate in the interlayer space was examined by thermogravimetry coupled with mass spectrometry (TG-MS) and in situ XRD. In a second experimental series, Zn/Al LDHs with only carbonate in the interlayer space were thermally treated in the presence of different amounts of an external nitrate source (NH4NO3). All obtained Zn/Al MMO samples were analysed by electron microscopy, nitrogen physisorption and powder X-ray diffraction. The gas phase formed during nitrate decomposition turned out to be responsible for the formation of crystalline ZnO nanoparticles. Accordingly, both interlayer nitrate and the presence of ammonium nitrate led to the formation of supported ZnO nanocrystals with mean diameters between 100 and 400 nm, and both methods offer the possibility to tailor the amount and size of the ZnO crystals by means of the amount of nitrate.

  17. Electrorecovery of actinides at room temperature

    Energy Technology Data Exchange (ETDEWEB)

    Stoll, Michael E [Los Alamos National Laboratory; Oldham, Warren J [Los Alamos National Laboratory; Costa, David A [Los Alamos National Laboratory

    2008-01-01

    There are a large number of purification and processing operations involving actinide species that rely on high-temperature molten salts as the solvent medium. One such application is the electrorefining of impure actinide metals to provide high purity material for subsequent applications. There are some drawbacks to the electrodeposition of actinides in molten salts including relatively low yields, lack of accurate potential control, maintaining efficiency in a highly corrosive environment, and failed runs. With these issues in mind we have been investigating the electrodeposition of actinide metals, mainly uranium, from room temperature ionic liquids (RTILs) and relatively high-boiling organic solvents. The RTILs we have focused on are comprised of 1,3-dialkylimidazolium or quaternary ammonium cations and mainly the {sup -}N(SO{sub 2}CF{sub 3}){sub 2} anion [bis(trif1uoromethylsulfonyl)imide {equivalent_to} {sup -}NTf{sub 2}]. These materials represent a class of solvents that possess great potential for use in applications employing electrochemical procedures. In order to ascertain the feasibility of using RTILs for bulk electrodeposition of actinide metals our research team has been exploring the electron transfer behavior of simple coordination complexes of uranium dissolved in the RTIL solutions. More recently we have begun some fundamental electrochemical studies on the behavior of uranium and plutonium complexes in the organic solvents N-methylpyrrolidone (NMP) and dimethylsulfoxide (DMSO). Our most recent results concerning electrodeposition will be presented in this account. The electrochemical behavior of U(IV) and U(III) species in RTILs and the relatively low vapor pressure solvents NMP and DMSO is described. These studies have been ongoing in our laboratory to uncover conditions that will lead to the successful bulk electrodeposition of actinide metals at a working electrode surface at room temperature or slightly elevated temperatures. The RTILs we

  18. Correlation of retention of lanthanide and actinide complexes with stability constants and their speciation

    Energy Technology Data Exchange (ETDEWEB)

    Datta, A.; Sivaraman, N.; Viswanathan, K.S.; Ghosh, Suddhasattwa; Srinivasan, T.G.; Vasudeva Rao, P.R. [Indira Gandhi Centre for Atomic Research, Kalpakkam (India). Chemistry Group

    2013-03-01

    The present study describes a correlation that is developed from retention of lanthanide and actinide complexes with the stability constant. In these studies, an ion-pairing reagent, camphor-10-sulphonic acid (CSA) was used as the modifier and organic acids such as {alpha}-hydroxy isobutyric acid ({alpha}-HIBA), mandelic acid, lactic acid and tartaric acid were used as complexing reagent for elution. From these studies, a correlation has been established between capacity factor of a metal ion, concentration of ion-pairing reagent and complexing agent with the stability constant of metal complex. Based on these studies, it has been shown that the stability constant of lanthanide and actinide complexes can be estimated using a single lanthanide calibrant. Validation of the method was carried out with the complexing agents such as {alpha}-HIBA and lactic acid. It was also demonstrated that data from a single chromatogram can be used for estimation of stability constant at various ionic strengths. These studies also demonstrated that the method can be applied for estimation of stability constant of actinides with a ligand whose value is not reported yet, e.g., ligands of importance in the lanthanide-actinide separations, chelation therapy etc. The chromatographic separation method is fast and the estimation of stability constant can be done in a very short time, which is a significant advantage especially in dealing with radioactive elements. The stability constant data was used to derive speciation data of plutonium in different oxidation states as well as that of americium with {alpha}-HIBA. The elution behavior of actinides such as Pu and Am from reversed phase chromatographic technique could be explained based on these studies. (orig.)

  19. The role of actinide burning and the Integral Fast Reactor in the future of nuclear power

    Energy Technology Data Exchange (ETDEWEB)

    Hollaway, W.R.; Lidsky, L.M.; Miller, M.M.

    1990-12-01

    A preliminary assessment is made of the potential role of actinide burning and the Integral Fast Reactor (IFR) in the future of nuclear power. The development of a usable actinide burning strategy could be an important factor in the acceptance and implementation of a next generation of nuclear power. First, the need for nuclear generating capacity is established through the analysis of energy and electricity demand forecasting models which cover the spectrum of bias from anti-nuclear to pro-nuclear. The analyses take into account the issues of global warming and the potential for technological advances in energy efficiency. We conclude, as do many others, that there will almost certainly be a need for substantial nuclear power capacity in the 2000--2030 time frame. We point out also that any reprocessing scheme will open up proliferation-related questions which can only be assessed in very specific contexts. The focus of this report is on the fuel cycle impacts of actinide burning. Scenarios are developed for the deployment of future nuclear generating capacity which exploit the advantages of actinide partitioning and actinide burning. Three alternative reactor designs are utilized in these future scenarios: The Light Water Reactor (LWR); the Modular Gas-Cooled Reactor (MGR); and the Integral Fast Reactor (FR). Each of these alternative reactor designs is described in some detail, with specific emphasis on their spent fuel streams and the back-end of the nuclear fuel cycle. Four separation and partitioning processes are utilized in building the future nuclear power scenarios: Thermal reactor spent fuel preprocessing to reduce the ceramic oxide spent fuel to metallic form, the conventional PUREX process, the TRUEX process, and pyrometallurgical reprocessing.

  20. Preparation of Nanocrystalline Rare Earth Mixed Oxides DyFexCo1-xO3-δ and Its Conductivity

    Institute of Scientific and Technical Information of China (English)

    任引哲; 王建英; 刘二保

    2002-01-01

    Nanocrystalline rare earth mixed oxides DyFexCo1-xO3-δ were prepared by sol-gel method and characterized by X-ray diffraction (XRD), thermogravimetric analysis (TG-DTA) and scanning electron microscope (SEM). The results show that DyFexCo1-xO3-δ has the structure of perovskite type at 800 ℃ for 2 h calcination. The conductivity of the materials at different temperature was measured by four-probe instrumentation and two-pole method. The results show that the conductivity of mixed oxides DyFexCo1-xO3-δ is higher than those of un-mixed oxides DyFeO3 and DyCoO3 and the conductivity is the best at x=0.8 in the matter of DyFexCo1-xO3-δ. The conductivity of these materials always increases with the temperature rising and there is an apparent change between 600 and 800 ℃. However, the spinodals are different with different ration of Fe3+ and Co3+. This kind of oxide is a conductive pottery material.

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

    Science.gov (United States)

    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.

  2. Synthesis of Mixed Cu/Ce Oxide Nanoparticles by the Oil-in-Water Microemulsion Reaction Method

    Directory of Open Access Journals (Sweden)

    Kelly Pemartin-Biernath

    2016-06-01

    Full Text Available Cerium oxide and mixed Cu/Ce oxide nanoparticles were prepared by the oil-in-water (O/W microemulsion reaction method in mild conditions. The Cu/Ce molar ratio was varied between 0/100 and 50/50. According to X-ray diffraction (XRD, below 30/70 Cu/Ce molar ratio, the materials presented a single phase consistent with cubic fluorite CeO2. However, above Cu/Ce molar ratio 30/70, an excess monoclinic CuO phase in coexistence with the predominant Cu/Ce mixed oxide was detected by XRD and High-Resolution Transmission Electron Microscopy (HRTEM. Raman spectroscopy showed that oxygen vacancies increased significantly as the Cu content was increased. Band gap (Eg was investigated as a function of the Cu/Ce molar ratio, resulting in values from 2.91 eV for CeO2 to 2.32 eV for the mixed oxide with 30/70 Cu/Ce molar ratio. These results indicate that below 30/70 Cu/Ce molar ratio, Cu2+ is at least partially incorporated into the ceria lattice and very well dispersed in general. In addition, the photodegradation of Indigo Carmine dye under visible light irradiation was explored for selected samples; it was shown that these materials can remove such contaminants, either by adsorption and/or photodegradation. The results obtained will encourage investigation into the optical and photocatalytic properties of these mixed oxides, for widening their potential applications.

  3. Ambient-temperature NO oxidation over amorphous CrOx-ZrO2 mixed oxide catalysts: Significant promoting effect of ZrO2

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Aiyong; Guo, Yanglong; Gao, Feng; Peden, Charles H. F.

    2017-03-01

    Three series of Cr-based mixed oxides (Cr-Co, Cr-Fe, and Cr-Ni oxides) with high specific surface areas and amorphous textures are synthesized using a novel sol-gel method. These mixed oxides, in comparison to their pure metal oxide (CrOx, Co3O4, FeOx and NiO) counterparts, display enhanced performance for catalytic oxidation of low-concentration NO at room temperature. Over best performing catalysts, 100% NO conversion can be maintained up to 30 h of operation at a high space velocity of 45,000 ml g-1 h-1. The amorphous structure is found to be critical for these catalysts to maintain high activity and durability. Cr/M (M=Co, Fe and Ni) molar ratio, nitrate precursor decomposition temperature and catalyst calcination temperature are important criteria for the synthesis of the highly active catalysts. This work was supported by National Basic Research Program of China (2013CB933200), National Natural Science Foundation of China (21577035, 21577034), Commission of Science and Technology of Shanghai Municipality (15DZ1205305) and 111 Project (B08021). Aiyong Wang gratefully acknowledges the China Scholarship Council for the Joint-Training Scholarship Program with the Pacific Northwest National Laboratory (PNNL). PNNL is operated for the U.S. Department of Energy (DOE) by Battelle. FG and CHFP are supported by the U.S. DOE/Office of Energy Efficiency and Renewable Energy, Vehicle Technologies Office.

  4. Ceria-Based Mixed Oxide Supported Nano-Gold as an Efficient and Durable Heterogeneous Catalyst for Oxidative Dehydrogenation of Amines to Imines Using Molecular Oxygen

    Directory of Open Access Journals (Sweden)

    Bashir Ahmad Dar

    2012-06-01

    Full Text Available The present work is intended to determine the catalytic activity of Mixed Oxide supported gold for aerobic oxidative dehydrogenation of amines to imines using Ceria as a main constituent of the each support. The model catalysts Au/CeO2:TiO2 Au/CeO2:SiO2, Au/CeO2:ZrO2 and Au/CeO2:Al2Os were prepared by deposition co-precipitation method and deposition of gold was determined by EDEX analysis. The supported nano-gold catalyzes the dehydrogenation of secondary amines to imines without loss of activity. On recycling good amount of product yield is obtained. Oxidation of secondary amines to imines is carried at 100˚C and almost 90 % conversion was obtained with >99% selectivity. © 2012 BCREC UNDIP. All rights reservedReceived: 26th December 2011; Revised: 7th June 2012; Accepted: 13rd June 2012[How to Cite: B.A. Dar, M. Sharma, B. Singh. (2012. Ceria-Based Mixed Oxide Supported Nano-Gold as an Efficient and Durable Heterogeneous Catalyst for Oxidative Dehydrogenation of Amines to Imines Using Molecular Oxygen. Bulletin of Chemical Reaction Engineering & Catalysis, 7(1: 79-84.  doi:10.9767/bcrec.7.1.1257.79-84][How to Link / DOI: http://dx.doi.org/10.9767/bcrec.7.1.1257.79-84 ] | View in 

  5. Recovery of actinides from actinide-aluminium alloys by chlorination: Part I

    Science.gov (United States)

    Cassayre, L.; Souček, P.; Mendes, E.; Malmbeck, R.; Nourry, C.; Eloirdi, R.; Glatz, J.-P.

    2011-07-01

    Pyrochemical processes in molten LiCl-KCl are being developed in ITU for recovery of actinides from spent nuclear fuel. The fuel is anodically dissolved to the molten salt electrolyte and actinides are electrochemically reduced on solid aluminium cathodes forming solid actinide-aluminium alloys. A chlorination route is being investigated for recovery of actinides from the alloys. This route consists in three steps: Vacuum distillation for removal of the salt adhered on the electrode, chlorination of the actinide-aluminium alloys by chlorine gas and sublimation of the formed AlCl 3. A thermochemical study showed thermodynamic feasibility of all three steps. On the basis of the conditions identified by the calculations, experiments using pure UAl 3 alloy were carried out to evaluate and optimise the chlorination step. The work was focused on determination of the optimal temperature and Cl 2/UAl 3 molar ratio, providing complete chlorination of the alloy without formation of volatile UCl 5 and UCl 6. The results showed high efficient chlorination at a temperature of 150 °C.

  6. Antimony (V) Oxide Adsorbed on a Silica-Zirconia Mixed Oxide Obtained by the Sol-Gel Processing Method: Preparation and Acid Properties

    OpenAIRE

    Zaitseva,Galina; Gushikem,Yoshitaka

    2002-01-01

    The preparation, degree of dispersion, thermal stability and Lewis and Brønsted acidity of antimony (V) oxide adsorbed on SiO2/ZrO2 mixed oxide, previously prepared by the sol-gel processing method, are described herein. The samples SiO2/ZrO2/Sb2O5, with compositions (in wt %): (a) Zr= 8.1 and Sb= 6.3; (b) Zr= 14.9 and Sb= 11.4, were prepared. Scanning electron microscopy images connected to a X-ray energy dispersive spectrometer showed that both metals, Zr and Sb, were highly dispersed ...

  7. Synthesis and characterization of composites of mixed oxides of iron and neodymium in polymer matrix of aniline–formaldehyde

    Indian Academy of Sciences (India)

    Sajdha; H N Sheikh; B L Kalsotra; N Kumar; S Kumar

    2011-07-01

    Nanocomposites of mixed oxides of iron and neodymium in polymer matrix of anilineformaldehyde are reported. The composites have been obtained by treating the aqueous solution of aniline, hydrochloric acid and formaldehyde with halide of iron and neodymium oxide. The infra-red spectra show broad peaks at ∼ 590 cm-1 and at ∼ 610 cm-1 due to the presence of oxides of both iron and neodymium. In heated samples, the absorption peaks due to metal oxides are better resolved. A broad and strong peak in XRD spectra at 2 value of 35.69920 corresponds to spinel -Fe2O3. 57Fe Mössbauer spectrum for unheated sample gives Mössbauer parameters, i.e. isomer shift (), quadrupole splitting ( ) and effective magnetic field (Heff). Transmission electron microscopy (TEM) micrographs reveal well dispersed particles at different magnifications. Vibrating sample magnetometry (VSM) studies indicate that the ferrite nanoparticles exhibit characteristics of ferromagnetism.

  8. Actinide Isotopes for the Synthesis of Superheavy Nuclei

    Science.gov (United States)

    Roberto, J. B.; Alexander, C. W.; Boll, R. A.; Dean, D. J.; Ezold, J. G.; Felker, L. K.; Rykaczewski, K. P.

    2014-09-01

    Recent research resulting in the synthesis of isotopes of new elements 113-118 has demonstrated the importance of actinide targets in superheavy element research. Oak Ridge National Laboratory (ORNL) has unique facilities for the production and processing of actinide target materials, including the High Flux Isotope Reactor (HFIR) and the Radiochemical Engineering Development Center (REDC). These facilities have provided actinide target materials that have been used for the synthesis of all superheavy (SHE) elements above Copernicium (element 112). In this paper, the use of actinide targets for SHE research and discovery is described, including recent results for element 117 using 249Bk target material from ORNL. ORNL actinide capabilities are reviewed, including production and separation/purification, availabilities of actinide materials, and future opportunities including novel target materials such as 251Cf.

  9. Oxidative stabilization of mixed mayonnaises made with linseed oil and saturated medium-chain triglyceride oil

    NARCIS (Netherlands)

    Raudsepp, P.; Brüggemann, D.A.; Lenferink, Aufrid T.M.; Otto, Cornelis; Andersen, M.L.

