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Sample records for synthesized uranyl phases

  1. Hydrothermal Phase Relations Among Uranyl Minerals at the Nopal I Analog Site

    International Nuclear Information System (INIS)

    Murphy, William M.

    2007-01-01

    Uranyl mineral paragenesis at Nopal I is an analog of spent fuel alteration at Yucca Mountain. Petrographic studies suggest a variety of possible hydrothermal conditions for uranium mineralization at Nopal I. Calculated equilibrium phase relations among uranyl minerals show uranophane stability over a broad range of realistic conditions and indicate that uranyl mineral variety reflects persistent chemical potential heterogeneity. (author)

  2. Np Incorporation into Uranyl Alteration Phases: A Quantum Mechanical Approach

    International Nuclear Information System (INIS)

    L.C. Huller; R.C. Win; U.Ecker

    2006-01-01

    Neptunium is a major contributor to the long-term radioactivity in a geologic repository for spent nuclear fuel (SNF) due to its long half-life (2.1 million years). The mobility of Np may be decreased by incorporation into the U 6+ phases that form during the corrosion of SNF. The ionic radii of Np (0.089nm) and U (0.087nm) are similar, as is their chemistry. Experimental studies have shown Np can be incorporated into uranyl phases at concentrations of ∼ 100 ppm. The low concentration of Np in the uranyl phases complicates experimental detection and presents a significant challenge for determining the incorporation mechanism. Therefore, we have used quantum mechanical calculations to investigate incorporation mechanisms and evaluate the energetics of Np substituting for U. CASTEP, a density functional theory based code that uses plane waves and pseudo-potentials, was used to calculate optimal H positions, relaxed geometry, and energy of different uranyl phases. The incorporation energy for Np in uranyl alteration phases was calculated for studtite, [(UO 2 )O 2 (H 2 O) 2 ](H 2 ) 2 , and boltwoodite, HK(UO 2 )(SiO 4 )* 1.5(H 2 O). Studtite is the rare case of a stable uranyl hydroxyl-peroxide mineral that forms in the presence of H 2 O 2 from the radiolysis of H 2 O. For studtite, two incorporation mechanisms were evaluated: (1) charge-balanced substitution of Np 5+ and H + for one U 6+ , and (2) direct substitution of Np 6+ for U 6+ . For boltwoodite, the H atomic positions prior to Np incorporation were determined, as well as the Np incorporation mechanisms and the corresponding substitution energies. The preferential incorporation of Np into different structure types of U 6+ minerals was also investigated. Quantum mechanical substitution energies have to be derived at Np concentrations higher than the ones found in experiments or expected in a repository. However, the quantum mechanical results are crucial for subsequent empirical force-field and Monte

  3. The Influence of the Linker Geometry in Bis(3-hydroxy-N-methyl-pyridin-2-one) Ligands on Solution-Phase Uranyl Affinity

    Energy Technology Data Exchange (ETDEWEB)

    Szigethy, Geza; Raymond, Kenneth

    2010-08-12

    Seven water-soluble, tetradentate bis(3-hydroxy-N-methyl-pyridin-2-one) (bis-Me-3,2-HOPO) ligands were synthesized that vary only in linker geometry and rigidity. Solution phase thermodynamic measurements were conducted between pH 1.6 and pH 9.0 to determine the effects of these variations on proton and uranyl cation affinity. Proton affinity decreases by introduction of the solubilizing triethylene glycol group as compared to un-substituted reference ligands. Uranyl affinity was found to follow no discernable trends with incremental geometric modification. The butyl-linked 4Li-Me-3,2-HOPO ligand exhibited the highest uranyl affinity, consistent with prior in vivo decorporation results. Of the rigidly-linked ligands, the o-phenylene linker imparted the best uranyl affinity to the bis-Me-3,2-HOPO ligand platform.

  4. Solid phase syntheses of oligoureas

    Energy Technology Data Exchange (ETDEWEB)

    Burgess, K.; Linthicum, D.S.; Russell, D.H.; Shin, H.; Shitangkoon, A.; Totani, R.; Zhang, A.J.; Ibarzo, J. [Texas A& M Univ., College Station, TX (United States)

    1997-02-19

    Isocyanates 7 were formed from monoprotected diamines 3 or 6, which in turn can be easily prepared from commercially available N-BOC- or N-FMOC-protected amino acid derivatives. Isocyanates 7, formed in situ, could be coupled directly to a solid support functionalized with amine groups or to amino acids anchored on resins using CH{sub 2}Cl{sub 2} as solvent and an 11 h coupling time at 25 {degree}C. Such couplings afforded peptidomimetics with an N-phthaloyl group at the N-terminus. The optimal conditions identified for removal of the N-phthaloyl group were to use 60% hydrazine in DMF for 1-3 h. Several sequences of amino acids coupled to ureas (`peptidic ureas`) and of sequential urea units (`oligoureas`) were prepared via solid phase syntheses and isolated by HPLC. Partition coefficients were measured for two of these peptidomimetics, and their water solubilities were found to be similar to the corresponding peptides. A small library of 160 analogues of the YGGFL-amide sequence was prepared via Houghten`s tea bag methodology. This library was tested for binding to the anti-{beta}-endorphin monoclonal antibody. Overall, this paper describes methodology for solid phase syntheses of oligourea derivatives with side chains corresponding to some of the protein amino acids. The chemistry involved is ideal for high-throughput syntheses and screening operations. 51 refs., 3 figs., 2 tabs.

  5. Formation of the second organic phase during uranyl nitrate extraction from aqueous solution by 30% tributylphosphate solution in paraffin

    International Nuclear Information System (INIS)

    Yhrkin, V.G.

    1996-01-01

    For extraction systems aqueous solution of uranyl nitrate-30% solution of tributylphosphate in individual paraffins from C 13 to C 17 the influence of the second organic phase of uranyl nitrate concentration in aqueous and organic phases, the length of hydrocarbon chain of paraffin hydrocarbon and temperature from 25 to 50 deg C on formation conditions has been defected. A special method of achieving the conditions of organic phase stratification from three-phase region, involving definition of equilibrium phases composition by density and refractive index, has been elaborated for more precise definition of organic phase homogeneity region. It has been revealed that without addition of nitric acid to uranyl nitrate solution the organic phase homogeneity limits can be achieved solely on paraffins C 15 , C 16 and C 17 and only under conditions similar to equeous phase saturation in terms of uranyl nitrate. 16 refs., 2 figs

  6. TBP assisted uranyl extraction from water to water/organic interface to organic phase: molecular dynamics of uranyl complex with water, acid and TBP

    International Nuclear Information System (INIS)

    Sahu, P.; Ali, Sk. M.; Shenoy, K.T.

    2016-01-01

    Reprocessing of the used fuel, not only diminishes the volume and toxicity of high level waste but is also required to produce the new fuel for nuclear reactors. It has been observed that the extraction of uranyl ions from dissolver solution to the organic phase is influenced by co extraction of other species, such as water and nitric acid and it is assumed that the presence of water or acid droplets in the organic phase intensifies the coordination mechanism of TBP. Present study is dedicated to revisit the molecular process of uranyl extraction from aqueous phase to organic phase, using molecular dynamic (MD) simulations. Here, we consider the biphasic systems to gain insights into the characteristics of the interface and humidity of organic phase under different acidic and neutral conditions. The consequences regarding the interfacial landscape, in the extraction process are considered by comparing the MD results of interfacial systems with various TBP and acid concentration. Further, the importance of charge transferability during uranyl-TBP complexation have been investigated with NO 3 - counter ions. Overall, this study aims at improving the description of molecular composition of various species and the structure of interface, in order to better understand the molecular-level complexation reaction occurring at the interface in different neutral and acidic environment

  7. Synthesizing lattice structures in phase space

    International Nuclear Information System (INIS)

    Guo, Lingzhen; Marthaler, Michael

    2016-01-01

    In one dimensional systems, it is possible to create periodic structures in phase space through driving, which is called phase space crystals (Guo et al 2013 Phys. Rev. Lett. 111 205303). This is possible even if for particles trapped in a potential without periodicity. In this paper we discuss ultracold atoms in a driven optical lattice, which is a realization of such a phase space crystals. The corresponding lattice structure in phase space is complex and contains rich physics. A phase space lattice differs fundamentally from a lattice in real space, because its coordinate system, i.e., phase space, has a noncommutative geometry, which naturally provides an artificial gauge (magnetic) field. We study the behavior of the quasienergy band structure and investigate the dissipative dynamics. Synthesizing lattice structures in phase space provides a new platform to simulate the condensed matter phenomena and study the intriguing phenomena of driven systems far away from equilibrium. (paper)

  8. Spherical agarose-coated magnetic nanoparticles functionalized with a new salen for magnetic solid-phase extraction of uranyl ion

    International Nuclear Information System (INIS)

    Serenjeh, Fariba Nazari; Hashemi, Payman; Ghiasvand, Ali Reza; Naeimi, Hossein; Zakerzadeh, Elham

    2016-01-01

    The authors describe a method for magnetic solid phase extraction of uranyl ions from water samples. It is based on the use of spherical agarose-coated magnetic nanoparticles along with magnetic field agitation. The salen type Schiff base N,N’-bis(4-hydroxysalicylidene)-1,2-phenylenediamine was synthesized from resorcinol in two steps and characterized by infrared and nucleic magnetic resonance spectroscopies. The particles were then activated by an epichlorohydrin method and functionalized with the Schiff base which acts as a selective ligand for the extraction of UO 2 (II). Following preconcentration and elution with HCl, the ions were quantified by spectrophotometry using Arsenazo III as the indicator. The effects of pH value, ionic strength and amount of the adsorbent on the extraction of UO 2 (II) were optimized by a multivariate central composite design method. Six replicate analyses under optimized conditions resulted in a recovery of 96.6 % with a relative standard deviation of 3.4 % for UO 2 (II). The detection limit of the method (at a signal-to-noise ratio of 3σ) is 10 μg L -1 . The method was successfully applied to the determination of UO 2 (II) in spiked water samples. (author)

  9. Synthesis of phosphorylated calix[4]arene derivatives for the design of solid phases immobilizing uranyl cations

    International Nuclear Information System (INIS)

    Maroun, E.B.; Hagege, A.; Asfari, Z.; Basset, CH.; Quemeneur, E.; Vidaud, C.

    2009-01-01

    With the aim of developing supports for uranyl cations immobilisation, new 1, 3-alternate calix[4]arenes bearing both phosphonic acid functions as chelating sites and N-succinimide-4-oxa-butyrate as the anchoring arm were synthesised in good yields. The coupling of such calixarenes to a gel was performed and a successful immobilisation of uranyl cations was obtained. (authors)

  10. Synthesis of phosphorylated calix[4]arene derivatives for the design of solid phases immobilizing uranyl cations

    Energy Technology Data Exchange (ETDEWEB)

    Maroun, E.B.; Hagege, A.; Asfari, Z. [Laboratoire de Chimie Analytique et Minerale, UMR 7178 ULP/CNRS/IN2P3 LC4, ECPM, Strasbourg Cedex (France); Basset, CH.; Quemeneur, E.; Vidaud, C. [CEA IBEB, SBTN, Centre de Marcoule, Bagnols-sur-Ceze (France)

    2009-07-01

    With the aim of developing supports for uranyl cations immobilisation, new 1, 3-alternate calix[4]arenes bearing both phosphonic acid functions as chelating sites and N-succinimide-4-oxa-butyrate as the anchoring arm were synthesised in good yields. The coupling of such calixarenes to a gel was performed and a successful immobilisation of uranyl cations was obtained. (authors)

  11. Complexation or uranyl ion. II. Complexation of uranyl ion in the VP-IAp anion exchanger phase during sorption from carbonate media

    International Nuclear Information System (INIS)

    Stupin, N.P.; Kakhaeva, T.V.; Buskina, I.A.; Rodionov, V.V.; Vodolazov, L.I.; Zhukova, N.G.

    1987-01-01

    The complicated process of increased uranium sorption from carbonate medium by the strongly basic anion exchanger VP-1Ap after additional treatment with alkaline solution was studied by IR spectroscopy. The process is related to the formation of certain complex forms of uranyl, differing in degree of polymerization, in which polynuclear forms predominate

  12. EXTRACTION OF URANYL NITRATE FROM AQUEOUS SOLUTIONS

    Science.gov (United States)

    Furman, N.H.; Mundy, R.J.

    1957-12-10

    An improvement in the process is described for extracting aqueous uranyl nitrate solutions with an organic solvent such as ether. It has been found that the organic phase will extract a larger quantity of uranyl nitrate if the aqueous phase contains in addition to the uranyl nitrate, a quantity of some other soluble nitrate to act as a salting out agent. Mentioned as suitable are the nitrates of lithium, calcium, zinc, bivalent copper, and trivalent iron.

  13. Phase Transformation of Hydrothermally Synthesized Nanoparticle ...

    African Journals Online (AJOL)

    NJD

    Mild hydrothermal hydrolysis of TiCl4 produces nanorods of the rutile phase of titanium dioxide in high yield, while in the presence of organic ..... Reading, MA, 1969. 39 H.P. Klug and L.E. Alexander, X-ray Diffraction Procedures for. Polycrystalline and Amorphous Materials, 2nd edn. John Wiley & Sons,. New York, 1974.

  14. Phase Transformation of Hydrothermally Synthesized Nanoparticle ...

    African Journals Online (AJOL)

    Mild hydrothermal hydrolysis of TiCl4 produces nanorods of the rutile phase of titanium dioxide in high yield, while in the presence of organic acids (citric, acetic, D-tartaric and benzoic acids) anatase is the only product. The effect of these organic acids on the products of the hydrolysis reaction as well as the reaction kinetics ...

  15. Tritium distribution ratios between the 30 % tributyl phosphate(TBP)-normal dodecane(nDD) organic phase and uranyl nitrate-nitric acid aqueous phase

    International Nuclear Information System (INIS)

    Fujine, Sachio; Uchiyama, Gunzou; Sugikawa, Susumu; Maeda, Mitsuru; Tsujino, Takeshi.

    1989-10-01

    Tritium distribution ratios between the organic and aqueous phases were measured for the system of 30 % tributyl phosphate(TBP)-normal dodecane(nDD)/uranyl nitrate-nitric acid water. It was confirmed that tritium is extracted by TBP into the organic phase in both chemical forms of tritiated water (HTO) and tritiated nitric acid (TNO 3 ). The value of tritium distribution ratio ranged from 0.002 to 0.005 for the conditions of 0-6 mol/L nitric acid, 0.5-800 mCi/L tritium in aqueous phase, and 0-125 g-U/L uranium in organic phase. Isotopic distribution coefficient of tritium between the organic and aqueous phases was observed to be about 0.95. (author)

  16. Stabilization of gas-phase uranyl complexes enables rapid speciation using electrospray ionization and ion mobility-mass spectrometry.

    Science.gov (United States)

    Davis, Austen L; Clowers, Brian H

    2018-01-01

    Significant challenges exist when characterizing f-element complexes in solution using traditional approaches such as electrochemical and spectroscopic techniques as they do not always capture information for lower abundance species. However, provided a metal-complex with sufficient stability, soft ionization techniques such as electrospray offer a means to quantify and probe the characteristics of such systems using mass spectrometry. Unfortunately, the gas-phase species observed in ESI-MS systems do not always reflect the solution phase distributions due to the inherent electrochemical mechanism of the electrospray process, ion transfer from ambient to low pressures conditions, and other factors that are related to droplet evaporation. Even for simple systems (e.g. hydrated cations), it is not always clear whether the distribution observed reflects the solution phase populations or whether it is simply a result of the ionization process. This complexity is further compounded in mixed solvent systems and when multiply charged species are present. Despite these challenges, the benefits of mass spectrometry with respect to speed, sensitivity, and the ability to resolve isotopes continue to drive efforts to develop techniques for the speciation of metal complexes. Using an electrospray ionization atmospheric pressure ion mobility mass spectrometer (ESI-apIMS-MS), we demonstrate an approach to stabilize simple uranyl complexes during the ionization process and mobility separation to aid speciation and isotope profile analysis. Specifically, we outline and demonstrate the capacity of ESI-apIMS-MS methods to measure mobilities of different uranyl species, in simple mixtures, by promoting stable gas phase conformations with the addition of sulfoxides (i.e. dimethyl sulfoxide (DMSO), dibutyl sulfoxide (DBSO), and methyl phenyl sulfoxide (MPSO)). Addition of these sulfoxides, as observed in the mass spectrum and mobility domain, produce stable gas-phase conformations that

  17. Phase-predictable tuning of single-frequency optical synthesizers.

    Science.gov (United States)

    Rohde, Felix; Benkler, Erik; Puppe, Thomas; Unterreitmayer, Reinhard; Zach, Armin; Telle, Harald R

    2014-07-15

    We investigate the tuning behavior of a novel type of single-frequency optical synthesizers by phase comparison of the output signals of two identical devices. We achieve phase-stable and cycle-slip free frequency tuning over 28.1 GHz with a maximum zero-to-peak phase deviation of 62 mrad. In contrast to previous implementations of single-frequency optical synthesizers, no comb line order switching is needed when tuned over more than one comb line spacing range of the employed frequency comb.

  18. Chemical phase analysis of seed mediated synthesized anisotropic silver nanoparticles

    Energy Technology Data Exchange (ETDEWEB)

    Bharti, Amardeep, E-mail: abharti@pu.ac.in; Goyal, Navdeep [Department of Physics, Panjab University, Chandigarh, INDIA-160014 (India); Singh, Suman; Singla, M. L. [Agrionics, Central Scientific Instruments Organization, CSIR, Chandigarh, INDIA-160030 (India)

    2015-08-28

    Noble-metal nanoparticles are of great interest because of its broad applications almost in every stream (i.e. biology, chemistry and engineering) due to their unique size/shape dependant properties. In this paper, chemical phase of seed mediated synthesized anisotropic silver nanoparticle (AgNPs) has been investigated via fourier transform infrared spectroscopy (FTIR) and thermogravimetric analysis (TGA). These nanaoparticles were synthesized by seed-growth method controlled by urea and dextrose results to highly stable 12-20 nm particle size revealed by zeta potential and transmission electron microscopy (TEM)

  19. Functionalized hydrothermal carbon derived from waste pomelo peel as solid-phase extractant for the removal of uranyl from aqueous solution.

    Science.gov (United States)

    Li, Feize; Tang, Yu; Wang, Huilin; Yang, Jijun; Li, Shoujian; Liu, Jun; Tu, Hong; Liao, Jiali; Yang, Yuanyou; Liu, Ning

    2017-10-01

    To develop a high-performance solid-phase extractant for the separation of uranyl f, pomelo peel, a kind of waste biomass, has been employed as carbon source to prepare carbonaceous matrix through low-temperature hydrothermal carbonization (200 °C, 24 h). After being oxidized by Hummers method, the prepared hydrothermal carbon matrix was functionalized with carboxyl and phenolic hydroxyl groups (1.75 mmol g -1 ). The relevant characterizations and batch studies had demonstrated that the obtained carbon material possessed excellent affinity toward uranyl (436.4 mg g -1 ) and the sorption process was a spontaneous, endothermic and rapid chemisorption. The selective sorption of U(VI) from the simulated nuclear effluent demonstrated that the sorbent displayed a desirable selectivity (56.14% at pH = 4.5) for the U(VI) ions over the other 11 competitive cations from the simulated industrial nuclear effluent. The proposed synthetic strategy in the present work had turned out to be effective and practical, which provides a novel approach to prepare functional materials for the recovery and separation of uranyl or other heavy metals from aqueous environment.

