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Sample records for actinide metal compounds

  1. Organometallic compounds of the lanthanides, actinides and early transition metals

    This book provides a reference compilation of physical and biographical data on over 1500 of the most important and useful organometallic compounds of the lanthanides, actinides and early transition metals representing 38 different elements. The compounds are listed in molecular formula order in a series of entries in dictionary format. Details of structure, physical and chemical properties, reactions and key references are clearly set out. All the data is fully indexed and a structural index is provided. (U.K.)

  2. Spin and orbital moments in actinide compounds

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

    1991-01-01

    -electron band-structure calculations, is that the orbital moments of the actinide 5f electrons are considerably reduced from the values anticipated by a simple application of Hund's rules. To test these ideas, and thus to obtain a measure of the hybridization, we have performed a series of neutron scattering...... 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 as...

  3. Photoelectron spectra of actinide compounds

    A brief overview of the application of photoelectron spectroscopy is presented for the study of actinide materials. Phenomenology as well as specific materials are discussed with illustrative examples

  4. Superconductivity in rare earth and actinide compounds

    Rare earth and actinide compounds and the extraordinary superconducting and magnetic phenomena they exhibit are surveyed. The rare earth and actinide compounds described belong to three classes of novel superconducting materials: high temperature, high field superconductors (intermetallics and layered cuprates); superconductors containing localized magnetic moments; heavy fermion superconductors. Recent experiments on the resistive upper critical field of high Tc cuprate superconductors and the peak effect in the critical current density of the f-electron superconductor CeRu2 are discussed. (orig.)

  5. Prediction of thermodynamic properties of actinide and lanthanide compounds

    LU Chunhai; NI Shijun; SUN Ying; CHEN Wenkai; ZHANG Chengjiang

    2008-01-01

    Several relationship models for thermodynamic functions of actinide and lanthanide compounds are built. The descriptors such as the difference of atomic radii between metal atoms and nonmetal atoms and the molecular mass are used in quantitative structure-activity/property relationships. The relative errors for entropy and heat capacity are less than 20% in the majority of gaseous compounds. Similar results are obtained from solid compounds.

  6. Calculated Atomic Volumes of the Actinide Metals

    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....

  7. Magnetic form factor studies of actinide compounds

    Some results obtained at ILL on Actinide compound form factors are reviewed. In the paramagnetic NpO2 single crystal (5mg), an induced magnetic moment of 0.07μsub(B) was obtained at 4.2K (4.6T). In the ferromagnetic phase of NpAs2 single crystal (0.2mm3), the magnetic moment (1.46μsub(B)/Np atom) has been found fixed along the [001] direction. In both cases, the Np form factors fit satisfactorily the Np4+ form factor calculated with relativistic atomic wave functions. The Fermi length for Np was deduced (b(Np) = 1.015(15)10-12cm). In the paramagnetic Laves phase UNi2 compound, equally small moments are observed on U atom (0.013(1)μsub(B)) and on Ni atom (0.016(1)μsub(B)) confirming important changes in 3d band structure of Ni by hybridization with U electrons

  8. Cerium compounds in the fashion of the light actinides

    Researchers familiar with the light actinides easily recognize in cerium compounds a microcosm of the rich variety of properties seen in the light actinides. The parallelism seen between comparable cerium and actinide compounds strongly suggests that the same physical models are applicable. The most significant is the relative size of the f-orbital. Localization is generally tighter in Ce compounds than uranium compounds, making Ce roughly analogous to Np through Am. A way to see the actinide parallelism is to compare Hill plots. Compounds in the different regions of the plots (representing different physics) are isostructural compounds with the same companion (B) elements. The most common materials exhibiting a direct f-f interaction are the cubic Laves compounds. Accordingly, we have determined the band structures of CeRu2, CeRh2, CeIr2, CeOs2, and CeNi2. Compounds illustrative of the interaction of f-orbitals with ligand orbitals are the Cu3Au structured materials. Materials calculated in this class are CeRh3, CePd3, and CeSn3 - the materials of much interest as mixed valent. Although the focus is on the Ce compounds, calculations performed on uranium isomorphs are used to highlight the interesting physics

  9. Synthesis and structural characterization of actinide oxalate compounds

    Oxalic acid is a well-known reagent to recover actinides thanks to the very low solubility of An(IV) and An(III) oxalate compounds in acidic solution. Therefore, considering mixed-oxide fuel or considering minor actinides incorporation in ceramic fuel materials for transmutation, oxalic co-conversion is convenient to synthesize mixed oxalate compounds, precursors of oxide solid solutions. As the existing oxalate single crystal syntheses are not adaptable to the actinide-oxalate chemistry or to their manipulation constrains in gloves box, several original crystal growth methods were developed. They were first validate and optimized on lanthanides and uranium before the application to transuranium elements. The advanced investigations allow to better understand the syntheses and to define optimized chemical conditions to promote crystal growth. These new crystal growth methods were then applied to a large number of mixed An1(IV)-An2(III) or An1(IV)-An2(IV) systems and lead to the formation of the first original mixed An1(IV)-An2(III) and An1(IV)-An2(IV) oxalate single crystals. Finally thanks to the first thorough structural characterizations of these compounds, single crystal X-ray diffraction, EXAFS or micro-RAMAN, the particularly weak oxalate-actinide compounds structural database is enriched, which is essential for future studied nuclear fuel cycles. (author)

  10. Ternary phase equilibria in the systems actinide-transition metal-carbon and actinide metal-nitrogen

    Isothermal sections in the ternary phase diagrams of actinide-transition metal-carbon and actinide-transition metal-nitrogen systems are compiled on the basis of new phase studies, using thermodynamic data of carbides and nitrides, and considering the structure and lattice parameters of binary compounds. The lack of experimental results is compensated by estimating the solution behaviour and the phase stabilities. Phase diagrams are given for the systems: Th-(U or Pu)-C, U-(Th or Pu)-N, (Th or U or Pu)-Y-C, (Th or U or Pu)-Ce-C, (Th or U or Pu)-Y-N, (Th or U or Pu)-Ce-N, U-(La or Ce or Pr or Nd)-N, (Th or U or Pu)-Ti-C, (Th or U or Pu)-Zr-C, (Th or U or Pu)-Nb-C, (Th or U or Pu)-Mo-C, U-(Ti or Zr or Hf or Mo)-N, (Th or Pu)-Zr-N, (Th or U or Pu)-Cr-N and (Th or U or Pu)-(Ru or Rh or Pd)-C. Of particular interest is the occurrence of ternary carbides and nitrides. (orig.)

  11. Non-compound nucleus fission in actinide and pre-actinide regions

    R Tripathi; S Sodaye; K Sudarshan

    2015-08-01

    In this article, some of our recent results on fission fragment/product angular distributions are discussed in the context of non-compound nucleus fission. Measurement of fission fragment angular distribution in 28Si+176Yb reaction did not show a large contribution from the non-compound nucleus fission. Data on the evaporation residue cross-sections, in addition to those on mass and angular distributions, are necessary for better understanding of the contribution from non-compound nucleus fission in the pre-actinide region. Measurement of mass-resolved angular distribution of fission products in 20Ne+232Th reaction showed an increase in angular anisotropy with decreasing asymmetry of mass division. This observation can be explained based on the contribution from pre-equilibrium fission. Results of these studies showed that the mass dependence of anisotropy may possibly be used to distinguish pre-equilibrium fission and quasifission.

  12. Hybridization effects in selected actinides and their compounds

    El-Khatib, Sami T.

    Many actinide systems exhibit 'unusual' phenomena that differ from the normal text-book behavior. This occurs because the 5f electrons of the actinides and their compounds experience a delicate balance between local-moment and itinerant magnetism. It is well established that strong-electron correlations affect the different properties in such systems. Even though the actinides and their compounds have been extensively studied in recent decades, both experimentally and theoretically, to date, no complete understanding of the full range of their properties has been achieved. My thesis focuses mainly on understanding the role of 5f electrons and their interactions with the electron states of the surrounding ligands. Particularly, the effect of the 5f-ligand hybridization in the development of bulk properties is investigated. The experimental studies utilized macroscopic techniques, such as magnetization, electrical-resistivity, specific-heat and resonant-ultrasound-spectroscopy measurements, as well as microscopic techniques, such as neutron-diffraction and muon-spin-resonance studies. The results are used to disentangle the importance of direct 5f--5f overlap and 5 f-ligand hybridization. The following features have been investigated in this thesis: (a) the dual nature of hybridization effects (magnetic moment reduction vs. exchange mediation) was studied for two isostructural uranium compounds U2Pd2Sn and U2Ni2 In; (b) the formation of complex magnetic structures and its connection to the hybridization effects was studied for UCuSn, UPdSn and UPdGe; (c) the tuning of the hybridization to critical values through substitutions was attempted for two single crystals of UCoAl1-xSn x and UNi1-xRh xAl alloys; (d) the effects of compositional deficiencies was studied for the copper-deficient compound in UCu1.5Sn 2; and finally, (e) the influence of strong electron correlations on the elastic properties was studied in the case of alpha-Pu.

  13. The chemical thermodynamics of actinide elements and compounds

    This compilation forms the twelfth part of a comprehensive assessment and selection of actinide thermodynamic data. The other parts of the compilation deal mostly with actinide elements and compounds. This part, which is the last one to be published in this Series, concerns inorganic actinide complexes in aqueous solution. The properties considered include the stability constant as a function of ionic strength and temperature and, whenever possible, enthalpy and entropy values. The present assessment is based on a literature survey that was terminated in early 1989. In tabulating literature data, only experimental results were used; estimates as well as recalculated data were ignored. Unlike in previous assessments of this kind in this assessment the selection of a best value is discussed and justified, and reasons are given for the rejection of data. In addition, our estimates of the thermodynamic properties, based on interrelationships between analogous systems, are given when this can be done reliably. Another essential aim of this assessment is to indicate those areas in which additional research is required. Refs

  14. Electronic Structure of the Actinide Metals

    Johansson, B.; Skriver, Hans Lomholt

    1982-01-01

    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...

  15. Actinide transmutation in the advanced liquid metal reactor (ALMR)

    The Advanced Liquid Metal Reactor (ALMR) is a US Department of Energy (DOE) sponsored fast reactor design based on the Power Reactor, Innovative Small Module (PRISM) concept originated by General Electric. The current reference design is a 471 MWt modular reactor loaded with ternary metal fuel. This paper discusses actinide transmutation core designs that fit the design envelope of the ALMR and utilize spent LWR fuel as startup material and makeup. Actinide transmutation may be accomplished in the ALMR by using either a breeding or burning configuration. Lifetime actinide mass consumption is calculated as well as changes in consumption behaviour throughout the lifetime of the reactor. Impacts on system operational and safety performance are evaluated in a preliminary fashion. (author). 3 refs, 6 figs, 3 tabs

  16. Calculated Bulk Properties of the Actinide Metals

    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...

  17. The advanced liquid metal reactor actinide recycle system

    The current U.S. National Energy Strategy includes four key goals for nuclear policy: enhance safety and design standards, reduce economic risk, reduce regulatory risk, and establish an effective high-level nuclear waste program. The U.S. Department of Energy's Advanced Liquid Metal Reactor Actinide Recycle System is consistent with these objectives. The system has the ability to fulfill multiple missions with the same basic design concept. In addition to providing an option for long-term energy security, the system can be effectively utilized for recycling of actinides in light water reactor (LWR) spent fuel, provide waste management flexibility, including the reduction in the waste quantity and storage time and utilization of the available energy potential of LWR spent fuel. The actinide recycle system is comprised of (1) a compact liquid metal (sodium) cooled reactor system with optimized passive safety characteristics, and (2) pyrometallurgical metal fuel cycle presently under development of Argonne National Laboratory. The waste reduction of LWR spent fuel is accomplished by transmutation or fissioning of the longer-lived transuranic isotopes to shorter-lived fission products in the reactor. In this presentation the economical and environmental incentive of the actinide recycle system is addressed and the status of development including licensing aspects is described. 3 refs., 1 tab., 6 figs

  18. Hydroxyaromatic compounds of tantalum, tungsten, and the lighter actinides

    Some hydroxyaromatic compounds of the elements tantalum, tungsten, thorium and uranium were prepared as well as the basic materials for these synthesis processes, i.e. metal halides and metal alkoxides. The hydroxyaromatic compounds were studied by elemental analysis, IR spectroscopy, 1H-NMR spectroscopy (if soluble in suitable solvents) and, in some cases, by X-ray fine structure analysis. (orig./EF)

  19. Electron-phonon coupling of the actinide metals

    Skriver, H. L.; Mertig, I.

    1985-01-01

    -phonon parameter λ is found to attain its maximum value in Ac, and they predict a transition temperature of 9K for this metal. In the light actinides Th through Pu, λ is found to be of order 0.4 and within a factor of 2 of experiments which is also the accuracy found in studies of the transition metals...... be related to the changeover from an s-to- d to an s-to-f electronic transition and a related change in the topology of the Fermi surface...

  20. Light metal compound casting

    Konrad; J.; M.; PAPIS; Joerg; F.; LOEFFLER; Peter; J.; UGGOWITZER

    2009-01-01

    Compound casting’simplifies joining processes by directly casting a metallic melt onto a solid metal substrate. A continuously metallurgic transition is very important for industrial applications, such as joint structures of spaceframe constructions in transport industry. In this project, ‘compound casting’ of light metals is investigated, aiming at weight-saving. The substrate used is a wrought aluminium alloy of type AA5xxx, containing magnesium as main alloying element. The melts are aluminium alloys, containing various alloying elements (Cu, Si, Zn), and magnesium. By replacing the natural oxygen layer with a zinc layer, the inherent wetting difficulties were avoided, and compounds with flawless interfaces were successfully produced (no contraction defects, cracks or oxides). Electron microscopy and EDX investigations as well as optical micrographs of the interfacial areas revealed their continu- ously metallic constitution. Diffusion of alloying elements leads to heat-treatable microstructures in the vicinity of the joining interfaces in Al-Al couples. This permits significant variability of mechanical properties. Without significantly cutting down on wettability, the formation of low-melting intermetallic phases (Al3Mg2 and Al12Mg17 IMPs) at the interface of Al-Mg couples was avoided by applying a protective coating to the substrate.

  1. Light metal compound casting

    Konrad J.M.PAPIS; Joerg F.LOEFFLER; Peter J.UGGOWITZER

    2009-01-01

    'Compound casting'simplifies joining processes by directly casting a metallic melt onto a solid metal substrate. A continuously metallurgic transition is very important for industrial applications, such as joint structures of spaceframe constructions in transport industry. In this project, 'compound casting' of light metals is investigated, aiming at weight-saving. The substrate used is a wrought aluminium alloy of type AA5xxx, containing magnesium as main alloying element. The melts are aluminium alloys, containing various alloying elements (Cu, Si, Zn), and magnesium. By replacing the natural oxygen layer with a zinc layer, the inherent wetting difficulties were avoided, and compounds with flawless interfaces were successfully produced (no contraction defects, cracks or oxides). Electron microscopy and EDX investigations as well as optical micrographs of the interfacial areas revealed their continu-ously metallic constitution. Diffusion of alloying elements leads to heat-treatable microstructures in the vicinity of the joining interfaces in Al-Al couples. This permits significant variability of mechanical properties. Without significantly cutting down on wettability, the formation of low-melting intermetallic phases (Al3Mg2 and AI12Mg17 IMPs) at the interface of Al-Mg couples was avoided by applying a protec-tive coating to the substrate.

  2. Effect of organic compounds for the advection of actinide elements in the environments

    Muraoka, Susumu; Nagao, Seiya; Tanaka, Tadao [Japan Atomic Energy Research Inst., Tokai, Ibaraki (Japan). Tokai Research Establishment; Hiraki, Keizo; Nakaguchi, Yuzuru; Suzuki, Yasuhiro

    1998-01-01

    The aim of this studies is understood the effects of humic substances for the advection of actinide elements in the environments. These substances are a major role of dissolved organic matter in natural waters. In order to obtain the informations on the structure of metal-humic substances complexes, these substances were studied by fluorescence spectroscopy. Observation the spectrum forms, peak positions of maximum intensity are related to these informations on the chemical structures and functional groups in organic compounds. Using three-dimensional excitation emission matrix (3-D EEM) spectroscopy, the characteristics of metal-humic substances complexes were studied. Observation the wavelengths and fluorescence intensity of the peaks were varied between humic substances before the complex to the metal and these substances after ones. Understanding the fluorescence properties of metal-humic substances complexes, working program of the 3-D EEM spectroscopy was studied to obtaining detailed data collection. New program was applied to copper-humic acid complex, the peak positions which different with before the complex and after ones were recorded. This program is supported by the interpreation of fluorescence properties in the metal-humic substances by the 3-D EEM spectroscopy. (author)

  3. Relations between structural and magnetic properties of actinide oxidic compounds

    In the present work ternary oxides of Pr(IV), U(VI), Np(IV) and Np(VI) have been synthesized and investigated by X-ray-, spectroscopic and magnetic methods. In the case of Pr(IV), the paramagnetic ion was diluted with the diamagnetic Ce(IV) to perform EPR studies. In all compounds with metal ions with the f1-electronic configuration, the central ion shows a distorted octahedral coordination. The experimental effective magnetic moments are lower than the theoretical value for a f1-system in an ideal octahedral symmetry. This leads to the conclusion, that the covalent part of the bond between the central ion and oxygen can not be neglected in the investigated compounds. Magnetic ordering phenomena can be correlated definitely with the existence of An-O-An-chains in the lattice at least in one direction. The experimental data support the assumption of a critical An-An-spacing. In compounds with An-An-distances greater than the critical value no magnetic ordering was observed within the investigated temperature range. In NpGeO4 with eightfold coordination of the 5f3-electronic system, the Np-O-Np-chains are not linear. The angle of the O-Np-O-bonds seems to favour orbital overlapping, as the compound orders magnetically with a Np-Np-distance above the critical value. On some Np-compounds, Moessbauer studies were performed in the Institute of Experimental Nuclear Physics of the University of Karlsruhe. The results confirm the suggested structural and magnetic properties. (orig./RB)

  4. Basic research on solvent extraction of actinide cations with diamide compounds

    Newly synthesized 4 diamide compounds were tested for solvent extraction of actinide cations. It is obvious that N,N'-dimethyl-N,N'-dihexyl-3-oxapentanediamide (DMDHOPDA) can extract Eu(III), Th(IV), U(VI), Np(V), and Am(III) into organic solvent. Other 3 diamides hardly extract actinide ions, which is supposed that the reasons come from the difference of their chemical structures. In the synergistic extraction with a diamide and thenoyltrifluoroacetone (TTA), all diamides work as a extractant. Furthermore, by examining extracted species, it was confirmed that there are 4 kinds of chemical species of actinides with diamide and TTA. Finally, the mutual separation method of actinide (III), (IV), (V) and (VI) ions by solvent extraction using DMDHOPDA and TTA were developed. (author). 147 refs

  5. Basic research on solvent extraction of actinide cations with diamide compounds

    Sasaki, Yuji [Japan Atomic Energy Research Inst., Tokai, Ibaraki (Japan). Tokai Research Establishment

    1998-11-01

    Newly synthesized 4 diamide compounds were tested for solvent extraction of actinide cations. It is obvious that N,N`-dimethyl-N,N`-dihexyl-3-oxapentanediamide (DMDHOPDA) can extract Eu(III), Th(IV), U(VI), Np(V), and Am(III) into organic solvent. Other 3 diamides hardly extract actinide ions, which is supposed that the reasons come from the difference of their chemical structures. In the synergistic extraction with a diamide and thenoyltrifluoroacetone (TTA), all diamides work as a extractant. Furthermore, by examining extracted species, it was confirmed that there are 4 kinds of chemical species of actinides with diamide and TTA. Finally, the mutual separation method of actinide (III), (IV), (V) and (VI) ions by solvent extraction using DMDHOPDA and TTA were developed. (author). 147 refs.

  6. Semi-microdetermination of nitrogen in actinide compounds by Dumas method

    This report describes the application of the Dumas method for the semi-micro determination of nitrogen in actinide compounds and actinide complexes with organic ligands. The usual set up has been modified to make it adaptable for glove box operations. The carbon dioxide generator and nitrometer assemblies were located outside the glove box while the reaction tube and combustion furnaces were housed inside. The nitrogen gas collected in the nitrometer was read with the help of a travelling microscope with a vernier attachment fitted in front of the nitrometer burette. The set up was standardised using acetanilide and employed for the determination of nirtogen in various substances such as uranium nitride, and a variety of substituted quinoline and pyrazolone derivatives of actinides as well as some ternary uranium-PMBR-sulphoxide complexes. Full details of the technique and the analytical data obtained are contained in this report. (author)

  7. Minor Actinide Transmutation Performance in Fast Reactor Metal Fuel. Isotope Ratio Change in Actinide Elements upon Low-Burnup Irradiation

    Metal fuel alloys containing 5 wt% or less minor actinide (MA) and rare earth (RE) were irradiated in the fast reactor Phénix. After nondestructive postirradiation tests, a chemical analysis of the alloys irradiated for 120 effective full power days was carried out by the inductively coupled plasma - mass spectrometry (ICP-MS) technique. From the analysis results, it was determined that the discharged burnups of U-19Pu-10Zr, U-19Pu-10Zr-2MA-2RE, and U-19Pu-10Zr-5MA were 2.17, 2.48, and 2.36 at.%, respectively. Actinide isotope ratio analyses before and after the irradiation experiment revealed that Pu, Am, and Cm nuclides added to U-Pu-Zr alloy and irradiated up to 2.0 - 2.5 at.% burnups in a fast reactor are transmuted properly as predicted by ORIGEN2 calculations. (author)

  8. Calculation of binary phase diagrams between the actinide elements, rare earth elements, and transition metal elements

    Attempts were made to apply the Kaufman method of calculating binary phase diagrams to the calculation of binary phase diagrams between the rare earths, actinides, and the refractory transition metals. Difficulties were encountered in applying the method to the rare earths and actinides, and modifications were necessary to provide accurate representation of known diagrams. To calculate the interaction parameters for rare earth-rare earth diagrams, it was necessary to use the atomic volumes for each of the phases: liquid, body-centered cubic, hexagonal close-packed, and face-centered cubic. Determination of the atomic volumes of each of these phases for each element is discussed in detail. In some cases, empirical means were necessary. Results are presented on the calculation of rare earth-rare earth, rare earth-actinide, and actinide-actinide diagrams. For rare earth-refractory transition metal diagrams and actinide-refractory transition metal diagrams, empirical means were required to develop values for the enthalpy of vaporization for rare earth elements and values for the constant (C) required when intermediate phases are present. Results of using the values determined for each element are presented

  9. The pressure-induced transformation B1 to B2 in actinide compounds

    The phase transformation from NaCl structure (B1) to CsCl structure (B2) in actinide compounds has been studied using X-ray powder diffraction in the pressure range up to about 60 GPa. It is shown that the transition is sluggish, has a strong hysteresis and is accompanied with a volume change in the range 8-12%. These features are similar to those of the corresponding transition in the alkali halides and other compounds, indicating a common mechanism for the transformation as concerns the lattice geometry. (orig.)

  10. Electron-phonon coupling of the actinide metals

    Skriver, H. L.; Mertig, I.

    1985-01-01

    The authors have estimated the strength of the electron-phonon coupling in Fr and Ra plus the light actinides Ac through Pu. The underlying self-consistent band-structure calculations were performed by the scalar relativistic linear-muffin-tin-orbital method including l quantum numbers s through g...

  11. The uncertainty analysis of a liquid metal reactor for burning minor actinides from light water reactors

    Choi, Hang Bok [Korea Atomic Energy Research Institute, Taejon (Korea, Republic of)

    1998-12-31

    The neutronics analysis of a liquid metal reactor for burning minor actinides has shown that uncertainties in the nuclear data of several key minor actinide isotopes can introduce large uncertainties in the predicted performance of the core. A comprehensive sensitivity and uncertainty analysis was performed on a 1200 MWth actinide burner designed for a low burnup reactivity swing, negative doppler coefficient, and low sodium void worth. Sensitivities were generated using depletion perturbation methods for the equilibrium cycle of the reactor and covariance data was taken ENDF-B/V and other published sources. The relative uncertainties in the burnup swing, doppler coefficient, and void worth were conservatively estimated to be 180%, 97%, and 46%, respectively. 5 refs., 1 fig., 3 tabs. (Author)

  12. Supercritical Fluid Extraction of Actinides and Heavy Metals for Environmental Cleanup: A Process Development Perspective

    The extraction of heavy metal ions and actinide ions is demonstrated using supercritical carbon dioxide (CO2) containing dissolved protonated ligands, such as diketones and organophosphinic acids. High efficiency extraction is observed. The mechanism of the extraction reaction is discussed and, in particular, the effect of addition of water to the sample matrix is highlighted. In-process dissociation of metal-ligand complexes for ligand regeneration and recycle is also discussed. A general concept for a process using this technology is outlined

  13. Preparations and mechanism of hydrolysis of ((8)annulene)actinide compounds. [Uranocene

    Moore, R.M. Jr.

    1985-07-01

    The mechanism of hydrolysis for bis(8)annulene actinide and lanthanide complexes has been studied in detail. The uranium complex, uranocene, decomposes with good pseudo-first order kinetics (in uranocene) in 1 M degassed solutions of H/sub 2/O in THF. Decomposition of a series of aryl-substituted uranocenes demonstrates that the hydrolysis rate is dependent on the electronic nature of the substituent (Hammett rho value = 2.1, r/sup 2/ = 0.999), with electron-withdrawing groups increasing the rate. When D/sub 2/O is substituted for H/sub 2/O, kinetic isotope effects of 8 to 14 are found for a variety of substituted uranocenes. These results suggest a pre-equilibrium involving approach of a water molecule to the central metal, followed by rate determining proton transfer to the eight membered ring and rapid decomposition to products. Each of the four protonations of the complex has a significant isotope effect. The product ratio of cyclooctatriene isomers formed in the hydrolysis varies, depending on the central metal of the complex. However, the general mechanism of hydrolysis, established for uranocene, can be extended to the hydrolysis and alcoholysis of all the (8)annulene complexes of the lanthanides and actinides.

  14. Preparations and mechanism of hydrolysis of ([8]annulene)actinide compounds

    The mechanism of hydrolysis for bis[8]annulene actinide and lanthanide complexes has been studied in detail. The uranium complex, uranocene, decomposes with good pseudo-first order kinetics (in uranocene) in 1 M degassed solutions of H2O in THF. Decomposition of a series of aryl-substituted uranocenes demonstrates that the hydrolysis rate is dependent on the electronic nature of the substituent (Hammett rho value = 2.1, r2 = 0.999), with electron-withdrawing groups increasing the rate. When D2O is substituted for H2O, kinetic isotope effects of 8 to 14 are found for a variety of substituted uranocenes. These results suggest a pre-equilibrium involving approach of a water molecule to the central metal, followed by rate determining proton transfer to the eight membered ring and rapid decomposition to products. Each of the four protonations of the complex has a significant isotope effect. The product ratio of cyclooctatriene isomers formed in the hydrolysis varies, depending on the central metal of the complex. However, the general mechanism of hydrolysis, established for uranocene, can be extended to the hydrolysis and alcoholysis of all the [8]annulene complexes of the lanthanides and actinides

  15. Alloy waste forms for metal fission products and actinides isolated by spent nuclear fuel treatment

    Waste form alloys are being developed at Argonne National Laboratory for the disposal of remnant metallic wastes from an electrometallurgical process developed to treat spent nuclear fuel. This metal waste form consists of the fuel cladding (stainless steel or Zircaloy), noble metal fission products (e.g., Ru, Pd, Mo and Tc), and other metallic wastes. The main constituents of the metal waste stream are the cladding hulls (85 to 90 wt%); using the hulls as the dominant alloying component minimizes the overall waste volume as compared to vitrification or metal encapsulation. Two nominal compositions for the waste form are being developed: (1) stainless steel-15 wt% zirconium for stainless steel-clad fuels and (2) zirconium-8 wt% stainless steel for Zircaloy-clad fuels. The noble metal fission products are the primary source of radiation in the metal waste form. However, inclusion of actinides in the metal waste form is being investigated as an option for interim or ultimate storage. Simulated waste form alloys were prepared and analyzed to determine the baseline alloy microstructures and the microstructural distribution of noble metals and actinides. Corrosion tests of the metal waste form alloys indicate that they are highly resistant to corrosion

  16. Method for decontamination of nickel-fluoride-coated nickel containing actinide-metal fluorides

    Windt, N.F.; Williams, J.L.

    In one aspect, the invention comprises contacting nickel-fluoride-coated nickel with gaseous ammonia at a temperature effecting nickel-catalyzed dissociation thereof and effecting hydrogen-reduction of the nickel fluoride. The resulting nickel is heated to form a melt and a slag and to effect transfer of actinide metals from the melt into the slag. The melt and slag are then separated. In another aspect, nickel contianing nickel oxide and actinide metals is contacted with ammonia at a temperature effecting nickel-catalyzed dissociation to effect conversion of the nickel oxide to the metal. The resulting nickel is then melted and separated as described. In another aspect nickel-fluoride-coated nickel containing actinide-metal fluorides is contacted with both steam and ammonia. The resulting nickel then is melted and separated as described. The invention is characterized by higher nickel recovery, efficient use of ammonia, a substantial decrease in slag formation and fuming, and a valuable increase in the service life of the furnace liners used for melting.

  17. Ultrasoft x-ray resonance emission bands of lanthanide and actinide compounds

    A study is reported of the ultrasoft emission spectra of some lanthanide and actinide compounds at a low accelerating voltage in the X-ray tube: a strong and wide emission band was observed in the region of the giant resonance. The following results are shown: the lanthanum emission spectra in La2O3 obtained at accelerating voltages of 4, 1.5 and 0.5 KV and the absorption spectrum at the 4d threshold; similar measurements for Th in ThO2 (and absorption spectrum at the 5d threshold) and U in U3O8 (and absorption spectrum at the 5d threshold); and for Ce in CeO2 (and absorption spectrum at the 4d threshold). The results are discussed. (U.K.)

  18. Rare-earth metal π-complexes of reduced arenes, alkenes, and alkynes: Bonding, electronic structure, and comparison with actinides and other electropositive metals

    Huang, W.; Diaconescu, PL

    2015-01-01

    © 2015 The Royal Society of Chemistry. Rare-earth metal complexes of reduced π ligands are reviewed with an emphasis on their electronic structure and bonding interactions. This perspective discusses reduced carbocyclic and acyclic π ligands; in certain categories, when no example of a rare-earth metal complex is available, a closely related actinide analogue is discussed. In general, rare-earth metals have a lower tendency to form covalent interactions with π ligands compared to actinides, m...

  19. Synthesis, growth, and studies (crystal chemistry, magnetic chemistry) of actinide-based intermetallic compounds and alloys with a 1.1.1 stoichiometry

    The first part of this research thesis reports the study of the synthesis and reactivity of intermetallic compounds with a 1.1.1 stoichiometry. It presents the thermal properties of 1.1.1 compounds: general presentation of physical transitions, and of solid solutions and formation heat, application to actinides (reactivity analysis from phase diagrams, techniques of crystal synthesis and crystal growth. It describes experimental techniques: synthesis, determination of fusion temperature by dilatometry, methods used for crystal growth, characterisation techniques (metallography, X ray diffraction on powders, dilatometry). It discusses the obtained results in terms of characterisation of synthesised samples, of crystal growth, and of measurements of fusion temperature. The second part addresses crystal chemistry studies: structure of compounds with a 1.1.1 stoichiometry (Laves structures, Zr, Ti and Pu compounds), techniques of analysis by X-ray diffraction (on powders and on single crystals), result interpretation (UNiX compounds, AnTAl compounds with T being a metal from group VIII, AnTGa compounds, AnNiGe compounds, distance comparison, structure modifications under pressure). The third part concerns physical issues. The author addresses the following topics: physical properties of intermetallic 1.1.1 compounds (magnetism of yttrium phases, behaviour of uranium-based Laves phases, analysis of pseudo-binary diagrams, physical characteristics of uranium-based 1.1.1 compounds, predictions of physical measurements), analysis techniques (Moessbauer spectroscopy, SQUID for Superconducting Quantum Interference Device), and result interpretation

  20. Optimizing advanced liquid metal reactors for burning actinides

    In this report, the process to design an Advanced Liquid Metal Reactor (ALMR) for burning the transuranic part of nuclear waste is discussed. The influence of design parameters on ALMR burner performance is studied and the results are incorporated in a design schedule for optimizing ALMRs for burning transuranics. This schedule is used to design a metallic and an oxide fueled ALMR burner to burn as much as possible transurancis. The two designs burn equally well. (orig.)

  1. Sol gel chemistry applied to the synthesis of actinide-based compounds for the fabrication of advanced fuels

    The chemistry of the sol-gel process is based on hydroxylation and condensation of molecular precursors and can be used for the elaboration of advanced nuclear fuel or transmutation targets. On the one hand, some fundamental studies are conducted, based on complexation reactions to modulate and control the reactivity of the different cations (Zr(IV) and minor actinides) prior to hydrolysis and condensation step. The purpose of this work is to obtain hetero poly-condensation in order to form homogenous compounds with a controlled microstructure. On the other hand, internal gelation process, one of the important sol-gel routes for the preparation of actinides microspheres (the dedicated design for advanced nuclear fuel or transmutation targets) is developed. Investigations are currently carried out to study the gelation behaviour of solutions containing actinides (III) or (IV) in comparison with the more well known behaviour of U(VI) studied during the development of process for beads production (1960 - 1990). (authors)

  2. Presence and Character of the 5f Electrons in the Actinide Metals

    Johansson, B.; Skriver, Hans Lomholt; Mårtensson, N.; Andersen, O. K.; Glotzel, D.

    The sensitivity of the Image level binding energy to the occupation of the 5f orbital is pointed out and used to demonstrate the presence of 5f electrons in the uranium metal. It is suggested that the valence band spectrum of uranium might contain satellites originating from excitations to...... localized 5f-electron configurations. Different kinds of core-hole screenings are discussed for the actinide metals as well as the difference between inner and outer core electron ionizations. Finally, the question of itinerant versus localized 5f behaviour is treated by means of a total energy comparison...... and the critical separation is found to take place between plutonium and americium....

  3. Actinides in metallic waste from electrometallurgical treatment of spent nuclear fuel

    Janney, D. E.; Keiser, D. D.

    2003-09-01

    Argonne National Laboratory has developed a pyroprocessing-based technique for conditioning spent sodium-bonded nuclear-reactor fuel in preparation for long-term disposal. The technique produces a metallic waste form whose nominal composition is stainless steel with 15 wt.% Zr (SS-15Zr), up to ˜ 11 wt.% actinide elements (primarily uranium), and a few percent metallic fission products. Actual and simulated waste forms show similar eutectic microstructures with approximately equal proportions of iron solid solution phases and Fe-Zr intermetallics. This article reports on an analysis of simulated waste forms containing uranium, neptunium, and plutonium.

  4. Actinide recycle utilizing oxide and metallic fuel in prism

    PRISM is a modular, pool-type sodium-cooled fast reactor employing innovative, passive features to provide an extremely high level of public safety. The PRISM reactor design can accommodate both oxide and metallic fuel forms. A comparison of core design and performance of these forms is made for various options. These options include low fuel cycle cost options, maximum transuranic burning options, and the addition of rare earth elements to the fuel mix. (authors)

  5. On the synthesis of actinide complexes with neutral organic phosphorus compounds

    The complexes of uranium (6) and (4) nitrates with trialkyl-phosphine oxides (TAPO) have been synthetized, and qeneral methods of their synthesis, separation and purification described. It has been found that, whatever the method of preparation, each compound of the synthesized homologous series of complexes corresponds only to disolvate stoichiometry of a qeneral formula, UO2(NO3)2 x 2(Csub(n)Hsub(2n+1))3PO and U(NO3)4 x 2(Csub(n)Hsub(2n+1))3PO. It is shown that the complexes prepared do not contain water and nitric acid. The absence of water and acid in the complex composition, as well as the possibility of preparing the same compounds by the methods where no nitric acid is used, make it possible to believe that formation of acidocomplexes is unlikely. The described methods pf complex synthesis may be of use for preparative and analytical purposes in separating (quantitatively, in some cases) complexes of actinide, rare-earth, noble, transplutonium, and other elements with phosphates, phosphinates, phosphine oxides, di- and polyoxides, as well as with other organic ligands. The experimental data on the thermal properties of the complexes separated are presented

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

    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.

  7. Preparation of thin actinide metal disks using a multiple disk casting technique

    A casting technique has been developed for preparing multiple actinide metal disks which have a minimum thickness of 0.006 inch. This technique was based on an injection casting procedure which utilizes the weight of a tantalum metal rod to force the molten metal into the mold cavity. Using the proper mold design and casting parameters, it has been possible to prepare ten 1/2 inch diameter neptunium or plutonium metal disks in a single casting. This casting technique is capable of producing disks which are very uniform. The average thickness of the disks from a typical casting will vary no more than 0.001 inch and the variation in the thickness of the individual disks will range from 0.0001 to 0.0005 inch. (author)

  8. Separation of actinides from lanthanides using acidic organophosphorus compounds: extraction chromatographic studies

    The partitioning of actinides from HLW using TBP and CMPO generates a mixture of actinides and lanthanides as one of the secondary streams. The paper discusses the results of the extraction chromatographic separation using KSM-17 and HDEHP supported on Chromosorb-102. (author)

  9. Stainless steel-zirconium alloy waste forms for metallic fission products and actinides during treatment of spent nuclear fuel

    Stainless steel-zirconium waste form alloys are being developed for the disposal of metallic wastes recovered from spent nuclear fuel using an electrometallurgical process developed by Argonne National Laboratory. The metal waste form comprises the fuel cladding, noble metal fission products and other metallic constituents. Two nominal waste form compositions are being developed: (1) stainless steel-15 wt% zirconium for stainless steel-clad fuels. The noble metal fission products are the primary source of radiation and their contribution to the waste form radioactivity has been calculated. The disposition of actinide metals in the waste alloys is also being explored. Simulated waste form alloys were prepared to study the baseline alloy microstructures and the microstructural distribution of noble metals and actinides, and to evaluate corrosion performance

  10. Detection of Metallic Compounds in Rocket Plumes

    Rogers, Chris; Dunn, Dr. Robert

    1998-04-01

    Recent experiments using metal mixed in hydroxyl-terminated polybutadiene (HTPB) fuel grains in small hybrid rocket indicates ion detectors may be effective in detection of metallic compounds in rocket plumes. We wanted to ascertain the extent to which the presence of metallic compounds in rocket plumes could be detected using ion probes and Gaussian rings. Charges that collide with or pass near the intruding probe are detected. Gaussian rings, short insulated cylindrical Gaussian surfaces, enclose the plume without intruding into the plume. Charges in the plume are detected by currents they induce in the cylinder.

  11. Polymers contamination by heavy metal compounds

    Jovanić Saša

    2002-01-01

    Full Text Available The contamination of important synthetic (surface unmodified polymers by various heavy metal compounds (such as copper, manganese and lead in aqueous medium was investigated in this study. The influence of the pH of the aqueous medium, temperature and metal type on contamination was investigated during a 10 day period. It was found that increasing pH contributed to higher polymer contamination (at higher pH 100 times for copper and up to 400 times for lead, as well as contact with easily penetrable substances. Increasing temperature decreased contamination by the metal compound for PELD and PET which was not the case for PEHD and PR.

  12. Removing actinides using a chromatographic resin from High Activity Waste Solutions containing metallic impurities

    At the Plutonium Recycling Facility of CEA Valduc, anion exchange is used for recovering plutonium from nitric acid solutions. Although this approach recovers more than 99,9 %, the trace amounts of actinides as americium remaining in the effluent require additional processing to reduce alpha activity under the maximum allowed for surface disposal. A new process has been developed to remove actinides from these effluents with a TRUspec resin. A pilot composed of an electrochemical reactor followed by a TRUSPEC column has been designed into a glove box. Laboratory scale studies and first results on the pilot have confirmed the interesting bibliography concerning this process. The reduction of iron is effective with a yield of 98-99% and no significant retention of metallic impurities has been observed during fixing time. Moreover, Pr and Ce used as surrogates for Pu and Am are totally recovered in the elution phases. Further work will be done to validate the previous results and to qualify the overall process with active solutions

  13. Optimisation of composite metallic fuel for minor actinide transmutation in an accelerator-driven system

    Uyttenhove, W.; Sobolev, V.; Maschek, W.

    2011-09-01

    A potential option for neutralization of minor actinides (MA) accumulated in spent nuclear fuel of light water reactors (LWRs) is their transmutation in dedicated accelerator-driven systems (ADS). A promising fuel candidate dedicated to MA transmutation is a CERMET composite with Mo metal matrix and (Pu, Np, Am, Cm)O 2-x fuel particles. Results of optimisation studies of the CERMET fuel targeting to increasing the MA transmutation efficiency of the EFIT (European Facility for Industrial Transmutation) core are presented. In the adopted strategy of MA burning the plutonium (Pu) balance of the core is minimized, allowing a reduction in the reactivity swing and the peak power form-factor deviation and an extension of the cycle duration. The MA/Pu ratio is used as a variable for the fuel optimisation studies. The efficiency of MA transmutation is close to the foreseen theoretical value of 42 kg TW -1 h -1 when level of Pu in the actinide mixture is about 40 wt.%. The obtained results are compared with the reference case of the EFIT core loaded with the composite CERCER fuel, where fuel particles are incorporated in a ceramic magnesia matrix. The results of this study offer additional information for the EFIT fuel selection.

  14. Optical spectra and electronic structure of actinide ions in compounds and in solution

    This report provides a summary of theoretical and experimental studies of actinide spectra in condensed phases. Much of the work was accomplished at Argonne National Laboratory, but references to related investigations by others are included. Spectroscopic studies of the trivlent actinides are emphasized, as is the use of energy level parameters, evaluated from experimental data, to investigate systematic trends in electronic structure and other properties. Some reference is made to correlations with atomic spectra, as well as with spectra of the (II), (IV), and higher valence states. 207 refs., 39 figs., 38 tabs

  15. The Use of Molybdenum-Based Ceramic-Metal (CerMet) Fuel for the Actinide Management in LWRs

    The technical and economic aspects of the use of molybdenum depleted in the isotope 95Mo (DepMo) for the transmutation of actinides in a light water reactor are discussed. DepMo has a low neutron absorption cross section and good physical and chemical properties. Therefore, DepMo is expected to be a good inert matrix in ceramic-metal fuel. The costs of the use of DepMo have been assessed, and it was concluded that these costs can be justified for the transmutation of the actinides neptunium, americium, and plutonium

  16. Molecular metal-metal bonds compounds, synthesis, properties

    Liddle, Stephen T

    2015-01-01

    Systematically covering all areas of the Periodic Table, this is a comprehensive and handy introduction to metal-metal bonding. The 15 chapters follow a uniform, coherent structure for a clear overview, allowing readers easy access to the information. The important molecules at the genesis of each area are mentioned but the focus lies principally on research published since 2005. Important topics such as synthesis, properties, structures,notable features, reactivity and examples of applications of the most important compounds in each group with metal-metal bonding throughout the periodic ta

  17. Spin–orbit coupling in actinide cations

    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...

  18. The local/non-local duality of 5f electrons in actinide compounds: A mean-field study

    The local/non-local duality of 5f electrons in actinide compounds has been observed in a great variety of experiments including photo-emission spectroscopy, inelastic neutron scattering, muon spin relaxation measurements, and X-ray inelastic scattering. A general microscopic mechanism leading to the partial localization of 5f orbitals has been proposed within the so-called dual model. It is a generalized multi-orbital Hubbard model which includes the direct Coulomb interaction as well as the Hund's rule correlations. Using a generalized slave boson method, we study this model for an electronic filling corresponding to the prototype compound UPt3. We then analyse the calculated phase diagram and discuss the local/non-local and magnetic/non-magnetic phases in terms of orbitally dependent quasi-particle residues and partial electronic occupations.

  19. High pressure studies of UFe5Al7 and UFe7Al5 actinide compounds

    The ternary inter-metallic compounds, UFe5Al7 and UFe7Al5, crystallize in a tetragonal ThMn12 type structure. In the as-cast samples a residual phase of FeAl (∼2%wt) was identified in the grain boundaries. The amount of the residual cubic phase of FeAl was determined by Rietveld analysis and reduced by the annealing process. UFe5Al7 and UFe7Al5 maintain the tetragonal symmetry as a function of pressure, while FeAl keeps the cubic structure as was determined by the Rietveld analysis. The volume-pressure curve calculated from the X-ray analysis gives V/V0=0.87 for UFe5Al7 at 26.0 GPa and 0.89 at 24.6 GPa for UFe7Al5. (author)

  20. Electronic Structure of Transition Metal Clusters, Actinide Complexes and Their Reactivities

    This is a continuing DOE-BES funded project on transition metal and actinide containing species, aimed at the electronic structure and spectroscopy of transition metal and actinide containing species. While a long term connection of these species is to catalysis and environmental management of high-level nuclear wastes, the immediate relevance is directly to other DOE-BES funded experimental projects at DOE-National labs and universities. There are a number of ongoing gas-phase spectroscopic studies of these species at various places, and our computational work has been inspired by these experimental studies and we have also inspired other experimental and theoretical studies. Thus our studies have varied from spectroscopy of diatomic transition metal carbides to large complexes containing transition metals, and actinide complexes that are critical to the environment. In addition, we are continuing to make code enhancements and modernization of ALCHEMY II set of codes and its interface with relativistic configuration interaction (RCI). At present these codes can carry out multi-reference computations that included up to 60 million configurations and multiple states from each such CI expansion. ALCHEMY II codes have been modernized and converted to a variety of platforms such as Windows XP, and Linux. We have revamped the symbolic CI code to automate the MRSDCI technique so that the references are automatically chosen with a given cutoff from the CASSCF and thus we are doing accurate MRSDCI computations with 10,000 or larger reference space of configurations. The RCI code can also handle a large number of reference configurations, which include up to 10,000 reference configurations. Another major progress is in routinely including larger basis sets up to 5g functions in thee computations. Of course higher angular momenta functions can also be handled using Gaussian and other codes with other methods such as DFT, MP2, CCSD(T), etc. We have also calibrated our RECP

  1. Electronic Structure of Transition Metal Clusters, Actinide Complexes and Their Reactivities

    Krishnan Balasubramanian

    2009-07-18

    This is a continuing DOE-BES funded project on transition metal and actinide containing species, aimed at the electronic structure and spectroscopy of transition metal and actinide containing species. While a long term connection of these species is to catalysis and environmental management of high-level nuclear wastes, the immediate relevance is directly to other DOE-BES funded experimental projects at DOE-National labs and universities. There are a number of ongoing gas-phase spectroscopic studies of these species at various places, and our computational work has been inspired by these experimental studies and we have also inspired other experimental and theoretical studies. Thus our studies have varied from spectroscopy of diatomic transition metal carbides to large complexes containing transition metals, and actinide complexes that are critical to the environment. In addition, we are continuing to make code enhancements and modernization of ALCHEMY II set of codes and its interface with relativistic configuration interaction (RCI). At present these codes can carry out multi-reference computations that included up to 60 million configurations and multiple states from each such CI expansion. ALCHEMY II codes have been modernized and converted to a variety of platforms such as Windows XP, and Linux. We have revamped the symbolic CI code to automate the MRSDCI technique so that the references are automatically chosen with a given cutoff from the CASSCF and thus we are doing accurate MRSDCI computations with 10,000 or larger reference space of configurations. The RCI code can also handle a large number of reference configurations, which include up to 10,000 reference configurations. Another major progress is in routinely including larger basis sets up to 5g functions in thee computations. Of course higher angular momenta functions can also be handled using Gaussian and other codes with other methods such as DFT, MP2, CCSD(T), etc. We have also calibrated our RECP

  2. Production and investigation of thin films of metal actinides (Pu, Am, Cm, Bk, Cf)

    Radchenko, V. M.; Ryabinin, M. A.; Stupin, V. A.

    2010-03-01

    Under limited availability of transplutonium metals some special techniques and methods of their production have been developed that combine the process of metal reduction from a chemical compound and preparation of a sample for examination. In this situation the evaporation and condensation of metal onto a substrate becomes the only possible technology. Thin film samples of metallic 244Cm, 248Cm and 249Bk were produced by thermal reduction of oxides with thorium followed by deposition of the metals in the form of thin layers on tantalum substrates. For the production of 249Cf metal in the form of a thin layer the method of thermal reduction of oxide with lanthanum was used. 238Pu and 239Pu samples in the form of films were prepared by direct high temperature evaporation and condensation of the metal onto a substrate. For the production of 241Am films a gram sample of plutonium-241 metal was used containing about 18 % of americium at the time of production. Thermal decomposition of Pt5Am intermetallics in vacuum was used to produce americium metal with about 80% yield. Resistivity of the metallic 249Cf film samples was found to decrease exponentially with increasing temperature. The 249Cf metal demonstrated a tendency to form preferably a DHCP structure with the sample mass increasing. An effect of high specific activity on the crystal structure of 238Pu nuclide thin layers was studied either.

  3. Production and investigation of thin films of metal actinides (Pu, Am, Cm, Bk, Cf)

    Under limited availability of transplutonium metals some special techniques and methods of their production have been developed that combine the process of metal reduction from a chemical compound and preparation of a sample for examination. In this situation the evaporation and condensation of metal onto a substrate becomes the only possible technology. Thin film samples of metallic 244Cm, 248Cm and 249Bk were produced by thermal reduction of oxides with thorium followed by deposition of the metals in the form of thin layers on tantalum substrates. For the production of 249Cf metal in the form of a thin layer the method of thermal reduction of oxide with lanthanum was used. 238Pu and 239Pu samples in the form of films were prepared by direct high temperature evaporation and condensation of the metal onto a substrate. For the production of 241Am films a gram sample of plutonium-241 metal was used containing about 18 % of americium at the time of production. Thermal decomposition of Pt5Am intermetallics in vacuum was used to produce americium metal with about 80% yield. Resistivity of the metallic 249Cf film samples was found to decrease exponentially with increasing temperature. The 249Cf metal demonstrated a tendency to form preferably a DHCP structure with the sample mass increasing. An effect of high specific activity on the crystal structure of 238Pu nuclide thin layers was studied either.

  4. Recent progress in actinide borate chemistry.

    Wang, Shuao; Alekseev, Evgeny V; Depmeier, Wulf; Albrecht-Schmitt, Thomas E

    2011-10-21

    The use of molten boric acid as a reactive flux for synthesizing actinide borates has been developed in the past two years providing access to a remarkable array of exotic materials with both unusual structures and unprecedented properties. [ThB(5)O(6)(OH)(6)][BO(OH)(2)]·2.5H(2)O possesses a cationic supertetrahedral structure and displays remarkable anion exchange properties with high selectivity for TcO(4)(-). Uranyl borates form noncentrosymmetric structures with extraordinarily rich topological relationships. Neptunium borates are often mixed-valent and yield rare examples of compounds with one metal in three different oxidation states. Plutonium borates display new coordination chemistry for trivalent actinides. Finally, americium borates show a dramatic departure from plutonium borates, and there are scant examples of families of actinides compounds that extend past plutonium to examine the bonding of later actinides. There are several grand challenges that this work addresses. The foremost of these challenges is the development of structure-property relationships in transuranium materials. A deep understanding of the materials chemistry of actinides will likely lead to the development of advanced waste forms for radionuclides present in nuclear waste that prevent their transport in the environment. This work may have also uncovered the solubility-limiting phases of actinides in some repositories, and allows for measurements on the stability of these materials. PMID:21915396

  5. Polymers contamination by heavy metal compounds

    Jovanić Saša; Stoiljković Dragoslav M.; Popović Ivanka G.

    2002-01-01

    The contamination of important synthetic (surface unmodified) polymers by various heavy metal compounds (such as copper, manganese and lead) in aqueous medium was investigated in this study. The influence of the pH of the aqueous medium, temperature and metal type on contamination was investigated during a 10 day period. It was found that increasing pH contributed to higher polymer contamination (at higher pH 100 times for copper and up to 400 times for lead), as well as contact with easily p...

  6. TUCS/phosphate mineralization of actinides

    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.

  7. Effects of Ammonium Molybdophosphate (AMP) on Strontium, Actinides, and RCRA Metals in SRS Simulated Waste

    High Level Waste samples contain elevated concentrations of radioactive cesium requiring marked dilution of the waste to facilitate handling in non-shielded facilities. The authors developed a sample treatment protocol, using ammonium molybdophosphate (AMP) to remove sufficient cesium to allow handling of the samples with minimal dilution. The sample treatment protocol includes the following steps: pH adjust the sample to the range of 0.01 to 1.0 M acidity; mix 30 mL of acidified sample with 40-60 mg of AMP; cap and shake the mixture for 30-60 seconds; filter AMP from the liquid using 0.45 PTFE syringe filters; and send filtrate directly forward for analysis. To develop the method, SRTC performed a series of tests with three different salt solutions designed to determine the propensity of ammonium molybdophosphate (AMP) to bind some of the common analytes such as the actinides (Pu, Am, Np, U), strontium, or the metals (Ag, As, Ba, Cd, Cr, Hg, Pb, Se) regulated by the Resource Conservation Recovery Act (RCRA). SRTC also examined relevant literature to summarize reported interactions between AMP and other elements

  8. A semi-micro combustion assembly for the determination of carbon and hydrogen in actinide compounds

    A rapid combustion unit (Baird and Tatlock) incorporating a combustion chamber provided with baffle plates for complete combustion of the sample without the use of a catalyst has been assembled in a glove box for the determination of carbon and hydrogen in actinide complexes. The unit has been modified employing a movable electric furnace and a proportional temperature controller, for decomposition of the sample at desired heating rates. The set-up was standardised employing various reference materials such as benzoic acid, acetanilide, sulphanilamide and 1-chloro 2:4 dinitrobenzene and the standard deviation in the measurements evaluated. It has also been used successfully for the determination of carbon in uranium carbide and carbon and hydrogen in some uranyl-β-diketone-amine N-oxide complexes and in plutonium(IV) oxalate. (auth.)

  9. Heavy metal screening in compounds feeds

    Tomas Toth

    2015-05-01

    Full Text Available Heavy metals are generally classified as basic groups of pollutants that are now a days found in different environmental compartments. This is quite a large group of contaminants, which have different characteristics, effects on the environment and sources of origin. For environment pose the greatest risks, especially heavy metals produced by anthropogenic activities that adversely affect the health and vitality of organisms and natural environmental conditions. Livestock nutrition is among the main factors which affect not only the deficiency of livestock production and quality of food of animal origin, but they are also a factor affecting the safety and wholesomeness and the animal health. Compound feeds is characterized as a mixture of two or more feed grain. Containing organic, inorganic nutrients and specifically active compound feed meet the nutritional requirements of a given kind and age category of animals. They are used mainly in the diet of pigs, poultry, but also the nutrition of cattle, sheep, horses and other animal categories. The basic ingredients are cereals in proportion of 60-70 %. The aim of this thesis was to analyze the content of hazardous elements (copper, zinc, iron, manganese, cobalt, nickel, chromium, lead, cadmium, mercury in 15 samples of compound feeds and then evaluating their content in comparison with maximum limits laid down by Regulation of the Government of the Slovak Republic and Regulation Commission (EC.

  10. Spin-Orbit Coupling in Actinide Cations

    Bagus, Paul S.; Ilton, Eugene S.; Martin, Richard L.; Jensen, Hans Jorgen A.; Knecht, Stefan

    2012-09-01

    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.

  11. Spin-orbit coupling in actinide cations

    Bagus, Paul S.; Ilton, Eugene S.; Martin, Richard L.; Jensen, Hans Jørgen Aa.; Knecht, Stefan

    2012-09-01

    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.