    2014-01-01

    Mayonnaises, made with either saturated medium chain triglyceride (MCT) oil or unsaturated purified linseed oil (LSO), were mixed. Raman confocal microspectrometry demonstrated that lipid droplets in mixed mayonnaise remained intact containing either MCT oil or LSO. Peroxide formation during storage

  10. Microbial Transformations of Actinides and Other Radionuclides

    Energy Technology Data Exchange (ETDEWEB)

    Francis,A.J.; Dodge, C. J.

    2009-01-07

    Microorganisms can affect the stability and mobility of the actinides and other radionuclides released from nuclear fuel cycle and from nuclear fuel reprocessing plants. Under appropriate conditions, microorganisms can alter the chemical speciation, solubility and sorption properties and thus could increase or decrease the concentrations of radionuclides in solution in the environment and the bioavailability. Dissolution or immobilization of radionuclides is brought about by direct enzymatic action or indirect non-enzymatic action of microorganisms. Although the physical, chemical, and geochemical processes affecting dissolution, precipitation, and mobilization of radionuclides have been extensively investigated, we have only limited information on the effects of microbial processes and biochemical mechanisms which affect the stability and mobility of radionuclides. The mechanisms of microbial transformations of the major and minor actinides U, Pu, Cm, Am, Np, the fission products and other radionuclides such as Ra, Tc, I, Cs, Sr, under aerobic and anaerobic conditions in the presence of electron donors and acceptors are reviewed.

  11. Seventeen-coordinate actinide helium complexes

    Energy Technology Data Exchange (ETDEWEB)

    Kaltsoyannis, Nikolas [School of Chemistry, The University of Manchester (United Kingdom)

    2017-06-12

    The geometries and electronic structures of molecular ions featuring He atoms complexed to actinide cations are explored computationally using density functional and coupled cluster theories. A new record coordination number is established, as AcHe{sub 17}{sup 3+}, ThHe{sub 17}{sup 4+}, and PaHe{sub 17}{sup 4+} are all found to be true geometric minima, with the He atoms clearly located in the first shell around the actinide. Analysis of AcHe{sub n}{sup 3+} (n=1-17) using the quantum theory of atoms in molecules (QTAIM) confirms these systems as having closed shell, charge-induced dipole bonding. Excellent correlations (R{sup 2}>0.95) are found between QTAIM metrics (bond critical point electron densities and delocalization indices) and the average Ac-He distances, and also with the incremental He binding energies. (copyright 2017 Wiley-VCH Verlag GmbH and Co. KGaA, Weinheim)

  12. Actinide and fission product separation and transmutation

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    1991-07-01

    The first international information exchange meeting on actinide and fission product separation and transmutation, took place in Mito in Japan, on 6-8 November 1990. It starts with a number of general overview papers to give us some broad perspectives. Following that it takes a look at some basic facts about physics and about the quantities of materials it is talking about. Then it proceeds to some specific aspects of partitioning, starting with evolution from today commercially applied processes and going on to other possibilities. At the end of the third session it takes a look at the significance of partitioning and transmutation of actinides before it embarks on two sessions on transmutation, first in reactors and second in accelerators. The last session is designed to throw back into the discussion the main points which need to be looked at when considering future work in this area. (A.L.B.)

  13. Preparation, properties, and some recent studies of the actinide metals

    Energy Technology Data Exchange (ETDEWEB)

    Haire, R.G.

    1985-01-01

    The actinide elements form a unique series of metals. The variation in their physial properties combined with the varying availability of the different elements offers a challenge to the preparative scientist. This article provides a brief review of selected methods used for preparing ..mu..g to kg amounts of the actinide metals and the properties of these metals. In addition, some recent studies on selected actinide metals are discussed. 62 refs.

  14. Thermodynamic systematics of oxides of americium, curium, and neighboring elements

    Energy Technology Data Exchange (ETDEWEB)

    Morss, L.R.

    1984-01-01

    Recently-obtained calorimetric data on the sesquioxides and dioxides of americium and curium are summarized. These data are combined with other properties of the actinide elements to elucidate the stability relationships among these oxides and to predict the behavior of neighboring actinide oxides. 45 references, 4 figures, 5 tables.

  15. Pourbaix diagrams of actinides in molten chlorides using an indicating electrode for oxide ion activity; Etablissement de diagrammes de Pourbaix des actinides dans les chlorures fondus au moyen d'une electrode indicatrice de l'activite des ions oxyde

    Energy Technology Data Exchange (ETDEWEB)

    Lambertin, D.; Lacquement, J. [CEA Valrho, (DCC/DRRV/SPHA), 30 - Marcoule (France)

    2000-07-01

    Pyrochemical separation methods using high temperature molten salt media could emerge as promising and valuable routes compared with aqueous methods for separation and transmutation strategies for long-lived radionuclides. A good knowledge of the molten salt chemistry is essential for controlling these separations, and elementary data are required for molten halide salts, which can be readily provided by electrochemical methods. Applying the chemical principles of aqueous solutions to the molten salt media, Pourbaix diagrams - called in this case potential-oxo-acidity (pO{sup 2-}) - can be plotted. They offer a rapid and comprehensive view of the thermodynamic properties of selected elements in a solvent of interest. Two methods are available for preparing these diagrams. The first is based on available thermodynamic data on pure element oxide (and oxychloride) compounds and on element chloride activity coefficients in melt (which can be electrochemically determined). In this method, we consider the oxide anion exchange reactions between the pure compounds, water and hydrogen chloride. The second method is a direct and experimental determination of the oxo-acidic properties of the studied element chlorides in melts. Use of an Yttria-Stabilised Zirconia Membrane (YSZM) electrode (oxide anion selective electrode) helps determine the nature of the stable oxide compounds in melts as well as their stabilities. The YSZM is used with a silver/silver chloride reference system, and was developed 25 years ago. Two examples of Potential-acidity diagrams. Employing the first method and the determination of the standard potential of plutonium in LiCl-KCl and NaCl-KCl eutectic mixtures, potential-oxo-acidity diagrams were plotted for these melts at various temperatures. It was found that the stability domain for plutonium chloride depends on the melt composition (influence of oxide anion solvation). We also used the Omega acidity function - based on reaction (1) - which is a

  16. SPECIFIC SEQUESTERING AGENTS FOR THE ACTINIDES

    Energy Technology Data Exchange (ETDEWEB)

    Raymond, Kenneth N.; Smith, William L.; Weitl, Frederick L.; Durbin, Patricia W.; Jones, E.Sarah; Abu-Dari, Kamal; Sofen, Stephen R.; Cooper, Stephen R.

    1979-09-01

    This paper summarizes the current status of a continuing project directed toward the synthesis and characterization of chelating agents which are specific for actinide ions - especially Pu(IV) - using a biomimetic approach that relies on the observation that Pu(IV) and Fe(III) has marked similarities that include their biological transport and distribution in mammals. Since the naturally-occurring Fe(III) sequestering agents produced by microbes commonly contain hydroxamate and catecholate functional groups, these groups should complex the actinides very strongly and macrocyclic ligands incorporating these moieties are being prepared. We have reported the isolation and structure analysis of an isostructural series of tetrakis(catecholato) complexes with the general stoichiometry Na{sub 4}[M(C{sub 6}H{sub 4}O{sub 2}){sub 4}] • 21 H{sub 2}O (M = Th, U, Ce, Hf). These complexes are structural archetypes for the cavity that must be formed if an actinide-specific sequestering agent is to conform ideally to the coordination requirements of the central metal ion. The [M(cat){sub 4}]{sup 4-} complexes have the D{sub 2d} symmetry of the trigonal-faced dodecahedron.. The complexes Th [R'C(0)N(O)R]{sub 4} have been prepared where R = isopropyl and R' = t-butyl or neopentyl. The neopentyl derivative is also relatively close to an idealized D{sub 2d} dodecahedron, while the sterically more hindered t-butyl compound is distorted toward a cubic geometry. The synthesis of a series of 2, 3-dihydroxy-benzoyl amide derivatives of linear and cyclic tetraaza- and diazaalkanes is reported. Sulfonation of these compounds improves the metal complexation and in vivo removal of plutonium from test animals. These results substantially exceed the capabilities of compounds presently used for the therapeutic treatment of actinide contamination.

  17. Actinide and fission product partitioning and transmutation

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    1997-07-01

    The fourth international information exchange meeting on actinide and fission product partitioning and transmutation, took place in Mito City in Japan, on 111-13 September 1996. The proceedings are presented in six sessions: the major programmes and international cooperation, the partitioning and transmutation programs, feasibility studies, particular separation processes, the accelerator driven transmutation, and the chemistry of the fuel cycle. (A.L.B.)

  18. Bioleaching of metal from municipal waste incineration fly ash using a mixed culture of sulfur-oxidizing and iron-oxidizing bacteria.

    Science.gov (United States)

    Ishigaki, Tomonori; Nakanishi, Akane; Tateda, Masafumi; Ike, Michihiko; Fujita, Masanori

    2005-08-01

    We investigated the behavior and characteristics of metal leaching from municipal solid waste incineration (MSWI) fly ash among pure cultures of a sulfur-oxidizing bacterium (SOB) and an iron-oxidizing bacterium (IOB) and a mixed culture. The IOB has a high metal-leaching ability, though its tolerability against the ash addition is low. The SOB might better tolerate an increase in ash addition than the IOB, though metal leaching ability of the SOB is limited. Mixed culture could compensate for these deficiencies, and high metal leachability was exhibited in the 1% ash culture, i.e., 67% and 78% of leachabilities for Cu and Zn, respectively, and 100% for Cr and Cd. Furthermore, comparably high leachabilities such as 42% and 78% for Cu and Zn were observed even in the 3% ash cultures. Characterization of metal leaching by the mixed culture revealed that the acidic and oxidizing condition had remained stable thorough the experimental period. Ferric iron remained in the mixed culture, and the metal leaching was enhanced by redox mechanisms coupling with the leaching by sulfate. An increase of ferrous iron enhanced the Cr, Cu, and As leaching. The optimum concentration of sulfur existed for As and Cr (5 gl(-1)) and Cu (2 gl(-1)). The presence of the degradable and non-degradable organic compound that must be existed in the natural environment or waste landfills made no significant change in the leachability of metals other than Zn. These results suggested that bioleaching using a mixed culture of SOB and IOB is a promising technology for recovering the valuable metals from MSWI fly ash.

  19. Studies of the formation of homogeneous mixed silicon-titanium/zirconium oxides by the sol-gel route

    OpenAIRE

    Hudson, Melanie

    1994-01-01

    This thesis was submitted for the degree of Doctor of Philosophy and awarded by Brunel University. This thesis is concerned with the preparation of mixed silicon-titanium oxides (Ti02=4.1-21.9wt%) and silicon-zirconium oxides (Zr02=4.1-22.Iwt%) by the sol-gel route. Methods of preparing homogeneous Si02-TiO2 gels and SiO2-Zr02 gels have been explored. In this work bis(acetylacetonato)titanium diisopropoxide or bis(acetylacetonato)zirconium dipropoxide and tetraethyl orthosilicate (TEOS...

  20. Actinide and lanthanide separation process (ALSEP)

    Science.gov (United States)

    Guelis, Artem V.

    2013-01-15

    The process of the invention is the separation of minor actinides from lanthanides in a fluid mixture comprising, fission products, lanthanides, minor actinides, rare earth elements, nitric acid and water by addition of an organic chelating aid to the fluid; extracting the fluid with a solvent comprising a first extractant, a second extractant and an organic diluent to form an organic extractant stream and an aqueous raffinate. Scrubbing the organic stream with a dicarboxylic acid and a chelating agent to form a scrubber discharge. The scrubber discharge is stripped with a simple buffering agent and a second chelating agent in the pH range of 2.5 to 6.1 to produce actinide and lanthanide streams and spent organic diluents. The first extractant is selected from bis(2-ethylhexyl)hydrogen phosphate (HDEHP) and mono(2-ethylhexyl)2-ethylhexyl phosphonate (HEH(EHP)) and the second extractant is selected from N,N,N,N-tetra-2-ethylhexyl diglycol amide (TEHDGA) and N,N,N',N'-tetraoctyl-3-oxapentanediamide (TODGA).

  1. Recovery of actinides from actinide-aluminium alloys by chlorination: Part II

    Science.gov (United States)

    Souček, P.; Cassayre, L.; Eloirdi, R.; Malmbeck, R.; Meier, R.; Nourry, C.; Claux, B.; Glatz, J.-P.

    2014-04-01

    A chlorination route is being investigated for recovery of actinides from actinide-aluminium alloys, which originate from pyrochemical recovery of actinides from spent metallic nuclear fuel by electrochemical methods in molten LiCl-KCl. In the present work, the most important steps of this route were experimentally tested using U-Pu-Al alloy prepared by electrodeposition of U and Pu on solid aluminium plate electrodes. The investigated processes were vacuum distillation for removal of the salt adhered on the electrode, chlorination of the alloy by chlorine gas and sublimation of the AlCl3 formed. The processes parameters were set on the base of a previous thermochemical study and an experimental work using pure UAl3 alloy. The present experimental results indicated high efficiency of salt distillation and chlorination steps, while the sublimation step should be further optimised.

  2. Managing plutonium in Britain. Current options[Mixed oxide nuclear fuels; Nuclear weapons

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    1998-09-01

    This is the report of a two day meeting to discuss issues arising from the reprocessing of plutonium and production of mixed oxide nuclear fuels in Britain. It was held at Charney Manor, near Oxford, on June 25 and 26, 1998, and was attended by 35 participants, including government officials, scientists, policy analysts, representatives of interested NGO's, journalists, a Member of Parliament, and visiting representatives from the US and Irish governments. The topic of managing plutonium has been a consistent thread within ORG's work, and was the subject of one of our previous reports, CDR 12. This particular seminar arose out of discussions earlier in the year between Dr. Frank Barnaby and the Rt. Hon. Michael Meacher MP, Minister for the Environment. With important decisions about the management of plutonium in Britain pending, ORG undertook to hold a seminar at which all aspects of the subject could be aired. A number of on-going events formed the background to this initiative. The first was British Nuclear Fuels' [BNFL] application to the Environment Agency to commission a mixed oxide fuel [MOX] plant at Sellafield. The second was BNFL's application to vary radioactive discharge limits at Sellafield. Thirdly, a House of Lords Select Committee was in process of taking evidence, on the disposal of radioactive waste. Fourthly, the Royal Society, in a recent report entitled Management of Separated Plutonium, recommended that 'the Government should commission a comprehensive review... of the options for the management of plutonium'. Four formal presentations were made to the meeting, on the subjects of Britain's plutonium policy, commercial prospects for plutonium use, problems of plutonium accountancy, and the danger of nuclear terrorism, by experts from outside the nuclear industry. It was hoped that the industry's viewpoint would also be heard, and BNFL were invited to present a paper, but declined on the grounds that they

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

    Science.gov (United States)

    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.

  4. High-level neutron-coincidence-counter (HLNCC) implementation: assay of the plutonium content of mixed-oxide fuel assemblies

    Energy Technology Data Exchange (ETDEWEB)

    Foley, J E; Bosler, G E

    1982-04-01

    The portable High-Level Neutron Coincidence Counter is used to assay the /sup 240/Pu-effective loading of a reference mixed-oxide fuel assembly by neutron coincidence counting. We have investigated the effects on the coincidence count rate of the total fuel loading (UO/sub 2/ + PuO/sub 2/), the fissile loading, the fuel rod diameter, and the fuel rod pattern. The coincidence count rate per gram of /sup 240/Pu-effective per centimeter is primarily dependent on the total fuel loading of the assembly; the higher the loading, the higher the coincidence count rate. Detailed procedures for the assay of mixed-oxide fuel assemblies are developed.

  5. Development of ORIGEN libraries for mixed oxide (MOX) fuel assembly designs

    Energy Technology Data Exchange (ETDEWEB)

    Mertyurek, Ugur, E-mail: mertyureku@ornl.gov; Gauld, Ian C., E-mail: gauldi@ornl.gov

    2016-02-15

    Highlights: • ORIGEN MOX library generation process is described. • SCALE burnup calculations are validated against measured MOX fuel samples from the MALIBU program. • ORIGEN MOX libraries are verified using the OECD Phase IV-B benchmark. • There is good agreement for calculated-to-measured isotopic distributions. - Abstract: 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. 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.