  20. Synthesis and complexation properties towards uranyl cation of carboxylic acid derivatives of p-tert-butyl-calix[6]arene; Synthese et proprietes complexantes vis-a-vis de l'ion uranyle de derives carboxyliques du p-tert-butyl-calix[6]arene

    Energy Technology Data Exchange (ETDEWEB)

    Souane, R

    2005-03-15

    In the fuel reprocessing plants radioactive metals, and more particularly, uranium in UO{sub 2}{sup 2+} form in the various installations, have many varied physico-chemical forms and there is a risk of exposure and internal contamination in the nuclear industry. It is necessary to exert a medical control to ensure the protection of the health of the workers. This medical control is done by dosing uranyl cation in the urine of the exposed people. This work forms part of this context. Indeed, we prepared a ligand able to complex the ion uranyl and which is also to be grafted on a solid support. In the family of calixarenes, the calix[6]arenes functionalized by three or four carboxylic functions were selected like chelating molecules of the ion uranyl. The properties of complexation of these calixarenes were studied by potentiometry in methanol, under these conditions balances of protonation and complexation were determined and the constant partners were obtained using the Hyperquad program. We synthesized tri-carboxylic calix[6]arenes comprising of the groupings nitro (NO{sub 2}) in para position of phenol in order to see the influence of a substitution in para position on the complexation. We also synthesized calix[6]arenes tetra-carboxylic in order to show the role of an additional carboxylic acid grouping. The potentiometric study determined thermodynamic parameters of protonation and complexation of carboxylic calix[6]arenes. The results of the complexation highlighted which complex UO{sub 2}L corresponding to the ligand para-tert-butyl-calix[6]arene tetra-acid is more stable than that corresponding to the ligand mono-nitro calix[6]arene tri-acid ({delta}log{beta}110 = 4.3), and than the effect of the groupings nitro in para position has low influence on the complexation of UO{sub 2}{sup 2+}. This makes it possible to consider as possible the grafting of the calix[6]arenes which one knows the behaviour of trapping. To this end we synthesized the ligand 23

  1. Influence of the organic phase property on the extraction of tenoil - trifluoroacetonate uranyl, Annex 6

    International Nuclear Information System (INIS)

    Milic, N.; Petruhin, O.M.; Zolotov, J.A.

    1963-01-01

    This paper describes the study of of uranium (VI) (2.5 10 -4 M) extraction from acetate puffer solutions with 0.01 M solution of tenoil trifluoroacetonate in benzene, chloroform, carbon tetrachloride, amyl acetate, cyclohexanon, n-butyl alcohol with the additions of 0.036 M TBP and 2.7 M acetone solution with 0.01 M solution of TTA. It was verified that the extraction depends on the property of the organic phase. Distribution coefficients for uranium when extracted by solvents containing oxygen is higher compared to the distribution coefficients obtained by solvents without oxygen (benzene, chloroform and carbon tetrachloride). TBP cyclohexanon, and acetone additions in the CCl 4 cause more significant increase of distribution coefficients

  2. Influence of nitric acid on the kinetic of complexation of uranyl nitrate extracted by TBP

    International Nuclear Information System (INIS)

    Pushlenkov, M.F.; Zimenkov, V.V.

    1982-02-01

    The effect of nitric acid on the solvatation rate of uranyl nitrate with tributyl phosphate is studied. In the process of mass transfer, it is shown that nitric acid enables the extraction of uranyl nitrate, therefore its concentration in the organic phase exceeds that in equilibrium solution. Subsequently uranyl nitrate ''displaces'' nitric acid. The presence of the acid in aqueous and organic phases affects in a complicated manner the rate of solvatation of uranyl nitrate with tributyl phosphate [fr

  3. Liquid-phase syntheses of cobalt ferrite nanoparticles

    Science.gov (United States)

    Sinkó, Katalin; Manek, Enikő; Meiszterics, Anikó; Havancsák, Károly; Vainio, Ulla; Peterlik, Herwig

    2012-06-01

    The aim of the present study was to synthesize cobalt-ferrite (CoFe2O4) nanoparticles using various liquid phase methods; sol-gel route, co-precipitation process, and microemulsion technique. The effects of experimental parameters on the particle size, size distribution, morphology, and chemical composition have been studied. The anions of precursors (chloride and nitrate), the solvents (water, n-propanol, ethanol, and benzyl alcohol), the precipitating agent (ammonia, sodium carbonate, and oxalic acid), the surfactants (polydimethylsiloxane, ethyl acetate, citric acid, cethyltrimethylammonium bromide, and sodium dodecil sulfate), their concentrations, and heat treatments were varied in the experiments. The smallest particles (around 40 nm) with narrow polydispersity and spherical shape could be achieved by a simple, fast sol-gel technique in the medium of propanol and ethyl acetate. The size characterization methods have also been investigated. Small-angle X-ray scattering (SAXS), dynamic light scattering (DLS), and scanning electron microscopy (SEM) provide the comparison of methods. The SAXS data correspond with the sizes detected by SEM and differ from DLS data. The crystalline phases, morphology, and chemical composition of the particles with different shapes have been analyzed by X-ray diffraction, SEM, and energy dispersive X-ray spectrometer.

  4. Conducting polymer networks synthesized by photopolymerization-induced phase separation

    Science.gov (United States)

    Yamashita, Yuki; Komori, Kana; Murata, Tasuku; Nakanishi, Hideyuki; Norisuye, Tomohisa; Yamao, Takeshi; Tran-Cong-Miyata, Qui

    2018-03-01

    Polymer mixtures composed of double networks of a polystyrene derivative (PSAF) and poly(methyl methacrylate) (PMMA) were alternatively synthesized by using ultraviolet (UV) and visible (Vis) light. The PSAF networks were generated by UV irradiation to photodimerize the anthracene (A) moieties labeled on the PSAF chains, whereas PMMA networks were produced by photopolymerization of methyl methacrylate (MMA) monomer and the cross-link reaction using ethylene glycol dimethacrylate (EGDMA) under Vis light irradiation. It was found that phase separation process of these networks can be independently induced and promptly controlled by using UV and Vis light. The characteristic length scale distribution of the resulting co-continuous morphology can be well regulated by the UV and Vis light intensity. In order to confirm and utilize the connectivity of the bicontinuous morphology observed by confocal microscopy, a very small amount, 0.1 wt%, of multi-walled carbon nanotubes (MWCNTs) was introduced into the mixture and the current–voltage (I–V) relationship was subsequently examined. Preliminary data show that MWCNTs are preferentially dispersed in the PSAF-rich continuous domains and the whole mixture became electrically conducting, confirming the connectivity of the observed bi-continuous morphology. The experimental data obtained in this study reveal a promising method to design various scaffolds for conducting soft matter taking advantages of photopolymerization-induced phase separation.

  5. Uranyl chelate lasers, realization

    International Nuclear Information System (INIS)

    Macheteau, Y.; Coste, A.; Luce, M.; Rigny, P.

    1975-01-01

    The absorption fluorescence and excitation spectra of uranyle chelates were determined. The corresponding fluorescence decay was measured at low temperature. The possibility of obtaining a stimulated emission with uranyl chelates is examined from the consideration made on the properties of Eu chelates (B 4 EuNa and B 4 Eu piperidine) which give the laser effect [fr

  6. Complexation of Oxovanadium(IV) and Dioxouranium(VI) with Synthesized 1,2-(Diimino-4′-antipyrinyl)-1,2-diphenylethane Schiff Base: A Thermodynamic, Kinetic, and Bioactivity Investigation

    OpenAIRE

    Shabnum Bashir; Syed Raashid Maqsood; Ghulam Mustafa Peerzada; Badruddin Khan; Masood Ahmad Rizvi

    2014-01-01

    We report the comparative synthetic methodologies and characterization of a tetradentate Schiff base ligand 1,2-(diimino-4′-antipyrinyl)-1,2-diphenylethane (DE). The target synthesis of oxovanadium(IV) and dioxouranium(VI) complexes (vanadyl and uranyl) with the (DE) ligand was also attempted to envisage the effect of metal ion steric factor on complexation process through solution phase thermodynamic and kinetic studies. The thermodynamic stabilities of synthesized vanadyl and uranyl (DE) co...

  7. Specific capture of uranyl protein targets by metal affinity chromatography

    Energy Technology Data Exchange (ETDEWEB)

    Basset, C.; Dedieu, A.; Guerin, P.; Quemeneur, E.; Meyer, D.; Vidaud, C. [CEA Valrho, DSV, IBEB, Serv Biochim et Toxicol Nucl, F-30207 Bagnols Sur Ceze (France)

    2008-07-01

    To improve general understanding of biochemical mechanisms in the field of uranium toxicology, the identification of protein targets needs to be intensified. Immobilized metal affinity chromatography (IMAC) has been widely developed as a powerful tool for capturing metal binding proteins from biological extracts. However uranyl cations (UO{sub 2}{sup 2+}) have particular physico-chemical characteristics which prevent them from being immobilized on classical metal chelating supports. We report here on the first development of an immobilized uranyl affinity chromatography method, based on the cation-exchange properties of amino-phosphonate groups for uranyl binding. The cation distribution coefficient and loading capacity on the support were determined. Then the stability of the uranyl-bonded phase under our chromatographic conditions was optimized to promote affinity mechanisms. The successful enrichment of uranyl binding proteins from human serum was then proven using proteomic and mass spectral analysis. (authors)

  8. Rapid hydrothermal route to synthesize cubic-phase gadolinium ...

    Indian Academy of Sciences (India)

    Administrator

    spectrum of a given specimen (pH = 10∙8) has revealed characteristic Fg + Ag modes of cubic phase of .... using the diffraction formula relevant to cubic phase: .... ground state. The energy absorption in Gd is mediated via transition of 4 f electrons to 5d level and then reorganiza- tion of 4 f electrons into various multiplets.

  9. Rapid hydrothermal route to synthesize cubic-phase gadolinium ...

    Indian Academy of Sciences (India)

    Administrator

    Dhananjaya et al 2012a, b), vapour-phase transport pro- cess (Wu and Yang 2000) and .... The colloids, while partially dissolved in water results in a metastable super- saturated solution under hydrothermal environment. On cooling back to room temperature, a large number of seed particles of Gd(OH)3 were formed ...

  10. Healthy Cities Phase V evaluation: further synthesizing realism.

    Science.gov (United States)

    de Leeuw, Evelyne; Green, Geoff; Tsouros, Agis; Dyakova, Mariana; Farrington, Jill; Faskunger, Johan; Grant, Marcus; Ison, Erica; Jackisch, Josephine; Lafond, Leah Janss; Lease, Helen; Mackiewicz, Karolina; Östergren, Per-Olof; Palmer, Nicola; Ritsatakis, Anna; Simos, Jean; Spanswick, Lucy; Webster, Premila; Zamaro, Gianna; Crown, June; Kickbusch, Ilona; Rasmussen, Niels; Scally, Gabriel; Biddle, Marian; Earl, Suzanne; Petersen, Connie; Devlin, Joan

    2015-06-01

    In this article we reflect on the quality of a realist synthesis paradigm applied to the evaluation of Phase V of the WHO European Healthy Cities Network. The programmatic application of this approach has led to very high response rates and a wealth of important data. All articles in this Supplement report that cities in the network move from small-scale, time-limited projects predominantly focused on health lifestyles to the significant inclusion of policies and programmes on systems and values for good health governance. The evaluation team felt that, due to time and resource limitations, it was unable to fully exploit the potential of realist synthesis. In particular, the synthetic integration of different strategic foci of Phase V designation areas did not come to full fruition. We recommend better and more sustained integration of realist synthesis in the practice of Healthy Cities in future Phases. © The Author 2015. Published by Oxford University Press. All rights reserved. For Permissions, please email: journals.permissions@oup.com.

  11. Sintering, microstructural and dilatometric studies of combustion synthesized Synroc phases

    International Nuclear Information System (INIS)

    Muthuraman, M.; Patil, K.C.; Senbagaraman, S.; Umarji, A.M.

    1996-01-01

    Sintering, microstructure, and linear thermal expansion properties of Synroc-B and constituent phases, viz. perovskite CaTiO 3 , zirconolite ZrTi 2 O 7 , hollandite (ideal formula BaAl2Ti 6 O 16 ) have been investigated. Synroc-B powder when pelletized and sintered at 1250 C for 2 h achieved >95% theoretical density. Sintered Synroc-B has a linear thermal expansion coefficient α of 8.72 x 10 -6 K -1 and Vicker's microhardness 9.88 GPa. The linear thermal expansion curves did not show any hysteresis indicating the absence of microcracking in the sintered bodies

  12. Properties of phase separation method synthesized superhydrophobic polystyrene films

    Energy Technology Data Exchange (ETDEWEB)

    Aruna, S.T., E-mail: aruna_reddy@nal.res.in [Surface Engineering Division, Council of Scientific and Industrial Research - National Aerospace Laboratories, Post Bag No. 1779, Bangalore 560 017 (India); Binsy, P.; Richard, Edna; Basu, Bharathibai J. [Surface Engineering Division, Council of Scientific and Industrial Research - National Aerospace Laboratories, Post Bag No. 1779, Bangalore 560 017 (India)

    2012-01-15

    Polystyrene (PS) based superhydrophobic films were prepared by non-solvent induced phase separation method using tetrahydrofuran (THF) as the solvent and different alcohols as non-solvents. Flory Huggins interaction parameter values of different alcohols and acetone with PS were calculated to qualify them as non-solvents for phase separation. The films were characterized using contact angle analyser, field emission scanning electron microscope, surface roughness profilometer, IR spectrometer and Raman spectrometer. The coatings exhibited a maximum water contact angle (WCA) of 159 Degree-Sign and a sliding angle (SA) < 2 Degree-Sign . With increase in the vol% of non-solvent, WCA increased and SA decreased. The microstructures of the films varied with the vol% of non-solvent and the amount of PS. The work of adhesion of PS films decreased with increasing WCA. The Raman spectral studies showed isotactic to atactic transformation of PS with the addition of non-solvents and these results corroborated well with the IR spectral studies.

  13. Nanosize stabilization of cubic and tetragonal phases in reactive plasma synthesized zirconia powders

    Energy Technology Data Exchange (ETDEWEB)

    Jayakumar, S., E-mail: sjayakumar.physics@gmail.com [Research and Development Centre, Bharathiar University, Coimbatore 641 014 (India); Department of Physics, Pollachi Institute of Engineering and Technology, Pollachi 642 205 (India); Ananthapadmanabhan, P.V.; Thiyagarajan, T.K. [Laser and Plasma Technology Division, BARC, Trombay, Mumbai 400 085 (India); Perumal, K. [Vision for Wisdom, Temple of Consciousness, Aliyar 642 101 (India); Mishra, S.C. [Department of Metallurgical and Materials Engg, National Institute of Technology, Rourkela 769 008 (India); Suresh, G. [Department of Physics, Park College of Engineering and Technology, Coimbatore 641 659 (India); Su, L.T.; Tok, A.I.Y. [School of Materials Science and Engg, Nanyang Technological University, 50 Nanyang Avenue, Singapore 639 798 (Singapore)

    2013-06-15

    Pure zirconium oxide powders with particle size 2–33 nm are synthesized by reactive plasma processing. Transmission electron microscopy investigation of these particles revealed size dependent behavior for their phase stabilization. The monoclinic phase is found to be stable when particle size is ≥20 nm; Tetragonal is found to be stabilized in the range of 7–20 nm and as the particle size decreases to 6 nm and less, the cubic phase is stabilized. - Highlights: ► Direct conversion of micron-sized zirconium hydride powder to single crystal ZrO{sub 2} nanopowder. ► Size dependent stabilization of cubic, tetragonal and monoclinic phases in the reactive plasma synthesized ZrO{sub 2} nanopowder. ► Transmission electron microscopic investigation to identify particles of different sizes and their corresponding phase structure.

  14. Phase and microstructure morphologies in combustion synthesized Nb-Al-B composites

    International Nuclear Information System (INIS)

    Ho, C.T.; Sekhar, J.A.

    1991-01-01

    In this paper results of an experimental study on unidirectional wave combustion synthesized Nb-Al-B composite alloys are described. The effect of combustion initiation temperature and composition on the microstructural morphology and phases is studied. Correlations with the initial parameters and reaction velocities have been sought to understand the kinetics of the rate controlling step for sustained combustion and for the explanation of the synthesized microstructures. Strategies for controlling the distribution of the reinforcement phases (both ductile and hard) in the composite are discussed

  15. Volatile uranyl hexafluoroacetoacetonate complexes

    International Nuclear Information System (INIS)

    Dines, M.B.; Hall, R.B.; Kaldor, A.; Kramer, G.M.; Maas, E.T. Jr.

    1980-01-01

    A composition of matter is described, characterized by the formula UO 2 (CF 3 COCHCOCF 3 ).L where L is a ligand selected from isopropanol, ethanol, isobutanol, tert-butanol, methanol, tetrahydrofuran, acetone, dimethylformamide, n-propanol and ethyl acetate. A process for producing the complex comprises reacting uranyl chloride with a hexafluoroacetylacetonate dissolved in a ligand L: experimental details are given. (U.K.)

  16. Synthesis of uranyl acetylacetonate free of thorium 234

    Energy Technology Data Exchange (ETDEWEB)

    Garcia-Rendon, R.; Solache R, M.; Tenorio, D. (Instituto Nacional de Investigaciones Nucleares, Mexico City)

    1983-01-01

    A technique is described for synthesizing uranyl acetylacetonate free of thorium-234, and the method utilized in identifying it. The aim in the preparation of the thorium-234 free compound was to study the chemical effects produced by U-238 decay by means of detection only of the thorium-234 decay product.

  17. Spectroscopic characterization of alkaline earth uranyl carbonates

    International Nuclear Information System (INIS)

    Amayri, Samer; Reich, Tobias; Arnold, Thuro; Geipel, Gerhard; Bernhard, Gert

    2005-01-01

    A series of alkaline uranyl carbonates, M[UO 2 (CO 3 ) 3 ].nH 2 O (M=Mg 2 , Ca 2 , Sr 2 , Ba 2 , Na 2 Ca, and CaMg) was synthesized and characterized by inductively coupled plasma mass spectrometry (ICP-MS) and atomic absorption spectrometry (AAS) after nitric acid digestion, X-ray powder diffraction (XRD), and thermal analysis (TGA/DTA). The molecular structure of these compounds was characterized by extended X-ray absorption fine-structure (EXAFS) spectroscopy and X-ray photoelectron spectroscopy (XPS). Crystalline Ba 2 [UO 2 (CO 3 ) 3 ].6H 2 O was obtained for the first time. The EXAFS analysis showed that this compound consists of (UO 2 )(CO 3 ) 3 clusters similar to the other alkaline earth uranyl carbonates. The average U-Ba distance is 3.90+/-0.02A.Fluorescence wavelengths and life times were measured using time-resolved laser-induced fluorescence spectroscopy (TRLFS). The U-O bond distances determined by EXAFS, TRLFS, XPS, and Raman spectroscopy agree within the experimental uncertainties. The spectroscopic signatures observed could be useful for identifying uranyl carbonate species adsorbed on mineral surfaces

  18. Benchmarking uranyl peroxide capsule chemistry in organic media

    International Nuclear Information System (INIS)

    Neal, Harrison A.; Nyman, May; Szymanowski, Jennifer; Fein, Jeremy B.; Burns, Peter C.

    2017-01-01

    Uranyl peroxide capsules are a recent addition to polyoxometalate (POM) chemistry. Ten years of development has ensued only in water, while transition metal POMs are commonly exploited in aqueous and organic media, controlled by counterions or ligation to render the clusters hydrophilic or hydrophobic. Here, new uranyl POM behavior is recognized in organic media, including (1) stabilization and immobilization of encapsulated hydrophilic countercations, identified by Li nuclear magnetic resonance (NMR) spectroscopy, (2) formation of new cluster species upon phase transfer, (3) extraction of uranyl clusters from different starting materials including simulated spent nuclear fuel, (4) selective phase transfer of one cluster type from a mixture, and (5) phase transfer of clusters from both acidic and alkaline media. The capsule morphology of the uranyl POMs renders accurate characterization by X-ray scattering, including the distinction of geometrically similar clusters. Compositional analysis of the aqueous phase post-extraction provided a quantitative determination of the ion exchange process that enables transfer of the clusters into the organic phase. Preferential partitioning of uranyl POMs into organic media presents new frontiers in metal ion behavior and chemical reactions in the confined space of the cluster capsules in hydrophobic media, as well as the reactivity of clusters at the organic/aqueous interface. (copyright 2017 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  19. Benchmarking uranyl peroxide capsule chemistry in organic media

    Energy Technology Data Exchange (ETDEWEB)

    Neal, Harrison A.; Nyman, May [Department of Chemistry, Oregon State University, Corvallis, OR (United States); Szymanowski, Jennifer; Fein, Jeremy B.; Burns, Peter C. [Department of Civil and Environmental Engineering and Earth Sciences, University of Notre Dame, Notre Dame, IN (United States)

    2017-01-03

    Uranyl peroxide capsules are a recent addition to polyoxometalate (POM) chemistry. Ten years of development has ensued only in water, while transition metal POMs are commonly exploited in aqueous and organic media, controlled by counterions or ligation to render the clusters hydrophilic or hydrophobic. Here, new uranyl POM behavior is recognized in organic media, including (1) stabilization and immobilization of encapsulated hydrophilic countercations, identified by Li nuclear magnetic resonance (NMR) spectroscopy, (2) formation of new cluster species upon phase transfer, (3) extraction of uranyl clusters from different starting materials including simulated spent nuclear fuel, (4) selective phase transfer of one cluster type from a mixture, and (5) phase transfer of clusters from both acidic and alkaline media. The capsule morphology of the uranyl POMs renders accurate characterization by X-ray scattering, including the distinction of geometrically similar clusters. Compositional analysis of the aqueous phase post-extraction provided a quantitative determination of the ion exchange process that enables transfer of the clusters into the organic phase. Preferential partitioning of uranyl POMs into organic media presents new frontiers in metal ion behavior and chemical reactions in the confined space of the cluster capsules in hydrophobic media, as well as the reactivity of clusters at the organic/aqueous interface. (copyright 2017 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  20. Thermochemical investigations on uranyl phosphates and arsenates

    International Nuclear Information System (INIS)

    Barten, H.