  12. Synthesis and evaluation of water-soluble chelating polymers for the selective removal of actinide metal ions

    A major goal of our research program is to develop polymer supported ion specific ligand systems for the removal of actinides and other hazardous metals from wastewaters. The advantage of water-soluble polymers in metal ion separation processes is that the homogeneity of the system allows for more rapid exchange kinetics than ion exchange or chelating resins. A number of water-soluble chelating polymers have been synthesized by the functionalization or commercially available polyamine precursors with various ligand moieties such as hydroxamates. The ability of these polymers to complex with metal ion to give soluble complexes which can be separated and concentrated by ultrafiltration under different pH conditions have been examined

  13. Characterization of f electrons in light lanthanide and actinide metals by electron-energy-loss and x-ray photoelectron spectroscopy

    Core-excitation edges in metallic La, Th, and U have been investigated by electron-energy-loss spectroscopy (EELS) and x-ray photoelectron spectroscopy (XPS). Strong excitation-energy-dependent variations of the EELS spectra are observed and shown to be due to the energy dependence of the scattering cross section. An analysis of the Th 4f spectra in an atomic scattering picture indicates 5f symmetry for the realized final states. Furthermore, for the La 3d and 4d as well as for the Th 5d core-excitation edges, a multiplet calculation in intermediate coupling was carried out, yielding excellent agreement with the observed fine structure in the EELS spectra. Thus, in analogy to La metal, it is concluded that a final state of the type 5d95f1 is observed in the Th-metal 5d spectrum. Qualitative arguments for an atomic picture of the core excitations of U are also presented. The knowledge of the final states realized in EELS, together with the measured threshold energies in EELS and XPS, allows a determination of the symmetry of the final-state screening orbitals in XPS. It is shown that the core holes in La are screened mainly by d conduction electrons, while in Th and U the screening is achieved predominantly by 5f electrons. It is demonstrated that the combined EELS-XPS technique constitutes a powerful tool for determining the degree of 5f localization in actinides and their compounds

  14. Performance comparison of metallic, actinide burning fuel in lead-bismuth and sodium cooled fast reactors

    Weaver, K.D.; Herring, J.S.; Macdonald, P.E. [Idaho National Engineering and Environment Lab., Advanced Nuclear Energy, Idaho (United States)

    2001-07-01

    Various methods have been proposed to ''incinerate'' or ''transmute'' the current inventory of transuranic waste (TRU) that exits in spent light-water-reactor (LWR) fuel, and weapons plutonium. These methods include both critical (e.g., fast reactors) and non-critical (e.g., accelerator transmutation) systems. The work discussed here is part of a larger effort at the Idaho National Engineering and Environmental Laboratory (INEEL) and at the Massachusetts Institute of Technology (MIT) to investigate the suitability of lead and lead-alloy cooled fast reactors for producing low-cost electricity as well as for actinide burning. The neutronics of non fertile fuel loaded with 20 or 30-wt% light water reactor (LWR) plutonium plus minor actinides for use in a lead-bismuth cooled fast reactor are discussed in this paper, with an emphasis on the fuel cycle life and isotopic content. Calculations show that the average actinide burn rate is similar for both the sodium and lead-bismuth cooled cases ranging from -1.02 to -1.16 g/MWd, compared to a typical LWR actinide generation rate of 0.303 g/MWd. However, when using the same parameters, the sodium-cooled case went subcritical after 0.2 to 0.8 effective full power years, and the lead-bismuth cooled case ranged from 1.5 to 4.5 effective full power years. (author)

  15. Performance Comparison of Metallic, Actinide Burning Fuel in Lead-Bismuth and Sodium Cooled Fast Reactors

    Weaver, Kevan Dean; Herring, James Stephen; Mac Donald, Philip Elsworth

    2001-04-01

    Various methods have been proposed to “incinerate” or “transmutate” the current inventory of trans-uranic waste (TRU) that exits in spent light-water-reactor (LWR) fuel, and weapons plutonium. These methods include both critical (e.g., fast reactors) and non-critical (e.g., accelerator transmutation) systems. The work discussed here is part of a larger effort at the Idaho National Engineering and Environmental Laboratory (INEEL) and at the Massachusetts Institute of Technology (MIT) to investigate the suitability of lead and lead-alloy cooled fast reactors for producing low-cost electricity as well as for actinide burning. The neutronics of non-fertile fuel loaded with 20 or 30-wt% light water reactor (LWR) plutonium plus minor actinides for use in a lead-bismuth cooled fast reactor are discussed in this paper, with an emphasis on the fuel cycle life and isotopic content. Calculations show that the average actinide burn rate is similar for both the sodium and lead-bismuth cooled cases ranging from -1.02 to -1.16 g/MWd, compared to a typical LWR actinide generation rate of 0.303 g/MWd. However, when using the same parameters, the sodium-cooled case went subcritical after 0.2 to 0.8 effective full power years, and the lead-bismuth cooled case ranged from 1.5 to 4.5 effective full power years.

  16. Performance comparison of metallic, actinide burning fuel in lead-bismuth and sodium cooled fast reactors

    Various methods have been proposed to ''incinerate'' or ''transmute'' the current inventory of transuranic waste (TRU) that exits in spent light-water-reactor (LWR) fuel, and weapons plutonium. These methods include both critical (e.g., fast reactors) and non-critical (e.g., accelerator transmutation) systems. The work discussed here is part of a larger effort at the Idaho National Engineering and Environmental Laboratory (INEEL) and at the Massachusetts Institute of Technology (MIT) to investigate the suitability of lead and lead-alloy cooled fast reactors for producing low-cost electricity as well as for actinide burning. The neutronics of non fertile fuel loaded with 20 or 30-wt% light water reactor (LWR) plutonium plus minor actinides for use in a lead-bismuth cooled fast reactor are discussed in this paper, with an emphasis on the fuel cycle life and isotopic content. Calculations show that the average actinide burn rate is similar for both the sodium and lead-bismuth cooled cases ranging from -1.02 to -1.16 g/MWd, compared to a typical LWR actinide generation rate of 0.303 g/MWd. However, when using the same parameters, the sodium-cooled case went subcritical after 0.2 to 0.8 effective full power years, and the lead-bismuth cooled case ranged from 1.5 to 4.5 effective full power years. (author)

  17. The clearance of Pu and Am from the respiratory system of rodents after the inhalation of oxide aerosols of these actinides either alone or in combination with other metals

    In this series of studies in rodents the lung clearance and tissue distribution of both plutonium and americium have been measured following their inhalation as mixed actinide oxides either alone or in combination with other metals. The aerosols used were materials to which workers in the nuclear industry may be occupationally exposed or which could be generated in the event of an accident in a reactor core or fuel fabrication plant. The studies showed that, at least for some PuO2 aerosols, the lung model currently being used by ICRP for estimating tissue doses from inhaled actinides may overestimate, by about a factor of ten, the amount of plutonium translocated to the blood. The presence of oxides of other metals can, however, appreciably influence the clearance of plutonium from the lung. While in some mixtures plutonium dioxide behaves as an insoluble (Class Y) compound and in others as a soluble (Class W) compound, it may also have transportability characteristics between these two extremes. Americium-241 behaves as a soluble (Class W) compound when inhaled as the oxide. However, if it is present in trace quantities in mixed-oxide aerosols its behaviour depends upon that of the materials present in greatest mass. (author)

  18. Task-specific ionic liquids for solubilizing metal compounds

    Thijs, Ben

    2007-01-01

    The main goal of this PhD thesis was to design new task-specific ionic liquids with the ability to dissolve metal compounds. Despite the large quantity of papers published on ionic liquids, not much is known about the mechanisms of dissolving metals in ionic liquids or about metal-containing ionic liquids. Additionally, many of the commercially available ionic liquids exhibit a very limited solubilizing power for metal compounds, although this is for many applications like electrodeposition a...

  19. Partition of actinides and fission products between metal and molten salt phases: Theory, measurement, and application to IFR pyroprocess development

    The chemical basis of Integral Fast Reactor fuel reprocessing (pyroprocessing) is partition of fuel, cladding, and fission product elements between molten LiCl-KCl and either a solid metal phase or a liquid cadmium phase. The partition reactions are described herein, and the thermodynamic basis for predicting distributions of actinides and fission products in the pyroprocess is discussed. The critical role of metal-phase activity coefficients, especially those of rare earth and the transuranic elements, is described. Measured separation factors, which are analogous to equilibrium constants but which involve concentrations rather than activities, are presented. The uses of thermodynamic calculations in process development are described, as are computer codes developed for calculating material flows and phase compositions in pyroprocessing

  20. Process for forming a metal compound coating on a substrate

    This patent describes a method of coating a substrate with a thin layer of a metal compound by forming a dispersion of an electrophoretically active organic colloid and a precursor of the metal compound in an electrolytic cell in which the substrate is an electrode. Upon application of an electric potential, the electrode is coated with a mixture of the organic colloid and the precursor to the metal compound, and the coated substrate is then heated in the presence of an atmosphere or vacuum to decompose the organic colloid and form a coating of either a combination of metal compound and carbon, or optionally forming a porous metal compound coating by heating to a temperature high enough to chemically react the carbon

  1. Actinides: from heavy fermions to plutonium metallurgy

    The actinide elements mark the emergence of 5f electrons. The f electrons possess sufficiently unusual characteristics that their participation in atomic binding often result in dramatic changes in properties. This provides an excellent opportunity to study the question of localization of electrons; a question that is paramount in predicting the physical and chemical properties of d and f electron transition metals. The transition region between localized (magnetic) and itinerant (often superconducting) behavior provides for many interesting phenomena such as structural instabilities (polymorphism), spin fluctuations, mixed valences, charge density waves, exceptional catalytic activity and hydrogen storage. This region offers most interesting behavior such as that exhibited by the actinide compounds UBe13 and UPt3. Both compounds are heavy-fermion superconductors in which both magnetic and superconducting behavior exist in the same electrons. The consequences of f-electron bonding (which appears greatest at Plutonium) show dramatic effects on phase stability, alloying behavior, phase transformations and mechanical behavior

  2. Hybrid conducting polymer materials incorporating poly-oxo-metalates for extraction of actinides; Materiaux polymeres conducteurs hybrides incorporant des polyoxometallates pour l'extraction d'actinides

    Racimor, D

    2003-09-15

    The preparation and characterization of hybrid conducting polymers incorporating poly-oxo-metalates for extracting actinides is discussed. A study of the coordination of various lanthanide cations (Ce(III), Ce(IV), Nd(III)) by the mono-vacant poly-oxo-metalate {alpha}{sub 2}-[P{sub 2}W{sub 17}O{sub 61}]{sup 10-} showed significant differences according to the cation.. Various {alpha}-A-[PW{sub 9}O{sub 34}(RPO){sub 2}]{sup 5-} hybrids were synthesized and their affinity for actinides or lanthanides was demonstrated through complexation. The first hybrid poly-oxo-metallic lanthanide complexes were then synthesized, as was the first hybrid functionalized with a pyrrole group. The electro-polymerization conditions of this pyrrole remain still to be optimized. Poly-pyrrole materials incorporating {alpha}{sub 2}-[P{sub 2}W{sub 17}O{sub 61}]{sup 10-} or its neodymium or cerium complexes as doping agents proved to be the first conducting polymer incorporating poly-oxo-metalates capable of extracting plutonium from nitric acid. (author)

  3. Actinides draw down process for pyrochemical reprocessing of spent metal fuel

    Perumal, Suyambu Vannia; Reddy, Bandi Prabhakara; Ravisankar, Guruswamy; Nagarajan, Krishnamurthy [Indira Gandhi Centre for Atomic Research, Kalpakkam (India). Chemistry Group

    2015-06-01

    An experimental system has been setup inside an argon atmosphere glove box to carry out studies on the actinide draw down process, an important step of the pyroprocess flow sheet. Studies have been carried out at 723 K on the extraction of uranium from LiCl-KCl eutectic salt containing 0.5% UCl{sub 3} using lithium-0.03% cadmium alloy. In these experiments, 5 L of the molten salt and 5 L of the molten alloy are fed to a single stage extractor where 250 mL of the salt and 250 mL of the alloy come into contact. A three stage stirrer having straight as well as pitched blade turbine impellers was used to mix the molten alloy and salt phases having high interfacial tension of 450 dyne/cm. The results of the studies indicate that a U extraction efficiency of 99% could be achieved.

  4. Photochemical route to actinide-transition metal bonds: synthesis, characterization and reactivity of a series of thorium and uranium heterobimetallic complexes

    Ward, Ashleigh; Lukens, Wayne; Lu, Connie; Arnold, John

    2014-04-01

    A series of actinide-transition metal heterobimetallics has been prepared, featuring thorium, uranium and cobalt. Complexes incorporating the binucleating ligand N[-(NHCH2PiPr2)C6H4]3 and Th(IV) (4) or U(IV) (5) with a carbonyl bridged [Co(CO)4]- unit were synthesized from the corresponding actinide chlorides (Th: 2; U: 3) and Na[Co(CO)4]. Irradiation of the isocarbonyls with ultraviolet light resulted in the formation of new species containing actinide-metal bonds in good yields (Th: 6; U: 7); this photolysis method provides a new approach to a relatively rare class of complexes. Characterization by single-crystal X-ray diffraction revealed that elimination of the bridging carbonyl is accompanied by coordination of a phosphine arm from the N4P3 ligand to the cobalt center. Additionally, actinide-cobalt bonds of 3.0771(5) and 3.0319(7) for the thorium and uranium complexes, respectively, were observed. The solution state behavior of the thorium complexes was evaluated using 1H, 1H-1H COSY, 31P and variable-temperature NMR spectroscopy. IR, UV-Vis/NIR, and variable-temperature magnetic susceptibility measurements are also reported.

  5. Production of metal powders and compounds, especially of refractory metals

    Since the invention of filament lamps and hard metals, powder metallurgy has increasingly been used for production of semifinished products and finished products from a multitude of metals, hard metals and composite materials. Methods have been developed by which powders can be made to measured, usually physical methods, chemical-metallurgical methods, or combined methods. Requirements on metal powders are listed as well as suitable methods of fabrication. (orig.)

  6. Identification of major metal complexing compounds in Blepharis aspera

    Verbascoside and isoverbascoside, present at 0.7% and 0.2% (w/w dryweight), were identified to be major compounds that could contribute to the metal complexation in Blepharis aspera collected in Botswana, Africa. The metallophyte B. aspera has high ability to cope with a high level of metal accumulation. The presence of metal complexing compounds and/or antioxidants can prevent oxidative reactions in lipids, proteins and DNA that take place due to the metal accumulation. On-line liquid chromatography-solid phase extraction-nuclear magnetic resonance (LC-SPE-NMR) was applied for the identification, while electrospray-mass spectrometry (ESI-MS) and UV-vis spectroscopy was used to assess whether these compounds can complex with metals. It was found that verbascoside and isoverbascoside may form complexes with nickel, iron (verbascoside only) and copper. Thus, the presence of verbascoside and isoverbascoside can explain the survival of B. aspera in mineral-rich areas

  7. Dissociation energies of the molecules RhTh and RhU from high temperature mass spectrometry and predicted thermodynamic stabilities of selected diatomic actinide--platinum metal intermetallic molecules

    Gaseous RhTh and RhU have been observed in a Knudsen effusion mass spectrometric investigation of a thorium--uranium-rhodium--graphite system at high temperatures (2400--2700 0K). Thermodynamic treatment of the experimental data yielded the atomization energies of RhTh and RhU as D0298(RhTh) =513 +- 21 kJ mole-1 or 122.6 +- 5 kcal mole-1 and D0298(RhU) =519 +- 17 kJ mole-1 or 124.0 +- 4 kcal mole-1. These values were derived from the third law enthalpies. The known experimental bond energies for the ligand-free gaseous intermetallic compounds between the actinides and the platinum metals have been interpretated in terms of a previously developed model based on the Brewer--Engel approach. Also, calculations are presented for the dissociation energies of certain selected actinide--platinum metal diatomic molecules which have not yet been experimentally observed

  8. Heavy metal screening in compounds feeds

    Tomas Toth

    2015-01-01

    Heavy metals are generally classified as basic groups of pollutants that are now a days found in different environmental compartments. This is quite a large group of contaminants, which have different characteristics, effects on the environment and sources of origin. For environment pose the greatest risks, especially heavy metals produced by anthropogenic activities that adversely affect the health and vitality of organisms and natural environmental conditions. Livestock nutrition is among t...

  9. New molecules for the separation of actinides (III): the picolinamides

    Minor actinide partitioning from high level liquid wastes produced during the reprocessing of nuclear fuels by the Purex process, requires the design of new extracting molecules. These new extractants must be able to separate, for example, actinides from lanthanides. This separation is very difficult, due to the similar chemical properties of these metallic species, but it can possibly be reached by using extractants with soft donor atoms (N or S). Some new molecules : the picolinamides are investigated in this way. The general chemical formula and the behaviour of these compounds in acidic media are given. (O.L.). 3 refs

  10. Superconductivity of ternary metal compounds prepared at high pressures

    Shirotani, I

    2003-01-01

    Various ternary metal phosphides, arsenides, antimonides, silicides and germanides have been prepared at high temperatures and high pressures. These ternary metal compounds can be classified into four groups: [1] metal-rich compounds MM' sub 4 X sub 2 and [2] MM'X, [3] non-metal-rich compounds MXX' and [4] MM' sub 4 X sub 1 sub 2 (M and M' = metal element; X and X' = non-metal element). We have studied the electrical and magnetic properties of these materials at low temperatures, and found many new superconductors with the superconducting transition temperature (T sub c) of above 10 K. The metal-rich compound ZrRu sub 4 P sub 2 with a tetragonal structure showed the superconducting transition at around 11 K, and had an upper critical field (H sub c sub 2) of 12.2 tesla (T) at 0 K. Ternary equiatomic compounds ZrRuP and ZrRuSi crystallize in two modifications, a hexagonal Fe sub 2 P-type structure [h-ZrRuP(Si)] and an orthorhombic Co sub 2 P-type structure [o-ZrRuP(Si)]. Both h-ZrRuP and h-ZrRuSi have rather h...

  11. Decomplexing metallic cations from metallo-organic compounds

    Melian, C.I.; Kapteijn F.; Moulijn, J.A.

    2006-01-01

    The invention is directed to a process for liberating metallic cations from metallo-organic compounds, said process comprising contacting an aqueous solution of the metallo-organic compound with an oxidising agent, thereby oxidising the organic component and obtaining the free cation

  12. SPECIFIC SEQUESTERING AGENTS FOR THE ACTINIDES

    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.

  13. Actinides-1981

    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.

  14. Actinides-1981

    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

  15. Elementary boron and metal-boron compounds

    Elementary boron is of interest for its peculiar and difficult bonding behaviour in solids. Due to its high oxygen affinity we find no elementary boron in nature. For the same reason it is difficult to isolate pure, elementary boron, and much confusion about 'boron crystals' has been the result of more than 100 years of research. The polymorphic forms of elementary boron and its closely related higher carbides and higher metal borides as well as the simple metal borides, B3C and BN are reported. The quantum-mechanical background responsible for structure and stoichiometry of these crystals is given. (orig.)

  16. Electrolytic extraction of fission noble metals for waste minimizing in advanced actinide separation system

    Electrochemistry for recovering fission platinum group elements (Pd. Ru) and Re (simulator of Te) from HNO3 solutions, Electrolytic Extraction (EE) method was applied as a basic technology in the new actinides separation process. The deposition yields of these elements increased by the decrease of the initial HNO3, concentration. Co-existence of Pd2+ ion accelerates the deposition of RuNO3- and ReO4- ions, and especially Ru deposition yield was over 99% when Pd2+ ion was added during the electrolysis in 2.SN HNO3 solution. Addition of reducing reagents (hydrazine nitrate and HAN) increased Pd2+ deposition rate, however, these and the other complexing reagents (e.g., oxalic acid and EDTA) decreased the Ru deposition because of preferential Pd2+ deposition as well as those complexation with RuNO3-, respectively. On the electrolytic extraction from the simulated HLLW, the elements which had nobler standard redox potential (E0) tended to show higher deposition yields; the elements which had E0 over 0.7 V (Ru, Te, Se, Rh, Pd) can be quantitatively recovered by 3 hr. electrolysis without dilution of HLLW. (author)

  17. High-pressure studies of a ThMn12-type actinide compound: UFe5Al7

    The ternary inter-metallic compound, UFe5Al7, crystallize in a tetragonal ThMn12 type structure. In the as-cast samples a residual phase of FeAl (∼2% wt) was identified in the grain boundaries. The amount of the residual cubic phase of FeAl was determined by Rietveld analysis and reduced by the annealing process. UFe5Al7 maintains the tetragonal symmetry as a function of pressure, while FeAl keeps the cubic structure as was determined by the Rietveld analysis. The volume-pressure curve calculated from the x-ray analysis is V/V0 = 0.87 for UFe5Al7 at 26.0 GPa

  18. Stabilization of explosive compounds on metallic surfaces

    Full text: Previous experiments on explosives like RDX, TNT or PETN in gas phase have shown that these molecules decay easily into several fragments upon low-energy electron attachment. These unimolecular decompositions are rather time consuming (several μs) and can be quenched when the molecules are embedded in helium nano droplets. With the use of a variable temperature scanning tunneling microscope, electron induced fragmentation of explosives is investigated for molecules adsorbed on single crystal metal surfaces. (author)

  19. Recovery of actinides from spent nuclear fuel by pyrochemical reprocessing

    The Partitioning and Transmutation (P and T) strategy is based on reduction of the long-term radiotoxicity of spent nuclear fuel by recovery and recycling of plutonium and minor actinides, i.e. Np, Am and Cm. Regardless if transmutation of actinides is conceived by a heterogeneous accelerator driven system, fast reactor concept or as integrated waste burning with a homogenous recycling of all actinides, the reprocessed fuels used are likely to be significantly different from the commercial fuels of today. Because of the fuel type and the high burn-up reached, traditional hydrometallurgical reprocessing such as used today might not be the most adequate method. The main reasons are the low solubility of some fuel materials in acidic aqueous solutions and the limited radiation stability of the organic solvents used in extraction processes. Therefore, pyrochemical separation techniques are under development worldwide, usually based on electrochemical methods, reductive extraction in a high temperature molten salt solvent or fluoride volatility techniques. The pyrochemical reprocessing developed in ITU is based on electrorefining of metallic fuel in molten LiCl-KCl using solid aluminium cathodes. This is followed by a chlorination process for the recovery of actinides from formed actinide-aluminium alloys, and exhaustive electrolysis is proposed for the clean-up of salt from the remaining actinides. In this paper, the main achievements in the electrorefining process are summarised together with results of the most recent experimental studies on characterisation of actinides-aluminium intermetallic compounds. U, Np and Pu alloys were investigated by electrochemical techniques using solid aluminium electrodes and the alloys formed by electrodeposition of the individual actinides were analysed by XRD and SEM-EDX. Some thermodynamic properties were determined from the measurements (standard electrode potentials, Gibbs energy, enthalpy and entropy of formation) as well as

  20. Single crystal synthesis methods dedicated to structural investigations of very low solubility mixed-actinide oxalate coordination polymers

    Two crystal growth methods dedicated to very low solubility actinide coordination polymers have been developed and applied to the synthesis of mixed actinide(IV) actinide(IV) or actinide(IV)-actinide(III) oxalate single crystals of a size (typically 100-300 μm) suitable for isolating them and examining their crystal structure. These methods have been optimized on mixed systems composed of U(IV) and lanthanide (surrogate of trivalent actinides) and then assessed on U(IV) Am(III), Pu(IV)-Am(III), and U(IV) Pu(IV) mixtures. Three types of single crystals characterized by different structures have been obtained according to the synthesis and the chemical conditions. This is the first time that these well-known or recently discovered key compounds are formed by crystal growth methods specifically developed for actinide crystal handling (i.e., in glove boxes), thus enabling direct structural studies on transuranium element systems and acquisition of basic data. Characterization by X-ray diffraction, UV-visible solid spectroscopy, thermal ionization mass spectroscopy (TIMS), energy-dispersive X-ray spectroscopy (EDS), and inductively coupled plasma atomic emission spectroscopy (ICP-AES) demonstrates the potentialities and complementarity of the two crystal growth methods for obtaining the targeted mixed oxalates (actinide oxidation state and presence of both metallic ions in the crystal). More generally, this development opens broad prospects for single crystal synthesis of novel actinide organic frameworks and their structural description. (authors)

  1. Chemical behaviors of actinides and lanthanides in molten salts and liquid metals

    Separation processes using molten salts or liquid metals are interesting in view of spent fuel reprocessing and partitioning for nuclear transmutation before final radioactive waste disposals. Nevertheless, chemical behaviors of transuranium and lanthanide elements in non-aqueous solvents such as molten salts and liquid metals have been rarely studied. In the present study, thermodynamic properties of La, Ce, Pr, Nd, Gd, Tb, Ho, Er, Tm, Lu, Np, Pu, Am, and Cm in two phase extraction system: molten LiCl-KCl and liquid Bi or Zn were investigated to obtain excess Gibbs free energy experimentally or by using thermodynamic relationships and to examine systematics of 4f and 5f elements in these phases. Thermodynamic stability and specificity of each elements in liquid metals and salts thus obtained can be successfully used to explain systematics of extractability of f-elements in these systems. (Ohno, S.)

  2. CH Bond Activation of Hydrocarbons Mediated by Rare-Earth Metals and Actinides: Beyond σ-Bond Metathesis and 1,2-Addition

    W. HUANG; Diaconescu, PL

    2015-01-01

    © 2015 Elsevier Inc. This review discusses C. H bond activation of hydrocarbons mediated by rare-earth metal complexes with an emphasis on type of mechanisms. The review is organized as follows: in the first part, C. H bond activations mediated by rare-earth metals and actinides following traditional reaction pathways, such as σ-bond metathesis and 1,2-addition, are summarized; in the second part, nontraditional C. H bond activation examples are discussed in detail in order to understand the ...

  3. Presence and Character of the 5f Electrons in the Actinide Metals

    Johansson, B.; Skriver, Hans Lomholt; Mårtensson, N.;

    1980-01-01

    The sensitivity of the Image level binding energy to the occupation of the 5f orbital is pointed out and used to demonstrate the presence of 5f electrons in the uranium metal. It is suggested that the valence band spectrum of uranium might contain satellites originating from excitations to locali...... and the critical separation is found to take place between plutonium and americium....

  4. Excited states and transition metal compounds with quantum Monte Carlo

    Bande, Annika

    2007-01-01

    To the most challenging electron structure calculations belong weak interactions, excited state calculations, transition metals and properties. In this work the performance of variational (VMC) and fixed-node diffusion quantum Monte Carlo (FN-DMC) is tested for challenging electron structure problems using the quantum Monte Carlo amolqc code by Lüchow et al. The transition metal compounds under consideration are vanadium oxides. Here excitation, ionization, oxygen atom and molecule abstractio...

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

    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.

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

    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.

  7. Raman scattering in transition metal compounds: Titanium and compounds of titanium

    Jimenez, J.; Ederer, D.L.; Shu, T. [Tulane Univ., New Orleans, LA (United States)] [and others

    1997-04-01

    The transition metal compounds form a very interesting and important set of materials. The diversity arises from the many states of ionization the transition elements may take when forming compounds. This variety provides ample opportunity for a large class of materials to have a vast range of electronic and magnetic properties. The x-ray spectroscopy of the transition elements is especially interesting because they have unfilled d bands that are at the bottom of the conduction band with atomic like structure. This group embarked on the systematic study of transition metal sulfides and oxides. As an example of the type of spectra observed in some of these compounds they have chosen to showcase the L{sub II, III} emission and Raman scattering in some titanium compounds obtained by photon excitation.

  8. Chemical compatibility between lithium compounds and transition metals

    The aim is to investigate the chemical reactions or otherwise of lithium compounds; Li7Pb2 (a tritium breeder), Li2O (breeder and impurity), Li3N and LiH (impurities) with containment and fusion reactor component metals - 316 and austenitic steels, titanium. Experimental details are given and results are summarized. (author)

  9. On thermal lattice dilatation of some transition metal compounds

    The report deals with the thermal lattice dilatation of cubic transition metal compounds. The thermal dilatation is determined through the variation of the lattice constants. The measurements are carried out 'in situ' by use of a high-temperature X-ray diffractometer chamber. The evaluation relates to both the linear thermal expansion coefficient α and, for some compounds, the specific heat at constant volume Csub(V) and the Grueneisen constant γ. In general a higher thermal dilatation is observed for nitrides than for carbides with the compounds formed by the transition metals belonging to the IVA and VA groups. The influence exerted by vacancies and by the oxygen dissolved in the lattice on the thermal dilatation of carbonitrides of zirconium, hafnium and tantalum is explained by the more pronounced anharmonic character of atomic vibrations in the crystal lattice. (orig.)

  10. Actinide co-conversion by internal gelation

    Suitable microstructures and homogenous microspheres of actinide compounds are of interest for future nuclear fuel or transmutation target concepts to prevent the generation and dispersal of actinide powder. Sol-gel routes are being investigated as one of the possible solutions for producing these compounds. Preliminary work is described involving internal gelation to synthesize mixed compounds including minor actinides, particularly mixed actinide or mixed actinide-inert element compounds. A parameter study is discussed to highlight the importance of the initial broth composition for obtaining gel microspheres without major defects (cracks, craters, etc.). In particular, conditions are defined to produce gel beads from Zr(IV)/Y(III)/Ce(III) or Zr(IV)/An(III) systems. After gelation, the heat treatment of these microspheres is described for the purpose of better understanding the formation of cracks after calcination and verifying the effective synthesis of an oxide solid-solution. (authors)

  11. Sensitivity to actinide doping of uranium compounds by resonant inelastic X-ray scattering at uranium L3 edge.

    Kvashnina, Kristina O; Kvashnin, Yaroslav O; Vegelius, Johan R; Bosak, Alexei; Martin, Philippe M; Butorin, Sergei M

    2015-09-01

    Valence-to-core resonant inelastic X-ray scattering (RIXS) and high energy resolution fluorescence detection (HERFD) X-ray absorption measurements were performed at the U L3 edges of UO2 and UO2(NO3)2(H2O)6. The results are compared with model calculations based on the local-density-approximation formalism, taking into account Coulomb interaction U (LDA + U). We show that despite strong 5f-5f electronic correlations in the studied systems and the use of core-level excitations in the intermediate stage of the spectroscopic process, the RIXS technique probes a convolution of the single-particle densities of states in the valence and conduction bands. For UO2, the detected crystal-field splitting between the U 6d eg and t2g orbitals from the RIXS spectra (∼3.5 eV) is larger than that previously derived from optical spectroscopy. Furthermore, by using an example of the U0.75Pu0.25O2 mixed oxide, we show that the RIXS technique at the U L3 edges is sensitive to the substitution of U with other actinide, in contrast to conventional X-ray absorption methods. That is, due to changes in the occupied part rather than in the unoccupied part of the U 6d states caused by the substitution. PMID:26255719

  12. Research on the chemical speciation of actinides

    A demand for the safe and effective management of spent nuclear fuel and radioactive waste generated from nuclear power plant draws increasing attention with the growth of nuclear power industry. The objective of this project is to establish the basis of research on the actinide chemistry by using advanced laser-based highly sensitive spectroscopic systems. Researches on the chemical speciation of actinides are prerequisite for the development of technologies related to nuclear fuel cycles, especially, such as the safe management of high level radioactive wastes and the chemical examination of irradiated nuclear fuels. For supporting these technologies, laser-based spectroscopies have been performed for the chemical speciation of actinide in an aqueous solutions and the quantitative analysis of actinide isotopes in spent nuclear fuels. In this report, results on the following subjects have been summarized. (1) Development of TRLFS technology for chemical speciation of actinides, (2) Development of LIBD technology for measuring solubility of actinides, (3) Chemical speciation of plutonium complexes by using a LWCC system, (4) Development of LIBS technology for the quantitative analysis of actinides, (5) Development of technology for the chemical speciation of actinides by CE, (6) Evaluation on the chemical reactions between actinides and humic substances, (7) Chemical speciation of actinides adsorbed on metal oxides surfaces, (8) Determination of actinide source terms of spent nuclear fuel

  13. Actinide recycle

    A multitude of studies and assessments of actinide partitioning and transmutation were carried out in the late 1970s and early 1980s. Probably the most comprehensive of these was a study coordinated by Oak Ridge National Laboratory. The conclusions of this study were that only rather weak economic and safety incentives existed for partitioning and transmuting the actinides for waste management purposes, due to the facts that (1) partitioning processes were complicated and expensive, and (2) the geologic repository was assumed to contain actinides for hundreds of thousands of years. Much has changed in the few years since then. A variety of developments now combine to warrant a renewed assessment of the actinide recycle. First of all, it has become increasingly difficult to provide to all parties the necessary assurance that the repository will contain essentially all radioactive materials until they have decayed. Assurance can almost certainly be provided to regulatory agencies by sound technical arguments, but it is difficult to convince the general public that the behavior of wastes stored in the ground can be modeled and predicted for even a few thousand years. From this point of view alone there would seem to be a clear benefit in reducing the long-term toxicity of the high-level wastes placed in the repository

  14. Molecular and electronic structure of actinide hexa-cyanoferrates

    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: AnIV[FeII(CN)6].xH2O (An = Th, U, Np, Pu); AmIII[FeIII(CN)6].xH2O; Pu III[CoIII(CN)6].xH2O and K(H?)AnIII[FeII(CN)6].xH2O (An = Pu, Am). The metal oxidation states have been obtained thanks to the νCN, stretching vibration and to the actinide LIII absorption edge studies. As Prussian Blue, the AnIV[FeII(CN)6].xH2O (An = Np, Pu) are class II of Robin and Day compounds. X-ray Diffraction has shown besides that these complexes crystallize in the P63/m space group, as the isomorphic LaKFe(CN)6.4H2O complex used as structural model. The EXAFS oscillations at the iron K edge and at the An LIII 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 AnIV versus LnIII 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)

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

    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)

  16. Alkaline-earth metal compounds. Oddities and applications

    This book contains the following six topics: heavy alkaline-earth metal organometallic and metal organic chemistry: synthetic methods and properties (Ana Torvisco, Karin Ruhlandt-Senge); Heavier group 2 Grignard reagents of the type aryl-ae(l)n-x post-Grignard reagents (Matthias Westerhausen, Jens Langer, Sven Krieck, Reinald Fischer, Helmar Goerls, Mathias Koehler); stable molecular magnesium(I) dimers: A fundamentally appealing yet synthetically versatile compound class (Cameron Jones, Andreas Stasch); Modern developments in magnesium reagent chemistry for synthesis (Robert E. Mulvey, Stuart D. Robertson); Alkaline-earth metal complexes in homogeneous polymerization catalysis (Jean-Francois Carpentier, Yann Sarazin); homogeneous catalysis with organometallic complexes of group 2 (Mark R. Crimmin, Michael S. Hill); Chiral Ca, Sr and Ba-catalyzed asymmetric direct-type aldol, Michael, and Mannich and related reactions (Tetsu Tsubogo, Yasuhiro Yamashita, Shu- Kobayashi).

  17. Rare Earth Metal/semiconductor Interfaces and Compounds

    Nogami, Jun

    Interfaces formed at room temperature by incremental deposition of rare earth metals onto semiconductor substrates have been studied with surface sensitive soft X-ray photoelectron spectroscopy. The trends in core level lineshape and intensity with increasing metal coverage have been used to deduce an outline of the evolution and the final morphology of the interfacial region on a microscopic scale. Measurements were taken for Ytterbium (Yb) on Silicon (Si), Germanium, and Gallium Arsenide, and for Gadolinium (Gd) and Europium (Eu) on Silicon. The Yb/Si interface work was supported by comparable measurements of bulk Yb silicide samples of known composition and crystal structure. In a general sense, the behavior of all the systems studied is similar. At very low metal coverages, the metal atoms chemisorb and are weakly bonded to the substrate. The 4f core levels indicate that the metal-metal atom coordination is relatively low at this stage. The interaction with the substrate strengthens with increasing coverage, culminating in the formation of a strongly reacted phase at between 1 and 3 monolayers (ML). The strong reaction is limited to a narrow region at room temperature. At less than 10 ML coverage, the surface of the sample is almost indistinguishable from the pure metal. Details of the behavior such as the reactivity at low coverage, the compounds formed at the interface, the morphology at the surface at intermediate coverages, the final interfacial width, and the amount of substrate atom outdiffusion and surface segregation can all vary from system to system. It is in explaining the causes of some of these differences that insight about what governs the behavior of all of these rare earth metal/semiconductor systems has been obtained. The divalent metals (Yb, Eu) are significantly less reactive than trivalent Gd at sub-monolayer coverages. For the divalent metals the formation of a metal-rich phase is strongly favored in the reaction at the interface, whereas

  18. Using Correlations to Understand Changes in Actinide Bonding

    An important issue in actinide science is the changing role of the 5f electrons, both when progressing across the series, as well as how experimental variables affect these roles in a particular element's chemistries and physics. The function of these 5f electrons can be changed by experimental conditions: temperature and pressure being two of many such variables. The 5f electrons of several actinide metals, their alloys and compounds are affected greatly by pressure, due to the very large decreases in interatomic distances encountered under pressure. The latter bring about significant changes in the total energy of the system and in the electronic energy levels, which in turn affect the potential for overlap/hybridization) of their orbitals, promotion of electrons to other orbitals, etc. The physical state, temperature, pressure, specific structures, magnetic interactions and spin polarization effects are all critical parameters for bonding. Often correlations of behavior with these parameters can provide unique insights and understanding into the bonding and the changes that occur in it. With the advancement of modern computation approaches using FPMTO, or other approaches, theory has enlightened greatly the understanding of not only the bonding behavior of these elements but also the understanding of changes observed experimentally. But these computational efforts have some complications and limitations, and at times experimental findings and theory are not always in full agreement. In contrast to the behaviors of the elements, changes observed with compounds often are not be linked directly to the involvement of 5f electrons, due in part to the presence and bonding role of non-actinide atoms. The latter affect both the actinide interatomic distances and the type of electronic orbitals that interact. Presented here is an overview of the pressure behavior several actinide elements, some insights into the bonding behavior of compounds under pressure and selected

  19. Recovering actinide values

    Actinide values are recovered from sodium carbonate scrub waste solutions containing these and other values along with organic compounds resulting from the radiolytic and hydrolytic degradation of neutral organophosphorus extractants such as tri-n butyl phosphate (TBP) and dihexyl-N, N-diethyl carbamylmethylene phosphonate (DHDECMP) which have been used in the reprocessing of irradiated nuclear reactor fuels. The scrub waste solution is made acidic with mineral acid, to form a feed solution which is then contacted with a water-immiscible, highly polar organic extractant which selectively extracts the degradation products from the feed solution. The feed solution can then be processed to recover the actinides for storage or recycled back into the high-level waste process stream. The extractant can be recycled after stripping the degradation products with a neutral sodium carbonate solution. (author)

  20. Thermodynamics of the volatilization of actinide metals in the high-temperature treatment of radioactive wastes. 1998 annual progress report

    'In this project, the authors perform a detailed study of the volatilization behavior of U, Pu and possibly Am and Np under conditions relevant to the thermal treatment (destruction) of actinide-containing organic-based mixed and radioactive wastes. The primary scientific goal of the proposed work is to develop a basic thermochemical understanding of actinide volatilization and partitioning/speciation behavior in the thermal processes that are central to DOE/EM''s mixed waste treatment program. This subject addresses several technical needs/problem areas recently identified by DOE/EM''s Office of Science and Technology. In the Low-Level and Mixed Low-Level Waste problem area, emission-free destruction of organic wastes is listed as the first exemplary science need. In the TRU Waste, Plutonium Materials, and Spent Nuclear Fuel problem areas, interactions between actinides and organic residues and materials stabilization are listed as exemplary science needs. Both of these needs require high-temperature thermodynamic studies of actinides and actinide-organic interactions. A sound basis for designing safe and effective thermal treatment systems and the ability to allay public concerns about radioactive fugitive emissions are the principal benefits of the project. The proposed work is a combination of experimental studies and thermodynamic modeling. Vapor pressure measurements will be made to determine U, Pu and possibly Am volatile species and the extent of their volatilization when UO2/U3O8, PuO2 and AmO2 solids are heated to temperatures of 500 to 1,500 C under pyrolyzing (reducing) conditions or under oxidizing conditions (i.e. O2 (g) + H2O(g) mixtures) in the presence of chlorine (Cl2 (g) or HCl(g)). Work on uranium volatilization under reducing conditions will be performed in a laboratory at U. C. Berkeley in a collaboration with Professor D. R. Olander. In parallel with the experimental effort, a complete thermodynamic database for expected actinide gaseous

  1. Physiochemical and spectroscopic behavior of actinides and lanthanides in solution, their sorption on minerals and their compounds formed with macromolecules; Comportamiento fisicoquimico y espectroscopico de actinidos y lantanidos en solucion, su sorcion sobre minerales y sus compuestos formados con macromoleculas

    Jimenez R, M., E-mail: melania.jimenez@inin.gob.m [ININ, Departamento de Quimica, Carretera Mexico-Toluca s/n, 52750 Ocoyoacac, Estado de Mexico (Mexico)

    2010-07-01

    From the chemical view point, the light actinides has been those most studied; particularly the uranium, because is the primordial component of the nuclear reactors. The chemical behavior of these elements is not completely defined, since they can behave as transition metals or metals of internal transition, as they are the lanthanides. The actinides are radioactive; between them they are emitters of radiation alpha, highly toxic, of live half long and some very long, and artificial elements. For all this, to know them sometimes is preferable to use their chemical similarity with the lanthanides and to study these. In particular, the migration of emitters of radiation alpha to the environment has been studied taking as model the uranium. It is necessary to mention that actinides and lanthanides elements are in the radioactive wastes of the nuclear reactors. In the Chemistry Department of the Instituto Nacional de Investigaciones Nucleares (ININ) the researches about the actinides and lanthanides began in 1983 and, between that year and 1995 several works were published in this field. In 1993 the topic was proposed as a Department project and from then around of 13 institutional projects and managerial activity have been developed, besides 4 projects approved by the National Council of Science and Technology. The objective of the projects already developed and of the current they have been contributing knowledge for the understanding of the chemical behavior of the lanthanides and actinides, as much in solution as in the solid state, their behavior in the environment and the chemistry of their complexes with recurrent and lineal macromolecules. (Author)

  2. Calculated electronic and magnetic properties of the half-metallic, transition metal based Heusler compounds

    Kandpal, Hem C.; FECHER, GERHARD H.; Felser, Claudia

    2006-01-01

    In this work, results of {\\it ab-initio} band structure calculations for $A_2BC$ Heusler compounds that have $A$ and $B$ sites occupied by transition metals and $C$ by a main group element are presented. This class of materials includes some interesting half-metallic and ferromagnetic properties. The calculations have been performed in order to understand the properties of the minority band gap and the peculiar magnetic behavior found in these materials. Among the interesting aspects of the e...

  3. Actinide recovery techniques utilizing electromechanical processes

    Under certain conditions, the separation of actinides using electromechanical techniques may be an effective means of residue processing. The separation of granular mixtures of actinides and other materials discussed in this report is based on appreciable differences in the magnetic and electrical properties of the actinide elements. In addition, the high density of actinides, particularly uranium and plutonium, may render a simultaneous separation based on mutually complementary parameters. Both high intensity magnetic separation and electrostatic separation have been investigated for the concentration of an actinide waste stream. Waste stream constituents include an actinide metal alloy and broken quartz shards. The investigation of these techniques is in support of the Integral Fast Reactor (IFR) concept currently being developed at Argonne National Laboratory under the auspices of the Department of Energy

  4. Electrochemical decontamination of metallic waste contaminated with uranium compounds

    A study on the electrolytic dissolution of SUS-304 and Inconel-600 specimen was carried out in neutral salt electrolyte to evaluate the applicability of electrochemical decontamination process for recycle ro self disposal with authorization of large amount of metallic wastes contamination with uranium compounds generated by dismantling a retired uranium conversion plant in Korea. Although the best electrolytic dissolution performance for the specimens was observed in a Na2SO4 electrolyte, a Na3NO3 neutral salt electrolyte, in which about 30% for SUS-304 and the same for Inconel-600 in the weight loss was shown in comparison with that in Na2 SO4 solution, was selected as an electrolyte for the electrochemical decontamination of metallic wastes with the consideration on the surface of system components contacted with nitric acid and the compatibility with lagoon wastes generated during the facility operation. The effects of current density, electrolytic dissolution time, and concentration of NaNO3 on the electrolytic dissolution of the specimens were investigated. On the basis of the results obtained through the basic inactive experiments, electrochemical decontamination tests using the specimens contaminated with uranium compounds such as UO2, AUC (ammonium uranyl carbonate) and ADU (ammonium diuranate) taken from an uranium conversion facility were performed in 1M NaNO3 solution with the current density of 100 mA/cm2. It was verified that the electrochemical decontamination of the metallic wastes contaminated uranium compounds was quite successful in a NaNO3 neutral salt electrolyte by reducing α and β radioactivities below the level of self disposal within 10 minutes regardless of the type of contaminants and the degree of contamination.

  5. Formation and properties of metallic nanoparticles on compound semiconductor surfaces

    Kang, Myungkoo

    When electromagnetic radiation is incident upon metallic nanoparticles (NPs), a collective oscillation, termed a surface plasmon resonance (SPR), is generated. Recently, metallic NPs on semiconductor surfaces have enabled the generation of SPR, promising for enhanced light emission, efficient solar energy harvesting, biosensing, and metamaterials. Metallic NPs have been fabricated by focused ion beam (FIB) which has an advantage of cost-effectiveness over conventional lithography process requiring multi-step processes. Here, we report formation and properties of FIB-induced metallic NPs on compound semiconductor surfaces. Results presented in this thesis study suggest that FIB-induced Ga NPs can be a promising alternative plasmonic material. In particular, using a combined experimental-computational approach, we discovered a universal mechanism for ion-induced NP formation, which is governed by the sputtering yield of semiconductor surfaces. We also discovered a governing mechanism for ion-induced NP motion, which is driven by thermal fluctuation and anisotropic mass transport. Furthermore, we demonstrated Ga NP arrays with plasmon resonances with performance comparable to those of traditionally-used silver and gold NPs. We then finally demonstrated the Ga NP plasmoninduced enhancement of light emission from GaAs, which is the first ever combination of a new plasmonic material (Ga) and a new fabrication method (FIB) for the plasmon-enhanced light emission.

  6. ALMR potential for actinide consumption

    The Advanced Liquid Metal Reactor (ALMR) is a US Department of Energy (DOE) sponsored fast reactor design based on the Power Reactor, Innovative Small Module (PRISM) concept originated by General Electric. This reactor combines a high degree of passive safety characteristics with a high level of modularity and factory fabrication to achieve attractive economics. The current reference design is a 471 MWt modular reactor fueled with ternary metal fuel. This paper discusses actinide transmutation core designs that fit the design envelope of the ALMR and utilize spent LWR fuel as startup material and for makeup. Actinide transmutation may be accomplished in the ALMR core by using either a breeding or burning configuration. Lifetime actinide mass consumption is calculated as well as changes in consumption behavior throughout the lifetime of the reactor. Impacts on system operational and safety performance are evaluated in a preliminary fashion. Waste disposal impacts are discussed. (author)

  7. Valence instabilities as a source of actinide system inconsistencies

    Light actinide elements alone, and in some of their alloys, may exist as a static or dynamic mixture of two configurations. Such a state can explain both a resistivity maximum and lack of magnetic order observed in so many actinide materials, and still be compatible with the existence of f-electrons in narrow bands. Impurity elements may stabilize slightly different intermediate valence states in U, Np, and Pu, thus contributing to inconsistencies in published results. The physical property behavior of mixed-valence, rare-earth compounds is very much like that observed in development of antiphase (martensitic) structures. Martensitic transformations in U, Np, and Pu, from high-temperature b. c. c. to alpha phase, may be a way of ordering an alloy-like metal of mixed or intermediate valence. The relative stability of each phase structure may depend upon its electron-valence ratio. A Hubbard model for electron correlations in a narrow energy band has been invoked in most recent theories for explaining light actinide behavior. Such a model may also be applicable to crystal symmetry changes in martensitic transformations in actinides

  8. Electron and nuclear magnetic resonances in compounds and metallic hydrides

    Proton pulsed Nuclear Magnetic Resonance measurements were performed on the metallic hydrides ZrCr2Hx (x = 2, 3, 4) and ZrV2Hy (y = 2, 3, 4, 5) as a function of temperature between 180 and 400K. The ultimate aim was the investigation of the relaxation mechanisms in these systems by means of the measurement of both the proton (1H) spin-lattice (T1) and spin-spin (T2) relaxation times and to use these data to obtain information about the diffusive motion of the hydrogen atoms. The diffusional activation energies, the jump frequencies and the Korringa constant, Ck, related with the conduction electron contribution to the 1H relaxation were determined for the above hydrides as a function of hydrogen concentration. Our results were analysed in terms of the relaxation models described by Bloembergen, Purcell and Pound (BPP model) and by Torrey. The Korringa type relaxation due to the conduction electrons in metallic systems was also used to interpret the experimental results. We also present the Electron Paramagnetic Ressonance (EPR) study of Gd3+, Nd3+ and Er3+ ions as impurities in several AB3 intermetallic compounds where A = LA, Ce, Y, Sc, Th, Zr and B = Rh, Ir, Pt. The results were analysed in terms of the multiband model previously suggested to explain the behaviour of the resonance parameter in AB2 Laves Phase compounds. (author)

  9. Experimental studies of actinides in molten salts

    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.

  10. Experimental studies of actinides in molten salts

    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

  11. Superconductivity of graphite intercalation compounds with alkali-metal amalgams

    Superconductivity of the alkali-metal amalgam graphite intercalation compounds of stage 1 (C4KHg, C4RbHg) and stage 2 (C8KHg, C8RbHg) has been studied as well as that of the pristine amalgams (KHg, RbHg). The transition temperatures are 0.73, 0.99, 1.90, and 1.40 K for C4KHg, C4RbHg, C8KHg, and C8RbHg, respectively. The critical-field anisotropy ratio H/sup parallel//sub c/2/H/sup perpendicular//sub c/2 is about 10 for the stage 1 and about 15 to 40 for the stage 2. It is argued that electrons in the intercalant bands rather than the graphitic bands play the main role in the superconductivity. An interesting feature is that the stage-2 compound, which has a lower density of states at the Fermi level, has a higher transition temperature than the corresponding state-1 compound

  12. Research on the chemical speciation of actinides

    A demand for the safe and effective management of spent nuclear fuel and radioactive waste generated from nuclear power plant draws increasing attention with the growth of nuclear power industry. The objective of this project is to establish the basis of research on the actinide chemistry by using highly sensitive and advanced laser-based spectroscopic systems. Researches on the chemical speciation of actinides are prerequisite for the development of technologies related to nuclear fuel cycles, especially, such as the safe management of high level radioactive wastes and the chemical examination of irradiated nuclear fuels. For supporting these technologies, laser-based spectroscopies have been applied for the chemical speciation of actinide in aqueous solutions and the quantitative analysis of actinide isotopes in spent nuclear fuels. In this report, results on the following subjects have been summarized. Development of TRLFS technology for the chemical speciation of actinides, Development of laser-induced photo-acoustic spectroscopy (LPAS) system, Application of LIBD technology to investigate dynamic behaviors of actinides dissolution reactions, Development of nanoparticle analysis technology in groundwater using LIBD, Chemical speciation of plutonium complexes by using a LWCC system, Development of LIBS technology for the quantitative analysis of actinides, Evaluation on the chemical reactions between actinides and humic substances, Spectroscopic speciation of uranium-ligand complexes in aqueous solution, Chemical speciation of actinides adsorbed on metal oxides surfaces

  13. Electronic structure and magnetic properties of actinides

    The study of the actinide series shows the change between transition metal behavior and lanthanide behavior, between constant weak paramagnetism for thorium and strong Curie-Weiss paramagnetism for curium. Curium is shown to be the first metal of the actinide series to be magnetically ordered, its Neel temperature being 52K. The magnetic properties of the actinides depending on all the peripheral electrons, their electronic structure was studied and an attempt was made to determine it by means of a phenomenological model. Attempts were also made to interrelate the different physical properties which depend on the outer electronic structure

  14. Investigating Actinide Molecular Adducts From Absorption Edge Spectroscopy

    Den Auwer, C.; Conradson, S.D.; Guilbaud, P.; Moisy, P.; Mustre de Leon, J.; Simoni, E.; /SLAC, SSRL

    2006-10-27

    Although Absorption Edge Spectroscopy has been widely applied to the speciation of actinide elements, specifically at the L{sub III} edge, understanding and interpretation of actinide edge spectra are not complete. In that sense, semi-quantitative analysis is scarce. In this paper, different aspects of edge simulation are presented, including semi-quantitative approaches. Comparison is made between various actinyl (U, Np) aquo or hydroxy compounds. An excursion into transition metal osmium chemistry allows us to compare the structurally related osmyl and uranyl hydroxides. The edge shape and characteristic features are discussed within the multiple scattering picture and the role of the first coordination sphere as well as contributions from the water solvent are described.

  15. Synthesis, chemistry, and catalytic activity of complexes of lanthanide and actinide metals in unusual oxidation states and coordination environments. Progress report, February 1, 1981-January 31, 1982

    The objectives of this research project are: (1) to demonstrate experimentally that the lanthanide and actinide metals have a more extensive chemistry than is presently known; (2) to develop a better understanding of the special features of the f orbital elements which will allow the design of f orbital complexes possessing unique chemical and physical properties; (3) to provide a basis for seeking unusual catalytic transformations involving these elements; and (4) to synthesize and explore the chemical and physical properties of mixed metal complexes which contain both lanthanide and transition metals. During the past year progress was made in each area. Some of the specific results are: (1) the first activation of CO by an organolanthanide complex was demonstrated; (2) the first, crystallograhically characterized, molecular lanthanide hydride complexes, the bridged dimers, [(C5H4R)2LnH(THF)]2 (R=H, CH3; Ln=Lu, Er, Y), were synthesized by hydrogenolysis of the appropriate (C5H4R)2Ln(C(CH3)3)(THF) complex; (3) [(C5H5)2(THF)ErH]2 was found to catalyze the homogeneous hydrogenation of alkynes; (4) the first trimetallic organolanthanide complex was synthesized; (5) the first polyhydridic organolanthanide complex was synthesized; (6) U(III) hydride was found to catalytically activate molecular hydrogen in alkene and alkyne hydrogenation reactions

  16. Bonding in transition-metal cluster compounds. 2. The metal cluster-borane analogy

    Following the detailed discussion of the transition-metal cluster moiety M6(μ3-X)8 in the preceding paper, a more general account of the importance of the d electrons in transition-metal cluster chemistry is presented. The putative analogy with borane clusters (and their derivatives) is examined critically. Although an isolobal relationship exists between, e.g., BH and appropriate ML/sub n/ fragments (e.g. conical Fe(CO)3), this does not imply that the BH and ML/sub n/ fragments behave in electronically similar ways when cluster formation occurs, even when structurally related clusters are formed. Nonidentical isolobal fragments have orbital differences that manifest themselves in interfragment resonance integrals and require a qualitative distinction to be drawn between the bonding modes and detailed electronic structures of (i) transition-metal cluster compounds and (ii) boranes, carboranes, and their metalla derivatives; an analysis developed in the electronic structure theory of transition-metal systems shows why this is the case. The isolobal principle and Wade's rule owe their generality and utility to being symmetry-based statements; the energetics and details of the electronic structure of cluster compounds however are a separate matter requiring appropriate methods of theoretical chemistry. 39 references, 3 figures

  17. X-ray study of chemical bonding in actinides(IV) and lanthanides(III) hexa-cyanoferrates

    Bimetallic cyanide molecular solids derived from Prussian blue are well known to foster long-range magnetic ordering and show an intense inter-valence charge transfer band resulting from an exchange interaction through the cyanide-bridge. For those reasons the ferrocyanide and ferricyanide building blocks have been chosen to study electronic delocalization and covalent character in actinide bonding using an experimental and theoretical approach based on X-ray absorption spectroscopy. In 2001, the actinide (IV) and early lanthanides (III) hexacyanoferrate have been found by powder X-ray diffraction to be isostructural (hexagonal, P63/m group). Here, extended X-ray Absorption Fine Structure (EXAFS) at the iron K-edge and actinide L3-edge have been undertaken to probe the local environment of both actinides and iron cations. In an effort to describe the cyano bridge, a double edge fitting procedure including both iron and actinide edges and based on multiple scattering approach has been developed. We have also investigated the electronic properties of these molecular solids. Low energy electronic transitions have been used iron L2,3 edge, nitrogen and carbon K-edge and also actinides N4,5 edge to directly probe the valence molecular orbitals of the complex. Using a phenomenological approach, a clear distinctive behaviour between actinides and lanthanides has been shown. Then a theoretical approach using quantum chemistry calculation has shown more specifically the effect of covalency in the actinide-ferrocyanide bond. More specifically, π interactions were underlined by both theoretical and experimental methods. Finally, in agreement with the ionic character of the lanthanide bonding no inter-valence charge transfer has been observed in the corresponding optical spectra of these compounds. On the contrary, optical spectra for actinides adducts (except for thorium) show an intense inter-valence charge transfer band like in the transition metal cases which is

  18. Actinide burning and waste disposal

    Here we review technical and economic features of a new proposal for a synergistic waste-management system involving reprocessing the spent fuel otherwise destined for a U.S. high-level waste repository and transmuting the recovered actinides in a fast reactor. The proposal would require a U.S. fuel reprocessing plant, capable of recovering and recycling all actinides, including neptunium americium, and curium, from LWR spent fuel, at recoveries of 99.9% to 99.999%. The recovered transuranics would fuel the annual introduction of 14 GWe of actinide-burning liquid-metal fast reactors (ALMRs), beginning in the period 2005 to 2012. The new ALMRs would be accompanied by pyrochemical reprocessing facilities to recover and recycle all actinides from discharged ALMR fuel. By the year 2045 all of the LWR spent fuel now destined f a geologic repository would be reprocessed. Costs of constructing and operating these new reprocessing and reactor facilities would be borne by U.S. industry, from the sale of electrical energy produced. The ALMR program expects that ALMRs that burn actinides from LWR spent fuel will be more economical power producers than LWRs as early as 2005 to 2012, so that they can be prudently selected by electric utility companies for new construction of nuclear power plants in that era. Some leaders of DOE and its contractors argue that recovering actinides from spent fuel waste and burning them in fast reactors would reduce the life of the remaining waste to about 200-300 years, instead of 00,000 years. The waste could then be stored above ground until it dies out. Some argue that no geologic repositories would be needed. The current view expressed within the ALMR program is that actinide recycle technology would not replace the need for a geologic repository, but that removing actinides from the waste for even the first repository would simplify design and licensing of that repository. A second geologic repository would not be needed. Waste now planned

  19. Catalytic mechanism of transition-metal compounds on Mg hydrogen sorption reaction.

    Barkhordarian, Gagik; Klassen, Thomas; Bormann, Rüdiger

    2006-06-01

    The catalytic mechanisms of transition-metal compounds during the hydrogen sorption reaction of magnesium-based hydrides were investigated through relevant experiments. Catalytic activity was found to be influenced by four distinct physico-thermodynamic properties of the transition-metal compound: a high number of structural defects, a low stability of the compound, which however has to be high enough to avoid complete reduction of the transition metal under operating conditions, a high valence state of the transition-metal ion within the compound, and a high affinity of the transition-metal ion to hydrogen. On the basis of these results, further optimization of the selection of catalysts for improving sorption properties of magnesium-based hydrides is possible. In addition, utilization of transition-metal compounds as catalysts for other hydrogen storage materials is considered. PMID:16771356

  20. Lanthanides and actinides in ionic liquids

    Binnemans, Koen

    2007-01-01

    This lecture gives an overview of the research possibilities offered by combining f-elements (lanthanides and actinides) with ionic liquids [1] Many ionic liquids are solvents with weakly coordinating anions. Solvation of lanthanide and actinide ions in these solvents is different from what is observed in conventional organic solvents and water. The poorly solvating behavior can also lead to the formation of coordination compounds with low coordination numbers. The solvation of f-elements can...