  6. Electrolytic trichloroethene degradation using mixed metal oxide coated titanium mesh electrodes.

    Science.gov (United States)

    Petersen, Matthew A; Sale, Thomas C; Reardon, Kenneth F

    2007-04-01

    Electrochemical systems provide a low cost, versatile, and controllable platform to potentially treat contaminants in water, including chlorinated solvents. Relative to bare metal or noble metal amended materials, dimensionally stable electrode materials such as mixed metal oxide coated titanium (Ti/MMO) have advantages in terms of stability and cost, important factors for sustainable remediation solutions. Here, we report the use of Ti/MMO as an effective cathode substrate for treatment of trichloroethene (TCE). TCE degradation in a batch reactor was measured as the decrease of TCE concentration over time and the corresponding evolution of chloride; notably, this occurred without the formation of commonly encountered chlorinated intermediates. The reaction was initiated when Ti/MMO cathode potentials were less than -0.8 V vs. the standard hydrogen electrode, and the rate of TCE degradation increased linearly with progressively more negative potentials. The maximum pseudo-first-order heterogeneous rate constant was approximately 0.05 cm min(-1), which is comparable to more commonly used cathode materials such as nickel. In laboratory-scale flow-though column reactors designed to simulate permeable reactive barriers (PRBs), TCE concentrations were reduced by 80-90%. The extent of TCE flux reduction increased with the applied potential difference across the electrodes and was largely insensitive to the spacing distance between the electrodes. This is the first report of the electrochemical reduction of a chlorinated organic contaminant at a Ti/MMO cathode, and these results support the use of this material in PRBs as a possible approach to manage TCE plume migration.

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

    Science.gov (United States)

    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.

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

    Energy Technology Data Exchange (ETDEWEB)

    Stevenson, J.W.; Armstrong, T.R.; Bates, J.L. [and others

    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.

  9. Pu-doped zirconolite for minor actinide containment

    Energy Technology Data Exchange (ETDEWEB)

    Deschanels, X.; Broudic, V.; Jegou, C.; Peuget, S.; Roudil, D.; Jorion, F.; Advocat, T

    2004-07-01

    Zirconolite is a potential matrix for the immobilization of the minor actinides stream produced by the reprocessing of the spent fuel. In order to check the incorporation of actinide into the structure, zirconolite ceramic pellets doped with 10 wt% in {sup 239}PuO{sub 2} were sintered. Characterization by SEM, XRD and XANES spectroscopy have been done on this material. The microstructural homogeneity of the pellets is good, and their relative density is higher than 90% of the theoretical density. XANES spectroscopy shows that Pu is at the oxidation state IV in this material. To investigate the effects of radiation damage on zirconolite structure, pellets doped with 10 wt% of {sup 238}PuO{sub 2} were fabricated. The {sup 238}Pu accelerates the radiation damage relative to the {sup 239}Pu because of its much higher specific activity (63.2 x 10{sup 10} Bq/g for {sup 238}Pu vs. 2.2 x 10{sup 9} Bq/g for {sup 238}Pu). Some pellets are storing at ambient, 250 deg. C and 500 deg C. Up 10{sup 19} {alpha}/cm{sup 3}, the macroscopic swelling of the samples stored at ambient is about 0.5% by 10{sup 18} {alpha}/cm{sup 3}, and the microscopic one near 0.35% by 10{sup 18} {alpha}/cm{sup 3}. Some microcracks are observed on these pellets. The samples started to become amorphous at 10{sup 19} {alpha}/cm{sup 3}. The swelling strongly decreases with the storage temperature of the samples. The leaching rate of {sup 239}Pu doped ceramics measured by Soxhlet tests at 100 deg. C in deionized water appears to be the same as inactive material. (authors)

  10. Actinide-specific complexing agents: their structural and solution chemistry

    Energy Technology Data Exchange (ETDEWEB)

    Raymond, K.N.; Freeman, G.E.; Kappel, M.J.

    1983-07-01

    The synthesis of a series of tetracatecholate ligands designed to be specific for Pu(IV) and other actinide(IV) ions has been achieved. Although these compounds are very effective as in vivo plutonium removal agents, potentiometric and voltammetric data indicate that at neutral pH full complexation of the Pu(IV) ion by all four catecholate groups does not occur. Spectroscopic results indicate that the tetracatecholates, 3,4,3-LICAMS and 3,4,3-LICAMC, complex Am(III). The Am(IV)/(III)-catecholate couple (where catecholate = 3,4,3-LICAMS or 3,4,3-LICAMC) is not observed, but may not be observable due to the large currents associated with ligand oxidation. However, within the potential range where ligand oxidation does not occur, these experiments indicate that the reduction potential of free Am(IV)/(III) is probably greater than or equal to + 2.6 V vs NHE or higher. Proof of the complexation of americium in the trivalent oxidation state by 3,4,3-LICAMS and 3,4,3-LICAMC elimates the possibility of tetracatholates stabilizing Am(IV) in vivo.

  11. STRONTIUM AND ACTINIDE SEPARATIONS FROM HIGH LEVEL NUCLEAR WASTE SOLUTIONS USING MONOSODIUM TITANATE 1. SIMULANT TESTING

    Energy Technology Data Exchange (ETDEWEB)

    HOBBS, D. T.; BARNES, M. J.; PULMANO, R. L.; MARSHALL, K. M.; EDWARDS, T. B.; BRONIKOWSKI, M. G.; FINK, S. D.

    2005-04-14

    High-level nuclear waste produced from fuel reprocessing operations at the Savannah River Site (SRS) requires pretreatment to remove {sup 137}Cs, {sup 90}Sr and alpha-emitting radionuclides (i.e., actinides) prior to disposal. Separation processes planned at SRS include caustic side solvent extraction, for {sup 137}Cs removal, and ion exchange/sorption of {sup 90}Sr and alpha-emitting radionuclides with an inorganic material, monosodium titanate (MST). The predominant alpha-emitting radionuclides in the highly alkaline waste solutions include plutonium isotopes {sup 238}Pu, {sup 239}Pu and {sup 240}Pu. This paper provides a summary of data acquired to measure the performance of MST to remove strontium and actinides from simulated waste solutions. These tests evaluated the influence of ionic strength, temperature, solution composition and the oxidation state of plutonium.

  12. Preparation of Well Dispersed and Ultra-Fine Ce(Zr)O2 Mixed Oxide by Mechanochemical Processing

    Institute of Scientific and Technical Information of China (English)

    程昌明; 李永绣; 周雪珍; 陈伟凡

    2004-01-01

    Ultra-fine CeO2-ZrO2 mixed oxide was successfully synthesized by wet-solid phase mechanochemical processing, Ce2(CO3)3·8H2O, ZrOCl2·xH2O and ammonia were used as reactants. It is found that the crystalline Ce2(CO3)3·8H2O and ZrOCl2·xH2O are changed to amorphous cerium and zirconium hydroxide precursor after milling with ammonia, and Ce0.15Zr0.85O2 mixed oxide with pure tetragonal phase structure and medium particle size(D50)less than 1μm is formed by calcining precursor over 673 K. The XRD patterns indicate that the crystal unite size increases with rising calcining temperature due to crystal growth. However, the particle size and BET surface area of the Ce(Zr)O2 mixed oxide decreases with rising calcining temperature, which may be attributed to the contract of particles and the vanish of holes inside grains.

  13. Rational design of Mg-Al mixed oxide-supported bimetallic catalysts for dry reforming of methane

    Energy Technology Data Exchange (ETDEWEB)

    Tsyganok, Andrey I. [Centre for Catalysis Research and Innovation, Department of Chemistry, University of Ottawa, D' Iorio Hall, 10 Marie Curie Street, Ottawa, Ont. (Canada); Inaba, Mieko [Natural Gas Technology Development Team, Teikoku Oil Co., 9-23-30 Kitakarasuyama, Setagaya-ku, Tokyo 157-0061 (Japan); Tsunoda, Tatsuo; Uchida, Kunio; Suzuki, Kunio; Hayakawa, Takashi [Institute for Materials and Chemical Process, National Institute of Advanced Industrial Science and Technology (AIST), Tsukuba Central 5, 1-1-1 Higashi, Tsukuba 305-8565 (Japan); Takehira, Katsuomi [Department of Applied Chemistry, Faculty of Engineering, Hiroshima University, 1-4-1 Kagamiyama, Higashi-Hiroshima 739-8527 (Japan)

    2005-09-18

    A novel synthetic strategy for preparing bimetallic Ru-M (M=Cr, Fe, Co, Ni and Cu) catalysts, supported on Mg-Al mixed oxide, has been introduced. It was based on a 'memory effect', i.e. on the ability of Mg-Al mixed oxide to reconstruct a layered structure upon rehydration with an aqueous solution. By repeated calcinations-rehydration cycles, layered double hydroxide (LDH) precursors of catalysts containing two different metals were synthesized. Bimetallic catalysts were then generated (1) in situ from LDH under methane reforming reaction conditions and (2) from mixed metal oxides obtained by preliminary LDH calcination. Among all the LDH-derived catalysts, a Ru{sup 0.1%}-Ni{sup 5.0%}/MgAlO{sub x} sample revealed the highest activity and selectivity to syngas, a suitable durability and a low coking capacity. A promoting effect of ruthenium on catalytic function of supported nickel was demonstrated. Preliminary LDH calcination was shown to markedly affect the catalytic activity of the derived catalysts and especially their coking properties.

  14. Mixed species biofilms of Fusobacterium necrophorum and Porphyromonas levii impair the oxidative response of bovine neutrophils in vitro.

    Science.gov (United States)

    Lockhart, Joey S; Buret, Andre G; Ceri, Howard; Storey, Douglas G; Anderson, Stefanie J; Morck, Douglas W

    2017-10-01

    Biofilms composed of anaerobic bacteria can result in persistent infections and chronic inflammation. Host immune cells have difficulties clearing biofilm-related infections and this can result in tissue damage. Neutrophils are a vital component of the innate immune system and help clear biofilms. The comparative neutrophilic response to biofilms versus planktonic bacteria remains incompletely understood, particularly in the context of mixed infections. The objective of this study was to generate mixed species anaerobic bacterial biofilms composed of two opportunistic pathogens, Fusobacterium necrophorum and Porphyromonas levii, and evaluate neutrophil responses to extracellular fractions from both biofilms and planktonic cell co-cultures of the same bacteria. Purified bovine neutrophils exposed to culture supernatants from mixed species planktonic bacteria showed elevated oxidative activity compared to neutrophils exposed to biofilms composed of the same bacteria. Bacterial lipopolysaccharide plays a significant role in the stimulation of neutrophils; biofilms produced substantially more lipopolysaccharide than planktonic bacteria under these experimental conditions. Removal of lipopolysaccharide significantly reduced neutrophil oxidative response to culture supernatants of planktonic bacteria. Oxidative responses to LPS-removed biofilm supernatants and LPS-removed planktonic cell supernatants were similar. The limited neutrophil response to biofilm bacteria observed in this study supports the reduced ability of the innate immune system to eradicate biofilm-associated infections. Lipopolysaccharide is likely important in neutrophil response; however, the presence of other extracellular, immune modifying molecules in the bacterial media also appears to be important in altering neutrophil function. Copyright © 2017 Elsevier Ltd. All rights reserved.

  15. Synthesis and Photocatalytic Activity of One-dimensional ZnO-Zn2SnO4 Mixed Oxide Nanowires

    Institute of Scientific and Technical Information of China (English)

    Xue-lian Bai; Nan Pan; Xiao-ping Wang; Hai-qian Wang

    2008-01-01

    Mixed oxide photocatalysts,ZnO-Zn2SnO4(ZnO-ZTO) nanowires with different sizes were prepared by a simple thermal evaporation method.The ZnO-ZTO nanowires were characterized with a scanning electron microscope,X-ray diffraction,high-resolution transmission electron microscopy,energy-dispersive spectrometer,and X-ray photoelectron spectra.The photocatalytic activity of the ZnO-ZTO mixed nanowires were studied by observing the photodegradation behaviors of methyl orange aqueous solution.The results suggest that the ZnO-ZTO mixed oxide nanowires have a higher photocatalytic activity than pure ZnO and Zn2SnO4 nanowires.The photocatalyst concentration in the solution distinctly affects the degradation rate,and our results show that higher photodegradation efficiency can be achieved with a smaller amount of ZnO-ZTO nanowire catalyst,as compared to the pure ZnO and ZTO nanowires.Moreover,the photocatalytic activity can also be enhanced by reducing the average diameter of the nanowires.The activity of pure ZnO and ZTO nanowires are also enhanced by physically mixing them.These results can be explained by the synergism between the two semiconductors.

  16. Advanced Extraction Methods for Actinide/Lanthanide Separations

    Energy Technology Data Exchange (ETDEWEB)

    Scott, M.J.

    2005-12-01

    The separation of An(III) ions from chemically similar Ln(III) ions is perhaps one of the most difficult problems encountered during the processing of nuclear waste. In the 3+ oxidation states, the metal ions have an identical charge and roughly the same ionic radius. They differ strictly in the relative energies of their f- and d-orbitals, and to separate these metal ions, ligands will need to be developed that take advantage of this small but important distinction. The extraction of uranium and plutonium from nitric acid solution can be performed quantitatively by the extraction with the TBP (tributyl phosphate). Commercially, this process has found wide use in the PUREX (plutonium uranium extraction) reprocessing method. The TRUEX (transuranium extraction) process is further used to coextract the trivalent lanthanides and actinides ions from HLLW generated during PUREX extraction. This method uses CMPO [(N, N-diisobutylcarbamoylmethyl) octylphenylphosphineoxide] intermixed with TBP as a synergistic agent. However, the final separation of trivalent actinides from trivalent lanthanides still remains a challenging task. In TRUEX nitric acid solution, the Am(III) ion is coordinated by three CMPO molecules and three nitrate anions. Taking inspiration from this data and previous work with calix[4]arene systems, researchers on this project have developed a C3-symmetric tris-CMPO ligand system using a triphenoxymethane platform as a base. The triphenoxymethane ligand systems have many advantages for the preparation of complex ligand systems. The compounds are very easy to prepare. The steric and solubility properties can be tuned through an extreme range by the inclusion of different alkoxy and alkyl groups such as methyoxy, ethoxy, t-butoxy, methyl, octyl, t-pentyl, or even t-pentyl at the ortho- and para-positions of the aryl rings. The triphenoxymethane ligand system shows promise as an improved extractant for both tetravalent and trivalent actinide recoveries form

  17. Sorption of actinides onto nanodiamonds

    Energy Technology Data Exchange (ETDEWEB)

    Buchatskaya, Yulia; Romanchuk, Anna; Yakovlev, Ruslan; Kulakova, Inna [Lomonosov Moscow State Univ., Moscow (Russian Federation). Dept. of Chemistry; Shiryaev, Andrei [Russian Academy of Sciences, Moscow (Russian Federation). Frumkin Institute of Physical Chemistry and Electrochemistry; Russian Academy of Sciences, Moscow (Russian Federation). Inst. of Geology of Ore Deposits, Petrography, Mineralogy and Geochemistry; Kalmykov, Stepan [Lomonosov Moscow State Univ., Moscow (Russian Federation). Dept. of Chemistry; Russian Academy of Sciences, Moscow (Russian Federation). Frumkin Institute of Physical Chemistry and Electrochemistry; Russian Academy of Sciences, Moscow (Russian Federation). Vernadsky Institute of Geochemistry and Analytical Chemistry

    2015-06-01

    Detonation nanodiamonds (ND) present a significant part of nanocarbons group, which could be produced on commercial scale by detonation of explosives in a closed chamber. Their unique properties of high surface area, low weight and radiation resistance make ND a prospective candidate for applications in sorption processes in radiochemistry. To study the influence of surface chemistry on sorption properties, apristine sample of ND was treated with acids and hydrogen. The surface chemistry of the samples was characterised by infrared spectroscopy, X-ray photoelectron spectroscopy and Boehm titration. The sorption properties of ND were tested fordifferent radionuclides. The sorption capacity of ND was shown to be higher than those of commonly used radionuclide sorbents like activated carbon and compariable to other members of nanocarbon group like graphene oxide and carbon nanotubes. The sorption properties were shown to be influenced by the presence of oxygen-containing groups on the surface of ND. This represents an opportunity to increase the sorption capacity of ND.

  18. A high-throughput reactor system for optimization of Mo–V–Nb mixed oxide catalyst composition in ethane ODH

    KAUST Repository

    Zhu, Haibo

    2015-01-01

    75 Mo-V-Nb mixed oxide catalysts with a broad range of compositions were prepared by a simple evaporation method, and were screened for the ethane oxidative dehydrogenation (ODH) reaction. The compositions of these 75 catalysts were systematically changed by varying the Nb loading, and the Mo/V molar ratio. Characterization by XRD, XPS, H2-TPR and SEM revealed that an intimate structure is formed among the 3 components. The strong interaction among different components leads to the formation of a new phase or an "intimate structure". The dependency of conversion and selectivity on the catalyst composition was clearly demonstrated from the results of high-throughput testing. The optimized Mo-V-Nb molar composition was confirmed to be composed of a Nb content of 4-8%, a Mo content of 70-83%, and a V content of 12-25%. The enhanced catalytic performance of the mixed oxides is obviously due to the synergistic effects of the different components. The optimized compositions for ethane ODH revealed in our high-throughput tests and the structural information provided by our characterization studies can serve as the starting point for future efforts to improve the catalytic performance of Mo-V-Nb oxides. This journal is © The Royal Society of Chemistry.