    1986-01-01

    Results are described of a study of the thermochemical stability of anhydrous phosphates and arsenates. The results of phase studies deal with compound formation and characterization, coexisting phases and limiting physical or chemical properties. The uranyl phosphates evolve oxygen at higher temperatures and the arsenates lose arsenic oxide vapour. These phenomena give the possibility to describe their thermodynamic stabilities. Thus oxygen pressures of uranyl phosphates have been measured using a static, non-isothermal method. Having made available the pure anhydrous compounds in the course of this investigation, molar thermodynamic quantities have been measured as well. These include standard enthalpies of formation from solution calorimetry and high-temperature heat-capacity functions derived from enthalpy increments measured. Some attention is given to compounds with uranium in valencies lower than six which have been met during the investigation. An evaluation is made of the thermodynamics of the compounds studied, to result in tabulized high-temperature thermodynamic functions. Relative stabilities within the systems are discussed and comparisons of the uranyl phosphates and the arsenates are made. (Auth.)

  1. Crystal chemistry of uranyl carboxylate coordination networks obtained in the presence of organic amine molecules

    Energy Technology Data Exchange (ETDEWEB)

    Mihalcea, Ionut; Henry, Natacha; Loiseau, Thierry [Unite de Catalyse et Chimie du Solide (UCCS) - UMR CNRS 8181, Universite de Lille Nord de France, USTL-ENSCL, Villeneuve d' Ascq (France)

    2014-03-15

    Three uranyl isophthalates (1,3-bdc) and two uranyl pyromellitates (btec) of coordination-polymer type were hydrothermally synthesized (200 C for 24 h) in the presence of different amine-based molecules [1,3-diaminopropane (dap) or dimethylamine (dma) originating from the in situ decomposition of N,N-dimethylformamide]. (UO{sub 2}){sub 2}(OH){sub 2}(H{sub 2}O)(1,3-bdc).H{sub 2}O (1) is composed of inorganic tetranuclear cores, which are linked to each other through the isophthalato ligand to generate infinite neutral ribbons, which are intercalated by free H{sub 2}O molecules. The compounds (UO{sub 2}){sub 1.5}(H{sub 2}O)(1,3-bdc){sub 2}.0.5H{sub 2}dap.1.5H{sub 2}O (2) and UO{sub 2}(1,3-bdc){sub 1.5}.0.5H{sub 2}dap.2H{sub 2}O (3) consist of discrete uranyl-centered hexagonal bipyramids connected to each other by a ditopic linker to form a single-layer network for 2 or a double-layer network for 3. The protonated diamine molecules are located between the uranyl-organic sheets and balance the negative charge of the layered sub-networks. The phase (UO{sub 2}){sub 2}O(btec).2Hdma.H{sub 2}O (4) presents a 2D structure built up from tetranuclear units, which consist of two central sevenfold coordinated uranium centers and two peripheral eightfold coordinated uranium centers. The connection of the resulting tetramers through the pyromellitate molecules generates an anionic layerlike structure, in which the protonated dimethylammonium species are inserted. The compound UO{sub 2}(btec).2Hdma (5) is also a lamellar coordination polymer, which contains isolated eightfold coordinated uranium cations linked through pyromellitate molecules and intercalated by protonated dimethylammonium species. In both phases 4 and 5, the btec linker has non-bonded carboxyl oxygen atoms, which preferentially interact with the protonated amine molecules through a hydrogen-bond network. The different illustrations show the structural diversity of uranyl-organic coordination polymers with organic

  2. Probing uranyl(VI) speciation in the presence of amidoxime ligands using electrospray ionization mass spectrometry.

    Science.gov (United States)

    Mustapha, Adetayo M; Pasilis, Sofie P

    2013-10-15

    Extraction processes using poly(acrylamidoxime) resins are being developed to extract uranium from seawater. The main complexing agents in these resins are thought to be 2,6-dihydroxyiminopiperidine (DHIP) and N(1),N(5)-dihydroxypentanediimidamide (DHPD), which form strong complexes with uranyl(VI) at the pH of seawater. It is important to understand uranyl(VI) speciation in the presence of these and similar amidoxime ligands to understand factors affecting uranyl(VI) adsorption to the poly(acrylamidoxime) resins. Experiments were carried out in positive ion mode on a quadrupole ion trap mass spectrometer equipped with an electrospray ionization source. The ligands investigated were DHIP, DHPD, and N(1),N(2)-dihydroxyethanediimidamide (DHED). DHED and DHPD differ only in the number of carbons separating the oxime groups. The effects on the mass spectra of changes in uranyl(VI):ligand ratio, pH, and ligand type were examined. DHIP binds uranyl(VI) more effectively than DHPD or DHED in the pH range investigated, forming ions derived from solution-phase species with uranyl(VI):DHIP stoichiometries of 1:1, 1:2, and 2:3. The 2:3 uranyl(VI):DHIP complex appears to be a previously undescribed solution species. Ions related to uranyl(VI):DHPD complexes were detected in very low abundance. DHED is a more effective complexing agent for uranyl(VI) than DHPD, forming ions having uranyl(VI):DHED stoichiometries of 1:1, 1:2, 1:3, and 2:3. This study presents a first look at the solution chemistry of uranyl(VI)-amidoxime complexes using electrospray ionization mass spectrometry. The appearance of previously undescribed solution species suggests that the uranyl-amidoxime system is a rich and relatively complex one, requiring a more in-depth investigation. Copyright © 2013 John Wiley & Sons, Ltd.

  3. Extraction of uranyl sulfate with tri-n-laurylamine

    International Nuclear Information System (INIS)

    Satrova, J.; Mrnka, M.; Kyrsova, V.

    1976-01-01

    Chemical analyses of the organic phase showed that uranyl sulfate was only extracted by TLA sulfate, forming the complex (TLAH) 4 UO 2 (SO 4 ) 3 .4H 2 O. A decrease in uranyl sulfate extraction occurs at higher concentrations of sulfuric acid in the aqueous phase. This decrease corresponds to the conversion of the normal amine sulfate to hydrosulfate, hence the equilibrium of the reaction 4(R 3 NH.HSO 4 )sub(org.)+(UO 2 SO 4 )sub(aq) reversible [(R 3 NH) 4 UO 2 (SO 4 ) 3 ]sub(org)+2(H 2 SO 4 )sub(aq) is highly shifted to the left side. The presence of octanol in the organic phase does not affect the mechanism of extraction of uranyl sulfate, as evidenced by the IR spectra. (author)

  4. A fully-differential phase-locked loop frequency synthesizer for 60-GHz wireless communication

    International Nuclear Information System (INIS)

    Kuang Lixue; Chi Baoyong; Chen Lei; Wang Zhihua; Jia Wen

    2014-01-01

    A 40-GHz phase-locked loop (PLL) frequency synthesizer for 60-GHz wireless communication applications is presented. The electrical characteristics of the passive components in the VCO and LO buffers are accurately extracted with an electromagnetic simulator HFSS. A differential tuning technique is utilized in the voltage controlled oscillator (VCO) to achieve higher common-mode noise rejection and better phase noise performance. The VCO and the divider chain are powered by a 1.0 V supply while the phase-frequency detector (PFD) and the charge pump (CP) are powered by a 2.5 V supply to improve the linearity. The measurement results show that the total frequency locking range of the frequency synthesizer is from 37 to 41 GHz, and the phase noise from a 40 GHz carrier is −97.2 dBc/Hz at 1 MHz offset. Implemented in 65 nm CMOS, the synthesizer consumes a DC power of 62 mW, including all the buffers. (semiconductor integrated circuits)

  5. A fully-differential phase-locked loop frequency synthesizer for 60-GHz wireless communication

    Science.gov (United States)

    Lixue, Kuang; Baoyong, Chi; Lei, Chen; Wen, Jia; Zhihua, Wang

    2014-12-01

    A 40-GHz phase-locked loop (PLL) frequency synthesizer for 60-GHz wireless communication applications is presented. The electrical characteristics of the passive components in the VCO and LO buffers are accurately extracted with an electromagnetic simulator HFSS. A differential tuning technique is utilized in the voltage controlled oscillator (VCO) to achieve higher common-mode noise rejection and better phase noise performance. The VCO and the divider chain are powered by a 1.0 V supply while the phase-frequency detector (PFD) and the charge pump (CP) are powered by a 2.5 V supply to improve the linearity. The measurement results show that the total frequency locking range of the frequency synthesizer is from 37 to 41 GHz, and the phase noise from a 40 GHz carrier is -97.2 dBc/Hz at 1 MHz offset. Implemented in 65 nm CMOS, the synthesizer consumes a DC power of 62 mW, including all the buffers.

  6. Uranyl sorption onto alumina

    International Nuclear Information System (INIS)

    Jacobsson, A.M.M.

    1997-01-01

    The mechanism for the adsorption of uranyl onto alumina from aqueous solution was studied experimentally and the data were modeled using a triple layer surface complexation model. The experiments were carried out at low uranium concentrations (9 x 10 -11 --5 x 10 -8 M) in a CO 2 free environment at varying electrolyte concentrations (0.01--1 M) and pH (4.5--12). The first and second acid dissociation constants, pK a1 and pK a2 , of the alumina surface were determined from potentiometric titrations to be 7.2 ± 0.6 and 11.2 ± 0.4, respectively. The adsorption of uranium was found to be independent of the electrolyte concentration. The authors therefore conclude that the uranium binds as an inner sphere complex. The results were modeled using the code FITEQL. Two reactions of uranium with the surface were needed to fit the data, one forming a uranyl complex with a single surface hydroxyl and the other forming a bridged or bidentate complex reacting with two surface hydroxyls of the alumina. There was no evidence from these experiments of site heterogeneity. The constants used for the reactions were based in part on predictions made utilizing the Hard Soft Acid Base, HSAB, theory, relating the surface complexation constants to the hydrolysis of the sorbing metal ion and the acid dissociation constants of the mineral oxide surface

  7. Synthesis and physicochemical properties of uranyl molybdate complexes of ammonium, potassium, rubidium, and cesium ions

    International Nuclear Information System (INIS)

    Fedoseev, A.M.; Budantseva, N.A.; Shirokova, I.B.; Yurik, T.K.; Andreev, G.B.; Krupa, Zh-K.

    2001-01-01

    Effect of experimental conditions on composition and intimacy of yield of crystal phases in the UO 2 MoO 4 -M 2 MoO 4 -H 2 O system, where M is cation of alkali metal or ammonium, is studied. The compounds of morphotropic raw with overall formula M 2 UO 2 (MoO 4 ) 2 ·H 2 O, where M=K, Ru, Cs, NH 4 , are synthesized by hydrothermal method from aqueous solutions at 160-180 Deg C. The dependence of composition and certain physico-chemical properties of the binary uranyl molybdates is investigated from the nature of out-spherical cation as well as IR-spectra and thermal behavior of synthesized compounds are inspected [ru

  8. Thermal decomposition of dinitratobis(carbamido) uranyl

    International Nuclear Information System (INIS)

    Kobets, L.V.; Kostyukov, N.N.; Umrejko, D.S.

    1987-01-01

    Thermal stability of dinitratobis (carbamido) uranyl was investigated by the methods of DTA, TG and isothermal heatings at different temperatures. It was revealed that urea as a whole was not removed from the complex. Urea loses ammonia simultaneously with substance melting (498K); biuret and cyanuric acid form at that. Ammonia removal to gaseous phase decelerates in 573-593 K range due to its binding with formation of amination products. Decomposition of nitrate groups begins at temperatures above 570 K. Heating products were studied by the methods of vibrational spectroscopy, chemical and X-ray phase analyses. Ideas about mechanism of decomposition were considered

  9. Syntheses of Two Vanadium Oxide–Fluoride Materials That Differ in Phase Matchability

    Science.gov (United States)

    2015-01-01

    The syntheses of two noncentrosymmetric (NCS) vanadium oxide–fluoride compounds that originate from the same synthetic reagent concentrations are presented. Hydrothermal and low-temperature syntheses allow the isolation of metastable products that may form new phases (or decompose) upon heating and allow creation of chemically similar but structurally different materials. NCS materials synthesis has been a long-standing goal in inorganic chemistry: in this article, we compare two chemically similar NCS inorganic materials, NaVOF4(H2O) (I) and NaVO2–xF2+x (II; x = 1/3). These materials originate from the same, identical reagent mixtures but are synthesized at different temperatures: 100 °C and 150 °C, respectively. Compound I crystallizes in Pna21: a = 9.9595(4) Å, b = 9.4423(3) Å, and c = 4.8186(2) Å. Compound II crystallizes in P21: a = 6.3742(3) Å, b = 3.5963(2) Å, c = 14.3641(7) Å, and β = 110.787(3)°. Both materials display second-harmonic-generation activity; however, compound I is type 1 non-phase-matchable, whereas compound II is type 1 phase-matchable. PMID:25137441

  10. Amorphous phase formation in intermetallic Mg2Ni alloy synthesized by ethanol wet milling

    International Nuclear Information System (INIS)

    Wang, H.-W.; Chyou, S.-D.; Wang, S.-H.; Yang, M.-W.; Hsu, C.-Y.; Tien, H.-C.; Huang, N.-N.

    2009-01-01

    The hydriding/dehydriding properties of an intermetallic Mg 2 Ni alloy synthesized by wet ball milling in ethanol have been investigated. The appearance of the particle surface after different milling methods is one obvious difference. The alloyed powders prepared by either dry milling or wet milling under ethanol were characterized for phase content by X-ray diffractometer (XRD). The results show that two broad diffuse peaks, which are an ionic-organic-Mg amorphous material, appear in addition to the nickel element peaks. This unexpected amorphous phase has the special hydrogen absorbing/desorbing features.

  11. Phase controlled synthesis and cathodoluminescence properties of ZnS nanobelts synthesized by PVD

    Science.gov (United States)

    Jin, Changqing; Zhu, Kexin; Peterson, George; Zhang, Zhihong; Jian, Zengyun; Wei, Yongxing; Zheng, Deshan

    2018-01-01

    Zinc sulfide (ZnS) nanobelts were synthesized via physical vapor deposition to explore the electronic properties of optoelectronic nano-devices. It was determined that the mass ratio of wurtzite (WZ) phase to zincblende (ZB) phase and the preferential orientation (100) are related to the carrier-gas flow rate. The high concentration of planar defects within the phase boundary enhances phase transition. Cathodoluminescence measurements show a red shift of the 337 nm band-gap emission due to stacking and twin faults. We find a direct correlation between the magnitude of the red shift and the mass ratio of ZB phase. With an increase in the ZB phase, there is an increase in the concentration of stacking and twin faults introduced by the phase transformation, as indicated by an increasing red shift in the data. The absorption peaks at 666 and 719 nm were found by UV-vis absorption spectrum, which is attributed to surface defects. This work would help to better understand the important roles of planar defects in the phase transition and also provide us with a feasible route to control phase ratio and cathodoluminescence properties of ZnS nanobelts and other II-VI semiconductor nanostructures.

  12. Comparative study of nanocarbons synthesized between electrodes in liquid phase by solution plasma

    Science.gov (United States)

    Lee, Hoonseung; Wada, Yuta; Kaneko, Amane; Lun Li, Oi; Ishizaki, Takahiro

    2018-01-01

    For several decades, the development of synthesis processes and designs for carbon materials such as graphites, carbon nanotubes, and graphenes has been continuous because of their superior physicochemical properties. The liquid-phase electric discharge process, known as the solution plasma process (SPP), has emerged as a potential synthesis process for carbon materials; however, liquid discharge in organic solutions has not yet been thoroughly investigated. In this study, plasma discharges in benzene (C6H6) and pyridine (C5H5N) were conducted. During the discharge, two types of nanocarbons with different crystallinities were synthesized simultaneously in different reaction fields: between electrodes and in a liquid phase. The nanocarbons grown between electrodes were collected and then compared with the nanocarbons produced in the liquid phase after discharge. All carbon samples were measured using various techniques such as transmission electron microscopy (TEM), the nitrogen absorption–desorption method, X-ray diffraction (XRD), Raman spectroscopy, CHN elemental analysis, and X-ray photoelectron spectroscopy (XPS). Nanocarbons grown between electrodes in benzene or pyridine were found to be graphite structures, while the nanocarbons produced in the liquid phase were amorphous carbons. On the basis of the results obtained, the formation and growth of the two types of nanocarbon materials synthesized by SPP and their dependence on the position of the reaction field in plasma in the liquid phase are discussed.

  13. Self-assembly of uranyl-peroxide nanocapsules in basic peroxidic environments

    Energy Technology Data Exchange (ETDEWEB)

    Miro, Pere; Vlaisavljevich, Bess [Department of Chemistry, Supercomputing Institute, and Chemical Theory Center, University of Minnesota, Minneapolis, MN (United States); Gil, Adria [Institute of Chemical Research of Catalonia (ICIQ), The Barcelona Institute of Science and Technology, Tarragona (Spain); Burns, Peter C. [Department of Civil Engineering and Geological Sciences, University of Notre Dame, South Bend, IN (United States); Nyman, May [Materials Science of Actinides, Department of Chemistry, Oregon State University, Corvallis, OR (United States); Bo, Carles [Institute of Chemical Research of Catalonia (ICIQ), The Barcelona Institute of Science and Technology, Tarragona (Spain); Departament de Quimica Fisica i Inorganica, Universitat Rovira i Virgili, Campus Sescelades, Tarragona (Spain)

    2016-06-13

    A wide range of uranyl-peroxide nanocapsules have been synthesized using very simple reactants in basic media; however, little is known about the process to form these species. We have performed a density functional theory study of the speciation of the uranyl ions under different experimental conditions and explored the formation of dimeric species via a ligand exchange mechanism. We shed some light onto the importance of the excess of peroxide and alkali counterions as a thermodynamic driving force towards the formation of larger uranyl-peroxide species. (copyright 2016 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  14. Surface complexation model of uranyl sorption on Georgia kaolinite

    Science.gov (United States)

    Payne, T.E.; Davis, J.A.; Lumpkin, G.R.; Chisari, R.; Waite, T.D.

    2004-01-01

    The adsorption of uranyl on standard Georgia kaolinites (KGa-1 and KGa-1B) was studied as a function of pH (3-10), total U (1 and 10 ??mol/l), and mass loading of clay (4 and 40 g/l). The uptake of uranyl in air-equilibrated systems increased with pH and reached a maximum in the near-neutral pH range. At higher pH values, the sorption decreased due to the presence of aqueous uranyl carbonate complexes. One kaolinite sample was examined after the uranyl uptake experiments by transmission electron microscopy (TEM), using energy dispersive X-ray spectroscopy (EDS) to determine the U content. It was found that uranium was preferentially adsorbed by Ti-rich impurity phases (predominantly anatase), which are present in the kaolinite samples. Uranyl sorption on the Georgia kaolinites was simulated with U sorption reactions on both titanol and aluminol sites, using a simple non-electrostatic surface complexation model (SCM). The relative amounts of U-binding >TiOH and >AlOH sites were estimated from the TEM/EDS results. A ternary uranyl carbonate complex on the titanol site improved the fit to the experimental data in the higher pH range. The final model contained only three optimised log K values, and was able to simulate adsorption data across a wide range of experimental conditions. The >TiOH (anatase) sites appear to play an important role in retaining U at low uranyl concentrations. As kaolinite often contains trace TiO2, its presence may need to be taken into account when modelling the results of sorption experiments with radionuclides or trace metals on kaolinite. ?? 2004 Elsevier B.V. All rights reserved.

  15. Synthesis and characterization of heterometallic uranyl pyridinedicarboxylate compounds

    Science.gov (United States)

    Jayasinghe, Ashini S.; Payne, Maurice K.; Forbes, Tori Z.