  1. Lanthanide and actinide extractions using functionalized cobalt bis(dicarbollide) ion derivatives substituted with metal ligating functions

    Several extractants based on cobalt bis(dicarbollide) ion of formula [(1,2-C2B9H10)(1',2'- C2B9H11)-3,3'-Co(III)]- with covalently bonded CMPO group of general formulation [(Ph)2P(0)(CH2)C(0)N(H)n=0,1] were prepared and tested for extraction of trivalent radionuclides. The compounds studied differ in mode of attachment of CMPO group to COSAN moiety. Compound 1 with diethylene glycol connector between the COSAN cage and CMPO group provided better extraction properties than compounds with direct attachment (2) and N-bridge connection of COSAN moiety to nitrogen of CMPO group (3a or 3b). The compounds allowed the use of a less-polar solvent mixture of hexyl-methylketone and n-dodecane, which could replace the polar and less environmentally friendly solvent nitrobenzene

  2. Coordination compounds of transition metal chlorides with tetrazoles

    Coordination compounds (CC) of Co(2), Ni(2), Cu(2), Cd(2) chlorides with tetrazole and Ni(2) and Cd(2) chloride CC with tetrazolylhydrazone benzaldehyde are synthesized. The compounds are characterized by electron- and IR-spectroscopy, magnetic measurements (78-300 K), radiography. Conclusions are made on polynuclear structure of coordination compounds and Msup((2)) octahedron coordination

  3. International Workshop on Orbital and Spin Magnetism of Actinides (IWOSMA-3)

    Temmerman, W; Tobin, J; der Laan, G v

    2006-11-08

    This International Workshop on Orbital and Spin Magnetism of Actinides (IWOSMA) is the third in a series. The first workshop took place in Daresbury in 1999 and the second in Berkeley, CA, USA in 2002. These workshops are informal gatherings of theoreticians and experimentalists addressing the latest issues in the electronic and magnetic properties of actinides. The magnetism of transition metal systems and lanthanide systems is now fairly well understood, where d and f electrons can be described in a delocalized and localized model, respectively. On the other hand, actinide systems do not fit in such a description. The localization of the 5f is in between that of the 3d and 4f and the strong spin-orbit interaction necessitates a relativistic approach. Furthermore, electron correlation effects play a major role in these compounds. Recently, it has become possible to determine element-specific magnetic moments using neutron diffraction and x-ray scattering and absorption. The latter technique makes it even possible to separate the orbital and spin contribution to the total magnetic moment. The results are very interesting but difficult to reproduce with present state-of-art calculations. Not only a very large orbital polarization but also a large magnetic dipole term has been measured in cubic compounds, such as US. This allows for severe testing of the extra terms included in band theory to account for orbital polarization. It is also clear that deeper insight in magnetism can be obtained by studying the unusual behavior of the actinides. The recent development and application of such techniques as DMFT could contribute to the understanding of magnetism in actinides. Despite the fact that actinides for health reasons will find less application in technological market products, the understanding of their magnetic and electronic properties will no doubt provide key elements for a general description of electron correlation and relativistic effects.

  4. Development of a glass-encapsulated calcium phosphate wasteform for the immobilization of actinide and halide containing radioactive wastes from the pyrochemical reprocessing of plutonium metal

    Chloride-containing radioactive wastes are generated during the pyrochemical reprocessing of Pu metal. Immobilization of these wastes in borosilicate glass or Synroc-type ceramics is not viable due to the very low solubility of chlorides in these hosts. Alternative wasteforms, including zeolites and direct vitrification in phosphate glasses, were therefore studied. However, the preferred option was to immobilize the waste in calcium phosphate ceramics, forming a number of stable mineral phases including chlorapatite, chloride-substituted fluorapatite and spodiosite. The immobilization process developed in this study involves a solid state process in which waste and host powders are reacted in air at temperatures in the range of 700-800 deg. C. The ceramic products obtained by this process are non-hygroscopic free-flowing powders that require encapsulation in glass to produce a monolithic wasteform suitable for storage and ultimate disposal. A suitable relatively low melting temperature phosphate-based glass was identified. Durability trials of both the ceramic powder and sintered glass-ceramic hybrid wasteform indicate that both the halides and actinide surrogate ions are satisfactorily immobilized

  5. The lanthanides and actinides

    This paper relates the chemical properties of the actinides to their position in the Mendeleev periodic system. The changes in the oxidation states of the actinides with increasing atomic number are similar to those of the 3d elements. Monovalent and divalent actinides are very similar to alkaline and alkaline earth elements; in the 3+ and 4+ oxidation states they resemble d elements in the respective oxidation states. However, in their highest oxidation states the actinides display their individual properties with only a slight resemblance to d elements. Finally, there is a profound similarity between the second half of the actinides and the first half of the lanthanides

  6. Metal, bond energy, and ancillary ligand effects on actinide-carbon σ-bond hydrogenolysis. A kinetic and mechanistic study

    A kineticmechanistic study of actinide hydrocarbyl ligand hydrogenolysis (An-R + H2 → An-H + RH) is reported. For the complex Cp'2TH(CH2-t-Bu)(O-t-Bu)(Cp' = eta5-Me5C5), the rate law is first-order in organoactinide and first-order in H2, with k/sub H2/k/sub D2/ = 2.5 (4) and k/sub THF/k/sub toluene/ = 2.9 (4). For a series of complexes, hydrogenolysis rates span a range of ca. 105 with Cp'2ThCH2C(CH3)2CH2 ≅ Cp'2U(CH2-t-Bu) (too rapid to measure accurately) > Cp'2Th(CH2-t-Bu)[OCH(t-Bu)2] = Cp'2Th(CH2-t-Bu)(O-t-Bu) > Cp'2Th(CH2-t-Bu)(Cl) > Me2Si(Me4C5)2Th(n-Bu)2 > Cp'2Th(n-Bu)2 ≅ Cp'2ThMe2 > Cp'2Th(Me)(O3SCF3) > Cp'2Th(n-Bu)[OCG(t-Bu)2] ≅ Cp'2Th(Me)[OSiMe2(t-Bu)] > Cp'2ZrMe2 = Cp'2Th(rho-C6H4NMe2)(O-tu-Bu) > Cp'2Th(Ph)(O-t-Bu) > Cp'2U(Me)[OCH(t-Bu)2] > Cp'2Th(Me)[OCH(t-Bu)2]. In the majority of cases, the rate law is cleanly first-order in organoactinide over 3 or more half-lives. However, for Cp'2ThMe2 → (Cp'2ThH2)2, an intermediate is observe by NMR that is probably [Cp'2Th(Me)(μ-H)]2. For Cp'2Th(Me)(O3SCF3), a follow-up reaction, which consumes Cp'2TH(H)(O3SCF3) is detected. Variable-temperature kinetic studies yield ΔH** = 3.7 (2) kcalmol and ΔS double dagger = -50.8 (7) eu for Cp'2Th(CH2-t-Bu)(O-t-Bu) and ΔH double dagger = 9 (2) kcalmol and ΔS double dagger = -45 (5) eu for Cp'2U(Me)[OCH(O-t-Bu)2

  7. Transformation of Heavy Metal Compounds during the Remediation of Contaminated Soils

    Tatiana Minkina

    2011-03-01

    Full Text Available The effect of ameliorants, chalk, glauconite and semidecomposed cattle manure, on ordinary chernozem contaminated with Zn and Pb was studied in a long-term field experiment. The application of ameliorants significantly decreased the mobility of metals. Their effect depended on the ameliorant and was most significant at the simultaneous application of chalk and manure. This effect was presumably due to the strong binding of metals by carbonates through chemisorption and formation of lowsoluble Zn and Pb compounds and to the additional fixation in the form of complexes at the addition of organic material. The share of loosely bound metal compounds in the contaminated soils decreased to the level typical for the clean soils or even below. The general evolution of the transformation of metal compounds (from less to more firmly bound compounds accelerated by ameliorants remained for both metals.

  8. THERMODYNAMICS OF THE ACTINIDES

    Cunningham, Burris B.

    1962-04-01

    Recent work on the thermodynamic properties of the transplutonium elements is presented and discussed in relation to trends in thermodynamic properties of the actinide series. Accurate values are given for room temperature lattice parameters of two crystallographic forms, (facecentred cubic) fcc and dhcp (double-hexagonal closepacked), of americium metal and for the coefficients of thermal expansion between 157 and 878 deg K (dhcp) and 295 to 633 deg K (fcc). The meiting point of the metal, and its magnetic susceptibility between 77 and 823 deg K are reported and the latter compared with theoretical values for the tripositive ion calculated from spectroscopic data. Similar data (crystallography, meiting point and magnetic susceptibility) are given for metallic curium. A value for the heat of formation of americium monoxide is reported in conjunction with crystallographic data on the monoxide and mononitride. A revision is made in the current value for the heat of formation of Am/O/sub 2/ and for the potential of the Am(III)-Am(IV) couple. The crystal structures and lattice parameters are reported for the trichloride, oxychloride and oxides of californium. (auth)

  9. Half-metallic ferromagnetism in the CsSe compound by density functional theory

    Karaca, Mustafa; Kervan, Selçuk; Kervan, Nazmiye, E-mail: nkervan@gazi.edu.tr

    2015-08-05

    Graphical abstract: The ferromagnetic ground state of the CsSe compound is the most stable with CsCl-type structure with a total magnetic moment of 1 μ{sub B}/f.u. although this compound does not include transition metal atoms. The CsSe compound is half-metallic ferromagnet with a half-metallic band gap of 3.75 eV. The half-metallicity is also found to be robust with respect to the lattice distortion in the CsCl-type structure. The Curie temperature is estimated to be 390 K in the mean field approximation (MFA). - Highlights: • The CsSe compound is the most stable with CsCl-type structure. • The half-metallic band gap is about 3.5 eV for all types of structure. • The total magnetic moment is of 1 μ{sub B}/f.u. • The Curie temperature is estimated to be 390 K. - Abstract: The full-potential linearized augmented plane wave (FPLAPW) method based on the density functional theory is used to investigate the structural, magnetic and half-metallic properties of the CsSe compound in the CsCl-type, NaCl-type, ZnS-type, NiAs-type and wurtzite structures. The results show that the ferromagnetic ground state of the CsSe compound is the most stable with CsCl-type structure with a total magnetic moment of 1 μ{sub B}/f.u. although this compound does not include transition metal atoms. The CsSe compound is half-metallic ferromagnet for all types of structure. The half-metallic band gap is about 3.5 eV for all types of structure. The Curie temperature is estimated to be 390 K in the mean field approximation (MFA)

  10. Half-metallic ferromagnetism in the CsSe compound by density functional theory

    Graphical abstract: The ferromagnetic ground state of the CsSe compound is the most stable with CsCl-type structure with a total magnetic moment of 1 μB/f.u. although this compound does not include transition metal atoms. The CsSe compound is half-metallic ferromagnet with a half-metallic band gap of 3.75 eV. The half-metallicity is also found to be robust with respect to the lattice distortion in the CsCl-type structure. The Curie temperature is estimated to be 390 K in the mean field approximation (MFA). - Highlights: • The CsSe compound is the most stable with CsCl-type structure. • The half-metallic band gap is about 3.5 eV for all types of structure. • The total magnetic moment is of 1 μB/f.u. • The Curie temperature is estimated to be 390 K. - Abstract: The full-potential linearized augmented plane wave (FPLAPW) method based on the density functional theory is used to investigate the structural, magnetic and half-metallic properties of the CsSe compound in the CsCl-type, NaCl-type, ZnS-type, NiAs-type and wurtzite structures. The results show that the ferromagnetic ground state of the CsSe compound is the most stable with CsCl-type structure with a total magnetic moment of 1 μB/f.u. although this compound does not include transition metal atoms. The CsSe compound is half-metallic ferromagnet for all types of structure. The half-metallic band gap is about 3.5 eV for all types of structure. The Curie temperature is estimated to be 390 K in the mean field approximation (MFA)

  11. NEXAFS investigations of transition metal oxides, nitrides, carbides, sulfides and other interstitial compounds

    Chen, J. G.

    Owing to their unique physical and chemical properties, transition metal compounds, especially transition metal oxides, nitrides, carbides and sulfides, have been the subject of many surface science investigations. In this article we will review applications of the near-edge X-ray absorption fine structure (NEXAFS) technique in the investigations of electronic and structural properties of transition metal compounds. This review covers NEXAFS studies of compounds in various physical forms, including bulk single crystals, well-characterized overlayers on surfaces of corresponding parent metals, and amorphous powder materials. In addition to transition metal oxides, nitrides, carbides and sulfides, we will also briefly discuss NEXAFS studies of interstitial compounds containing other 2p and 3p non-metal components, namely boron, fluorine, silicon, phosphorus and chlorine. We will discuss the correlation between experimental NEXAFS spectra and the local bonding environment of these compounds, such as the number of d-electrons, spin configurations, ligand-field splitting, coordination numbers, local symmetries, and crystal structures. In addition, NEXAFS investigations of the adsorption and reaction of probing molecules will also be discussed to reveal the underlying chemical reactivities of these materials. We will use many examples to demonstrate the importance of NEXAFS studies in the overall understanding of the physical and chemical properties of transition metal compounds. Finally, we will conclude this review by summarizing the current applications, as well as potential research opportunities, of NEXAFS in several technologically important research areas, including materials science, catalysis, biological science, earth science and environmental science.

  12. Superconductivity in ferromagnetic metals and in compounds without inversion centre

    Mineev, V. P.

    2004-01-01

    The symmetry properties and the general overview of the superconductivity theory in the itinerant ferromagnets and in materials without space parity are presented. The basic notions of unconventional superconductivity are introduced in broad context of multiband superconductivity which is inherent property of ferromagnetic metals or metals without centre of inversion.

  13. Spin Hamiltonians for actinide ions

    The breakdown of Russel Saunders coupling for correlated f-levels of actinide ions is due to both spin orbit coupling and the crystalline electric field (CEF). Experiments on curium, an S-state ion in the metal for which the CEF is weak indicate a g-factor close to the Russel-Saunders value. Spin-orbit coupling is therefore too weak to produce jj coupling. This suggests a model for magnetic actinide ions in which the CEF ground multiplet is well separated from higher levels, completely determining thermodynamic magnetic properties. On this basis simplified spin Hamiltonians are derived for GAMMA1-GAMMA5 ground states in order to interpret thermodynamic measurements and ordering phenomena. (author)

  14. From carbanions to organometallic compounds: quantification of metal ion effects on nucleophilic reactivities.

    Corral-Bautista, Francisco; Klier, Lydia; Knochel, Paul; Mayr, Herbert

    2015-10-12

    The influence of the metal on the nucleophilic reactivities of indenyl metal compounds was quantitatively determined by kinetic investigations of their reactions with benzhydrylium ions (Ar2 CH(+) ) and structurally related quinone methides. With the correlation equation log k2 =sN (N+E), it can be derived that the ionic indenyl alkali compounds are 10(18) to 10(24) times more reactive (depending on the reference electrophile) than the corresponding indenyltrimethylsilane. PMID:25951612

  15. A Case Study of In Silico Modelling of Ciprofloxacin Hydrochloride/Metallic Compound Interactions

    Stojkovic, Aleksandra; Parojcic, Jelena; Djuric, Zorica; Corrigan, Owen I.

    2013-01-01

    With the development of physiologically based absorption models, there is an increased scientific and regulatory interest in in silico modelling and simulation of drug–drug and drug–food interactions. Clinically significant interactions between ciprofloxacin and metallic compounds are widely documented. In the current study, a previously developed ciprofloxacin-specific in silico absorption model was employed in order to simulate ciprofloxacin/metallic compound interaction observed in vivo. C...

  16. Structure and bonding in metal-rich compounds: pnictides, chalcides and halides

    The subject is reviewed under the following headings: introduction (compounds included in the review; purpose of the review); MX compounds with M = transition metal and X = O,N,S or P; sulfides and selenides of the transition metals; transition-metal phosphides; alkali oxides; transition-metal oxides and nitrides with X/M < 1; metal-rich halides; conclusion. The references number 238. Compounds of the following principal elements of nuclear interest are included in the tables and text: Am, Ce, Cs, Eu, Gd, Hf, La, Mo, Np, Nb, Pu, Pr, Pa, Re, Ru, Sc, Ta, Tb, Th, W, U, V, Y, Zr. The information in the tables is presented under: structure type, space group, lattice parameters and remarks. (U.K.)

  17. Actinide environmental chemistry

    In order to predict release and transport rates, as well as design cleanup and containment methods, it is essential to understand the chemical reactions and forms of the actinides under aqueous environmental conditions. Four important processes that can occur with the actinide cations are: precipitation, complexation, sorption and colloid formation. Precipitation of a solid phase will limit the amount of actinide in solution near the solid phase and have a retarding effect on release and transport rates. Complexation increases the amount of actinide in solution and tends to increase release and migration rates. Actinides can sorb on to mineral or rock surfaces which tends to retard migration. Actinide ions can form or become associated with colloidal sized particles which can, depending on the nature of the colloid and the solution conditions, enhance or retard migration of the actinide. The degree to which these four processes progress is strongly dependent on the oxidation state of the actinide and tends to be similar for actinides in the same oxidation state. In order to obtain information on the speciation of actinides in solution, i.e., oxidation state, complexation form, dissolved or colloidal forms, the use of absorption spectroscopy has become a method of choice. The advent of the ultrasensitive, laser induced photothermal and fluorescence spectroscopies has made possible the detection and study of actinide ions at the parts per billion level. With the availability of third generation synchrotrons and the development of new fluorescence detectors, X-ray absorption spectroscopy (XAS) is becoming a powerful technique to study the speciation of actinides in the environment, particularly for reactions at the solid/solution interfaces. (orig.)

  18. Overview of actinide chemistry in the WIPP

    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

  19. PEROXOTITANATE- AND MONOSODIUM METAL-TITANATE COMPOUNDS AS INHIBITORS OF BACTERIAL GROWTH

    Hobbs, D.

    2011-01-19

    Sodium titanates are ion-exchange materials that effectively bind a variety of metal ions over a wide pH range. Sodium titanates alone have no known adverse biological effects but metal-exchanged titanates (or metal titanates) can deliver metal ions to mammalian cells to alter cell processes in vitro. In this work, we test a hypothesis that metal-titanate compounds inhibit bacterial growth; demonstration of this principle is one prerequisite to developing metal-based, titanate-delivered antibacterial agents. Focusing initially on oral diseases, we exposed five species of oral bacteria to titanates for 24 h, with or without loading of Au(III), Pd(II), Pt(II), and Pt(IV), and measuring bacterial growth in planktonic assays through increases in optical density. In each experiment, bacterial growth was compared with control cultures of titanates or bacteria alone. We observed no suppression of bacterial growth by the sodium titanates alone, but significant (p < 0.05, two-sided t-tests) suppression was observed with metal-titanate compounds, particularly Au(III)-titanates, but with other metal titanates as well. Growth inhibition ranged from 15 to 100% depending on the metal ion and bacterial species involved. Furthermore, in specific cases, the titanates inhibited bacterial growth 5- to 375-fold versus metal ions alone, suggesting that titanates enhanced metal-bacteria interactions. This work supports further development of metal titanates as a novel class of antibacterials.

  20. Volatile Metals Coordination Compounds as Precursors for Functional Materials Synthesis by CVD-Method

    Mazurenko, E.; Gerasimchuk, A.

    1995-01-01

    The applications of such coordination compounds (chelates) as metal β-diketonates in different CVD techniques were examined. It was shown that high chemical and physical characteristics of these compounds allow their favourable use comparatively with other volatile compounds. The general rules in volatility and thermal stability of β-diketonates and their fluorine derivatives were discussed. The ways of preparation of various functional materials with specific properties were determined.

  1. Composites for removing metals and volatile organic compounds and method thereof

    Coronado, Paul R.; Coleman, Sabre J.; Reynolds, John G.

    2006-12-12

    Functionalized hydrophobic aerogel/solid support structure composites have been developed to remove metals and organic compounds from aqueous and vapor media. The targeted metals and organics are removed by passing the aqueous or vapor phase through the composite which can be in molded, granular, or powder form. The composites adsorb the metals and the organics leaving a purified aqueous or vapor stream. The species-specific adsorption occurs through specific functionalization of the aerogels tailored towards specific metals and/or organics. After adsorption, the composites can be disposed of or the targeted metals and/or organics can be reclaimed or removed and the composites recycled.

  2. 50 years of superbases made from organolithium compounds and heavier alkali metal alkoxides

    Lochmann, Lubomír; Janata, Miroslav

    2014-01-01

    Roč. 12, č. 5 (2014), s. 537-548. ISSN 1895-1066 R&D Projects: GA ČR GAP106/12/0844 Institutional support: RVO:61389013 Keywords : superbases * heavier alkali metal compounds * lithium -heavier alkali metal interchange Subject RIV: CD - Macromolecular Chemistry Impact factor: 1.329, year: 2013

  3. Physicochemical aspects of inhibition of acid corrosion of metals by unsaturated organic compounds

    Avdeev, Ya G.; Kuznetsov, Yurii I.

    2012-12-01

    The state-of-the-art in the development and improvement of methods for protecting metals from corrosion in mineral acid solutions using unsaturated organic compounds is considered. Characteristic features of the mechanism of their protective action on metal corrosion in acidic media are discussed. The bibliography includes 203 references.

  4. The chemistry of molten salt mixtures: application to the reductive extraction of lanthanides and actinides by a liquid metal

    The design of a process of An/Ln separation by liquid - liquid extraction can be used for on-line purification of the molten salt in a molten salt nuclear reactor (Generation IV) as well as reprocessing various spent fuels. In order to establish the chemical properties of An and Ln in molten salt mediums, E - pO2 - diagrams were established for the relevant chemical elements. With the purpose of checking the possibilities of separating the An from Ln, the real activity coefficients in liquid metals were measured. An experimental protocol was developed and validated on the Gd/Ga system. It was then transferred to radioactive environment to measure the activity coefficient of Pu in Ga. The results made it possible to estimate the effectiveness of the Pu extraction and its separation from Gd and Ce. The selectivity was shown to decrease with the temperature and Al and Ga showed a good selectivity between Pu and the Ce in fluoride medium. (author)

  5. Single crystal growth of europium and ytterbium based intermetallic compounds using metal flux technique

    Sumanta Sarkar; Sebastian C Peter

    2012-11-01

    This article covers the use of indium as a potential metal solvent for the crystal growth of europium and ytterbium-based intermetallic compounds. A brief view about the advantage of metal flux technique and the use of indium as reactive and non-reactive flux are outlined. Large single crystals of EuGe2, EuCoGe3 and Yb2AuGe3 compounds were obtained in high yield from the reactions of the elements in liquid indium. The results presented here demonstrate that considerable advances in the discovery of single crystal growth of complex phases are achievable utilizing molten metals as solvents.

  6. Electron dynamics of transition metal compounds studied with resonant soft X-ray scattering

    High resolution experimental data for resonant soft x-ray scattering of transition metal compounds are shown. The compounds studied are the ionic transition metal di-fluorides, ionic and covalent ortho vanadates and members of the La1-xSrxCoO3 perovskite family. In all compounds we studied the transition metal L2,3 edge and also the ligand (oxygen or fluorine) K edge. For the ionic compounds the transition metal data are in good agreement with atomic multiplet ligand field calculations that include charge transfer effects. Density functional calculations give very useful information to interpret the ligand x-ray emission data. The experimental metal Lα emission data show that the region between valence and conduction bands in the di-fluorides has several d-excited states. At the L2 edge of the ionic ortho vanadates we found the signature of a fast Coster-Kronig decay process that results in a very localized emission peak. Changes in the oxidation states in the La1-xSrxCoO3 compounds are observed at both the metal L2,3 edge and the oxygen K edge absorption spectra. (Author)

  7. The Systematic Study of the Organotransition Metal Compounds.

    Carriedo, Gabino A.

    1990-01-01

    Discussed is an extension of the conventional method for studying the organometallic chemistry of transition metals that may be useful to show how the various existing types of low-valence complexes can be constructed. This method allows students to design new types of complexes that may still be nonexistent. (CW)

  8. Alkali-doped metal-phthalocyanine and pentacene compounds

    Craciun, M.F.

    2006-01-01

    The ability to introduce charge carriers in organic molecular materials and control their concentration is of great relevance for both fundamental research and applications. In this thesis, it has been demonstrated that the electronic properties of Metal Phthalocyanines (MPc) and pentacene (PEN) mol

  9. Electronic and thermodynamic properties of transition metal elements and compounds

    This thesis focuses on the use of band-structure calculations for studying thermodynamic properties of solids. We discuss 3d-, 4d- and 5d-transition metal carbides and nitrides. Through a detailed comparison between theoretical and experimental results, we draw conclusions on the character of the atomic bonds in these materials. We show how electronic structure calculations can be used to give accurate predictions for bonding energies. Part of the thesis is devoted to the application of the generalized gradient approximation in electronic structure calculations on transition metals. For structures with vibrational disorder, we present a method for calculating averaged phonon frequencies without using empirical information. For magnetic excitations, we show how a combined use of theoretical results and experimental data can yield information on magnetic fluctuations at high temperatures. The main results in the thesis are: Apart for an almost constant shift, theoretically calculated bonding energies for transition metal carbides and nitrides agree with experimental data or with values from analysis of thermochemical information. The electronic spectrum of transition metal carbides and nitrides can be separated into bonding, antibonding and nonbonding electronic states. The lowest enthalpy of formation for substoichiometric vanadium carbide VC1-X at zero temperature and pressure occurs for a structure containing vacancies (x not equal to 0). The generalized gradient approximation improves theoretical calculated cohesive energies for 3d-transition metals. Magnetic phase transitions are sensitive to the description of exchange-correlation effects in electronic structure calculations. Trends in Debye temperatures can be successfully analysed in electronic structure calculations on disordered lattices. For the elements, there is a clear dependence on the crystal structure (e.g., bcc, fcc or hcp). Chromium has fluctuating local magnetic moments at temperatures well above

  10. Coordination polymers: trapping of radionuclides and chemistry of tetravalent actinides (Th, U) carboxylates

    The use of nuclear energy obviously raises the question of the presence of radionuclides in the environment. Currently, their mitigation is a major issue associated with nuclear chemistry. This thesis focuses on both the trapping of radionuclides by porous solids called Metal-Organic Frameworks (MOF) and the crystal chemistry of the carboxylate of tetravalent actinides (AnIV). The academic knowledge of the reactivity of carboxylate of AnIV could help the understanding of actinides speciation in environment. We focused on the sequestration of iodine by aluminum based MOF. The functionalization (electron-donor group) of the MOF drastically enhances the iodine capture capacity. The removal of light actinides (Th and U) from aqueous solution was also investigated as well as the stability of (Al)-MOF under γ radiation. More than twenty coordination polymers based on tetravalent actinides have been synthesized and characterized by single crystal X-ray diffraction. The use of controlled hydrolysis promotes the formation of coordination polymers exhibiting polynuclear cluster ([U4], [Th6], [U6] and [U38]). In order to understand the formation of the largest cluster, the ex-situ study of the solvo-thermal synthesis of compound {U38} has also been investigated. (author)

  11. Use of fast reactors for actinide transmutation

    The management of radioactive waste is one of the key issues in today's discussions on nuclear energy, especially the long term disposal of high level radioactive wastes. The recycling of plutonium in liquid metal fast breeder reactors (LMFBRs) would allow 'burning' of the associated extremely long life transuranic waste, particularly actinides, thus reducing the required isolation time for high level waste from tens of thousands of years to hundreds of years for fission products only. The International Working Group on Fast Reactors (IWGFR) decided to include the topic of actinide transmutation in liquid metal fast breeder reactors in its programme. The IAEA organized the Specialists Meeting on Use of Fast Breeder Reactors for Actinide Transmutation in Obninsk, Russian Federation, from 22 to 24 September 1992. The specialists agree that future progress in solving transmutation problems could be achieved by improvements in: Radiochemical partitioning and extraction of the actinides from the spent fuel (at least 98% for Np and Cm and 99.9% for Pu and Am isotopes); technological research and development on the design, fabrication and irradiation of the minor actinides (MAs) containing fuels; nuclear constants measurement and evaluation (selective cross-sections, fission fragments yields, delayed neutron parameters) especially for MA burners; demonstration of the feasibility of the safe and economic MA burner cores; knowledge of the impact of maximum tolerable amount of rare earths in americium containing fuels. Refs, figs and tabs

  12. Research in actinide chemistry

    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-, CO32-, PO43-, humates). The research undertakes fundamental studies of actinide complexes which can increase understanding of the environmental behavior of these elements

  13. Crossover from metal to insulator in dense lithium-rich compound CLi4.

    Jin, Xilian; Chen, Xiao-Jia; Cui, Tian; Mao, Ho-kwang; Zhang, Huadi; Zhuang, Quan; Bao, Kuo; Zhou, Dawei; Liu, Bingbing; Zhou, Qiang; He, Zhi

    2016-03-01

    At room environment, all materials can be classified as insulators or metals or in-between semiconductors, by judging whether they are capable of conducting the flow of electrons. One can expect an insulator to convert into a metal and to remain in this state upon further compression, i.e., pressure-induced metallization. Some exceptions were reported recently in elementary metals such as all of the alkali metals and heavy alkaline earth metals (Ca, Sr, and Ba). Here we show that a compound of CLi4 becomes progressively less conductive and eventually insulating upon compression based on ab initio density-functional theory calculations. An unusual path with pressure is found for the phase transition from metal to semimetal, to semiconductor, and eventually to insulator. The Fermi surface filling parameter is used to describe such an antimetallization process. PMID:26884165

  14. Metal(loid)organic compounds in contaminated soil

    Hirner, A.V.; Grueter, U.M.; Kresimon, J. [Univ. of Essen (Germany). Inst. of Environmental Analytical Chemistry

    2000-10-01

    13 samples of soils contaminated with petrol, coaly residues, shredder and domestic waste have been investigated by low temperature gas chromatography with plasma mass spectrometry detection after sample derivatisation by hydride generation (HG/LT-GC/ICP-MS). 24 organic compounds of 9 elements could be analysed, one fifth of them exceeding the concentration of 1 {mu}g/kg. These results are roughly comparable with those on harbour and river sediments, and are discussed in respect to a preliminary evaluation of the emission potential of solid waste and contaminated soil as well as waste treatment processes. (orig.)

  15. Crystalline and amorphous rare-earth metallic compounds

    During the last years the study of magnetic behaviour of rare-earth (or yttrium) compounds with cobalt and iron has growth of interest. This interest of justified by a large area of experimental and theoretical problems coming into being in the study of some rare-earth materials as well as in their technical applications. In the last three years a great number of new rare earth materials were studied and also new models explaining the magnetic behaviour of these systems have been used. In this paper we refer especially to some typical systems in order to analyse the magnetic behaviour of iron and cobalt and also the part played by the magnetic interactions in the values of the cobalt or iron moments. The model used will be generally the molecular field model. In the second chapter we present comparatively the structure of crystalline and amorphous compounds for further correlation with the magnetic properties. In chapter III we analyse the magnetic interactions in some crystalline and amorphous rare-earth alloys. Finally, we exemplify the ways in which we ensure better requried characteristics by the technical utilizations of these materials. These have in view the modifications of the magnetic interactions and are closely related with the analysis made in chapter III

  16. METALLIC COMPOUNDS IN THE PHASE OF THE RETICULATED IONIC POLYMERS

    Vasilii Gutsanu

    2010-12-01

    Full Text Available Using the Mossbauer spectroscopy and other physical methods it was demonstrated the presence of different iron compounds like β-FeOOH, α-Fe2O3, and jarosite mineral type compounds: (R4N,H3O[Fe3(OH6(SO42] or coordination modes: {RCOO-Fe(L4-OOCR}1+, {R-CO2=Fe(X2=O2C-R}n, {R-COO-Fe(X4-OOC-R}n, and {(-NCH2CH2N-= Fe(X2 =(-NCH2CH2N-}, where X= H2O, OH-, SO42-., n= from 3- to 1+ in the ion-exchange resins (KU-2, AN-31, AV-17, Varian – AD, EDE-10P after the contact with sulphate of iron(III solutions at different conditions: type of solvent, temperature, air atmosphere. In special conditions the ultrafine superparamagnetic particles of Fe2O3 have been obtained

  17. Theoretical Investigation of Compounds with Triple Bonds

    Devarajan, Deepa

    2011-01-01

    In this thesis, compounds with potential triple-bonding character involving the heavier main-group elements, Group 4 transition metals, and the actinides uranium and thorium were studied by using molecular quantum mechanics. The triple bonds are described in terms of the individual orbital contributions (σ, π||, and π┴), involving electron-sharing covalent or donor–acceptor interactions between the orbitals of two atoms or fragmen...

  18. Carbon based secondary compounds do not provide protection against heavy metal road pollutants in epiphytic macrolichens.

    Gauslaa, Yngvar; Yemets, Olena A; Asplund, Johan; Solhaug, Knut Asbjørn

    2016-01-15

    Lichens are useful monitoring organisms for heavy metal pollution. They are high in carbon based secondary compounds (CBSCs) among which some may chelate heavy metals and thus increase metal accumulation. This study quantifies CBSCs in four epiphytic lichens transplanted for 6months on stands along transects from a highway in southern Norway to search for relationships between concentrations of heavy metals and CBSCs along a gradient in heavy metal pollutants. Viability parameters and concentrations of 21 elements including nutrients and heavy metals in these lichen samples were reported in a separate paper. Medullary CBSCs in fruticose lichens (Ramalina farinacea, Usnea dasypoga) were reduced in the most polluted sites, but not in foliose ones (Parmelia sulcata, Lobaria pulmonaria), whereas cortical CBSC did not change with distance from the road in any species. Strong positive correlations only occurred between the major medullary compound stictic acid present in L. pulmonaria and most heavy metals, consistent with a chelating role of stictic acid, but not of other studied CBSCs or in other species. However, heavy metal chelating did not protect L. pulmonaria against damage because this species experienced the strongest reduction in viability in the polluted sites. CBSCs with an accumulation potential for heavy metals should be quantified in lichen biomonitoring studies of heavy metals because they, like stictic acid, could overshadow pollutant inputs in some species rendering biomonitoring data less useful. In the two fruticose lichen species, CBSCs decreased with increasing heavy metal concentration, probably because heavy metal exposure impaired secondary metabolism. Thus, we found no support for a heavy metal protection role of any CBSCs in studied epiphytic lichens. No intraspecific relationships occurred between CBSCs versus N or C/N-ratio. Interspecifically, medullary CBSCs decreased and cortical CBSCs increased with increasing C/N-ratio. PMID:26437350

  19. In vitro removal of actinide (IV) ions

    Weitl, Frederick L.; Raymond, Kenneth N.

    1982-01-01

    A compound of the formula: ##STR1## wherein X is hydrogen or a conventional electron-withdrawing group, particularly --SO.sub.3 H or a salt thereof; n is 2, 3, or 4; m is 2, 3, or 4; and p is 2 or 3. The present compounds are useful as specific sequestering agents for actinide (IV) ions. Also described is a method for the 2,3-dihydroxybenzamidation of azaalkanes.

  20. Modeling of Intermetallic Compounds Growth Between Dissimilar Metals

    Wang, Li; Wang, Yin; Prangnell, Philip; Robson, Joseph

    2015-09-01

    A model has been developed to predict growth kinetics of the intermetallic phases (IMCs) formed in a reactive diffusion couple between two metals for the case where multiple IMC phases are observed. The model explicitly accounts for the effect of grain boundary diffusion through the IMC layer, and can thus be used to explore the effect of IMC grain size on the thickening of the reaction layer. The model has been applied to the industrially important case of aluminum to magnesium alloy diffusion couples in which several different IMC phases are possible. It is demonstrated that there is a transition from grain boundary-dominated diffusion to lattice-dominated diffusion at a critical grain size, which is different for each IMC phase. The varying contribution of grain boundary diffusion to the overall thickening kinetics with changing grain size helps explain the large scatter in thickening kinetics reported for diffusion couples produced under different conditions.

  1. Neutron scattering studies of the actinides

    The electronic structure of actinide materials presents a unique example of the interplay between localized and band electrons. Together with a variety of other techniques, especially magnetization and the Mossbauer effect, neutron studies have helped us to understand the systematics of many actinide compounds that order magnetically. A direct consequence of the localization of 5f electrons is the spin-orbit coupling and subsequent spin-lattice interaction that often leads to strongly anisotropic behavior. The unusual phase transition in UO2, for example, arises from interactions between quadrupole moments. On the other hand, in the monopnictides and monochalcogenides, the anisotropy is more difficult to understand, but probably involves an interaction between actinide and anion wave functions. A variety of neutron experiments, including form-factor studies, critical scattering and measurements of the elementary excitations have now been performed, and the conceptual picture emerging from these studies will be discussed

  2. Heavy metal ion extraction of crownether compounds with supercritical CO2 fluid

    Benzocrownether-diarylethene derivatives (5BCD, 6BCD) were synthesized and utilized to extract metal ions into supercritical CO2. In order to enhance the CO2-phillicity and the extraction capability, synthesized compounds have both perfluoro unit and benzocrown moiety and were compared with dicyclohexano 18-crown-6(DC18C6). With minimal amount of water and counter ions such as perfluorooctanesulphonic acid or perfluorooctanic acid, their metal ion(Sr2+, Co+2, Na+) extraction efficiency was investigated. 5BCD, 6BCD showed more than 50% extraction for Sr+2, Na+ions and their extraction efficiency was better than that of DC18C6 compound

  3. Soft X-Ray Spectroscopic Study of Fullerene Based Transition-Metal Compounds and Related Systems

    Qian, Limin

    2001-01-01

    This thesis addresses the electronic and geometric structures of fullerene based transition-metal compounds and other related systems. The formation of TixC60, VxC60 and NbxC60 compounds has been examined by X-ray photoelectron, soft X-ray absorption and emission and spectroscopy techniques, including resonant inelastic X-ray scattering (RIXS). The symmetry and character of the chemical bond of transition metal-fulleride has been determined. A related study of single-walled carbon nanotubes i...

  4. Pyrometallurgical process of actinide metal

    Major subject on pyrometallurgical partitioning technology is to separate transmutation elements (TRU) from rare earth elements(RE). Distribution coefficients of TRU and RE between molten chloride and liquid cadmium were measured for reductive extraction, and TRU were separated from RE in simplified molten chloride system by electrorefining. And separation efficiency between TRU and RE were estimated by using thermodynamics data. The results indicate that uranium, neptunium and plutonium are easy to separate from RE but some amount of RE accompany americium, and that processes have to be optimized to attain good separation efficiency of TRU. (author)

  5. Pyrometallurgical process of actinide metal

    Yoo, Jae Hyung; Kang, Young Ho; Woo, Mun Sik; Hwang, Sung Chan

    1999-06-01

    Major subject on pyrometallurgical partitioning technology is to separate transmutation elements (TRU) from rare earth elements(RE). Distribution coefficients of TRU and RE between molten chloride and liquid cadmium were measured for reductive extraction, and TRU were separated from RE in simplified molten chloride system by electrorefining. And separation efficiency between TRU and RE were estimated by using thermodynamics data. The results indicate that uranium, neptunium and plutonium are easy to separate from RE but some amount of RE accompany americium, and that processes have to be optimized to attain good separation efficiency of TRU. (author)

  6. Separation of actinides with alkylpyridinium salts

    Various f-elements are separated as anionic complexes from both acidic and alkaline solutions by precipitation with alkylpyridinium salts. The precipitates are also cationic surfactants where the simple counter-ion (e.g. nitrate or chloride) is replaced by the negatively charged complex anion of an actinide or lanthanide. The low solubility of these precipitates is explained by a strong affinity of divalent complex counter-ions of f-elements to the quaternary nitrogen. Precipitations in solutions of nitric acid allow to separate tetravalent f-elements from other metals, in alkaline carbonate solutions tetravalent and hexavalent actinides are precipitated simultaneously. The last procedure yields precipitates, which are very intimate mixtures of hexavalent and tetravalent actinides. This allows to prepare mixed oxides in a simple way. (author) 6 refs.; 3 figs.; 3 tabs

  7. The electrochemical properties of actinide amalgams

    Standard potentials are selected for actinides (An) and their amalgams. From the obtained results, energy characteristics are calculated and analyzed for alloy formation in An-Hg systems. It is found that solutions of the f-elements in mercury are very close in properties to amalgams of the alkali and alkaline-earth metals, except that, for the active Group III metals, the ion skeletons have a greater number of realizable charged states in the condensed phase

  8. A study of contaminated soils near Crucea-Botus, ana uranium mine (East Carpathians, Romania): metal distribution and partitioning of natural actinides with implications for vegetation uptake

    Petrescu, L.; Bilal, E.

    2012-04-01

    total uranium can be found in the specifically absorbed and carbonate bound fraction, indicated the important role played by the carbonates in the retention of U; one the other hand this fraction is liable to release the uranium if the pH should happen to change. Thorium appear in high-enough concentration in the soil is scarcely available because 70.29% is present in residual fraction, and about 21.78% in the crystalline iron oxides occluded fraction and organically and secondary sulfide bound fraction. This is certainly due to the fact that this naturally occurring radionuclide can be associated with relatively insoluble mineral phases like alumino-silicates and refractory oxides. Its association with the organic matter (10.93%) suggests that it can form soluble organic complexes that can facilitate its removal by the stream waters. Grounded on these results, we were able to prove that the examined mine dumps can represent an impact on the environment, which constitute an argument in favor of the initiation of a program of remedying the quality of the environment from this mining zone. Although from our research it resulted that the natural actinides does not concentrate in the exchangeable fraction (Th) or it concentrates very little in it (U), the isolation of the mineral fraction of soil rich in U and Th helps us in the future identification of the links between the bioavailability and the pedogenesis, connections which control the cycle of the radioactive metals.

  9. Development of an experimental protocol for uptake studies of metal compounds in adherent tumor cells

    Egger, Alexander E.; Rappel, Christina; Jakupec, Michael A.; Hartinger, Christian G.; Heffeter, Petra; Keppler, Bernhard K.

    2009-01-01

    Cellular uptake is being widely investigated in the context of diverse biological activities of metal compounds on the cellular level. However, the applied techniques differ considerably, and a validated methodology is not at hand. Therefore, we have varied numerous aspects of sample preparation of the human colon carcinoma cell line SW480 exposed in vitro to the tumor-inhibiting metal complexes cisplatin and indazolium trans-[tetrachlorobis(1H-indazole)ruthenate(iii)] (KP1019) prior to analy...

  10. Distribution of actinide elements in sediments: leaching studies

    Previous investigations have shown that Fe and Mn oxides and organic matter can significantly influence the behavior of Pu and other actinides in the environment. A sequential leaching procedure has been developed in order to investigate the solid phase distribution of the actinides in riverine and marine sediments. Seven different sedimentary fractions are defined by this leaching experiment: an exchangeable metals fraction, an organic fraction, a carbonate fraction, a Mn oxide fraction, an amorphous Fe fraction, a crystalline Fe oxide fraction and a lattice-held or residual fraction. There is also the option of including a metal sufide fraction. A preliminary experiment, analyzing only the metals and not the actinide elements, indicates that this leaching procedure (with some modifications) is a viable procedure. The subsequent data should result in information concerning the geochemical history and behavior of these actinide elements in the environment

  11. Research in actinide chemistry

    1991-01-01

    This report contains research results on studies of inorganic and organic complexes of actinide and lanthanide elements. Special attention is given to complexes of humic acids and to spectroscopic studies.

  12. Actinide coordination chemistry: towards the limits of the periodic table

    Actinide elements represent a distinct chemical family at the bottom of the periodic table. Among the major characteristics of this 14 element family is their high atomic numbers and their radioactivity. Actinide chemistry finds its roots in the history of the 20. century and plays a very important role in our contemporary world. Energetic as well as technical challenges are facing the development of nuclear energy. In this pedagogical introduction to actinide chemistry, the authors draw a comparison between the actinides family and the chemistry of two other families, lanthanides and transition metals. This article focuses on molecular and aqueous chemistry. It has been based on class notes aiming to present an overview of the chemical diversity of actinides, and its future challenges for modern science. (authors)

  13. Oligomer and mixed-metal compounds potential multielectron transfer catalysts

    Rillema, D.P.

    1992-03-30

    Projects related to the design and characterization of multimetallic complexes has proceeded forward with a number of achievements. First, photoprocesses in hydrogel matrices lead to the conclusion that cationic metallochromophores could be ion exchanged into a hydrogel matrix ({kappa}-carageenan) and substantial photocurrents could be generated. Second, X-ray structures of Ru(bpy){sub 3}{sup 2+}, Ru(bpm){sub 3}{sup 2+} and Ru(bpz){sub 3}{sup 2+}, where bpy is 2,2{prime}-bipyridine, bpm is 2,2{prime}-bipyrimidine and bpz is 2,2{prime}-bipyrizine, were obtained and revealed similar Ru-N bond distances in each complex even though their {sigma}-donor and {pi}-acceptor character differ markedly. The structure parameters are expected to provide theoreticians with the information needed to probe the electronic character of the molecular systems and provide us with direction in our synthetic strategies. Third, a copper(I) complex was synthesized with a dimeric-ethane-bridged, 1,10-phenanthroline ligand that resulted in isolation of a bimetallic species. The copper(I) complex did luminesce weakly, suggesting that the dimer possesses potential electron transfer capability. Fourth, the photophysical properties of (Re(CO){sub 4}(L-L)){sup +}, where L-L = heterocyclic diimine ligands, and Pt(bph)X{sub 2}, where bph = the dianion of biphenyl and X = CH{sub 3}CN, py or ethylendiamine, displayed luminescence at high energy and underwent excited-state electron transfer. Such high energy emitters provide high driving forces for undergoing excited-state electron transfer. Fifth, both energy and electron transfer were observed in mixed-metal complexes bridged by 1,2-bis(2,2{prime}-bipyridyl-4{prime}-yl) ethane.

  14. The ALMR actinide burning system

    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. The role of a solvent in synthesis of organometallic and metal-containing compounds by direct oxidation of metal

    Solubility of magnesium, zinc and cadmium iodides in some organic solvents at 293 K was determined to study the role of solvent in the synthesis of organometallic and metal-containing compounds by direct oxidation of metal in the medium of polar solvent. On the basis of comparison of the experimental data on solubility and published data on oxidation rate of magnesium, zinc and cadmium by halogenated hydrocarbons in polar solvents it was shown that solubility of the reaction products in the reactive mixture is not responsible for the process rate in the systems studied

  16. Subsurface Biogeochemistry of Actinides

    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).

  17. Use of high gradient magnetic separation for actinide application

    Decontamination of materials such as soils or waste water that contain radioactive isotopes, heavy metals, or hazardous components is a subject of great interest. Magnetic separation is a physical separation process that segregates materials on the basis of magnetic susceptibility. Because the process relies on physical properties, separations can be achieved while producing a minimum of secondary waste. Most traditional physical separation processes effectively treat particles larger than 70 microns. In many situations, the radioactive contaminants are found concentrated in the fine particle size fraction of less than 20 microns. For effective decontamination of the fine particle size fraction most current operations resort to chemical dissolution methods for treatment. High gradient magnetic separation (HGMS) is able to effectively treat particles from 90 to ∼0.1 micron in diameter. The technology is currently used on the 60 ton per hour scale in the kaolin clay industry. When the field gradient is of sufficiently high intensity, paramagnetic particles can be physically captured and separated from extraneous nonmagnetic material. Because all actinide compounds are paramagnetic, magnetic separation of actinide containing mixtures is feasible. The advent of reliable superconducting magnets also makes magnetic separation of weakly paramagnetic species attractive. HGMS work at Los Alamos National Laboratory (LANL) is being developed for soil remediation, waste water treatment and treatment of actinide chemical processing residues. LANL and Lockheed Environmental Systems and Technologies Company (LESAT) have worked on a co-operative research and development agreement (CRADA) to develop HGMS for radioactive soil decontamination. The program is designed to transfer HGMS from the laboratory and other industries for the commercial treatment of radioactive contaminated materials. 9 refs., 2 figs., 2 tabs

  18. Adsorption of volatile organic compounds in porous metal-organic frameworks functionalized by polyoxometalates

    The functionalization of porous metal-organic frameworks (Cu3(BTC)2) was achieved by incorporating Keggin-type polyoxometalates (POMs), and further optimized via alkali metal ion-exchange. In addition to thermal gravimetric analysis, IR, single-crystal X-ray diffraction, and powder X-ray diffraction, the adsorption properties were characterized by N2 and volatile organic compounds (VOCs) adsorption measurements, including short-chain alcohols (C<4), cyclohexane, benzene, and toluene. The adsorption enthalpies estimated by the modified Clausius-Clapeyron equation provided insight into the impact of POMs and alkali metal cations on the adsorption of VOCs. The introduction of POMs not only improved the stability, but also brought the increase of adsorption capacity by strengthening the interaction with gas molecules. Furthermore, the exchanged alkali metal cations acted as active sites to interact with adsorbates and enhanced the adsorption of VOCs. - Graphical Abstract: The adsorption behavior of volatile organic compounds in porous metal-organic frameworks functionalized by polyoxometalates has been systematically evaluated. Highlights: → Functionalization of MOFs was achieved by incorporating Keggin-type POMs. → Introduction of POMs improved the thermal stability and adsorption capacity. → Alkali metal ion-exchange modified the inclusion state and also enhanced the adsorption. → Adsorption enthalpies were estimated to study the impact of POMs and alkali metal cations.

  19. Structure and catalytic properties of metal β-diketonate complexes with oxygen-containing compounds

    The results of researches published in recent 15-20 years of complexes of metal β-diketonates (including Cr3+, VO2+, MoOΛ22+, Co3+, Mn3+, Ni2+, Fe3+) with oxygen-containing compounds (alcohols, glycols, phenols, hydroperoxides, aldehydes, esters, etc.) playing an important role in catalytic processes of oxidation, addition, polymerization and copolymerization are reviewed. Data on the nature of chemical bond of oxygen-containing reacting agents with metal β-diketonates, on structure of metal β-diketonate complexes with oxygen-containing reacting agents and thermodynamics of complexing as well as on activation of reacting agents in complexes and catalytic properties of metal β-diketonates are discussed. Stored materials make it possible to exercise directed control of metal β-diketonate activity

  20. Structure, production and properties of high-melting compounds and systems (hard materials and hard metals)

    The report contains contributions by various authors to the research project on the production, structure, and physical properties of high-melting compounds and systems (hard metals and hard materials), in particular WC-, TaC-, and MoC-base materials. (GSCH)

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

    Harrison, Stephen [SIMBOL Materials

    2014-04-30

    Executive Summary Simbol Materials studied various methods of extracting valuable minerals from geothermal brines in the Imperial Valley of California, focusing on the extraction of lithium, manganese, zinc and potassium. New methods were explored for managing the potential impact of silica fouling on mineral extraction equipment, and for converting silica management by-products into commercial products.` Studies at the laboratory and bench scale focused on manganese, zinc and potassium extraction and the conversion of silica management by-products into valuable commercial products. The processes for extracting lithium and producing lithium carbonate and lithium hydroxide products were developed at the laboratory scale and scaled up to pilot-scale. Several sorbents designed to extract lithium as lithium chloride from geothermal brine were developed at the laboratory scale and subsequently scaled-up for testing in the lithium extraction pilot plant. Lithium The results of the lithium studies generated the confidence for Simbol to scale its process to commercial operation. The key steps of the process were demonstrated during its development at pilot scale: 1. Silica management. 2. Lithium extraction. 3. Purification. 4. Concentration. 5. Conversion into lithium hydroxide and lithium carbonate products. Results show that greater than 95% of the lithium can be extracted from geothermal brine as lithium chloride, and that the chemical yield in converting lithium chloride to lithium hydroxide and lithium carbonate products is greater than 90%. The product purity produced from the process is consistent with battery grade lithium carbonate and lithium hydroxide. Manganese and zinc Processes for the extraction of zinc and manganese from geothermal brine were developed. It was shown that they could be converted into zinc metal and electrolytic manganese dioxide after purification. These processes were evaluated for their economic potential, and at the present time Simbol

  2. Ionic conduction in alkali metal doped ZnFe/sub 2/O/sub 4/ compound

    Zinc ferric oxide (ZnFe/sub 2/O/sub 4/) has been synthesized by liquid phase chemical reaction from aqueous mixture of zinc chloride and ferric chloride in sodium hydroxide (4N) solution and effect of alkali metal on electrical characteristics was explored. The well characterized powder was pressed into pellets and dried at 80 degree C. Samples with alkali metal concentrations 10-100 ppm have been investigated to I-V measurements. The conductivity of pure compound (10-/sub 2/omega-cm)/sup-1/) lies in the semiconductor range but due to alkali metal doping the compound shows ionic conduction at room temperature. The ionic conduction is found to be increased as the dopant concentration increases.(author)

  3. A Initio Lcao Electronic Structure Calculations of Layered Transition Metal Compounds.

    Dawson, William G.

    1987-09-01

    Available from UMI in association with The British Library. In this work the electronic structure of three systems of layered transition metal compounds are examined using an ab initio tight binding (LCAO) method using the Xalpha exchange/correlation approximation: group VI ditellurides, group IV trichalcogenides and quaternary copper oxide defect-perovskites. A chemical pseudopotential argument is presented in order to justify the use of a small basis set of atomic orbitals. The group VI transition metal compounds MoTe_2 and WTe _2 show strong metal-metal interactions and MoTe_2 undergoes an unusual phase transition with the lattice parameter perpendicular to the layers decreasing with increasing temperature. The group IV transition metal trichalcogenides provide a useful series for study due to their quasi-1-dimensional character and the occurrence of two closely related structural variants. The atypical compound ZrTe_3 is given special attention because of its apparent semimetallic nature. The final group of compounds studied are the high Tc superconducting ceramics Ba-La-Cu-O and Ba-Y-Cu-O. The technological importance of compounds with zero resistance and showing the Meissner effect (expelling magnetic fields) above liquid nitrogen temperatures and the, as yet, undefined nature of the mechanism of superconductivity stresses the need to carefully examine the electronic structure of these materials. The role of oxygen vacancies, the charge state of the copper ions and the possibility of structural phase transitions are some of the topics considered here. The use of an atomic-orbital basis allows a comparatively straightforward description of the chemical bonding in a crystal--especially useful when the unit cell contains a large number of atoms.

  4. Treatment of actinide-containing organic waste

    A method has been developed for reducing the volume of organic wastes and recovering the actinide elements. The waste, together with gaseous oxygen (air) is introduced into a molten salt, preferably an alkali metal carbonate such as sodium carbonate. The bath is kept at 7500 - 10000C and 0.5 - 10 atm to thermally decompose and partially oxidize the waste, while substantially reducing its volume. The gaseous effluent, mainly carbon dioxide and water vapour, is vented to the atmosphere through a series of filters to remove trace amounts of actinide elements or particulate alkali metal salts. The remaining combustion products are entrained in the molten salt. Part of the molten salt-combustion product mixture is withdrawn and mixed with an aqueous medium. Insoluble combustion products are then removed from the aqueous medium and are leached with a mixture of hydrofluoric and nitric acids to solubilize the actinide elements. The actinide elements are easily recovered from the acid solution using conventional techniques. (DN)

  5. Hydration Gibbs free energies of open and closed shell trivalent lanthanide and actinide cations from polarizable molecular dynamics.