  19. Development of Impregnated Agglomerate Pelletization (IAP) process for fabrication of (Th,U)O 2 mixed oxide pellets

    Science.gov (United States)

    Khot, P. M.; Nehete, Y. G.; Fulzele, A. K.; Baghra, Chetan; Mishra, A. K.; Afzal, Mohd.; Panakkal, J. P.; Kamath, H. S.

    2012-01-01

    Impregnated Agglomerate Pelletization (IAP) technique has been developed at Advanced Fuel Fabrication Facility (AFFF), BARC, Tarapur, for manufacturing (Th, 233U)O 2 mixed oxide fuel pellets, which are remotely fabricated in hot cell or shielded glove box facilities to reduce man-rem problem associated with 232U daughter radionuclides. This technique is being investigated to fabricate the fuel for Indian Advanced Heavy Water Reactor (AHWR). In the IAP process, ThO 2 is converted to free flowing spheroids by powder extrusion route in an unshielded facility which are then coated with uranyl nitrate solution in a shielded facility. The dried coated agglomerate is finally compacted and then sintered in oxidizing/reducing atmosphere to obtain high density (Th,U)O 2 pellets. In this study, fabrication of (Th,U)O 2 mixed oxide pellets containing 3-5 wt.% UO 2 was carried out by IAP process. The pellets obtained were characterized using optical microscopy, XRD and alpha autoradiography. The results obtained were compared with the results for the pellets fabricated by other routes such as Coated Agglomerate Pelletization (CAP) and Powder Oxide Pelletization (POP) route.

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

    Science.gov (United States)

    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.

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

    Directory of Open Access Journals (Sweden)

    Kenichi Shimizu

    2011-02-01

    Full Text Available 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.

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

    Science.gov (United States)

    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

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

    Science.gov (United States)

    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.

  4. Comparison of actinides and fission products recycling scheme with the normal plutonium recycling scheme in fast reactors

    Directory of Open Access Journals (Sweden)

    Salahuddin Asif

    2013-01-01

    Full Text Available Multiple recycling of actinides and non-volatile fission products in fast reactors through the dry re-fabrication/reprocessing atomics international reduction oxidation process has been studied as a possible way to reduce the long-term potential hazard of nuclear waste compared to that resulting from reprocessing in a wet PUREX process. Calculations have been made to compare the actinides and fission products recycling scheme with the normal plutonium recycling scheme in a fast reactor. For this purpose, the Karlsruhe version of isotope generation and depletion code, KORIGEN, has been modified accordingly. An entirely novel fission product yields library for fast reactors has been created which has replaced the old KORIGEN fission products library. For the purposes of this study, the standard 26 groups data set, KFKINR, developed at Forschungszentrum Karlsruhe, Germany, has been extended by the addition of the cross-sections of 13 important actinides and 68 most important fission products. It has been confirmed that these 68 fission products constitute about 95% of the total fission products yield and about 99.5% of the total absorption due to fission products in fast reactors. The amount of fissile material required to guarantee the criticality of the reactor during recycling schemes has also been investigated. Cumulative high active waste per ton of initial heavy metal is also calculated. Results show that the recycling of actinides and fission products in fast reactors through the atomics international reduction oxidation process results in a reduction of the potential hazard of radioactive waste.

  5. High-temperature thermochemical energy storage based on redox reactions using Co-Fe and Mn-Fe mixed metal oxides

    Science.gov (United States)

    André, Laurie; Abanades, Stéphane; Cassayre, Laurent

    2017-09-01

    Metal oxides are potential materials for thermochemical heat storage via reversible endothermal/exothermal redox reactions, and among them, cobalt oxide and manganese oxide are attracting attention. The synthesis of mixed oxides is considered as a way to answer the drawbacks of pure metal oxides, such as slow reaction kinetics, loss-in-capacity over cycles or sintering issues, and the materials potential for thermochemical heat storage application needs to be assessed. This work proposes a study combining thermodynamic calculations and experimental measurements by simultaneous thermogravimetric analysis and calorimetry, in order to identify the impact of iron oxide addition to Co and Mn-based oxides. Fe addition decreased the redox activity and energy storage capacity of Co3O4/CoO, whereas the reaction rate, reversibility and cycling stability of Mn2O3/Mn3O4 was significantly enhanced with added Fe amounts above 15 mol%, and the energy storage capacity was slightly improved. The formation of a reactive cubic spinel explained the improved re-oxidation yield of Mn-based oxides that could be cycled between bixbyite and cubic spinel phases, whereas a low reactive tetragonal spinel phase showing poor re-oxidation was formed below 15 mol% Fe. Thermodynamic equilibrium calculations predict accurately the behavior of both systems. The possibility to identify other suitable mixed oxides becomes conceivable, by enabling the selection of transition metal additives for tuning the redox properties of mixed metal oxides destined for thermochemical energy storage applications.

  6. AECL/US INERI - Development of Inert Matrix Fuels for Plutonium and Minor Actinide Management in Power Reactors -- Fuel Requirements and Down-Select Report

    Energy Technology Data Exchange (ETDEWEB)

    William Carmack; Randy D. Lee; Pavel Medvedev; Mitch Meyer; Michael Todosow; Holly B. Hamilton; Juan Nino; Simon Philpot; James Tulenko

    2005-06-01

    The U.S. Advanced Fuel Cycle Program and the Atomic Energy Canada Ltd (AECL) seek to develop and demonstrate the technologies needed to minimize the overall Pu and minor actinides present in the light water reactor (LWR) nuclear fuel cycles. It is proposed to reuse the Pu from LWR spent fuel both for the energy it contains and to decrease the hazard and proliferation impact resulting from storage of the Pu and minor actinides. The use of fuel compositions with a combination of U and Pu oxide (MOX) has been proposed as a way to recycle Pu and/or minor actinides in LWRs. It has also been proposed to replace the fertile U{sup 238} matrix of MOX with a fertile-free matrix (IMF) to reduce the production of Pu{sup 239} in the fuel system. It is important to demonstrate the performance of these fuels with the appropriate mixture of isotopes and determine what impact there might be from trace elements or contaminants. Previous work has already been done to look at weapons-grade (WG) Pu in the MOX configuration [1][2] and the reactor-grade (RG) Pu in a MOX configuration including small (4000 ppm additions of Neptunium). This program will add to the existing database by developing a wide variety of MOX fuel compositions along with new fuel compositions called inert-matrix fuel (IMF). The goal of this program is to determine the general fabrication and irradiation behavior of the proposed IMF fuel compositions. Successful performance of these compositions will lead to further selection and development of IMF for use in LWRs. This experiment will also test various inert matrix material compositions with and without quantities of the minor actinides Americium and Neptunium to determine feasibility of incorporation into the fuel matrices for destruction. There is interest in the U.S. and world-wide in the investigation of IMF (inert matrix fuels) for scenarios involving stabilization or burn down of plutonium in the fleet of existing commercial power reactors. IMF offer the

  7. Mg-AI Mixed Oxides Supported Bimetallic Au-Pd Nanoparticles with Superior Catalytic Properties in Aerobic Oxidation of Benzyl Alcohol and Glycerol

    Institute of Scientific and Technical Information of China (English)

    王亮; 张伟; 曾尚景; 苏党生; 孟祥举; 肖丰收

    2012-01-01

    Nano-sized Au and Pd catalysts are favorable for oxidations with molecular oxygen, and the preparation of this kind of nanoparticles with high catalytic activities is strongly desirable. We report a successful synthesis of bimetal- lic Au-Pd nanoparticles with rich edge and comer sites on unique support of Mg-AI mixed oxides (Au-Pd/MAO), which are favorable for producing metal nanoparticles with high degree of coordinative unsaturation of metal atoms The systematic microscopic characterizations confirm the bimetallic Au-Pd nanoparticles are present as Au-Pd alloy The irregular shape of the bimetallic nanoparticles are directly observed in HRTEM images. As we expected, Au-Pd/MAO gives very excellent catalytic performances in the aerobic oxidation of benzyl alcohol and glycerol. For example, Au-Pd/MAO shows very high TOF of 91000 h i at 433 K with molecular oxygen at air pressure in solvent-free oxidation of benzyl alcohol; this catalyst also shows relatively high selectivity for tartronic acid (TA- RAC, 36.6%) at high conversion (98.5%) in aerobic oxidation of glycerol. The superior catalytic properties of Au-Pd/MAO would be potentially important tbr production of fine chemicals.

  8. Synthesis, characterization and magnetic behavior of Mg–Fe–Al mixed oxides based on layered double hydroxide

    Energy Technology Data Exchange (ETDEWEB)

    Heredia, Angélica C., E-mail: angelicacheredia@gmail.com [Universidad Tecnológica Nacional, Facultad Regional Córdoba-CITeQ, Maestro López esq. Cruz Roja Argentina, Ciudad Universitaria, 5016 Córdoba (Argentina); Oliva, Marcos I. [IFEG, Universidad Nacional de Córdoba, Córdoba (Argentina); CONICET (Argentina); Agú, Ulises [Universidad Tecnológica Nacional, Facultad Regional Córdoba-CITeQ, Maestro López esq. Cruz Roja Argentina, Ciudad Universitaria, 5016 Córdoba (Argentina); CONICET (Argentina); Zandalazini, Carlos I. [CONICET (Argentina); INFIQC, FCQ Universidad Nacional de Córdoba, Córdoba (Argentina); Marchetti, Sergio G. [CINDECA, UNLP, Buenos Aires (Argentina); Herrero, Eduardo R.; Crivello, Mónica E. [Universidad Tecnológica Nacional, Facultad Regional Córdoba-CITeQ, Maestro López esq. Cruz Roja Argentina, Ciudad Universitaria, 5016 Córdoba (Argentina)

    2013-09-15

    In the present work, Mg–Al–Fe layered double hydroxides were prepared by coprecipitation reaction with hydrothermal treatment. The characterization of precursors and their corresponding calcinated products (mixed oxides) were carried out by X ray diffraction, X-ray photoelectron spectroscopy (XPS), termogravimetric analysis and differential scanning calorimetry, diffuse reflectance UV–vis spectroscopy, specific surface area, Mössbauaer and magnetic properties. The Fe{sup 3+} species were observed in tetrahedrally and octahedrally coordination in brucite layered. The XPS analysis shows that the Fe{sup 3+} ions can be found in two coordination environments (tetrahedral and octahedral) as mixed oxides, and as spinel-structure. Oxides show a decrease in the specific surface areas when the iron loading is increased. The magnetic and Mössbauaer response show that MgAlFe mixed oxides are different behaviours such as different population ratios of ferromagnetic, weak-ferromagnetic, paramagnetic and superparamagnetic phases. The better crystallization of spinel structure with increased temperature, is correlated with the improved magnetic properties. - Highlights: • Mg–Al–Fe were successfully prepared by coprecipitation with hydrothermal treatment. • MgO, α-Fe{sub 2}O{sub 3,} MgFe{sub 2}O{sub 4} were detected by XRD in the calcined samples. • The Fe{sup 3+} is in tetrahedral and octahedral coordination in the brucite layered. • The specific surface area is directly related with the iron content. • The magnetic properties and MgFe{sub 2}O{sub 4} improve with increasing calcination temperature.

  9. Electron-phonon coupling of light-actinides. Effect of spin-orbit coupling

    Energy Technology Data Exchange (ETDEWEB)

    Gonzalez-Castelazo, Paola; Pena-Seaman, Omar de la [Benemerita Universidad Autonoma de Puebla (BUAP), Institute of Physics (IFUAP) (Mexico); Heid, Rolf; Bohnen, Klaus-Peter [Karlsruher Institut fuer Technologie (KIT), Institut fuer Festkoerperphysik (IFP) (Germany)

    2014-07-01

    The physics of actinide metals is quite complex and rich due to the behavior of 5f electrons in the valence region: it goes from itinerant on the early stages of the actinide series to highly localized for the elements with a higher number of 5f electrons involved. In addition, in this systems should be mandatory the inclusion of spin-orbit coupling (SOC). However, only in few cases on electronic and lattice dynamical properties the SOC has been taking into account, while for the electron-phonon (e-ph) coupling such analysis has not been performed so far. Thus, as a first approach we have systematically studied the SOC influence on the full-phonon dispersion and the e-ph coupling for the simplest light-actinide metals: Ac and Th. These elements have been studied within the framework of density functional perturbation theory, using a mixed-basis pseudopotential method. The full-phonon dispersion as well as the Eliashberg spectral function and the electron-phonon coupling parameter have been calculated with and without SOC. The observed effects of SOC in the full-phonon dispersion and Eliashberg function are discussed in detail, together with an analysis of the differences on the electronic properties due to the SOC inclusion in the calculations.

  10. Potentiometric Sensor for Real-Time Remote Surveillance of Actinides in Molten Salts

    Energy Technology Data Exchange (ETDEWEB)

    Natalie J. Gese; Jan-Fong Jue; Brenda E. Serrano; Guy L. Fredrickson

    2012-07-01

    A potentiometric sensor is being developed at the Idaho National Laboratory for real-time remote surveillance of actinides during electrorefining of spent nuclear fuel. During electrorefining, fuel in metallic form is oxidized at the anode while refined uranium metal is reduced at the cathode in a high temperature electrochemical cell containing LiCl-KCl-UCl3 electrolyte. Actinides present in the fuel chemically react with UCl3 and form stable metal chlorides that accumulate in the electrolyte. This sensor will be used for process control and safeguarding of activities in the electrorefiner by monitoring the concentrations of actinides in the electrolyte. The work presented focuses on developing a solid-state cation conducting ceramic sensor for detecting varying concentrations of trivalent actinide metal cations in eutectic LiCl-KCl molten salt. To understand the basic mechanisms for actinide sensor applications in molten salts, gadolinium was used as a surrogate for actinides. The ß?-Al2O3 was selected as the solid-state electrolyte for sensor fabrication based on cationic conductivity and other factors. In the present work Gd3+-ß?-Al2O3 was prepared by ion exchange reactions between trivalent Gd3+ from GdCl3 and K+-, Na+-, and Sr2+-ß?-Al2O3 precursors. Scanning electron microscopy (SEM) was used for characterization of Gd3+-ß?-Al2O3 samples. Microfocus X-ray Diffraction (µ-XRD) was used in conjunction with SEM energy dispersive X-ray spectroscopy (EDS) to identify phase content and elemental composition. The Gd3+-ß?-Al2O3 materials were tested for mechanical and chemical stability by exposing them to molten LiCl-KCl based salts. The effect of annealing on the exchanged material was studied to determine improvements in material integrity post ion exchange. The stability of the ß?-Al2O3 phase after annealing was verified by µ-XRD. Preliminary sensor tests with different assembly designs will also be presented.

  11. A new definition of coordination number and its use in lanthanide and actinide coordination and organometallic chemistry

    Energy Technology Data Exchange (ETDEWEB)

    Marcalo, J.; Pires de Matos, A. (ICEN, LNETI, Sacavem (Portugal). Dept. de Quimica)

    1989-01-01

    A steric coordination number of a ligand is defined, based on the solid angle comprising the van der Waals' spheres of the atoms of that ligand, as an alternative to the formal coordination number in discussing structural aspects of lanthanide and actinide coordination and organometallic compounds. The study of the bond lengths in 274 structurally characterized compounds of the lanthanides (including scandium and Yttrium), in oxidation states II and III, and the actinides (thorium and uranium), in oxidation states III and IV, was the basis to derive ligand effective radii which are discussed in relation to bonding, coordination geometries, metal ionic radii and oxidation states. Potential uses of the new definition of coordination number and of the ligand effective radii obtained in molecular structure comparison and bond length prediction are also discussed. (author).