    2017-10-01

    The incorporation of transition metals into hybrid uranyl materials can result in more diverse structural topologies and variations in physical and chemical properties. To explore the impact of transition metals on the uranyl cation, five uranium containing bimetallic chain compounds, [(UO2)M(PDC)2(H2O)4]·4(H2O) (PDC = 2,6 pyridinedicarboxylate; M = Ni2+, Co2+, Fe2+, Zn2+, and Cu2+) were synthesized by evaporation of aqueous solutions at room temperature. The uranyl cation is complex by two PDC ligands and the transition metal cations bond to the complex to form a one-dimensional chain topology. The presence of the transition metal leads to the presence of a stronger uranyl oxo bonds as shown by the single-crystal X-ray diffraction data and the Raman spectra. Solid state diffuse reflectance UV/Visible spectra confirmed the presence of the transition metals in the structure by the broad bands that appeared at relevant wavelengths.

  16. Direct investigations of the immobilization of radionuclides in the alteration phases of spent nuclear fuel. 1998 annual progress report

    International Nuclear Information System (INIS)

    Burns, P.C.; Finch, R.J.

    1998-01-01

    'In an oxidizing environment, such as in the proposed repository at Yucca Mountain, rapid alteration rates are expected for spent nuclear fuel. Lab.-scale simulations have repeatedly shown that the dominant alteration products under repository conditions will be uranyl phases. There is an inadequate database that relates to the effects of the alteration products on the release of radionuclides, but this information is essential to provide a radionuclide release estimate. It is likely that many of the radionuclides contained in the fuel will be incorporated into the alteration products that form, potentially with a profound impact on the future mobility of radionuclides in the repository. The authors objective is to characterize the incorporation of radionuclides into alteration products by synthesis of uranyl phases doped with radionuclides, appropriate surrogate elements, or non-radioactive isotopes, followed by detailed phase characterization by diffraction and spectroscopic techniques. The research will permit a more realistic estimate of the release rates of the radionuclides from the near-field environment. This report summarizes work after 8 months of a 3-year project. The objective of investigating radionuclide incorporation in uranyl phases has required the development of synthesis techniques for various uranyl phases that are expected to form under repository conditions. The authors have synthesized and determined the structures of several uranyl phases that are new to science and that may be important alteration products under repository conditions. They have also undertaken the determination and refinement of the crystal structures of various uranyl phases that are likely to form under repository conditions. Other experiments include the investigation of the ion-exchange properties of uranyl phases under repository conditions.'

  17. EXAFS Phase Retrieval Solution Tracking for Complex Multi-Component System: Synthesized Topological Inverse Computation

    International Nuclear Information System (INIS)

    Lee, Jay Min; Yang, Dong-Seok; Bunker, Grant B

    2013-01-01

    Using the FEFF kernel A(k,r), we describe the inverse computation from χ(k)-data to g(r)-solution in terms of a singularity regularization method based on complete Bayesian statistics process. In this work, we topologically decompose the system-matched invariant projection operators into two distinct types, (A + AA + A) and (AA + AA + ), and achieved Synthesized Topological Inversion Computation (STIC), by employing a 12-operator-closed-loop emulator of the symplectic transformation. This leads to a numerically self-consistent solution as the optimal near-singular regularization parameters are sought, dramatically suppressing instability problems connected with finite precision arithmetic in ill-posed systems. By statistically correlating a pair of measured data, it was feasible to compute an optimal EXAFS phase retrieval solution expressed in terms of the complex-valued χ(k), and this approach was successfully used to determine the optimal g(r) for a complex multi-component system.

  18. Detailed investigation of proposed gas-phase syntheses of ammonia in dense interstellar clouds

    International Nuclear Information System (INIS)

    Herbst, E.; Defrees, D.J.; Mclean, A.D.; Molecular Research Institute, Palo Alto, CA; IBM Almaden Research Center, San Jose, CA)

    1987-01-01

    The initial reactions of the Herbst and Klemperer (1973) and the Dalgarno (1974) schemes (I and II, respectively) for the gas-phase synthesis of ammonia in dense interstellar clouds were investigated. The rate of the slightly endothermic reaction between N(+) and H2 to yield NH(+) and H (scheme I) under interstellar conditions was reinvestigated under thermal and nonthermal conditions based on laboratory data. It was found that the relative importance of this reaction in synthesizing ammonia is determined by how the laboratory data at low temperature are interpreted. On the other hand, the exothermic reaction between N and H3(+) to form NH2(+) + H (scheme II) was calculated to possess significant activation energy and, therefore, to have a negligible rate coefficient under interstellar conditions. Consequently, this reaction cannot take place appreciably in interstellar clouds. 41 references

  19. Nanographene synthesized in triple-phase plasmas as a highly durable support of catalysts for polymer electrolyte fuel cells

    Science.gov (United States)

    Amano, Tomoki; Kondo, Hiroki; Takeda, Keigo; Ishikawa, Kenji; Hiramatsu, Mineo; Sekine, Makoto; Hori, Masaru

    2018-04-01

    Nanographene was synthesized in triple-phase plasmas comprising a gaseous phase, a gas-liquid boundary layer, and an in-liquid phase using a setup in which one electrode was placed in the gaseous phase while the other was immersed in the liquid phase. The triple-phase plasmas were generated using a pure alcohol, such as ethanol, 1-propanol, or 1-butanol, by applying a high voltage to a pair of electrodes made of copper or graphite. The nanographene synthesized using ethanol had high durability and thus could serve as a catalyst support in polymer electrolyte fuel cells (PEFCs). The PEFCs exhibited low degradation rates in the high-potential cycle test of a half-cell, as a result of which, a loss of only 10% was observed in the effective electrochemical surface area of Pt, even after 10,000 cycles.

  20. Uranyl fluoride luminescence in acidic aqueous solutions

    International Nuclear Information System (INIS)

    Beitz, J.V.; Williams, C.W.

    1996-01-01

    Luminescence emission spectra and decay rates are reported for uranyl species in acidic aqueous solutions containing HF or added NaF. The longest luminescence lifetime, 0.269 ± 0.006 ms, was observed from uranyl in 1 M HF + 1 M HClO 4 at 296 K and decreased with increasing temperature. Based on a luminescence dynamics model that assumes equilibrium among electronically excited uranyl fluoride species and free fluoride ion, this long lived uranyl luminescence in aqueous solution is attributed primarily to UO 2 F 2 . Studies on the effect of added LiNO 3 or Na 2 WO 4 ·2H 2 O showed relatively weak quenching of uranyl fluoride luminescence which suggests that high sensitivity determination of the UF 6 content of WF 6 gas should be feasible via uranyl luminescence analysis of hydrolyzed gas samples of impure WF 6

  1. Uranyl butyrate complexes with divalent cations

    International Nuclear Information System (INIS)

    Rojas, R.M.; Gonzalez, V.; Bermudez, J.; De Paz, M.L.

    1977-01-01

    Mixed uranium(VI) oxides with magnesium or manganese have been extensively studied. From the solid state reactions between uranium(VI) oxide and magnesium or manganese oxides, two different types of compound have been identified, MUO 4 and MU 3 O 10 , (M = Mg,Mn) and their crystallographic properties determinated. The formation of cubic magnesium uranate Mg, Usub(1-y)Osub(2+x) has also been reported and a similar phase for the manganese uranium oxide, MnU 2 O 6 , with a fluorite type structure has been described. In the present paper, the synthesis and thermal behaviour of two new uranyl butyrate complexes with magnesium and manganese are described. Taking into account the U/M ratio in these complexes, the processes of thermal decomposition have been investigated in detail. (author)

  2. Synthesis and characterization of solid complexes of thorium, uranyl perchlorates with bis-quinolylmethylene

    International Nuclear Information System (INIS)

    He Liangyou; Tang Ning; Gan Xinmin; Tan Minyu

    1990-01-01

    The solid complexes of thorium, uranyl perchlorates with bis-quinolylmethylene (Biqm) having the composition Th(Biqm) 5 (ClO 4 ) 4 , UO 2 (Biqm) 2 (ClO 4 ) 2 have been synthesized in nonaqueous solvents. These two complexes have been characterized by elemental analysis, IR and UV spectra, differential thermal analysis (DTA) and thermogravimetry (TG), fluorescence spectra and molar conductances

  3. Adsorption of an Uranyl Carbonate Complex onto an Amidoxime Resin

    Energy Technology Data Exchange (ETDEWEB)

    Joe, Kih-Soo; Lee, Eil-Hee; Kim, Kwang-Wook; Jung, Euo-Chang; Jee, Kwang-Yong [Korea Atomic Energy Research Institute, Daejeon (Korea, Republic of)

    2007-10-15

    Uranium is a major element in the management of spent nuclear fuel or radioactive waste. Uranium is also present in sea water at a trace level ({approx}3ppb). Usually, an acid medium in a solvent extraction or ion exchange system have been used for the separation of uranium from a radioactive waste solution. Especially, some adsorbants containing amidoxime functional groups selective for the uranyl ion have been developed for the recovery of uranium in sea water. An amidoxime resin as an anion exchanger synthesized using divinylbenzene copolymer as a supporting material was applied for the separation of uranium and plutonium from simulated fission products in carbonate solution by making an uranyl tricarbonate complex, UO{sub 2}(CO{sub 3}){sub 3}{sup 4-}, in an alkaline solution of a carbonate (pH>8). A carbonate leaching of uranium from uranium contaminated soils was also successfully performed using a sodium carbonate and a sodium bicarbonate solution. In this work, the distribution coefficients of uranyl ions were measured for the amidoxime resins with a variation of carbonate concentration and the pH of the solutions as a preliminary work for a spent fuel treatment with a strong alkaline carbonate solution because this system has an advantage to reduce a high level waste volume by a selective oxidation and an adsorption of uranium from spent fuels.

  4. Phase formation study of noble metal (Au, Ag and Pd) doped lanthanum perovskites synthesized by hydrothermal method

    Energy Technology Data Exchange (ETDEWEB)

    Nikam, Shrikant K. [Department of Chemistry, Savitribai Phule Pune University, Pune 411007 (India); Anantrao Thopte College, Bhor, Pune 412206 (India); Athawale, Anjali A., E-mail: agbed@chem.unipune.ac.in [Department of Chemistry, Savitribai Phule Pune University, Pune 411007 (India)

    2015-04-01

    Noble metal (Au, Ag and Pd) doped Lanthanum perovskites (LaMnO{sub 3}, LaCrO{sub 3} and LaFeO{sub 3}) have been synthesized by hydrothermal method. The effect of dopant and their concentration on the phase purity, crystallite size, morphology and magnetic character of the synthesized perovskites were systematically studied by FTIR spectroscopy, XRD, TGA, SEM, ICP-AES and VSM. The results show that phase pure products were obtained only after calcining the hydrothermally synthesized products above 760 °C for a minimum of 6 h. Nature and concentration of the dopant plays an important role in determining the phase formation temperature, morphology and magnetic character. The dopant ion preferentially occupies A-site and homogeneous phase of product is obtained upto a dopant concentration of 4%, higher concentration results in phase separation. The products exhibit spherical morphology. Lanthanum ferrite shows ferromagnetic nature, while the doped samples show weak magnetic properties. - Highlights: • Hydrothermal synthesis of noble metal doped lanthanum perovskites. • Site preference of noble metal (Au, Ag and Pd) doping in LaBO{sub 3} (B = Mn, Cr and Fe). • Dopant ions affect the phase formation temperature and morphology the perovskites. • 4% appears to be the maximum limit of doping at A-site.

  5. EXPERIMENTAL AND SIMULATION ANALYSIS OF BREAKLOCK IN PHASE LOCKED LOOP SYNTHESIZER FOR FREQUENCY TRACKING APPLICATIONS

    Directory of Open Access Journals (Sweden)

    HARIKRISHNA PAIK

    2017-02-01

    Full Text Available Modern missile seekers invariably employ monopulse radar with phase locked loop (PLL as a frequency (angle tracking subsystem in the receiver. The frequency locking and/or unlocking of these receivers can be achieved either by introducing imperfections in the monopulse design or using multiple repeater sources. In the present paper, the break-lock of PLL synthesizer in the monopulse radar receiver is presented. The linear frequency modulated (LFM signal has been used as a repeater interference signal, which is injected into the PLL along with radar echo signal. The frequency deviation as a function of LFM signal power required to break-lock is presented for different values of modulation rate and echo signal power. The simulation results show that breaklock is achieved at frequency deviation of 0.36 MHz (0.35 MHz measured value for a typical jammer power of -14 dBm and modulation rate of 200 kHz with radar echo signal power of -14 dBm at the PLL input. The measured results show that at a typical jammer power of -14 dBm, break-lock is achieved at frequency deviations of 0.35 and 0.9 MHz for modulation rates of 200 and 500 kHz respectively, revealing that at lower values of modulation rate, breaklock is achieved at lower values of frequency deviation. The computer simulation is carried out for performance prediction and experimental measurement results are presented in support of the simulated results. With fairly good and consistent agreement between the measured and simulated results, the PLL is well suited to be integrated within monopulse radar receivers for LFM jamming.

  6. Room-temperature saturated ferroelectric polarization in BiFeO3 ceramics synthesized by rapid liquid phase sintering

    International Nuclear Information System (INIS)

    Wang, Y.P.; Zhou, L.; Zhang, M.F.; Chen, X.Y.; Liu, J.-M.; Liu, Z.G.

    2004-01-01

    Single-phased ferroelectromagnet BiFeO 3 ceramics with high resistivity were synthesized by a rapid liquid phase sintering technique. Saturated ferroelectric hysteresis loops were observed at room temperature in the ceramics sintered at 880 deg. C for 450 s. The spontaneous polarization, remnant polarization, and the coercive field are 8.9 μC/cm 2 , 4.0 μC/cm 2 , and 39 kV/cm, respectively, under an applied field of 100 kV/cm. It is proposed that the formation of Fe 2+ and an oxygen deficiency leading to the higher leakage can be greatly suppressed by the very high heating rate, short sintering period, and liquid phase sintering technique. The latter was also found effective in increasing the density of the ceramics. The sintering technique developed in this work is expected to be useful in synthesizing other ceramics from multivalent or volatile starting materials

  7. Investigation of uranyl nitrate complexes with trialkylphosphine oxides

    International Nuclear Information System (INIS)

    Kobets, L.V.; Kopashova, I.M.; Dik, T.A.; Volodin, I.A.; Kovalenko, M.A.; Semenij, V.Ya.

    1982-01-01

    Using the methods of vibrational spectroscopy and thermal analysis a number of uranyl complexes with trialkylphosphine oxides of the general formula UO 2 (NO 3 ) 2 x2R 3 PO, where R-C 2 H 5 -C 10 H 21 have been studied. Infrared and Raman spectra are interpreted according to vibration types. Comparison of vibrational spectra of the complexes in solid phase and solutions of organic solvents permitted to find the differences in position and amount of acids responsible for complexing. It is detected that in the series of complexes investigated the strength of uranyl bond with phosphoryl group oxygen practically remains stable, whereas degree of covalence of nitrate groups is observed. The pointed out peculiarities are interpreted proceeding from the presence of bridge nitrate groups in the structure of the complexes. Thermal stability of the complexes is studied, chemism of their decomposition being suggested

  8. Balanced Photodetection in One-Step Liquid-Phase-Synthesized CsPbBr3 Micro-/Nanoflake Single Crystals.

    Science.gov (United States)

    Zheng, Wei; Xiong, Xufan; Lin, Richeng; Zhang, Zhaojun; Xu, Cunhua; Huang, Feng

    2018-01-17

    Here, we reported a low-cost and high-compatibility one-step liquid-phase synthesis method for synthesizing high-purity CsPbBr 3 micro-/nanoflake single crystals. On the basis of the high-purity CsPbBr 3 , we further prepared a low-dimensional photodetector capable of balanced photodetection, involving both high external quantum efficiency and rapid temporal response, which is barely realized in previously reported low-dimensional photodetectors.

  9. Morphology and phase transformations of tin oxide nanostructures synthesized by the hydrothermal method in the presence of dicarboxylic acids

    Energy Technology Data Exchange (ETDEWEB)

    Zima, Tatyana, E-mail: zima@solid.nsc.ru [Institute of Solid State Chemistry and Mechanochemistry SB RAS, 18 Kutateladze, Novosibirsk 630128 (Russian Federation); Novosibirsk State Technical University, 20 K. Marx Prospect, Novosibirsk 630092 (Russian Federation); Bataev, Ivan [Novosibirsk State Technical University, 20 K. Marx Prospect, Novosibirsk 630092 (Russian Federation)

    2016-11-15

    A new approach to the synthesis of non-stoichiometric tin oxide structures with different morphologies and the phase compositions has been evaluated. The nanostructures were synthesized by hydrothermal treatment of the mixtures of dicarboxylic acids ― aminoterephthalic or oxalic ― with nanocrystalline SnO{sub 2} powder, which was obtained via the sol-gel technology. The products were characterized by Raman and IR spectroscopy, SEM, HRTEM, and XRD analysis. It was shown that the controlled addition of a dicarboxylic acid leads not only to a change in the morphology of the nanostructures, but also to SnO{sub 2}–SnO{sub 2}/Sn{sub 3}O{sub 4}–Sn{sub 3}O{sub 4}–SnO phase transformations. A single-phase Sn{sub 3}O{sub 4} in the form of the well-separated hexagonal nanoplates and mixed SnO{sub 2}/Sn{sub 3}O{sub 4} phases in the form of hierarchical flower-like structures were obtained in the presence of organic additives. The effects of concentration, redox activity of the acids and heat treatment on the basic characteristics of the synthesized tin oxide nanostructures and phase transformations in the synthesized materials are discussed. - Graphical abstract: The controlled addition of aminoterephthalic or oxalic acid leads not only to a change in the morphology of the nanostructures, but also to SnO{sub 2}–SnO{sub 2}/Sn{sub 3}O{sub 4}–Sn{sub 3}O{sub 4}–SnO phase transformations. - Highlights: • A new approach to the synthesis of non-stoichiometric tin oxide structures is studied. • Tin oxide structures are synthesized via hydrothermal method with dicarboxylic acids. • Morphology and phase composition are changed with redox activity and dosage of acid. • The redox activity of acid has an effect on ratio of SnO and SnO{sub 2} in crystal structure. • A pure phase Sn{sub 3}O{sub 4} nanoplates and SnO{sub 2}/Sn{sub 3}O{sub 4} hierarchical structures are formed.

  10. Electrochemical behavior of uranyl in anhydrous polar organic media

    Energy Technology Data Exchange (ETDEWEB)

    Burn, Adam G.; Nash, Kenneth L. [Washington State Univ., Pullmann, WA (United States). Dept. of Chemistry

    2017-09-01

    Weak complexes between pentavalent and hexavalent actinyl cations have been reported to exist in acidic, non-complexing high ionic strength aqueous media. Such ''cation-cation complexes'' were first identified in the context of actinide-actinide redox reactions in acidic aqueous media relevant to solvent extraction-based separation systems, hence their characterization is of potential interest for advanced nuclear fuel reprocessing. This chemistry could be relevant to efforts to develop advanced actinide separations based on the upper oxidation states of americium, which are of current interest. In the present study, the chemical behavior of pentavalent uranyl was examined in non-aqueous, aprotic polar organic solvents (propylene carbonate and acetonitrile) to determine whether UO{sub 2}{sup +} cations generated at the reducing working electrode surface would interact with the UO{sub 2}{sup 2+} cations in the bulk phase to form cation-cation complexes in such media. In magnesium perchlorate media, the electrolyte adsorbed onto the working electrode surface and interfered with the uranyl reduction/diffusion process through an ECE (electron transfer/chemical reaction/electron transfer) mechanism. In parallel studies of uranyl redox behavior in tetrabutylammonium hexafluorophosphate solutions, an EC (electron transfer/chemical reaction) mechanism was observed in the cyclic voltammograms. Ultimately, no conclusive electrochemical evidence demonstrated uranyl cation-cation interactions in the non-aqueous, aprotic polar organic solvent solutions, though the results reported do not completely rule out the presence of UO{sub 2}{sup +}.UO{sub 2}{sup 2+} complexes.

  11. Mesomorphic phase behaviour of low molar mass PEP-PDMS diblock copolymers synthesized by anionic polymerization

    International Nuclear Information System (INIS)

    Vigild, M.E.