    Marjolin, Aude; Gourlaouen, Christophe; Clavaguéra, Carine; Ren, Pengyu Y; Piquemal, Jean-Philip; Dognon, Jean-Pierre

    2014-10-01

    The hydration free energies, structures, and dynamics of open- and closed-shell trivalent lanthanide and actinide metal cations are studied using molecular dynamics simulations (MD) based on a polarizable force field. Parameters for the metal cations are derived from an ab initio bottom-up strategy. MD simulations of six cations solvated in bulk water are subsequently performed with the AMOEBA polarizable force field. The calculated first-and second shell hydration numbers, water residence times, and free energies of hydration are consistent with experimental/theoretical values leading to a predictive modeling of f-elements compounds. PMID:25296890

  6. In-situ mineralization of actinides with phytic acid

    A new approach to the remediation of actinide contamination is described. A hydrolytically unstable organophosphorus compound, phytic acid, is introduced into the contaminated environment. In the short term (up to several hundred years), phytate acts as a cation exchanger to absorb mobile actinide ions from ground waters. Ultimately, phytate decomposes to release phosphate and promote the formation of insoluble phosphate mineral phases, considered an ideal medium to immobilize actinides, as it forms compounds with the lowest solubility of any candidate mineral species. This overview will discuss the rate of hydrolysis of phytic acid, the formation of lanthanide/actinide phosphate mineral forms, the cation exchange behavior of insoluble phytate, and results from laboratory demonstration of the application to soils from the Fernald site

  7. Low-temperature properties of rare-earth and actinide iron phosphide compounds MFe4P/sub 12/ (M = La, Pr, Nd, and Th)

    The low-temperature properties of MFe4P/sub 12/ (M = La, Pr, Nd, and Th) single crystals have been studied by means of electrical-resistivity, magnetization, specific-heat, and magnetoresistivity measurements. Superconductivity among these compounds is known to occur only in LaFe4P/sub 12/, which has a superconducting transition temperature T/sub c/ of ∼4 K. The compounds PrFe4P/sub 12/ and NdFe4P/sub 12/ display features that suggest the occurrence of antiferromagnetic ordering below ∼6.2 K and ferromagnetic ordering below ∼2 K, respectively. Isothermal magnetization curves for PrFe4P/sub 12/ below 6 K reveal a spin-flop or metamagnetic transition

  8. The Eighth International Ural Seminar Radiation damage physics of metals and alloys. Abstracts

    The book includes abstracts of the Eight International Ural Seminar Radiation damage physics of metals and alloys (Snezhinsk, 23 February - 1 March, 2009). Reports on the characteristics of point defects in different alloys and compounds including Fe-Cr(Ni) systems are presented. Effects of irradiation and strong deformation on changing microstructure and properties of metals and alloys are discussed. Gaseous impurities in irradiated metals and alloys, materials problems in nuclear and thermonuclear powers, physical properties and atomic defects in actinides and actinide alloys, and model analogs are discussed. Reports on physics of radiation effects in magnetics, superconductors, semiconductors and nonconductors, as well as technology and experimental technique, ion implantation are performed

  9. New spintronic superlattices composed of half-metallic compounds with zinc-blende structure

    Fong, C. Y.; Qian, M. C.

    2004-12-01

    The successful growth of zinc-blende half-metallic compounds, namely CrAs and CrSb, in thin film forms offers a new direction to search for novel spintronic materials. By using a well documented first-principles algorithm, the VASP code, we predict the electronic and magnetic properties of superlattices made of these exciting half-metallic materials. Not only are the superlattices constructed with two of the half-metallic compounds (CrAs/MnAs) but also they are modelled to combine with both a III-V (GaAs-MnAs/CrAs/GaAs) and a IV-IV (MnC/SiC) semiconductor. We investigate variable thicknesses for the combinations. For every case, we find the equilibrium lattice constant as well as the lattice constant at which the superlattice exhibits the half-metallic properties. For CrAs/MnAs, the half-metallic properties are presented and the magnetic moments are shown to be the sum of the moments for MnAs and CrAs. The half-metallic properties of GaAs-MnAs/CrAs/GaAs are found to be crucially dependent on the completion of the d-p hybridization. The magnetic properties of MnC/SiC are discussed with respect to the properties of MnC.

  10. New spintronic superlattices composed of half-metallic compounds with zinc-blende structure

    Fong, C Y; Qian, M C [Department of Physics, University of California, Davis, CA 95616-8677 (United States)

    2004-12-08

    The successful growth of zinc-blende half-metallic compounds, namely CrAs and CrSb, in thin film forms offers a new direction to search for novel spintronic materials. By using a well documented first-principles algorithm, the VASP code, we predict the electronic and magnetic properties of superlattices made of these exciting half-metallic materials. Not only are the superlattices constructed with two of the half-metallic compounds (CrAs/MnAs) but also they are modelled to combine with both a III-V (GaAs-MnAs/CrAs/GaAs) and a IV-IV (MnC/SiC) semiconductor. We investigate variable thicknesses for the combinations. For every case, we find the equilibrium lattice constant as well as the lattice constant at which the superlattice exhibits the half-metallic properties. For CrAs/MnAs, the half-metallic properties are presented and the magnetic moments are shown to be the sum of the moments for MnAs and CrAs. The half-metallic properties of GaAs-MnAs/CrAs/GaAs are found to be crucially dependent on the completion of the d-p hybridization. The magnetic properties of MnC/SiC are discussed with respect to the properties of MnC.

  11. Hydrolytic stability of heavy metal compounds in fly ash of a heat power plant

    Ash and slag from solid fuels are utilized widely in building materials and road surfaces, and in agriculture for soil acidulation. For all these uses it is important to know the amount and form of heavy metal compounds contained in ash and their likely behavior when ash and slag wastes are utilized. Studying the behavior of heavy metals in ash residues at contact with water media is important also because, for most trace elements, the authors lack experimental data that would enable us to predict their behavior after prolonged storage and industrial utilization. The present paper describes a study of lixiviation (at various pH in static conditions) of heavy metals form fly ash obtained by burning Azeisk coal. Homogenized ash selected from electric filter sections 1-4 was used, which has the following composition (%): SiO2 59.8; Al2O3; Fe23O3 7.1; CaO 4.1; MgO 1.3; other 2.8. In a neutral medium, Ni, Cu, Zn, Pb, and Mn lixiviation was slight, amounting to 0.01-0.4%. During coal combustion, these elements apparently form compounds that are slightly soluble in water, although it is also possible that ash retains high adsorptivity for heavy metals. As a result, in these conditions the reverse process of sorption of heavy metals from the solution by fly ash is also possible, which would reduce the heavy metal concentration in the solution

  12. New spintronic superlattices composed of half-metallic compounds with zinc-blende structure

    The successful growth of zinc-blende half-metallic compounds, namely CrAs and CrSb, in thin film forms offers a new direction to search for novel spintronic materials. By using a well documented first-principles algorithm, the VASP code, we predict the electronic and magnetic properties of superlattices made of these exciting half-metallic materials. Not only are the superlattices constructed with two of the half-metallic compounds (CrAs/MnAs) but also they are modelled to combine with both a III-V (GaAs-MnAs/CrAs/GaAs) and a IV-IV (MnC/SiC) semiconductor. We investigate variable thicknesses for the combinations. For every case, we find the equilibrium lattice constant as well as the lattice constant at which the superlattice exhibits the half-metallic properties. For CrAs/MnAs, the half-metallic properties are presented and the magnetic moments are shown to be the sum of the moments for MnAs and CrAs. The half-metallic properties of GaAs-MnAs/CrAs/GaAs are found to be crucially dependent on the completion of the d-p hybridization. The magnetic properties of MnC/SiC are discussed with respect to the properties of MnC

  13. An atomic beam source for actinide elements: concept and realization

    For ultratrace analysis of actinide elements and studies of their atomic properties with resonance ionization mass spectroscopy (RIMS), efficient and stable sources of actinide atomic beams are required. The thermodynamics and kinetics of the evaporation of actinide elements and oxides from a variety of metals were considered, including diffusion, desorption, and associative desorption. On this basis various sandwich-type filaments were studied. The most promising system was found to consist of tantalum as the backing material, an electrolytically deposited actinide hydroxide as the source of the element, and a titanium covering layer for its reduction to the metal. Such sandwich sources were experimentally proven to be well suited for the production of atomic beams of plutonium, curium, berkelium and californium at relatively low operating temperatures and with high and reproducible yields. (orig.)

  14. Electronic structure and properties of rare earth and actinide intermetallics

    There are 188 contributions, experimental and theoretical, a few on rare earth and actinide elements but mostly on rare earth and actinide intermetallic compounds and alloys. The properties dealt with include 1) crystal structure, 2) magnetic properties and magnetic structure, 3) magnetic phase transformations and valence fluctuations, 4) electrical properties and superconductivity and their temperature, pressure and magnetic field dependence. A few papers deal with crystal growth and novel measuring methods. (G.Q.)

  15. Actinide isotopic analysis systems

    This manual provides instructions and procedures for using the Lawrence Livermore National Laboratory's two-detector actinide isotope analysis system to measure plutonium samples with other possible actinides (including uranium, americium, and neptunium) by gamma-ray spectrometry. The computer program that controls the system and analyzes the gamma-ray spectral data is driven by a menu of one-, two-, or three-letter options chosen by the operator. Provided in this manual are descriptions of these options and their functions, plus detailed instructions (operator dialog) for choosing among the options. Also provided are general instructions for calibrating the actinide isotropic analysis system and for monitoring its performance. The inventory measurement of a sample's total plutonium and other actinides content is determined by two nondestructive measurements. One is a calorimetry measurement of the sample's heat or power output, and the other is a gamma-ray spectrometry measurement of its relative isotopic abundances. The isotopic measurements needed to interpret the observed calorimetric power measurement are the relative abundances of various plutonium and uranium isotopes and americium-241. The actinide analysis system carries out these measurements. 8 figs

  16. Heavy-metal compounds in the environment of the Zagorsk pumped-storage station region

    The Zagorsk pumped-storage station (ZPSS) is being constructed in a rather developed area. Pollution of the environment by compounds of metals is, in particular, a consequence. The tasks of this investigation included: the establishment of the main sources of pollution of terrestrial and aquatic ecosystems by metal compounds in the region of construction of the ZPSS; determination of the level of content of these substances in various components of the landscape; and evaluation of the effect of regulating the Kun'ya River on processes of migration and accumulation of heavy metals in aquatic ecosystems. In conformity with these tasks, a comprehensive geochemical study was performed in 1990-1991 of the drainage basin of the Kun'ya River, the results of which are presented here. Samples were collected of soil, forest litter, snow, bottom sediments, and surface waters. The investigation showed that the main sources of pollution of the aquatic environment in the ZPSS construction region by heavy-metal compounds were surface runoff from developed territories and insufficiently treated industrial wastewaters. 5 refs., 2 figs., 4 tabs

  17. Oxidation of oil sulfur compounds to sulfones under foam-emulsion conditions in presence of metals

    Oxidation of sulfur compounds in diesel fraction, as well as of sulfoxide concentrate, by hydrogen peroxide to sulfones under foam-emulsion conditions in the presence of variable valency metal (V, Mo, W, Ti, Cr) compounds has been studied. It is ascertained that organic derivatives of molybdenum and vanadium are effective catalysts of sulfides to sulfones. The best results are obtained in the presence of water soluble ethylene glycolate of molybdenum. The mechanisms of chemical reactions occurring in the process is considered. Refs. 10

  18. Optical properties across the insulator to metal transitions in vanadium oxide compounds

    Perucchi, A; Baldassarre, L [Sincrotrone Trieste S.C.p.A., Area Science Park, I-34012 Basovizza, Trieste (Italy); Postorino, P; Lupi, S, E-mail: andrea.perucchi@elettra.trieste.i [CNR-INFM Coherentia and Dipartimento di Fisica, Universita di Roma ' La Sapienza' , Piazzale Aldo Moro 2, I-00185 Roma (Italy)

    2009-08-12

    We review the optical properties of three vanadium oxide compounds V{sub 2}O{sub 3}, VO{sub 2} and V{sub 3}O{sub 5}, belonging to the so-called Magneli phase. Their electrodynamics across a metal to insulator transition is investigated as a function of both temperature and pressure. We analyse thoroughly the optical results, with a special emphasis on the infrared spectral weight. This allows us to discuss the nature of the mechanisms driving the phase transitions in the three compounds, pointing out the role of electron-electron and electron-phonon interactions in the various cases. (topical review)

  19. Optical properties across the insulator to metal transitions in vanadium oxide compounds

    We review the optical properties of three vanadium oxide compounds V2O3, VO2 and V3O5, belonging to the so-called Magneli phase. Their electrodynamics across a metal to insulator transition is investigated as a function of both temperature and pressure. We analyse thoroughly the optical results, with a special emphasis on the infrared spectral weight. This allows us to discuss the nature of the mechanisms driving the phase transitions in the three compounds, pointing out the role of electron-electron and electron-phonon interactions in the various cases. (topical review)

  20. Optical properties across the insulator to metal transitions in vanadium oxide compounds.

    Perucchi, A; Baldassarre, L; Postorino, P; Lupi, S

    2009-08-12

    We review the optical properties of three vanadium oxide compounds V(2)O(3), VO(2) and V(3)O(5), belonging to the so-called Magnéli phase. Their electrodynamics across a metal to insulator transition is investigated as a function of both temperature and pressure. We analyse thoroughly the optical results, with a special emphasis on the infrared spectral weight. This allows us to discuss the nature of the mechanisms driving the phase transitions in the three compounds, pointing out the role of electron-electron and electron-phonon interactions in the various cases. PMID:21693963

  1. Stability and electronic structure of Zr-based ternary metallic glasses and relevant compounds

    The electronic structure of the Zr-based metallic glasses has been investigated by theoretical and experimental approaches. One approach is band calculations of the Zr2Ni (Zr66.7Ni33.3) compound to investigate the electronic structure of the Zr66.7Ni33.3 metallic glass (ΔT x = 0 K) of which the local atomic structure is similar to that of the Zr2Ni compound. The other is photoemission spectroscopy of the Zr50Cu35Al15 bulk metallic glass (BMG) (ΔT x = 69 K). Here ΔT x = T x - T g where T x and T g are crystallization and glass transition temperature, respectively. Both results and previous ones on the Zr55Cu30Ni5Al10 BMG indicate that there is a pseudogap at the Fermi level in the electronic structure of these Zr-based metallic glasses, independent of the value of the ΔT x. This implies that the pseudogap at the Fermi level is one of the factors that stabilize the glass phase of Zr-based metallic glasses

  2. Radiochemistry and actinide chemistry

    The analysis of trace amounts of actinide elements by means of radiochemistry, is discussed. The similarities between radiochemistry and actinide chemistry, in the case of species amount by cubic cm below 1012, are explained. The parameters which allow to define what are the observable chemical reactions, are given. The classification of radionuclides in micro or macrocomponents is considered. The validity of the mass action law and the partition function in the definition of the average number of species for trace amounts, is investigated. Examples illustrating the results are given

  3. Generation, detection and characterization of gas-phase transition metal aggregates and compounds

    The goal of our research is to employ spectroscopic techniques to characterize the bound portions of the potential energy surface (PES) for chemical systems involving diatomic and triatomic transition metal molecules. The approach incorporates the generation and isolation of new metal compounds via supersonic laser ablation molecular beam techniques. Detection and characterization is achieved using high resolution dye laser induced fluorescence spectroscopy. A major objective is to produce information which can be compared to theoretical predictions and thereby provide guidelines and insight into the development of reaction models

  4. Non-aqueous synthesis of isotropic and anisotropic actinide oxide nano-crystals

    In summary, a non-aqueous method based on the 'heating- up' approach was developed to prepare well-defined and non-agglomerated actinide (Th, U) oxide NCs. To the best of our knowledge this is the first time that such a method has been successfully applied to prepare ThO2 NCs. Surprisingly, it has been shown that the experimental conditions well suited for the formation of uranium oxide NCs do not allow the formation of thorium oxide NCs. Our results show that for a given organic medium, the nature of the actinide precursor and/or the nature of the actinide centre drastically influence the reactivity and hence the characteristics of the final actinide oxide NCs. This work proves the feasibility of the controlled synthesis of actinide oxide NCs by a non-aqueous approach. It contributes to our understanding of the controlled synthesis of actinide oxide NCs and prepares the ground for the synthesis of transuranium-based (particularly Np and Pu) nano-objects. Even if the controlled synthesis of nano-objects of actinide compounds is not an end in itself, it is the cornerstone of investigation into the nano-world of actinides. Indeed, successful investigations of the size and shape effects on the properties of actinide compounds depends on our capability to synthesize well-defined actinide-based nano-objects. Without any doubt, we are at least one decade late compared to what has been (and is still) done with stable elements. (authors)

  5. Electrochemical decontamination of metallic wastes contaminated with uranium compounds in a neutral salt electrolyte

    Choi, W. K.; Yang, Y. M.; Jung, C. H.; Won, H. J.; Oh, W. Z.; Park, J. H. [KAERI, Taejon (Korea, Republic of)

    2003-07-01

    Electrochemical decontamination process has been applied for recycle or self disposal with authorization of large amount of metallic wastes contaminated with uranium compounds such as UO{sub 2}, ammonium uranyl carbonate (AUC), ammonium di-uranate (ADU), and uranyl nitrate (UN) with tributylphosphate (TBP) and dodecane, which are generated by dismantling the contaminated system components and equipment of a retired uranium conversion plant in Korea Atomic Energy Research Institute (KAERI). Electrochemical decontamination for metallic wastes contaminated with uranium compounds was evaluated through the experiments on the electrolytic dissolution of stainless steel as the material of the system components in neutral concentration of electrolyte on the dissolution of the materials were evaluated. Decontamination performance tests using the specimens taken from a uranium conversion plant were quite successful with the application electrochemical decontamination conditions obtained through the basic studies on the electrolytic dissolution of structural material of the system components.

  6. Technology Development and Production of Certain Chemical Platinum Metals Compounds at JSC "Krastsvetmet"

    ILYASHEVICH V.D.; PAVLOVA E.I.; KORITSKAYA N.G.; MAMONOV S.N.; SHULGIN D.R.; MALTSEV E.V.

    2012-01-01

    In recent years JSC "Krastsvetmet" has successfully developed the production of chemically pure compounds of precious metals.Currently methods have been developed and facilities have been provided for industrial production of the following platinum metals compounds:- Rhodium (Ⅲ) chloride hydrate,rhodium (Ⅲ) chloride solution,rhodium ( Ⅲ) nitrate solution,rhodium ( Ⅲ)iodide,rhodium ( Ⅲ) sulfate,hydrated rhodium ( Ⅲ) oxide,ammonium hexachlororodiate,rhodium ( Ⅲ)phosphate solution,rhodium electrolytes;Iridium (Ⅳ) chloride hydrate,iridium (Ⅲ) chloride hydrate,ammonium hexachloroiridate (Ⅳ),hexachloriridium acid solution,hexachloriridium crystalline acid;- Ruthenium (Ⅲ) chloride hydrate,ruthenium (Ⅳ) hydroxide chloride,ruthenium (Ⅳ) hydroxide chloride solution,ammonium hexachlororuthenate,ruthenium (Ⅲ) chloride solution,potassium,diaquaoctachloronitrido diruthenate.The quality of the production meets the requirements of Russian and foreign consumers.

  7. A standardized evaluation of artifacts from metallic compounds during fast MR imaging

    Murakami, Shumei; Verdonschot, Rinus G; Kataoka, Miyoshi;

    2016-01-01

    OBJECTIVE: Metallic compounds present in the oral and maxillofacial regions (OMR) cause large artifacts during MR scanning. We quantitatively assessed these artifacts embedded within a phantom according to standards set by the American Society for Testing and Materials (ASTM). MATERIALS AND METHODS...... according to the ASTM-F2119 standard and artifact volumes were assessed using OsiriX MD software Results: Tukey-Kramer post-hoc tests were used for statistical comparisons. For most materials, scanning sequences eliciting artifact volumes in the following (ascending) order FSE-T1/FSE-T2 ... plane (i.e. a circular pattern for axial plane and a "clover-like" pattern for sagittal plane). CONCLUSION: The availability of standardized information on artifact size and configuration during MR imaging will enhance diagnosis when faced with metallic compounds in the OMR....

  8. Electrochemical decontamination of metallic wastes contaminated with uranium compounds in a neutral salt electrolyte

    Electrochemical decontamination process has been applied for recycle or self disposal with authorization of large amount of metallic wastes contaminated with uranium compounds such as UO2, ammonium uranyl carbonate (AUC), ammonium di-uranate (ADU), and uranyl nitrate (UN) with tributylphosphate (TBP) and dodecane, which are generated by dismantling the contaminated system components and equipment of a retired uranium conversion plant in Korea Atomic Energy Research Institute (KAERI). Electrochemical decontamination for metallic wastes contaminated with uranium compounds was evaluated through the experiments on the electrolytic dissolution of stainless steel as the material of the system components in neutral concentration of electrolyte on the dissolution of the materials were evaluated. Decontamination performance tests using the specimens taken from a uranium conversion plant were quite successful with the application electrochemical decontamination conditions obtained through the basic studies on the electrolytic dissolution of structural material of the system components

  9. X-ray absorption to determine the metal oxidation state of transition metal compounds

    Jiménez-Mier, J.; Olalde-Velasco, P.; Carabalí-Sandoval, G.; Herrera-Pérez, G.; Chavira, E.; Yang, W.-L.; Denlinger, J.

    2013-07-01

    We present three examples where x-ray absorption at the transition metal L2,3 edges is used to investigate the valence states of various strongly correlated (SC) and technological relevant materials. Comparison with ligand field multiplet calculations is needed to determine the metal oxidation states. The examples are CrF2, the La1-xSrxCoO3 family and YVO3. For CrF2 the results indicate a disproportionation reaction that generates Cr+, Cr2+ and Cr3+ in different proportions that can be quantified directly from the x-ray spectra. Additionally, it is shown that Co2+ is present in the catalytic La1-xSrxCoO3 perovskite family. Finally, surface effects that change the vanadium valence are also found in YVO3 nanocrystals.

  10. Apoptosis induction in human lymphocytes after in vitro exposure to cobalt/hard metal compounds

    Full text: An increased risk of lung cancer is associated with occupational exposure to mixtures of cobalt metal (Co) and tungsten carbide (WC) particles, but apparently not when exposure is to cobalt alone. The mechanism for this increased cancer risk is not fully understood. The evaluation of the in vitro genotoxic effects in lymphocytes exposed to varying cobalt species demonstrated that the WC-Co hard metal mixture is more genotoxic (DNA damage, chromosome/genome mutations) than metallic Co alone. WC alone was not genotoxic. Thus, WC-Co represents a specific (geno)toxic entity. In order to assess the survival of human lymphocytes after in vitro exposure to metallic Co, CoCl2, WC and the WC-Co mixture, two apoptosis/necrosis detection methods were applied (annexin V staining and flow cytometry). Annexin-V staining of early apoptotic cells demonstrated a dose- and time dependent induction of apoptosis by metallic Co, CoCl2, WC and the WC-Co mixture. The time course of the process varied according to the metal species tested. Metallic Co and CoCl2 caused a gradually increasing frequency of apoptotic cells with time (up to 24 h). WC-induced apoptosis displayed a typical 6 hour peak, which was not the case for the WC-Co mixture or for Co. Apoptosis induction by the WC-Co mixture was intermediate between that induced by Co and WC separately. Analysis of propidium iodide stained cells by flow cytometry was performed as a later marker for apoptosis induction. Preliminary data indicate similar tendencies of apoptosis induction as those detected by annexin-V. Identification of the apoptotic pathway triggered by the metal compounds was studied by inhibition of the ceramide-apoptosis pathway by fumonisin causing reduction of apoptosis induction for all compounds, but strongest after 6 hour exposure to WC. The use of specific caspase inhibitors will allow to further elucidate the different pathways involved. The current data demonstrating in vitro the apoptosis induction by

  11. Thermodynamic Properties and Mixing Thermodynamic Parameter of Binary Metallic Melt Involving Compound Formation

    ZHANG Jian

    2005-01-01

    Based on the coexistence theory of metallic melts involving compound formation,the theoretical cal culation equations of mixing thermodynamic parameters are established by giving up some empirical parameters in the associated solution model.For Fe-Al,Mn-Al and Ni-Al,the calculated results agree well with the experimental values,testifying that these equations can exactly embody mixing thermodynamic characteristics of these melts.

  12. μSR-studies of magnetic properties of metallic rare earth compounds

    Positive muons can probe the magnitude and the time dependence of the magnetic field at interstitial sites in condensed matter. Thus the relatively new techniques of muons spin rotation and muon spin relaxation have become unique tools for studying magnetism. After a brief introduction into the experimental method we then discuss measurements on the elemental rare earth metals and on intermetallic compounds, in particular on the cubic Laves phases REAl2

  13. Calculations of hyperfine interactions in transition metal compounds in the local density approximation

    A survey is made of some theoretical calculations of electrostatic and magnetic hyperfine interactions in transition metal compounds and complex irons. The molecular orbital methods considered are the Multiple Scattering and Discrete Variational, in which the local Xα approximation for the exchange interaction is employed. Emphasis is given to the qualitative informations, derived from the calculations, relating the hyperfine parameters to characteristics of the chemical bonds. (Author)

  14. Chemical shifts and EXAFS in some rare-earth metals and compounds

    The positions of the Lsub(111) absorption edge and accompanying Kossel and EXAFS oscillations of terbium, dysprosium and holmium in metals and compounds (acetate, carbonate, chloride, fluoride, nitrate, oxalate, oxide, phosphate and sulphate) have been measured. The chemical shifts of the main edge range from about 1 eV to about 10 eV and the EXAFS are observed up to about 150 eV. (author)

  15. Actinide recovery from pyrochemical residues

    We demonstrated a new process for recovering plutonium and americium from pyrochemical waste. The method is based on chloride solution anion exchange at low acidity, or acidity that eliminates corrosive HCl fumes. Developmental experiments of the process flow chart concentrated on molten salt extraction (MSE) residues and gave >95% plutonium and >90% americium recovery. The recovered plutonium contained 62- from high-chloride low-acid solution. Americium and other metals are washed from the ion exchange column with lN HNO3-4.8M NaCl. After elution, plutonium is recovered by hydroxide precipitation, and americium is recovered by NaHCO3 precipitation. All filtrates from the process can be discardable as low-level contaminated waste. Production-scale experiments are in progress for MSE residues. Flow charts for actinide recovery from electro-refining and direct oxide reduction residues are presented and discussed

  16. Corrosion behavior of Zr(Fe, Cr)2 metallic compounds in 500 degree C superheated steam

    Zr(Fe, Cr)2 metallic compounds with different Fe/Cr ratio of 1.75 and 4.50 were prepared by non-consumable arc melting. X-ray diffraction, electron microprobe and transmission electron microscopy were employed for analyzing the corrosion products, the composition distribution and structure morphology after corrosion test of Zr(Fe, Cr)2 metallic compound powder at 500 degree C superheated steam with different exposure time. The corrosion products are the same for Zr(Fe, Cr)2 with different Fe/Cr ratio, but the corrosion resistant is better for Fe/Cr ratio of 1.75 than that of 4.50. Cubic ZrO2 and alpha Fe(Cr) are formed at the beginning of Zr(Fe, Cr)2 oxidation, then monoclinic ZrO2 transformed from cubic ZrO2 and (Fe, Cr)3O4 are observed at the late stage of oxidation. When the segregation of iron and chromium atoms occurs during the oxidation of Zr(Fe, Cr)2 metallic compounds, the diffusion rate of iron atoms is faster than that of chromium atoms. Based on the results obtained in present work, the effect of second phase particles on the corrosion behavior of Zircaloy-4 has been discussed

  17. Trivalent metal ions based on inorganic compounds with in vitro inhibitory activity of matrix metalloproteinase 13.

    Wen, Hanyu; Qin, Yuan; Zhong, Weilong; Li, Cong; Liu, Xiang; Shen, Yehua

    2016-10-01

    Collagenase-3 (MMP-13) inhibitors have attracted considerable attention in recent years and have been developed as a therapeutic target for a variety of diseases, including cancer. Matrix metalloproteinases (MMPs) can be inhibited by a multitude of compounds, including hydroxamic acids. Studies have shown that materials and compounds containing trivalent metal ions, particularly potassium hexacyanoferrate (III) (K3[Fe(CN)6]), exhibit cdMMP-13 inhibitory potential with a half maximal inhibitory concentration (IC50) of 1.3μM. The target protein was obtained by refolding the recombinant histidine-tagged cdMMP-13 using size exclusion chromatography (SEC). The secondary structures of the refolded cdMMP-13 with or without metal ions were further analyzed via circular dichroism and the results indicate that upon binding with metal ions, an altered structure with increased domain stability was obtained. Furthermore, isothermal titration calorimetry (ITC) experiments demonstrated that K3[Fe(CN)6]is able to bind to MMP-13 and endothelial cell tube formation tests provide further evidence for this interaction to exhibit anti-angiogenesis potential. To the best of our knowledge, no previous report of an inorganic compound featuring a MMP-13 inhibitory activity has ever been reported in the literature. Our results demonstrate that K3[Fe(CN)6] is useful as a new effective and specific inhibitor for cdMMP-13 which may be of great potential for future drug screening applications. PMID:27542739

  18. Strongly correlated transition metal compounds investigated by soft X-ray spectroscopies and multiplet calculations

    Jiménez-Mier, J., E-mail: jimenez@nucleares.unam.mx [Instituto de Ciencias Nucleares, UNAM, 04510 México, DF (Mexico); Olalde-Velasco, P. [Instituto de Ciencias Nucleares, UNAM, 04510 México, DF (Mexico); The Advanced Light Source, Lawrence Berkeley Laboratory, Berkeley, CA 94720 (United States); Herrera-Pérez, G.; Carabalí -Sandoval, G. [Instituto de Ciencias Nucleares, UNAM, 04510 México, DF (Mexico); Chavira, E. [Instituto de Investigaciones en Materiales, UNAM, 04510 México, DF (Mexico); Yang, W.-L.; Denlinger, J. [The Advanced Light Source, Lawrence Berkeley Laboratory, Berkeley, CA 94720 (United States)

    2014-10-15

    Direct probe of Mott–Hubbard (MH) to charge-transfer (CT) insulator transition in the MF{sub 2} (M = Cr–Zn) family of compounds was observed by combining F K and M L X-ray emission spectra (XES). This transition is evident as a crossover of the F-2p and M-3d occupied states. By combining F K XES data with F K edge X-ray absorption (XAS) data we directly obtained values for the M-3d Hubbard energy (U{sub dd}) and the F-2p to M-3d charge-transfer energy (Δ{sub CT}). Our results are in good agreement with the Zaanen–Sawatzky–Allen theory. We also present three examples where X-ray absorption at the transition metal L{sub 2,3} edges is used to study the oxidation state of various strongly correlated transition metal compounds. The metal oxidation state is obtained by direct comparison with crystal field multiplet calculations. The compounds are CrF{sub 2}, members of the La{sub 1−x}Sr{sub x}CoO{sub 3} family, and the MVO{sub 3} (M = La and Y) perovskites.

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

    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.

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

    Fine X-ray photoelectron spectral (XPS) structure of uranium dioxide UO2 in the binding energy (BE) range 0 - ∼40 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 absolute value 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. (author)

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

    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.

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

    The study of partial oxidation of methane (POM) over bimetallic nickel- or copper-actinide oxides was undertaken. Binary intermetallic compounds of the type AnNi2 (An = Th, U) and ThCu2 were used as precursors and the products (2NiO.UO3, 2NiO.ThO2 and 2CuO.ThO2) 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 H2 and CO and stable for a period of time of ∼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/Al2O3. 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 H2-TPR, XPS and Raman analysis of the catalysts before and after reaction.

  3. APPLICABILITY OF THE MASS ACTION LAW IN COMBINATION WITH THE COEXISTENCE THEORY OF METALLIC MELTS INVOLVING COMPOUND TO BINARY METALLIC MELTS

    J. Zhang

    2002-01-01

    Based on the atomicity and molecularity as well as the consistency of thermodynamicproperties and activities of metallic melts with their structures, the coexistence the-ory of metallic melts structure involving compound has been suggested. According tothis theory, the calculating models of mass action concentrations for different binarymetallic melts have been formulated. The calculated mass action concentrations agreewell with corresponding measured activities, which confirms that the suggested theorycan reflect the structural characteristics of metallic melts involving compound and thatthe mass action law is widely applicable to this kind of metallic melts.

  4. Evolution of phenolic compounds and metal content of wine during alcoholic fermentation and storage.

    Bimpilas, Andreas; Tsimogiannis, Dimitrios; Balta-Brouma, Kalliopi; Lymperopoulou, Theopisti; Oreopoulou, Vassiliki

    2015-07-01

    Changes in the principal phenolic compounds and metal content during the vinification process and storage under modified atmosphere (50% N2, 50% CO2) of Merlot and Syrah wines, from grapes cultivated in Greece, have been investigated. Comparing the variation of metals at maceration process, with the variation of monomeric anthocyanins and flavonols, an inverse relationship was noticed, that can be attributed to complexing reactions of polyphenols with particular trace elements. Cu decreased rapidly, whereas a similar behavior that could be expected for Fe and Mn was not confirmed. Differences in the profile of anthocyanins and flavonols in the fresh Merlot and Syrah wines are reported. During 1 year of storage monomeric anthocyanins declined almost tenfold, probably due to polymerization reactions and copigmentation. Also, a decrease in flavonol glycosides and increase in the respective aglycones was observed, attributed to enzymatic hydrolysis. The concentration of total phenols and all metals remained practically constant. PMID:25704697

  5. Safety Evaluation of Osun River Water Containing Heavy Metals and Volatile Organic Compounds (VOCs) in Rats.

    Azeez, L; Salau, A K; Adewuyi, S O; Osineye, S O; Tijani, K O; Balogun, R O

    2015-01-01

    This study evaluated the pH, heavy metals and volatile organic compounds (VOCs) in Osun river water. It also evaluated its safety in rats. Heavy metals were determined by atomic absorption spectrophotometry (AAS) while VOCs were determined by gas chromatography coupled with flame ionization detector (GC-FID). Male and female rats were exposed to Osun river water for three weeks and then sacrificed. The abundance of heavy metals in Osun river followed the trend Pb > Cd > Zn > Fe > Cr > Cu while VOCs followed the trend benzene water for three weeks had increased WBC, thiobarbituric acid reactive substances (TBARS), serum proteins and serum aminotransferases. There were also significant decreases in HCT, PLT, liver aminotransferases and liver glutathione compared to the control. These results show that the pollutants in Osun river water are capable of inducing hematological imbalance and liver cell injury. The toxicity induced in blood was sex-dependent affecting female rats more than male rats. PMID:27506174

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

    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. Actinide separative chemistry

    Actinide separative chemistry has focused very heavy work during the last decades. The main was nuclear spent fuel reprocessing: solvent extraction processes appeared quickly a suitable, an efficient way to recover major actinides (uranium and plutonium), and an extensive research, concerning both process chemistry and chemical engineering technologies, allowed the industrial development in this field. We can observe for about half a century a succession of Purex plants which, if based on the same initial discovery (i.e. the outstanding properties of a molecule, the famous TBP), present huge improvements at each step, for a large part due to an increased mastery of the mechanisms involved. And actinide separation should still focus R and D in the near future: there is a real, an important need for this, even if reprocessing may appear as a mature industry. We can present three main reasons for this. First, actinide recycling appear as a key-issue for future nuclear fuel cycles, both for waste management optimization and for conservation of natural resource; and the need concerns not only major actinide but also so-called minor ones, thus enlarging the scope of the investigation. Second, extraction processes are not well mastered at microscopic scale: there is a real, great lack in fundamental knowledge, useful or even necessary for process optimization (for instance, how to design the best extracting molecule, taken into account the several notifications and constraints, from selectivity to radiolytic resistivity?); and such a need for a real optimization is to be more accurate with the search of always cheaper, cleaner processes. And then, there is room too for exploratory research, on new concepts-perhaps for processing quite new fuels- which could appear attractive and justify further developments to be properly assessed: pyro-processes first, but also others, like chemistry in 'extreme' or 'unusual' conditions (supercritical solvents, sono-chemistry, could be

  8. Actinides and rare earths complexation with adenosine phosphate nucleotides

    Organophosphorus compounds are important molecules in both nuclear industry and living systems fields. Indeed, several extractants of organophosphorus compounds (such as TBP, HDEHP) are used in the nuclear fuel cycle reprocessing and in the biological field. For instance, the nucleotides are organophosphates which play a very important role in various metabolic processes. Although the literature on the interactions of actinides with inorganic phosphate is abundant, published studies with organophosphate compounds are generally limited to macroscopic and / or physiological approaches. The objective of this thesis is to study the structure of several organophosphorus compounds with actinides to reach a better understanding and develop new specific buildings blocks. The family of the chosen molecules for this procedure consists of three adenine nucleotides mono, bi and triphosphate (AMP, adenosine monophosphate - ADP, adenosine diphosphate - ATP, adenosine triphosphate) and an amino-alkylphosphate (AEP O-phosphoryl-ethanolamine). Complexes synthesis was conducted in aqueous and weakly acidic medium (2.8-4) for several lanthanides (III) (Lu, Yb, Eu) and actinides (U (VI), Th (IV) and Am (III)). Several analytical and spectroscopic techniques have been used to describe the organization of the synthesized complexes: spectrometric analysis performed by FTIR and NMR were used to identify the functional groups involved in the complexation, analysis by ESI-MS and pH-metric titration were used to determine the solution speciation and EXAFS analyzes were performed on Mars beamline of the SOLEIL synchrotron, have described the local cation environment, for both solution and solid compounds. Some theoretical approaches of DFT were conducted to identify stable structures in purpose of completing the experimental studies. All solid complexes (AMP, ADP, ATP and AEP) have polynuclear structures, while soluble ATP complexes are mononuclear. For all synthesized complexes, it has been

  9. Advanced Extraction Methods for Actinide/Lanthanide Separations

    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

  10. Advanced Extraction Methods for Actinide/Lanthanide Separations

    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

  11. Studies about interaction of hydrogen isotopes with metals and intermetallic compounds

    Hydrogen is a nontoxic but highly inflammable gas. Compared to other inflammable gasses, its range of inflammability in air is much broader (4-74.5%) but it also vaporizes much more easily. Handling of hydrogen in form of hydrides enhances safety. Experiments with gaseous and liquid hydrogen should be performed in rooms with good ventilation. The interaction of hydrogen with metals and intermetallic compounds is a major field within physical chemistry. The essential feature of hydrogen-element system consists in the formation of chemical bond between hydrogen and metal atoms. The study of the interactions of hydride-forming metals and intermetallic compounds with heavy hydrogen isotopes -deuterium and tritium- offers new possibilities for investigating hydrogen behavior on surfaces and in a solid matrix. Using hydride-forming metals and intermetallic compounds, for example, recovery, purification and storage of heavy isotopes in tritium containing systems, can solve many problems arising in the nuclear-fuel cycle. The Nuclear Power Plant Cernavoda is equipped with a Canadian reactor of CANDU type. In the long term, Cernavoda area will be contaminated with on increasing quantity of tritium. In addition, the continuous contamination of heavy water from the reactor reduces the moderator's efficiency. For these reasons, ICSI - Rm. Valcea has developed a detritiation technology, based on catalytic isotopic exchange and cryogenic distillation. Tritium should be removed from the tritiated heavy water, and this will require the storage of tritium in a special vessel that can provide a high level of protection and safety of environment and personnel. Several metals have been studied as storage beds for hydrogen isotopes. One of the reference materials used for storing of hydrogen isotopes is uranium, a material with a great storage capacity, but unfortunately it is a radioactive metal and can react with the impurities in the stored gas. Other metals and alloys as ZrCo, Ti

  12. ACTINET: a European Network for Actinide Sciences

    Full text of publication follows: The research in Actinide sciences appear as a strategic issue for the future of nuclear systems. Sustainability issues are clearly in connection with the way actinide elements are managed (either addressing saving natural resource, or decreasing the radiotoxicity of the waste). The recent developments in the field of minor actinide P and T offer convincing indications of what could be possible options, possible future processes for the selective recovery of minor actinides. But they point out, too, some lacks in the basic understanding of key-issues (such as for instance the control An versus Ln selectivity, or solvation phenomena in organic phases). Such lacks could be real obstacles for an optimization of future processes, with new fuel compounds and facing new recycling strategies. This is why a large and sustainable work appears necessary, here in the field of basic actinide separative chemistry. And similar examples could be taken from other aspects of An science, for various applications (nuclear fuel or transmutation targets design, or migration issues,): future developments need a strong, enlarged, scientific basis. The Network ACTINET, established with the support of the European Commission, has the following objectives: - significantly improve the accessibility of the major actinide facilities to the European scientific community, and form a set of pooled facilities, as the corner-stone of a progressive integration process, - improve mobility between the member organisations, in particular between Academic Institutions and National Laboratories holding the pooled facilities, - merge part of the research programs conducted by the member institutions, and optimise the research programs and infrastructure policy via joint management procedures, - strengthen European excellence through a selection process of joint proposals, and reduce the fragmentation of the community by putting critical mass of resources and expertise on

  13. Method for purifying bidentate organophosphorus compounds

    Schulz, Wallace W.

    1977-01-01

    Bidentate organophosphorus compounds useful for extracting actinide elements from acidic nuclear waste solutions are purified of undesirable acidic impurities by contacting the compounds with ethylene glycol which preferentially extracts the impurities found in technical grade bidentate compounds.

  14. Impact of metal-induced degradation on the determination of pharmaceutical compound purity and a strategy for mitigation.

    Dotterer, Sally K; Forbes, Robert A; Hammill, Cynthia L

    2011-04-01

    Case studies are presented demonstrating how exposure to traces of transition metals such as copper and/or iron during sample preparation or analysis can impact the accuracy of purity analysis of pharmaceuticals. Some compounds, such as phenols and indoles, react with metals in the presence of oxygen to produce metal-induced oxidative decomposition products. Compounds susceptible to metal-induced decomposition can degrade following preparation for purity analysis leading to falsely high impurity results. Our work has shown even metals at levels below 0.1 ppm can negatively impact susceptible compounds. Falsely low results are also possible when the impurities themselves react with metals and degrade prior to analysis. Traces of metals in the HPLC mobile phase can lead to chromatographic artifacts, affecting the reproducibility of purity results. To understand and mitigate the impact of metal induced decomposition, a proactive strategy is presented. The pharmaceutical would first be tested for reactivity with specific transition metals in the sample solvent/diluents and in the HPLC mobile phase. If found to be reactive, alternative sample diluents and/or mobile phases with less reactive solvents or addition of a metal chelator would be explored. If unsuccessful, glassware cleaning or sample solution refrigeration could be investigated. By employing this strategy during method development, robust purity methods would be delivered to the quality control laboratories, preventing future problems from potential sporadic contamination of glassware with metals. PMID:21163601

  15. Factors affecting actinide solubility in a repository for spent fuel, 1

    The main tasks in the study were to get information on the chemical conditions in a repository for spent fuel and information on factors affecting releases of actinides from spent fuel and solubility of actinides in a repository for spent fuel. The work in this field started at the Reactor Laboratory of the Technical Research Centre of Finland (VTT) in 1982. This is a report on the effects on the main parameters, Eh, pH, carbonate, organic compounds, colloids, microbes and radiation on the actinide solubility in the nearfield of the repository. Another task has been to identify available models and reported experience from actinide solubility calculations with different codes. 167 refs

  16. Study of reactions of metals with sulphur and phosphorus compounds by pulsed temperatures

    The anti-wear action of sulphur and phosphorus compounds which are usually added to gear-oils depends on chemical reactions with the metallic surfaces of the gears. These reactions occur both at the bulk oil temperature (approx. 100°C) and during high temperatures (approx. 600°C) of short duration when the gearteeth come into contact under lead. The temperature flashes were simulated in an apparatus in which short pulses of electric current were used to heat metal wires immersed in mineral oil containing S35 and P32 labelled compounds in solution. The radioactivity acquired by the wires was measured. The extent of the reactions was determined as a function of temperature and time and the results were interpreted in terms of conventional kinetic laws. The modification of the reaction rates by the presence of other compounds in the solution was studied. The effect of pre-formed surface films containing sulphur phosphorus, chlorine and/or oxygen was also determined. In explaining the results, the structure of the materials used and the diffusion processes whereby the reactions occur beyond the initial stages were considered. (author)

  17. The electrochemical properties of actinide amalgams

    Selection of the values of standard potentials of An actinides and their amalgams was made. On the basis of the data obtained energy characteristics of alloy formation processes in the systems An-Hg were calculated and analyzed. It is ascertained that the properties of f-element solutions in mercury are similar to those of alkali and alkaline-earth metal amalgams with the only difference, i.e. in case of active metals of group 3 the number of realized charge value of ionic frames in condensed phase increases

  18. Thermochemistry of some binary lead and transition metal compounds by high temperature direct synthesis calorimetry

    Meschel, S.V., E-mail: meschel@jfi.uchicago.edu [Illinois Institute of Technology,Thermal Processing Technology Center, 10 W. 32nd Street, Chicago, Illinois 60615 (United States); Gordon Center for Integrated Science, 929 E. 57th Street, Chicago, Illinois 60637 (United States); Nash, P. [Illinois Institute of Technology,Thermal Processing Technology Center, 10 W. 32nd Street, Chicago, Illinois 60615 (United States); Chen, X.Q.; Wei, P. [Materials processing Modeling Division, Shenyang National Laboratory for Materials Science, Institute of Metals Research, 72 Wenhua Road, Shenyang City (China)

    2015-06-05

    Highlights: • Studied binary lead-transition metal alloys by high temperature calorimetry. • Determined the enthalpies of formation of 8 alloys. • Compared the measurements with predictions by the model of Miedema and by the ab initio method. - Abstract: The standard enthalpies of formation of some binary lead and transition metal compounds have been measured by high temperature direct synthesis calorimetry. The reported results are: Pb{sub 3}Sc{sub 5}(−61.3 ± 2.9); PbTi{sub 4}(−16.6 ± 2.4); Pb{sub 3}Y{sub 5}(−64.8 ± 3.6); Pb{sub 3}Zr{sub 5}(−50.6 ± 3.1); PbNb{sub 3}(−10.4 ± 3.4); PbRh(−16.5 ± 3.3); PbPd{sub 3}(−29.6 ± 3.1); PbPt(−34.7 ± 3.3) kJ/mole of atoms. We will compare our results with previously published measurements. We will also compare the experimental measurements with enthalpies of formation of transition metal compounds with elements in the same vertical column in the periodic table. We will compare our measurements with predicted values on the basis of the semi empirical model of Miedema and coworkers and with ab initio values when available.

  19. Photo-induced charge-orbital switching in transition-metal compounds probed by photoemission spectroscopy

    Takubo, K; Mizokawa, T [Department of Physics and Department of Complexity Science and Engineering, University of Tokyo, Kashiwa, Chiba 277-8561 (Japan); Takubo, N; Miyano, K [Research Center for Advanced Science and Technology (RCAST), University of Tokyo, Tokyo 153-8904 (Japan); Matsumoto, N; Nagata, S, E-mail: takubo@sces.k.u-tokyo.ac.j [Department of Materials Science and Engineering, Muroran Institute of Technology, 27-1 Mizumoto-cho, Muroran, Hokkaido, 050-8585 Japan (Japan)

    2009-02-01

    Transition-metal compounds with spin, charge, and orbital degrees of freedom tend to have frustrated electronic states coupled with local lattice distortions and to show drastic response to external stimuli such as photo-excitation. We have studied the charge-orbital states in perovskite-type Pr{sub 0.55}(Ca{sub 1-y}Sr{sub y}){sub 0.45}MnO{sub 3} thin films (PCSMO) and spinel-type CuIr{sub 2}S{sub 4} using photoemission spectroscopy combined with additional laser illumination. PCSMO and CuIr{sub 2}S{sub 4} are clear-cut examples of transition-metal compounds showing photo-induced metallic conductivities but the charge-orbital states in the two systems show contrasting responses to the photo-excitation. The charge-orbital states in PCSMO are stabilized by Jahn-Teller or Breathing-type lattice distortions and can be destroyed by photo-excitation. On the other hand, the charge-orbital states in CuIr{sub 2}S{sub 4} are stabilized by dimer formation and tend to be robust against photo-excitation.

  20. Thermochemistry of some binary lead and transition metal compounds by high temperature direct synthesis calorimetry

    Highlights: • Studied binary lead-transition metal alloys by high temperature calorimetry. • Determined the enthalpies of formation of 8 alloys. • Compared the measurements with predictions by the model of Miedema and by the ab initio method. - Abstract: The standard enthalpies of formation of some binary lead and transition metal compounds have been measured by high temperature direct synthesis calorimetry. The reported results are: Pb3Sc5(−61.3 ± 2.9); PbTi4(−16.6 ± 2.4); Pb3Y5(−64.8 ± 3.6); Pb3Zr5(−50.6 ± 3.1); PbNb3(−10.4 ± 3.4); PbRh(−16.5 ± 3.3); PbPd3(−29.6 ± 3.1); PbPt(−34.7 ± 3.3) kJ/mole of atoms. We will compare our results with previously published measurements. We will also compare the experimental measurements with enthalpies of formation of transition metal compounds with elements in the same vertical column in the periodic table. We will compare our measurements with predicted values on the basis of the semi empirical model of Miedema and coworkers and with ab initio values when available

  1. Photochemistry of the actinides

    It has been found that all three major actinides have a useful variety of photochemical reactions which could be used to achieve a separations process that requires fewer reagents. Several features merit enumerating: (1) Laser photochemistry is not now as uniquely important in fuel reprocessing as it is in isotopic enrichment. The photochemistry can be successfully accomplished with conventional light sources. (2) The easiest place to apply photo-reprocessing is on the three actinides U, Pu, and Np. The solutions are potentially cleaner and more amenable to photoreactions. (3) Organic-phase photoreactions are probably not worth much attention because of the troublesome solvent redox chemistry associated with the photochemical reaction. (4) Upstream process treatment on the raffinate (dissolver solution) may never be too attractive since the radiation intensity precludes the usage of many optical materials and the nature of the solution is such that light transmission into it might be totally impossible

  2. Actinides: why are they important biologically

    The following topics are discussed: actinide elements in energy systems; biological hazards of the actinides; radiation protection standards; and purposes of actinide biological research with regard to toxicity, metabolism, and therapeutic regimens

  3. Optical Parameters and Absorption of Azo Dye and Its Metal-Substituted Compound Thin Films

    魏斌; 吴谊群; 顾冬红; 干福熹

    2003-01-01

    We determine the complex refractive indices N ( N = n - ik), dielectric constants ε(ε = ε1 - iε2), and absorption coefficients α of a new azo dye [2-(6-methyl-2-benzothiazolyazo)-5-diethylaminophenol(MBADP)]-doped polymer and its nickel- and zinc-substituted compounds(Ni-MBADP and Zn-MBADP) spin-coated thin films from a scanning ellipsometer in the wavelength 400-700 nm region. Metal chelation strongly (about one times) enhances the optical and dielectric parameters at the peaks and results in a large bathochromic shift (50-60nm) of absorption band. Bathochromic shift of Ni-MBADP is about 10nm larger than that of Zn-MBADP due to different spatial configurations formed in the metal-azo complexes.

  4. Influence of main-group element on half-metallic properties in half-Heusler compound

    Liu, Hongyan; Li, Yushan; Tian, Fuyang; Li, Getian

    2016-04-01

    We investigate the band structure, magnetism and density of states of half-Heusler compounds CoCrZ (Z = Si,Ge,P,As) based on the first-principle calculations. Combined with molecular orbital hybridization theory, we discuss the influence of the main-group element on half-metallic properties of CoCrZ. It is found that the replacement of Ge for Si in CoCrSi can adjust the position of the Fermi level, and while it has no impact on the energy gap width and magnetic structure. However, the substitution of P for Si can effectively adjust the magnetism without disrupting its half-metallicity. Our results demonstrate that the electronic structure of CoCrZ is mainly dependent on the number of valence electrons of the main-group element.

  5. Enhancement of nonlinear optical properties of compounds of silica glass and metallic nanoparticle

    GHARAATI A; KAMALDAR A

    2016-06-01

    The aim of this paper is to introduce a method for enhancing the nonlinear optical properties in silica glass by using metallic nanoparticles. First, the T-matrix method is developed to calculate the effective dielectric constant for the compound of silica glass and metallic nanoparticles, both of which possess nonlinear dielectric constants. In the second step, the Maxwell–Garnetttheory is exploited to replace the spherical nanoparticles with cylindrical and ellipsoidal ones, facilitating the calculation of the third-order nonlinear effective susceptibility for a degenerate four-wave mixing case. The results are followed by numerical computations for silver, copper and gold nanoparticles. It is shown, graphically, that the maximum and minimum of the real part of thereflection coefficient for nanoparticles of silver occurs in smaller wavelengths compared to that of copper and gold. Further, it is found that spherical nanoparticles exhibit greater figure-of-merit compared to those with cylindrical or ellipsoidal geometries.

  6. Composite materials obtained by the ion-plasma sputtering of metal compound coatings on polymer films

    Khlebnikov, Nikolai; Polyakov, Evgenii; Borisov, Sergei; Barashev, Nikolai; Biramov, Emir; Maltceva, Anastasia; Vereshchagin, Artem; Khartov, Stas; Voronin, Anton

    2016-01-01

    In this article, the principle and examples composite materials obtained by deposition of metal compound coatings on polymer film substrates by the ion-plasma sputtering method are presented. A synergistic effect is to obtain the materials with structural properties of the polymer substrate and the surface properties of the metal deposited coatings. The technology of sputtering of TiN coatings of various thicknesses on polyethylene terephthalate films is discussed. The obtained composites are characterized by X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy dispersive X-ray spectroscopy (EDX), atomic force microscopy (AFM), and scanning tunneling microscopy (STM) is shown. The examples of application of this method, such as receiving nanocomposite track membranes and flexible transparent electrodes, are considered.

  7. Incorporating functional groups on the structure of Acrylic fibers for adsorption of metal ionic compounds

    Common commercial acrylic fibers were modified by incorporating different suitable ion adsorbing functional groups into their structures. To study the ion adsorption ability of modified fibers against ionic compounds, the raw fibers were treated with hydroxylamine, hydrazine and urea. The new incorporated functional groups were characterized and appropriate formula for each reaction was suggested. In order to evaluate the ion adsorption capacity of the system, the modified fibers were immersed in separated metal salt solutions. The results show that the samples modified by hydroxylamine, have higher adsorption capacity than others, however, by pretreatment with hydrazine or urea not only the functional groups were increased but also the efficiency of the adsorption was improved

  8. On features of metal and binary compound sputtering by low-energy ions

    Molecular dynamic simulation has been used to study how the characteristics of metal and binary compound sputtering change under the bombardment by different low-energy ions. The influence of the target parameters on the anomalous mass dependence of sputtering yield has been investigated, both for targets with similar and very different values of density, the lattice constant and the surface binding energy. Together with the ratio of the target atoms' mass to the mass of the ions, the density of the target and the binding energy turn out to be the important parameters that determine the unusual shape of the mass dependence of sputtering by low-energy ions.

  9. On features of metal and binary compound sputtering by low-energy ions

    Zykova, E.Yu. [Physics Faculty, Moscow State University, 119992 Moscow (Russian Federation)], E-mail: zykova@rambler.ru; Yurasova, V.E.; Elovikov, S.S. [Physics Faculty, Moscow State University, 119992 Moscow (Russian Federation)

    2009-08-15

    Molecular dynamic simulation has been used to study how the characteristics of metal and binary compound sputtering change under the bombardment by different low-energy ions. The influence of the target parameters on the anomalous mass dependence of sputtering yield has been investigated, both for targets with similar and very different values of density, the lattice constant and the surface binding energy. Together with the ratio of the target atoms' mass to the mass of the ions, the density of the target and the binding energy turn out to be the important parameters that determine the unusual shape of the mass dependence of sputtering by low-energy ions.

  10. Micro- and Nanostructured Metal Oxide Chemical Sensors for Volatile Organic Compounds

    Alim, M. A.; Penn, B. G.; Currie, J. R., Jr.; Batra, A. K.; Aggarwal, M. D.

    2008-01-01

    Aeronautic and space applications warrant the development of chemical sensors which operate in a variety of environments. This technical memorandum incorporates various kinds of chemical sensors and ways to improve their performance. The results of exploratory investigation of the binary composite polycrystalline thick-films such as SnO2-WO3, SnO2-In2O3, SnO2-ZnO for the detection of volatile organic compound (isopropanol) are reported. A short review of the present status of the new types of nanostructured sensors such as nanobelts, nanorods, nanotube, etc. based on metal oxides is presented.

  11. Non-traditional metal electrode materials in electrochemical nvironmental analysis of biologically active compounds

    Josypčuk, Bohdan; Šestáková, Ivana

    Tenerife: WSEAS, 2007 - (Otesteanu, M.; Celikyay, S.; Mastorakis, N.; Lache, S.; Benra, F.), s. 181-185 ISBN 978-960-6766-20-6. [WSEAS International Conference on ENVIRONMENT, ECOSYSTEMS and DEVELOPMENT (EED'07) /5./. Tenerife (ES), 14.12.2007-16.12.2007] R&D Projects: GA ČR GA203/07/1195; GA ČR GA521/06/0496 Institutional research plan: CEZ:AV0Z40400503 Keywords : metal electrode materials * biologically actove compounds * electrochemistry Subject RIV: CG - Electrochemistry

  12. Evolution of metal-compound residues on the walls of plasma etching reactor and their effect on critical dimensions of high-k/metal gate

    It was found that critical dimensions of high-k/metal gates obey the multivariate linear approximation with the precision of 3σ=±0.86 nm, whose explanatory variables are amounts of metal compounds remaining on the plasma reactor walls. To measure their amounts, the authors assumed they are proportional to amounts of atoms sputtered out by Ar plasma and falling onto a Si wafers placed on a wafer stage. In this study, effects of metal compounds of W, Ti, Ta, and Hf, which are used to construct full-metal/high-k gates, were measured. It was found that Ti and Ta compounds dominate the fluctuation of critical dimensions and the dependency of their amount on wafer numbers being etched obeys a simple difference equation. From these results, they can estimate and minimize the fluctuations of critical dimensions in mass fabrications.