  12. Preparation of mixed oxides (Th,U)O{sub 2}: an evaluation of different techniques; Estudos de diferentes rotas de preparacao de oxidos binarios de torio e uranio

    Energy Technology Data Exchange (ETDEWEB)

    Ayoub, Jamil Mahmoud Said

    1999-07-01

    An evaluation of different ways of obtaining (Th-U)O{sub 2} mixed oxides is described. Coprecipitation, mechanical mixing of uranium and thorium powders, and the sol-gel technique were studied in order to get a large spectrum of knowledge of the process performance. The use of ultrasonic waves for the homogenization of the hydroxide mixture and microwave heating for powder drying was also investigated. Sol-gel showed the best results regarding the specific area for obtained samples. Oxide drying by microwave is an effective method to get mixed oxides for fuel fabrication. Neither coprecipitation nor mechanical mixing of the thorium and uranium oxide powders is suitable for the purpose. The obtained data are less than 70% than those achieved when sol-gel process is performed. Electronic microscopy, X-ray fluorescence and diffraction, thermogravimetry, specific gravidity and specific area determination (BET) used for sample characterization were convenient and accomplished good results. (author)

  13. Chemistry of lower valent actinide halides

    Energy Technology Data Exchange (ETDEWEB)

    Lau, K.H.; Hildenbrand, D.L.

    1992-01-01

    This research effort was concerned almost entirely with the first two members of the actinide series, thorium and uranium, although the work was later extended to some aspects of the neptunium-fluorine system in a collaborative program with Los Alamos National Laboratory. Detailed information about the lighter actinides will be helpful in modeling the properties of the heavier actinide compounds, which will be much more difficult to study experimentally. In this program, thermochemical information was obtained from high temperature equilibrium measurements made by effusion-beam mass spectrometry and by effusion-pressure techniques. Data were derived primarily from second-law analysis so as to avoid potential errors in third-law calculations resulting from uncertainties in spectroscopic and molecular constants. This approach has the additional advantage of yielding reaction entropies that can be checked for consistency with various molecular constant assignments for the species involved. In the U-F, U-Cl, and U-Br systems, all of the gaseous species UX, UX{sub 2}, UX{sub 3}, UX{sub 4}, and UX{sub 5}, where X represents the halogen, were identified and characterized; the corresponding species ThX, ThX{sub 2}, ThX{sub 3}, and ThX{sub 4} were studied in the Th-F, Th-Cl, and Th-Br systems. A number of oxyhalide species in the systems U-0-F, U-0-Cl, Th-0-F, and Th-O-Cl were studied thermochemically. Additionally, the sublimation thermodynamics of NpF{sub 4}(s) and NpO{sub 2}F{sub 2}(s) were studied by mass spectrometry.

  14. Fission cross section measurements for minor actinides

    Energy Technology Data Exchange (ETDEWEB)

    Fursov, B. [IPPE, Obninsk (Russian Federation)

    1997-03-01

    The main task of this work is the measurement of fast neutron induced fission cross section for minor actinides of {sup 238}Pu, {sup 242m}Am, {sup 243,244,245,246,247,248}Cm. The task of the work is to increase the accuracy of data in MeV energy region. Basic experimental method, fissile samples, fission detectors and electronics, track detectors, alpha counting, neutron generation, fission rate measurement, corrections to the data and error analysis are presented in this paper. (author)

  15. Calculated Bulk Properties of the Actinide Metals

    DEFF Research Database (Denmark)

    Skriver, Hans Lomholt; Andersen, O. K.; Johansson, B.

    1978-01-01

    Self-consistent relativistic calculations of the electronic properties for seven actinides (Ac-Am) have been performed using the linear muffin-tin orbitals method within the atomic-sphere approximation. Exchange and correlation were included in the local spin-density scheme. The theory explains...... the variation of the atomic volume and the bulk modulus through the 5f series in terms of an increasing 5f binding up to plutonium followed by a sudden localisation (through complete spin polarisation) in americium...

  16. Actinide management with commercial fast reactors

    Energy Technology Data Exchange (ETDEWEB)

    Ohki, Shigeo [Japan Atomic Energy Agency, 4002, Narita-cho, O-arai-machi, Higashi-Ibaraki-gun, Ibaraki 311-1393 (Japan)

    2015-12-31

    The capability of plutonium-breeding and minor-actinide (MA) transmutation in the Japanese commercial sodium-cooled fast reactor offers one of practical solutions for obtaining sustainable energy resources as well as reducing radioactive toxicity and inventory. The reference core design meets the requirement of flexible breeding ratio from 1.03 to 1.2. The MA transmutation amount has been evaluated as 50-100 kg/GW{sub e}y if the MA content in fresh fuel is 3-5 wt%, where about 30-40% of initial MA can be transmuted in the discharged fuel.

  17. Electronic structure and magnetism in actinide compounds

    Energy Technology Data Exchange (ETDEWEB)

    Durakiewicz, T. [Los Alamos National Laboratory, Los Alamos, NM 87545 (United States)]. E-mail: tomasz@lanl.gov; Joyce, J.J. [Los Alamos National Laboratory, Los Alamos, NM 87545 (United States); Lander, G.H. [JRC, Institute of Transuranium Elements, Postfach 2340, 76125 Karlsruhe (Germany); Olson, C.G. [Ames Laboratory, Iowa State University, Ames, Iowa 5011 (United States); Butterfield, M.T. [Lawrence Livermoore National Laboratory, Livermoore, CA 94550 (United States); Guziewicz, E. [Institute of Physics, Polish Academy of Sciences, 02-668 Warsaw (Poland); Batista, C.D. [Los Alamos National Laboratory, Los Alamos, NM 87545 (United States); Arko, A.J. [Los Alamos National Laboratory, Los Alamos, NM 87545 (United States); Morales, L. [Los Alamos National Laboratory, Los Alamos, NM 87545 (United States); Mattenberger, K. [Laboratorium fur Festkorperphysik, ETH, CH-8093, Zurich (Switzerland); Vogt, O. [Laboratorium fur Festkorperphysik, ETH, CH-8093, Zurich (Switzerland)

    2006-05-01

    A close relationship between electronic structure and magnetic properties is observed in actinide compounds. The exact nature of this relationship is under investigation. We present examples of a direct link between electronic structure and ordered magnetic moment and/or magnetization. Specifically, results obtained for cubic U, Np and Pu compounds and quasi-2D U compounds are be presented. In the case of cubic compounds, a direct relationship between binding energy of valence band features and magnetic moment will be discussed. A Stoner-like mechanism and simple mean-field explanation is proposed for ferromagnetic UTe.

  18. Calculated Bulk Properties of the Actinide Metals

    DEFF Research Database (Denmark)

    Skriver, Hans Lomholt; Andersen, O. K.; Johansson, B.

    1978-01-01

    Self-consistent relativistic calculations of the electronic properties for seven actinides (Ac-Am) have been performed using the linear muffin-tin orbitals method within the atomic-sphere approximation. Exchange and correlation were included in the local spin-density scheme. The theory explains t...... the variation of the atomic volume and the bulk modulus through the 5f series in terms of an increasing 5f binding up to plutonium followed by a sudden localisation (through complete spin polarisation) in americium...

  19. Actinide management with commercial fast reactors

    Science.gov (United States)

    Ohki, Shigeo

    2015-12-01

    The capability of plutonium-breeding and minor-actinide (MA) transmutation in the Japanese commercial sodium-cooled fast reactor offers one of practical solutions for obtaining sustainable energy resources as well as reducing radioactive toxicity and inventory. The reference core design meets the requirement of flexible breeding ratio from 1.03 to 1.2. The MA transmutation amount has been evaluated as 50-100 kg/GWey if the MA content in fresh fuel is 3-5 wt%, where about 30-40% of initial MA can be transmuted in the discharged fuel.

  20. Fission cross section measurements for minor actinides

    Energy Technology Data Exchange (ETDEWEB)

    Fursov, B. [IPPE, Obninsk (Russian Federation)

    1997-03-01

    The main task of this work is the measurement of fast neutron induced fission cross section for minor actinides of {sup 238}Pu, {sup 242m}Am, {sup 243,244,245,246,247,248}Cm. The task of the work is to increase the accuracy of data in MeV energy region. Basic experimental method, fissile samples, fission detectors and electronics, track detectors, alpha counting, neutron generation, fission rate measurement, corrections to the data and error analysis are presented in this paper. (author)

  1. Status of nuclear data for actinides

    Energy Technology Data Exchange (ETDEWEB)

    Guzhovskii, B.Y.; Gorelov, V.P.; Grebennikov, A.N. [Russia Federal Nuclear Centre, Arzamas (Russian Federation)] [and others

    1995-10-01

    Nuclear data required for transmutation problem include many actinide nuclei. In present paper the analysis of neutron fission, capture, (n,2n) and (n,3n) reaction cross sections at energy region from thermal point to 14 MeV was carried out for Th, Pa, U, Np, Pu, Am and Cm isotops using modern evaluated nuclear data libraries and handbooks of recommended nuclear data. Comparison of these data indicates on substantial discrepancies in different versions of files, that connect with quality and completeness of original experimental data.

  2. Noise-like pulse based on dissipative four-wave-mixing with photonic crystal fiber filled by reduced graphene oxide

    CERN Document Server

    Gao, Lei; Huang, Wei

    2014-01-01

    A noise-like pulse based on dissipative four-wave-mixing in a fiber cavity with photonic crystal fiber filled by reduced graphene oxide is proposed. Due to large evanescent field provided by 3 cm photonic crystal fiber and ultrahigh nonlinearity of reduced graphene oxide, this mixed structure provides excellent saturable absorption and high nonlinearity, which are necessary for generating four-wave-mixing (FWM). We experimentally prove that the mode-locked laser transfers its energy from center wavelength to sidebands through degenerate FWM, and new frequencies are generated via cascaded FWM among those sidebands. During this process, the frequencies located in various orders of longitudinal modes of the ring cavity are supported, and others are suppressed due to destructive interference. As the longitudinal modes of the cavity with a spacing of 6.874 MHz are partially supported, the loosely fixed phase relationship results in noise-like pulse with a coherent peak of 530 fs locating on a pedestal of 730.693 p...

  3. Some recent results on the correlation of nano-structural and redox properties in ceria-zirconia mixed oxides

    Energy Technology Data Exchange (ETDEWEB)

    Bernal, S. [Departamento de Ciencia de los Materiales, Ingenieria Metalurgica y Quimica Inorganica, Facultad de Ciencias, Universidad de Cadiz, Campus Rio San Pedro, E-11510 Puerto Real (Cadiz) (Spain)], E-mail: serafin.bernal@uca.es; Blanco, G.; Calvino, J.J.; Hernandez, J.C.; Perez-Omil, J.A.; Pintado, J.M.; Yeste, M.P. [Departamento de Ciencia de los Materiales, Ingenieria Metalurgica y Quimica Inorganica, Facultad de Ciencias, Universidad de Cadiz, Campus Rio San Pedro, E-11510 Puerto Real (Cadiz) (Spain)

    2008-02-28

    Some recent results on the redox behaviour of thermally aged ceria-zirconia mixed oxides with Ce/Zr molar ratios typically ranging from 50/50 to 70/30 are briefly reviewed. In accordance with them, a tentative model allowing us to correlate ageing conditions, surface and bulk nano-structural properties of the oxides, and changes occurred in their redox behaviour is proposed. As revealed by the analysis of appropriate chemical studies and the nano-structural information provided with High Resolution Transmission (HREM) and High Angle Annular Dark Field-Scanning Transmission (HAADF-STEM) electron microscopies, the presence/absence of a pyrochlore-related {kappa}-phase in the aged oxides plays a key role in determining their redox response. In the low-temperature region (T{sub red} {<=} 773 K), the enhanced reducibility exhibited by the oxide resulting from a high-temperature reduction/mild re-oxidation ageing cycle (SR-MO sample) is interpreted as due to kinetic reasons, the occurrence of the {kappa}-like phase in its surface being responsible for a faster H{sub 2} chemisorption, the rate controlling step of the overall reduction process. By contrast, in the high-temperature range (T{sub red} {>=} 973 K), the observed differences of reducibility would have a thermodynamic origin, which may be correlated with the total amount of {kappa}-like phase present in the aged sample.

  4. Influence of Na diffusion on thermochromism of vanadium oxide films and suppression through mixed-alkali effect

    Energy Technology Data Exchange (ETDEWEB)

    Miller, Mark J.; Wang, Junlan, E-mail: junlan@u.washington.edu

    2015-10-15

    Highlights: • Vanadium oxide films were reactively sputtered on three types of glass substrates. • Na diffusion from soda-lime glass undesirably inhibited thermochromism. • Na diffusion was suppressed by replacing half of sodium in glass with potassium. • Mixed-alkali effect promotes thermochromic VO{sub 2} films on glass substrates. - Abstract: Vanadium(IV) oxide possesses a reversible first-order phase transformation near 68 °C. Potential applications of the material include advanced optical devices and thermochromic smart windows. In this study, vanadium oxide films were grown on three types of glass substrates using reactive DC magnetron sputtering and were then annealed in air. The substrates were characterized with energy-dispersive X-ray spectroscopy, and the films were characterized with X-ray photoelectron spectroscopy, X-ray diffraction, scanning electron microscopy, atomic force microscopy, transmission electron microscopy, and UV-Vis-NIR spectrophotometry. The results show that the composition of the substrate has a major impact on the microstructure and optical properties of the deposited films. Sodium (Na) in the glass can undesirably inhibit thermochromism; however, replacing half of the Na with potassium (K) suppresses the Na diffusion and promotes the nucleation of pure VO{sub 2} with superior thermochromic functionality. The improved performance is attributed to the mixed-alkali effect between Na and K. These findings are both scientifically and technologically important since soda (Na{sub 2}O) is an essential flux material in glass products such as windows.

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

    Science.gov (United States)

    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

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

    Science.gov (United States)

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

    2014-05-07

    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.

  7. Nanocomposites of polyimide and mixed oxide nanoparticles for high performance nanohybrid gate dielectrics in flexible thin film transistors

    Science.gov (United States)

    Kim, Ju Hyun; Hwang, Byeong-Ung; Kim, Do-Il; Kim, Jin Soo; Seol, Young Gug; Kim, Tae Woong; Lee, Nae-Eung

    2017-01-01

    Organic gate dielectrics in thin film transistors (TFTs) for flexible display have advantages of high flexibility yet have the disadvantage of low dielectric constant (low-k). To supplement low-k characteristics of organic gate dielectrics, an organic/inorganic nanocomposite insulator loaded with high-k inorganic oxide nanoparticles (NPs) has been investigated but high loading of high-k NPs in polymer matrix is essential. Herein, compositing of over-coated polyimide (PI) on self-assembled (SA) layer of mixed HfO2 and ZrO2 NPs as inorganic fillers was used to make dielectric constant higher and leakage characteristics lower. A flexible TFT with lower the threshold voltage and high current on/off ratio could be fabricated by using the hybrid gate dielectric structure of the nanocomposite with SA layer of mixed NPs on ultrathin atomic-layer deposited Al2O3.

  8. Crystal growth and first crystallographic characterization of mixed uranium(IV)-plutonium(III) oxalates.

    Science.gov (United States)

    Tamain, Christelle; Arab Chapelet, Bénédicte; Rivenet, Murielle; Abraham, Francis; Caraballo, Richard; Grandjean, Stéphane

    2013-05-06

    The mixed-actinide uranium(IV)-plutonium(III) oxalate single crystals (NH4)0.5[Pu(III)0.5U(IV)0.5(C2O4)2·H2O]·nH2O (1) and (NH4)2.7Pu(III)0.7U(IV)1.3(C2O4)5·nH2O (2) have been prepared by the diffusion of different ions through membranes separating compartments of a triple cell. UV-vis, Raman, and thermal ionization mass spectrometry analyses demonstrate the presence of both uranium and plutonium metal cations with conservation of the initial oxidation state, U(IV) and Pu(III), and the formation of mixed-valence, mixed-actinide oxalate compounds. The structure of 1 and an average structure of 2 were determined by single-crystal X-ray diffraction and were solved by direct methods and Fourier difference techniques. Compounds 1 and 2 are the first mixed uranium(IV)-plutonium(III) compounds to be structurally characterized by single-crystal X-ray diffraction. The structure of 1, space group P4/n, a = 8.8558(3) Å, b = 7.8963(2) Å, Z = 2, consists of layers formed by four-membered rings of the two actinide metals occupying the same crystallographic site connected through oxalate ions. The actinide atoms are nine-coordinated by oxygen atoms from four bidentate oxalate ligands and one water molecule, which alternates up and down the layer. The single-charged cations and nonbonded water molecules are disordered in the same crystallographic site. For compound 2, an average structure has been determined in space group P6/mmm with a = 11.158(2) Å and c = 6.400(1) Å. The honeycomb-like framework [Pu(III)0.7U(IV)1.3(C2O4)5](2.7-) results from a three-dimensional arrangement of mixed (U0.65Pu0.35)O10 polyhedra connected by five bis-bidentate μ(2)-oxalate ions in a trigonal-bipyramidal configuration.