    1997-10-01

    The phase behaviour of low molar mass poly(ethylene-alt-propylene) -poly(dimethylsiloxane) (PEP-PDMS) is investigated in this thesis by the combination of dynamical mechanical spectroscopy (rheology) to measure phase transition temperatures, and small-angle x-ray scattering to identify the morphology of encountered phases. Samples of PEP-PDMS in the range of 0.2-0.7 in volume fraction of PEP are studied. This diblock copolymer system exhibits the three classical phases of lamellar sandwich structure (LAM), hexagonally packed cylinders (HEX), and spheres arranged on a body centered cubic lattice (BCC). Furthermore the gyroid phase (Ia3d symmetry) of two interpenetrating networks was also identified as a stable phase of the PEP-PDMS system. Time resolved measurements of small-angle neutron scattering in tandem with simultaneous in-situ rheological measurements are performed on samples showing transitions between different ordered phases. The identification of especially the BCC and gyroid phases from scattering experiments is treated. By performing mesoscopic crystallographic measurements using a custom built goniometer it was unambiguously shown that the application of shear to an unoriented powder-like sample introduces uniaxial orientation of the gyroid phase. The orientation of the ordered phase is otherwise random, causing a two-dimensional powder. Finally this dissertation presents a discussion of relevant parameters for the description of diblock copolymer phase behaviour together with descriptions of anionic polymerization for the synthesis of copolymers, and various experimental techniques for the characterization of diblocks. (au)

  12. A microscopic study of the action of uranyl acetate on the erythrocyte at varying molarity and toxicity

    International Nuclear Information System (INIS)

    Wyatt, J.H.

    1977-03-01

    Phase contrast and dark field microphotographs were made to record variation of the shape and size changes seen when human erythrocytes are exposed in a number of ways to uranyl acetate in vitro. The degree of hemolysis produced by varying the toxicity of the uranyl acetate solutions was measured, and the results are discussed with particular reference to the possible influence of pH. (author)

  13. Design and Characterization of a 5.2 GHz/2.4 GHz Fractional- Frequency Synthesizer for Low-Phase Noise Performance

    Directory of Open Access Journals (Sweden)

    Dai Foster F

    2006-01-01

    Full Text Available This paper presents a complete noise analysis of a -based fractional- phase-locked loop (PLL based frequency synthesizer. Rigorous analytical and empirical formulas have been given to model various phase noise sources and spurious components and to predict their impact on the overall synthesizer noise performance. These formulas have been applied to an integrated multiband WLAN frequency synthesizer RFIC to demonstrate noise minimization through judicious choice of loop parameters. Finally, predicted and measured phase jitter showed good agreement. For an LO frequency of 4.3 GHz, predicted and measured phase noise was rms and rms, respectively.

  14. Electrospray ionization mass spectrometric studies on uranyl complex with α-hydroxyisobutyric acid in water-methanol medium.

    Science.gov (United States)

    Jaison, P G; Kumar, Pranaw; Telmore, Vijay M; Aggarwal, Suresh K

    2013-05-30

    Hydroxycarboxylic acids are extensively used as chelating agents in the liquid chromatographic separation of actinides and lanthanides. They are also used as model compounds to understand the binding characteristics of humic substances. A systematic study of the speciation of uranyl-α-hyydroxyisobutyric acid (HIBA) in water-methanol is essential, as it is important to understand the various mechanisms responsible for the separation of these species in liquid chromatography. ESI-MS studies were carried out using a tandem quadrupole-time-of-flight mass spectrometer in positive and negative ion mode. The effects of solution composition, solute concentration and supporting electrolyte concentration on the ESI-MS behavior of the uranyl species were studied. Transmission parameters such as the quadrupole ion energy and collision cell energy were optimized for acquiring the spectra of uranyl-HIBA species, ensuring that the spectra reflect the solution equilibrium conditions. The solution composition and concentration of the uranyl salt were found to influence the major uncomplexed uranyl species. Although the ESI parameters did not influence the species distribution of uranyl-HIBA, the transmission parameters did have a significant effect. The overall trend in the complexation reaction between uranyl and HIBA was studied as a function of ligand-to-metal ratio. The species distribution obtained in positive ion mode was similar to that obtained in negative ion mode. The study presents the optimization of the mobile phase conditions and the ESI-MS parameters for the speciation of the uranyl-HIBA system. The methodology was applied to obtaining the distribution of complexed and uncomplexed uranyl species for monitoring the trend in the complexation reaction. Copyright © 2013 John Wiley & Sons, Ltd.

  15. Mesomorphic phase behaviour of low molar mass PEP-PDMS diblock copolymers synthesized by anionic polymerization

    Energy Technology Data Exchange (ETDEWEB)

    Vigild, M.E.

    1997-10-01

    The phase behaviour of low molar mass poly(ethylene-alt-propylene) -poly(dimethylsiloxane) (PEP-PDMS) is investigated in this thesis by the combination of dynamical mechanical spectroscopy (rheology) to measure phase transition temperatures, and small-angle x-ray scattering to identify the morphology of encountered phases. Samples of PEP-PDMS in the range of 0.2-0.7 in volume fraction of PEP are studied. This diblock copolymer system exhibits the three classical phases of lamellar sandwich structure (LAM), hexagonally packed cylinders (HEX), and spheres arranged on a body centered cubic lattice (BCC). Furthermore the gyroid phase (Ia3d symmetry) of two interpenetrating networks was also identified as a stable phase of the PEP-PDMS system. Time resolved measurements of small-angle neutron scattering in tandem with simultaneous in-situ rheological measurements are performed on samples showing transitions between different ordered phases. The identification of especially the BCC and gyroid phases from scattering experiments is treated. By performing mesoscopic crystallographic measurements using a custom built goniometer it was unambiguously shown that the application of shear to an unoriented powder-like sample introduces uniaxial orientation of the gyroid phase. The orientation of the ordered phase is otherwise random, causing a two-dimensional powder. Finally this dissertation presents a discussion of relevant parameters for the description of diblock copolymer phase behaviour together with descriptions of anionic polymerization for the synthesis of copolymers, and various experimental techniques for the characterization of diblocks. (au). 9 tabs., 40 ills., 81 refs.

  16. Thermolysis of urea complexes of uranyl nitrate

    International Nuclear Information System (INIS)

    Kostyuk, N. N.

    2005-01-01

    Quantitative parameters of thermolysis of uranyl nitrate urea complexes, [UO 2 (NO 3 ) 2 {(NH 2 ) 2 CO} 2 ], [UO 2 (H 2 O){(NH 2 ) 2 CO} 4 ](NO 3 ) 2 , and [UO 2 (H 2 O){(NH 2 ) 2 CO} 5 ](NO 3 ) 2 at 175, 200, and 225 deg C were measured. Thermolysis of [UO 2 (NO 3 ) 2 {(NH 2 ) 2 CO} 2 ] at 200 deg C affords the biuret complex of uranyl nitrate in a 90% yield. The urea ligands in the hydrated complexes completely transform into biuret at 175 deg C. Thermolysis of [UO 2 (H 2 O){(NH 2 ) 2 CO} 5 ](NO 3 ) 2 yields the biuret-cyanurate complexes of uranyl nitrate. The features of thermolysis of the uranyl nitrate complexes originate from the chemical transformations of urea at elevated temperatures [ru

  17. Phase transformations of high-purity PbI{sub 2} nanoparticles synthesized from lead-acid accumulator anodes

    Energy Technology Data Exchange (ETDEWEB)

    Malevu, T.D., E-mail: malevutd@ufs.ac.za; Ocaya, R.O.; Tshabalala, K.G.

    2016-09-01

    High-purity hexagonal lead iodide nanoparticles have been synthesized from a depleted sealed lead acid battery anode. The synthesized product was found to consist of the rare 6R polytype form of PbI{sub 2} that is thought to have good potential in photovoltaic applications. We investigate the effects of annealing time and post-melting temperature on the structure and optical properties using 1.5418 Å CuKα radiation. Photoluminescence measurements were done under 150 W/221 nm wavelength xenon excitation. Phase transformation was observed through XRD peaks when annealing time increased from 0.5–5 h. The nanoparticle grain size and inter-planar distance appeared to be independent of annealing time. PL measurements show three broad peaks in a range of 400 nm to 700 nm that are attributed to excitonic, donor–acceptor pair and luminescence bands from the deep levels.

  18. The dehydration of uranyl nitrate hexahydrate

    International Nuclear Information System (INIS)

    Badalov, A.; Kamalov, D.D.; Khamidov, B.O.; Mirsaidov, I.U.; Eshbekov, N.R.

    2010-01-01

    Present article is devoted to study of dehydration process of uranyl nitrate hexahydrate. The dehydration process of uranyl nitrate hexahydrate was studied by means of tensimeter method with membrane zero-manometer. The research was carried out under equilibrium conditions. It was defined that in studied temperature ranges (300-450 K) the dehydration process of UO 2 (NO 3 ) 2 has a three stage character.

  19. Selectivity in ligand binding to uranyl compounds: A synthetic, structural, thermodynamic and computational study

    International Nuclear Information System (INIS)

    Arnold, John

    2015-01-01

    The uranyl cation (UO 2 2+ ) is the most abundant form of uranium on the planet. It is estimated that 4.5 billion tons of uranium in this form exist in sea water. The ability to bind and extract the uranyl cation from aqueous solution while separating it from other elements would provide a limitless source of nuclear fuel. A large body of research concerns the selective recognition and extraction of uranyl. A stable molecule, the cation has a linear O=U=O geometry. The short U-O bonds (1.78 Å) arise from the combination of uranium 5f/6d and oxygen 2p orbitals. Due to the oxygen moieties being multiply bonded, these sites were not thought to be basic enough for Lewis acidic coordination to be a viable approach to sequestration. The goal of this research is thus to broaden the coordination chemistry of the uranyl ion by studying new ligand systems via synthetic, structural, thermodynamic and computational methods. It is anticipated that this fundamental science will find use beyond actinide separation technologies in areas such as nuclear waste remediation and nuclear materials. The focus of this study is to synthesize uranyl complexes incorporating amidinate and guanidinate ligands. Both synthetic and computational methods are used to investigate novel equatorial ligand coordination and how this affects the basicity of the oxo ligands. Such an understanding will later apply to designing ligands incorporating functionalities that can bind uranyl both equatorially and axially for highly selective sequestration. Efficient and durable chromatography supports for lanthanide separation will be generated by (1) identifying robust peptoid-based ligands capable of binding different lanthanides with variable affinities, and (2) developing practical synthetic methods for the attachment of these ligands to Dowex ion exchange resins.

  20. Selectivity in ligand binding to uranyl compounds: A synthetic, structural, thermodynamic and computational study

    Energy Technology Data Exchange (ETDEWEB)

    Arnold, John [Univ. of California, Berkeley, CA (United States)

    2015-01-21

    The uranyl cation (UO₂²⁺) is the most abundant form of uranium on the planet. It is estimated that 4.5 billion tons of uranium in this form exist in sea water. The ability to bind and extract the uranyl cation from aqueous solution while separating it from other elements would provide a limitless source of nuclear fuel. A large body of research concerns the selective recognition and extraction of uranyl. A stable molecule, the cation has a linear O=U=O geometry. The short U-O bonds (1.78 Å) arise from the combination of uranium 5f/6d and oxygen 2p orbitals. Due to the oxygen moieties being multiply bonded, these sites were not thought to be basic enough for Lewis acidic coordination to be a viable approach to sequestration. The goal of this research is thus to broaden the coordination chemistry of the uranyl ion by studying new ligand systems via synthetic, structural, thermodynamic and computational methods. It is anticipated that this fundamental science will find use beyond actinide separation technologies in areas such as nuclear waste remediation and nuclear materials. The focus of this study is to synthesize uranyl complexes incorporating amidinate and guanidinate ligands. Both synthetic and computational methods are used to investigate novel equatorial ligand coordination and how this affects the basicity of the oxo ligands. Such an understanding will later apply to designing ligands incorporating functionalities that can bind uranyl both equatorially and axially for highly selective sequestration. Efficient and durable chromatography supports for lanthanide separation will be generated by (1) identifying robust peptoid-based ligands capable of binding different lanthanides with variable affinities, and (2) developing practical synthetic methods for the attachment of these ligands to Dowex ion exchange resins.

  1. Selective complexation of the uranyl ion using modified polymeric supports

    International Nuclear Information System (INIS)

    Roundhill, D.M.

    1993-01-01

    We have recently examined the complexation properties of aminomethylenebis(phosphonic acids) towards selected trivalent metal ions, and have found that they form highly stable complexes with these oxophilic metal centers. These metal complexes were found resistant to metal ion dissociation in acidic media and present in aqueous solution as both 1:1 and 1:2 (metal ion:ligand, M:L) species. The uranyl ion, although structurally different from simple M 3+ ions because of its linear geometry, possesses a similar +3 to +4 charge at the metal center. Because of the high positive charge on uranium in the ion UO 2 2+ , and because of the potential capacity of the axial oxygens on this ion to form intramolecular hydrogen bonds with a proton on the ligand, there is a good possibility that the uranyl ion will form stable complexes having 1:1,1:2 and 1:3 (M:L) stoichometries with aminomethylenebis(phosphonates) as ligand. There is considerable precedent that a phosphonate group will form strong complexes with the UO 2 , 2+ ion, and there is the additional possibility that the amino moiety on these ligands will provide further selectivity for complexation via hydrogen bonding. Furthermore, these ligands are simple and inexpensive to synthesize, thus making them potentially useful for application in large scale batch separation processes. To test these concepts, we have measured the stability and protonation constants of the different complexes formed in aqueous solution. From this data we can evaluate the potential for compounds of this type to be useful as uranyl ion sequestering agents

  2. Thermodynamics of Uranyl Minerals: Enthalpies of Formation of Uranyl Oxide Hydrates

    Energy Technology Data Exchange (ETDEWEB)

    K. Kubatko; K. Helean; A. Navrotsky; P.C. Burns

    2005-05-11

    The enthalpies of formation of seven uranyl oxide hydrate phases and one uranate have been determined using high-temperature oxide melt solution calorimetry: [(UO{sub 2}){sub 4}O(OH){sub 6}](H{sub 2}O){sub 5}, metaschoepite; {beta}-UO{sub 2}(OH){sub 2}; CaUO{sub 4}; Ca(UO{sub 2}){sub 6}O{sub 4}(OH){sub 6}(H{sub 2}O){sub 8}, becquerelite; Ca(UO{sub 2}){sub 4}O{sub 3}(OH){sub 4}(H{sub 2}O){sub 2}; Na(UO{sub 2})O(OH), clarkeite; Na{sub 2}(UO{sub 2}){sub 6}O{sub 4}(OH){sub 6}(H{sub 2}O){sub 7}, the sodium analogue of compreignacite and Pb{sub 3}(UO{sub 2}){sub 8}O{sub 8}(OH){sub 6}(H{sub 2}O){sub 2}, curite. The enthalpy of formation from the binary oxides, {Delta}H{sub f-ox}, at 298 K was calculated for each compound from the respective drop solution enthalpy, {Delta}H{sub ds}. The standard enthalpies of formation from the elements, {Delta}H{sub f}{sup o}, at 298 K are -1791.0 {+-} 3.2, -1536.2 {+-} 2.8, -2002.0 {+-} 3.2, -11389.2 {+-} 13.5, -6653.1 {+-} 13.8, -1724.7 {+-} 5.1, -10936.4 {+-} 14.5 and -13163.2 {+-} 34.4 kJ mol{sup -1}, respectively. These values are useful in exploring the stability of uranyl oxide hydrates in auxiliary chemical systems, such as those expected in U-contaminated environments.

  3. Dehydration and dehydroxylation of C-S-H phases synthesized on silicon wafers

    Science.gov (United States)

    Giraudo, Nicolas; Bergdolt, Samuel; Laye, Fabrice; Krolla, Peter; Lahann, Joerg; Thissen, Peter

    2018-03-01

    In this work, the synthesis of specific ultrathin Calcium-Silicate-Hydrate (C-S-H) phases on silicon wafers and their transformation into C-S phases is achieved. Specific mineral phases are identified, and the synthesis is successful controlled. Samples are investigated by means of Fourier Transform Infrared (FTIR) spectroscopy and X-ray Diffraction (XRD) and the results are analyzed based on first-principles calculations. When C-S-H phases are transformed into C-S phases, only a few reflexes are detected on XRD, and the coherent scattering domains decrease with the increment of the temperature and time of exposure. This behavior is explained by the Ca/Si changes, which are identified by changes in the FTIR spectra. A thermodynamic analysis is performed with the help of first-principles calculations to underline the influence of the calcium-to-silicon (Ca/Si) ratio in the process of dehydroxylation. To increase the Ca/Si ratio water is partially substituted by methanol at the synthesis. This is observed in the FTIR spectra and is confirmed by lower temperatures of dehydroxylation. The catalytic nature of calcium towards the dehydroxylation is confirmed. The core of this work lies in the preparation of a model, which perfection makes possible to model reactivity, stability and mechanical properties using first-principles calculations, and is the starting point for the synthesis of many others.

  4. Structural phase transformations in KYF4:Er3+ nanoparticles synthesized by hydrothermal method for upconversion applications

    Science.gov (United States)

    Yamini, S.; Priya, P. Sakthi; Gunaseelan, M.; Senthilselvan, J.

    2017-05-01

    KYF4:10%Er3+ upconversion nanoparticles was synthesized by hydrothermal method with potassium hydroxides (KOH) as precursor. Prepared samples were calcined at 600 °C using double crucible method. XRD patterns of as prepared KYF4 and KYF4:Er3+ samples confirm the tetragonal structure, which is well matched with the standard data. Surface morphology is recorded for 600 °C calcined samples using High resolution scanning electron microscopy (HRSEM) shows spheroidal shape with particle sizes of ˜80 nm. From UV-Visible and EDX spectroscopy presence of Er3+ in KYF4:10%Er3+ is confirmed. The prepared KYF4:10%Er3+ can be used to improve efficiency of solar cells, display devices and fiber optical telecommunication applications.

  5. FEBEX: Full-Scale engineered barriers experiment in crystalline host-rock: preoperational phase. Synthesized report

    International Nuclear Information System (INIS)

    1997-01-01

    The FEBEX project is being cofinanced by the EC under contract F 14WCT950006. In addition to the EC, seven partners from three countries of the EU. (France, Germany, and Spain) as well as one from EFTA (Switzerland) are participating in the project. ENRESA is the coordinating partner with NAGRA assisting in coordinating some aspects. The project consists of two large-scale tests and a series of complimentary laboratory tests. The work is being executed by the following organizations: CIEMAT, AITEMIN, UP-DIT (CIMNE), ULC, CSIC-Zaidin, and UPM (SPAIN) ANDRA and G.3S (FRANCE) GRS (GERMANY). This report includes a synthesized description of the experiment from its conception through the installation of the two large-scale tests (from the middle of 1994 to the beginning of 1997, preoperation stage). The experiment is described in detail in a series of specific reports. (Author)

  6. Bonding, elastic and vibrational properties in low and high pressure synthesized diamond-like BCx phases

    Energy Technology Data Exchange (ETDEWEB)

    Zinin, P.; Liu, X. R.; Jia, R.; Sharma, S. K.; Ming, L. C.; Kutuza, I.; Troyan, I.

    2017-10-01

    Recent studies demonstrate that low pressure chemical vapor deposition at 950 K leads to the synthesis of diamond-like boron carbides with high concentrations of boron (0.66 < x < 4) in which the sp 2 fraction depends on the boron concentration [1]. This indicates that the graphitic BC3 (g-BC3) phases obtained by chemical vapor deposition materials are mixtures of diamond-like and graphitic BCx phases. This finding allows us to revise the interpretation of the x-ray diffraction (XRD) patterns of the g-BC3 phases discussed previously [2, 3]. To support the new interpretation, we conducted a laser heating experiment of the g-BC3 phase. We found that after laser heating at 1100 K and 25 GPa in a diamond anvil cell (DAC) almost all graphitic layers of the g-BC3 transform into a cubic structure. The XRD pattern of the cubic BC3 phase (c-BC3) can be indexed with a cubic unit cell a = 3.619 (0.165) Å. Measurements of the equation of state of the g-BC3 phase demonstrated that boron atoms were incorporated into the graphitic B-C network. The linear compressibility along the c axis can be characterized by the value of the linear modulus Bc = 29.2 ± 1.8 GPa. Linear fitting of the experimental data for the a/a o parameter as a function of pressure gives us the value of the linear elastic modulus along the a axes: Ba = 800 ± 75 GPa.

  7. Bonding, elastic and vibrational properties in low and high pressure synthesized diamond-like BCx phases

    Science.gov (United States)

    Zinin, P.; Liu, X. R.; Jia, R.; Sharma, S. K.; Ming, L. C.; Kutuza, I.; Troyan, I.