  13. Some reduced ternary and quaternary oxides of molybdenum. A family of compounds with strong metal-metal bonds

    Several new, reduced ternary and quaternary oxides of molybdenum are reported, each containing molybdenum in an average oxidation state 2 sealed in Mo tubes held at 11000C for ca. 7 days. Refinement of the substructure of the new compound Ba062Mo4O6 was based on an orthorhombic cells, with a = 9.509(2), b = 9.825(2), c = 2.853(1) A, Z = 2 in space group Pbam; weak supercell reflections indicate the true structure has c = 8(2.853) A. The chief structural feature is closely related to that of NaMo4O6 which consists of infinite chains of Mo6 octahedral clusters fused on opposite edges, bridged on the outer edges by O atoms and crosslinked by Mo-O-Mo bonding to create four-sided tunnels in which the Ba2+ ions are located. The structure of Ba113Mo8O16 is triclinic, a = 7.311(1), b = 7.453(1), c = 5.726(1) A, α = 101.49(2), β = 99.60(2), γ = 89.31(2)0, Z = 1, space group P1. It is a low-symmetry, metal-metal bonded variant of the hollandite structure, in which two different infinite chains, built up from Mo4O82- and Mo4O8026- cluster units, respectively, are interlinked via Mo-O-Mo bridge bonding to create again four-sided tunnels in which the Ba2+ ions reside. Other compounds prepared and characterized by analyses and x-ray powder diffraction data are Pb/sub x/Mo4O6 (x approx. 0.6), LiZn2Mo3O8, , CaMo5O8, K2Mo12O19, and Na2Mo12O19

  14. On the indenyl compounds of actinide elements

    The complexes (eta5-C9H7)AnX3.Lsub(a).Lsub(b) (X = Cl or Br, An = U or Th, Lsub(a) = C4H8O (THF) or (C6H5)3PO (TPO), Lsub(b) = TPO or THF) have been prepared. Infrared, Raman, electronic and mass spectra as well as magnetic susceptibility measurements are reported and discussed. The solid-state molecular structure of (eta5-C9H7)UBr3. C4H8O. (C6H5)3PO is reported. The complexes (eta5-C9H7)AnX3.2(C6H5)3 PO in solution show a strong tendency to disproportionate giving (eta5-C9H7)3AnX. 2 AnX4.2(C6H5)3PO and free ligand. (author)

  15. Actinide transmutation in nuclear reactors

    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)

  16. Electrolytic decontamination of the dismantled metallic wastes contaminated with uranium compounds in neutral salt solutions

    Choi, Wang Kyu; Lee, Sung Yeal; Kim, Kye Nam; Won, Hee Jun; Jung, Jong Heon; Oh, Won Zin [KAERI, Taejon (Korea, Republic of)

    2004-07-01

    Electrolytic dissolution study was carried out to evaluate the applicability of electrochemical decontamination process using a neutral salt electrolyte as a decontamination technology for the recycle or self disposal with authorization of large amount of metallic wastes contaminated with uranium compounds generated by dismantling a retired uranium conversion plant using SUS-304 and Inconel-600 specimen as the main materials of internal system components of the plant. The effects of type of neutral salt as an electrolyte, current density, and concentration of electrolyte on the dissolution of the materials were evaluated. On the basis of the results obtained through the basic inactive experiments, electrochemical decontamination tests using the specimens contaminated with uranium compounds such as UO{sub 2}, AUC (ammonium uranyl carbonate) and ADU (ammonium diuranate) taken from an uranium conversion plant were performed in Na{sub 2}SO{sub 4} and NaNO{sub 3} solution. It was verified that the electrochemical decontamination of the dismantled metallic wastes was quite successful in Na{sub 2}SO{sub 4} and NaNO{sub 3} neutral salt electrolyte by reducing {beta} radioactivities below the level of self disposal with authorization within 10 minutes regardless of the type of contaminants and the degree of contamination.

  17. Electrolytic decontamination of the dismantled metallic wastes contaminated with uranium compounds in neutral salt solutions

    Electrolytic dissolution study was carried out to evaluate the applicability of electrochemical decontamination process using a neutral salt electrolyte as a decontamination technology for the recycle or self disposal with authorization of large amount of metallic wastes contaminated with uranium compounds generated by dismantling a retired uranium conversion plant using SUS-304 and Inconel-600 specimen as the main materials of internal system components of the plant. The effects of type of neutral salt as an electrolyte, current density, and concentration of electrolyte on the dissolution of the materials were evaluated. On the basis of the results obtained through the basic inactive experiments, electrochemical decontamination tests using the specimens contaminated with uranium compounds such as UO2, AUC (ammonium uranyl carbonate) and ADU (ammonium diuranate) taken from an uranium conversion plant were performed in Na2SO4 and NaNO3 solution. It was verified that the electrochemical decontamination of the dismantled metallic wastes was quite successful in Na2SO4 and NaNO3 neutral salt electrolyte by reducing β radioactivities below the level of self disposal with authorization within 10 minutes regardless of the type of contaminants and the degree of contamination

  18. Pressure induced structural phase transition in IB transition metal nitrides compounds

    Soni, Shubhangi; Kaurav, Netram; Jain, A.; Shah, S.; Choudhary, K. K.

    2015-06-01

    Transition metal mononitrides are known as refractory compounds, and they have, relatively, high hardness, brittleness, melting point, and superconducting transition temperature, and they also have interesting optical, electronic, catalytic, and magnetic properties. Evolution of structural properties would be an important step towards realizing the potential technological scenario of this material of class. In the present study, an effective interionic interaction potential (EIOP) is developed to investigate the pressure induced phase transitions in IB transition metal nitrides TMN [TM = Cu, Ag, and Au] compounds. The long range Coulomb, van der Waals (vdW) interaction and the short-range repulsive interaction upto second-neighbor ions within the Hafemeister and Flygare approach with modified ionic charge are properly incorporated in the EIOP. The vdW coefficients are computed following the Slater-Kirkwood variational method, as both the ions are polarizable. The estimated value of the phase transition pressure (Pt) and the magnitude of the discontinuity in volume at the transition pressure are consistent as compared to the reported data.

  19. Impedance study of tea with added taste compounds using conducting polymer and metal electrodes.

    Dhiman, Mopsy; Kapur, Pawan; Ganguli, Abhijit; Singla, Madan Lal

    2012-09-01

    In this study the sensing capabilities of a combination of metals and conducting polymer sensing/working electrodes for tea liquor prepared by addition of different compounds using an impedance mode in frequency range 1 Hz-100 KHz at 0.1 V potential has been carried out. Classification of six different tea liquor samples made by dissolving various compounds (black tea liquor + raw milk from milkman), (black tea liquor + sweetened clove syrup), (black tea liquor + sweetened ginger syrup), (black tea liquor + sweetened cardamom syrup), (black tea liquor + sweet chocolate syrup) and (black tea liquor + vanilla flavoured milk without sugar) using six different working electrodes in a multi electrode setup has been studied using impedance and further its PCA has been carried out. Working electrodes of Platinum (Pt), Gold (Au), Silver (Ag), Glassy Carbon (GC) and conducting polymer electrodes of Polyaniline (PANI) and Polypyrrole (PPY) grown on an ITO surface potentiostatically have been deployed in a three electrode set up. The impedance response of these tea liquor samples using number of working electrodes shows a decrease in the real and imaginary impedance values presented on nyquist plots depending upon the nature of the electrode and amount of dissolved salts present in compounds added to tea liquor/solution. The different sensing surfaces allowed a high cross-selectivity in response to the same analyte. From Principal Component Analysis (PCA) plots it was possible to classify tea liquor in 3-4 classes using conducting polymer electrodes; however tea liquors were well separated from the PCA plots employing the impedance data of both conducting polymer and metal electrodes. PMID:23035436

  20. Pore size dynamics in interpenetrated metal organic frameworks for selective sensing of aromatic compounds.

    Myers, Matthew; Podolska, Anna; Heath, Charles; Baker, Murray V; Pejcic, Bobby

    2014-03-28

    The two-fold interpenetrated metal-organic framework, [Zn2(bdc)2(dpNDI)]n (bdc=1,4-benzenedicarboxylate, dpNDI=N'N'-di(4-pyridyl)-1,4,5,8-naphthalenediimide) can undergo structural re-arrangement upon adsorption of chemical species changing its pore structure. For a competitive binding process with multiple analytes of different sizes and geometries, the interpenetrated framework will adopt a conformation to maximize the overall binding interactions. In this study, we show for binary mixtures that there is a high selectivity for the larger methylated aromatic compounds, toluene and p-xylene, over the small non-methylated benzene. The dpNDI moiety within [Zn2(bdc)2(dpNDI)]n forms an exciplex with these aromatic compounds. The emission wavelength is dependent on the strength of the host-guest CT interaction allowing these compounds to be distinguished. We show that the sorption selectivity characteristics can have a significant impact on the fluorescence sensor response of [Zn2(bdc)2(dpNDI)]n towards environmentally important hydrocarbons based contaminants (i.e., BTEX, PAH). PMID:24636414

  1. Optical techniques for actinide research

    In recent years, substantial gains have been made in the development of spectroscopic techniques for electronic properties studies. These techniques have seen relatively small, but growing, application in the field of actinide research. Photoemission spectroscopies, reflectivity and absorption studies, and x-ray techniques will be discussed and illustrative examples of studies on actinide materials will be presented

  2. Tuning the luminescence of metal-organic frameworks for detection of energetic heterocyclic compounds.

    Guo, Yuexin; Feng, Xiao; Han, Tianyu; Wang, Shan; Lin, Zhengguo; Dong, Yuping; Wang, Bo

    2014-11-01

    Herein we report three metal-organic frameworks (MOFs), TABD-MOF-1, -2, and -3, constructed from Mg(2+), Ni(2+), and Co(2+), respectively, and deprotonated 4,4'-((Z,Z)-1,4-diphenylbuta-1,3-diene-1,4-diyl)dibenzoic acid (TABD-COOH). The fluorescence of these three MOFs is tuned from highly emissive to completely nonemissive via ligand-to-metal charge transfer by rational alteration of the metal ion. Through competitive coordination substitution, the organic linkers in the TABD-MOFs are released and subsequently reassemble to form emissive aggregates due to aggregation-induced emission. This enables highly sensitive and selective detection of explosives such as five-membered-ring energetic heterocyclic compounds in a few seconds with low detection limits through emission shift and/or turn-on. Remarkably, the cobalt-based MOF can selectively sense the powerful explosive 5-nitro-2,4-dihydro-3H-1,2,4-triazole-3-one with high sensitivity discernible by the naked eye (detection limit = 6.5 ng on a 1 cm(2) testing strip) and parts per billion-scale sensitivity by spectroscopy via pronounced fluorescence emission. PMID:25325884

  3. Actinide coordination chemistry: towards the limits of the periodic table; Chimie de coordination des actinides: vers les frontieres du tableau periodique

    Den Auwer, C.; Moisy, P. [CEA Marcoule (DEN/DRCP/SCPS), 30 (France); Simoni, E. [Paris-11 Univ., 91 - Orsay (France). Inst. de Physique Nucleaire

    2009-05-15

    Actinide elements represent a distinct chemical family at the bottom of the periodic table. Among the major characteristics of this 14 element family is their high atomic numbers and their radioactivity. Actinide chemistry finds its roots in the history of the 20. century and plays a very important role in our contemporary world. Energetic as well as technical challenges are facing the development of nuclear energy. In this pedagogical introduction to actinide chemistry, the authors draw a comparison between the actinides family and the chemistry of two other families, lanthanides and transition metals. This article focuses on molecular and aqueous chemistry. It has been based on class notes aiming to present an overview of the chemical diversity of actinides, and its future challenges for modern science. (authors)

  4. The actinides-a beautiful ending of the Periodic Table

    The 5f elements, actinides, show many properties which have direct correspondence to the 4f transition metals, the lanthanides. The remarkable similarity between the solid state properties of compressed Ce and the actinide metals is pointed out in the present paper. The α-γ transition in Ce is considered as a Mott transition, namely, from delocalized to localized 4f states. An analogous behavior is also found for the actinide series, where the sudden volume increase from Pu to Am can be viewed upon as a Mott transition within the 5f shell as a function of the atomic number Z. On the itinerant side of the Mott transition, the earlier actinides (Pa-Pu) show low symmetry structures at ambient conditions; while across the border, the heavier elements (Am-Cf) present the dhcp structure, an atomic arrangement typical for the trivalent lanthanide elements with localized 4f magnetic moments. The reason for an isostructural Mott transition of the f electron in Ce, as opposed to the much more complicated cases in the actinides, is identified. The strange appearance of the δ-phase (fcc) in the phase diagram of Pu is another consequence of the border line behavior of the 5f electrons. The path leading from δ-Pu to α-Pu is identified

  5. The actinides-a beautiful ending of the Periodic Table

    Johansson, Boerje [Condensed Matter Theory Group, Department of Physics, Uppsala University, Box 530, S-751 21 Uppsala (Sweden); Applied Materials Physics, Department of Materials Science and Engineering, Royal Institute of Technology, Brinellvaegen 23, SE-100 44 Stockholm (Sweden)], E-mail: borje.johansson@fysik.uu.se; Li, Sa [Applied Materials Physics, Department of Materials Science and Engineering, Royal Institute of Technology, Brinellvaegen 23, SE-100 44 Stockholm (Sweden); Department of Physics, Virginia Commonwealth University, Richmond, VA 23284 (United States)

    2007-10-11

    The 5f elements, actinides, show many properties which have direct correspondence to the 4f transition metals, the lanthanides. The remarkable similarity between the solid state properties of compressed Ce and the actinide metals is pointed out in the present paper. The {alpha}-{gamma} transition in Ce is considered as a Mott transition, namely, from delocalized to localized 4f states. An analogous behavior is also found for the actinide series, where the sudden volume increase from Pu to Am can be viewed upon as a Mott transition within the 5f shell as a function of the atomic number Z. On the itinerant side of the Mott transition, the earlier actinides (Pa-Pu) show low symmetry structures at ambient conditions; while across the border, the heavier elements (Am-Cf) present the dhcp structure, an atomic arrangement typical for the trivalent lanthanide elements with localized 4f magnetic moments. The reason for an isostructural Mott transition of the f electron in Ce, as opposed to the much more complicated cases in the actinides, is identified. The strange appearance of the {delta}-phase (fcc) in the phase diagram of Pu is another consequence of the border line behavior of the 5f electrons. The path leading from {delta}-Pu to {alpha}-Pu is identified.

  6. Magnetism in the actinides: the role of neutron scattering

    Neutron scattering has played a crucial and unique role of elucidating the magnetism in actinide compounds. Examples are given of elastic scattering to determine magnetic structures, measure spatial correlations in the critical regime, and magnetic form factors, and of inelastic scattering to measure the (often elusive) spin excitations. Some future directions will be discussed

  7. Selective extraction of actinides from high level liquid wastes. Study of the possibilities offered by the Redox properties of actinides

    Partitioning of high level liquid wastes coming from nuclear fuel reprocessing by the PUREX process, consists in the elimination of minor actinides (Np, Am, and traces of Pu and U). Among the possible processes, the selective extraction of actinides with oxidation states higher than three is studied. First part of this work deals with a preliminary step; the elimination of the ruthenium from fission products solutions using the electrovolatilization of the RuO4 compound. The second part of this work concerns the complexation and oxidation reactions of the elements U, Np, Pu and Am in presence of a compound belonging to the insaturated polyanions family: the potassium phosphotungstate. For actinide ions with oxidation state (IV) complexed with phosphotungstate anion the extraction mechanism by dioctylamine was studied and the use of a chromatographic extraction technic permitted successful separations between tetravalents actinides and trivalents actinides. Finally, in accordance with the obtained results, the basis of a separation scheme for the management of fission products solutions is proposed

  8. Airborne Release of Particles in Overheating Incidents Involving Plutonium Metal and Compounds

    Ever-increasing utilization of nuclear fuels will result in wide-scale plutonium recovery processing, reconstitution of fuels, transportation, and extensive handling of this material. A variety of circumstances resulting in overheating and fires involving plutonium may occur, releasing airborne particles. This work describes the observations from a study in which the airborne release of plutonium and its compounds was measured during an exposure of the material of interest containing plutonium to temperatures which may result from fires. Aerosol released from small cylinders of metallic plutonium ignited in air at temperatures from 410 to 650°C ranged from 3 x 10-6 to 5 x 10-5 wt%. Particles smaller than 15μm in diameter represented as much as 0.03% of the total released. Large plutonium pieces weighing from 456 to 1770 g were ignited and allowed to oxidize completely in air with a velocity of around 500 cm/sec. Release rates of from 0.0045 to 0.032 wt% per hour were found. The median mass diameter of airborne material was 4 μm. Quenching the oxidation with magnesium oxide sand reduced the release to 2.9 X 10-4 wt% per hour. Many experiments were carried out in which plutonium compounds as powders were heated at temperatures ranging from 700 to 1000°C with several air flows. Release rates ranged from 5 x 10-8 to 0.9 wt% per hour, depending upon the compound and the conditions imposed. The airborne release from boiling solutions of plutonium nitrate were roughly related to energy of boiling, and ranged from 4 x 10-4 to 2 x 10-1 % for the evaporation of 90% of the solution. The fraction airborne when combustibles contaminated with plutonium are burned is under study. The data reported can be used in assessing the consequences of off-standard situations involving plutonium and its compounds in fires. (author)

  9. Extraction of DBP and MBP from actinides: application to the recovery of actinides from TBP--Na2CO3 scrub solutions

    A flowsheet for the recovery of actinides from TBP--Na2CO3 scrub waste solutions has been developed, based on batch extraction data, and tested, using laboratory scale counter-current extraction techniques. The process utilizes 2-ethyl-1-hexanol (2-EHOH) to extract the TBP degradation products (HDBP and H2MBP) from acidified Na2CO3 scrub waste leaving the actinides in the aqueous phase. Dibutyl and monobutyl phosphoric acids are attached to the 2-EHOH molecules through hydrogen bonds. These hydrogen bonds also diminish the ability of the HDBP and H2MBP to complex actinides and thus all actinides remain in the aqueous raffinate. Dilute sodium hydroxide solutions can be used to back-extract the dibutyl and monobutyl phosphoric acid esters as their sodium salts. The 2-EHOH can then be recycled. After extraction of the acidified carbonate waste with 2-EHOH, the actinides may be readily extracted from the raffinate with DHDECMP or, in the case of tetra- and hexavalent actinides, with TBP. The alcohol extraction (ARALEX) process is relatively simple and involves inexpensive and readily available chemicals. The ARALEX process can also be applied to other actinide waste streams which contain appreciable concentrations of polar organic compounds that interfere with conventional actinide ion exchange and liquid--liquid extraction procedures

  10. Promising pyrochemical actinide/lanthanide separation processes using aluminum

    Thermodynamic calculations have shown that aluminum is the most promising metallic solvent or support for the separation of actinides (An)from lanthanides (Ln). In molten fluoride salt, the technique of reductive extraction is under development in which the separation is based on different distributions of An and Ln between the salt and metallic Al phases. In this process molten aluminum alloy acts as both a reductant and a solvent into which the actinides are selectively extracted. It was demonstrated that a one-stage reductive extraction process, using a concentrated solution, allows a recovery of more than 99.3% of Pu and Am. In addition excellent separation factors between Pu and Ln well above 103 were obtained. In molten chloride media similar separations are developed by constant current electrorefining between a metallic alloy fuel (U60Pu20-Zr10Am2Nd3.5Y0.5Ce0.5Gd0.5) and an Al solid cathode. In a series of demonstration experiments, almost 25 g of metallic fuel was reprocessed and actinides collected as An-Al alloys on the cathode. Analysis of the An-Al deposits confirmed that an excellent An/Ln separation (An/Ln mass ratio = 2400) had been obtained. These results show that Al is a very promising material to be used in pyrochemical reprocessing of actinides. (authors)

  11. Design, synthesis, and evaluation of polyhydroxamate chelators for selective complexation of actinides

    Specific chelating polymers targeted for actinides have much relevance to problems involving remediation of nuclear waste. Goal is to develop polymer supported, ion specific extraction systems for removing actinides and other hazardous metal ions from wastewaters. This is part of an effort to develop chelators for removing actinide ions such as Pu from soils and waste streams. Selected ligands are being attached to polymeric backbones to create novel chelating polymers. These polymers and other water soluble and insoluble polymers have been synthesized and are being evaluated for ability to selectively remove target metal ions from process waste streams

  12. Coordination compounds of nitrates and sulfates of some metals with isonicotinic acid hydrazide

    The complexes M(No3)2x2HINA, MSO4x2HINA, Cu(NO3)2xHINA, and CuSO4xHINAx1, 5C2H5OH (where M=Co, Ni, Cu, Zn, Cd; HINA is hydrazide of isonicotinic acid) are obtained, their infrared (400-4000 cm-1) and Raman (50-4000 cm-1) spectra are studied. It is shown that HINA molecules in all compounds are bound with the metal by the nitrogen atoms of the amino group. In nickel, zink, and cadmium complexes the nitrogen atoms of the heterocycle are also bound with the central atom, thus forming tubazid bridges

  13. Metals elements and chlorinated compounds in cetaceans; Elementi metallici e composti organoclorurati in cetacei

    Cardellicchio, N. [Consiglio Nazionale delle Ricerche. Ist. Sperimentale Talassografico, Taranto (Italy)

    1997-01-01

    Non-degradable pollutants determination in cetacea, high tropic level organisms, represents an evaluating element both for bioaccumulation phenomena and sea ecosystem quality. In this paper is shown determination results for metals, chlorinated pesticides, and polychlorinated biphenyls (PCB) in Stenella coeruleoalba specimens, beached along the coast of Puglia (Italy), in the period February-June 1987. Chemical-toxicological surveys verified that in there Mediterranean marine mammals pollutant accumulation is higher than in Atlantic species. Lipophylous toxical compounds transferred from mothers to offspring represents a high risk for their survival. even though this survey failed to establish a direct cause-effect relationship between pollutant levels and anatomical-pathological lesions, it is apparent that sea pollution phenomena are reflected negatively in the top of the food chains.

  14. Study by X-ray diffraction of structure modifications induced by pressure in different actinide compounds: AnO2 dioxides (An=Th, Pu, Am), AnCl4 tetrachlorides (An=Th, U), UBx borides (x=2,4,12) and the carbide UC2

    Structural transitions, induced by pressure, of actinide compounds are studied by X-ray diffraction, the determination of incompressibility is also studied at atmospheric pressure. The crystal structure of ThO2, PuO2 and AmO2 evolves, near 40 MPa from a fcc lattice to an orthorhombic lattice. Incompressibility values associated to UO2 and NpO2 incompressibility evidence an important discontinuity between UO2 and NpO2 and other dioxides due to their different electronic structure. Tetragonal ThCl4 and UCl4 undergo a structure transition respectively at 2 and 5 GPa. UCl4 becomes monoclinic and its color changes. At higher pressure these compounds become progressively amorphous. The crystal structure of uranium borides is not changed up to 50 GPa. UC2 presents a phase transition at 17.6 GPa from a tetragonal to a hexagonal lattice

  15. Application of humic compounds for remediation of soils contaminated with heavy metals: the benefits and risks

    Motuzova, Galina; Barsova, Natalia; Stepanov, Andrey; Kiseleva, Violetta; Kolchanova, Ksenia; Starkova, Irina; Karpukhin, Mikhail

    2015-04-01

    found to contain only 3-9% of copper. The content of free Cu2+ ions in the sample extract was negligible. The samples used for field experiments were tested in laboratory to estimate their sorption capacity for Cu. For this purpose, 300 g of substrate (loam and mixed organic substrate) with addition of water (control) and humic preparation (same dose as in the field experiment) were kept in the laboratory for 1 week. Soil samples were then dried and brought into equilibrium with the solution of copper sulfate at concentration of 50 mg/l. The concentration of copper in the solution in equilibrium with HC was 2.5-4 times higher than in the control variant; absorption of copper by solid phase decreased by 5-6%. Results of the laboratory study were in good agreement with the results of the field experiment. Addition of HC increased the content of soluble organic matter and copper complexation by an order of magnitude and thus reduced the activity of copper ions in the liquid phase that was treated as a possible remediation effect of the humic compound for plants and biota. However the increased total metal content mainly in a migration-capable form (negatively charged complexes with organic matter) may increase the risk of contaminating ground waters with heavy metals. Therefore, application of the artificial humic compounds for remediation of soils contaminated with heavy metals requires monitoring and further development of means to prevent their migration.

  16. Managing Inventories of Heavy Actinides

    The Department of Energy (DOE) has stored a limited inventory of heavy actinides contained in irradiated targets, some partially processed, at the Savannah River Site (SRS) and Oak Ridge National Laboratory (ORNL). The 'heavy actinides' of interest include plutonium, americium, and curium isotopes; specifically 242Pu and 244Pu, 243Am, and 244/246/248Cm. No alternate supplies of these heavy actinides and no other capabilities for producing them are currently available. Some of these heavy actinide materials are important for use as feedstock for producing heavy isotopes and elements needed for research and commercial application. The rare isotope 244Pu is valuable for research, environmental safeguards, and nuclear forensics. Because the production of these heavy actinides was made possible only by the enormous investment of time and money associated with defense production efforts, the remaining inventories of these rare nuclear materials are an important part of the legacy of the Nuclear Weapons Program. Significant unique heavy actinide inventories reside in irradiated Mark-18A and Mark-42 targets at SRS and ORNL, with no plans to separate and store the isotopes for future use. Although the costs of preserving these heavy actinide materials would be considerable, for all practical purposes they are irreplaceable. The effort required to reproduce these heavy actinides today would likely cost billions of dollars and encompass a series of irradiation and chemical separation cycles for at least 50 years; thus, reproduction is virtually impossible. DOE has a limited window of opportunity to recover and preserve these heavy actinides before they are disposed of as waste. A path forward is presented to recover and manage these irreplaceable National Asset materials for future use in research, nuclear forensics, and other potential applications.

  17. High energy magnetic neutron scattering in heavy fermion compounds

    High energy magnetic inelastic neutron scattering measurements of intermultiplet transitions in rare earth and actinide metals have established the importance of intra-atomic correlations even in the presence of strong hybridisation. Well defined transitions are observed up to an energy of 1766 meV in thulium metal. The 3H4→3F2 transition is observed across the alloy series U(Pd1-xPtx)3, showing that localised 5f2 excitations persist in the heavy fermion compound UPt3. The splitting of the spin-orbit transition in CeAl3 suggests that hybridisation is an important component in the crystal field potential. (author)

  18. Electronic computer prediction of properties of binary refractory transition metal compounds on the base of their simplificated electronic structure

    An attempt is made to obtain calculation equations of macroscopic physico-chemical properties of transition metal refractory compounds (density, melting temperature, Debye characteristic temperature, microhardness, standard formation enthalpy, thermo-emf) using the method of the regression analysis. Apart from the compound composition the argument of the regression equation is the distribution of electron bands of d-transition metals, created by the energy electron distribution in the simplified zone structure of transition metals and approximated by Chebishev polynoms, by the position of Fermi energy on the map of distribution of electron band energy depending upon the value of quasi-impulse, multiple to the first, second and third Brillouin zone for transition metals. The maximum relative error of the regressions obtained as compared with the literary data is 15-20 rel.%

  19. A synthetic, spectroscopic and magnetic susceptibility study of selected main group and transition metal fluoro compounds

    Cader, M.S.R.

    1992-01-01

    This study was initiated in order to synthesize and to investigate the magnetic properties of selected main group and transition metal cationic complexes, all stabilized by weakly basic fluoro anions derived either from the Broensted superacids HSO[sub 3]F and HSO[sub 3]CF[sub 3], or the Lewis acids SbF[sub 5] and AsF[sub 5]. The solvolysis of metal(II) fluorosulfates in excess SbF[sub 5] is found to be a useful synthetic route to the corresponding divalent hexafluoro antimonates. The Sn(SbF[sub 6])[sub 2] product from the above synthesis, and its precursor Sn(SO[sub 3]F)[sub 2], react with excess 1,3,5-trimethylbenzene(mes) to give the [pi]-arene adducts Sn(SbF[sub 6])[sub 2][center dot]2mes and Sn(SO[sub 3]F)[sub 2][center dot]mes in high yield. The adducts are characterized by elemental analysis and infrared spectra. The adduct formation is followed by [sup 119]Sn Moessbauer spectroscopy. The divalent fluorosulfates Ni(SO[sub 3]F)[sub 2], Pd(SO[sub 3]F)[sub 2], Pd(SO[sub 3]F)[sub 2] and Ag(SO[sub 3]F)[sub 2], precursors to the M(SbF[sub 6])[sub 2] compounds, and the mixed valency Pd(II) [Pd(IV)(SO[sub 3]F)[sub 6

  20. Investigation of Dissolution Behavior of Metallic Substrates and Intermetallic Compound in Molten Lead-free Solders

    Yen, Yee-Wen; Chou, Weng-Ting; Tseng, Yu; Lee, Chiapyng; Hsu, Chun-Lei

    2008-01-01

    This study investigates the dissolution behavior of the metallic substrates Cu and Ag and the intermetallic compound (IMC)-Ag3Sn in molten Sn, Sn-3.0Ag-0.5Cu, Sn-58Bi and Sn-9Zn (in wt.%) at 300, 270 and 240°C. The dissolution rates of both Cu and Ag in molten solder follow the order Sn > Sn-3.0Ag-0.5Cu >Sn-58Bi > Sn-9Zn. Planar Cu3Sn and scalloped Cu6Sn5 phases in Cu/solders and the scalloped Ag3Sn phase in Ag/solders are observed at the metallic substrate/solder interface. The dissolution mechanism is controlled by grain boundary diffusion. The planar Cu5Zn8 layer formed in the Sn-9Zn/Cu systems. AgZn3, Ag5Zn8 and AgZn phases are found in the Sn-9Zn/Ag system and the dissolution mechanism is controlled by lattice diffusion. Massive Ag3Sn phases dissolved into the solders and formed during solidification processes in the Ag3Sn/Sn or Sn-3.0Ag-0.5Cu systems. AgZn3 and Ag5Zn8 phases are formed at the Sn-9Zn/Ag3Sn interface. Zn atoms diffuse through Ag-Zn IMCs to form (Ag, Zn)Sn4 and Sn-rich regions between Ag5Zn8 and Ag3Sn.

  1. Adsorptive removal of nitrogen-containing compounds from fuel by metal-organic frameworks

    Zhaoyang; Wang; Zhiguo; Sun; Linghao; Kong; Gang; Li

    2013-01-01

    The adsorptive denitrogenation from fuels over three metal-organic frameworks(MIL-96(Al),MIL-53(Al)and MIL-101(Cr))was studied by batch adsorption experiments.Four nitrogen-containing compounds(NCCs)pyridine,pyrrole,quinoline and indole were used as model NCCs in fuels to study the adsorption mechanism.The physicochemical properties of the adsorbents were characterized by XRD,N2physical adsorption,FT-IR spectrum and Hammett indicator method.The metal-organic frameworks(MOFs),especially the MIL-101(Cr)containing Lewis acid sites as well as high specific surface area,can adsorb large quantities of NCCs from fuels.In addition,the adsorptive capacity over MIL-101(Cr)will be different for NCCs with different basicity.The stronger basicity of the NCC is,the more it can be absorbed over MIL-101(Cr).Furthermore,pore size and shape also affect the adsorption capacity for a given adsorbate,which can be proved by the adsorption over MIL-53(Al)and MIL-96(Al).The pseudo-second-order kinetic model and Langmuir equation can be used to describe kinetics and thermodynamics of the adsorption process,respectively.Finally,the regeneration of the used adsorbent has been conducted successfully by just washing it with ethanol.

  2. Electronic Structures of Square Planar Coordinated Transition Metal Ions in Compounds with Gillespite Structure

    林传易

    1990-01-01

    Electronic structures of square planar coordinated transition metal ions in BaCuSi4O10 and CaCrSi4O10 are investigated using the ligand-field theory(LFT),angular overlap model(AOM) and iterative extended Hueckel molecular orbital theory(IET).The electronic energy levels of the natural mineral dioptase are also investigated,in which the Cu2+ ions occupy the sites of pseudo D4h symmetry,Both LFT and AOM predict that the crystal-field levels of transition metal ions in these compounds follow such an order that E(2B1g)

  3. Concentration of actinides in the food chain

    Considerable concern is now being expressed over the discharge of actinides into the environment. This report presents a brief review of the chemistry of the actinides and examines the evidence for interaction of the actinides with some naturally-occurring chelating agents and other factors which might stimulate actinide concentration in the food chain of man. This report also reviews the evidence for concentration of actinides in plants and for uptake through the gastrointestinal tract. (author)

  4. Determination of volatile metal and metalloid compounds in gases from domestic waste deposits with GC/ICP-MS

    Feldmann, J. (Inst. of Environmental Analytical Chemistry, Univ. of Essen (Germany)); Gruemping, R. (Inst. of Environmental Analytical Chemistry, Univ. of Essen (Germany)); Hirner, A.V. (Inst. of Environmental Analytical Chemistry, Univ. of Essen (Germany))

    1994-10-01

    Low temperature GC coupled on-line with ICP-MS was used to identify volatile metal and metalloid compounds in gases and condensates from a domestic waste deposit. Seven tin species could be identified by external standard addition and further volatile compounds of tin, bismuth, mercury, arsenic, antimony and tellurium could be found by boiling point calibration, respectively. Some technical and methodical concepts towards quantification of the results are indicated. (orig.)

  5. Calorimetric assay of minor actinides

    Rudy, C.; Bracken, D.; Cremers, T.; Foster, L.A.; Ensslin, N.

    1996-12-31

    This paper reviews the principles of calorimetric assay and evaluates its potential application to the minor actinides (U-232-4, Am-241, Am- 243, Cm-245, Np-237). We conclude that calorimetry and high- resolution gamma-ray isotopic analysis can be used for the assay of minor actinides by adapting existing methodologies for Pu/Am-241 mixtures. In some cases, mixtures of special nuclear materials and minor actinides may require the development of new methodologies that involve a combination of destructive and nondestructive assay techniques.

  6. Calorimetric assay of minor actinides

    This paper reviews the principles of calorimetric assay and evaluates its potential application to the minor actinides (U-232-4, Am-241, Am- 243, Cm-245, Np-237). We conclude that calorimetry and high- resolution gamma-ray isotopic analysis can be used for the assay of minor actinides by adapting existing methodologies for Pu/Am-241 mixtures. In some cases, mixtures of special nuclear materials and minor actinides may require the development of new methodologies that involve a combination of destructive and nondestructive assay techniques

  7. Results of storage studies of separated minor actinides

    In the framework of the French law of 1991 about the management of radioactive wastes, studies have been carried out on the separation, conditioning and storage of minor actinides in order to dispose of a complete and thorough processing file for spent fuels: conversion of actinide nitrate liquid solutions from deep separation processes into solid compounds, conversion of these compounds into a physical form suitable for storage, conditioning of these compounds in the form of packages, and design of storage facilities compatible with the specificities (thermal, radioactive) of separated minor actinides and with storage durations of few decades. The already-tested industrial processes have been favored, the feasibility of conditioning and storage operations have been evaluated for curium, in particular concerning the thermal aspect. The studies carried out so far have permitted to define the conversion process and the conditioning solution and to evaluate different possibilities of storage facility concepts. The future studies will focus on the development of optimized versions of facilities specific to each category of separated minor actinides. (J.S.)

  8. Serum heavy metals and hemoglobin related compounds in Saudi Arabia firefighters

    Al-Malki Abdulrahman L

    2009-07-01

    Full Text Available Abstract Background Firefighters are frequently exposed to significant concentrations of hazardous materials including heavy metals, aldehydes, hydrogen chloride, dichlorofluoromethane and some particulates. Many of these materials have been implicated in the triggering of several diseases. The aim of the present study is to investigate the effect of fire smoke exposure on serum heavy metals and possible affection on iron functions compounds (total iron binding capacity, transferrin saturation percent, ferritin, unsaturated iron-binding capacity blood hemoglobin and carboxyhemoglobin,. Subjects and methods Two groups of male firefighter volunteers were included; the first included 28 firefighters from Jeddah city, while the second included 21 firefighters from Yanbu city with an overall age rang of 20–48 years. An additional group of 23 male non-firefighters volunteered from both cities as normal control subjects. Blood samples were collected from all volunteer subjects and investigated for relevant parameters. Results The results obtained showed that there were no statistically significant changes in the levels of serum heavy metals in firefighters as compared to normal control subjects. Blood carboxyhemoglobin and serum ferritin were statistically increased in Jeddah firefighters, (p Conclusion Such results might point to the need for more health protective and prophylactic measures to avoid such hazardous health effects (elevated Blood carboxyhemoglobin and serum ferritin and decreased serum TIBC and UIBC that might endanger firefighters working under dangerous conditions. Firefighters must be under regular medical follow-up through standard timetabled medical laboratory investigations to allow for early detection of any serum biochemical or blood hematological changes.

  9. Actinides and the environment

    The book combines in one volume the opinions of experts regarding the interaction of radionuclides with the environment and possible ways to immobilize and dispose of nuclear waste. The relevant areas span the spectrum from pure science, such as the fundamental physics and chemistry of the actinides, geology, environmental transport mechanisms, to engineering issues such as reactor operation and the design of nuclear waste repositories. The cross-fertilization between these various areas means that the material in the book will be accessible to seasoned scientists who may wish to obtain an overview of the current state of the art in the field of environmental remediation of radionuclides, as well as to beginning scientists embarking on a career in this field. refs

  10. Reversible optical sensor for the analysis of actinides in solution

    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 P2W17O6110- or SiW11O398- 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.)

  11. Molecular solids of actinide hexacyanoferrate: Structure and bonding

    The hexacyanometallate family is well known in transition metal chemistry because the remarkable electronic delocalization along the metal-cyano-metal bond can be tuned in order to design systems that undergo a reversible and controlled change of their physical properties. We have been working for few years on the description of the molecular and electronic structure of materials formed with [Fe(CN)6]n- building blocks and actinide ions (An = Th, U, Np, Pu, Am) and have compared these new materials to those obtained with lanthanide cations at oxidation state +III. In order to evaluate the influence of the actinide coordination polyhedron on the three-dimensional molecular structure, both atomic number and formal oxidation state have been varied : oxidation states +III, +IV. EXAFS at both iron K edge and actinide LIII edge is the dedicated structural probe to obtain structural information on these systems. Data at both edges have been combined to obtain a three-dimensional model. In addition, qualitative electronic information has been gathered with two spectroscopic tools : UV-Near IR spectrophotometry and low energy XANES data that can probe each atom of the structural unit : Fe, C, N and An. Coupling these spectroscopic tools to theoretical calculations will lead in the future to a better description of bonding in these molecular solids. Of primary interest is the actinide cation ability to form ionic - covalent bonding as 5f orbitals are being filled by modification of oxidation state and/or atomic number.

  12. Effects of Different Lead Compounds on Growth and Heavy Metal Uptake of Wetland Rice

    CHENHUAI-MAN; ZHENGCHUN-RONG; 等

    1991-01-01

    Effects of different lead compounds,PbCl2,Pb(NO3)2 and Pb(OAc)2,on the rice growth and uptake of lead and some microelements by wetland rice were studied.The results showed that the seed germination,rice seedling growth,chlorophyl content,grain yield and uptake of Pb,Cu,Zn,Fe and Mn by rice plant were affected by the chemical forms of Pb compunds added in soil to a certain degree.The germination rate and the amount of chlorophyl decreased remarkably with increasing Pb concentration,the root extension was restrained obviously by the presence of Pb,and the effect of PbCl2 was more evident than that of Pb(NO3)2 or Pb(OAc)2.The pot incubation test with yellow brown soil and redsoil showed that there was no significant regularity in effect of Pb on grain yield,but the difference in the influence of various Pb compounds on yield was clearer.The effect on the amount of Pb in straw and brown rice was in the sequence of Pb(NO3)2>Pb(OAc)2>PbCl1.In case the content of Pb in brown rice was 0.5mg/kg,the relative loading capacities of yellow brown soil for Pb added as PbCl2,Pb(OAc)2 and Pb(NO3)2 were 100,90 and 60 respectively.Pb uptake by wetland rice was closely related to the chemical species of Pb in soil,but there was no comparability among chemical forms of different Pb compounds in the same soil.The uptake of Cu,Zn,Fe and Mn by wetland rice was markedly affected by the addition of Pb,and different Pb compounds varied in their impacts on the uptake of other metals by different organs of wetland rice,e.g.the concentration of Fe in root increased significantly (r=0.92**),while opposite was true for Fe in brown rice (r=-0.92**) due to the application of Pb(OAc)2 in soil.These results demonstrate that the effect of accompanying anions of Pb on the physiological and biochemical processes of wetland rice was rather complex.

  13. Comparative Studies of Chemical Effects following Nuclear Reactions and Transformations on Metal Organic Phenyl Compounds

    A study of the chemical effects created by the energetic recoil atoms of nuclear reactions in solids and liquids was made on the basis of a broad comparison of the products formed by (n, γ) and (n, 2n) processes in the metalphenyl compounds of germanium, tin, lead, arsenic and antimony. In addition, the radioactive recoil products formed after the K-capture process on Ge68 - tetraphenyl are compared with the results from the (n, γ) -process on Ga-triphenyl and the (n,p) process on Ge-tetra phenyl. Finally, the studies include the β- transition on Ge77-tetraphenyl to As77. Applying different separation methods, e.g. adsorption chromatography on alumina, ion exchange and electrophoresis, the various radioactive recoil products were separated and the individual yields determined. It was found that in nuclear reactions the compounds of the mentioned metals having identical ligands formed practically the same classes of recoil products. The yield distribution however reveals characteristic alterations between the (n, γ) and (n, 2n) reaction. Only a small influence on the yields is perceptible when irradiations are performed in liquids and solutions. The large differences found for the new compounds formed by nuclear transformations are striking, not only in the kind of typical products but also in their percentage yields. Thus, several recoil products of Ge and Ga with metalorganic character were found by nuclear reactions on Ge-tetraphenyl that could not be detected at all by the K-capture process on Ge68-tetraphenyl. The β- decay on Ge77-tetraphenyl produces practically the same chemical compounds as were observed by nuclear reactions. However, a remarkable increase in the portion of the labelled parent molecules (retention) is typical for the β- transition. The results are discussed on the basis of theoretical considerations of the amount of kinetic energy transferred to the reacting molecule by the nuclear recoil and the resulting excitation. The hypothesis is

  14. Environmental research on actinide elements

    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

  15. Lanthanides and actinides among other groups of elements of the D.I. Mendeleev's Periodic Table

    The extent to which actinides are similar to other elements of the periodic table is discussed. Actinides show certain similarity with transition metals in trends in variation of stability of the highest and lowest oxidation states with increasing atomic number. Similarity between elements of the first half of the lanthanide family and those of the second half of the actinides family is demonstrated. In the lowest oxidation states, actinides and lanthanide are analogs of alkali and alkaline-earth elements, and in the tetravalent state they start to exhibit noticeable similarity with d elements. The formation of Pu(VIII) is suggested on the basis of essentially similar volatility of oxides of Os and Ru with that of Pu. Bivalent actinides and lanthanide ions with one d electron are of particular interest. Being analogs of bivalent elements, they form various types of clusters

  16. Properties of minor actinide nitrides

    The present status of the research on properties of minor actinide nitrides for the development of an advanced nuclear fuel cycle based on nitride fuel and pyrochemical reprocessing is described. Some thermal stabilities of Am-based nitrides such as AmN and (Am, Zr)N were mainly investigated. Stabilization effect of ZrN was cleary confirmed for the vaporization and hydrolytic behaviors. New experimental equipments for measuring thermal properties of minor actinide nitrides were also introduced. (author)

  17. Metal ion selectivities of the highly preorganized tetradentate ligand 1,10-phenanthroline-2,9-dicarboxamide with lanthanide(III) ions and some actinide ions

    Merill, D.; Hancock, R.D. [North Carolina Univ., Wilmington, NC (United States). Dept. of Chemistry and Biochemistry

    2011-07-01

    Metal ion complexing properties of the ligand PDAM (1,10-phenanthroline-2,9-dicarboxamide) are reported in relation to its possible use as a functional group for solvent extractants in the separation of Am(III) from Ln(III) (lanthanide) ions. PDAM is only slightly water soluble, but variation of the intense {pi}-{pi}{sup *} transitions in the UV spectrum of 2 x 10{sup -5} M PDAM solutions as a function of pH or metal ion concentration allowed for the determination of the protonation constant (pK) and logK{sub 1} values with metal ions. The pK of PDAM is 0.6 {+-} 0.1 in 1.0 M NaClO{sub 4}, the lowest for any 1,10-phenanthroline (phen) derivative (in contrast, pK phen=5.1), which is attributed to the electron-withdrawing properties of the amide substituents of PDAM. The weak proton basicity of PDAM may be an important factor in its use as the functional group of a solvent extractant from acidic solutions. The formation constants are determined by UV-Visible spectroscopy for the Ln(III) ions from La(III) to Lu(III) (excluding Pm(III)), as well as for Y(III), Sc(III), Th(IV), and the UO{sub 2}{sup 2+} cation in 0.1 M NaClO{sub 4} at 25 C. The log K{sub 1} values for the Ln(III) ions show only small changes from La(III) to Lu(III) (both have log K{sub 1} = 3.80). The amide O-donors (oxygen donors) of the amide groups of PDAM appear to cause considerable stabilization of the complexes of PDAM as compared to those of phen, consistent with the idea that the neutral O-donor is a strong Lewis base towards large metal ions such as the Ln(III) ions. A reviewer has pointed out that the amide groups would also stabilize the complexes of PDAM by virtue of the chelate effect, in that PDAM is tetradentate, while phen is only bidentate. The small change in complex stability for PDAM complexes in passing from La(III) to Lu(III) is rationalized in terms of the idea that neutral O-donors stabilize the complexes of the large La(III) ion more than the smaller Lu(III) ion, offsetting the

  18. Measurement of standard potentials of actinides (U,Np,Pu,Am) in LiCl-KCl eutectic salt and separation of actinides from rare earths by electrorefining

    Pyrochemical separation of actinides from rare earths in LiCl-KCl eutectic-liquid metal systems has been studied. The electromotive forces of galvanic cells of the form, Ag vertical stroke Ag(I), LiCl-KCl parallel actinide(III), LiCl-KCl vertical stroke actinide, were measured and standard potentials were determined for uranium, neptunium and plutonium to be -1.283 V, -1.484 V and -1.593 V (at 450 C vs. Ag/AgCl (1wt%-AgCl)), respectively. A typical cyclic voltammogram of americium chloride has two cathodic peaks, which suggests reduction Am(III)→Am(II) occurs followed by reduction of Am(II) to americium metal. Standard potential of Am(II)/Am(0) was estimated to be -1.642 V. Electrorefining experiments to separate actinides (U, Np, Pu and Am) from rare earths (Y, La, Ce, Nd and Gd) in LiCl-KCl eutectic salt were carried out. It was shown that the actinide metals were recovered on the cathodes and that americium was the most difficult to separate from rare earths. The actinide separation will be achieved by means of the combination of electrorefining with multistage extraction. (orig.)

  19. Semivolatile organic compounds, organochlorine pesticides and heavy metals in sediments and risk assessment in Huaihe River of China

    2006-01-01

    The concentrations of semivolatile organic compounds, organochlorine pesticides and heavy metals in sediments from Jiangsu reach of Huaihe River, China, were presented. The organic compounds were extracted by acetone: n-hexane using a Soxhlet apparatus and concentrations were performed using HP6890 gas chromatography coupled by FID and ECD detector. The total contents of 8 heavy metals by inductively coupled plasma atomic emission spectrometry or cold-vapor/atomic absorption spectrometry were developed. 30 semivolatile organic compounds were detected, including substituted benzenes, phenols, phthalates and polycyclic aromatic hydrocarbons, from 0.01 to 3.01 mg/kg. 16 organochlorine pesticides were almost detected and from 0.010 to 2.339 μg/kg.Concentrations of major metals were 50 mg/kg or less, mean level of mercury was only 0.055 mg/kg. Compared to sediment quality guidelines (SQGs), concentrations of some semivolatile organic compounds were high enough to cause possible toxic effects to living resources. The organochlorine pesticides presented relatively low, lower than threshold effect concentrations (TECs), harmful effects on sediment-dwelling organisms were not expected. Chromium posed probable toxic effects to the living resources, other heavy metals had no threat temporarily according to SQGs.

  20. Theoretical models for intensities of d→f transitions in electron-energy-loss spectra of rare-earth and actinide metals

    We calculate cross sections for electron-impact excitation of core electrons for La and Th metal within the local-density approximation (LDA), in particular, for the 4d→4f and 3d→4f transitions in La and for the 5d→5f and 4d→5f transitions in Th. The purpose is to account for the intensity variation of experimental electron-energy-loss spectra (EELS) when the incident-electron energy is lowered from high energies down to threshold, and, in particular, the appearance of structure due to exchange scattering involving capture into localized f levels. We use the distorted-wave approximation (DWA) at low incident energies and calculate direct and exchange inelastic-scattering cross sections for LS-resolved core excitations (neglecting spin-orbit interaction). In addition we have also made use of the Born approximation over the whole energy range. In general, the LDA DWA cross sections account rather well for the relative intensities of groups of spectral features connected with localized d→f excitations in EELS for La and Th metal. In La, the 3d→4f and 4d→4f transitions show similar exchange to direct inelastic-scattering cross-section ratios as functions of incident electron energy on the scale of the excitation energy. The ratio is of the order of unity at threshold. Our calculated branching ratios for 3L to 1P and 1F to 1P in La are in reasonable agreement with experimental trends. We find a clear difference between 4f and 5f elements in what concerns low-energy and threshold behavior. In particular, the 4d→5f transition in Th seems to be very special

  1. The electronic g matrix of some actinide complexes

    Complete text of publication follows: The molecular g-factors are crucial parameters in Electron Paramagnetic Resonance (EPR) spectroscopy. They parametrize the Zeeman effect that involves the interaction of a spin magnetic moment with a magnetic field. Before the 90's, g-factors were mostly calculated by semi-empirical methods while in the last decade, ab initio techniques have been developed based on wave functions or density functional theories either using a sum over states (SOS) expansion or using response theory [1]. We have recently proposed an alternative method based on wave function theory including spin-orbit effects by the SO-RASSI method [2]. This method has been applied with success to small molecules containing atoms until the third series of the transition metals and to a mixed-valence bimetallic complex[3] and in this work, it is applied to actinide complexes with a 5f1 configuration. To our knowledge, only few attempts have been made to calculate g-factors of actinide complexes from first principles [4, 5]. Relativistic effects in actinide complexes are important, so the deviation of g-factors from the value of the free electron is large and can even become negative. Most of the experiments measuring magnetic properties of actinide complexes date from the sixties. EPR and magnetic susceptibilities give the absolute values of the g-factors while experiment using circularly polarized light provide the sign of the product of the three factors. Magnetic properties of these compounds are easily understood using ligand field theory models. In the first part of this presentation, we will discuss the arbitrary character of the g-matrix and specially of the effect of phase factors and of the choice of the spin quantification axis and we will show that only the G tensor gg* has a physical significance. In the second part, equilibrium distances, excitation energies and g-factors of the AnXq-6 series with An = Pa,U,Np and X = F,Cl,Br are calculated using the

  2. Flexible metal-organic framework compounds: In situ studies for selective CO{sub 2} capture

    Allen, A.J., E-mail: andrew.allen@nist.gov [Material Measurement Laboratory, National Institute of Standards and Technology (NIST), Gaithersburg, MD 20899-8520 (United States); Espinal, L.; Wong-Ng, W. [Material Measurement Laboratory, National Institute of Standards and Technology (NIST), Gaithersburg, MD 20899-8520 (United States); Queen, W.L. [NIST Center for Neutron Research, Gaithersburg, MD 20899-6102 (United States); The Molecular Foundry, Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA 94720 (United States); Brown, C.M. [NIST Center for Neutron Research, Gaithersburg, MD 20899-6102 (United States); Department of Chemical and Biomolecular Engineering, University of Delaware, Newark, DE 19716 (United States); Kline, S.R. [NIST Center for Neutron Research, Gaithersburg, MD 20899-6102 (United States); Kauffman, K.L. [National Energy Technology Laboratory (NETL), US Department of Energy, Pittsburgh, PA 15236 (United States); Culp, J.T. [National Energy Technology Laboratory (NETL), US Department of Energy, Pittsburgh, PA 15236 (United States); URS Corporation, South Park, PA 15219 (United States); Matranga, C. [National Energy Technology Laboratory (NETL), US Department of Energy, Pittsburgh, PA 15236 (United States)

    2015-10-25

    Results are presented that explore the dynamic structural changes occurring in two highly flexible nanocrystalline metal-organic framework (MOF) compounds during the adsorption and desorption of pure gases and binary mixtures. The Ni(1,2-bis(4-pyridyl)ethylene)[Ni(CN){sub 4}] and catena-bis(dibenzoylmethanato)-(4,4′-bipyridyl)nickel(II) chosen for this study are 3-D and 1-D porous coordination polymers (PCP) with a similar gate opening pressure response for CO{sub 2} isotherms at 303 K, but with differing degrees of flexibility for structural change to accommodate guest molecules. As such, they serve as a potential model system for evaluating the complex kinetics associated with dynamic structure changes occurring in response to gas adsorption in flexible MOF systems. Insights into the crystallographic changes occurring as the MOF pore structure expands and contracts in response to interactions with CO{sub 2}, N{sub 2}, and CO{sub 2}/N{sub 2} mixtures have been obtained from in situ small-angle neutron scattering and neutron diffraction, combined with ex situ X-ray diffraction structure measurements. The role of structure in carbon capture functionality is discussed with reference to the ongoing characterization challenges and a possible materials-by-design approach. - Graphical abstract: We present in situ small-angle neutron scattering results for two flexible metal-organic frameworks (MOFs). The figure shows that for one (NiBpene, high CO{sub 2} adsorption) the intensity of the Bragg peak for the expandable d-spacing most associated with CO{sub 2} adsorption varies approximately with the isotherm, while for the other (NiDBM-Bpy, high CO{sub 2} selectivity) the d-spacing, itself, varies with the isotherm. The cartoons show the proposed modes of structural change. - Highlights: • Dynamic structures of two flexible MOF CO{sub 2} sorbent compounds are compared in situ. • These porous solid sorbents serve as models for pure & dual gas adsorption. • Different

  3. Synthesis and characterization of porous metal oxides and desulfurization studies of sulfur containing compounds

    Garces Trujillo, Hector Fabian

    This thesis contains two parts: 1) synthesis and characterization of porous metal oxides that include zinc oxide and a porous mixed-valent manganese oxide with an amorphous structure (AMO) 2) the desulfurization studies for the removal of sulfur compounds. Zinc oxide with different nano-scale morphologies may result in various porosities with different adsorption capabilities. A tunable shape microwave synthesis of ZnO nano-spheres in a co-solvent mixture is presented. The ZnO nano-sphere material is investigated as a desulfurizing sorbent in a fixed bed reactor in the temperature range 200 to 400 °C and compared with ZnO nanorods and platelet-like morphologies. Fresh and sulfided materials were characterized by X-ray diffraction (XRD), BET specific surface area, pore volume, scanning electron microscopy (SEM), X-ray energy dispersive spectroscopy (SEM/EDX), Raman spectroscopy, and thermogravimetric analysis (TGA). The tunable shape microwave synthesis of ZnO presents a high sulfur sorption capacity at temperatures as low as 200 °C which accounts for a three and four fold enhancement over the other preparations presented in this work, and reached 76 % of the theoretical sulfur capacity (TSC) at 300 °C. Another ZnO material with a bimodal micro- and mesopore size distribution investigated as a desulfurizing sorbent presents a sorption capacity that reaches 87% of the theoretical value for desulfurization at 400 °C at breakthrough time. A deactivation model that considers the activity of the solid reactant was used to fit the experimental data. Good agreement between the experimental breakthrough curves and the model predictions are obtained. Manganese oxides are a type of metal oxide materials commonly used in catalytic applications. Little is known about the adsorption capabilities for the removal of sulfur compounds. One of these manganese oxides; amorphous manganese oxide (AMO) is highly promising material for low temperature sorption processes. Amorphous

  4. Flexible metal-organic framework compounds: In situ studies for selective CO2 capture

    Results are presented that explore the dynamic structural changes occurring in two highly flexible nanocrystalline metal-organic framework (MOF) compounds during the adsorption and desorption of pure gases and binary mixtures. The Ni(1,2-bis(4-pyridyl)ethylene)[Ni(CN)4] and catena-bis(dibenzoylmethanato)-(4,4′-bipyridyl)nickel(II) chosen for this study are 3-D and 1-D porous coordination polymers (PCP) with a similar gate opening pressure response for CO2 isotherms at 303 K, but with differing degrees of flexibility for structural change to accommodate guest molecules. As such, they serve as a potential model system for evaluating the complex kinetics associated with dynamic structure changes occurring in response to gas adsorption in flexible MOF systems. Insights into the crystallographic changes occurring as the MOF pore structure expands and contracts in response to interactions with CO2, N2, and CO2/N2 mixtures have been obtained from in situ small-angle neutron scattering and neutron diffraction, combined with ex situ X-ray diffraction structure measurements. The role of structure in carbon capture functionality is discussed with reference to the ongoing characterization challenges and a possible materials-by-design approach. - Graphical abstract: We present in situ small-angle neutron scattering results for two flexible metal-organic frameworks (MOFs). The figure shows that for one (NiBpene, high CO2 adsorption) the intensity of the Bragg peak for the expandable d-spacing most associated with CO2 adsorption varies approximately with the isotherm, while for the other (NiDBM-Bpy, high CO2 selectivity) the d-spacing, itself, varies with the isotherm. The cartoons show the proposed modes of structural change. - Highlights: • Dynamic structures of two flexible MOF CO2 sorbent compounds are compared in situ. • These porous solid sorbents serve as models for pure & dual gas adsorption. • Different degrees of structural freedom give different CO2 adsorption

  5. Bioavailability of Heavy Metals in Soil: Impact on Microbial Biodegradation of Organic Compounds and Possible Improvement Strategies

    Balakrishna Pillay

    2013-05-01

    Full Text Available Co-contamination of the environment with toxic chlorinated organic and heavy metal pollutants is one of the major problems facing industrialized nations today. Heavy metals may inhibit biodegradation of chlorinated organics by interacting with enzymes directly involved in biodegradation or those involved in general metabolism. Predictions of metal toxicity effects on organic pollutant biodegradation in co-contaminated soil and water environments is difficult since heavy metals may be present in a variety of chemical and physical forms. Recent advances in bioremediation of co-contaminated environments have focussed on the use of metal-resistant bacteria (cell and gene bioaugmentation, treatment amendments, clay minerals and chelating agents to reduce bioavailable heavy metal concentrations. Phytoremediation has also shown promise as an emerging alternative clean-up technology for co-contaminated environments. However, despite various investigations, in both aerobic and anaerobic systems, demonstrating that metal toxicity hampers the biodegradation of the organic component, a paucity of information exists in this area of research. Therefore, in this review, we discuss the problems associated with the degradation of chlorinated organics in co-contaminated environments, owing to metal toxicity and shed light on possible improvement strategies for effective bioremediation of sites co-contaminated with chlorinated organic compounds and heavy metals.