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

    Science.gov (United States)

    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.

  10. Synthesis, characterization, and activity of yttrium(III) nitrate complexes bearing tripodal phosphine oxide and mixed phosphine-phosphine oxide ligands.

    Science.gov (United States)

    Sues, Peter E; Lough, Alan J; Morris, Robert H

    2012-09-03

    A series of four tripodal phosphine oxide ligands, (OPR(2))(2)CHCH(2)POR(2) (1a-1d), and four mixed phosphine-phosphine oxide ligands, (OPR(2))(2)CHCH(2)PR(2) (3a-3d), were synthesized and coordinated to yttrium to produce Y(NO(3))(3)[(OPR(2))(2)CHCH(2)POR(2)] (2a-2d) and Y(NO(3))(3)[(OPR(2))(2)CHCH(2)PR(2)](OPPh(3)) (4a-4d) complexes. The previously reported ligand 1a and unknown phosphine oxide ligands 1b-1d were generated in an unprecedented trisubstitution reaction of bromoacetaldehyde diethyl acetal, while the novel partially reduced ligands 3a-3d were synthesized from 1a-1d according to a known literature protocol for the selective monoreduction of bisphosphine oxides. The neutral yttrium complexes 2a-2d are nine-coordinate and display a tricapped trigonal-prismatic geometry. Complexes 4a-4d are also neutral, nine-coordinate species and have a pendant phosphine functionality, which provides the potential to form bimetallic early-late transition-metal complexes. Additionally, yttrium complexes 2a-2d were activated with base and tested for the ring-opening polymerization of ε-caprolactone, but the results showed that base by itself was significantly more effective than the yttrium species investigated.

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

    Directory of Open Access Journals (Sweden)

    J. A. Geddes

    2013-10-01

    Full Text Available 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.

  12. Solar energy as an alternate energy source to mixed oxide fuels in light-water cooled reactors

    Energy Technology Data Exchange (ETDEWEB)

    Bertini, H.W.

    1977-06-30

    Supplemental information pertaining to the generic environmental impact statement on the Pu recycling process for mixed oxide light-water cooled reactors (GESMO) was requested from several sources. In particular, the role of alternate sources of energy was to be explored and the implications of these alternate sources to the question of Pu recycle in LWRs were to be investigated. In this vein, solar energy as an alternate source is the main subject of this report, along with other information related to solar energy. The general conclusion is that solar energy should have little effect on the decisions concerning GESMO.

  13. Destruction of hazardous and mixed wastes using mediated electrochemical oxidation in a Ag(II)HNO3 bench scale system

    Energy Technology Data Exchange (ETDEWEB)

    Balazs, B.; Chiba, Z.; Hsu, P.; Lewis, P.; Murguia, L.; Adamson, M.

    1997-02-01

    Mediated Electrochemical Oxidation (MEO) is a promising technology for the destruction of organic containing wastes and the remediation of mixed wastes containing transuranic components. The combination of a powerful oxidant and an acid solution allows the conversion of nearly all organics, whether present in hazardous or in mixed waste, to carbon dioxide. Insoluble transuranics are dissolved in this process and may be recovered by separation and precipitation. The oxidant, or mediator, is a multivalent transition metal ion which is cleanly recycled in a number of charge transfer steps in an electrochemical cell. The MEO technique offers several advantages which are inherent in the system. First, the oxidation/dissolution processes are accomplished at near ambient pressures and temperatures (30-70{degrees}C). Second, all waste stream components and oxidation products (with the exception of evolved gases) are contained in an aqueous environment. This electrolyte acts as an accumulator for inorganics which were present in the original waste stream, and the large volume of electrolyte provides a thermal buffer for the energy released during oxidation of the organics. Third, the generation of secondary waste is minimal, as the process needs no additional reagents. Finally, the entire process can be shut down by simply turning off the power, affording a level of control unavailable in some other techniques. Although the oxidation of organics and the dissolution of transuranics by higher valency metal ions has been known for some time, applying the MEO technology to waste treatment is a relatively recent development. Numerous groups, both in the United States and Europe, have made substantial progress in the last decade towards understanding the mechanistic pathways, kinetics, and engineering aspects of the process. At Lawrence Livermore National Laboratory, substantial contributions have been made to this knowledge base in these areas and others. Conceptual design and

  14. NO(x) decomposition, storage and reduction over novel mixed oxide catalysts derived from hydrotalcite-like compounds.

    Science.gov (United States)

    Yu, Jun Jie; Cheng, Jie; Ma, Chun Yan; Wang, Hai Lin; Li, Lan Dong; Hao, Zheng Ping; Xu, Zhi Ping

    2009-05-15

    Effective control and removal of nitrogen oxides (NO(x)) emission from vehicles exhausts under lean-burn condition is one of the most important targets in scientific research of environmental protection. A comprehensive introduction of NO(x) storage and reduction (NSR), the most promising lean-NO(x) control technology, is given including the sum-up of NSR materials, catalytic activity and related reaction mechanisms. Emphasis is put on the novel multifunctional NSR catalysts, derived from hydrotalcite-like compounds, with characteristic of simultaneous NO(x) strorage-decomposition-reduction. Finally, future research directions in the area of lean-NO(x) control based on mixed oxide catalysts derived from hydrotalcite-like materials is also proposed.

  15. Preparation and conductivity of nanocrystalline rare earth mixed oxides SmFe1-xCoxO3-δ

    Institute of Scientific and Technical Information of China (English)

    2002-01-01

    Nanocrystalline rare earth mixed oxides SmFe1 xCoxO3-δ were prepared by sol-gel method at 1 073 K for 2h calcination and characterized by X-ray diffraction (XRD) and scanning electron microscope (SEM). The results show that SmFe1-xCoxO3-δ has the structure ofperovskite type. The conductivity of the materials increases with the temperature rising and the maximum conductivity at 1 073 K is 2.6 S/cm with the best mole ratio of Fe3+ to Co3+ being 1: 4. This kind of oxide is a conductive ceramic material by means of conduction of electron and oxygen anion.

  16. ORNL actinide materials and a new detection system for superheavy nuclei

    Directory of Open Access Journals (Sweden)

    Rykaczewski Krzysztof P.

    2016-01-01

    Full Text Available The actinide resources and production capabilities at Oak Ridge National Laboratory (ORNL are reviewed, including potential electromagnetic separation of rare radioactive materials. The first experiments at the Dubna Gas Filled Recoil Separator (DGFRS with a new digital detection system developed at ORNL and University of Tennessee Knoxville (UTK are presented. These studies used 240Pu material provided by ORNL and mixed-Cf targets made at ORNL. The proposal to use an enriched 251Cf target and a large dose of 58Fe beam to reach the N = 184 shell closure and to observe new elements with Z = 124, 122 and 120 is discussed.

  17. End point control of an actinide precipitation reactor

    Energy Technology Data Exchange (ETDEWEB)

    Muske, K.R. [Villanova Univ., PA (United States). Dept. of Chemical Engineering; Palmer, M.J. [Los Alamos National Lab., NM (United States)

    1997-10-01

    The actinide precipitation reactors in the nuclear materials processing facility at Los Alamos National Laboratory are used to remove actinides and other heavy metals from the effluent streams generated during the purification of plutonium. These effluent streams consist of hydrochloric acid solutions, ranging from one to five molar in concentration, in which actinides and other metals are dissolved. The actinides present are plutonium and americium. Typical actinide loadings range from one to five grams per liter. The most prevalent heavy metals are iron, chromium, and nickel that are due to stainless steel. Removal of these metals from solution is accomplished by hydroxide precipitation during the neutralization of the effluent. An end point control algorithm for the semi-batch actinide precipitation reactors at Los Alamos National Laboratory is described. The algorithm is based on an equilibrium solubility model of the chemical species in solution. This model is used to predict the amount of base hydroxide necessary to reach the end point of the actinide precipitation reaction. The model parameters are updated by on-line pH measurements.

  18. Separation of actinides from spent nuclear fuel: A review.

    Science.gov (United States)

    Veliscek-Carolan, Jessica

    2016-11-15

    This review summarises the methods currently available to extract radioactive actinide elements from solutions of spent nuclear fuel. This separation of actinides reduces the hazards associated with spent nuclear fuel, such as its radiotoxicity, volume and the amount of time required for its' radioactivity to return to naturally occurring levels. Separation of actinides from environmental water systems is also briefly discussed. The actinide elements typically found in spent nuclear fuel include uranium, plutonium and the minor actinides (americium, neptunium and curium). Separation methods for uranium and plutonium are reasonably well established. On the other hand separation of the minor actinides from lanthanide fission products also present in spent nuclear fuel is an ongoing challenge and an area of active research. Several separation methods for selective removal of these actinides from spent nuclear fuel will be described. These separation methods include solvent extraction, which is the most commonly used method for radiochemical separations, as well as the less developed but promising use of adsorption and ion-exchange materials.

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

    Science.gov (United States)

    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; Panimals, 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 biomarkers of autophagy (Beclin 1, LC3-II/LC3-I ratio) and muscle antioxidant defense (TAA, SOD, CAT) in the muscle tissue within the

  20. Hydroxylation of benzene to phenol over magnetic recyclable nanostructured CuFe mixed-oxide catalyst

    CSIR Research Space (South Africa)

    Makgwane, PR

    2015-03-01

    Full Text Available A highly active and magnetically recyclable nanostructured copper–iron oxide (CuFe) catalyst has been synthesized for hydroxylation of benzene to phenol under mild reaction conditions. The obtained catalytic results were correlated with the catalyst...

  1. Physical Properties of Mixed Conductor Solid Oxide Fuel Cell Anodes of Doped CeO2

    DEFF Research Database (Denmark)

    Mogensen, Mogens Bjerg; Lindegaard, Thomas; Hansen, Uffe Rud

    1994-01-01

    Samples of CeO2 doped with oxides such as CaO and Gd2O3 were prepared. Their conductivities and expansions onreduction were measured at 1000°C, and the thermal expansion coefficients in the range 50 to 1000°C were determined. Theionic and electronic conductivity were derived from curves of total...... for solid oxide fuel cell anodes. Not all requirements are fulfilled. Measures to compensate for this arediscussed....

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

    Energy Technology Data Exchange (ETDEWEB)

    De Bremaecker, A., E-mail: adbremae@sckcen.be [Belgian Nuclear Research Center (SCK-CEN), NMS, Mol (Belgium); Ayrault, L., E-mail: laurent.ayrault@cea.fr [Institut de Radio-Protection et Sûreté Nucléaire/DPAM/SEMIC, Bât 702, CEN de Cadarache BP3, F-13115 Saint-Paul-lez-Durance (France); Clément, B. [Institut de Radio-Protection et Sûreté Nucléaire/DPAM/SEMIC, Bât 702, CEN de Cadarache BP3, F-13115 Saint-Paul-lez-Durance (France)

    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 (B{sub 2}O{sub 3}): either tests under steam between 1230° and 1700 °C with B{sub 4}C alone or B{sub 4}C 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 YBO{sub 3} 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 UO{sub 2} or as inert matrix for Am-transmutation.

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

    Science.gov (United States)

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

    2014-06-11

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

  4. Synthesis and characterization of ordered hexagonal and cubic mesoporous tin oxides via mixed-surfactant templates route.

    Science.gov (United States)

    Wang, Yude; Ma, Chunlai; Sun, Xiaodan; Li, Hengde

    2005-06-15

    Ordered hexagonal and cubic mesoporous tin oxides were synthesized for the first time in the presence of mixed cationic and neutral surfactants (a mixture of cetyltrimethylammonium bromide cationic surfactant and dodecylamine neutral surfactant) with different alkali and simple inorganic precursors at room temperature. In the synthesis systems, the dodecylamine neutral surfactant may function as a polar organic cosolvent and cosurfactant. The formation of the tin oxide mesostructured material was proposed to be due to the presence of hydrogen-bonding interactions between the supramolecular template and inorganic precursors Sn4+ and OH-, which were assumed to self-assemble around the cationic surfactant molecules. The materials are characterized by X-ray powder diffraction, transmission electron microscopy, thermogravimetric analysis, and N2 adsorption/desorption isotherm. The surface areas of materials evaluated from the N2 sorption isotherms are about 248 m(2)/g for hexagonal mesoporous tin oxide (SnH) and 281 m(2)/g for cubic mesoporous tin oxide (Sn-C) for calcination at 350 degrees C.

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

    Science.gov (United States)

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

    2014-08-01

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

  6. Critical analysis of the data on complexation of lanthanides and actinides by natural organic matter: particular case of humic substances; Analyse critique des donnees de complexation des lanthanides et actinides par la matiere organique naturelle: cas des substances humiques

    Energy Technology Data Exchange (ETDEWEB)

    Reiller, P.

    2010-07-01

    This document proposes a critical analysis of the models that describe the actinides and lanthanides complexation by natural organic matter in general and by humic substances in particular. In order to better delimit the particular properties of these substances the most influent physical and chemical properties on complexation are recalled as a preamble. Models as well as data that has been used are reviewed, compiled, and eventually compared to independent data in order to identify (i) their application domain, (ii) the possible simplifications which permit to obtain operational models, (iii) the conditions in which simplifications cannot be ascertained yet, and (iv) the data or fields of knowledge which are still too uncertain. A comparison between the different models is proposed in order to adapt parameters from one model to another minimising the experimental acquisitions, or at least to focus on missing data. Usually, data on the complexation of free ions M{sup z+} are reliable; as soon as hydrolysis, or competition with another ligand in general, in at stake data are much less reliable. Predictions from models are much more uncertain: formation of mixed complexes with hydroxide or carbonate anions is not univocal whatever the modelling strategy. Hints for transfer functions between models which are believed to be incompatible could be explored in order to justify necessary simplifications for using operational modelling. Influence on the solubility of oxides could be quantified, but it is difficult to clearly separate it from colloidal particles stabilisation. The account of the competition between cations by the models has also been tested. In view of the small number of available experimental data there still lie some uncertainties especially for the media that are close to neutrality and in the case of competition with magnesium, but overall in the case of the competition with aluminium and iron. The influence of redox activity of humic substances is

  7. Mechanical environmental transport of actinides and ¹³⁷Cs from an arid radioactive waste disposal site.

    Science.gov (United States)

    Snow, Mathew S; Clark, Sue B; Morrison, Samuel S; Watrous, Matthew G; Olson, John E; Snyder, Darin C

    2015-10-01

    Aeolian and pluvial processes represent important mechanisms for the movement of actinides and fission products at the Earth's surface. Soil samples taken in the early 1970's near a Department of Energy radioactive waste disposal site (the Subsurface Disposal Area, SDA, located in southeastern Idaho) provide a case study for studying the mechanisms and characteristics of environmental actinide and (137)Cs transport in an arid environment. Multi-component mixing models suggest actinide contamination within 2.5 km of the SDA can be described by mixing between 2 distinct SDA end members and regional nuclear weapons fallout. The absence of chemical fractionation between (241)Am and (239+240)Pu with depth for samples beyond the northeastern corner and lack of (241)Am in-growth over time (due to (241)Pu decay) suggest mechanical transport and mixing of discrete contaminated particles under arid conditions. Occasional samples northeast of the SDA (the direction of the prevailing winds) contain anomalously high concentrations of Pu with (240)Pu/(239)Pu isotopic ratios statistically identical to those in the northeastern corner. Taken together, these data suggest flooding resulted in mechanical transport of contaminated particles into the area between the SDA and a flood containment dike in the northeastern corner, following which subsequent contamination spreading in the northeastern direction resulted from wind transport of discrete particles. Copyright © 2015 Elsevier Ltd. All rights reserved.