    2017-10-01

    Recent studies demonstrate that low pressure chemical vapor deposition at 950 K leads to the synthesis of diamond-like boron carbides with high concentrations of boron (0.66 x boron concentration [1]. This indicates that the graphitic BC3 (g-BC3) phases obtained by chemical vapor deposition materials are mixtures of diamond-like and graphitic BCx phases. This finding allows us to revise the interpretation of the x-ray diffraction (XRD) patterns of the g-BC3 phases discussed previously [2, 3]. To support the new interpretation, we conducted a laser heating experiment of the g-BC3 phase. We found that after laser heating at 1100 K and 25 GPa in a diamond anvil cell (DAC) almost all graphitic layers of the g-BC3 transform into a cubic structure. The XRD pattern of the cubic BC3 phase (c-BC3) can be indexed with a cubic unit cell a = 3.619 (0.165) Å. Measurements of the equation of state of the g-BC3 phase demonstrated that boron atoms were incorporated into the graphitic B-C network. The linear compressibility along the c axis can be characterized by the value of the linear modulus Bc = 29.2 ± 1.8 GPa. Linear fitting of the experimental data for the a/a o parameter as a function of pressure gives us the value of the linear elastic modulus along the a axes: Ba = 800 ± 75 GPa.

  8. Crystallization Mechanism and Phase Transition Properties of W-doped VO2 Synthesized by Hydrothermal Method

    Directory of Open Access Journals (Sweden)

    LI Yao

    2017-11-01

    Full Text Available VO2 sol was firstly prepared using vanadyl sulfate as a vanadium source by precipitation-peptization method. Then tungsten(W doping vanadium dioxide(W-VO2 was prepared by hydrothermal crystallization of prepared sol with the presence of ammonium metatungstate. The morphologies, crystal structure of the as-prepared samples and phase transition properties were studied by X-ray diffraction(XRD, field emission scanning electron microscope(FESEMand differential scanning calorimetry(DSC analysis. The results indicate that rod-like W-VO2(B crystal with length of 1-2μm and radius of 100-200nm is firstly formed during hydrothermal treatment for 4-48h at 280℃, then the rod-like crystal dissolves gradually and sheet-like or snowflake-like crystal is formed with the phase transition from W-VO2(B to W-VO2(M and eventually, the W-VO2(M crystals can further grow up while the W-VO2(B gradually dissolves; the phase transition temperature of VO2 decreases with the increase in W doping content, and the phase transition temperature of W-VO2(M reduces to about 28℃ when the nominal dopant concentration is 6.0%(atom fraction.The "nucleation-growth-transformation-ripening" mechanism is proposed as the formation mechanism based on the hydrothermal crystallization and morphological evolution process of W-VO2(M.

  9. Solid solution and amorphous phase in Ti–Nb–Ta–Mn systems synthesized by mechanical alloying

    Energy Technology Data Exchange (ETDEWEB)

    Aguilar, C., E-mail: claudio.aguilar@usm.cl [Departamento de Ingeniería Metalúrgica y Materiales, Universidad Técnica Federico Santa María, Av. España 1680, Valparaíso (Chile); Guzman, P. [Departamento de Ingeniería Metalúrgica y Materiales, Universidad Técnica Federico Santa María, Av. España 1680, Valparaíso (Chile); Lascano, S. [Departamento de Ingeniería Mecánica, Universidad Técnica Federico Santa María, Av. España 1680, Valparaíso (Chile); Parra, C. [Departamento de Física, Universidad Técnica Federico Santa María, Av. España 1680, Valparaíso (Chile); Bejar, L. [Instituto de Investigaciones Metalúrgicas, Universidad Michoacana de San Nicolás de Hidalgo, Ciudad Universitaria, Morelia C.P. 58000, Michoacán (Mexico); Medina, A. [Facultad de Ingeniería Mecánica, Universidad Michoacana de San Nicolás de Hidalgo, Ciudad Universitaria, C.P. 58000, Michoacán (Mexico); Guzman, D. [Departamento de Metalurgia, Universidad de Atacama, Av. España 485, Copiapó (Chile)

    2016-06-15

    This work discusses the formation of Ti–30Nb–13Ta–xMn (x: 2, 4 and 6 wt%) solid solution by mechanical alloying using a shaker mill. A solid solution was formed after 15 h of milling and an amorphous phase was formed after 30 h of milling, according to X-ray diffraction results. Disappearance of strongest X-ray diffraction peaks of Nb, Ta and Mn indicated the formation of solid solution, while, X-ray diffraction patterns of powders milled for 30 h showed an amorphous hump with crystalline peaks in the angular range of 35–45° in 2θ. TEM image analysis showed the presence of nanocrystalline intermetallic compounds embedded in an amorphous matrix. Mn{sub 2}Ti, MnTi and NbTi{sub 4} intermetallic compounds were detected and revealed crystallites with size ranging from 3 to 20 nm. The Gibbs free energy for the formation of solid solution and amorphous phase of three ternary systems (Ti–Nb–Ta, Ti–Nb–Mn and Ti–Ta–Mn) was calculated using extended Miedema's model. Experimental and thermodynamic data confirmed that solid solution was first formed in the alloy with 6wt% Mn followed by the formation of an amorphous phase as milling time increases. The presence of Mn promoted the formation of amorphous phase because the atomic radius difference between Mn with Ti, Nb and Ta. - Highlights: • Thermodynamics analysis of extension of solid solution of the Ti–Nb–Ta–Mn system. • Formation of amorphous phase and intermetallic compounds were observed. • Nanocrystalline intermetallic compounds were formed with the sizes between 3 and 20 nm.

  10. Synthesis of thermally stable extra-large pore crystalline materials: a uranyl germanate with 12-ring channels.

    Science.gov (United States)

    Lin, Chia-Hui; Chiang, Ray-Kuang; Lii, Kwang-Hwa

    2009-02-18

    A thermally stable extra-large pore uranyl germanate is synthesized under high-temperature, high-pressure hydrothermal conditions at 585 degrees C and 150 MPa. The structure contains U(6+)O(6) tetragonal bipyramids which are interconnected by digermanate groups to form a 3D framework with 12-ring pore openings.

  11. Can uranyl complexes encapsulate to carbon nanotubes? A ...

    Indian Academy of Sciences (India)

    K SRINIVASU

    novel nanomaterials for nuclear waste management processes. Keywords. Carbon nanotubes; density functional theory; uranyl encapsulation; uranyl functionalization. 1. Introduction. Presently, the energy demands are exponentially increas- ing, thus alternative energy resources such as nuclear energy are unavoidable ...

  12. Self-assembly of gas-phase synthesized magnesium nanoparticles on room temperature substrates

    Science.gov (United States)

    Venturi, F.; Calizzi, M.; Bals, S.; Perkisas, T.; Pasquini, L.

    2015-01-01

    Magnesium nanoparticles (NPs) with initial size in the 10-50 nm range were synthesized by inert gas condensation under helium flow and deposited on room temperature substrates. The morphology and crystal structure of the NPs ensemble were investigated as a function of the deposition time by complementary electron microscopy techniques, including high resolution imaging and chemical mapping. With increasing amount of material, strong coarsening phenomena were observed at room temperature: small NPs disappeared while large faceted NPs developed, leading to a 5-fold increase of the average NPs size within a few minutes. The extent of coarsening and the final morphology depended also on the nature of the substrate. Furthermore, large single-crystal NPs were seen to arise from the self-organization of primary NPs units, providing a mechanism for crystal growth. The dynamics of the self-assembly process involves the basic steps of NPs sticking, diffusion on substrate, coordinated rotation and attachment/coalescence. Key features are the surface energy anisotropy, reflected by the faceted shape of the NPs, and the low melting point of the material. The observed phenomena have strong implications in relation to the synthesis and stability of nanostructures based on Mg or other elements with similar features.

  13. Recycling polymer residues to synthesize magnetic nanocomposites for dispersive micro-solid phase extraction.

    Science.gov (United States)

    Ghambari, Hoda; Reyes-Gallardo, Emilia M; Lucena, Rafael; Saraji, Mohammad; Cárdenas, Soledad

    2017-08-01

    The ubiquitous presence of plastics, an obvious consequence of their usefulness and low price, has turned them into a problem of environmental and safety concern. The new plastic economy, an initiative recently launched by the World Economic Forum and Ellen MacArthur Foundation, with analytical support from McKinsey & Company, promotes a change in the use of plastic worldwide around three main pillars: redesign, reusing and recycling. Recycled plastics, with the aim of extending their life spam, can be used to synthesize materials for analytical purposes. In this article polystyrene (PS) trays, previously used for food packaging, are proposed as polymeric source for the synthesis of magnetic nanocomposites. The synthesis plays with the solubility of PS in different solvents in such a way that PS is gelated in the presence of cobalt ferrite nanoparticles which are finally embedded in the polymeric network. The extraction capability of the magnetic PS nanocomposite was evaluated using the determination of four parabens (methylparaben, ethylparaben, propylparaben and butylparaben) in water using liquid chromatography-tandem mass spectrometry as model analytical problem. Under the optimum conditions, limits of detection and quantification were in the range of 0.05-0.15 and 0.15-0.5ng/mL, respectively. The precisions, expressed as relative standard deviation (RSD), varied between 4.4% and 8.5% and the relative recoveries for analysis of the water samples were in the interval 81.2-104.5%. Copyright © 2017 Elsevier B.V. All rights reserved.

  14. Novel Viologen Derivative Based Uranyl Coordination Polymers Featuring Photochromic Behaviors.

    Science.gov (United States)

    Hu, Kong-Qiu; Wu, Qun-Yan; Mei, Lei; Zhang, Xiao-Lin; Ma, Lei; Song, Gang; Chen, Di-Yun; Wang, Yi-Tong; Chai, Zhi-Fang; Shi, Wei-Qun

    2017-12-19

    A series of novel uranyl coordination polymers have been synthesized by hydrothermal reactions. Both complexes 1 and 2 prosess two ipbp - ligands (H 2 ipbpCl=1-(3,5-dicarboxyphenyl)-4,4'-bipyridinium chloride), one uranyl cation, and two coordination water molecules, which can further extend to 2D networks through hydrogen bonding. In complex 1, two sets of equivalent nets are entangled together, resulting in a 2D + 2D → 3D polycatenated framework. In complex 2, the neighbouring equivalent nets interpenetrate each other, forming a twofold interpenetrated network. Complexes 3 and 4 are isomers, and both of them are constructed from (UO 2 ) 2 (OH) 2 dinuclear units, which are connected with four ipbp - ligands. The 3D structures of complexes 3 and 4 are similar along the b axis. Similar to other viologen-based coordination polymers, complexes 3 and 4 exhibit photochromic and thermochromic properties, which are rarely observed in actinide coordination polymers. Unlike the monotonous coordination mode in complexes 1-4, the ipbp - ligands feature a μ 3 -bridge through two kinds of coordination modes in complex 5. Notably, complex 5 presents a unique example in which terminal pyridine nitrogen atom is involved in the coordination. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. Complete two-dimensional gel electrophoresis pattern of de novo synthesized acute phase reactants.

    Science.gov (United States)

    Pluschke, G; Jenni, L; van Alphen, L; Lefkovits, I

    1986-01-01

    The early stages of inflammatory responses are characterized by the rapid synthesis of a heterogenous group of plasma proteins known as acute phase reactants. We show that the complex changes in the serum protein composition of mice in response to infections can easily be analysed by two-dimensional (2D) gel electrophoresis, which allows simultaneous analysis of numerous proteins from small volume samples. While changes in the protein composition can be visualized by silver staining, radiofluorography of gels loaded with serum samples from mice that had been labelled in vivo with 35S-methionine allows an analysis of the changes in the pattern of protein synthesis. Thus, these techniques should allow the evaluation of the relative contributions of alterations of protein synthesis and catabolism to the changes in the overall concentration of individual acute phase reactants. Identification of proteins in the 2 D gel pattern can be easily accomplished by co-electrophoresing small serum samples together with immunoprecipitates obtained from in-vivo labelled serum. Using this approach we were able to identify some of the major acute phase reactants of mice. Some of these proteins, like haptoglobin and haemopexin, show concentration increases that are characteristic for type III reactants like C-reactive protein (CRP) or serum amyloid A component (SAA) in man. Results obtained with serum from healthy and infected human newborns indicate that 2D gel electrophoresis could be used to analyse changes in human plasma protein profiles, which would make it a valuable tool for diagnosis and management in certain clinical situations. Images Fig. 1 Fig. 2 Fig. 3 Fig. 4 PMID:2434273

  16. Synthesis, characterization, anticancer activity, thermal and electrochemical studies of some novel uranyl Schiff base complexes

    Energy Technology Data Exchange (ETDEWEB)

    Asadi, Zahra; Asadi, Mozaffar; Firuzabadi, Fahimeh Dehghani [Shiraz Univ. (Iran, Islamic Republic of). Dept. of Chemistry; Yousefi, Reza; Jamshidi, Mehrnaz [Shiraz Univ. (Iran, Islamic Republic of). Protein Chemistry Lab. (PCL)

    2014-04-15

    Some tetradentate N{sub 2}O{sub 2} Schiff base ligands, such as N,N{sup '}-bis(naphtalidene)-1,2-phenylenediamine, N,N{sup '}-bis(naphtalidene)-4-methyl-1,2-phenylenediamine, N,N{sup '}-bis(naphtalidene)-4-chloro-1,2-phenylenediamine, N,N{sup '}-bis(naphtalidene)-4-nitro-1,2-phenylenediamine, N,N{sup '}-bis(naphtalidene)-4-carboxyl-1,2-phenylenediamine, and their uranyl complexes were synthesized and characterized by {sup 1}H NMR, IR, UV-Vis spectroscopy, TG (thermogravimetry), and elemental analysis (C.H.N.). Thermogravimetric analysis shows that uranyl complexes have very different thermal stabilities. This method is used also to establish that only one solvent molecule is coordinated to the central uranium ion and this solvent molecule does not coordinate strongly and is removed easier than the tetradentate ligand and also trans oxides. The electrochemical properties of the uranyl complexes were investigated by cyclic voltammetry. Electrochemistry of these complexes showed a quasireversible redox reaction without any successive reactions. Also, the kinetic parameters of thermal decomposition were calculated using Coats-Redfern equation. According to Coats-Redfern plots the kinetics of thermal decomposition of the studied complexes is first-order in all stages. Anticancer activity of the uranyl Schiff base complexes against cancer cell lines (Jurkat) was studied and determined by MTT (3-[4,5-dimethylthiazol-2-yl]-2,5-diphenyltetrazoliumbromide) assay.

  17. Rapid hydrothermal route to synthesize cubic-phase gadolinium oxide nanorods

    International Nuclear Information System (INIS)

    Hazarika, Samiran; Paul, Nibedita; Mohanta, Dambarudhar

    2014-01-01

    An inexpensive fabrication route and growth mechanism is being reported for obtaining quality gadolinium oxide ( Gd 2 O 3 ) nanoscale rods. The elongated nanoscale systems, as produced via a hydrothermal process, were characterized by X-ray diffraction (XRD), high resolution transmission electron microscopy (HRTEM), optical absorption spectroscopy, photoluminescence (PL) spectroscopy, Raman spectroscopy and magnetic hysteresis measurements. XRD patterns of the nanorods, as-prepared from independent precursors of different pH, depict a cubic crystal phase and an average crystallite size of 5-6.5 nm. As revealed from HRTEM micrographs, diameter of the nanorods prepared at pH = 13.3 (∼7 nm) was much smaller than the rods prepared at pH = 10.8 (∼19 nm). However, the aspect ratio was more than double in the former case than the latter case. PL response was found to be dominated by defect mediated emissions, whereas Raman spectrum of a given specimen (pH = 10.8) has revealed characteristic F g + A g modes of cubic phase of Gd 2 O 3 nanorods, apart from other independent modes. Furthermore, M ∼ H plot of the nanorod system (pH = 10.8) exhibited slight departure from the ideal superparamagnetic behaviour, with low remanence and coercive field values. The exploitation of one-dimensional Gd 2 O 3 nanorods have immense potential in the production of advanced contrast agents, smart drives and also in making novel ferrofluids of technological relevance. (author)

  18. New double sulfates of uranyl

    International Nuclear Information System (INIS)

    Serezhkin, V.N.; Serezhkina, L.B.

    1977-01-01

    The possibility has been established of the formation of double uranyl sulphates with the composition MUO 2 (SO 4 ) 2 x5H 2 O (M=Mn or Co). These compounds are formed upon dissolution of MnSO 4 x5H 2 O or CoSO 4 x7H 2 O and UO 2 SO 4 x2.5H 2 O in a minimum amount of water with subsequent evaporation to dryness. The obtained monocrystals have been studied by X-ray structural analysis and the parameters of monoclinic elementary cells have been determined: MnUO 2 (SO 4 ) 2 x5H 2 O (a=6.524; b=11.396; c=8.362 A; β=90 deg 47') and CoUO 2 (SO 4 ) 2 x5H 2 O (a=6.448; b=11.305; c=8.286 A; β=90 deg). Possible spatial groups are P 2sub(1/m) or P2 1 ; Z=2. Thermographic study of the obtained compounds has been performed

  19. Photochemical reduction of uranyl nitrate

    Energy Technology Data Exchange (ETDEWEB)

    Duerksen, W.K.

    1993-10-20

    The photochemical reduction of uranyl nitrate solutions to tetravalent uranium was investigated as a means of producing uranium dioxide feed for the saltless direct oxide reduction (SDOR) process. At high uranium concentrations, reoxidation of U{sup +4} occurs rapidly. The kinetics of the nitric oxidation of tetravalent uranium depend on the concentrations of hydrogen ion, nitrate ion, nitrous acid, and tetravalent uranium in the same manner as was reported elsewhere for the nitrate oxidation of PU{sup +3}. Reaction rate data were successfully correlated with a mechanism in which nitrogen dioxide is the reactive intermediate. Addition of a nitrous acid scavenger suppresses the reoxidation reaction. An immersion reactor employing a mercury vapor lamp gave reduction times fast enough for routine production usage. Precipitation techniques for conversion of aqueous U(NO{sub 3}){sub 4} to hydrous UO{sub 2} were evaluated. Prolonged dewatering times tended to make the process time consuming. Use of 3- to 4-M aqueous NaOH gave the best dewatering times observed. Reoxidation of the UO{sub 2} by water of hydration was encountered, which required the drying process to be carried out under a reducing atmosphere.

  20. Vapor-phase-synthesized fluoroacrylate polymer thin films: thermal stability and structural properties.

    Science.gov (United States)

    Christian, Paul; Coclite, Anna Maria

    2017-01-01

    In this study, the thermal, chemical and structural stability of 1 H ,1 H ,2 H ,2 H -perfluorodecyl acrylate polymers (p-PFDA) synthetized by initiated chemical vapor deposition (iCVD) were investigated. PFDA polymers are known for their interesting crystalline aggregation into a lamellar structure that induces super-hydrophobicity and oleophobicity. Nevertheless, when considering applications which involve chemical, mechanical and thermal stresses, it is important to know the limits under which the crystalline aggregation and the resulting polymer properties are stable. For this, chemical, morphological and structural properties upon multiple heating/cooling cycles were investigated both for linear PFDA polymers and for differently strong cross-linked alterations thereof. Heat treatment leaves the chemical composition of the linear PFDA polymers largely unchanged, while a more ordered crystalline structure with smoother morphology is observed. At the same time, the hydrophobicity and the integrity of the polymer deteriorate upon heating. The integrity and hydrophobicity of cross-linked p-PFDA films was preserved likely because of the lack of internal strain due to the coexistence of both crystalline and amorphous phases. The possibility to finely tune the degree of cross-linking can therefore expand the application portfolio in which PFDA polymers can be utilized.

  1. Room temperature ferromagnetism in liquid-phase pulsed laser ablation synthesized nanoparticles of nonmagnetic oxides

    International Nuclear Information System (INIS)

    Singh, S. C.; Gopal, R.; Kotnala, R. K.