  6. Radiochemical studies of neutron deficient actinide isotopes

    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, 242Bk, was produced with a cross-section of approximately 10 μb 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, αxn) 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.,αxn) reaction may be higher than its production via an xn compound nucleus reaction. These results have dire consequences for proponents of the ''Z1 + Z2 = Z/sub 1+2/'' philosophy. It is no longer acceptable to assume that (H.I.,pxn) and (H.I.,αxn) product yields are of no consequence when studying compound nucleus reactions. No evidence for spontaneous fission decay of 228Pu, 230Pu, 232Cm, or 238Cf 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

  7. Radiochemical studies of neutron deficient actinide isotopes

    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.

  8. Actinide 5f systems: experimental determination of the magnetic response function

    Understanding of metallic actinide systems is in confusion. Searches for crystal-field levels with neutron spectroscopy have, for the most part, been unsuccessful, despite the acknowledged importance of the 5f electrons in determining the magnetic behavior. In systems such as UAl2, USn3 and UN a broad response function, S(Q vector,ω), reminiscent of that found in intermediate valent compounds, exists. Neutron inelastic scattering experiments on single crystals have shown the small influence of the crystal field. Instead we find an unusual response function dominated by the longitudinal susceptibility chi/sup zz/(Q vector,,ω) such that transverse excitations - conventional spin waves - do not exist at low energies. As yet a detailed theoretical interpretation of the measurements does not exist. Indeed, the small, although not necessarily negligible, role of the crystal field presents conceptual difficulties if we anticipate behavior analogous to that found in many lanthanide 4f systems. Some alternate approaches are discussed

  9. The Dirac equation in electronic structure calculations: Accurate evaluation of DFT predictions for actinides

    Wills, John M [Los Alamos National Laboratory; Mattsson, Ann E [Sandia National Laboratories

    2012-06-06

    Brooks, Johansson, and Skriver, using the LMTO-ASA method and considerable insight, were able to explain many of the ground state properties of the actinides. In the many years since this work was done, electronic structure calculations of increasing sophistication have been applied to actinide elements and compounds, attempting to quantify the applicability of DFT to actinides and actinide compounds and to try to incorporate other methodologies (i.e. DMFT) into DFT calculations. Through these calculations, the limits of both available density functionals and ad hoc methodologies are starting to become clear. However, it has also become clear that approximations used to incorporate relativity are not adequate to provide rigorous tests of the underlying equations of DFT, not to mention ad hoc additions. In this talk, we describe the result of full-potential LMTO calculations for the elemental actinides, comparing results obtained with a full Dirac basis with those obtained from scalar-relativistic bases, with and without variational spin-orbit. This comparison shows that the scalar relativistic treatment of actinides does not have sufficient accuracy to provide a rigorous test of theory and that variational spin-orbit introduces uncontrolled errors in the results of electronic structure calculations on actinide elements.

  10. A glass-encapsulated calcium phosphate wasteform for the immobilization of actinide-, fluoride-, and chloride-containing radioactive wastes from the pyrochemical reprocessing of plutonium metal

    Chloride-containing radioactive wastes are generated during the pyrochemical reprocessing of Pu metal. Immobilization of these wastes in borosilicate glass or Synroc-type ceramics is not feasible due to the very low solubility of chlorides in these hosts. Alternative candidates have therefore been sought including phosphate-based glasses, crystalline ceramics and hybrid glass/ceramic systems. These studies have shown that high losses of chloride or evolution of chlorine gas from the melt make vitrification an unacceptable solution unless suitable off-gas treatment facilities capable of dealing with these corrosive by-products are available. On the other hand, both sodium aluminosilicate and calcium phosphate ceramics are capable of retaining chloride in stable mineral phases, which include sodalite, Na8(AlSiO4)6Cl2, chlorapatite, Ca5(PO4)3Cl, and spodiosite, Ca2(PO4)Cl. The immobilization process developed in this study involves a solid state process in which waste and precursor powders are mixed and reacted in air at temperatures in the range 700-800 deg. C. The ceramic products are non-hygroscopic free-flowing powders that only require encapsulation in a relatively low melting temperature phosphate-based glass to produce a monolithic wasteform suitable for storage and ultimate disposal

  11. A glass-encapsulated calcium phosphate wasteform for the immobilization of actinide-, fluoride-, and chloride-containing radioactive wastes from the pyrochemical reprocessing of plutonium metal

    Donald, I. W.; Metcalfe, B. L.; Fong, S. K.; Gerrard, L. A.; Strachan, D. M.; Scheele, R. D.

    2007-03-01

    Chloride-containing radioactive wastes are generated during the pyrochemical reprocessing of Pu metal. Immobilization of these wastes in borosilicate glass or Synroc-type ceramics is not feasible due to the very low solubility of chlorides in these hosts. Alternative candidates have therefore been sought including phosphate-based glasses, crystalline ceramics and hybrid glass/ceramic systems. These studies have shown that high losses of chloride or evolution of chlorine gas from the melt make vitrification an unacceptable solution unless suitable off-gas treatment facilities capable of dealing with these corrosive by-products are available. On the other hand, both sodium aluminosilicate and calcium phosphate ceramics are capable of retaining chloride in stable mineral phases, which include sodalite, Na 8(AlSiO 4) 6Cl 2, chlorapatite, Ca 5(PO 4) 3Cl, and spodiosite, Ca 2(PO 4)Cl. The immobilization process developed in this study involves a solid state process in which waste and precursor powders are mixed and reacted in air at temperatures in the range 700-800 °C. The ceramic products are non-hygroscopic free-flowing powders that only require encapsulation in a relatively low melting temperature phosphate-based glass to produce a monolithic wasteform suitable for storage and ultimate disposal.

  12. Intra-chain superexchange couplings in quasi-1D 3d transition-metal magnetic compounds

    Xiang, Hongping; Tang, Yingying; Zhang, Suyun; He, Zhangzhen

    2016-07-01

    The electronic structure and magnetic properties of the quasi-1D transition-metal borates PbMBO4 (M  =  Ti, V, Cr, Mn, Fe, Co) have been investigated by density functional theory, including electronic correlation. The results evidence PbCrBO4 and PbFeBO4 as antiferromagnetic (AFM) semiconductors (intra-chain AFM and inter-chain FM) and PbMnBO4 as a ferromagnetic (FM) semiconductor (both intra- and inter-chain FM) in accordance with experimental observations. For non-synthesized PbTiBO4, PbVBO4, and PbCoBO4, the ground-state magnetic structures are paramagnetic, FM, and paramagnetic, respectively. In this series of compounds, there are two kinds of superexchange couplings dominating their magnetic properties, i.e. the direction M–M delocalization superexchange and indirect M–O–M correlation superexchange. For PbMBO4 with M 3+ d  n , n  ⩽  3 (M  =  V and Cr), the main intra-chain spin coupling is the M–M t 2g–t 2g direct delocalization superexchange, while for PbMBO4 with M 3+ d  n , n  >  3 (M  =  Mn and Fe), the main intra-chain spin coupling is the near 90° M–O–M e g–p–e g indirect correlation superexchange.

  13. Intra-chain superexchange couplings in quasi-1D 3d transition-metal magnetic compounds.

    Xiang, Hongping; Tang, Yingying; Zhang, Suyun; He, Zhangzhen

    2016-07-13

    The electronic structure and magnetic properties of the quasi-1D transition-metal borates PbMBO4 (M  =  Ti, V, Cr, Mn, Fe, Co) have been investigated by density functional theory, including electronic correlation. The results evidence PbCrBO4 and PbFeBO4 as antiferromagnetic (AFM) semiconductors (intra-chain AFM and inter-chain FM) and PbMnBO4 as a ferromagnetic (FM) semiconductor (both intra- and inter-chain FM) in accordance with experimental observations. For non-synthesized PbTiBO4, PbVBO4, and PbCoBO4, the ground-state magnetic structures are paramagnetic, FM, and paramagnetic, respectively. In this series of compounds, there are two kinds of superexchange couplings dominating their magnetic properties, i.e. the direction M-M delocalization superexchange and indirect M-O-M correlation superexchange. For PbMBO4 with M (3+) d  (n) , n  ⩽  3 (M  =  V and Cr), the main intra-chain spin coupling is the M-M t 2g-t 2g direct delocalization superexchange, while for PbMBO4 with M (3+) d  (n) , n  >  3 (M  =  Mn and Fe), the main intra-chain spin coupling is the near 90° M-O-M e g-p-e g indirect correlation superexchange. PMID:27213502

  14. Sequestering agents for the removal of actinides from waste streams

    Raymond, K.N.; White, D.J.; Xu, Jide; Mohs, T.R. [Univ. of California, Berkeley, CA (United States)

    1997-10-01

    The goal of this project is to take a biomimetic approach toward developing new separation technologies for the removal of radioactive elements from contaminated DOE sites. To achieve this objective, the authors are investigating the fundamental chemistry of naturally occurring, highly specific metal ion sequestering agents and developing them into liquid/liquid and solid supported actinide extraction agents. Nature produces sideophores (e.g., Enterobactin and Desferrioxamine B) to selectivity sequester Lewis acidic metal ions, in particular Fe(III), from its surroundings. These chelating agents typically use multiple catechols or hydroxamic acids to form polydentate ligands that chelate the metal ion forming very stable complexes. The authors are investigating and developing analogous molecules into selective chelators targeting actinide(IV) ions, which display similar properties to Fe(III). By taking advantage of differences in charge, preferred coordination number, and pH stability range, the transition from nature to actinide sequestering agents has been applied to the development of new and highly selective actinide extraction technologies. Additionally, the authors have shown that these chelating ligands are versatile ligands for chelating U(VI). In particular, they have been studying their coordination chemistry and fundamental interactions with the uranyl ion [UO{sub 2}]{sup 2+}, the dominant form of uranium found in aqueous media. With an understanding of this chemistry, and results obtained from in vivo uranium sequestration studies, it should be possible to apply these actinide(IV) extraction technologies to the development of new extraction agents for the removal of uranium from waste streams.

  15. Phytosiderophore Effects on Subsurface Actinide Contaminants: Potential for Phytostabilization and Phytoextraction

    Ruggiero, Christy

    2005-06-01

    This project seeks to understand the influence of phytosiderophore-producing plants (grasses, including crops such as wheat and barley) on the biogeochemistry of actinide and other metal contaminants in the subsurface environment, and to determine the potential of phytosiderophore-producing plants for phytostabilization and phytoextraction of actinides and some metal soil contaminants. Phytosiderophores are secreted by graminaceous plants such as barley and wheat for the solubilization, mobilization and uptake of Fe and other essential nutrients from soils. The ability for these phytosiderophores to chelate and absorb actinides using the same uptake system as for Fe is being investigated though characterization of actinide-phytosiderophore complexes (independently of plants), and characterization of plant uptake of such complexes. We may also show possible harm caused by these plants through increased chelation of actinides that increase in actinide mobilization & migration in the subsurface environment. This information can then be directly applied by either removal of harmful plants, or can be used to develop plant-based soil stabilization/remediation technologies. Such technologies could be the low-cost, low risk solution to many DOE actinide contamination problems.

  16. Compound surface-plasmon-polariton waves guided by a thin metal layer sandwiched between a homogeneous isotropic dielectric material and a structurally chiral material

    Chiadini, Francesco; Scaglione, Antonio; Lakhtakia, Akhlesh

    2015-01-01

    Multiple compound surface plasmon-polariton (SPP) waves can be guided by a structure consisting of a sufficiently thick layer of metal sandwiched between a homogeneous isotropic dielectric (HID) material and a dielectric structurally chiral material (SCM). The compound SPP waves are strongly bound to both metal/dielectric interfaces when the thickness of the metal layer is comparable to the skin depth but just to one of the two interfaces when the thickness is much larger. The compound SPP waves differ in phase speed, attenuation rate, and field profile, even though all are excitable at the same frequency. Some compound SPP waves are not greatly affected by the choice of the direction of propagation in the transverse plane but others are, depending on metal thickness. For fixed metal thickness, the number of compound SPP waves depends on the relative permittivity of the HID material, which can be useful for sensing applications.

  17. Conception, synthesis and application of tripodands in actinide/lanthanide separation

    The purpose of this work is the synthesis of C, H, O and N containing compounds able to separate '4f' and '5f' elements by liquid/liquid extraction. In a first part, the literature's study allow us to point out actinide and lanthanide ions actual nature and the different ways offered by organic chemistry to share two metallic ions between two liquid phases. On one hand, these trivalent cations' high coordination numbers drive us to synthesize tripodands with hard sites which were fitted for complexation. On the other hand, it appeared that carboxylate or even less-hard site like pyridine chelate selectively actinides, allowing separation. In a second part, 60 ligands were synthesized. In each of the ligands families, a structural parameter changes (site nature, distance between two neighbouring sites, sites respective orientation, lipophilicity and rigidity). 2,2-dihydroxymethyl-dodecanol and 1,3,5- tri(chlorocarbonyl) benzene were chosen as core. O-alkylation and amidation reactions were also peculiarly studied. Rekker's proceeding for lipophilicity calculation was used in order to establish a structure-activity relationship. In a third part, extraction assays with radioactive effluents (152Eu and 241Am) point out extraction and separation abilities of our compounds. Different operating ways were used according as ligand is soluble in aqueous or organic phase. Organic phase-soluble compounds were compared to DcH18C6, pyridine ones to 2,4,6-tri(2-pyridyl)-l,3,5-triazine (TPTZ) and carboxylate ones to diethylenetriamine-tetracetic acid (DTPA, Talspeak proceeding). The third phase phenomenon was encountered and studied. Influence of salt, pH and organic phase were also studied. (author)

  18. Actinide coordination sphere in various U, Np and Pu nitrato coordination complexes

    Waste management of nuclear fuel represents one of the major environmental concerns of the decade. To recycle fissile valuable materials, intimate knowledge of complexation mechanisms involved in the solvent extraction processes is indispensable. Evolution of the actinide coordination sphere of AnO2(NO3)2TBP-type complexes (an = U, Np, Pu; TBP = tributylphosphate) with the actinide valence state have been probed by XAS at the metal LIII edge. Dramatic changes in the actinide coordination sphere appeared when the An(VI) metal is reduced to An(IV). However, no significant evolution in the actinide environment has been noticed across the series UO22+, NpO22+ and PuO22+. (au)

  19. Kinetics of actinide complexation reactions

    Though the literature records extensive compilations of the thermodynamics of actinide complexation reactions, the kinetics of complex formation and dissociation reactions of actinide ions in aqueous solutions have not been extensively investigated. In light of the central role played by such reactions in actinide process and environmental chemistry, this situation is somewhat surprising. The authors report herein a summary of what is known about actinide complexation kinetics. The systems include actinide ions in the four principal oxidation states (III, IV, V, and VI) and complex formation and dissociation rates with both simple and complex ligands. Most of the work reported was conducted in acidic media, but a few address reactions in neutral and alkaline solutions. Complex formation reactions tend in general to be rapid, accessible only to rapid-scan and equilibrium perturbation techniques. Complex dissociation reactions exhibit a wider range of rates and are generally more accessible using standard analytical methods. Literature results are described and correlated with the known properties of the individual ions

  20. 33rd Actinide Separations Conference

    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.

  1. Decorporation of inhaled actinides by chelation therapy

    This article describes recent work in NRPB laboratories that has identified some of the factors influencing the behaviour of plutonium, americium and curium compounds in the body after inhalation, together with a number of experimental approaches that are being developed to optimise their treatment with DTPA. It is concluded that the most effective treatment has yet to be developed, but progress must depend on a better understanding of the factors governing the transport of actinides in the body. It cannot be assumed that because the inhaled material is readily translocated to blood, that treatment regimens with Ca-DTPA based solely on previous understanding of the metabolic fate of soluble actinide complexes will be successful. In fact, depending on the nature of the material involved in the accident, inhalation alone or combined with prolonged infusion of DTPA may be more effective than the periodic intravenous injections of the chelating agent alone. For poorly transportable materials such as insoluble plutonium-239 dioxide, chelation treatment remains essentially ineffective. (U.K.)

  2. Synthesis, characterization and thermal behaviour of solid-state compounds of benzoates with some bivalent transition metal ions

    Adriano B. Siqueira

    2007-04-01

    Full Text Available Solid-state MBz compounds, where M stands for bivalent Mn, Fe, Co, Ni, Cu and Zn and Bz is benzoate, have been synthesized. Simultaneous thermogravimetry and differential thermal analysis (TG-DTA, differential scanning calorimetry (DSC, infrared spectroscopy and complexometry were used to characterize and to study the thermal behaviour of these compounds. The procedure used in the preparation of the compounds via reaction of basic carbonates with benzoic acid is not efficient in eliminating excess acid. However the TG-DTA curves permitted to verify that the binary compounds can be obtained by thermosynthesis, because the benzoic acid can be eliminated before the thermal decomposition of these compounds. The results led to information about the composition, dehydration, thermal stability, thermal decomposition and structure of the isolated compounds. On heating, these compounds decompose in two (Mn, Co, Ni, Zn or three (Fe, Cu steps with formation of the respective oxide (Mn3O4, Fe2O3, Co3O4, NiO, CuO and ZnO as final residue. The theoretical and experimental spectroscopic studies suggest a covalent bidentate bond between ligand and metallic center.

  3. Emergence of californium as the second transitional element in the actinide series

    Cary, Samantha K.; Vasiliu, Monica; Baumbach, Ryan E.; Stritzinger, Jared T.; GREEN, THOMAS D.; Diefenbach, Kariem; Cross, Justin N.; Knappenberger, Kenneth L.; Liu, Guokui; Silver, Mark A.; DePrince, A. Eugene; Polinski, Matthew J.; Van Cleve, Shelley M.; House, Jane H.; Kikugawa, Naoki

    2015-01-01

    A break in periodicity occurs in the actinide series between plutonium and americium as the result of the localization of 5f electrons. The subsequent chemistry of later actinides is thought to closely parallel lanthanides in that bonding is expected to be ionic and complexation should not substantially alter the electronic structure of the metal ions. Here we demonstrate that ligation of californium(III) by a pyridine derivative results in significant deviations in the properties of the resu...

  4. Thermal-hydraulics of actinide burner reactors

    As a part of conceptual study of actinide burner reactors, core thermal-hydraulic analyses were conducted for two types of reactor concepts, namely (1) sodium-cooled actinide alloy fuel reactor, and (2) helium-cooled particle-bed reactor, to examine the feasibility of high power-density cores for efficient transmutation of actinides within the maximum allowable temperature limits of fuel and cladding. In addition, calculations were made on cooling of actinide fuel assembly. (author)

  5. MICROBIAL TRANSFORMATIONS OF PLUTONIUM AND OTHER ACTINIDES IN TRANSURANIC AND MIXED WASTES

    The presence of the actinides Th, U, Np, Pu, and Am in transuranic (TRU) and mixed wastes is a major concern because of their potential for migration from the waste repositories and long-term contamination of the environment. The toxicity of the actinide elements and the long half-lives of their isotopes are the primary causes for concern. In addition to the radionuclides the TRU waste consists a variety of organic materials (cellulose, plastic, rubber, chelating agents) and inorganic compounds (nitrate and sulfate). Significant microbial activity is expected in the waste because of the presence of organic compounds and nitrate, which serve as carbon and nitrogen sources and in the absence of oxygen the microbes can use nitrate and sulfate as alternate electron acceptors. Biodegradation of the TRU waste can result in gas generation and pressurization of containment areas, and waste volume reduction and subsidence in the repository. Although the physical, chemical, and geochemical processes affecting dissolution, precipitation, and mobilization of actinides have been investigated, we have only limited information on the effects of microbial processes. Microbial activity could affect the chemical nature of the actinides by altering the speciation, solubility and sorption properties and thus could increase or decrease the concentrations of actinides in solution. Under appropriate conditions, dissolution or immobilization of actinides is brought about by direct enzymatic or indirect non-enzymatic actions of microorganisms. Dissolution of actinides by microorganisms is brought about by changes in the Eh and pH of the medium, by their production of organic acids, such as citric acid, siderophores and extracellular metabolites. Immobilization or precipitation of actinides is due to changes in the Eh of the environment, enzymatic reductive precipitation (reduction from higher to lower oxidation state), biosorption, bioaccumulation, biotransformation of actinides complexed

  6. Actinides and Life's Origins.

    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

  7. MOVPE Growth of InP-based III-V compounds doped with transition metals (Fe,Mn)

    Jakomin, Roberto

    2008-01-01

    The project of thesis has concerned the growth through phase epitassia vapor with metal-organic precursors (MOVPE) of semiconductors compounds III-V "InP-based" (InGaAsp/ InP o GaAs)and their structural optimization, electric and optics to the goals of the study of the effects of the introduction of metals of transition (Fe, Mn) obtained through ionic implantation after the growth or through doping during the same one. The first aspect is concerning the possibility of obtaining areas to h...

  8. Diffusion of alkali metals in the first stage graphite intercalation compounds by vdW-DFT calculations

    Wang, Zhaohui; Ratvik, Arne Petter; Grande, Tor; Selbach, Sverre Magnus

    2015-01-01

    Diffusion of alkali metal cations in the first stage graphite intercalation compounds (GIC) LiC6, NaC6, NaC8 and KC8 has been investigated with density functional theory (DFT) calculations using the optPBE-vdW van der Waals functional. The formation energies of alkali vacancies, interstitials and Frenkel defects were calculated and vacancies were found to be the dominating point defects. The diffusion coefficients of the alkali metals in GIC were evaluated by a hopping model of point defects ...

  9. Coexistence of ferromagnetism and metallic conductivity in a molecule-based layered compound.

    Coronado, E; Galán-Mascarós, J R; Gómez-García, C J; Laukhin, V

    2000-11-23

    Crystal engineering--the planning and construction of crystalline supramolecular architectures from modular building blocks--permits the rational design of functional molecular materials that exhibit technologically useful behaviour such as conductivity and superconductivity, ferromagnetism and nonlinear optical properties. Because the presence of two cooperative properties in the same crystal lattice might result in new physical phenomena and novel applications, a particularly attractive goal is the design of molecular materials with two properties that are difficult or impossible to combine in a conventional inorganic solid with a continuous lattice. A promising strategy for creating this type of 'bi-functionality' targets hybrid organic/inorganic crystals comprising two functional sub-lattices exhibiting distinct properties. In this way, the organic pi-electron donor bis(ethylenedithio)tetrathiafulvalene (BEDT-TTF) and its derivatives, which form the basis of most known molecular conductors and superconductors, have been combined with molecular magnetic anions, yielding predominantly materials with conventional semiconducting or conducting properties, but also systems that are both superconducting and paramagnetic. But interesting bulk magnetic properties fail to develop, owing to the discrete nature of the inorganic anions. Another strategy for achieving cooperative magnetism involves insertion of functional bulky cations into a polymeric magnetic anion, such as the bimetallic oxalato complex [MnIICrIII(C2O4)3]-, but only insoluble powders have been obtained in most cases. Here we report the synthesis of single crystals formed by infinite sheets of this magnetic coordination polymer interleaved with layers of conducting BEDT-TTF cations, and show that this molecule-based compound displays ferromagnetism and metallic conductivity. PMID:11100721

  10. Actinide cation-cation complexes

    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

  11. Electrochemical separation of actinides and fission products in molten salt electrolyte

    Gay, R. L.; Grantham, L. F.; Fusselman, S. P.; Grimmett, D. L.; Roy, J. J.

    1995-09-01

    Molten salt electrochemical separation may be applied to accelerator-based conversion (ABC) and transmutation systems by dissolving the fluoride transport salt in LiCl-KCl eutectic solvent. The resulting fluoride-chloride mixture will contain small concentrations of fission product rare earths (La, Nd, Gd, Pr, Ce, Eu, Sm, and Y) and actinides (U, Np, Pu, Am, and Cm). The Gibbs free energies of formation of the metal chlorides are grouped advantageously such that the actinides can be deposited on a solid cathode with the majority of the rare earths remaining in the electrolyte. Thus, the actinides are recycled for further transmutation. Rockwell and its partners have measured the thermodynamic properties of the metal chlorides of interest (rare earths and actinides) and demonstrated separation of actinides from rare earths in laboratory studies. A model is being developed to predict the performance of a commercial electrochemical cell for separations starting with PUREX compositions. This model predicts excellent separation of plutonium and other actinides from the rare earths in metal-salt systems.

  12. Electrocatalysis of the oxidations of some organic compounds on noble-metal electrodes by foreign-metal ad-atoms

    Electrochemical oxidation of formic acid was studied on Pt electrodes in acid, and that of dextrose was studied on Pt and Au in alkali. Poisoning was observed on Pt but not on Au. Several heavy-metal ad-atoms (Pb, Bi, Tl) enhance greatly the anodic currents on Pt, while transition metals (Cu, Zn) inhibit the oxidation on Pt. The enhancement effect of the metal ad-atoms is correlated with electron structure. All metal ad-atoms showed an inhibitory effect on Au. Amperometry showed that Pt electrodes are completely deactivated within 10 s during dextrose oxidation without ad-atoms, while Au retains much of its activity even after 10 min. Ad-atoms maintains the Pt activity over much more than 10 s. 50 figures, 38 tables

  13. Orbital effects in actinide systems

    Actinide magnetism presents a number of important challenges; in particular, the proximity of 5f band to the Fermi energy gives rise to strong interaction with both d and s like conduction electrons, and the extended nature of the 5f electrons means that they can interact with electron orbitals from neighboring atoms. Theory has recently addressed these problems. Often neglected, however, is the overwhelming evidence for large orbital contributions to the magnetic properties of actinides. Some experimental evidence for these effects are presented briefly in this paper. They point, clearly incorrectly, to a very localized picture for the 5f electrons. This dichotomy only enhances the nature of the challenge

  14. Fabrication of actinide mononitride fuel

    Fabrication of actinide mononitride fuel in JAERI is summarized. Actinide mononitride and their solid solutions were fabricated by carbothermic reduction of the oxides in N2 or N2-H2 mixed gas stream. Sintering study was also performed for the preparation of pellets for the property measurements and irradiation tests. The products were characterized to be high-purity mononitride with a single phase of NaCl-type structure. Moreover, fuel pins containing uranium-plutonium mixed nitride pellets were fabricated for the irradiation tests in JMTR and JOYO. (author)

  15. Some new developments in actinide solvent extraction systems

    Consideration is given to application of neutral and acid organophosphoric compounds, adsorbed on various natural and synthetic carriers, in extraction chromatography for separation and isolation of actinides. It is shown that trioctylphosphine oxide (TOPO) on a solid combustible carrier represents the promising material for plutonium extraction. It was established experimentally that polyurethane foam possessed the maximal capacity with respect to TOPO; extractant losses at that after passing of 50 column volumes of nitric acid don't exceed 2 %

  16. Electrochemistry of actinide and lanthanide in molten salt system

    In the partition and transmutation processes of reprocessing of spent fuel or radioactive waste in nuclear power plant, the dry type reprocessing method using molten salt and liquid metal as a solvent is studied. Most especially researches on the electrolysis of the actinide nitride in the molten salts corresponding to reprocessing of nitride fuel cannot be found. This report is a research result about the electro-chemical behavior of actinide and lanthanide on the electrode in molten LiCL-KCL eutectic system. When anode potential was less than -0.4V in recovery of U metal by the molten salt electrolysis of UN, the electrolysis efficiency of the recovery is not influenced by the generation of UNCL and the oxidation-reduction reaction of U4+/U3+. Moreover, generation of a chlorination nitride was not seen in the case where PuN and NpN are used. (H. Katsuta)

  17. Isolation and characterization of nanosheets containing few layers of the Aurivillius family of oxides and metal-organic compounds

    Sreedhara, M.B.; Prasad, B.E.; Moirangthem, Monali [Chemistry and Physics of Materials Unit, New Chemistry Unit, International Centre for Materials Science and Sheik Saqr Laboratory, Jawaharlal Nehru Centre for Advanced Scientific Research, Jakkur P.O., Bangalore 560064 (India); Murugavel, R. [Department of Chemistry, Indian Institute of Technology–Bombay, Powai, Mumbai 400076 (India); Rao, C.N.R., E-mail: cnrrao@jncasr.ac.in [Chemistry and Physics of Materials Unit, New Chemistry Unit, International Centre for Materials Science and Sheik Saqr Laboratory, Jawaharlal Nehru Centre for Advanced Scientific Research, Jakkur P.O., Bangalore 560064 (India)

    2015-04-15

    Nanosheets containing few-layers of ferroelectric Aurivillius family of oxides, Bi{sub 2}A{sub n−1}B{sub n}O{sub 3n+3} (where A=Bi{sup 3+}, Ba{sup 2+} etc. and B=Ti{sup 4+}, Fe{sup 3+} etc.) with n=3, 4, 5, 6 and 7 have been prepared by reaction with n-butyllithium, followed by exfoliation in water. The few-layer samples have been characterized by Tyndall cones, atomic force microscopy, optical spectroscopy and other techniques. The few-layer species have a thickness corresponding to a fraction of the c-parameter along which axis the perovskite layers are stacked. Magnetization measurements have been carried out on the few-layer samples containing iron. Few-layer species of a few layered metal-organic compounds have been obtained by ultrasonication and characterized by Tyndall cones, atomic force microscopy, optical spectroscopy and magnetic measurements. Significant changes in the optical spectra and magnetic properties are found in the few-layer species compared to the bulk samples. Few-layer species of the Aurivillius family of oxides may find uses as thin layer dielectrics in photovoltaics and other applications. - Graphical abstract: Exfoliation of the layered Aurivillius oxides into few-layer nanosheets by chemical Li intercalation using n-BuLi followed by reaction in water. Exfoliation of the layered metal-organic compounds into few-layer nanosheets by ultrasonication. - Highlights: • Few-layer nanosheets of Aurivillius family of oxides with perovskite layers have been generated by lithium intercalation. • Few-layer nanosheets of few layered metal-organic compounds have been generated by ultrasonication. • Few-layer nanosheets of the Aurivillius oxides have been characterized by AFM, TEM and optical spectroscopy. • Aurivillius oxides containing Fe show layer dependent magnetic properties. • Exfoliated few-layer metal-organic compounds show changes in spectroscopic and magnetic properties compared with bulk materials.

  18. Metal-free oxidation of alcohols to their corresponding carbonyl compounds using NH4NO3/Silica sulfuric acid

    A metal-free and efficient procedure for the oxidation of alcohols into the corresponding carbonyl compounds has been described using ammonium nitrate in the presence of silica sulfuric acid under mild and heterogeneous conditions. The use of non-toxic and inexpensive materials, simple and clean work-up, short reaction times and good yields of the products are among the advantages of this method

  19. Preparing poly(aryl ethers) using alkaline earth metal carbonates, organic acid salts, and optionally copper compounds, as catalysts

    This patent describes an improved process for preparing poly(aryl ethers) and poly(aryl ether ketones) by the reaction of a mixture of at least one bisphenol and at least one dihalobenzenoid compound, and/or a halophenol. The improvement comprises providing to the reaction, a base which is a combination of an alkaline earth metal carbonate and/or bicarbonate and a potassium, rubidium, or cesium salt of an organic acid or combination of organic salts thereof

  20. Preparing poly(aryl ethers) using alkaline earth metal carbonates, organic acid salts, and optionally copper compounds, as catalysts

    Winslow, P.A.; Kelsey, D.R.; Matzner, M.

    1988-09-27

    This patent describes an improved process for preparing poly(aryl ethers) and poly(aryl ether ketones) by the reaction of a mixture of at least one bisphenol and at least one dihalobenzenoid compound, and/or a halophenol. The improvement comprises providing to the reaction, a base which is a combination of an alkaline earth metal carbonate and/or bicarbonate and a potassium, rubidium, or cesium salt of an organic acid or combination of organic salts thereof.

  1. Isolation and characterization of nanosheets containing few layers of the Aurivillius family of oxides and metal-organic compounds

    Nanosheets containing few-layers of ferroelectric Aurivillius family of oxides, Bi2An−1BnO3n+3 (where A=Bi3+, Ba2+ etc. and B=Ti4+, Fe3+ etc.) with n=3, 4, 5, 6 and 7 have been prepared by reaction with n-butyllithium, followed by exfoliation in water. The few-layer samples have been characterized by Tyndall cones, atomic force microscopy, optical spectroscopy and other techniques. The few-layer species have a thickness corresponding to a fraction of the c-parameter along which axis the perovskite layers are stacked. Magnetization measurements have been carried out on the few-layer samples containing iron. Few-layer species of a few layered metal-organic compounds have been obtained by ultrasonication and characterized by Tyndall cones, atomic force microscopy, optical spectroscopy and magnetic measurements. Significant changes in the optical spectra and magnetic properties are found in the few-layer species compared to the bulk samples. Few-layer species of the Aurivillius family of oxides may find uses as thin layer dielectrics in photovoltaics and other applications. - Graphical abstract: Exfoliation of the layered Aurivillius oxides into few-layer nanosheets by chemical Li intercalation using n-BuLi followed by reaction in water. Exfoliation of the layered metal-organic compounds into few-layer nanosheets by ultrasonication. - Highlights: • Few-layer nanosheets of Aurivillius family of oxides with perovskite layers have been generated by lithium intercalation. • Few-layer nanosheets of few layered metal-organic compounds have been generated by ultrasonication. • Few-layer nanosheets of the Aurivillius oxides have been characterized by AFM, TEM and optical spectroscopy. • Aurivillius oxides containing Fe show layer dependent magnetic properties. • Exfoliated few-layer metal-organic compounds show changes in spectroscopic and magnetic properties compared with bulk materials

  2. Program and presentations of the 33th Actinide Days

    The 'Journees des Actinides' (JDA) is an annual conference which provides a forum for discussions on all aspects related to the chemical and physical properties of the actinides. At the 2003 meeting, mainly the following properties were discussed of actinides and a number of actinide compounds and complexes: crystal structure, crystal-phase transformations and transformation temperatures; electrical properties including superconductivity and superconducting transition temperatures; magnetic properties; specific heat and other thermodynamic properties; electronic structure, especially in condensed matter; chemical and physico-chemical properties. The relevant experimental techniques were also dealt with, such as neutron diffraction; X-ray diffraction, in particular using synchrotron radiation; photoemission techniques, electron microscopy and spectroscopy, etc. Altogether 96 contributions were presented, of which 42 were oral presentations and 54 poster presentations. A program of the meeting and texts of both type of presentations were published in electronic form in the PDF format. All contributions were inputted to INIS; the full text of the program and the presentations has been incorporated into the INIS collection of non-conventional literature on CD-ROM. (A.K.)

  3. SYNTHESIS, STRUCTURE AND BIOLOGICAL ACTIVITY OF N(4-ALLYL-3-THIOSEMICARBAZONES AND THEIR COORDINATION COMPOUNDS WITH SOME 3D METALS

    Vasilii GRAUR

    2016-02-01

    Full Text Available The paper presents a review of different N(4-allyl-3-thiosemicarbazones and their coordination compounds described in literature. N(4-allyl-3-thiosemicarbazide can form corresponding thiosemicarbazones with aliphatic, aromatic and heteroaromatic carbonyl compounds. In the presence of transitional metal ions they can form coordination compounds of different structures. Both coordination compounds and proligands manifest antitumor, antibacterial, antiviral, and antimalarial activities. Copper(II coordination compounds with these ligands manifest better antitumor activity than corresponding proligands. SINTEZA, STRUCTURA ŞI ACTIVITATEA BIOLOGICĂ A N(4-ALIL-3-TIOSEMICARBAZONELOR ŞI A COMPUŞILOR COORDINATIVI AI UNOR METALE 3D CU ACEŞTI LIGANZILucrarea prezintă o revistă a N(4-alil-3-tiosemicarbazonelor şi a compuşilor coordinativi cu aceşti liganzi descrise în literatura de specialitate. N(4-alil-3-tiosemicarbazida formează tiosemicarbazone cu aldehide şi cetone alifatice, aro­matice şi heteroaromatice. În prezenţa ionilor de metale de tranziţie acestea pot forma compuşi coordinativi cu diferite structuri. N(4-alil-3-tiosemicarbazonele şi compuşii coordinativi manifestă activitate antitumorală, antibacterială, antivirală şi antimalarică. Compuşii coordinativi ai cuprului cu aceşti liganzi manifestă activitate antitumorală sporită în comparaţie cu N(4-alil-3-tiosemicarbazonele corespunzătoare. 

  4. New pathway for the formation of metallic cubic phase Ge-Sb-Te compounds induced by an electric current

    Park, Yong-Jin; Cho, Ju-Young; Jeong, Min-Woo; Na, Sekwon; Joo, Young-Chang

    2016-02-01

    The novel discovery of a current-induced transition from insulator to metal in the crystalline phase of Ge2Sb2Te5 and GeSb4Te7 have been studied by means of a model using line-patterned samples. The resistivity of cubic phase Ge-Sb-Te compound was reduced by an electrical current (~1 MA/cm2), and the final resistivity was determined based on the stress current density, regardless of the initial resistivity and temperature, which indicates that the conductivity of Ge-Sb-Te compound can be modulated by an electrical current. The minimum resistivity of Ge-Sb-Te materials can be achieved at high kinetic rates by applying an electrical current, and the material properties change from insulating to metallic behavior without a phase transition. The current-induced metal transition is more effective in GeSb4Te7 than Ge2Sb2Te5, which depends on the intrinsic vacancy of materials. Electromigration, which is the migration of atoms induced by a momentum transfer from charge carriers, can easily promote the rearrangement of vacancies in the cubic phase of Ge-Sb-Te compound. This behavior differs significantly from thermal annealing, which accompanies a phase transition to the hexagonal phase. This result suggests a new pathway for modulating the electrical conductivity and material properties of chalcogenide materials by applying an electrical current.

  5. Impact of actinide recycle on nuclear fuel cycle health risks

    The purpose of this background paper is to summarize what is presently known about potential impacts on the impacts on the health risk of the nuclear fuel cycle form deployment of the Advanced Liquid Metal Reactor (ALMR)1 and Integral Fast Reactor (IF)2 technology as an actinide burning system. In a companion paper the impact on waste repository risk is addressed in some detail. Therefore, this paper focuses on the remainder of the fuel cycle

  6. Analytical applications of superacid dissolution of actinide and lanthanide substrates

    The superacid system HF/SbF5 is extraordinarily effective for total dissolution of actinide and lanthanide ceramic oxides, fluorides, and metals. Optical or gamma spectroscopy can be used directly on the solutions. Evaporation of the HF/SbF5 solvent under vacuum leaves a residue which is easily dissolved by ordinary mineral acids. The resulting aqueous solutions are readily amenable to conventional analytical methods. (author) 14 refs.; 1 tab

  7. Electronic structure and bulk ground state properties of the actinides

    The principal aim of this chapter is to examine in detail how the actinide elements fit into the periodic table. The actinides are neither a d transition series nor a series like the lanthanides. The electronic structure of the early part of the series finds a close conceptual parallel in a d transition series and the later part of the series is more like the lanthanides. The region of transition between the two parts of the series is of special interest and importance. Among the bulk properties of the elements there are three which are of particular importance; (a) the equilibrium volume, (b) the cohesive energy, and (c) the compressibility, or its inverse, the bulk modulus. The room temperature entropy of the actinides is discussed and its behaviour is related to the room temperature entropy of the other transition metal series. Finally, the ground state magnetism of the actinides is discussed in the context of our understanding of ground state magnetism across the periodic table. (Auth.)

  8. Analysis of rhodium-base intermetallic compound, white metal and high speed steel by ICP-AES

    The determination procedures of major component of intermetallic compound and alloys which were difficult to dissolve was investigated with ICP-AES. NdRhxBy as intermetallic compound was dissolved in aqua regia, and the residue was fused with NaHSO4 · H2O. RhAl as intermetallic compound was dissolved in hydrochloric acid after fusion with NaHSO4 · H2O. Nd, Rh, B, Al and Cu in these samples were determined with correction of spectral interference caused by Nd. White metal was dissolved in mixture of nitric acid and hydrochloric acid containing tartaric acid for prevention of hydrolysis of Sn and Sb in the sample. Pb, Sn, Sb and Cu as major element in it were determined. High speed steel was dissolved in mixture of sulfuric acid and phosphoric acid. Mo, V, Co, W and Cr as minor component were determined. Spectral interferences caused by Fe, V and Co were corrected. (author)

  9. Unusual regenerable porous metal-organic framework based on a new triple helical molecular necklace for separating organosulfur compounds.

    Li, Shun-Li; Lan, Ya-Qian; Sakurai, Hiroaki; Xu, Qiang

    2012-12-14

    Desulfurization of fuels is receiving more and more attention all over the world due to the increase of stringent environmental regulations and fuel specifications. The metal-organic framework (MOF) is a new class of crystalline materials, and high porosity, one of the most important properties of MOFs, plays a central role in the functional properties. However, the investigation of MOFs, being employed as sorbents for adsorptive desulfurization, is still scarce. In this regard, we have constructed a new 3D porous compound 1 by using rigidly designed carboxylate ligands, which, for the first time, exhibit an unusual triple molecular necklace-like helix. The N(2) sorption isotherms of 1 show that it has a large Brunauer-Emmett-Teller (BET) surface area and pore volume. With the stable pore structure and appropriate pore sizes, compound 1 has been used as a sorbent for adsorptive desulfurization. The results indicate that compound 1 shows an excellent adsorption property and, more importantly, displays excellent stability, repeatability, and regenerability. Thus, the design and synthesis of targeted MOFs with appropriate pore size and increased interactions between organosulfur compounds and ligands/metals from MOFs is crucial for adsorptive desulfurization, which might be an effective guide to find an efficient and green adsorbent for desulfurization. PMID:23168579

  10. An expert system for process planning of sheet metal parts produced on compound die for use in stamping industries

    SACHIN SALUNKHE; DEEPAK PANGHAL; SHAILENDRA KUMAR; H M A HUSSEIN

    2016-08-01

    Process planning of sheet metal part is an important activity in the design of compound die. Traditional methods of carrying out this task are manual, tedious, time-consuming, error-prone and experiencebased. This paper describes the research work involved in the development of an expert system for process planning of sheet metal parts produced on compound die. The proposed system is organized in six modules. For development of system modules, domain knowledge acquired from various sources of knowledge acquisition is refined and then framed in form of ‘IF-Then’ variety of production rules. System modules are coded in AutoLISP language and user interface is created using visual basic (VB). The system is capable to automate various activities of process planning including blank modeling, blank nesting, determining punch force required, election of clearance between punch and die, identifying sheet metal operations, and determining proper sequence of operations for manufacturing the part. The proposed system can be implemented on a PC having VB and AutoCAD software, therefore its low cost of implementation makes it affordable even for small scale sheet metal industries.

  11. Environmental research on actinide elements

    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)

  12. ENDF/B-V actinides

    This document summarizes the contents of the actinides part of the ENDF/B-V nuclear data library released by the US National Nuclear Data Center. This library or selective retrievals of it, are available from the IAEA Nuclear Data Section. (author)

  13. Pyrometallurgical processes for recovery of actinide elements

    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.

  14. Pyrometallurgical processes for recovery of actinide elements

    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

  15. Band model for d- and f-metals

    The application of band theory to metallic systems with d- and f-orbitals in the valence and conduction bands is discussed. Because such an application pushes theory and technique to their limits, several important features are briefly recapitulated. Within the transition metal systems, the elemental systems are used to discuss the fundamental formalism being applied and the newer directions into more complex systems are mentioned. Here we focus more on anisotropic properties and Fermi surface properties. Within the f-orbital systems, the focus is more on Ce and its compounds because of current interest with a relatively brief discussion of the actinides. the point of view advanced, however, has its origins in actinide research

  16. Band model for d- and f-metals

    Koelling, D.D.

    1982-01-01

    The application of band theory to metallic systems with d- and f-orbitals in the valence and conduction bands is discussed. Because such an application pushes theory and technique to their limits, several important features are briefly recapitulated. Within the transition metal systems, the elemental systems are used to discuss the fundamental formalism being applied and the newer directions into more complex systems are mentioned. Here we focus more on anisotropic properties and Fermi surface properties. Within the f-orbital systems, the focus is more on Ce and its compounds because of current interest with a relatively brief discussion of the actinides. the point of view advanced, however, has its origins in actinide research.

  17. Metals, pesticides, and semivolatile organic compounds in sediment in Valley Forge National Historical Park, Montgomery County, Pennsylvania

    Reif, Andrew G.; Sloto, Ronald A.

    1997-01-01

    The Schuylkill River flows through Valley Forge National Historical Park in Lower Providence and West Norriton Townships in Montgomery County, Pa. The concentration of selected metals, pesticides, semivolatile organic compounds, and total carbon in stream-bottom sediments from Valley Forge National Historical Park were determined for samples collected once at 12 sites in and around the Schuylkill River. Relatively low concentrations of arsenic, chromium, copper, and lead were detected in all samples. The concentrations of these metals are similar to concentrations in other stream-bottom sediment samples collected in the region. The concentrations of iron, manganese, and zinc were elevated in samples from four sites in the Schuylkill River, and the concentration of mercury was elevated in a sample from an impoundment along the river. The organophosphorus insecticide diazinon was detected in relatively low concentrations in half of the 12 samples analyzed. The organo-chlorine insecticide DDE was detected in all 12 samples analyzed; dieldrin was detected in 10 samples, chlordane, DDD, and DDT were detected in 9 samples, and heptachlor epoxide was detected in one sample. The concentrations of organo-chlorine and organophosphorus insecticides were relatively low and similar to concentrations in samples collected in the region. Detectable concentrations of 17 semivolatile organic compounds were measured in the 12 samples analyzed. The most commonly detected compounds were fluoranthene, phenanthrene, and pyrene. The maximum concentration detected was 4,800 micrograms per kilogram of phenanthrene. The highest concentrations of compounds were detected in Lamb Run, a small tributary to the Schuylkill River with headwaters in an industrial corporate center. The concentration of compounds in the Schuylkill River below Lamb Run is higher than the Schuylkill River above Lamb Run, indicating that sediment from Lamb Run is increasing the concentration of semivolatile organic

  18. New quaternary compounds resulting from the reaction of copper and f-block metals in molten polychalcogenide salts at intermediate temperatures. Valence fluctuations in the layered CsCuCeS3

    From the reaction of elemental copper and either lanthanides or actinides in molten alkali metal/polychalcogenide salts, several new quaternary phases have been discovered. Specifically, these phases are ACuM2Q6(where A = K, M = La, Q =S: A = Cs, M = Ce, Q = S; or A = K, M = Ce, Q = Se) and ACuMQ3 (where A = Cs, M = Ce, Q = S; or A = K, M = U, Q = Se). The CsCuCe2S6 crystallizes in the orthorhombic space group Immm with a = 5.500-(1) Angstrom, b = 22.45(1) Angstrom, c = 4.205(4) Angstrom. The KCuCe2Se6 is isostructural. The CsCuCeS3 crystallizes in the orthorhombic space group Cmcm with a = 4.024(2) Angstrom, b = 15.154(2) Angstrom, c = 10.353(3) Angstrom. The KCuUSe3 is isostructural. In ACuM2Q6, the lanthanides bond to a mixture of mono- and disulfides in a bicapped trigonal prismatic geometry; these polyhedra subsequently connect in two dimensions, forming layers equivalent to those seen in the ZrSe3 structure type with Cu+ atoms residing in tetrahedral sites within the layers and alkali cations in the interlayer gallery. The compounds of the formula ACuMQ3 also possess a layered structure. Here the [MQ6] octahedral units form corrugated, two-dimensional sheets via edge-sharing in the first dimension and corner-sharing in the second. Copper cations are coordinated to tetrahedral sites in the folds of the corrugations, and alkali cations are again in the intergallery region. Detailed of the synthesis, structure, and properties of these compounds are discussed. 42 refs., 14 figs., 8 tabs

  19. ACTINET: Establishment of a network of excellence for actinide sciences

    During the past decades, the actinide sciences have stagnated and become less attractive for young scientists, particularly in European countries. The safety requirements for maintaining up-to-date experimental capacities for handling alpha-emitting compounds, such as actinides, have gradually made researches very costly, and many radiochemistry laboratories have restricted their activities largely to beta- and gamma-emitting materials. This trend has dramatically reduced basic research in actinide sciences in Europe, and at present, only few national research institutions and one institute of the Joint Research Centre (ITU) are able to maintain the necessary research infrastructure. Very few laboratories in Europe possess now the expertise, technical competence and tools at the scale required by the technical challenges faced by the European countries, and none of them alone covers the full spectrum required. Furthermore, there are only a few places in Europe that have the appropriate research facilities to support education in actinide sciences with the appropriate research experience. Because of its strategic importance, the research in actinide sciences must therefore be revitalized, and become attractive again to students so that a next generation of actinide scientists and engineers can rise from the radiochemistry laboratories of universities. To sustain and disseminate the indispensable knowledge and expertise, as well as to maintain the threshold level of research activity in actinide sciences in Europe, success can only be envisaged by the use of Europe-wide networking. This particular research area requires reinforced links between national nuclear research institutes, the JRC, and radiochemistry laboratories of a number of academic research organisations: networking will not only facilitate the coordination and utilization of available facilities, but will also consolidate, optimise, and give the necessary impetus to enliven the research and training

  20. Organophosphorus reagents in actinide separations: Unique tools for production, cleanup and disposal

    Interactions of actinide ions with phosphate and organophosphorus reagents have figured prominently in nuclear science and technology, particularly in the hydrometallurgical processing of irradiated nuclear fuel. Actinide interactions with phosphorus-containing species impact all aspects from the stability of naturally occurring actinides in phosphate mineral phases through the application of the bismuth phosphate and PUREX processes for large-scale production of transuranic elements to the development of analytical separation and environment restoration processes based on new organophosphorus reagents. In this report, an overview of the unique role of organophosphorus compounds in actinide production, disposal, and environment restoration is presented. The broad utility of these reagents and their unique chemical properties is emphasized

  1. Actinide partitioning-transmutation program final report. I. Overall assessment

    This report is concerned with an overall assessment of the feasibility of and incentives for partitioning (recovering) long-lived nuclides from fuel reprocessing and fuel refabrication plant radioactive wastes and transmuting them to shorter-lived or stable nuclides by neutron irradiation. The principal class of nuclides considered is the actinides, although a brief analysis is given of the partitioning and transmutation (P-T) of 99Tc and 129I. The results obtained in this program permit us to make a comparison of the impacts of waste management with and without actinide recovery and transmutation. Three major conclusions concerning technical feasibility can be drawn from the assessment: (1) actinide P-T is feasible, subject to the acceptability of fuels containing recycle actinides; (2) technetium P-T is feasible if satisfactory partitioning processes can be developed and satisfactory fuels identified (no studies have been made in this area); and (3) iodine P-T is marginally feasible at best because of the low transmutation rates, the high volatility, and the corrosiveness of iodine and iodine compounds. It was concluded on the basis of a very conservative repository risk analysis that there are no safety or cost incentives for actinide P-T. In fact, if nonradiological risks are included, the short-term risks of P-T exceed the long-term benefits integrated over a period of 1 million years. Incentives for technetium and iodine P-T exist only if extremely conservative long-term risk analyses are used. Further RD and D in support of P-T is not warranted

  2. XAFS study on electronic structure analysis of actinide complexes

    Structures and electronic states of actinide complexes in solution were reviewed in relation to chemical separation required from nuclear fuel processing and nuclear waste disposal. Actinide complexes formed from organic compounds were studied in respect of solvent extraction in a wet method for nuclear fuel reprocessing. Particular attention was paid to the experiments by XAFS using synchrotron radiation. A Fourier transformation form of EXAFS oscillation was shown for a U(VI)-amide complex in dodecane solution. The structure radial function of Uranium-DH2EHA (N, N-dihyxyl-2-ethylhexanamice) in solution was determined by EXAFS, and the contributions of two oxygens in an axial direction and of ligand atoms coordinated in an equatorial plane, which combined with a central uranium ion, were indicated in the structure radial function. Structure parameters for U-, Np- and Pu-TBP(Tributyl phosphate) complexes, and for U-amide complexes were listed in Table. A theory predicted a systematic increase of covalency for complexes formed from UO22+∼PO22+ and TEP with an increase of atomic number of actinides, but for U-amide and U∼Pu-TBP complexes the effect of covalency was not reflected in interatomic distances. Some correlations between distribution ratios and different substituents were found in the interatomic distances between uranium and ligand atoms-Distribution ratios of U(VI) depended on interatomic distances between actinide atoms and oxygen ions in carbonyl and in nitric acid. Similarity of chemical bonds in all U-amide complexes except DH2EHA was indicated from XANES spectra of U LIII absorption edge. Three structures for Np(V)-carbon complexes were shown in a ball-and-stick model, and the structure parameters determined by EXAFS were also summarized in Table. Separation of trivalent actinide from the same valent lanthanide was described in connection with soft donors, which have donors such as sulfur and nitrogen atoms. (Kazumata, Y.)