  8. Scenarios for the transmutation of actinides in CANDU reactors

    Energy Technology Data Exchange (ETDEWEB)

    Hyland, Bronwyn, E-mail: hylandb@aecl.ca [Atomic Energy of Canada Limited, Chalk River Laboratories, Chalk River, Ontario, K0J 1J0 (Canada); Gihm, Brian, E-mail: gihmb@aecl.ca [Atomic Energy of Canada Limited, 2251 Speakman Drive, Mississauga, Ontario, L5K 1B2 (Canada)

    2011-12-15

    With world stockpiles of used nuclear fuel increasing, the need to address the long-term utilization of this resource is being studied. Many of the transuranic (TRU) actinides in nuclear spent fuel produce decay heat for long durations, resulting in significant nuclear waste management challenges. These actinides can be transmuted to shorter-lived isotopes to reduce the decay heat period or consumed as fuel in a CANDU(R) reactor. Many of the design features of the CANDU reactor make it uniquely adaptable to actinide transmutation. The small, simple fuel bundle simplifies the fabrication and handling of active fuels. Online refuelling allows precise management of core reactivity and separate insertion of the actinides and fuel bundles into the core. The high neutron economy of the CANDU reactor results in high TRU destruction to fissile-loading ratio. This paper provides a summary of actinide transmutation schemes that have been studied in CANDU reactors at AECL, including the works performed in the past. The schemes studied include homogeneous scenarios in which actinides are uniformly distributed in all fuel bundles in the reactor, as well as heterogeneous scenarios in which dedicated channels in the reactor are loaded with actinide targets and the rest of the reactor is loaded with fuel. The transmutation schemes that are presented reflect several different partitioning schemes. Separation of americium, often with curium, from the other actinides enables targeted destruction of americium, which is a main contributor to the decay heat 100-1000 years after discharge from the reactor. Another scheme is group-extracted transuranic elements, in which all of the transuranic elements, plutonium (Pu), neptunium (Np), americium (Am), and curium (Cm) are extracted together and then transmuted. This paper also addresses ways of utilizing the recycled uranium, another stream from the separation of spent nuclear fuel, in order to drive the transmutation of other actinides.

  9. Effect of mixed rare earth oxides and CaCO3 modification on the microstructure of an in-situ Mg2Si/Al-Si composite

    Institute of Scientific and Technical Information of China (English)

    LIU Zheng; LIN Jixing; JING Qingxiu

    2009-01-01

    The effects of mixed rare earth oxides and CaCO3 on the microstructure of an in-situ Mg2Si/Al-Si hypereutectic alloy composite were investigated by optical microscope, scanning electron microscope, and energy dispersive spectrum analysis. The results showed that the morphology of the primary Mg2Si phase particles changed from irregular or crosses to polygonal shape, their sizes decreased from 75 μm to about 25 μm, and the compound of both the oxide and CaCO3 was better than either the single mixed rare earth oxides or CaCO3.

  10. Nanostructured Metal Oxides And Mixed Metal Oxides, Methods Of Making These Nanoparticles, And Methods Of Their Use

    KAUST Repository

    Polshettiwar, Vivek

    2013-04-11

    Embodiments of the present disclosure provide for nanoparticles, methods of making nanoparticles, methods of using the nanoparticles, and the like. Nanoparticles of the present disclosure can have a variety of morphologies, which may lead to their use in a variety of technologies and processes. Nanoparticles of the present may be used in sensors, optics, mechanics, circuits, and the like. In addition, nanoparticles of the present disclosure may be used in catalytic reactions, for CO oxidation, as super-capacitors, in hydrogen storage, and the like.

  11. Review of actinide nitride properties with focus on safety aspects

    Energy Technology Data Exchange (ETDEWEB)

    Albiol, Thierry [CEA Cadarache, St Paul Lez Durance Cedex (France); Arai, Yasuo [Japan Atomic Energy Research Inst., Tokai, Ibaraki (Japan). Tokai Research Establishment

    2001-12-01

    This report provides a review of the potential advantages of using actinide nitrides as fuels and/or targets for nuclear waste transmutation. Then a summary of available properties of actinide nitrides is given. Results from irradiation experiments are reviewed and safety relevant aspects of nitride fuels are discussed, including design basis accidents (transients) and severe (core disruptive) accidents. Anyway, as rather few safety studies are currently available and as many basic physical data are still missing for some actinide nitrides, complementary studies are proposed. (author)

  12. Distribution of actinides in SFR1; Aktinidfoerdelning i SFR1

    Energy Technology Data Exchange (ETDEWEB)

    Ingemansson, Tor [ALARA Engineering, Skultuna (Sweden)

    2000-02-01

    The amount of actinides in the Swedish repository for intermediate level radioactive wastes has been estimated. The sources for the actinides are mainly the purification filters of the reactors and the used fuel pools. Defect fuel elements are the originating source of the actinides. It is estimated that the 12 Swedish reactors, in total, have had 2.2 kg of fuel dissolved in their systems since start-up. About 880 g of this amount has been brought to the intermediate-level repository.

  13. Self-interaction corrected local spin density calculations of actinides

    DEFF Research Database (Denmark)

    Petit, Leon; Svane, Axel; Szotek, Z

    2010-01-01

    We use the self-interaction corrected local spin-density approximation in order to describe localization-delocalization phenomena in the strongly correlated actinide materials. Based on total energy considerations, the methodology enables us to predict the ground-state valency configuration...... of the actinide ions in these compounds from first principles. Here we review a number of applications, ranging from electronic structure calculations of actinide metals, nitrides and carbides to the behaviour under pressure of intermetallics, and O vacancies in PuO2....

  14. Separating the Minor Actinides Through Advances in Selective Coordination Chemistry

    Energy Technology Data Exchange (ETDEWEB)

    Lumetta, Gregg J.; Braley, Jenifer C.; Sinkov, Sergey I.; Carter, Jennifer C.

    2012-08-22

    This report describes work conducted at the Pacific Northwest National Laboratory (PNNL) in Fiscal Year (FY) 2012 under the auspices of the Sigma Team for Minor Actinide Separation, funded by the U.S. Department of Energy Office of Nuclear Energy. Researchers at PNNL and Argonne National Laboratory (ANL) are investigating a simplified solvent extraction system for providing a single-step process to separate the minor actinide elements from acidic high-level liquid waste (HLW), including separating the minor actinides from the lanthanide fission products.

  15. Recovery of minor actinides from spent fuel using TPEN-immobilized gels

    Energy Technology Data Exchange (ETDEWEB)

    Koyama, S.; Suto, M.; Ohbayashi, H. [Oarai Research and Development Center, Japan Atomic Energy Agency, Oarai (Japan); Oaki, H. [Solutions Research Organization, Tokyo Institute of Technology, Tokyo (Japan); Takeshita, K. [Research Laboratory for Nuclear Reactors, Tokyo Institute of Technology, Tokyo (Japan)

    2013-07-01

    A series of separation experiments was performed in order to study the recovery process for minor actinides (MAs), such as americium (Am) and curium (Cm), from the actual spent fuel by using an extraction chromatographic technique. N,N,N',N'-tetrakis-(4-propenyloxy-2-pyridylmethyl) ethylenediamine (TPPEN) is an N,N,N',N'-tetrakis (2-pyridylmethyl) ethylenediamine (TPEN) analogue consisting of an incorporated pyridine ring that acts as not only a ligand but also as a site for polymerization and crosslinking of the gel. The TPPEN and N-isopropylacrylamide (NIPA) were dissolved into dimethylformamide (DMF, Wako Co., Ltd.) and a silica beads polymer, and then TTPEN was immobilized chemically in a polymer gel (so called TPEN-gel). Mixed oxide (MOX) fuel, which was highly irradiated up to 119 GWD/MTM in the experimental fast reactor Joyo, was used as a reference spent fuel. First, uranium (U) and plutonium (Pu) were separated from the irradiated fuel using an ion-exchange method, and then, the platinum group elements were removed by CMPO to leave a mixed solution of MAs and lanthanides. The 3 mol% TPPEN-gel was packed with as an extraction column (CV: 1 ml) and then rinsed by 0.1 M NaNO{sub 3}(pH 4.0) for pH adjustment. After washing the column by 0.01 M NaNO{sub 3} (pH 4.0), Eu was detected and the recovery rate reached 93%. The MAs were then recovered by changing the eluent to 0.01 M NaNO{sub 3} (pH 2.0), and the recovery rate of Am was 48 %. The 10 mol% TPPEN-gel was used to improve adsorption coefficient of Am and a condition of eluent temperature was changed in order to confirm the temperature swing effect on TPEN-gel for MA. More than 90% Eu was detected in the eluent after washing with 0.01 M NaNO{sub 3} (pH 3.5) at 5 Celsius degrees. Americium was backwardly detected and eluted continuously during the same condition. After removal of Eu, the eluent temperature was changed to 32 Celsius degrees, then Am was detected (pH 3.0). Finally remained

  16. 40 CFR 721.10148 - Acryloxy alkanoic alkane derivative with mixed metal oxides (generic).

    Science.gov (United States)

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Acryloxy alkanoic alkane derivative... Significant New Uses for Specific Chemical Substances § 721.10148 Acryloxy alkanoic alkane derivative with...) The chemical substance identified generically as acryloxy alkanoic alkane derivative with mixed...

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

    Energy Technology Data Exchange (ETDEWEB)

    Cosano, Daniel; Esquinas, Carlos; Jiménez-Sanchidrián, César; Ruiz, José Rafael, E-mail: qo1ruarj@uco.es

    2016-02-28

    Graphical abstract: - Highlights: • Raman is used by first time for adsorption of cyanide on calcined LDHs. • Raman is an effective, accurate and expeditious method for monitoring this process. • Cyanide is adsorbed by a rehydration process based on the “memory effect”. • The metal ratio of the LDH has a crucial influence on the adsorption capacity. - Abstract: 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.

  18. Electrical Conductivity of Sintered Chromia Mixed with TiO2,CuO and Mn-Oxides

    Institute of Scientific and Technical Information of China (English)

    2006-01-01

    The electrical conductivity of sintered Cr2O3 mixed with 2% and 5% (in molar fraction) TiO2 or CuO was investigated in the temperature range 500~900℃ in air and in Ar/4 vol. pct H2 atmospheres. The effect of different Mn-oxides on the electrical conductivity of Cr2O3 was also studied under the same conditions.From the conductivity measurements it is established that additions of TiO2 change the defect structure of Cr2O3 and the effect of TiO2 on the electrical conductivity is controlled by TiO2 concentration as well as temperature and O2 partial pressure of the surrounding atmosphere. The conductivity of Cr2O3 increased in air and decreased in the Ar/H2 atmosphere by CuO additions. The effect of CuO was discussed with possible changes in the defect concentration in Cr2O3. Mixing of Cr2O3 with different Mn-oxides at the same Mn to metal atom fraction decreased the conductivity in air and in Ar/H2 atmospheres. No clear correlation between the spinel fraction and the changes in conductivity could be found.

  19. Synthesis, characterization and photocatalytic activity of mixed oxides derived from ZnAlTi ternary layered double hydroxides

    Science.gov (United States)

    Sahu, R. K.; Mohanta, B. S.; Das, N. N.

    2013-09-01

    A new series of Ti4+ containing ZnAl-LDHs with varying Zn:Al:Ti (~3:1:0-3:0.5:0.5) ratio were prepared by coprecipitation of homogeneous solution metal salts and characterized by various physicochemical methods. Powder XRD revealed the formation of well crystallized LDH even at the highest Ti4+ content. On thermal treatment at 450 °C, the well crystallized LDH precursors yielded mixed oxides with BET surface area in the range 92-118 m2/g. UV-vis diffuse reflection spectroscopy (DRS) showed a marginal decrease of band gap energy for calcined ZnAlTi-LDHs in comparison to either ZnO or TiO2-P25. The TEM analyses of a representative sample (as-synthesized and calcined) indicated more or less uniform distribution of titanium species. The derived mixed oxides from titanium containing LDH precursors demonstrated better activity toward photodegradation of methylene blue and rhodamine B than those of a physical mixture of ZnO and TiO2. Moreover, the present work not only provided a first hand understanding about semiconductor properties of ZnAlTi-LDHs but also demonstrated their potential as photocatalysts for degradation of organic pollutants.

  20. The surface behaviour and catalytic properties of Nd2-XSrXCoO4±Λ mixed oxides

    Directory of Open Access Journals (Sweden)

    Laitao Luo

    2006-12-01

    Full Text Available The mixed oxides, Nd2-xSrxCoO4±λ (0.4 ≤ x ≤ 1.2, ( = non-stochiometric oxygen with the K2NiF4 structure were prepared by the polyglycol gel method and used as catalysts for NO reduction. The samples were investigated by IR, TPD, TPR, and XRD methods and iodometry and the effects of the coefficient x on the structure and catalytic activity of the samples were studied. The results show that the Nd2-xSrxCoO4±λ mixed oxides have the K2NiF4 structure; other phases are found when x 1.2. The amount of Co3+ and the lattice oxygen in Nd2-xSrxCoO4±λ increase with increasing x. The catalytic activity of Nd2-xSrxCoO4±λfor NO reduction is closely correlated with the concentration of oxygen vacancies and the amount of Co3+.

  1. Design of amphoteric mixed oxides of zinc and Group 3 elements (Al, Ga, In): migration effects on basic features.

    Science.gov (United States)

    Mekki-Berrada, Adrien; Grondin, Didier; Bennici, Simona; Auroux, Aline

    2012-03-28

    The design of new amphoteric catalysts is of great interest for several industrial processes, especially those covering dehydration and dehydrogenation phenomena. Adsorption microcalorimetry was used to monitor the design of mixed oxides of zinc with Group 3 elements (aluminium, gallium, indium) with amphoteric character and enhanced specific surface area. Acid-base features were found to evolve non-linearly with the relative amounts of metal, and the strengths of the created acidic or basic sites were measured by adsorption microcalorimetry. A panel of bifunctional catalysts of various acid-base (amounts, strengths) and redox character was obtained. Besides, special interest was given to In-Zn mixed oxides for their enhanced basicity: this series of catalysts displays important basic features of high strength (q(diff) (SO₂ ads.) > 200 kJ mol(SO₂)⁻¹ in substantial amounts (1 - 2 μmol m(catalyst)⁻²), whose impact on efficiency or selectivity in catalytic dehydration/dehydrogenation can be valuable.

  2. Mechanisms of oxidative stress and alterations in gene expression by Libby six-mix in human mesothelial cells

    Directory of Open Access Journals (Sweden)

    Hillegass Jedd M

    2010-09-01

    Full Text Available Abstract Background Exposures to an amphibole fiber in Libby, Montana cause increases in malignant mesothelioma (MM, a tumor of the pleural and peritoneal cavities with a poor prognosis. Affymetrix microarray/GeneSifter analysis was used to determine alterations in gene expression of a human mesothelial cell line (LP9/TERT-1 by a non-toxic concentration (15×106 μm2/cm2 of unprocessed Libby six-mix and negative (glass beads and positive (crocidolite asbestos controls. Because manganese superoxide dismutase (MnSOD; SOD2 was the only gene upregulated significantly (p 6 μm2/cm2 and toxic concentrations (75×106 μm2/cm2 of Libby six-mix. Results Exposure to 15×106 μm2/cm2 Libby six-mix elicited significant (p SOD2; 4-fold at 8 h and 111 gene changes at 24 h, including a 5-fold increase in SOD2. Increased levels of SOD2 mRNA at 24 h were also confirmed in HKNM-2 normal human pleural mesothelial cells by qRT-PCR. SOD2 protein levels were increased at toxic concentrations (75×106 μm2/cm2 of Libby six-mix at 24 h. In addition, levels of copper-zinc superoxide dismutase (Cu/ZnSOD; SOD1 protein were increased at 24 h in all mineral groups. A dose-related increase in SOD2 activity was observed, although total SOD activity remained unchanged. Dichlorodihydrofluorescein diacetate (DCFDA fluorescence staining and flow cytometry revealed a dose- and time-dependent increase in reactive oxygen species (ROS production by LP9/TERT-1 cells exposed to Libby six-mix. Both Libby six-mix and crocidolite asbestos at 75×106 μm2/cm2 caused transient decreases (p HO-1 in LP9/TERT-1 and HKNM-2 cells. Conclusions Libby six-mix causes multiple gene expression changes in LP9/TERT-1 human mesothelial cells, as well as increases in SOD2, increased production of oxidants, and transient decreases in intracellular GSH. These events are not observed at equal surface area concentrations of nontoxic glass beads. Results support a mechanistic basis for the importance of SOD2

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

    Science.gov (United States)

    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.

  4. Polyphosphazene-poly(olefin oxide) mixed polymer electrolytes. II - Characterization of MEEP/PPO-(LiX)n

    Science.gov (United States)

    Abraham, K. M.; Alamgir, M.; Moulton, R. D.

    1991-04-01

    The preparation, and the conductivity, calorimetric,, and electrochemical studies of MEEP/PPO-(LiX)n mixed polymer electrolytes, where MEEP = poly(bis-methoxyethoxy ethoxide phosphazene) PPO = poly(propylene oxide) and LiX = LiBF4, LiClO4, LiCF3SO3, LiAsF6, and LiAlCl4, are described. The addition of PPO in various proportions to MEEP-(LiX)n electrolytes significantly improved the latter's dimensional stability but caused a slight decrease in its conductivity. The conductivities of these mixed-polymer electrolytes are much higher than that of PPO-(LiX)n. The Li(+) transport number in MEEP/PPO-(LiX)0.13 electrolytes, with LiX = LiBF4 and LiClO4, was determined to be between 0.3 and 0.5. Differential scanning calorimetric data established the predominantly amorphous nature of the mixed polymer complexes. Cyclic voltammetric studies at a stainless steel electrode indicated a stability domain between 1 and 4.5V and established the good Li plating and stripping efficiency in these electrolytes.