    2015-01-01

    Intrinsic Room Temperature Ferromagnetism (RTF) has been observed in undoped/uncapped zinc oxide and titanium dioxide spherical nanoparticles (NPs) obtained by a purely green approach of liquid phase pulsed laser ablation of corresponding metal targets in pure water. Saturation magnetization values observed for zinc oxide (average size, 9 ± 1.2 nm) and titanium dioxide (average size, 4.4 ± 0.3 nm) NPs are 62.37 and 42.17 memu/g, respectively, which are several orders of magnitude larger than those of previous reports. In contrast to the previous works, no postprocessing treatments or surface modification is required to induce ferromagnetism in the case of present communication. The most important result, related to the field of intrinsic ferromagnetism in nonmagnetic materials, is the observation of size dependent ferromagnetism. Degree of ferromagnetism in titanium dioxide increases with the increase in particle size, while it is reverse for zinc oxide. Surface and volume defects play significant roles for the origin of RTF in zinc oxide and titanium dioxide NPs, respectively. Single ionized oxygen and neutral zinc vacancies in zinc oxide and oxygen and neutral/ionized titanium vacancies in titanium dioxide are considered as predominant defect centres responsible for observed ferromagnetism. It is expected that origin of ferromagnetism is a consequence of exchange interactions between localized electron spin moments resulting from point defects

  2. Phase evolution, mechanical and corrosion behavior of Fe(100-x) Ni(x) alloys synthesized by powder metallurgy

    Science.gov (United States)

    Singh, Neera; Parkash, Om; Kumar, Devendra

    2018-03-01

    In the present investigation, Fe(100-x) Ni(x) alloys (x = 10, 20, 30, 40 and 50 wt%) were synthesized through the evolution of γ-taenite and α-kamacite phases by powder metallurgy route using commercially available Fe and Ni powders. Mechanically mixed powders of Fe and Ni were compacted at room temperature and sintered at three different temperatures 1000, 1200 and 1250 °C for 1 h. Both Ni concentration and sintering temperature have shown a strong impact on the phase formation, tribological and electrochemical behavior. Micro structural study has shown the formation of taenite (γ-Fe,Ni) and kamacite (α-Fe,Ni) phases in the sintered specimens. An increase in Ni fraction resulted in formation of more taenite which reduces hardness and wear resistance of specimens. Increasing the sintering temperature decreased the defect concentration with enhanced taenite formation, aiding to higher densification. Taenite formed completely in Fe50Ni50 after sintering at 1250 °C. Tribological test revealed the maximum wear resistance for Fe70Ni30 specimen due to the presence of both kamacite and taenite in significant proportions. The formation of taenite as well as the decrease in defect concentration improves the corrosion resistance of the specimens significantly in 1M HCl solution. A maximum corrosion protection efficiency of around ∼87% was achieved in acidic medium for Fe50Ni50, sintered at 1250 °C.

  3. Multi-phase structures of boron-doped copper tin sulfide nanoparticles synthesized by chemical bath deposition for optoelectronic devices

    Science.gov (United States)

    Rakspun, Jariya; Kantip, Nathakan; Vailikhit, Veeramol; Choopun, Supab; Tubtimtae, Auttasit

    2018-04-01

    We investigated the influence of boron doping on the structural, optical, and electrical properties of copper tin sulfide (CTS) nanoparticles coated on a WO3 surface and synthesized using chemical bath deposition. Boron doping at concentrations of 0.5, 1.0, 1.5, and 2.0 wt% was investigated. The X-ray diffraction pattern of CTS showed the presence of monoclinic Cu2Sn3S7, cubic Cu2SnS3, and orthorhombic Cu4SnS4. Boron doping influenced the preferred orientation of the nanoparticles for all phase structures and produced a lattice strain effect and changes in the dislocation density. Increasing the concentration of boron in CTS from 0.5 wt% to 2.0 wt% reduced the band gap for all phases of CTS from 1.46 to 1.29 eV and reduced the optical transmittance. Optical constants, such as the refractive index, extinction coefficient, and dissipation factor, were also obtained for B-doped CTS. The dispersion behavior of the refractive index was investigated in terms of a single oscillator model and the physical parameters were determined. Fourier transform infrared spectroscopy confirmed the successful synthesis of CTS nanoparticles. Cyclic voltammetry indicated that optimum boron doping (<1.5 wt% for all phases) resulted in desirable p-n junction behavior for optoelectronic applications.

  4. Splitting of the luminescent excited state of the uranyl ion

    International Nuclear Information System (INIS)

    Flint, C.D.; Sharma, P.; Tanner, P.A.

    1982-01-01

    The luminescence spectra of some uranyl compounds has been studied. It has been proposed that the splitting of the luminescent excited state of the uranyl ion is due to a descent in symmetry experienced by the uranyl ion when it is placed in a crystal field. In recent years there has been developed a highly successful model of the electronic structure of the uranyl ion. In this paper the authors use this model to interpret the luminescence spectra of a variety of uranyl compounds

  5. New investigations on shock-wave synthesized high-pressure phases in the system Si-Al-O-N

    Science.gov (United States)

    Schlothauer, T.; Greif, A.; Keller, K.; Schwarz, M. R.; Kroke, E.; Heide, G.

    2012-12-01

    The shock-wave synthesis of nanostructured high-pressure phases at a gram-scale permits the analysis of spinel type nitrides with different chemical composition using methods not suitable for microgram amounts of material. Methods with a significant mass loss through the analytical process like TG-MS or FT-IR or bulk methods at the g-scale like 29Si-MAS-NMR or neutron diffraction were used. The synthesis of pure high-pressure modifications (gamma-phases) of different SiAlON-compounds using amorphous H-bearing precursors at pressures of 30-40 GPa is a necessary prerequisite for precise determinations of crystal chemical features. Etching with HF is a well-known method to purify the high-pressure nitrides (Sekine 2002). The etched parts were analyzed by neutron diffraction, TG-MS, and carrier gas hot extraction (CGHE). Volatile elements like H2 and Cl2, as well as non-stoichiometric oxygen and nitrogen, and NOx, H2O are enriched in the disordered rims. This degassing process ends at temperatures of approximately 600°C, while the spinel structure remains well preserved up to 1300°C. Under these conditions the gamma-phases stay unchanged under air, argon and vacuum. Furthermore chlorine, an important impurity of the H-bearing precursors neither influences the synthesized products nor the synthesis process itself. IR-spectroscopy of gamma-Si3(O,N)4 shows that peak shifts of octahedral lattice vibrations (≈ 680 cm-1) and both tetrahedral vibrations (ny3 and ny4) (Jeanloz 1980, Preudhomme & Tarte 1971) to higher frequencies with decreasing oxygen content occur. This effect is also visible in samples contaminated with impurities of low pressure modifications. The more complex structure of gamma-SiAlON and the simultaneously exchange of the cation- and the anion-positions prevents the appearance of this important feature. Yet to be synthesized pure gamma-SiAlON using similar H-bearing precursors is necessary to resolve its structure. Sekine, T., H. He, T. Kobayashi, K

  6. Study of the extraction mechanisms by TBP saturated by uranyl nitrate; Etude des mecanismes d'extraction du TBP sature par le nitrate d'uranyle

    Energy Technology Data Exchange (ETDEWEB)

    Meze, F

    2004-02-15

    This work deals with a particular phenomenon likely to occur in the nuclear waste reprocessing process PUREX. It was shown earlier by Russian works that the extractant molecule, tributyl phosphate (TBP), saturated by uranyl nitrate keeps its extraction capacities for nitric acid and tetravalent actinides. This study is composed of three parts. Firstly, some liquid-liquid extraction experiments were conducted to verify the ability of TBP saturated by uranyl nitrate to conserve its extraction capacities for nitric acid. Then, during these experiments, the UV and infrared spectra of both phases were recorded to obtain the organic phase speciation. At last, the informations gathered during the experimental part were used to build a general species distribution model of the H{sub 2}O/HNO{sub 3}/UO{sub 2}(NO{sub 3}){sub 2}/TBP system. (author)

  7. The system uranyl nitrate-dietyl ether-water. Extraction by water in spray and packed columns from uranyl nitrate-either solutions

    International Nuclear Information System (INIS)

    Perez Luina, A.; Gutierrez Jodra, L.

    1960-01-01

    This paper is a continuation of the one published in Chemical Engineering Progress. Symposium Series, 50, n. 12, 127 (1954). New runs for spray columns, are given and other concentrations in uranyl nitrate for the packed columns. New correlations for the overall H.T.U. are also given. The individual H.T.U. have been grapycally calculated and show that the film resistances have similar values, being independent of the concentration of the ether phase. (Author) 24 refs

  8. A Voltage Controlled Oscillator for a Phase-Locked Loop Frequency Synthesizer in a Silicon-on-Sapphire Process

    Energy Technology Data Exchange (ETDEWEB)

    Garrison, Sean [Univ. of Missouri, Rolla, MO (United States)

    2009-05-21

    Engineers from a government-owned engineering and manufacturing facility were contracted by government-owned research laboratory to design and build an S-band telemetry transmitter using Radio Frequency Integrated Circuit (RFIC) technology packaged in a Low-Temperature Co-fired Ceramic (LTCC) Multi-Chip Module. The integrated circuit technology chosen for the Phase-Locked Loop Frequency Synthesizer portion of the telemetry transmitter was a 0.25 um CMOS process that utilizes a sapphire substrate and is fabricated by Peregrine Semiconductor corporation. This thesis work details the design of the Voltage Controlled Oscillator (VCO) portion of the PLL frequency synthesizer and constitutes an fully integrated VCO core circuit and a high-isolation buffer amplifier. The high-isolation buffer amplifier was designed to provide 16 dB of gain for 2200-3495 MHz as well as 60 dB of isolation for the oscillator core to provide immunity to frequency pulling due to RF load mismatch. Actual measurements of the amplifier gain and isolation showed the gain was approximately 5 dB lower than the simulated gain when all bond-wire and test substrate parasitics were taken into account. The isolation measurements were shown to be 28 dB at the high end of the frequency band but the measurement was more than likely compromised due to the aforementioned bond-wire and test substrate parasitics. The S-band oscillator discussed in this work was designed to operate over a frequency range of 2200 to 2300 MHz with a minimum output power of 0 dBm with a phase-noise of -92 dBc/Hz at a 100 kHz offset from the carrier. The tuning range was measured to be from 2215 MHz to 2330 MHz with a minimum output power of -7 dBm over the measured frequency range. A phase-noise of -90 dBc was measured at a 100 kHz offset from the carrier.

  9. Solid-state dynamics of uranyl polyoxometalates

    International Nuclear Information System (INIS)

    Alam, Todd M.; Liao, Zuolei; Zakharov, Lev N.; Nyman, May

    2014-01-01

    Understanding fundamental uranyl polyoxometalate (POM) chemistry in solution and the solid state is the first step to defining its future role in the development of new actinide materials and separation processes that are vital to every step of the nuclear fuel cycle. Many solid-state geometries of uranyl POMs have been described, but we are only beginning to understand their chemical behavior, which thus far includes the role of templates in their self-assembly, and the dynamics of encapsulated species in solution. This study provides unprecedented detail into the exchange dynamics of the encapsulated species in the solid state through Magic Angle Spinning Nuclear Magnetic Resonance (MAS NMR) spectroscopy. Although it was previously recognized that capsule-like molybdate and uranyl POMs exchange encapsulated species when dissolved in water, analogous exchange in the solid state has not been documented, or even considered. Here, we observe the extremely high rate of transport of Li + and aqua species across the uranyl shell in the solid state, a process that is affected by both temperature and pore blocking by larger species. These results highlight the untapped potential of emergent f-block element materials and vesicle-like POMs. (copyright 2014 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  10. Nucleobase assemblies supported by uranyl cation coordination ...

    Indian Academy of Sciences (India)

    by nucleobases and aqua ligands, result in the generation of complex 3-D architectures containing embedded nucleobase ribbons. Keywords. ... ing, are commonly employed to design inorganic– organic hybrid materials using smaller .... via hydrothermal reaction by dissolving stoichiometric amounts of uranyl nitrate ...

  11. Treatment of uranyl nitrate and flouride solutions

    International Nuclear Information System (INIS)

    Rodrigo Otero, A.; Rodrigo Vilaseca, F.; Morales Calvo, G.

    1977-01-01

    A theoretical study on the fluoride complexes contained in uranyl and aluminium solutions has been carried out. Likewise concentration limits and Duhring diagrams for those solutions have been experimentally established. As a result, the optimum operation conditions for concentration by evaporation in the treatment plant, have been deduced. (Author) 12 refs

  12. Identification of uranyl binding proteins from human kidney-2 cell extracts by immobilized uranyl affinity chromatography and mass spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Dedieu, A.; Berenguer, F.; Basset, Ch.; Prat, O.; Quemeneur, E.; Pible, O.; Vidaud, C. [CEA/IBEB/SBTN, F-30207 Bagnols sur Ceze (France)

    2009-07-01

    To improve our knowledge on protein targets of uranyl ion (UO{sub 2}{sup 2+}), we set up a proteomic strategy based on immobilized metal-affinity chromatography (IMAC). The successful enrichment of UO{sub 2}{sup 2+}-interacting proteins from human kidney-2 (HK-2) soluble cell extracts was obtained using an ion-exchange chromatography followed by a dedicated IMAC process previously described and designed for the uranyl ion. By mass spectrometry analysis we identified 64 proteins displaying varied functions. The use of a computational screening algorithm along with the particular ligand-based properties of the UO{sub 2}{sup 2+} ion allowed the analysis and categorization of the protein collection. This profitable approach demonstrated that most of these proteins fulfill criteria which could rationalize their binding to the UO{sub 2} {sup 2+}-loaded phase. The obtained results enable us to focus on some targets for more in-depth studies and open new insights on its toxicity mechanisms at molecular level. (authors)

  13. Synthesis, structural characterization, and dehydration analysis of uranyl zinc mellitate, (UO{sub 2})Zn(H{sub 2}O){sub 4}(H{sub 2}mel).2H{sub 2}O

    Energy Technology Data Exchange (ETDEWEB)

    Olchowka, Jakub; Volkringer, Christophe; Henry, Natacha; Loiseau, Thierry [Unite de Catalyse et Chimie du Solide (UCCS) - UMR CNRS 8181, Universite de Lille Nord de France, USTL-ENSCL, Villeneuve d' Ascq (France)

    2013-04-15

    A new heterometallic uranyl zinc carboxylate, (UO{sub 2})Zn(H{sub 2}O){sub 4}(H{sub 2}mel).2H{sub 2}O, has been hydrothermally prepared (150 C, 24 h) by using 1,2,3,4,5,6-benzenehexacarboxylic acid (mellitic acid) as organic linker in order to form a three-dimensional network. Four of the six carboxylate groups of the mellitate ligand interact with mononuclear uranyl or zinc cations, which are eightfold (hexagonal bipyramid, UO{sub 8}) or sixfold [octahedron, ZnO{sub 2}(H{sub 2}O){sub 4}] coordinated, respectively. The remaining free carboxylate arms of the mellitate species preferentially interact through hydrogen bonds with water molecules trapped within the framework. Thermogravimetric and X-ray thermodiffraction (up to 800 C) analyses and in situ infrared spectroscopy (up to 210 C) indicated that both free and bound water species are evacuated from the structure in one step between 80 and 170 C, followed by its transformation into an unknown, anhydrous, poorly crystalline phase [UO{sub 2}Zn(mel)] up to 320 C. After the formation of an amorphous phase, the re-crystallization of oxides α-ZnU{sub 3}O{sub 10} and ZnO was observed from 460 C. The fluorescence spectrum of the as-synthesized uranyl zinc mellitate shows the six bands that are typical for vibronic couplings of the [O=U=O]{sup 2+} moiety. (Copyright copyright 2013 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  14. Comparison of morphology and phase composition of hydroxyapatite nanoparticles sonochemically synthesized with dual- or single-frequency ultrasonic reactor

    Science.gov (United States)

    Deng, Shi-ting; Yu, Hong; Liu, Di; Bi, Yong-guang

    2017-10-01

    To investigate how a dual- or single-frequency ultrasonic reactor changes the morphology and phase composition of hydroxyapatite nanoparticles (nHAPs), we designed and constructed the preparation of nHAPs using dual- or single-frequency ultrasonic devices, i.e., the single frequency ultrasonic generator with ultrasonic horn (25 kHz), the ultrasonic bath (40 kHz) and the dual-frequency sonochemical systems combined with the ultrasonic horn and the ultrasonic bath simultaneously (25 + 40 kHz). The results showed that the sonicated samples displayed a more uniform shape with less agglomeration than non-sonicated sample. The rod-shaped particles with 1.66 stoichiometry and without a second phase were synthesized successfully in the ultrasonic bath or horn systems. The nHAPs obtained from the dual-frequency ultrasonic systems exhibited a regular rod-shaped structure with better dispersion and more uniform shapes than those of obtained in either ultrasonic bath or horn systems. Additionally, the size of rod-shaped particles obtained in the dual-frequency ultrasound with a mean width of 35 nm and a mean length of 64 nm was smaller than other samples. A possible mechanism is that the dual-frequency ultrasound significantly enhances the cavitation yield over single frequency ultrasound and thus improves the dispersion of particles and reduces the size of the crystals. In addition, irregular holes can be observed in the nanoparticles obtained in the dual-frequency ultrasound. Therefore, the dual-frequency ultrasonic systems are expected to become a convenient, efficient and environmentally friendly synthetic technology to obtain well-defined nHAPs for specific biomedical applications.

  15. Dynamics of a nanometer-sized uranyl cluster in solution

    International Nuclear Information System (INIS)

    Johnson, Rene L.; Ohlin, C. Andre; Pellegrini, Kristi; Burns, Peter C.; Casey, William H.

    2013-01-01

    A class of uranyl peroxide clusters was discovered before as nanometer-sized ions that form spontaneously in aqueous solutions. The uranyl(VI) cluster investigated here is approximately 2 nm in diameter, contains 24 uranyl moieties, and 12 pyrophosphate units. NMR spectroscopy shows that the ion has two distinct forms that interconvert in milliseconds to seconds depending on the temperature and the size of the counterions. (Copyright copyright 2013 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  16. Robust generation of Fourier-synthesized laser fields and their estimation of the optical phase by using quantum control of molecular tunneling ionization

    Science.gov (United States)

    Yoshida, Tsuyoshi; Saito, Naoaki; Ohmura, Hideki

    2018-03-01

    Intense (5.0 × 1012 W cm-2) nanosecond Fourier-synthesized laser fields consisting of fundamental, second-, third-, and fourth-harmonic light generated by an interferometer-free Fourier-synthesized laser field generator induce orientation-selective ionization based on directionally asymmetric molecular tunneling ionization (TI). The laser field generator ensures adjustment-free operation, high stability, and high reproducibility. Phase-sensitive, orientation-selective molecular TI provides a simple way to estimate the relative phase differences between the fundamental light and each harmonic by data-fitting analysis. This application of Fourier-synthesized laser fields will facilitate not only lightwave engineering but also the control of matter.

  17. Micro-SHINE Uranyl Sulfate Irradiations at the Linac

    Energy Technology Data Exchange (ETDEWEB)

    Youker, Amanda J. [Argonne National Lab. (ANL), Argonne, IL (United States); Kalensky, Michael [Argonne National Lab. (ANL), Argonne, IL (United States); Chemerisov, Sergey [Argonne National Lab. (ANL), Argonne, IL (United States); Schneider, John [Argonne National Lab. (ANL), Argonne, IL (United States); Byrnes, James [Argonne National Lab. (ANL), Argonne, IL (United States); Vandegrift, George F. [Argonne National Lab. (ANL), Argonne, IL (United States)

    2016-08-01

    Peroxide formation due to water radiolysis in a uranyl sulfate solution is a concern for the SHINE Medical Technologies process in which Mo-99 is generated from the fission of dissolved low enriched uranium. To investigate the effects of power density and fission on peroxide formation and uranyl-peroxide precipitation, uranyl sulfate solutions were irradiated using a 50-MeV electron linac as part of the micro-SHINE experimental setup. Results are given for uranyl sulfate solutions with both high and low enriched uranium irradiated at different linac powers.

  18. A wide bandwidth fractional-N synthesizer for LTE with phase noise cancellation using a hybrid-ΔΣ-DAC and charge re-timing

    NARCIS (Netherlands)

    Ye, D.; Lu, Ping; Andreani, Pietro; van der Zee, Ronan A.R.

    2013-01-01

    This paper presents a 1MHz bandwidth, ΔΣ fractional-N PLL as the frequency synthesizer for LTE. A noise cancellation path composed of a novel hybrid ΔΣ DAC with 9 output bits is incorporated into the PLL in order to cancel the out-of-band phase noise caused by the quantization error. Further, a

  19. Uranyl sulfate irradiations at the Van de Graaff: A means to combat uranyl peroxide precipitation

    Energy Technology Data Exchange (ETDEWEB)

    Youker, Amanda J. [Argonne National Lab. (ANL), Argonne, IL (United States); Kalensky, Michael [Argonne National Lab. (ANL), Argonne, IL (United States); Quigley, Kevin J. [Argonne National Lab. (ANL), Argonne, IL (United States); Brossard, Thomas [Argonne National Lab. (ANL), Argonne, IL (United States); Chemerisov, Sergey D. [Argonne National Lab. (ANL), Argonne, IL (United States); Vandegrift, George F. [Argonne National Lab. (ANL), Argonne, IL (United States)

    2017-05-01

    As part of an effort to support SHINE Medical Technologies in developing a process to produce Mo-99 by neutron-induced fission, a series of irradiation experiments was performed with a 3 MeV Van de Graaff accelerator to generate high radiation doses in 0.5–2 mL uranyl sulfate solutions. The purpose was to determine what conditions result in uranyl peroxide precipitation and what can be done to prevent its formation. The effects of temperature, dose rate, uranium concentration, and the addition of known catalysts for the destruction of peroxide were determined.