  3. Extraction studies on the partitioning of actinides from HLW

    TRUEX process uses Octyl(phenyl)-N,N-diisobutylcarbamoylmethylphosphine oxide (CMPO) for the partitioning of actinides from acidic waste. CMPO is one of the most effective organophosphorus compounds. CMPO has drawbacks like third phase formation. A two-step process is developed using TBP and CMPO as extractants. The first step of the proposed process is a 'uranium depletion step' in which uranium in HLW is removed using 30% TBP in n-dodecane. Neptunium and plutonium, extracted in TBP, are recovered using a mixture of hydrogen peroxide (0.25 M) and ascorbic acid (0.05 M) in 2.0 M nitric acid medium. Neptunium and plutonium are reduced to Np(V) and Pu(III). Americium and curium as well as traces of uranium, neptunium and plutonium are partitioned in the second step. The separation of neptunium and plutonium from large quantities of uranium from loaded TBP will simplify their further separation. Use of citrate containing buffer solution for the recovery of actinides extracted in CMPO-TBP phase eliminates the problem of reflux of americium. This reduces the generation of secondary wastes. The process has been standardised based on the data generated in the batch and counter-current studies. Solvent extraction studies have also been carried out using a mixture of di-(2-ethylhexyl)phosphoric acid (HDEHP) and CMPO in n-paraffin. It is seen that the actinides can be extracted even from solutions of HLW at high acid concentration of 3 M using the mixed extractant. Plutonium is also stripped along with the trivalent actinides. This mixed solvent may find useful applications in the partitioning of actinides from waste solutions. Supported liquid membrane (SLM) technique for partitioning of actinides from high level waste of PUREX origin uses solution of CMPO in n-dodecane with polytetrafluoroethylene support and a mixture of citric acid, formic acid and hydrazine hydrate as a receiving phase. Studies indicated good transport of actinides across the membrane from nitric acid

  4. Effects of complexing compounds on sorption of metal ions to cement

    Loevgren, Lars [Umeaa Univ. (Sweden). Inorganic chemistry

    2005-12-15

    This present report is a literature review addressing the effects of complexing ligands on the sorption of radionuclides to solid materials of importance for repositories of radioactive waste. Focus is put on laboratory studies of metal ion adsorption to cement in presence of chelating agents under strongly alkaline conditions. As background information, metal sorption to different mineral and cement phases in ligand free systems is described. Furthermore, surface complexation model (SCM) theories are introduced. According to surface complexation theories these interactions occur at specific binding sites at the particle/water interface. Adsorption of cationic metals is stronger at high pH, and the adsorption of anions occurs preferentially at low pH. The adsorption of ions to mineral surfaces is a result of both chemical bonding and electrostatic attraction between the ions and charged mineral surfaces. By combining uptake data with spectroscopic information the sorption can be explained on a molecular level by structurally sound surface complexation models. Most of the metal sorption studies reviewed are dealing with minerals exhibiting oxygen atoms at their surfaces, mainly oxides of Fe(II,III) and Al(III), and aluminosilicates. Investigations of radionuclides are focused on clay minerals, above all montmorillonite and illite. Which mechanism that is governing the metal ion adsorption to a given mineral is to a large extent depending on the metal adsorbed. For instance, sorption of Ni to montmorillonite can occur by formation of inner-sphere mononuclear surface complexes located at the edges of montmorillonite platelets and by formation of a Ni phyllosilicate phase parallel to montmorillonite layers. Also metal uptake to cement materials can occur by different mechanisms. Cationic metals can both be attached to cement (calcium silicate hydrate, CSH) and hardened cement paste (HCP) by formation of inner-sphere complexes at specific surface sites and by

  5. Effects of complexing compounds on sorption of metal ions to cement

    This present report is a literature review addressing the effects of complexing ligands on the sorption of radionuclides to solid materials of importance for repositories of radioactive waste. Focus is put on laboratory studies of metal ion adsorption to cement in presence of chelating agents under strongly alkaline conditions. As background information, metal sorption to different mineral and cement phases in ligand free systems is described. Furthermore, surface complexation model (SCM) theories are introduced. According to surface complexation theories these interactions occur at specific binding sites at the particle/water interface. Adsorption of cationic metals is stronger at high pH, and the adsorption of anions occurs preferentially at low pH. The adsorption of ions to mineral surfaces is a result of both chemical bonding and electrostatic attraction between the ions and charged mineral surfaces. By combining uptake data with spectroscopic information the sorption can be explained on a molecular level by structurally sound surface complexation models. Most of the metal sorption studies reviewed are dealing with minerals exhibiting oxygen atoms at their surfaces, mainly oxides of Fe(II,III) and Al(III), and aluminosilicates. Investigations of radionuclides are focused on clay minerals, above all montmorillonite and illite. Which mechanism that is governing the metal ion adsorption to a given mineral is to a large extent depending on the metal adsorbed. For instance, sorption of Ni to montmorillonite can occur by formation of inner-sphere mononuclear surface complexes located at the edges of montmorillonite platelets and by formation of a Ni phyllosilicate phase parallel to montmorillonite layers. Also metal uptake to cement materials can occur by different mechanisms. Cationic metals can both be attached to cement (calcium silicate hydrate, CSH) and hardened cement paste (HCP) by formation of inner-sphere complexes at specific surface sites and by

  6. Radionuclides, Trace Metals, and Organic Compounds in Shells of Native Freshwater Mussels Along the Hanford Reach of the Columbia River: 6000 Years Before Present to Current Times

    B. L. Tiller; T. E. Marceau

    2006-01-25

    This report documents concentrations of radionuclides, trace metals, and semivolatile organic compounds measured in shell samples of the western pearl shell mussel collected along the Hanford Reach of the Columbia River.

  7. Investigating the molecule-substrate interaction of prototypic tetrapyrrole compounds: Adsorption and self-metalation of porphine on Cu(111)

    We report on the adsorption and self-metalation of a prototypic tetrapyrrole compound, the free-base porphine (2H-P), on the Cu(111) surface. Our multitechnique study combines scanning tunneling microscopy (STM) results with near-edge X-ray absorption fine-structure (NEXAFS) and X-ray photoelectron spectroscopy (XPS) data whose interpretation is supported by density functional theory calculations. In the first layer in contact with the copper substrate the molecules adsorb coplanar with the surface as shown by angle-resolved NEXAFS measurements. The quenching of the first resonance in the magic angle spectra of both carbon and nitrogen regions indicates a substantial electron transfer from the substrate to the LUMO of the molecule. The stepwise annealing of a bilayer of 2H-P molecules sequentially transforms the XP and NEXAFS signatures of the nitrogen regions into those indicative of the coordinated nitrogen species of the metalated copper porphine (Cu-P), i.e., we observe a temperature-induced self-metalation of the system. Pre- and post-metalation species are clearly discriminable by STM, corroborating the spectroscopic results. Similar to the free-base porphine, the Cu-P adsorbs flat in the first layer without distortion of the macrocycle. Additionally, the electron transfer from the copper surface to the molecule is preserved upon metalation. This behavior contrasts the self-metalation of tetraphenylporphyrin (2H-TPP) on Cu(111), where both the molecular conformation and the interaction with the substrate are strongly affected by the metalation process.

  8. Investigating the molecule-substrate interaction of prototypic tetrapyrrole compounds: Adsorption and self-metalation of porphine on Cu(111)

    Diller, K.; Klappenberger, F.; Allegretti, F.; Papageorgiou, A. C.; Fischer, S.; Wiengarten, A.; Joshi, S.; Seufert, K.; Ecija, D.; Auwaerter, W.; Barth, J. V. [Physik Department E20, Technische Universitaet Muenchen, James-Franck-Str. 1, D-85748 Garching (Germany)

    2013-04-21

    We report on the adsorption and self-metalation of a prototypic tetrapyrrole compound, the free-base porphine (2H-P), on the Cu(111) surface. Our multitechnique study combines scanning tunneling microscopy (STM) results with near-edge X-ray absorption fine-structure (NEXAFS) and X-ray photoelectron spectroscopy (XPS) data whose interpretation is supported by density functional theory calculations. In the first layer in contact with the copper substrate the molecules adsorb coplanar with the surface as shown by angle-resolved NEXAFS measurements. The quenching of the first resonance in the magic angle spectra of both carbon and nitrogen regions indicates a substantial electron transfer from the substrate to the LUMO of the molecule. The stepwise annealing of a bilayer of 2H-P molecules sequentially transforms the XP and NEXAFS signatures of the nitrogen regions into those indicative of the coordinated nitrogen species of the metalated copper porphine (Cu-P), i.e., we observe a temperature-induced self-metalation of the system. Pre- and post-metalation species are clearly discriminable by STM, corroborating the spectroscopic results. Similar to the free-base porphine, the Cu-P adsorbs flat in the first layer without distortion of the macrocycle. Additionally, the electron transfer from the copper surface to the molecule is preserved upon metalation. This behavior contrasts the self-metalation of tetraphenylporphyrin (2H-TPP) on Cu(111), where both the molecular conformation and the interaction with the substrate are strongly affected by the metalation process.

  9. Review of magnetic properties and magnetocaloric effect in the intermetallic compounds of rare earth with low boiling point metals

    Ling-Wei, Li

    2016-03-01

    The magnetocaloric effect (MCE) in many rare earth (RE) based intermetallic compounds has been extensively investigated during the last two decades, not only due to their potential applications for magnetic refrigeration but also for better understanding of the fundamental problems of the materials. This paper reviews our recent progress on studying the magnetic properties and MCE in some binary or ternary intermetallic compounds of RE with low boiling point metal(s) (Zn, Mg, and Cd). Some of them exhibit promising MCE properties, which make them attractive for low temperature magnetic refrigeration. Characteristics of the magnetic transition, origin of large MCE, as well as the potential application of these compounds are thoroughly discussed. Additionally, a brief review of the magnetic and magnetocaloric properties in the quaternary rare earth nickel boroncarbides RENi2B2C superconductors is also presented. Project supported by the National Natural Science Foundation of China (Grant Nos. 11374081 and 11004044), the Fundamental Research Funds for the Central Universities, China (Grant Nos. N150905001, L1509006, and N140901001), the Japan Society for the Promotion of Science Postdoctoral Fellowships for Foreign Researchers (Grant No. P10060), and the Alexander von Humboldt (AvH) Foundation (Research stipend to L. Li).

  10. Actinides recycling assessment in a thermal reactor

    Highlights: • Actinides recycling is assessed using BWR fuel assemblies. • Four fuel rods are substituted by minor actinides rods in a UO2 and in a MOX fuel assembly. • Performance of standard fuel assemblies and the ones with the substitution is compared. • Reduction of actinides is measured for the fuel assemblies containing minor actinides rods. • Thermal reactors can be used for actinides recycling. - Abstract: Actinides recycling have the potential to reduce the geological repository burden of the high-level radioactive waste that is produced in a nuclear power reactor. The core of a standard light water reactor is composed only by fuel assemblies and there are no specific positions to allocate any actinides blanket, in this assessment it is proposed to replace several fuel rods by actinides blankets inside some of the reactor core fuel assemblies. In the first part of this study, a single uranium standard fuel assembly is modeled and the amount of actinides generated during irradiation is quantified for use it as reference. Later, in the same fuel assembly four rods containing 6 w/o of minor actinides and using depleted uranium as matrix were replaced and depletion was simulated to obtain the net reduction of minor actinides. Other calculations were performed using MOX fuel lattices instead of uranium standard fuel to find out how much reduction is possible to obtain. Results show that a reduction of minor actinides is possible using thermal reactors and a higher reduction is obtained when the minor actinides are embedded in uranium fuel assemblies instead of MOX fuel assemblies

  11. Toxicity assessment of heavy metals and organic compounds using CellSense biosensor with E.coli

    Hong Wang; Xue Jiang Wang; Jian Fu Zhao; Ling Chen

    2008-01-01

    A new strategy using an amperometric biosensor with Escherichia coli(E.coli)that provides a rapid toxicity determination of chemical compounds is described.The CellSense biosensor system comprises a biological component immobilized in intimate contact with a transducer which converts the biochemical signal into a quantifiable electrical signal.Toxicity assessment of heavy metals using E.coli biosensors could be finished within 30 min and the 50% effective concentrations(EC50)values of four heavy metals were determined.The results shows that inhibitory effects of four heavy metals to E.coli can be ranked in a decreasing order of Hg2+>Cu2+>Zn2+>Ni2+,which accords to the results of conventional bacterial counting method.The toxicity test of organic compounds by using CellSense biosensor was also demonstrated.The CellSense biosensor with E.coli shows a good,reproducible behavior and can be used for reproducible measurements.

  12. Zirconium behaviour during electrorefining of actinide-zirconium alloy in molten LiCl-KCl on aluminium cathodes

    Meier, R.; Souček, P.; Malmbeck, R.; Krachler, M.; Rodrigues, A.; Claux, B.; Glatz, J.-P.; Fanghänel, Th.

    2016-04-01

    A pyrochemical electrorefining process for the recovery of actinides from metallic nuclear fuel based on actinide-zirconium alloys (An-Zr) in a molten salt is being investigated. In this process actinides are group-selectively recovered on solid aluminium cathodes as An-Al alloys using a LiCl-KCl eutectic melt at a temperature of 450 °C. In the present study the electrochemical behaviour of zirconium during electrorefining was investigated. The maximum amount of actinides that can be oxidised without anodic co-dissolution of zirconium was determined at a selected constant cathodic current density. The experiment consisted of three steps to assess the different stages of the electrorefining process, each of which employing a fresh aluminium cathode. The results indicate that almost a complete dissolution of the actinides without co-dissolution of zirconium is possible under the applied experimental conditions.

  13. Transient compounds of high alkaline earth metals with custom-made organic ligands as potential precursors for the gas phase separator of high temperature ceramic superconductors

    The aim of this work was the representation of new transient custom-made metal/organic compounds of the high alkaline earth metals Ca, Sr and Ba as potential precursors for the gas phase separation (chemical vapour deposition, CVD) of high temperature ceramic superconductors. There is a report on the synthesis and comprehensive characterisation of representatives of the class of compounds of substituted metallocenes and the B diketone compounds of these metals. Some selected compounds were examined as regards their suitability for CVD. The main task was the examination of the effect of structural and electronic parameters of ligands on the properties of the compounds, where the volatility was to the fore. (orig./MM)

  14. Bonding in the Extended Metal Chain Compound La{sub 4}Cl{sub 5}C{sub 2}

    Kang, Daebok [Kyungsung Univ., Busan (Korea, Republic of)

    2014-06-15

    The bonding in La{sub 4}Cl{sub 5}C{sub 2} is dominated by strong covalent La-C with lesser La-Cl and La-La interactions. Interstitial C{sub 2} units are essential to the stability of the compound; formally, they provide electrons to the La{sub 6} cage and engage in strong La-C bonding that is much stronger than the La-La bonding. The band structure calculations for a La{sub 4}Cl{sub 6}C{sub 2}. chain reveal that 2σ{sub g} and 1π{sub g} levels of C{sub 2} are substantially stabilized. All La-C and La-Cl bonding states are occupied and La x{sup 2}-y{sup 2} orbitals combine to form the highest occupied x{sup 2}-y{sup 2} bonding band. The shortened C-C single bond may be understood by π{sup *}-backbonding from the occupied C{sub 2} 1π{sub g} orbitals into the empty La dπ states, in agreement with the formal charge distribution of (La{sup 3+}){sub 4-}(Cl{sup -}){sub 5}(C{sub 2}{sup 5-})·2e{sup -}. The two excess electrons are available for intra-cluster bonding and are likely to be localized in the shortened La-La bonds forming the shared edges between the La{sub 6}C{sub 2} octahedra within the chain. The rare-earth metal halides form a variety of highly reduced phases that contain metal clusters. The basic framework in most of these compounds consists of either discrete or condensed edge-sharing M{sub 6}X{sub 12}-type octahedral cluster units that are interstitially centered by an endohedral entity ranging from main group atoms to transition metals. The halogen atoms are located over free edges of the metal octahedra. Over the past 30 years the structures of a large number of new cluster compounds of rare-earth metal halides have been described in the literature. These rare-earth cluster units may be understood as anti-Werner complexes with the endohedral atom surrounded by a first coordination sphere of rare earth metal atoms and a second coordination sphere of halogen atoms.

  15. Results of coupled channels calculations for the neutrons cross sections of a set of actinide nuclei

    This report gathers recents results of neutrons interactions with the following actinide nuclei: 230Th, 232Th, 234U, 238U, 242Pu, 246Cm and 252Cf from the use of the coupled channels optical model. Tabulations of the following quantities are given in Annexe: total, direct elastic and inelastic scattering (integrated and differential), and compound nucleus formation cross sections; ground state generalized transmission coefficients needed to calculate the cross sections of partial compound nucleus processes. This work was carried out within the framework of the IAEA-NDS Coordinated Research Programme on the Intercomparison of Actinide Neutron Cross Section Evaluations

  16. Metal Complexes Containing Natural and and Artificial Radioactive Elements and Their Applications

    Oxana V. Kharissova

    2014-07-01

    Full Text Available Recent advances (during the 2007–2014 period in the coordination and organometallic chemistry of compounds containing natural and artificially prepared radionuclides (actinides and technetium, are reviewed. Radioactive isotopes of naturally stable elements are not included for discussion in this work. Actinide and technetium complexes with O-, N-, N,O, N,S-, P-containing ligands, as well π-organometallics are discussed from the view point of their synthesis, properties, and main applications. On the basis of their properties, several mono-, bi-, tri-, tetra- or polydentate ligands have been designed for specific recognition of some particular radionuclides, and can be used in the processes of nuclear waste remediation, i.e., recycling of nuclear fuel and the separation of actinides and fission products from waste solutions or for analytical determination of actinides in solutions; actinide metal complexes are also usefulas catalysts forcoupling gaseous carbon monoxide,as well as antimicrobial and anti-fungi agents due to their biological activity. Radioactive labeling based on the short-lived metastable nuclide technetium-99m (99mTc for biomedical use as heart, lung, kidney, bone, brain, liver or cancer imaging agents is also discussed. Finally, the promising applications of technetium labeling of nanomaterials, with potential applications as drug transport and delivery vehicles, radiotherapeutic agents or radiotracers for monitoring metabolic pathways, are also described.

  17. Metal complexes containing natural and and artificial radioactive elements and their applications.

    Kharissova, Oxana V; Méndez-Rojas, Miguel A; Kharisov, Boris I; Méndez, Ubaldo Ortiz; Martínez, Perla Elizondo

    2014-01-01

    Recent advances (during the 2007-2014 period) in the coordination and organometallic chemistry of compounds containing natural and artificially prepared radionuclides (actinides and technetium), are reviewed. Radioactive isotopes of naturally stable elements are not included for discussion in this work. Actinide and technetium complexes with O-, N-, N,O, N,S-, P-containing ligands, as well π-organometallics are discussed from the view point of their synthesis, properties, and main applications. On the basis of their properties, several mono-, bi-, tri-, tetra- or polydentate ligands have been designed for specific recognition of some particular radionuclides, and can be used in the processes of nuclear waste remediation, i.e., recycling of nuclear fuel and the separation of actinides and fission products from waste solutions or for analytical determination of actinides in solutions; actinide metal complexes are also usefulas catalysts forcoupling gaseous carbon monoxide,as well as antimicrobial and anti-fungi agents due to their biological activity. Radioactive labeling based on the short-lived metastable nuclide technetium-99m ((99m)Tc) for biomedical use as heart, lung, kidney, bone, brain, liver or cancer imaging agents is also discussed. Finally, the promising applications of technetium labeling of nanomaterials, with potential applications as drug transport and delivery vehicles, radiotherapeutic agents or radiotracers for monitoring metabolic pathways, are also described. PMID:25061724

  18. Metal-Organic Framework (MOF) Compounds: Photocatalysts for Redox Reactions and Solar Fuel Production.

    Dhakshinamoorthy, Amarajothi; Asiri, Abdullah M; García, Hermenegildo

    2016-04-25

    Metal-organic frameworks (MOFs) are crystalline porous materials formed from bi- or multipodal organic linkers and transition-metal nodes. Some MOFs have high structural stability, combined with large flexibility in design and post-synthetic modification. MOFs can be photoresponsive through light absorption by the organic linker or the metal oxide nodes. Photoexcitation of the light absorbing units in MOFs often generates a ligand-to-metal charge-separation state that can result in photocatalytic activity. In this Review we discuss the advantages and uniqueness that MOFs offer in photocatalysis. We present the best practices to determine photocatalytic activity in MOFs and for the deposition of co-catalysts. In particular we give examples showing the photocatalytic activity of MOFs in H2 evolution, CO2 reduction, photooxygenation, and photoreduction. PMID:26970539

  19. Thin films of metal-organic compounds and metal nanoparticle-embedded polymers for nonlinear optical applications

    S Philip Anthony; Shatabdi Porel; D Narayana Rao; T P Radhakrishnan

    2005-11-01

    Thin films based on two very different metal-organic systems are developed and some nonlinear optical applications are explored. A family of zinc complexes which form perfectly polar assemblies in their crystalline state are found to organize as uniaxially oriented crystallites in vapor deposited thin films on glass substrate. Optical second harmonic generation from these films is investigated. A simple protocol is developed for the in-situ fabrication of highly monodisperse silver nanoparticles in a polymer film matrix. The methodology can be used to produce free-standing films. Optical limiting capability of the nanoparticle-embedded polymer film is demonstrated.

  20. Behavior of actinides in the Integral Fast Reactor fuel cycle

    Courtney, J.C. [Louisiana State Univ., Baton Rouge, LA (United States). Nuclear Science Center; Lineberry, M.J. [Argonne National Lab., Idaho Falls, ID (United States). Technology Development Div.

    1994-06-01

    The Integral Fast Reactor (IFR) under development by Argonne National Laboratory uses metallic fuels instead of ceramics. This allows electrorefining of spent fuels and presents opportunities for recycling minor actinide elements. Four minor actinides ({sup 237}Np, {sup 240}Pu, {sup 241}Am, and {sup 243}Am) determine the waste storage requirements of spent fuel from all types of fission reactors. These nuclides behave the same as uranium and other plutonium isotopes in electrorefining, so they can be recycled back to the reactor without elaborate chemical processing. An experiment has been designed to demonstrate the effectiveness of the high-energy neutron spectra of the IFR in consuming these four nuclides and plutonium. Eighteen sets of seven actinide and five light metal targets have been selected for ten day exposure in the Experimental Breeder Reactor-2 which serves as a prototype of the IFR. Post-irradiation analyses of the exposed targets by gamma, alpha, and mass spectroscopy are used to determine nuclear reaction-rates and neutron spectra. These experimental data increase the authors` confidence in their ability to predict reaction rates in candidate IFR designs using a variety of neutron transport and diffusion programs.

  1. Behavior of actinides in the Integral Fast Reactor fuel cycle

    The Integral Fast Reactor (IFR) under development by Argonne National Laboratory uses metallic fuels instead of ceramics. This allows electrorefining of spent fuels and presents opportunities for recycling minor actinide elements. Four minor actinides (237Np, 240Pu, 241Am, and 243Am) determine the waste storage requirements of spent fuel from all types of fission reactors. These nuclides behave the same as uranium and other plutonium isotopes in electrorefining, so they can be recycled back to the reactor without elaborate chemical processing. An experiment has been designed to demonstrate the effectiveness of the high-energy neutron spectra of the IFR in consuming these four nuclides and plutonium. Eighteen sets of seven actinide and five light metal targets have been selected for ten day exposure in the Experimental Breeder Reactor-2 which serves as a prototype of the IFR. Post-irradiation analyses of the exposed targets by gamma, alpha, and mass spectroscopy are used to determine nuclear reaction-rates and neutron spectra. These experimental data increase the authors' confidence in their ability to predict reaction rates in candidate IFR designs using a variety of neutron transport and diffusion programs

  2. Actinide behavior in the Integral Fast Reactor. Final project report

    The Integral Fast Reactor (IFR) under development by Argonne National Laboratory uses metallic fuels instead of ceramics. This allows electrorefining of spent fuels and presents opportunities for recycling minor actinide elements. Four minor actinides (237Np, 240Pu, 241Am, and 243Am) determine the waste storage requirements of spent fuel from all types of fission reactors. These nuclides behave the same as uranium and other plutonium isotopes in electrorefining, so they can be recycled back to the reactor without elaborate chemical processing. An experiment has been designed to demonstrate the effectiveness of the high-energy neutron spectra of the IFR in consuming these four nuclides and weapons grade plutonium. Eighteen sets of seven actinide and five light metal targets have been selected for seven day exposure in the Experimental Breeder Reactor-II which serves as a prototype of the IFR. Post-irradiation analyses of the exposed targets by gamma, alpha, and mass spectroscopy are used to determine nuclear reaction rates and neutron spectra. These experimental data increase the authors confidence in their ability to predict reaction rates in candidate IFR designs using a variety of neutron transport and diffusion programs

  3. Fundamental Studies of the Reforming of Oxygenated Compounds over Supported Metal Catalysts

    Dumesic, James

    2016-01-04

    The main objective of our research has been to elucidate fundamental concepts associated with controlling the activity, selectivity, and stability of bifunctional, metal-based heterogeneous catalysts for tandem reactions, such as liquid-phase conversion of oxygenated hydrocarbons derived from biomass. We have shown that bimetallic catalysts that combine a highly-reducible metal (e.g., platinum) with an oxygen-containing metal promoter (e.g., molybdenum) are promising materials for conversion of oxygenated hydrocarbons because of their high activity for selective cleavage for carbon-oxygen bonds. We have developed methods to stabilize metal nanoparticles against leaching and sintering under liquid-phase reaction conditions by using atomic layer deposition (ALD) to apply oxide overcoat layers. We have used controlled surface reactions to produce bimetallic catalysts with controlled particle size and controlled composition, with an important application being the selective conversion of biomass-derived molecules. The synthesis of catalysts by traditional methods may produce a wide distribution of metal particle sizes and compositions; and thus, results from spectroscopic and reactions kinetics measurements have contributions from a distribution of active sites, making it difficult to assess how the size and composition of the metal particles affect the nature of the surface, the active sites, and the catalytic behavior. Thus, we have developed methods to synthesize bimetallic nanoparticles with controlled particle size and controlled composition to achieve an effective link between characterization and reactivity, and between theory and experiment. We have also used ALD to modify supported metal catalysts by addition of promoters with atomic-level precision, to produce new bifunctional sites for selective catalytic transformations. We have used a variety of techniques to characterize the metal nanoparticles in our catalysts, including scanning transmission electron

  4. Observation of an unconventional metal-insulator transition in overdoped CuO_2 compounds

    Venturini, F.; Opel, M.; Devereaux, T. P.; Freericks, J. K.; Tüttő, I.; Revaz, B.; Walker, E.; Berger, H; Forró, L.; Hackl, R.

    2002-01-01

    The electron dynamics in the normal state of Bi$_2$Sr$_2$CaCu$_2$O$_{8+\\delta}$ is studied by inelastic light scattering over a wide range of doping. A strong anisotropy of the electron relaxation is found which cannot be explained by single-particle properties alone. The results strongly indicate the presence of an unconventional quantum-critical metal-insulator transition where "hot" (antinodal) quasiparticles become insulating while "cold" (nodal) quasiparticles remain metallic. A phenomen...

  5. Synergistic extraction of actinides : Part II. Tetra-and trivalent actinides

    A detailed discussion on the synergistic solvent extraction behaviour of tetra- and trivalent actinide ions is presented. Structural aspects of the natural donor adducts of the tetravalent actinide ion chelates involved in synergism are also discussed. (author)

  6. Recovery of actinides from TBP-Na2Co3 scrub-waste solutions: the ARALEX process

    A flowsheet for the recovery of actinides from TBP-Na2CO3 scrub-waste solutions has been developed, based on batch extraction data, and tested, using laboratory-scale countercurrent extraction techniques. The process, called the ARALEX process, uses 2-ethyl-1-hexanol (2-EHOH) to extract the TBP degradation products (HDBP and H2MBP) from acidified Na2CO3 scrub waste leaving the actinides in the aqueous phase. Dibutyl and monobutyl phosphoric acids are attached to the 2-EHOH molecules through hydrogen bonds, which also diminish the ability of the HDBP and H2MBP to complex actinides. Thus all actinides remain in the aqueous raffinate. Dilute sodium hydroxide solutions can be used to back-extract the dibutyl and monobutyl phosphoric acid esters as their sodium salts. The 2-EHOH can then be recycled. After extraction of the acidified carbonate waste with 2-EHOH, the actinides may be readily extracted from the raffinate with DHDECMP or, in the case of tetra- and hexavalent actinides, with TBP. The ARALEX process can also be applied to other actinide waste streams which contain appreciable concentrations of polar organic compounds (e.g., detergents) that interfere with conventional actinide ion exchange and liquid-liquid extraction procedures. 20 figures, 6 tables

  7. Noble metal catalyzed aqueous phase hydrogenation and hydrodeoxygenation of lignin-derived pyrolysis oil and related model compounds.

    Mu, Wei; Ben, Haoxi; Du, Xiaotang; Zhang, Xiaodan; Hu, Fan; Liu, Wei; Ragauskas, Arthur J; Deng, Yulin

    2014-12-01

    Aqueous phase hydrodeoxygenation of lignin pyrolysis oil and related model compounds were investigated using four noble metals supported on activated carbon. The hydrodeoxygenation of guaiacol has three major reaction pathways and the demethylation reaction, mainly catalyzed by Pd, Pt and Rh, produces catechol as the products. The presence of catechol and guaiacol in the reaction is responsible for the coke formation and the catalysts deactivation. As expected, there was a significant decrease in the specific surface area of Pd, Pt and Rh catalysts during the catalytic reaction because of the coke deposition. In contrast, no catechol was produced from guaiacol when Ru was used so a completely hydrogenation was accomplished. The lignin pyrolysis oil upgrading with Pt and Ru catalysts further validated the reaction mechanism deduced from model compounds. Fully hydrogenated bio-oil was produced with Ru catalyst. PMID:25280108

  8. Actinide chemistry in ionic liquids.

    Takao, Koichiro; Bell, Thomas James; Ikeda, Yasuhisa

    2013-04-01

    This Forum Article provides an overview of the reported studies on the actinide chemistry in ionic liquids (ILs) with a particular focus on several fundamental chemical aspects: (i) complex formation, (ii) electrochemistry, and (iii) extraction behavior. The majority of investigations have been dedicated to uranium, especially for the 6+ oxidation state (UO2(2+)), because the chemistry of uranium in ordinary solvents has been well investigated and uranium is the most abundant element in the actual nuclear fuel cycles. Other actinides such as thorium, neptunium, plutonium, americium, and curiumm, although less studied, are also of importance in fully understanding the nuclear fuel engineering process and the safe geological disposal of radioactive wastes. PMID:22873132

  9. Preparation of isotopes and sources of actinide elements

    As the C.E.A. possesses no isotopic separation facility, the productions of isotopes of actinide elements are performed: a) by neutron irradiation and chemical treatment of special targets, b) by milking decay products from stocks of aged actinide elements, c) by chemical treatment of alpha active wastes. These productions concern the following isotopes: 233U, 238Pu, 242Pu, 243Cm, 242Cm, 244Cm (a); 228Th, 229Th, 234U, 237U, 239Np, 240Pu, 241Am, 248Cm (b); 237Np, 241Am (c). These isotopes are produced to satisfy French and international needs and are sent to users in various forms: solutions, metals, oxides, fluorides, or in different sources forms. The preparation of the sources represents an important field of activities divided into two parts: 1/Industrial sources: production of large series of different sources, 2/ Scientific sources: production of sources suitable for a specific scientific problem. A large overview of these activities is given

  10. Actinide-specific sequestering agents and decontamination applications

    Smith, William L. [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Materials and Molecular Research Division; Univ. of California, Berkeley, CA (United States). Dept. of Chemistry; Raymond, Kenneth N. [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Materials and Molecular Research Division; Univ. of California, Berkeley, CA (United States). Dept. of Chemistry

    1981-04-07

    With the commercial development of nuclear reactors, the actinides have become very important industrial elements. A major concern of the nuclear industry is the biological hazard associated with nuclear fuels and their wastes. The acute chemical toxicity of tetravalent actinides, as exemplified by Th(IV), is similar to Cr(III) or Al(III). However, the acute toxicity of 239Pu(IV) is similar to strychnine, which is much more toxic than any of the non-radioactive metals such as mercury. Although the more radioactive isotopes of the transuranium elements are more acutely toxic by weight than plutonium, the acute toxicities of 239Pu, 241Am, and 244Cm are nearly identical in radiation dose, ~100 μCi/kg in rodents. Finally and thus, the extreme acute toxicity of 239Pu is attributed to its high specific activity of alpha emission.

  11. Magnetic susceptibilities of actinide cations in aqueous solution

    Paramagnetic cations serve as a useful and efficient NMR probes of coordination environment and can also give insight into dynamics on the millisecond timescale. In an effort to extend the powerful analytical techniques employed with the lanthanide series, some studies to characterize the actinide paramagnetic behavior have been undertaken in our labs under the auspices of the European ACTINET Integrated Infrastructure Initiative and the DOE, NEUP program. We will present a series of magnetic susceptibility measurements spanning all of the readily accessible actinide cations. Variable temperature data has been collected to gather information on the ground electronic state of the cations. The effects of the counter anion in solution are also discussed as they relate to 'softness' and the apparent reduction in free electron character on the metal. Comparisons with first-order Van Vleck and Russell-Saunders predictions will also be shown. (authors)

  12. The adsorption and reaction of halogenated volatile organic compounds (VOC's) on metal oxides. 1998 annual progress report

    'The goal of the research is to elucidate the properties of the materials responsible for the activation of halocarbons and the nature of the intermediates formed in the dissociative adsorption of this class of compounds. This information is essential for interpreting and predicting stoichiometric and catalytic pathways for the safe destruction of halocarbon pollutants. The specific objectives are: (1) to study the adsorption and reactivity of chloromethanes and chloroethanes on metal oxides; (2) to identify the reaction intermediates using spectroscopic methods; and (3) to develop kinetic models for the reaction of these halocarbons with oxide surfaces. This report summarizes work after 20 months of a 36-month project. Emphasis has been placed understanding the surfaces phases, as well as the bulk phases that are present during the reactions of chlorinated hydrocarbons with strongly basic metal oxides. Most of the research has been carried out with carbon tetrachloride.'

  13. Actinide Waste Forms and Radiation Effects

    Ewing, R. C.; Weber, W. J.

    Over the past few decades, many studies of actinides in glasses and ceramics have been conducted that have contributed substantially to the increased understanding of actinide incorporation in solids and radiation effects due to actinide decay. These studies have included fundamental research on actinides in solids and applied research and development related to the immobilization of the high level wastes (HLW) from commercial nuclear power plants and processing of nuclear weapons materials, environmental restoration in the nuclear weapons complex, and the immobilization of weapons-grade plutonium as a result of disarmament activities. Thus, the immobilization of actinides has become a pressing issue for the twenty-first century (Ewing, 1999), and plutonium immobilization, in particular, has received considerable attention in the USA (Muller et al., 2002; Muller and Weber, 2001). The investigation of actinides and

  14. Relation between various chromium compounds and some other elements in fumes from manual metal arc stainless steel welding.

    Matczak, W; Chmielnicka, J

    1993-01-01

    For the years 1987-1990 160 individual samples of manual metal arc stainless steel (MMA/SS) welding fumes from the breathing zone of welders in four industrial plants were collected. Concentrations of soluble and insoluble chromium (Cr) III and Cr VI compounds as well as of some other welding fume elements (Fe, Mn, Ni, F) were determined. Concentration of welding fumes in the breathing zone ranged from 0.2 to 23.4 mg/m3. Total Cr amounted to 0.005-0.991 mg/m3 (including 0.005-0.842 mg/m3 Cr V...

  15. Antimicrobial activity of seven metallic compounds against penicillinase producing and non-penicillinase producing strains of Neisseria gonorrhoeae.

    Peeters, M.; Vanden Berghe, D; Meheus, A.

    1986-01-01

    The in vitro activity of seven metallic compounds was tested against penicillinase (beta lactamase) producing strains of Neisseria gonorrhoeae (PPNG) and non-PPNG strains. On a weight basis, the mercurials showed the greatest in vitro activity. Phenylmercuric borate, thiomersal, and mercuric chloride inhibited 90% of all strains at concentrations of 5 mg/l, 5 mg/l, and 20 mg/l respectively. Silver nitrate inhibited 90% of the strains at 80 mg/l and the MIC90 for mild silver protein was 200 mg...

  16. Anthropogenic Actinides in the Environment

    The use of nuclear energy and the testing of nuclear weapons have led to significant releases of anthropogenic isotopes, in particular a number of actinide isotopes generally not abundant in nature. Most prominent amongst these are 239Pu, 240Pu, and 236U. The study of these actinides in nature has been an active field of study ever since. Measurements of actinides are applied to nuclear safeguards, investigating the sources of contamination, and as a tracer for a number of erosion and hydrology studies. Accelerator Mass Spectrometry (AMS) is ideally suited for these studies and generally offers higher sensitivities than competing techniques, like ICP-MS or decay counting. Recent advances in AMS allow the study of “minor” plutonium isotopes (241Pu, 242Pu, and 244Pu). Furthermore, 236U can now be measured at the levels expected from the global stratospheric fall-out of the atmospheric nuclear weapon tests in the 1950s and 1960s. Even the pre-anthropogenic isotope ratios could be within reach. However, the distribution and abundance levels of these isotopes are not well known yet. I will present an overview of the field, and in detail two recent studies on minor plutonium isotopes and 236U, respectively.(author)

  17. Volatile organic compounds and metal leaching from composite products made from fiberglass-resin portion of printed circuit board waste.

    Guo, Jie; Jiang, Ying; Hu, Xiaofang; Xu, Zhenming

    2012-01-17

    This study focused on the volatile organic compounds (VOCs) and metal leaching from three kinds of composite products made from fiberglass-resin portion (FRP) of crushed printed circuit board (PCB) waste, including phenolic molding compound (PMC), wood plastic composite (WPC), and nonmetallic plate (NMP). Released VOCs from the composite products were quantified by air sampling on adsorbent followed by thermal desorption and GC-MS analysis. The results showed that VOCs emitted from composite products originated from the added organic components during manufacturing process. Phenol in PMC panels came primarily from phenolic resin, and the airborne concentration of phenol emitted from PMC product was 59.4 ± 6.1 μg/m(3), which was lower than odor threshold of 100% response for phenol (180 μg/m(3)). VOCs from WPC product mainly originated from wood flour, e.g., benzaldehyde, octanal, and d-limonene were emitted in relatively low concentrations. For VOCs emitted from NMP product, the airborne concentration of styrene was the highest (633 ± 67 μg/m(3)). Leaching characteristics of metal ions from composite products were tested using acetic acid buffer solution and sulphuric acid and nitric acid solution. Then the metal concentrations in the leachates were tested by ICP-AES. The results showed that only the concentration of Cu (average = 893 mg/L; limit = 100 mg/L) in the leachate solution of the FRP using acetic acid buffer solution exceeded the standard limit. However, concentrations of other metal ions (Pb, Cd, Cr, Ba, and Ni) were within the standard limit. All the results indicated that the FRP in composite products was not a major concern in terms of environmental assessment based upon VOCs tests and leaching characteristics. PMID:22142243

  18. Compound surface-plasmon-polariton waves guided by a thin metal layer sandwiched between a homogeneous isotropic dielectric material and a periodically multilayered isotropic dielectric material

    Chiadini, Francesco; Scaglione, Antonio; Lakhtakia, Akhlesh

    2015-01-01

    Multiple p- and s-polarized compound surface plasmon-polariton (SPP) waves at a fixed frequency can be guided by a structure consisting of a metal layer sandwiched between a homogeneous isotropic dielectric (HID) material and a periodic multilayered isotropic dielectric (PMLID) material. For any thickness of the metal layer, at least one compound SPP wave must exist. It possesses the p-polarization state, is strongly bound to the metal/HID interface when the metal thickness is large but to both metal/dielectric interfaces when the metal thickness is small. When the metal layer vanishes, this compound SPP wave transmutes into a Tamm wave. Additional compound SPP waves exist, depending on the thickness of the metal layer, the relative permittivity of the HID material, and the period and the composition of the PMLID material. Some of these are p polarized, the others being s polarized. All of them differ in phase speed, attenuation rate, and field profile, even though all are excitable at the same frequency. The...

  19. Computational Design of Metal Ion Sequestering Agents

    Hay, Benjamin P.; Rapko, Brian M.

    2005-06-15

    Organic ligands that exhibit a high degree of metal ion recognition are essential precursors for developing separation processes and sensors for metal ions. Since the beginning of the nuclear era, much research has focused on discovering ligands that target specific radionuclides. Members of the Group 1A and 2A cations (e.g., Cs, Sr, Ra) and the f-block metals (actinides and lanthanides) are of primary concern to DOE. Although there has been some success in identifying ligand architectures that exhibit a degree of metal ion recognition, the ability to control binding affinity and selectivity remains a significant challenge. The traditional approach for discovering such ligands has involved lengthy programs of organic synthesis and testing that, in the absence of reliable methods for screening compounds before synthesis, have resulted in much wasted research effort.

  20. Computational Design of Metal Ion Sequestering Agents

    Hay, Benjamin P.; Rapko, Brian M.

    2006-06-01

    Organic ligands that exhibit a high degree of metal ion recognition are essential precursors for developing separation processes and sensors for metal ions. Since the beginning of the nuclear era, much research has focused on discovering ligands that target specific radionuclides. Members of the Group 1A and 2A cations (e.g., Cs, Sr, Ra) and the f-block metals (actinides and lanthanides) are of primary concern to DOE. Although there has been some success in identifying ligand architectures that exhibit a degree of metal ion recognition, the ability to control binding affinity and selectivity remains a significant challenge. The traditional approach for discovering such ligands has involved lengthy programs of organic synthesis and testing that, in the absence of reliable methods for screening compounds before synthesis, have resulted in much wasted research effort.

  1. Magnetic behavior of inorganic-organic hybrid phosphite compounds with 3-d transition metals

    The (C2H10N2)[M(HPO3)F3](MIII=V, Cr, Fe) [I], (C2H10N2)[M3(HPO3)4] (MII=Mn, Co) [II] and (C2H10N2)0.5[Fe(HPO3)2](MIII=V, Fe) [III] compounds have been synthesized by using mild hydrothermal conditions. The crystal structure of the compounds shows different dimensionality. The compounds exhibit antiferromagnetic behavior, with hysteresis loops for the bimetallic (C2H10N2)[Mn2.09Co0.91(HPO3)4] and (C2H10N2)0.5[V0.48Fe0.52(HPO3)2] phases, indicating the existence of a ferrimagnetic behavior probably due to a spin descompensation

  2. Characterization of actinide bonding in Th(S2PMe2)4 by synchrotron X-ray diffraction

    Extensive synchrotron (28 K) and conventional sealed-tube (9 K) X-ray diffraction data have been collected on Th(S2PMe2)4. Modeling of the electron density of the complex shows the bonding is quite ionic with little diffuse f or d type bonding density. Furthermore a large polarization of the Th core is observed revealing some 5d-like involvement in the bonding. High-quality ab initio density functional calculations are not able to reproduce these features and instead predict rather covalent bonding with considerable 6d-5f mixing. The study suggests that this theoretical method exaggerates the covalent nature of actinide bonds. It is shown that the most direct measure of covalence -- charge transfer and electron distributions -- can be usefully estimated by X-ray diffraction even in this most unfavorable of cases, where many actinide core electrons are present. The use of very low temperature data is crucial in the study of heavy metal complexes in order to minimize systematic errors such as thermal diffuse scattering and anharmonicity. The fact that accurate synchrotron radiation diffraction data can be measured within days makes studies of compounds beyond the first transition series more frequently within reach

  3. Transport Properties of YbCu4.4 Giant-unit-cell Metallic Compound

    Popčević, Petar; Smiljanić, Igor; Barišić, Neven; Smontara, Ana; Dolinšek, Janez; Gottlieb-Schönmeyer, Saskia

    2010-01-01

    The experimental results of the transport properties: electrical resistivity, ρ, thermopower, S, and thermal conductivity, κ, of a polycrystalline sample of YbCu4.4, in the temperature range 2 to 300 K, are presented. In contrast to the divalent YbCu2 compound, YbCu4.4 has transport properties typical of an intermediate valence compound: relatively high electrical resistivity and large thermoelectric power. The electrical resistivity ρ(T) exhibits a typical Kondo lattice systems’ behaviour, w...

  4. The chemistry of molten salt mixtures: application to the reductive extraction of lanthanides and actinides by a liquid metal; Chimie des melanges de sels fondus. Application a l'extraction reductrice d'actinides et de lanthanides par un metal liquide

    Finne, J

    2005-10-15

    The design of a process of An/Ln separation by liquid - liquid extraction can be used for on-line purification of the molten salt in a molten salt nuclear reactor (Generation IV) as well as reprocessing various spent fuels. In order to establish the chemical properties of An and Ln in molten salt mediums, E - pO{sub 2} - diagrams were established for the relevant chemical elements. With the purpose of checking the possibilities of separating the An from Ln, the real activity coefficients in liquid metals were measured. An experimental protocol was developed and validated on the Gd/Ga system. It was then transferred to radioactive environment to measure the activity coefficient of Pu in Ga. The results made it possible to estimate the effectiveness of the Pu extraction and its separation from Gd and Ce. The selectivity was shown to decrease with the temperature and Al and Ga showed a good selectivity between Pu and the Ce in fluoride medium. (author)

  5. Actinides-lanthanides (neodymium) separation by electrolytical extraction in molten fluoride media; Separation actinides-lanthanides (neodyne) par extraction electrolytique en milieux fluorures fondus

    Hamel, C

    2005-02-15

    The aim of this thesis is to assess the potentialities of pyrochemical processes for futur nuclear fuels and Generation IV reactors (more particularly molten salt reactors). This study concerns the Actinides-Lanthanides and Lanthanides-Solvent separation by electrolytical extraction in molten fluoride media at high temperature. Three elements are selected for this study: neodymium (NdF{sub 3}), uranium (UF{sub 4}) and plutonium (PuF{sub 3}). Firstly, the electrochemical study of these three compounds in molten fluoride media is performed to evaluate the separations. Electrodeposition processes are studied and the values of formal potentials of U(III)/U(0), Pu(III)/Pu(0) and Nd(III)/Nd(0) are obtained in LiF-CaF{sub 2} eutectic mixture. Thermodynamically, the values of potentials differences are enough to separate U-Nd and Pu-Nd with a yield of extraction of 99.99%; this value is just sufficient for the Pu-Nd separation. Concerning the Nd-solvent separation this potential difference is too small. Next, the electrodeposition of solid metals on inert electrodes is performed. This study showed that the uranium and neodymium deposits are unstable in several fluoride media. In addition, the presence of salts in the dendritic metal is observed for the U solid deposits. Finally, a reactive cathode is used to improve these separation results and the shape of the deposits. The experimental results on nickel electrodes showed an improvement of the Pu-Nd separation and the Nd-solvent separation with the depolarisation phenomenon of the metal deposit on the nickel. Moreover, U and Nd metal are stabilized in the alloy which allows the elimination of reactions with the solvent as observed for the solid deposit. The formation of liquids alloys makes also easier the recovery of these three. (author)

  6. Actinides-lanthanides (neodymium) separation by electrolytic extraction in molten fluoride media; Separation actinides-lanthanides (neodyne) par extraction electrolytique en milieux fluorures fondus

    Hamel, C

    2005-02-15

    The aim of this thesis is to assess the potentialities of pyrochemical processes for future nuclear fuels and Generation IV reactors (more particularly molten salt reactors). This study concerns the Actinides-Lanthanides and Lanthanides-Solvent separation by electrolytic extraction in molten fluoride media at high temperature. Three elements are selected for this study: neodymium (NdF{sub 3}), uranium (UF{sub 4}) and plutonium (PuF{sub 3}). Firstly, the electrochemical study of these three compounds in molten fluoride media is performed to evaluate the separations. Electrodeposition processes are studied and the values of formal potentials of U(III)/U(0), Pu(III)/Pu(0) and Nd(III)/Nd(0) are obtained in LiF-CaF{sub 2} eutectic mixture. Thermodynamically, the values of potentials differences are enough to separate U-Nd and Pu-Nd with a yield of extraction of 99.99%; this value is just sufficient for the Pu-Nd separation. Concerning the Nd-solvent separation this potential difference is too small. Next, the electrodeposition of solid metals on inert electrodes is performed. This study showed that the uranium and neodymium deposits are unstable in several fluoride media. In addition, the presence of salts in the dendritic metal is observed for the U solid deposits. Finally, a reactive cathode is used to improve these separation results and the shape of the deposits. The experimental results on nickel electrodes showed an improvement of the Pu-Nd separation and the Nd-solvent separation with the depolarization phenomenon of the metal deposit on the nickel. Moreover, U and Nd metal are stabilized in the alloy which allows the elimination of reactions with the solvent as observed for the solid deposit. The formation of liquids alloys makes also easier the recovery of these three. (author)

  7. PWRs potentialities for minor actinides burning

    In the frame of the SPIN program at CEA, the impacts of the minor actinides (MA) incineration in PWRs are analysed. The aim is to reduce the mass, the potential radiotoxicity level. The recycling of all actinide elements is evaluated in a PWR nuclear yard. A sensitivity study is done to evaluate the incineration for each minor actinide element. This gives the most efficient way of incineration for each MA elements in a PWR and helps to design a PWR burner. This burner is disposed in a PWR nuclear system in which the actinides are recycled until equilibrium. (author)

  8. Chemistry of actinides and fission products

    This task is concerned primarily with the fundamental chemistry of the actinide and fission product elements. Special efforts are made to develop research programs in collaboration with researchers at universities and in industry who have need of national laboratory facilities. Specific areas currently under investigation include: (1) spectroscopy and photochemistry of actinides in low-temperature matrices; (2) small-angle scattering studies of hydrous actinide and fission product polymers in aqueous and nonaqueous solvents; (3) kinetic and thermodynamic studies of complexation reactions in aqueous and nonaqueous solutions; and (4) the development of inorganic ion exchange materials for actinide and lanthanide separations. Recent results from work in these areas are summarized here

  9. Long-term plant availability of actinides

    Environmental releases of actinide elements raise issues about which data are very limited. Quantitative information is required to assess the long-term behavior of actinides and their potential hazards resulting from the transport through food chains leading to man. Of special interest is the effect of time on the changes in the availability of actinide elements for uptake by plants from soil. This study provides valuable information on the effects of weathering and aging on the uptake of actinides from soil by range and crop plants grown under realistic field conditions

  10. Trends in air concentration and deposition at background monitoring sites in Sweden - major inorganic compounds, heavy metals and ozone

    Kindbom, K.; Svensson, Annika; Sjoeberg, K.; Pihl Karlsson, G.

    2001-09-01

    This report describes concentrations in air of sulphur compounds, soot, nitrogen compounds and ozone in Sweden between 1985-1998. Time trends of concentration in precipitation and deposition of sulphate, nitrate, ammonium, acidity, base cations and chloride in six different regions covering Sweden are evaluated during the period 1983-1998. Trends of heavy metals in precipitation have been analysed for the period 1983-1998 and the change in heavy metal concentration, 1975-1995, in mosses is described. Data used in the trend analyses originates from measurements performed at six Swedish EMEP stations and from approximately 25 stations within the national Precipitation Chemistry Network. Two different statistical methods, linear regression and the non-parametric Mann Kendall test, have been used to evaluate changes in annual mean values. Time trends of concentration of sulphur dioxide, particulate sulphate, soot, nitrogen dioxide, total nitrate and total ammonium in air show highly significant decreasing trends, except for soot at one station in northern Sweden. Concentrations of ozone have a strong seasonal variation with a peak occurring in spring every year. However, annual ozone concentrations show no obvious trends in spite of decreasing emissions of the precursors NOx and VOC. A slight indication of a decreasing trend in the number of ozone episodes might be seen from 1990 to 1998. Sulphate concentrations in precipitation and deposition show strongly significant decreasing trends in the whole country. Concentrations and deposition of nitrate and ammonium have been decreasing in all areas except for nitrate at stations in south-west and north-west Sweden and ammonium in south-west Sweden. Acidity has decreased in all areas since 1989, resulting in increasing pH values in Sweden. The interannual variations of concentration and deposition of base cations and chloride are large and few general trends can be seen during 1983-1997. Time trends of four heavy metals in

  11. HPIC separation and quantification of Ca and Fe in uranium metal and alloy compounds

    The paper describes the separation and quantification of Ca and Fe from uranium metal and uranium based alloy fuels employing ion chromatography (IC). Ca separation from other metal ions of alkali and alkaline groups was carried out on a cation exchange column and the same was detected and quantified by means of conductivity detector. In case of Fe, it was separated from other transition elements using chelation ion chromatography where detection and quantification was carried out photometrically after the addition of PAR as post column reagent. For both the analyses a preliminary column chromatography separation for eliminating the bulk matrix uranium was performed. (author)

  12. New electrolyte systems for capillary zone electrophoresis of metal cations and non-ionic organic compounds

    Shi, Y.

    1995-06-19

    Excellent separations of metal ions can be obtained very quickly by capillary electrophoresis provided a weak complexing reagent is incorporated into the electrolyte to alter the effective mobilities of the sample ions. Indirect photometric detection is possible by also adding a UV-sensitive ion to the electrolyte. Separations are described using phthalate, tartrate, lactate or hydroxyisobutyrate as the complexing reagent. A separation of twenty-seven metal ions was achieved in only 6 min using a lactate system. A mechanism for the separation of lanthanides is proposed for the hydroxyisobutyrate system.

  13. Interaction between graphite and some refractory metallic compounds at high temperature

    The behavior of thermocouples, used in nuclear reactors, made of molybdenum, niobium, rhenium or ceramic compounds such as titanium nitride and molybdenum borides in contact with graphite under vacuum in a temperature range between 1000 to 16000C during 500 hours is studied. Phases and growth rates are examined

  14. Structure of metal-rich (001) surfaces of III-V compound semiconductors

    Kumpf, C.; Smilgies, D.; Landemark, E.; Nielsen, M.; Feidenhans'l, R.; Bunk, O.; Zeysing, J.H.; Su, Y.; Johnson, R.L.; Cao, L.; Zegenhagen, J.; Fimland, B.O.; Marks, L.D.; Ellis, D.

    2001-01-01

    feature of the structure is accompanied by linear arrays of atoms on nonbulklike sites at the surface which, depending on the compounds, exhibit a certain degree of disorder. A tendency to group-III-dimer formation within these chains increases when descending the periodic table. We propose that all the c...

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

    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.

  16. Fertile-Free Fast Lead-Cooled Incinerators for Efficient Actinide Burning

    Fertile-free fast lead-cooled modular reactors are proposed as efficient incinerators of plutonium and minor actinides (MAs) for application to advanced fuel cycles devoted to transmutation. Two concepts are presented: (1) an actinide burner reactor, designed to incinerate mostly plutonium and some MAs, and (2) a minor actinide burner reactor, devoted to burning mostly minor actinides and some plutonium. These transuranics are loaded in a fertile-free Zr-based metallic fuel to maximize the incineration rate. Both designs feature streaming fuel assemblies that enhance neutron leakage to achieve favorable neutronic feedback and a double-entry control rod system that reduces reactivity perturbations during seismic events and flattens the axial power profile. A detailed neutronic analysis shows that both designs have favorable neutronic characteristics and reactivity feedback mechanisms that yield passive safety features comparable to those of the Integral Fast Reactor. A safety analysis presents the response of the burners to anticipated transients without scram on the basis of (1) the integral parameter approach and (2) simulations of thermal-hydraulic accident scenario conditions. It is shown that both designs have large thermal margins that lead to safe shutdown without structural damage to the core components for a large spectrum of unprotected transients. Furthermore, the actinide destruction rates are comparable to those of the accelerator transmutation of waste concept, and a fuel cycle cost analysis shows the potential for economical accomplishment of the transmutation mission compared to other proposed actinide-burning options

  17. Congruent evaporation and epitaxy in thin film laser ablation deposition (LAD) of rare earth transition metal elements and compounds

    This paper reports that laser ablation deposition (LAD) is a versatile thin film preparation technique which has been slowly developing for a number of years, and is currently receiving a lot of attention as demand increasingly exploits its advantages over other established techniques. Apart from its simplicity, one of its main advantages is the possibility of congruently evaporating any solid compound target, be it metal or insulator, due to the extremely high energy and instantaneous power densities attainable with pulsed lasers (up to 50 Jcm-2 and 1012 Wcm-2 for picosecond pulses). In this paper, we report on tests for both congruent evaporation in LAD of a number of rate earth -- transition metal intermetallic compounds including Nd2Fe13B, YZn0.7, YNi3, Y2Fe15 and YNi5 for different preparation conditions (using a Nd:YAG laser λ = 1064, 532, 355 nm, τ = 35 ps and 20 ns) and on the epitaxial growth of YNi5 and W on monocrystalline sapphire substrates. Optical and electron microscopy were used to examine film morphology while congruent evaporation was confirmed using x-ray microprobe analysis. In-situ RHEED revealed good epitax of the films deposited on sapphire, with the hexagonal diffraction patterns obtained for YNi5 being identical to those of an YNi5 reference single crystal

  18. A novel stir bar sorptive extraction coating based on monolithic material for apolar, polar organic compounds and heavy metal ions.

    Huang, Xiaojia; Qiu, Ningning; Yuan, Dongxing; Huang, Benli

    2009-04-15

    In this study, a novel stir bar sorptive extraction (SBSE) based on monolithic material (SBSEM) was prepared. The monolithic material was obtained by in situ copolymerization of vinylpyrrolidone and divinylbenzene in the presence of a porogen solvent containing cyclohexanol and 1-dodecanol with azobisisobutyronitrile as initiator. The influences of polymerization conditions on the extraction efficiencies were investigated, using phenol and p-nitrophenol as detected solutes. The monolithic material was characterized by various techniques, such as elemental analysis, scanning electron microscopy, mercury intrusion porosimetry, infrared spectroscopy. Polycyclic aromatic hydrocarbons were used to investigate the extraction efficiencies of SBSEM for apolar analytes. Hormones, aromatic amines and phenols were selected as test analytes to investigate the extraction efficiencies of SBSEM for weakly and strongly polar compounds. The results showed that the new SBSEM could enrich the above-mentioned organic compounds effectively. It is worthy to mention that the SBSEM can enrich some heavy metal ions, such as Cu(2+), Pb(2+), Cr(3+) and Cd(2+), through coordination adsorption. To our best knowledge, that is the first to use SBSE to enrich heavy metal ions. PMID:19174210

  19. Effects of heavy metals and nitroaromatic compounds on horseradish glutathione S-transferase and peroxidase

    Nepovím, Aleš; Podlipná, Radka; Soudek, Petr; Schröder, P.; Vaněk, Tomáš

    2004-01-01

    Roč. 57, - (2004), s. 1007-1015. ISSN 0045-6535 R&D Projects: GA ČR GP206/02/P065; GA MŠk OC 837.10 Institutional research plan: CEZ:AV0Z4055905 Keywords : GST * POX * heavy metals Subject RIV: CE - Biochemistry Impact factor: 2.359, year: 2004

  20. Depolymerization of organosolv lignin to aromatic compounds over Cu-doped porous metal oxides

    Barta, Katalin; Warner, Genoa R.; Beach, Evan S.; Anastas, Paul T.