  5. Oxidative performance and surface properties of Co-containing mixed oxides having the K2NiF4 structure

    Directory of Open Access Journals (Sweden)

    XIAOMAO YANG

    2004-10-01

    Full Text Available The complexed oxides Nd2–xSrxCoO4 (0.4 0.8, the lattice distortion decreased with increasing x. The results of O2–TPD showed that amount of desorption of lattice oxygen over Nd2–xSrxCoO4 increased with x, however, the amount of chemidesorption of oxygen decreased. With increasing x, the high-temperature reduction peak in H2–TPR of Nd2–xSrxCoO4 shifted to higher temperatures, however, the low-temperature reduction peak shifted to lower temperatures, which showed that the activity of the lattice oxygen and the thermal stability of Nd2–xSrxCoO4 increased with increasing x.

  6. Quantum Mechanical Studies of the Early Actinide Compounds

    Science.gov (United States)

    Obodo, Kingsley Onyebuchi

    This study involves the investigation of the early actinide systems using ab initio techniques based on density functional theory (DFT). It was motivated by: (i) the incomplete description of these systems using conventional DFT because they are strongly correlated, (ii) the usefulness of these systems in nuclear energy generation, (iii) the complexity that arises in experimentally studying these systems due to their inherent radioactive nature and (iv) their limited availability. The results obtained from this study are divided into two broad sections. The first comprises chapters 3 and 4 while the second comprises chapters 5 and 6. Thorium based compounds are studied in chapters 3 and 4. In the first section, the Hubbard U parameter is not necessary to accurately describe the electronic, elastic and mechanical properties of these systems. In the second, the inclusion of the Hubbard U parameter is shown to be paramount for the accurate description of most compounds considered. Chapter 3 presents the electronic, structural and bonding character of thorium based nitrides. We obtained the result that Th2N2 NH, which is crystallographically equivalent to metallic Th2N 3, is insulating. Chapter 4 demonstrates that the formation of a meta-stable thorium-titanium based alloy is plausible and also further information on bonding, electronic and elastic properties of the determined meta-stable alloy is provided. This has provided important new knowledge about these bulk systems. In Chapter 5 the DFT + U based study on Pa and its oxides is presented. The electronic, structural and bonding character of these systems was studied. We found that PaO2 is a Mott-Hubbard insulator with an indirect band gap of 3.48 eV within the generalized gradient approximation GGA + U. Chapter 6 discusses various actinide nitrides. We explored the electronic properties, elastic properties, lattice dynamics and the energetics of the various compounds using GGA + U. Also, we investigated the effect

  7. Development of Metallic Fuels for Actinide Transmutation

    Energy Technology Data Exchange (ETDEWEB)

    Hayes, Steven Lowe [Idaho National Laboratory; Fielding, Randall Sidney [Idaho National Laboratory; Benson, Michael Timothy [Idaho National Laboratory; Chichester, Heather Jean MacLean [Idaho National Laboratory; Carmack, William Jonathan [Idaho National Laboratory

    2015-09-01

    Research and development activities on metallic fuels are focused on their potential use for actinide transmutation in future sodium fast reactors. As part of this application, there is also a need for a near zero-loss fabrication process and a desire to demonstrate a multifold increase in burnup potential. The incorporation of Am and Np into the traditional U-20Pu-10Zr metallic fuel alloy was demonstrated in the US during the Integral Fast Reactor Program of the 1980’s and early 1990’s. However, the conventional counter gravity injection casting method performed under vacuum, previously used to fabricate these metallic fuel alloys, was not optimized for mitigating loss of the volatile Am constituent in the casting charge; as a result, approximately 40% of the Am casting charge failed to be incorporated into the as-cast fuel alloys. Fabrication development efforts of the past few years have pursued an optimized bottom-pour casting method to increase utilization of the melted charge to near 100%, and a differential pressure casting approach, performed under an argon overpressure, has been demonstrated to result in essentially no loss of Am due to volatilization during fabrication. In short, a path toward zero-loss fabrication of metallic fuels including minor actinides has been shown to be feasible. Irradiation testing of advanced metallic fuel alloys in the Advanced Test Reactor (ATR) has been underway since 2003. Testing in the ATR is performed inside of cadmium-shrouded positions to remove >99% of the thermal flux incident on the test fuels, resulting in an epi-thermal driven fuel test that is free from gross flux depression and producing an essentially prototypic radial temperature profile inside the fuel rodlets. To date, three irradiation test series (AFC-1,2,3) have been completed. Over 20 different metallic fuel alloys have been tested to burnups as high as 30% with constituent compositions of Pu up to 30%, Am up to 12%, Np up to 10%, and Zr between 10

  8. Factors affecting the placental transfer of actinides

    Energy Technology Data Exchange (ETDEWEB)

    Sikov, M.R.; Kelman, B.J. (Pacific Northwest Laboratory, Richland, WA (USA))

    1989-01-01

    The primary goal of this paper is to consider factors that affect the availability and transport of actinides from maternal blood, through the placenta, to the conceptus. These factors, of particular importance in scaling results from animals to man, include the route and temporal pattern of administration, the mass and physicochemical state of material administered, metabolism of the pregnant animal and fetal organs or tissue, and species-specific changes in placental structure relative to stage of gestation at exposure. Preliminary concepts for descriptive and kinetic models are proposed to integrate these results, to identify additional information required for developing more comprehensive models, and to provide a basis for scaling to human pregnancies for purposes of radiation dosimetry.

  9. Solidification of simulated actinides by natural zircon

    Institute of Scientific and Technical Information of China (English)

    YANG Jian-Wen; LUO Shang-Geng

    2004-01-01

    Natural zircon was used as precursor material to produce a zircon waste form bearing 20wt% simulated actinides (Nd2O3 and UO2) through a solid state reaction by a typical synroc fabrication process. The fabricated zircon waste form has relatively good physical properties (density 5.09g/cm3, open porosity 4.0%, Vickers hardness 715kg/mm2). The XRD, SEM/EDS and TEM/EDS analyses indicate that there are zircon phases containing waste elements formed through the reaction. The chemical durability and radiation stability are determined by the MCC-1method and heavy ion irradiation; the results show that the zircon waste form is highly leach resistance and relatively stable under irradiation (amorphous dose 0.7dpa). From this study, the method of using a natural mineral to solidify radioactive waste has proven to be feasible.

  10. Gamma spectroscopy of neutron rich actinide nuclei

    Energy Technology Data Exchange (ETDEWEB)

    Birkenbach, Benedikt; Geibel, Kerstin; Vogt, Andreas; Hess, Herbert; Reiter, Peter; Steinbach, Tim; Schneiders, David [Koeln Univ. (Germany). IKP; Collaboration: AGATA-Collaboration

    2013-07-01

    Excited states in neutron-rich actinide Th and U nuclei were investigated after multi nucleon transfer reactions employing the AGATA demonstrator and PRISMA setup at LNL (INFN, Italy). A primary {sup 136}Xe beam of 1 GeV hitting a {sup 238}U target was used to produce the nuclei of interest. Beam-like reaction products of Xe- and Ba isotopes after neutron transfer were selected by the PRISMA spectrometer. The recoil like particles were registered by a MCP detector inside the scattering chamber. Coincident γ-rays from excited states in beam and target like particles were measured with the position sensitive AGATA HPGe detectors. Improved Doppler correction and quality of the γ-spectra is based on the novel γ-ray tracking technique which was successfully exploited. First results on the collective properties of various Th and U isotopes are discussed.

  11. Radiochemical studies of neutron deficient actinide isotopes

    Energy Technology Data Exchange (ETDEWEB)

    Williams, K.E.

    1978-04-01

    The production of neutron deficient actinide isotopes in heavy ion reactions was studied using alpha, gamma, x-ray, and spontaneous fission detection systems. A new isotope of berkelium, /sup 242/Bk, was produced with a cross-section of approximately 10 ..mu..b in reactions of boron on uranium and nitrogen on thorium. It decays by electron capture with a half-life of 7.0 +- 1.3 minutes. The alpha-branching ratio for this isotope is less than 1% and the spontaneous fission ratio is less than 0.03%. Studies of (Heavy Ion, pxn) and (Heavy Ion, ..cap alpha..xn) transfer reactions in comparison with (Heavy ion, xn) compound nucleus reactions revealed transfer reaction cross-sections equal to or greater than the compound nucleus yields. The data show that in some cases the yield of an isotope produced via a (H.I.,pxn) or (H.I.,..cap alpha..xn) reaction may be higher than its production via an xn compound nucleus reaction. These results have dire consequences for proponents of the ''Z/sub 1/ + Z/sub 2/ = Z/sub 1+2/'' philosophy. It is no longer acceptable to assume that (H.I.,pxn) and (H.I.,..cap alpha..xn) product yields are of no consequence when studying compound nucleus reactions. No evidence for spontaneous fission decay of /sup 228/Pu, /sup 230/Pu, /sup 232/Cm, or /sup 238/Cf was observed indicating that strictly empirical extrapolations of spontaneous fission half-life data is inadequate for predictions of half-lives for unknown neutron deficient actinide isotopes.

  12. Studies of actinides in a superanoxic fjord

    Energy Technology Data Exchange (ETDEWEB)

    Roos, P.

    1997-04-01

    Water column and sediment profiles of Pu, Am, Th and U have been obtained in the superanoxic Framvaren fjord, southern Norway. The concentration of bomb test fallout Pu, Am as well as `dissolved` Th in the bottom water are the highest recorded in the marine environment. The behaviour of the actinides in the anoxic water mass is to a large extent governed by the behaviour of the colloidal material. Ultrafiltration reveals that 40-60% of the actinides are associated to the large colloids, surprisingly this is valid also for U. The sediment acts as a source for Pu, Am, and Th to the water column but primarily as a sink for U. The remobilization of Pu, Am and Th is evident from the water column profiles which have similar diffusion shape profiles as other constituents originating from the sediments. The vertical eddy diffusion coefficient calculated from the Pu profile is in the same order of magnitude as reported from the H{sub 2}S profile. Decreased bottom water concentrations (but a constant water column inventory) between 1989 and 1995 as well as pore water Pu concentrations nearly identical to the overlaying bottom water indicates that the present Pu flux from the sediments are low. Contrary to Pu and Am, the water column Th inventory ({sup 232}Th and {sup 230}Th) continues to increase. The flux of {sup 232}Th from the sediments was determined from changes in water column inventory between 1989 and 1995 and from a pore water profile to be in the order of 2-8 Bq/m{sup 2}/y. 208 refs.

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

    Science.gov (United States)

    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

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

    Directory of Open Access Journals (Sweden)

    Hongbin Yu

    Full Text Available 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%.

  15. A comparative study of actinide complexation in three ligand systems with increasing complexity

    Science.gov (United States)

    Jeanson, A.; Dahou, S.; Guillaumont, D.; Moisy, P.; Den Auwer, C.; Scheinost, A.; Hennig, C.; Vidaud, C.; Subra, G.; Solari, P. L.

    2009-11-01

    The complexation of thorium, neptunium and plutonium at oxidation state +IV with three ligands of increasing complexity has been investigated. These ligands are relevant for bio inorganic systems. The first ligand is the small nitrilotriacetic acid that often play the role of protecting ligands against hydrolysis. EXAFS results for the Th to Pu series have been correlated to quantum chemical calculations and show an homogeneous behavior of the actinide at oxidation state +IV. For larger ligands, steric effects may become significant and one can ask how the ligand may accommodate the large actinide cation coordination sphere. Model pentapeptides have been synthesized and tested as complexing agents. Comparison with NTA shows that the molecular arrangements are radically different. The third ligand system is transferrin, a diferric metalloptrotein that is well known to coordinate a large variety of cations from transition metals of f-elements. Metalloproteins bear primary, secondary and tertiary structures that all play a crucial role in bonding. At a given oxidation state (+IV), but for various atomic numbers (Th, Np, Pu) EXAFS data at the cation LIII edge exhibit significant coordination discrepancies that are related to a changes in protein geometry. In that sense, the metalloprotein may be viewed as a complex system.

  16. A comparative study of actinide complexation in three ligand systems with increasing complexity

    Energy Technology Data Exchange (ETDEWEB)

    Jeanson, A; Dahou, S; Guillaumont, D; Moisy, P; Auwer, C Den [CEA Marcoule, DEN/DRCP/SCPS, 30207 Bagnols sur Ceze (France); Scheinost, A; Hennig, C [Forschungszentrum Dresden-Rossendorf, 01314 Dresden (Germany); Vidaud, C [CEA Marcoule DSV/iBEB/SBTN, 30207 Bagnols sur Ceze (France); Subra, G [Institut des Biomolecules Max Mousseron, CNRS UMR-5247, Universite Montpellier I-II, 34093 Montpellier (France); Solari, P L, E-mail: Christophe.denauwer@cea.f [Synchrotron SOLEIL, MARS beam line, 91192 Gif sur Yvette (France)

    2009-11-15

    The complexation of thorium, neptunium and plutonium at oxidation state +IV with three ligands of increasing complexity has been investigated. These ligands are relevant for bio inorganic systems. The first ligand is the small nitrilotriacetic acid that often play the role of protecting ligands against hydrolysis. EXAFS results for the Th to Pu series have been correlated to quantum chemical calculations and show an homogeneous behavior of the actinide at oxidation state +IV. For larger ligands, steric effects may become significant and one can ask how the ligand may accommodate the large actinide cation coordination sphere. Model pentapeptides have been synthesized and tested as complexing agents. Comparison with NTA shows that the molecular arrangements are radically different. The third ligand system is transferrin, a diferric metalloptrotein that is well known to coordinate a large variety of cations from transition metals of f-elements. Metalloproteins bear primary, secondary and tertiary structures that all play a crucial role in bonding. At a given oxidation state (+IV), but for various atomic numbers (Th, Np, Pu) EXAFS data at the cation L{sub III} edge exhibit significant coordination discrepancies that are related to a changes in protein geometry. In that sense, the metalloprotein may be viewed as a complex system.

  17. The inverse-trans-influence in tetravalent lanthanide and actinide bis(carbene) complexes

    Science.gov (United States)

    Gregson, Matthew; Lu, Erli; Mills, David P.; Tuna, Floriana; McInnes, Eric J. L.; Hennig, Christoph; Scheinost, Andreas C.; McMaster, Jonathan; Lewis, William; Blake, Alexander J.; Kerridge, Andrew; Liddle, Stephen T.

    2017-02-01

    Across the periodic table the trans-influence operates, whereby tightly bonded ligands selectively lengthen mutually trans metal-ligand bonds. Conversely, in high oxidation state actinide complexes the inverse-trans-influence operates, where normally cis strongly donating ligands instead reside trans and actually reinforce each other. However, because the inverse-trans-influence is restricted to high-valent actinyls and a few uranium(V/VI) complexes, it has had limited scope in an area with few unifying rules. Here we report tetravalent cerium, uranium and thorium bis(carbene) complexes with trans C=M=C cores where experimental and theoretical data suggest the presence of an inverse-trans-influence. Studies of hypothetical praseodymium(IV) and terbium(IV) analogues suggest the inverse-trans-influence may extend to these ions but it also diminishes significantly as the 4f orbitals are populated. This work suggests that the inverse-trans-influence may occur beyond high oxidation state 5f metals and hence could encompass mid-range oxidation state actinides and lanthanides. Thus, the inverse-trans-influence might be a more general f-block principle.

  18. Element Partitioning in Glass-Ceramic Designed for Actinides Immobilization

    Institute of Scientific and Technical Information of China (English)

    2008-01-01

    <正>Glass-ceramics were designed for immobilization of actinides. In order to immobilizing more wastes in the matrix and to develop the optimum formulation for the glass-ceramic, it is necessary to study the

  19. Advanced techniques for actinide spectroscopy (ATAS 2012). Abstract book

    Energy Technology Data Exchange (ETDEWEB)

    Foerstendorf, Harald; Mueller, Katharina; Steudtner, Robin (eds.)

    2012-07-01

    The abstract book of the International workshop on advanced techniques for actinide spectroscopy (ATAS 2012) include contributions concerning the following issues: environmental applications, NMR spectroscopy, vibrational spectroscopy, X-ray spectroscopy and theory, technical application: separation processes, emission spectroscopy.

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

    Science.gov (United States)

    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.