    2014-01-01

    Isolated, solvent-extracted lignin from candlenut (Aleurites moluccana) biomass was subjected to catalytic depolymerization in methanol with an added pressure of H-2, using a porous metal oxide catalyst (PMO) derived from a Cu-doped hydrotalcite-like precursor. The Cu-PMO was effective in converting

  1. Simultaneous removal of metals and organic compounds from a heavily polluted soil

    Szpyrkowicz, L. [University of Venice, Department of Environmental Sciences, Dorsoduro 2137, 30123 Venice (Italy)]. E-mail: lidia@unive.it; Radaelli, M. [University of Venice, Department of Environmental Sciences, Dorsoduro 2137, 30123 Venice (Italy); Bertini, S. [University of Venice, Department of Environmental Sciences, Dorsoduro 2137, 30123 Venice (Italy); Daniele, S. [University of Venice, Department of Physical Chemistry, Dorsoduro 2137, 30123 Venice (Italy); Casarin, F. [Via S. Trentin 5A, 30171 Mestre-Venice (Italy)

    2007-02-25

    The paper describes the results of treatment of soil samples, deriving from a dismissed industrial site, contaminated with several metals: Hg, Ni, Co, Zn, Pb, Cu, Cr, As and organic substances. The soil was subjected to remediation based on a process in which an oxidising leaching agent was produced electrochemically in-line in an undivided electrochemical cell reactor equipped with a Ti/Pt-Ir anode and a stainless steel cathode. Leaching of the soil samples was performed under dynamic conditions using a leaching column. A subsequent regeneration of the leaching solution, which consisted in electrodeposition of metals and electro-oxidation of organic substances, was carried out in a packed-bed reactor equipped with a centrally positioned graphite rod, serving as an anode, and stainless steel three-dimensional filling as a cathode. The study was focused on how and to which extent the metals present in the soil, as organic complexes, can be solubilised and how the process rates are impacted by the solution pH and other process variables. Data obtained under non-oxidising conditions, typically adopted for leaching of metals, are compared with the performance of chlorine-enriched leaching solutions. The results obtained under various conditions are also discussed in terms of the total organic carbon (TOC) removal from the water phase.

  2. Impedance spectroscopy based conductivity study of two aluminum metal – organic framework compound

    Konale, M.; Lin, C. H.; Patil, D.; Zima, Vítězslav; Wágner, T.; Shimakawa, K.

    Pardubice: Univerzita Pardubice, 2014. s. 36-36. ISBN 978-80-7395-820-6. [International Days of Materials Science 2014 - ReAdMat. 16.09.2014-17.09.2014, Pardubice] Institutional support: RVO:61389013 Keywords : proton conductivity * metal organic framework * aluminium Subject RIV: CA - Inorganic Chemistry

  3. Selective hydrogenation of dienic and acetylenic compounds on metal-containing catalysts

    Stytsenko, V. D.; Mel'nikov, D. P.

    2016-05-01

    Studies on selective hydrogenation of dienic and acetylenic hydrocarbons and their derivatives on metal-containing catalysts are reviewed. The review covers publications over a wide period of time and concentrates on the fundamental principles of catalyst operation. The catalysts modified in the surface layer were shown to be promising for selective hydrogenation.

  4. Transition-Metal-Mediated or -Catalyzed Syntheses of Steroids and Steroid-Like Compounds

    Kotora, Martin; Hessler, F.; Eignerová, B.

    -, č. 1 (2012), s. 29-42. ISSN 1434-193X R&D Projects: GA MŠk 1M0508 Institutional research plan: CEZ:AV0Z40550506 Keywords : steroids * synthesis design * synthetic methods * asymmetric synthesis * transition metals Subject RIV: CC - Organic Chemistry Impact factor: 3.344, year: 2012

  5. Effects of Ga substitution on the structural and magnetic properties of half metallic Fe{sub 2}MnSi Heusler compound

    Pedro, S. S., E-mail: sandrapedro@uerj.br; Caraballo Vivas, R. J.; Andrade, V. M.; Cruz, C.; Paixão, L. S.; Contreras, C.; Costa-Soares, T.; Rocco, D. L.; Reis, M. S. [Instituto de Física, Universidade Federal Fluminense, Niterói-RJ (Brazil); Caldeira, L. [IF Sudeste MG, Campus Juiz de Fora - Núcleo de Física, Juiz de Fora-MG (Brazil); Coelho, A. A. [Instituto de Física Gleb Wataghin, Universidade Estadual de Campinas - Unicamp, Campinas-SP (Brazil); Carvalho, A. Magnus G. [Laboratório Nacional de Luz Sincrotron, CNPEM, Campinas-SP (Brazil)

    2015-01-07

    The so-called half-metallic magnets have been proposed as good candidates for spintronic applications due to the feature of exhibiting a hundred percent spin polarization at the Fermi level. Such materials follow the Slater-Pauling rule, which relates the magnetic moment with the valence electrons in the system. In this paper, we study the bulk polycrystalline half-metallic Fe{sub 2}MnSi Heusler compound replacing Si by Ga to determine how the Ga addition changes the magnetic, the structural, and the half-metal properties of this compound. The material does not follow the Slater-Pauling rule, probably due to a minor structural disorder degree in the system, but a linear dependence on the magnetic transition temperature with the valence electron number points to the half-metallic behavior of this compound.

  6. Effects of metallic nanoparticle doped flux on the interfacial intermetallic compounds between lead-free solder ball and copper substrate

    Sujan, G.K., E-mail: sgkumer@gmail.com; Haseeb, A.S.M.A., E-mail: haseeb@um.edu.my; Afifi, A.B.M., E-mail: amalina@um.edu.my

    2014-11-15

    Lead free solders currently in use are prone to develop thick interfacial intermetallic compound layers with rough morphology which are detrimental to the long term solder joint reliability. A novel method has been developed to control the morphology and growth of intermetallic compound layers between lead-free Sn–3.0Ag–0.5Cu solder ball and copper substrate by doping a water soluble flux with metallic nanoparticles. Four types of metallic nanoparticles (nickel, cobalt, molybdenum and titanium) were used to investigate their effects on the wetting behavior and interfacial microstructural evaluations after reflow. Nanoparticles were dispersed manually with a water soluble flux and the resulting nanoparticle doped flux was placed on copper substrate. Lead-free Sn–3.0Ag–0.5Cu solder balls of diameter 0.45 mm were placed on top of the flux and were reflowed at a peak temperature of 240 °C for 45 s. Angle of contact, wetting area and interfacial microstructure were studied by optical microscopy, field emission scanning electron microscopy and energy-dispersive X-ray spectroscopy. It was observed that the angle of contact increased and wetting area decreased with the addition of cobalt, molybdenum and titanium nanoparticles to flux. On the other hand, wettability improved with the addition of nickel nanoparticles. Cross-sectional micrographs revealed that both nickel and cobalt nanoparticle doping transformed the morphology of Cu{sub 6}Sn{sub 5} from a typical scallop type to a planer one and reduced the intermetallic compound thickness under optimum condition. These effects were suggested to be related to in-situ interfacial alloying at the interface during reflow. The minimum amount of nanoparticles required to produce the planer morphology was found to be 0.1 wt.% for both nickel and cobalt. Molybdenum and titanium nanoparticles neither appear to undergo alloying during reflow nor have any influence at the solder/substrate interfacial reaction. Thus, doping

  7. Effects of metallic nanoparticle doped flux on the interfacial intermetallic compounds between lead-free solder ball and copper substrate

    Lead free solders currently in use are prone to develop thick interfacial intermetallic compound layers with rough morphology which are detrimental to the long term solder joint reliability. A novel method has been developed to control the morphology and growth of intermetallic compound layers between lead-free Sn–3.0Ag–0.5Cu solder ball and copper substrate by doping a water soluble flux with metallic nanoparticles. Four types of metallic nanoparticles (nickel, cobalt, molybdenum and titanium) were used to investigate their effects on the wetting behavior and interfacial microstructural evaluations after reflow. Nanoparticles were dispersed manually with a water soluble flux and the resulting nanoparticle doped flux was placed on copper substrate. Lead-free Sn–3.0Ag–0.5Cu solder balls of diameter 0.45 mm were placed on top of the flux and were reflowed at a peak temperature of 240 °C for 45 s. Angle of contact, wetting area and interfacial microstructure were studied by optical microscopy, field emission scanning electron microscopy and energy-dispersive X-ray spectroscopy. It was observed that the angle of contact increased and wetting area decreased with the addition of cobalt, molybdenum and titanium nanoparticles to flux. On the other hand, wettability improved with the addition of nickel nanoparticles. Cross-sectional micrographs revealed that both nickel and cobalt nanoparticle doping transformed the morphology of Cu6Sn5 from a typical scallop type to a planer one and reduced the intermetallic compound thickness under optimum condition. These effects were suggested to be related to in-situ interfacial alloying at the interface during reflow. The minimum amount of nanoparticles required to produce the planer morphology was found to be 0.1 wt.% for both nickel and cobalt. Molybdenum and titanium nanoparticles neither appear to undergo alloying during reflow nor have any influence at the solder/substrate interfacial reaction. Thus, doping of flux with

  8. Fundamental experimental determinations of thermal and radiolytic gas generation over actinide oxides

    In the areas of actinide waste disposition and storage and medium- to long-term retrievable U and Pu materials storage, the issue of water and other small molecule interactions with pure or impure actinide oxide materials and metal has become a major concern. Small molecule reactions in these systems have led to changes in materials stoichiometry, containment corrosion and breaches, dispersal of material resulting from pressurization, and the collapse of sealed containers due to the formation of partial vacuum. The exact nature of these reactions and the resulting implications for medium- to long-term storage are not well understood, although some studies have attempted to explain them from a large body of observations and experiments. The interaction of water with actinide and actinide oxide surfaces constitutes the fundamental technical basis for understanding and predicting long-term actinide material storage behavior. In this paper some of the studies that pertain to these efforts are summarized with particular emphasis on gas generation and/or consumption events relevant to actinide materials storage. These studies include fundamental surface studies of actinide and actinide oxide materials with water vapor using a wide variety of physical chemical and surface-specific techniques. In addition, radical surface chemistry arising from radiolytic decomposition of adsorbed water molecules is experimentally examined using unique gas exposure techniques. Preliminary studies are described and compared with conventional molecular gas-solid chemical model systems. Where possible, the relevant results from the surface science studies are utilized in understanding the back reaction of H2 and O2 to form H2O at relevant pressures in actual storage scenarios (described by Morales)

  9. The complex formation of selected actinides (U, Np, Cm) with microbial ligands

    One of the urgent tasks in the field of nuclear technology is the final storage of radioactive substances. As a part of the safety requirements the protection of humans and the environment from the danger of radioactive substances in case of the release from the final storage is essential. For performing long-term safety calculations the detailed understanding of the physico-chemical effects and influences which cause the mobilisation and transport of actinides are necessary. The presented work was a discrete part of a project, which was focused on the clarification of the influence of microorganisms on the migration of actinides in case of the release of actinides from a final storage. The influence of microbial produced substances on the mobilisation of selected actinides was studied thereby. The microbial produced substances studied in this project were synthesized by bacteria from the Pseudomonas genus under special conditions. Fluorescent Pseudomonads secrete bacterial pyoverdin-type siderophores with a high potential to complex and transport metals, especially iron(III). The aim of the project was to determine how and under which conditions the bioligands are able to complex also radioactive substances and therefore to transport them. For this work the alpha-emitting actinides uranium, curium and neptunium were chosen because their long-life cycle and their radiotoxicity are a matter of particular interest. This work dealed with the interaction of the actinides U(VI), Np(V) and Cm(III) with model ligands simulating the functionality of the pyoverdins. So, such bioligands can essentially influence the behaviour of actinides in the environment. The results of this work contribute to a better understanding and assessment of the influence of the microbial ligands to the mobilisation and migration of the radionuclides. The outcomes could be used to quantify the actinide-mobilising effect of the bioligands, which are released, for example, in the vicinity of a

  10. Synchrotron Diffraction Studies of Spontaneous Magnetostriction in Rare Earth Transition Metal Compounds

    Ning Yang

    2004-12-19

    Thermal expansion anomalies of R{sub 2}Fe{sub 14}B and R{sub 2}Fe{sub 17}C{sub x} (x = 0,2) (R = Y, Nd, Gd, Tb, Er) stoichiometric compounds are studied with high-energy synchrotron X-ray powder diffraction using Debye-Schemer geometry in temperature range 10K to 1000K. Large spontaneous magnetostriction up to their Curie temperatures (T{sub c}) is observed. The a-axes show relatively larger invar effects than c-axes in the R{sub 2}Fe{sub 14}B compounds whereas the R{sub 2}Fe{sub 17}C{sub x} show the contrary anisotropies. The iron sub-lattice is shown to dominate the spontaneous magnetostriction of the compounds. The contribution of the rare earth sublattice is roughly proportional to the spin magnetic moment of the rare earth in the R{sub 2}Fe{sub 14}B compounds but in R{sub 2}Fe{sub 17}C{sub x}, the rare earth sub-lattice contribution appears more likely to be dominated by the local bonding. The calculation of spontaneous magnetostrain of bonds shows that the bonds associated with Fe(j2) sites in R{sub 2}Fe{sub 14}B and the dumbbell sites in R{sub 2}Fe{sub 17}C{sub x} have larger values, which is strongly related to their largest magnetic moment and Wigner-Seitz atomic cell volume. The roles of the carbon atoms in increasing the Curie temperatures of the R{sub 2}Fe{sub 17} compounds are attributed to the increased separation of Fe hexagons. The R{sub 2}Fe{sub 17} and R{sub 2}Fe{sub 14}B phases with magnetic rare earth ions also show anisotropies of thermal expansion above T{sub c}. For R{sub 2}Fe{sub 17} and R{sub 2}Fe{sub 14}B the a{sub a}/a{sub c} > 1 whereas the anisotropy is reversed with the interstitial carbon in R{sub 2}Fe{sub 17}. The average bond magnetostrain is shown to be a possible predictor of the magnetic moment of Fe sites in the compounds. Both of the theoretical and phenomenological models on spontaneous magnetostriction are discussed and a Landau model on the spontaneous magnetostriction is proposed.

  11. Predicting density functional theory total energies and enthalpies of formation of metal-nonmetal compounds by linear regression

    Deml, Ann M.; O'Hayre, Ryan; Wolverton, Chris; Stevanović, Vladan

    2016-02-01

    The availability of quantitatively accurate total energies (Etot) of atoms, molecules, and solids, enabled by the development of density functional theory (DFT), has transformed solid state physics, quantum chemistry, and materials science by allowing direct calculations of measureable quantities, such as enthalpies of formation (Δ Hf ). Still, the ability to compute Etot and Δ Hf values does not, necessarily, provide insights into the physical mechanisms behind their magnitudes or chemical trends. Here, we examine a large set of calculated Etot and Δ Hf values obtained from the DFT+U -based fitted elemental-phase reference energies (FERE) approach [V. Stevanović, S. Lany, X. Zhang, and A. Zunger, Phys. Rev. B 85, 115104 (2012), 10.1103/PhysRevB.85.115104] to probe relationships between the Etot/Δ Hf of metal-nonmetal compounds in their ground-state crystal structures and properties describing the compound compositions and their elemental constituents. From a stepwise linear regression, we develop a linear model for Etot, and consequently Δ Hf , that reproduces calculated FERE values with a mean absolute error of ˜80 meV/atom. The most significant contributions to the model include calculated total energies of the constituent elements in their reference phases (e.g., metallic iron or gas phase O2), atomic ionization energies and electron affinities, Pauling electronegativity differences, and atomic electric polarizabilities. These contributions are discussed in the context of their connection to the underlying physics. We also demonstrate that our Etot/Δ Hf model can be directly extended to predict the Etot and Δ Hf of compounds outside the set used to develop the model.

  12. Effect of transition metal compounds on the formation of LaAlO3 by the sol-gel method

    LaAlO3 is used industrially as an oxygen ion dielectric material. In La2O3-Al2O3 system, usually two kinds of the compound have been known. One of them is the cubic crystals LaAlO3 having Perovskite structure, and as to the formation of its single phase, the different results have been obtained. Therefore, it seems necessary to clarify this point. Recently, the author synthesized La2O3 or α-Al2O3 utilizing sol-gel method, one of the methods of synthesizing ceramic powder, from the mixed solution prepared by adding a small quantity of ethyl silicate Si(OC2H5)4 as a hydrolysis agent to La(NO3)3 solution or Al(NC3)3 solution. In this study, LaAlO3 was synthesized at low temperature by sol-gel method from the mixed solution prepared by adding small quantities of the aqueous solution of transition metal compounds and ethyl silicate to the aqueous solution containing La(NO3)3 and Al(NO3)3, therefore, the results are reported. The experimental method is explained. The formation of LaAlO3 became conspicuous from 1100 deg C of the heat treatment temperature of the gel made from the solution without the addition of transition metal compounds, but the single phase was not obtained. By adding Fe(NO3)3, the temperature of LaAlO3 formation lowered, and the nearly single phase was obtained. (Kako, I.)

  13. Volatile organic compounds and trace metal level in some beers collected from Romanian market

    Voica, Cezara; Kovacs, Melinda; Vadan, Marius

    2013-11-01

    Beer is one of the most popular beverages at worldwide level. Through this study fifteen different types of beer collected from Romanian market were analysed in order to evaluate their mineral, trace element as well the their organic content. Importance of such characterization of beer samples is supported by the fact that their chemical composition can affect both taste and stability of beer, as well the consumer health. Minerals and trace elements analysis were performed on ICP-MS while organic compounds analysis was done through GC-MS. Through ICP-MS analysis, elements as Ca, Na, K and Mg were evidenced at mgṡkg-1 order while elements as Cr, Ba, Co, Ni were detected at lower level. After GC-MS analysis the major volatile compounds that were detected belong to alcohols namely ethanol, propanol, isobutanol, isoamyl alcohol and linalool. Selected fatty acids and esters were evidenced also in the studied beer samples.

  14. Large scale simulations of the mechanical properties of layered transition metal ternary compounds for fossil energy power system applications

    Ching, Wai-Yim [Univ. of Missouri, Kansas City, MO (United States)

    2014-12-31

    Advanced materials with applications in extreme conditions such as high temperature, high pressure, and corrosive environments play a critical role in the development of new technologies to significantly improve the performance of different types of power plants. Materials that are currently employed in fossil energy conversion systems are typically the Ni-based alloys and stainless steels that have already reached their ultimate performance limits. Incremental improvements are unlikely to meet the more stringent requirements aimed at increased efficiency and reduce risks while addressing environmental concerns and keeping costs low. Computational studies can lead the way in the search for novel materials or for significant improvements in existing materials that can meet such requirements. Detailed computational studies with sufficient predictive power can provide an atomistic level understanding of the key characteristics that lead to desirable properties. This project focuses on the comprehensive study of a new class of materials called MAX phases, or Mn+1AXn (M = a transition metal, A = Al or other group III, IV, and V elements, X = C or N). The MAX phases are layered transition metal carbides or nitrides with a rare combination of metallic and ceramic properties. Due to their unique structural arrangements and special types of bonding, these thermodynamically stable alloys possess some of the most outstanding properties. We used a genomic approach in screening a large number of potential MAX phases and established a database for 665 viable MAX compounds on the structure, mechanical and electronic properties and investigated the correlations between them. This database if then used as a tool for materials informatics for further exploration of this class of intermetallic compounds.

  15. Catalytic Oxidation of Volatile Organic Compounds over Ceria-zirconia Supported Noble Metal Catalysts

    Topka, Pavel; Kaluža, Luděk

    - : -, 2014, O9. ISBN N. [Pannonian Symposium on Catalysis /12./. Třešť (CZ), 16.09.2014-20.09.2014] R&D Projects: GA ČR GP13-24186P Institutional support: RVO:67985858 Keywords : volatile organic compounds * platinum * ceria Subject RIV: CF - Physical ; Theoretical Chemistry http://pannonia2014.icpf.cas.cz/wp-content/uploads/2014/09/abstrakty_final.pdf

  16. Palladium-mediated borylation of pentafluorosulfanyl functionalized compounds: the crucial role of metal fluorido complexes.

    Berg, Claudia; Braun, Thomas; Laubenstein, Reik; Braun, Beatrice

    2016-03-11

    Stoichiometric reactions of SF5 functionalized bromo or iodo aromatics at [Pd(PiPr3)2] (1) led to the oxidative addition products 3, 5 and 7. They were converted into their corresponding palladium fluorido complexes, which reacted readily with bis(pinacolato)diboron (B2pin2) to give the borylated SF5 aromatic compounds. Based on these studies a catalytic borylation of SF5 organyls was developed. PMID:26872070

  17. Chemical reactions of actinides with groundwater colloids. Studies of transferability of laboratory data to natural conditions. The aquiferous system in Gorleben. Interim report. Reported period: 1.2.1993-31.12.1993

    This study deals with the chemical interreaction between actinides and groundwater-colloids in selected aquiferes in the overburden of the planned final storage site for radioactive matter near Gorleben (Lower Saxony). As colloids have other transport properties than dissolved metal ions the interaction of actinides and groundwater-colloids has an important influence on their migration and is therefore essentially important for longterm-safety analyses. In order to study interaction of actinides with groundwater-colloids selected groundwaters were conditioned with trace concentrations of the actinides TH, Np, Pu, Am and Cm. For hexavalent actinides one used the analytical data of natural uranium in the groundwaters. In order to determine the humic-colloid-bound parts of the actinides the conditioned ground waters were filtered with a pore width of 1 nm and actinide concentration was determined with radiometry. (orig./EF)

  18. The Oxidation of Sulfur-Containing Compounds Using Heterogeneous Catalysts of Transition Metal Oxides Deposited on the Polymeric Matrix

    Dinh Vu, Ngo; Dinh Bui, Nhi; Thi Minh, Thao; Thi Thanh Dam, Huong; Thi Tran, Hang

    2016-05-01

    We investigate the activity of heterogeneous catalysts of transition metal oxides deposited on the polymeric matrix in the oxidation of sulfur-containing compounds. It is shown that MnO2-10/CuO-10 has the highest catalytic activity. The physicomechanical properties of polymeric heterogeneous catalysts of transition-metal oxides, including the specific surface area, elongation at break and breaking strength, specific electrical resistance, and volume resistivity were studied by using an Inspekt mini 3 kN universal tensile machine in accordance with TCVN 4509:2006 at a temperature of 20 ± 2°C. Results show that heterogeneous polymeric catalysts were stable under severe reaction conditions. Scanning electron microscopy, and energy-dispersive analysis are used to study the surfaces of the catalysts. Microstructural characterization of the catalysts is performed by using x-ray computed tomography. We demonstrate the potential application of polymeric heterogeneous catalysts of transition-metal oxides in industrial wastewater treatment.

  19. Loadings of polynuclear aromatic compounds and metals to the Athabasca River watershed by oil sands mining and processing

    The contribution of oil sands operations to pollution in the Athabasca River has not yet been determined. Wastes from oil sands processes include recycled water, sand, silt, clay, bitumen, and polycyclic aromatic compounds (PAC) and metals. Upgrading processes can also release significant quantities of PAC and heavy metals. This paper discussed a study in which PAC and metals in the snow pack and river water of the Athabasca watershed were assessed. The study showed that the oil sands industry is a significant source of contamination. The equivalent of 600 T of bitumen was observed at sites within 50 km of oil sands upgrading facilities. The strongest contamination signals occurred during the summer months, which suggested that the surface run-off of contaminated water was related to recent oil sands developments. Samples taken from tributaries in watersheds with little or no development indicated that increased concentrations of oil sands related contaminants were not caused by natural erosion. The contaminants may contribute to higher levels of mercury (Hg) and cadmium (Cd) in the flesh of fish and wildlife and increase toxicity to the embryos of spring-spawning fish.

  20. Electrochemical reduction of actinides oxides in molten salts

    Reactive metals are currently produced from their oxide by multiple steps reduction techniques. A one step route from the oxide to the metal has been suggested for metallic titanium production by electrolysis in high temperature molten chloride salts. In the so-called FFC process, titanium oxide is electrochemically reduced at the cathode, generating O2- ions, which are converted on a graphite anode into carbon oxide or dioxide. After this process, the spent salt can in principle be reused for several batches which is particularly attractive for a nuclear application in terms of waste minimization. In this work, the electrochemical reduction process of cerium oxide (IV) is studied in CaCl2 and CaCl2-KCl melts to understand the oxide reduction mechanism. Cerium is used as a chemical analogue of actinides. Electrolysis on 10 grams of cerium oxide are made to find optimal conditions for the conversion of actinides oxides into metals. The scale-up to hundred grams of oxide is also discussed. (author)

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

    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.)

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

    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.

  3. Structure and constitution of glass and steel compound in glass-metal composite

    The research using methods of optical and scanning electronic microscopy was conducted and it discovered common factors on structures and diffusing zone forming after welding glass C49-1 and steel Ct3sp in technological process of creating new glass-metal composite. Different technological modes of steel surface preliminary oxidation welded with and without glass were investigated. The time of welding was varied from minimum encountering time to the time of stabilizing width of diffusion zone

  4. Random and block copolymerization in metal oxide gel synthesis from metalorganic compounds

    Mukherjee, S. P.

    1985-01-01

    The introduction and development of the block copolymerization concept in metal oxide gel synthesis will in the future generate a new class of glass/microcrystalline materials. By the year 2004, better scientific understanding of the chemical principles controlling the distribution of network formers or modifiers in silicate gels will permit the synthesis of architecturally well-defined block polymers with unique high-performance behavior.

  5. The interaction of metal carbonyl compounds with organic polymers and monomers

    Lyons, Michael P.

    1993-01-01

    The photochemistry of W(CO)6, Mo(CO)6, and Cr(CO)6 in the presence of monomeric and polymeric triphenylphosphine ligands was investigated in toluene solution, using laser flash photolysis with 355nm excitation. The mechanism and kinetics of interaction of the primary photoproducts M(CO)5(toluene) (M = W, Mo, or Cr) with the various monomeric ligands were investigated. Interaction of the metal carbonyl photofragments with various homopolymers is also discussed. The polymerisation methods used ...

  6. Structure and constitution of glass and steel compound in glass-metal composite

    Lyubimova, Olga N.; Morkovin, Andrey V.; Dryuk, Sergey A. [School of Engineering, Mechanics and Mathematical Modeling Department, Far Eastern Federal University, Vladivostok, 690950 (Russian Federation); Nikiforov, Pavel A., E-mail: nikiforovpa@gmail.com [School of Engineering, Materials Science and Technology Department, Far Eastern Federal University, Vladivostok, 690950 (Russian Federation)

    2014-11-14

    The research using methods of optical and scanning electronic microscopy was conducted and it discovered common factors on structures and diffusing zone forming after welding glass C49-1 and steel Ct3sp in technological process of creating new glass-metal composite. Different technological modes of steel surface preliminary oxidation welded with and without glass were investigated. The time of welding was varied from minimum encountering time to the time of stabilizing width of diffusion zone.

  7. Uptake and transport of actinides by a polymer inclusion membrane containing a diglycolamide-functionalized Calix(4)arene

    A novel polymer inclusion membrane (PIM) containing a diglycolamide-functionalized Calix(4)arene (C4DGA) was used for the separation of actinide ions from acidic feeds and the studies included uptake and transport of the actinide ions from 1 M HNO3 medium. The uptake of metal ions follows the trend Am(III) > Pu(IV) > Th(IV) >> U(VI) while the trend for the transport studies was: Pu(IV) > Am(III) > Th(IV). (author)

  8. Metal compounds in zeolites as active components of chemisorption and catalysis. Quantum chemical approach

    A short review of possible catalitic active sites associated with various types of metal species in zoolite is presented. The structural and electronic peculiarity of aluminum ions in zeolite lattice and their distribution in the lattice are discussed on the basis of quantum chemical calculations in connection with the formation of Broensted activity of zeolites. Various molecular models of Lewis Acid Sites associated the extra-lattice oxide-hydroxide aluminum species have been investigated by means of density functional model cluster calculations using CO molecule as a probe. Probable ways of formation of the selective oxidation center in FeZSM-5 by decomposition of dinitrogen monoxide have been studied by ab-initio quantum chemical calculations. The immediate oxidizing site is reasonably represented by the binuclear iron-hydroxide cluster with peroxo-like fragment located between iron atoms. Various probable intermediates of the selective oxidation center formation resulted from interaction of a hydroperoxide molecule with a lattice titanium ion in titanium silicalite have been investigated by quantum chemical calculations. It was concluded that this reaction requires essential structural reconstruction in the vicinity of the titanium ion. Probability of this structural reconstruction is discussed. Possible reasons of an electron-deficient and electron-enriched state of metal particles entrapped in zoolite cavities are discussed. Also, various probable molecular models of such modified metal particles in zeolite are considered

  9. Determination of polycyclic aromatic compounds and heavy metals in sludges from biological sewage treatment plants.

    Bodzek, D; Janoszka, B; Dobosz, C; Warzecha, L; Bodzek, M

    1997-07-11

    The procedure of the analysis of polycyclic aromatic hydrocarbons (PAHs) and their derivatives in the sludges from biological sewage treatment plants has been worked out. The analysis included isolation of organic matter from sludges, separation of the extract into fractions of similar chemical character, qualitative-quantitative analysis of individual PAHs and their nitrogenated and oxygenated derivatives. Liquid-solid chromatography, solid-phase extraction and semipreparative band thin-layer chromatography techniques were used for the separation. Capillary gas chromatography-mass spectrometry analysis of the separated fractions enabled identification of more than 21 PAHs, including hydrocarbons which contained 2-6 aromatic rings as well as their alkyl derivatives, 10 oxygen derivatives, 9 nitroarenes, aminoarenes and over 20 azaarenes and carbazoles. Using the capillary gas chromatography-flame ionization detection technique the content of 17 dominant PAHs was determined. The content of heavy metals was determined in investigated sludges with the use of atomic absorption spectrometry. The concentrations of the respective metals could be ranked in the order Cd coal mine wastes, taking into consideration the contents of toxic organic pollutants and heavy metals. PMID:9253190

  10. Environmental chemistry of the actinide elements

    The environmental chemistry of the actinide elements is a new branch of science developing with the application of nuclear energy on a larger and larger scale. Various aspects of the environmental chemistry of the actinide elements are briefly reviewed in this paper, such as its significance in the nuclear waste disposal, its coverage of research fields and possible directions for future study

  11. A fast lead-cooled incinerator for economical actinide burning

    A fast lead-cooled modular reactor is proposed as an efficient incinerator of plutonium and minor actinides (MAs) for application to advanced fuel cycles devoted to transmutation. This actinide burner reactor (ABR) is loaded only with transuranics (TRU) in a fertile-free Zr-based metallic fuel to maximize the incineration rates and features (a) streaming fuel assemblies that enhance neutron leakage to achieve favorable neutronic feedbacks and (b) a double-entry control rod system that reduces reactivity perturbations during seismic events and flattens the axial power profile. A detailed neutronic analysis shows that the delayed neutron fraction is comparable to that of fast reactors and that negative reactivity feedbacks from lead voiding, Doppler, fuel thermal expansion and core radial expansion lead to safety characteristics similar to those of the Integral Fast Reactor. The ABR TRU destruction rate is the same as that of the ATW and fuel cycle cost analysis shows potential for economical accomplishment of the transmutation mission compared to other proposed actinide burning options. (author)

  12. Molecular cluster theory of chemical bonding in actinide oxide

    The electronic structure of actinide monoxides AcO and dioxides AcO2, where Ac = Th, U, Np, Pu, Am, Cm and Bk has been studied by molecular cluster methods based on the first-principles one-electron local density theory. Molecular orbitals for nearest neighbor clusters AcO10-6 and AcO12-8 representative of monoxide and dioxide lattices were obtained using non-relativistic spin-restricted and spin-polarized Hartree-Fock-Slater models for the entire series. Fully relativistic Dirac-Slater calculations were performed for ThO, UO and NpO in order to explore magnitude of spin-orbit splittings and level shifts in valence structure. Self-consistent iterations were carried out for NpO, in which the NpO6 cluster was embedded in the molecular field of the solid. Finally, a ''moment polarized'' model which combines both spin-polarization and relativistic effects in a consistent fashion was applied to the NpO system. Covalent mixing of oxygen 2p and Ac 5f orbitals was found to increase rapidly across the actinide series; metal s,p,d covalency was found to be nearly constant. Mulliken atomic population analysis of cluster eigenvectors shows that free-ion crystal field models are unreliable, except for the light actinides. X-ray photoelectron line shapes have been calculated and are found to compare rather well with experimental data on the dioxides

  13. The pressure behaviour of actinides via synchrotron radiation

    Various aspects of performing high-pressure studies with radioactive f-elements using synchrotrons as sources of X-rays are discussed. For ultra-high pressures, intense well-focused beams of 10 to 30 microns in diameter and a single wavelength of 0.3 to 0.7 angstrom are desired for angle dispersive diffraction measurements. Special considerations are necessary for the studies of transuranium elements under pressure at synchrotron facilities. Normally, with these actinides the pressure cells are prepared off-site and shipped to the synchrotron for study. Approved containment techniques must be provided to assure there is not a potential for the release of sample material. The goal of these high-pressure studies is to explore the fundamental science occurring as pressure is applied to the actinide samples. One of the primary effects of pressure is to reduce interatomic distances, and the goal is to ascertain the changes in bonding and electronic nature of the system that result as atoms and electronic orbitals are forced closer together. Concepts of the science being pursued with these f-elements are outlined. A brief discussion of the behaviour of americium metal under pressure performed recently at the ESRF is provided as an example of the high-pressure research being performed with synchrotron radiation. Also discussed here is the important role synchrotrons play and the techniques/procedures employed in high-pressure studies with actinides. (authors)

  14. Characterization of partitioning relevant lanthanide and actinide complexes by NMR spectroscopy

    In the present work the interaction of N-donor ligands, such as 2,6-Bis(5,6-dipropyl-1,2,4-triazin-3-yl)pyridine (nPrBTP) and 2,6-Bis(5-(2,2-dimethylpropyl)1H-pyrazol)-3-yl-pyridine (C5-BPP), with trivalent lanthanide and actinide ions was studied. Ligands of this type show a high selectivity for the separation of trivalent actinide ions over lanthanides from nitric acid solutions. However, the reason for this selectivity, which is crucial for future partitioning and transmutation strategies for radioactive wastes, is still unknown. So far, the selectivity of some N-donor ligands is supposed to be an effect of an increased covalency in the actinide-ligand bond, compared to the lanthanide compounds. NMR spectroscopy on paramagnetic metal complexes is an excellent tool for the elucidation of bonding modes. The overall paramagnetic chemical shift consists of two contributions, the Fermi Contact Shift (FCS), due to electron spin delocalisation through covalent bonds, and the Pseudo Contact Shift (PCS), which describes the dipolar coupling of the electron magnetic moment and the nuclear spin. By assessing the FCS share in the paramagnetic shift, the degree of covalency in the metal-ligand bond can be gauged. Several methods to discriminate FCS and PCS have been used on the data of the nPrBTP- and C5-BPP-complexes and were evaluated regarding their applicability on lanthanide and actinide complexes with N-donor ligands. The study comprised the synthesis of all Ln(III) complexes with the exceptions of Pm(III) and Gd(III) as well as the Am(III) complex as a representative of the actinide series with both ligands. All complexes were fully characterised (1H, 13C and 15N spectra) using NMR spectroscopy. By isotope enrichment with the NMR-active 15N in positions 8 and 9 in both ligands, resonance signals of these nitrogen atoms were detected for all complexes. The Bleaneymethod relies on different temperature dependencies for FCS (T-1) and PCS (T-2) that occur upon description

  15. PIE analysis for minor actinide

    Minor actinide (MA) is generated in nuclear fuel during the operation of power reactor. For fuel design, reactivity decrease due to it should be considered. Out of reactors, MA plays key role to define the property of spent fuel (SF) such as α-radioactivity, neutron emission rate, and criticality of SF. In order to evaluate the calculation codes and libraries for predicting the amount of MA, comparison between calculation results and experimentally obtained data has been conducted. In this report, we will present the status of PIE data of MA taken by post irradiation examinations (PIE) and several calculation results. (author)

  16. Emissions of organo-metal compounds via the leachate and gas pathway from two differently pre-treated municipal waste materials - A landfill reactor study

    Due to their broad industrial production and use as PVC-stabilisers, agro-chemicals and anti-fouling agents, organo-metal compounds are widely distributed throughout the terrestrial and marine biogeosphere. Here, we focused on the emission dynamics of various organo-metal compounds (e.g., di,- tri-, tetra-methyl tin, di-methyl mercury, tetra-methyl lead) from two different kinds of pre-treated mass waste, namely mechanically-biologically pre-treated municipal solid waste (MBP MSW) and municipal waste incineration ash (MWIA). In landfill simulation reactors, the emission of the organo-metal compounds via the leachate and gas pathway was observed over a period of 5 months simulating different environmental conditions (anaerobic with underlying soil layer/aerated/anaerobic). Both waste materials differ significantly in their initial amounts of organo-metal compounds and their environmental behaviour with regard to the accumulation and depletion rates within the solid material during incubation. For tri-methyl tin, the highest release rates in leachates were found in the incineration ash treatments, where anaerobic conditions in combination with underlying soil material significantly promoted its formation. Concerning the gas pathway, anaerobic conditions considerably favour the emission of organo-metal compounds (tetra-methyl tin, di-methyl mercury, tetra-methyl lead) in both the MBP material and especially in the incineration ash

  17. Zinc-blende compounds of transition elements with N, P, As, Sb, S, Se, and Te as half-metallic systems

    Galanakis, Iosif; Mavropoulos, Phivos

    2003-03-01

    We report systematic first-principles calculations for ordered zinc-blende compounds of the transition metal elements V, Cr, and Mn with the sp elements N, P, As, Sb, S, Se, and Te, motivated by a recent fabrication of zinc-blende CrAs, CrSb, and MnAs. They show a ferromagnetic half-metallic behavior for a wide range of lattice constants. We discuss the origin and trends of half-metallicity, present the calculated equilibrium lattice constants, and examine the half-metallic behavior of their transition element terminated (001) surfaces.

  18. Actinides analysis by accelerator mass spectrometry

    At the ANTARES accelerator at ANSTO a new beamline has been commissioned, incorporating new magnetic and electrostatic analysers, to optimise the efficiency for Actinides detection by Accelerator Mass Spectrometry (AMS). The detection of Actinides, particularly the isotopic ratios of uranium and plutonium, provide unique signatures for nuclear safeguards purposes. We are currently engaged in a project to evaluate the application of AMS to the measurement of Actinides in environmental samples for nuclear safeguards. Levels of certain fission products, Actinides and other radioactive species can be used as indicators of undeclared nuclear facilities or activities, either on-going or in the past Other applications of ultra-sensitive detection of Actinides are also under consideration. neutron-attenuation images of a porous reservoir rock

  19. Actinide ion sensor for pyroprocess monitoring

    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. Evaluation of properties of concrete using fluosilicate salts and metal (Ni,W) compounds

    Gyu-Yong KIM; Eui-Bae LEE; Bae-Su KHIL; Seung-Hum LEE

    2009-01-01

    To improve watertightness and antibiosis of sewage structure concrete, the antimierobial watertight admixture was made with fluosilicate salts and antimicrobial compounds. And fresh properties, watertightness, harmlessness and antibiosis of concrete were investigated experimentally. As a result, the fresh properties of concrete were similar to those of an ordinary concrete, without setting time delay. Compressive strength and carbonation resistance of concrete were better than those of an ordinary concrete. Finally it was confirmed that the antimierobial watenight admixture of concrete had an antibiosis inhibiting SOB growth.

  1. Rapid coastal survey of anthropogenic radionuclides, metals, and organic compounds in surficial marine sediments

    A towed survey system, the GIMS/CS3, has been developed to enable the rapid measurement and mapping of a variety of physical and geochemical parameters in the surficial sediments of aquatic environments while the survey vessel is underway. With its capability for measuring radiometric, elemental and organic compound constituents of sediments, as well as bathymetry and water quality parameters, the GIMS/CS3 provides a cost-effective means of performing reconnaissance determinations of contaminant distributions and environmental monitoring tasks over broad geographic regions

  2. Chemical properties of the heavier actinides and transactinides

    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 5f147s27p. 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

  3. Chemical properties of the heavier actinides and transactinides

    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.

  4. Electronic, thermal, and superconducting properties of metal nitrides (MN) and metal carbides (MC) (M=V, Nb, Ta) compounds by first principles studies

    Subhashree, G.; Sankar, S.; Krithiga, R. [Anna Univ., Chennai, Tamil Nadu (India). Condensed Matter Lab.

    2015-07-01

    Structural, electronic, and superconducting properties of carbides and nitrides of vanadium (V), niobium (Nb), and tantalum (Ta) (group V transition elements) have been studied by computing their electronic band structure characteristics. The electronic band structure calculations have been carried out based on the density functional theory (DFT) within the local density approximation (LDA) by using the tight binding linear muffin tin orbital method. The NaCl-type cubic structures of MN and MC (M=V, Nb, Ta) compounds have been confirmed from the electronic total energy minimum of these compounds. The ground state properties, such as equilibrium lattice constant (a{sub 0}), bulk modulus (B), and Wigner-Seitz radius (S{sub 0}) are determined and compared with available data. The electronic density of states reveals the metallic nature of the chosen materials. The electronic specific heat coefficient, Debye temperature, and superconducting transition temperature obtained from the band structure results are found to agree well with the earlier reported literature.

  5. Theoretical modelling of intermediate band solar cell materials based on metal-doped chalcopyrite compounds

    Electronic structure calculations are carried out for CuGaS2 partially substituted with Ti, V, Cr or Mn to ascertain if some of these systems could provide an intermediate band material able to give a high efficiency photovoltaic cell. Trends in electronic level positions are analyzed and more accurate advanced theory levels (exact exchange or Hubbard-type methods) are used in some cases. The Ti-substituted system seems more likely to yield an intermediate band material with the desired properties, and furthermore seems realizable from the thermodynamic point of view, while those with Cr and Mn might give half-metal structures with applications in spintronics

  6. Ambient air monitoring for organic compounds, acids, and metals at Los Alamos National Laboratory, January 1991

    Los Alamos National Laboratory (LANL) contracted Radian Corporation (Radian) to conduct a short-term, intensive air monitoring program whose goal was to estimate the impact of chemical emissions from LANL on the ambient air environment. A comprehensive emission inventory had identified more than 600 potential air contaminants in LANL's emissions. A subset of specific target chemicals was selected for monitoring: 20 organic vapors, 6 metals and 5 inorganic acid vapors. These were measured at 5 ground level sampling sites around LANL over seven consecutive days in January 1991. The sampling and analytical strategy used a combination of EPA and NIOSH methods modified for ambient air applications

  7. Theoretical modelling of intermediate band solar cell materials based on metal-doped chalcopyrite compounds

    Palacios, P. [Instituto de Energia Solar and Dpt. de Tecnologias Especiales, ETSI de Telecomunicacion, UPM, Ciudad Universitaria s/n, 28040 Madrid (Spain)]. E-mail: pablop@etsit.upm.es; Sanchez, K. [Instituto de Energia Solar and Dpt. de Tecnologias Especiales, ETSI de Telecomunicacion, UPM, Ciudad Universitaria s/n, 28040 Madrid (Spain); Conesa, J.C. [Instituto de Catalisis y Petroleoquimica, CSIC, Marie Curie 2, Cantoblanco, 28049 Madrid (Spain); Fernandez, J.J. [Dpt. de Fisica Fundamental, Universidad Nacional de Educacion a Distancia, 28080, Madrid (Spain); Wahnon, P. [Instituto de Energia Solar and Dpt. de Tecnologias Especiales, ETSI de Telecomunicacion, UPM, Ciudad Universitaria s/n, 28040 Madrid (Spain)

    2007-05-31

    Electronic structure calculations are carried out for CuGaS{sub 2} partially substituted with Ti, V, Cr or Mn to ascertain if some of these systems could provide an intermediate band material able to give a high efficiency photovoltaic cell. Trends in electronic level positions are analyzed and more accurate advanced theory levels (exact exchange or Hubbard-type methods) are used in some cases. The Ti-substituted system seems more likely to yield an intermediate band material with the desired properties, and furthermore seems realizable from the thermodynamic point of view, while those with Cr and Mn might give half-metal structures with applications in spintronics.

  8. Actinide consumption: Nuclear resource conservation without breeding

    A new approach to the nuclear power issue based on a metallic fast reactor fuel and pyrometallurgical processing of spent fuel is showing great potential and is approaching a critical demonstration phase. If successful, this approach will complement and validate the LWR reactor systems and the attendant infrastructure (including repository development) and will alleviate the dominant concerns over the acceptability of nuclear power. The Integral Fast Reactor (IFR) concept is a metal-fueled, sodium-cooled pool-type fast reactor supported by a pyrometallurgical reprocessing system. The concept of a sodium cooled fast reactor is broadly demonstrated by the EBR-II and FFTF in the US; DFR and PFR in the UK; Phenix and SuperPhenix in France; BOR-60, BN-350, BN-600 in the USSR; and JOYO in Japan. The metallic fuel is an evolution from early EBR-II fuels. This fuel, a ternary U-Pu-Zr alloy, has been demonstrated to be highly reliable and fault tolerant even at very high burnup (160-180,000 MWd/MT). The fuel, coupled with the pool type reactor configuration, has been shown to have outstanding safety characteristics: even with all active safety systems disabled, such a reactor can survive a loss of coolant flow, a loss of heat sink, or other major accidents. Design studies based on a small modular approach show not only its impressive safety characteristics, but are projected to be economically competitive. The program to explore the feasibility of actinide recovery from spent LWR fuel is in its initial phase, but it is expected that technical feasibility could be demonstrated by about 1995; DOE has not yet committed funds to achieve this objective. 27 refs

  9. Analysis of metal in organic compound used in the agriculture by x-ray fluorescence

    Using energy dispersive X-ray fluorescence analysis with an X-ray tube filtered with Ti. It was possible to determine the concentration of the elements at ppm level of several elements: K, Ca, Ti, Cr, Mn, Fe, Ni, Cu, Zn As, Rb, Sr, Y, Zr, and Pb in two types of organic compound enough used in the agriculture: organic compound of urban garbage (Fertilurb) and birds manure. The experimental setup is composed of: X-ray tube (Oxford, 30 kV, 50 mA and W anode), an ORTEC Si-Li detector, with an energy resolution of about 180 eV at 5.9 keV and an ORTEC multichannel-analyser. The X-ray beam is quasi-monochromatic by using Ti filter. The samples were prepared in pellet form with superficial density in the range of 100 mg/cm2. The fundamental parameter method was used in order to verify the elemental concentration. The radiation transmission method was going used to the radiation absorption effects correction in the samples

  10. On the R 5d band polarization in rare-earth-transition metal compounds.

    Burzo, E; Chioncel, L; Tetean, R; Isnard, O

    2011-01-19

    Magnetic measurements and band structure calculations were performed on RT(2) and RT(5) compounds, where R is a heavy rare-earth and T = Fe, Co, Ni, Al, as well as on pseudobinary compounds GdCo(2 - x)A(x) (A = Ni, Cu, Si), YFe(2 - x)V(x) and YCo(4 - x)Ni(x)B. The calculated moments per formula unit described well the experimentally determined magnetizations. By considering the 4f-5d-3d exchange interactions, we evaluate the contributions of local 4f-5d and short range 5d-3d interactions to R 5d and Y 4d band polarizations. The 4f-5d induced polarizations are proportional to the De Gennes factor and are the same for a given R and a similar type structure. The R 5d and Y 4d band polarizations induced by R 5d-T3d or Y 4d-T3d hybridizations are proportional to the number of neighbouring T atoms, to a given R, and their magnetic moments. Previous results on the matter are also discussed. PMID:21406851

  11. Theoretical investigation of compounds with triple bonds

    In this thesis, compounds with potential triple-bonding character involving the heavier main-group elements, Group 4 transition metals, and the actinides uranium and thorium were studied by using molecular quantum mechanics. The triple bonds are described in terms of the individual orbital contributions (σ, π parallel, and π perpendicular to), involving electron-sharing covalent or donor-acceptor interactions between the orbitals of two atoms or fragments. Energy decomposition, natural bond orbital, and atoms in molecules analyses were used for the bonding analysis of the triple bonds. The results of this thesis suggest that the triple-bonding character between the heavier elements of the periodic table is important and worth further study and exploration.

  12. Metal-based carboxamide-derived compounds endowed with antibacterial and antifungal activity.

    Hanif, Muhammad; Chohan, Zahid H; Winum, Jean-Yves; Akhtar, Javeed

    2014-08-01

    A series of three bioactive thiourea (carboxamide) derivatives, N-(dipropylcarbamothioyl)-thiophene-2-carboxamide (L(1)), N-(dipropylcarbamothioyl)-5-methylthiophene-2-carboxamide (L(2)) and 5-bromo-N-(dipropylcarbamothioyl)furan-2-carboxamide (L(3)) and their cobalt(II), copper(II), nickel(II) and zinc(II) complexes (1)-(12) have been synthesized and characterized by their IR,(1)H-NMR spectroscopy, mass spectrometry and elemental analysis data. The Crystal structure of one of the ligand, N-(dipropylcarbamothioyl)thiophene-2-carboxamide (L(1)) and its nickel(II) and copper(II) complexes were determined from single crystal X-ray diffraction data. All the ligands and metal(II) complexes have been subjected to in vitro antibacterial and antifungal activity against six bacterial species (Escherichia coli. Shigella flexneri. Pseudomonas aeruginosa. Salmonella typhi. Staphylococcus aureus and Bacillus subtilis) and for antifungal activity against six fungal strains (Trichophyton longifusus. Candida albicans. Aspergillus flavus. Microsporum canis. Fusarium solani and Candida glabrata). The in vitro antibacterial and antifungal bioactivity data showed the metal(II) complexes to be more potent than the parent ligands against one or more bacterial and fungal strains. PMID:23914928

  13. First-principles calculations: The elemental transition metals and their compounds

    If done with sufficient care, present day a priori theory yields calculated enthalpies of formation whose agreement with experiment (when such data is available) is of the order of the experimental scatter. Comparisons will be made for the Pt-Ti systems for which such data exist and for which one crystal structure involves atomics sites of low symmetry. Two other cases will be considered for which there is no direct experimental heats data. The first of these will be the structural stabilities of the 4d elemental metals. Such structural stabilities have been an issue of contention between electronic structure theorists and those who construct phase diagrams for some twenty-five years. The second involves the energetics of forming metal adlayers and artificial multilayers. The distortion energies associated with the requirement that adlayers (or multilayers) conform to some given substrate are often the controlling factors in the fabrication of multilayer materials. This contribution is best understood by invoking a combination of elemental structural promotion energies plus elastic distortions from these structures. As will be seen, the fabrication of multilayers also involves a term not normally encountered in bulk phase diagram considerations, namely the difference in surface energies of the two multilayer constituents. 22 refs., 4 figs

  14. Fe based amorphous and compounds metallic alloys for magnetic and structural use

    Massive amorphous metals (thicker than 1mm) are new types of material that could have a wide range of future applications due to a unique combination of their physical properties, mechanics and magnetics. Among these are the elevated tension of fracture and hardness, and excellent soft magnetic properties. Since 1960, when an amorphous metallic alloy was first discovered, progress has continued on the application possibilities for these materials. One of their main limitations, maximum obtainable thickness, has continued to increase, since at first thicknesses of a few microns were obtained. Now amorphous alloys more than 70 mm thick are obtained using different metallic elements. Since 1995 massive amorphous metals can be produced using Fe as the base element. At first they were made in order to achieve good soft magnetic properties (thicknesses of ∼5 mm) and later a renewed interest in their use as structural material led to the development of materials with thicknesses of 16 mm and paramagnetics at room temperature. Increasing the toughness of these materials is also a challenge and investigators have proposed several solutions, among them is the development of composite materials where dendrites from a solid solution act as crack stoppers of fissures that are spread by an amorphous matrix. This work presents the results of studies with two types of synthesized materials using the rapid cooling technique from injection copper mold casting at air temperature: 1) a massive amorphous metallic alloy with composition (Fe0.375Co0.375B0.2Si0.05)96Nb4 (at.%) and 2) a composite of solid solution dendrites α-(FeCo) scattered in an amorphous matrix with a composition similar to alloy 1. Using the samples obtained structural studies were made (optic and electronic microscopy SEM, XRD, EDAX, DTA), magnetic studies (coercive field and saturation magnetization) and mechanical studies (Vickers microhardness). The fully amorphous alloy could be obtained with a maximum

  15. Enhanced Optical Transmission and Sensing of a Thin Metal Film Perforated with a Compound Subwavelength Circular Hole Array

    Zhang, Xiangnan; Liu, Guiqiang; Liu, Zhengqi; Hu, Ying; Cai, Zhengjie

    2015-12-01

    We propose and numerically investigate the optical transmission behaviors of a sub-wavelength metal film perforated with a two-dimensional square array of compound circular holes. Enhanced optical transmission is obtained by using the finite-difference time-domain (FDTD) method, which can be mainly attributed to the excitation and coupling of localized surface plasmon resonances (LSPRs) and surface plasmon polaritons (SPPs), and Fano Resonances. The redshift of the transmission peak can be achieved by enlarging the size and number of small holes, the environmental dielectric constant. These indicate that the proposed structure has potential applications in integrated optoelectronic devices such as plasmonic filters and sensors. supported by National Natural Science Foundation of China (Nos. 11464019, 11264017, 11004088), Young Scientist Development Program of China (No. 20142BCB23008) and the Natural Science Foundation of Jiangxi Province, China (Nos. 2014BAB212001, 20112BBE5033)

  16. Fast neutron scattering on actinide nuclei

    More and more sophisticated neutron experiments have been carried out with better samples in several laboratories and it was necessary to intercompare them. In this respect, let us quote for example (n,n'e) and (n,n'#betta#) measurements. Moreover, high precision (p,p), (p,p') and (p,n) measurements have been made, thus supplementing neutron experiments in the determination of the parameters of the optical model, still widely used to describe the neutron-nucleus interaction. The optical model plays a major role and it is therefore essential to know it well. The spherical optical model is still very useful, especially because of its simplicity and of the relatively short calculation times, but is obviously insufficient to treat deformed nuclei such as actinides. For accurate calculations about these nuclei, it is necessary to use a deformed potential well and solve a set of coupled equations, hence long computational times. The importance of compound nucleus formation at low energy requires also a good knowledge of the statistical model together with that of all the reaction mechanisms which are involved, including fission for which an accurate barrier is necessary and, of course, well-adjusted level densities. The considerations form the background of the Scientific Programme set up by a Programme Committee whose composition is given further on in this book

  17. Extraction chromatographic studies of actinides and fission products using CMPO

    The uptake behaviour of U(VI), Pu(IV), Am(III), Eu(III), Zr(IV), Fe(III), Ru(III) and Tc from nitric acid medium by octyl (phenyl)-N,N-diisobutyl carbomylmethylphosphine oxide (CMPO) adsorbed on chromosorb has been studied. Actinide metal ions along with rare earths are taken up to a greater extent as compared to the other fission products. The loading experiments have shown that at lower concentrations of the rare earths or U(VI), the uptake of Pu(IV), U(VI) and Am(III) are reasonably high. (author). 3 refs., 1 fig

  18. Removal of actinides from dilute waste waters using polymer filtration

    More stringent US Department of Energy discharge regulations for waste waters containing radionuclides (30 pCi/L total alpha) require the development of new processes to meet the new discharge limits for actinide metal ions, particularly americium and plutonium, while minimizing waste. We have been investigating a new technology, polymer filtration, that has the potential for effectively meeting these new limits. Traditional technology uses basic iron precipitation which produces large amounts of waste sludge. The new technology is based on using water-soluble chelating polymers with ultrafiltration for physical separation. The actinide metal ions are selectively bound to the polymer and can not pass through the membrane. Small molecules and nonbinding metals pass through the membrane. Advantages of polymer filtration technology compared to ion, exchange include rapid kinetics because the binding is occurring in a homogenous solution and no mechanical strength requirement on the polymer. We will present our results on the systematic development of a new class of water-soluble chelating polymers and their binding ability from dilute acid to near neutral waters

  19. On the crystallographic relationship between monoborides (CrB, α-MoB) and actinide-borocarbides (UBC, ThBC)

    Previously, (see ibid, vol. 73, p. 198, 1978), a simple geometrical relationship between actinide borocarbides of the formula MBC was derived for the pair ThBC-UBC. Similarity of the metal-boron sublattice within the crystal structures of UBC and CrB was earlier recognized by Toth et al. (1961). A closer inspection of the crystal symmetry relations between transition metal monoborides and actinide borocarbides is the subject of the present work. (Auth.)

  20. Microbial transformations of actinides in the environment

    The diversity of microorganisms is still far from understood, although many examples of the microbial biotransformation of stable, pollutant and radioactive elements, involving Bacteria, Archaea and Fungi, are known. In estuarine sediments from the Irish Sea basin, which have been labelled by low level effluent discharges, there is evidence of an annual cycle in Pu solubility, and microcosm experiments have demonstrated both shifts in the bacterial community and changes in Pu solubility as a result of changes in redox conditions. In the laboratory, redox transformation of both U and Pu by Geobacter sulfurreducens has been demonstrated and EXAFS spectroscopy has been used to understand the inability of G. sufurreducens to reduce Np(V). Fungi promote corrosion of metallic U alloy through production of a range of carboxylic acid metabolites, and are capable of translocating the dissolved U before precipitating it externally to the hyphae, as U(VI) phosphate phases. These examples illustrate the far-reaching but complex effects which microorganisms can have on actinide behaviour.