  20. New uranyl(VI) complexes with hydrazone-oximes derived from aromatic acid hydrazides and biacetylmonoxime—I

    Science.gov (United States)

    Shallaby, A. M.; Mostafa, M. M.; Ibrahim, K. M.; Moussa, M. N. H.

    Several new uranyl(VI) complexes of some hydrazone-oximes, derived from o-chloro-, o-methyl-, o-hydroxy-, p-chloro-, p-methyl-, p-nitro-, p-methoxybenzoylhydrazines and biacetylmonoxime, have been synthesized in absolute ethanol. The isolated solid complexes have been characterized by elemental analysis, molar conductance, molecular weights, spectral (i.r., u.v., NMR) and magnetic measurements. The ν (UO) stretching frequency of the complexes occurs at ca 920 cm-1

  1. Can uranyl complexes encapsulate to carbon nanotubes? A ...

    Indian Academy of Sciences (India)

    K SRINIVASU

    ent toxic and radioactive nature of the heavy metal ions, the design of novel materials for waste management is .... metal ion were considered and investigated here. Uranyl hydroxo species ([UO2(OH)4]2−), uranyl ..... Shi W 2012 Uranium(VI) adsorption on graphene oxide nanosheets from aqueous solutions Chem. Eng. J.

  2. Densities concentrations of aqueous of uranyl nitrate solutions

    International Nuclear Information System (INIS)

    Rodrigo Otero, A.; Rodriguez Hernandez, B.; Fernandez Rodriguez, L.

    1966-01-01

    The ratio density-concentration of aqueous uranyl nitrate solutions expressed as U 3 O 8 grams/liter, U grams/liter and hexahydrate uranyl nitrate weight percent at different temperatures, are established. Experimental values are graphically correlated and compared whit some published data. (Author) 2 refs

  3. Uranyl(VI)-acetylacetonate coordination compounds with various N-heterocyclic ligands

    International Nuclear Information System (INIS)

    Kawasaki, Takeshi; Nishimura, Tatsuru; Kitazawa, Takafumi

    2010-01-01

    Seven uranyl(VI) complexes, [UO 2 (acac) 2 (L)] [L=4-methylpyridine (1), 4-ethylpyridine (2), 2,4-dimethylpyridine (3), (-)-nicotine (4), and imidazole (5)], [{UO 2 (acac) 2 } 2 -(4,4'-bipyridine)] (6), and [(2,2'-bipyridine) 2 H][UO 2 (acac)(NO 3 ) 2 ] (7) have been synthesized and characterized crystallographically. The coordination geometry of U has a UNO 6 pentagonal-bipyramidal coordination in 1-6, and a UO 8 hexagonal-bipyramidal coordination in 7. (author)

  4. Synthesis and characterization of uranyl (UO22+) complexes with benzothiazolyl hydrazones of benzil and diacetyl

    International Nuclear Information System (INIS)

    Dash, D.C.; Mahapatra, A.; Mishra, S.K.; Naik, S.K.; Mishra, U.K.

    2007-01-01

    A few uranyl complexes of the type(UO 2 L(H 2 O) 2 NO 3 )and (UO 2 L 2 (H 2 O) 2 ); where HL is a Schiff base obtained by the condensation of 2-hydrazinobenzothiazole with benzil and diacetyl such as 2-(benzothiazolyl-2'-amino)imino-1,2-diphenylethanone (HBTDPE) and 2-(benzothiazolyl-2'-amino)imino-1,2-dimethylethanone(HBTDME) have been synthesized and characterized on the basis of elemental analysis, molar conductance, thermal analysis, infrared, electronic spectra and 1 H NMR studies. The later series of complexes are eight coordinated. (author)

  5. Quantification of uranyl in presence of citric acid

    International Nuclear Information System (INIS)

    Garcia G, N.; Barrera D, C.E.; Ordonez R, E.

    2007-01-01

    To determine the influence that has the organic matter of the soil on the uranyl sorption on some solids is necessary to have a detection technique and quantification of uranyl that it is reliable and sufficiently quick in the obtaining of results. For that in this work, it intends to carry out the uranyl quantification in presence of citric acid modifying the Fluorescence induced by UV-Vis radiation technique. Since the uranyl ion is very sensitive to the medium that contains it, (speciation, pH, ionic forces, etc.) it was necessary to develop an analysis technique that stands out the fluorescence of uranyl ion avoiding the out one that produce the organic acids. (Author)

  6. Synthese et caracterisation de recouvrements organises de nanofibres de carbone par depot chimique en phase vapeur assiste par laser

    Science.gov (United States)

    Longtin, Remi

    The miniaturisation of the transistor that began 50 years ago continues to revolutionise the microelectronics industry by allowing the fabrication of increasingly powerful microprocessors. Unfortunately, the industry is approaching a miniaturisation limit that threatens to slow down its progression unless present day microfabrication techniques are improved or if new nanofabrication techniques are developed. The solution to this challenge not only resides in the nanometre scale patterning of conventional materials such as gold and copper, but also in the synthesis of novel materials. Carbon nanofibers and nanotubes are ideal replacement nanomaterials for microelectronic components such as transistors and both horizontal and vertical interconnects. This is justified by their excellent electrical properties, their nanometre range dimensions and their fiber or tube shape. The goal of this experimental research project is to apply the laser-assisted chemical vapor deposition technique (LCVD) to the synthesis of carbon nanofibers. LCVD utilises a laser beam to initiate and maintain a chemical reaction leading to the deposition of a solid product from the gas phase. More specifically, the goal is to obtain different nanofiber assemblies locally on the surface of a substrate. This thesis focuses primarily on the synthesis of carbon nanofibers. Therefore, its scope includes the synthesis and characterisation of nanofibers as well as a partial process parameter study. Different carbon nanofiber assemblies in the form of non-aligned thin films, vertically aligned nanofiber arrays, horizontally aligned nanofiber mats and carbon-carbon composite coatings were locally synthesized on the surface of an alumina substrate by LCVD. The thin films are 100-200 nm thick and are composed of vermicular nanofibers with a multi-walled internal structure. These nanofibers are 12 to 47 nm in diameter and are several hundred nanometers in length. The vertically aligned nanofibers part of the

  7. The effect of poly vinyl alcohol (PVA) surfactant on phase formation and magnetic properties of hydrothermally synthesized CoFe{sub 2}O{sub 4} nanoparticles

    Energy Technology Data Exchange (ETDEWEB)

    Jalalian, M.; Mirkazemi, S.M., E-mail: mirkazemi@iust.ac.ir; Alamolhoda, S.

    2016-12-01

    Nanoparticles of CoFe{sub 2}O{sub 4} were synthesized by hydrothermal process at 190 °C with and without poly vinyl alcohol (PVA) addition using treatment durations of 1.5–6 h. The synthesized powders were characterized with X-ray diffraction (XRD), Raman spectroscopy, scanning electron microscope (SEM), Field emission scanning electron microscope (FESEM) and vibration sample magnetometer (VSM) techniques. XRD results show presence of CoFe{sub 2}O{sub 4} as the main phase and Co{sub 3}O{sub 4} as the lateral phase in some samples. The results show that in the samples synthesized without PVA addition considerable amount of lateral phase is present after 3 h of hydrothermal treatment while with PVA addition this phase is undetectable in the XRD patterns of the sample synthesized at the same conditions. Microstructural studies represent increasing of particle size with increasing of hydrothermal duration and formation of coarser particles with PVA addition. The highest maximum magnetization (M{sub max}) values in both of the samples that were synthesized with and without PVA addition are about 59 emu/g that were obtained after 4.5 h of hydrothermal treatment. Intrinsic coercive field ({sub i}H{sub c}) value of the sample without PVA addition increases from 210 to 430 Oe. While with PVA addition the {sub i}H{sub c} value changes from 83 Oe to 493 Oe. The mechanism of changes in M{sub max} and {sub i}H{sub c} values has been explained. - Highlights: • Nanoparticles of CoFe{sub 2}O{sub 4} hydrothermally synthesized with and without PVA addition. • PVA addition facilitates formation of single phase cobalt ferrite. • Coarser particles would be obtained with PVA addition. • The highest M{sub max} values in the samples with and without PVA are equal to 59 emu/g. • The highest {sub i}H{sub c} values are equalt to 320 and 493 Oe without and with PVA respectively.

  8. Electronic structure and properties of uranyl compounds. Quasi-relativistic calculation of uranyl by the MO LCAO method

    International Nuclear Information System (INIS)

    Glebov, V.A.; Nefedov, V.S.

    1981-01-01

    Matrix elements of non-relativiitic secular equation of MO LCAO method of uranyl and the means to correct molecular integrals included in them, taking account of relativistic effects, are described. In the bais 7ssub(1/2), 6dsub(5/2), 6dsub(3/2), 5fsub(7/2), 5fsub(5/2), 6psub(3/2), 6psub(1/2), 6ssub(1/2)-AO of uranium and 2ssub(1/2), 2psub(1/2), and 2psub(3/2)-AO of of oxygen the calculations of quasirelativistic MO of uranyl and clusters, modelling real compounds of uranyl, are made. On the basis of analysis of the chemical bonding nature a conclusion is drawn that in uranyl the contribution of internal 6p-AO of uranium into population of OUO bonds can reach 40% of total population of uranyl MO [ru

  9. Different Mechanisms Govern the Two-Phase Brust–Schiffrin Dialkylditelluride Syntheses of Ag and Au Nanoparticles

    Energy Technology Data Exchange (ETDEWEB)

    Li, Ying; Zaluzhna, Oksana; Zangmeister, Christopher D.; Allison, Thomas C.; Tong, YuYe J.

    2012-02-01

    Here we report the first unambiguous identification of the chemical structures of the precursor species involving metal (Au and Ag) ions and Te containing ligands in the Brust-Schiffrin syntheses of the respective metal nanoparticles, through which the different reaction pathways involved are delineated.

  10. Different mechanisms govern the two-phase Brust-Schiffrin dialkylditelluride syntheses of Ag and Au nanoparticles.

    Science.gov (United States)

    Li, Ying; Zaluzhna, Oksana; Zangmeister, Christopher D; Allison, Thomas C; Tong, YuYe J

    2012-02-01

    Here we report the first unambiguous identification of the chemical structures of the precursor species involving metal (Au and Ag) ions and Te-containing ligands in the Brust-Schiffrin syntheses of the respective metal nanoparticles, through which the different reaction pathways involved are delineated. © 2012 American Chemical Society

  11. Investigation of uranyl ions complexing

    International Nuclear Information System (INIS)

    Komarova, N.I.; Kakhaeva, T.V.; Kvaratskheli, Yu.K.; Vodolazov, L.I.; Rodionov, V.V.

    1986-01-01

    Spatial distribution of uranium in anionite VP-1AP grains during elevated auc sorption from carbonate media is investigated by the X-ray microanalysis. The form of the concentration profile in the grain depth varies from uniform after the first sorption and alkaline treatment then meniscus during the repeated sorption with 1-3 h phase contact time to volume in a grain after 4 h of contract. In this case the nonuniformity coefficient of uranium distribution in grains increases from 0.026 to 0.045. Capacity on uranium determined in regions along the grain diameter after alkaline treatment of saturated sorbent and repeated uranium sorption from carbonate solutions increases practically two times

  12. Contribution to the study of the mechanism of extraction of uranyl chloride by long chain aliphatic amines

    International Nuclear Information System (INIS)

    Rubinstein, G.R.

    1965-06-01

    After having studied and developed the mechanisms which may 'a priori' explain the extraction process (co-ordination, ion association or intermediate mechanism), experience shows that ion association only should be taken into consideration. The structure of the organic complex of uranyl chloride has been defined on the basis of the study of the variation of the distribution coefficient of uranium between the two phases at the equilibrium as a function of successively the activity of Cl - ions in the aqueous phase, the concentration of amine salt in the organic phase and finally of the concentration of uranium in the aqueous phase. The plotting of the results in bi-logarithmic co-ordinates enables us to propose the following formula for the extracted compound: UO 2 Cl 4 -- (NR 3 H + ) 2 . The calculation of the equilibrium constant of formation of the organic compound of uranyl chloride has been possible in the case of diluted solutions of uranium only. (author) [fr

  13. Magnetic properties of nanocrystalline ε-Fe{sub 3}N and Co{sub 4}N phases synthesized by newer precursor route

    Energy Technology Data Exchange (ETDEWEB)

    Theerthagiri, J.; Dalavi, Shankar B. [Department of Chemistry, Birla Institute of Technology and Science, Pilani, K.K. Birla, Goa Campus, Zuari Nagar, Goa 403726 (India); Manivel Raja, M. [Defence Metallurgical Research Laboratory, Hyderabad 500058 (India); Panda, R.N., E-mail: rnp@goa.bits-pilani.ac.in [Department of Chemistry, Birla Institute of Technology and Science, Pilani, K.K. Birla, Goa Campus, Zuari Nagar, Goa 403726 (India)

    2013-11-15

    Graphical abstract: Nanocrystalline ε-Fe{sub 3}N and Co{sub 4}N nitride phases are synthesized first time by newer chemical routes. The ε-Fe{sub 3}N phase crystallizes in hexagonal structure with unit cell parameters, a = 4.76 Å and c = 4.41 Å. The Co{sub 4}N phase crystallizes in face centred cubic (fcc) structure with unit cell parameters, a = 3.55 Å. The estimated crystallite size for ε-Fe{sub 3}N and Co{sub 4}N phases are 29 nm and 22 nm, respectively. The values of saturation magnetization for ε-Fe{sub 3}N and Co{sub 4}N phases are found to be 28.1 emu/g and 123.6 emu/g respectively. The reduction of magnetic moments in ultrafine materials compared to bulk materials has been explained by fine particle size and surface effects. We have synthesized the high moment ε-Fe{sub 3}N and Co{sub 4}N nitride with reduced coercivity which may find applications as soft magnetic materials. - Highlights: • Nanocrystalline ε-Fe{sub 3}N and Co{sub 4}N nitride phases are synthesized. • The ε-Fe{sub 3}N and Co{sub 4}N crystallizes in hexagonal and fcc structure respectively. • The observed magnetic parameters indicate soft magnetic properties. • The magnetic properties have been explained on the basis of fine particle magnetism. - Abstract: Nanocrystalline ε-Fe{sub 3}N and Co{sub 4}N nitride phases are synthesized first time by using tris(1,2-diaminoethane)iron(II) chloride and tris(1,2-diaminoethane)cobalt(III) chloride precursors, respectively. To prepare ε-Fe{sub 3}N and Co{sub 4}N nitride phases, the synthesized precursors were mixed with urea in 1:12 ratio and heat treated at various temperatures in the range of 450–900 °C under the ultrapure nitrogen gas atmosphere. The precursors are confirmed by FT-IR study. The ε-Fe{sub 3}N phase crystallizes in hexagonal structure with unit cell parameters, a = 4.76 Å and c = 4.41 Å. The Co{sub 4}N phase crystallizes in face centred cubic (fcc) structure with unit cell parameters, a = 3.55 Å. The

  14. Stability of sulfate complexes of electronically excited uranyl

    Energy Technology Data Exchange (ETDEWEB)

    Ostakhov, S.S.; Kazakov, V.P.; Afonichev, D.D. [Inst. of Organic Chemistry, Ufa (Russian Federation)

    1995-11-01

    The complex formation of electronically excited uranyl ions with SO{sub 4}{sup 2-}anions in 0.1 M aqueous HClO{sub 4} has been studied by time-resolved luminescence spectroscopy. The stability constants of uranyl sulfate complexes (UO{sub 2}SO{sub 4}) (K=870 1 mol{sup -1}) and [UO{sub 2}(SO{sub 4}){sub 2}{sup 2-}](K=47000 1 mol{sup -1}) in excited state have been determined; they are more than an order of magnitude greater than those reported for complex formation of uranyl ions in the ground state. The complex formation of uranyl with sulfate ions is accompanied by the increase of the quantum yield of the uranyl lumenescence. The maxima of luminescence and absorption bands of uranyl ions are shifted with increasing the total concentration of SO{sub 4}{sup 2-} in solution, which supports the data obtained. The shift of the maxima of luminescence bands is observed at a sulfate concentration that is considerably lower than that causing the same shift of the maxima of the absorption bands. Such effect is consistent with the calculated stability constants of sulfate complexes of excited uranyl ions.

  15. The extraction and effect in the system uranyl nitrate-dietyl ether-water

    International Nuclear Information System (INIS)

    Perez Luina, A.; Gutierrez Jodra, L.; Rius Miro, A.

    1960-01-01

    The solute transfer of uranyl nitrate from diethyl ether to water has been studied in a spray column using water as dispersed phase and a direction of extraction from ether to water. The column is 102 cm long and has a diameter of 4,7 cm. The entrances of the phases are 77 cm apart. The rates of flow of both phases have been used as variables and the concentration of the continuous phase has been determined at different heights. The curves of logarithm of concentration of the continuous phase vs. distance to interphase show the present of a drop of concentration in the entrance of the continuous phase. This depends on the rates of flow of the phases. No effect in the entrance of the dispersed phase has been found. (Author) 20 refs

  16. The final effect of extraction system in the uranyl nitrate-water-diethyl ether

    International Nuclear Information System (INIS)

    Perez Luina, A.; Gutierrez Jodra, L.; Miro, A. R.

    1957-01-01

    The solute transfer of uranyl nitrate from diallylether to water has been studied in a spray column using water as dispersed phase and a direction of extraction from ether to water. The column is 102 cm. long has a diameter of 4. 7 cm. The entrances of the phases are 7 7 cm. apart. The rates of flow of both phases have been used as variables and the concentration of the continuous phase has been determined; at different heights. The curves of logarithm of concentration of the continuous phase vs , distance to interphase show the presence of a drop of concentration in the entrance of the continuous phase. This depends on the rates of flow of the phases. No effect in the entrance of the dispersed phase has been found. (Author)

  17. Prediction of unknown uranyl oxide hydrate structure types: Comparison of calculated and measured XRD powder patterns

    International Nuclear Information System (INIS)

    Finch, R.J.; Hawthorne, F.C.; Ewing, R.C.

    1995-01-01

    The accurate identification of uranium-bearing corrosion products from spent fuel leaching studies is often difficult because the XRD powder patterns for many U(VI) phases are closely similar. Standard pattern-matching techniques commonly used for phase identification (e.g., JCPDS) make confident phase identification difficult and can oversimplify complex mixtures of UOHs. Refinement methods that fit the full XRD powder pattern, such as Rietveld, may be the only methods for accurate UOH identification, especially for data from sample mixtures. Rietveld refinement of XRD powder data for uranium oxides can be accomplished for phases whose structures are well defined. Unfortunately, many of the uranyl oxide hydrates are still ill-defined, both structurally and compositionally. The uranyl oxide hydrates have large unit cells and relatively low symmetries, as well as close structural similarities, all of which complicates the simultaneous refinement of mixed UOH phases. Modeling peak shape profiles can also hamper refinements of mixed-UOH samples due to extreme peak overlap. Because of these difficulties, Rietveld structure determination for UOHs from sample mixtures remains intractable, although structure determination may be possible for fine-grained, single-phase samples. Nonetheless, Rietveld refinement is the most promising method for accurately identifying the component phases in a mixture, but the unknown UOH structures must be determined before this technique can be applied successfully

  18. Determination of formation constants of uranyl(VI complexes with a hydrophilic SO3-Ph-BTP ligand, using liquid-liquid extraction

    Directory of Open Access Journals (Sweden)

    Steczek Lukasz

    2015-12-01

    Full Text Available Complex formation between uranyl ion, UO22+, and a hydrophilic anionic form of SO3-Ph-BTP4- ligand, L4-, in water was studied by liquid-liquid extraction experiments performed over a range of the ligand and HNO3 concentrations in the aqueous phase, at a constant concentration of nitrate anions at 25°C . The competition for UO22+ ions between the lipophilic TODGA extractant and the hydrophilic L4- ligand leads to the decrease in the uranyl distribution ratios, D, with an increasing L4- concentration. The model of the solvent extraction process used accounts - apart from uranyl complexation by TODGA and SO3-Ph-BTP4- - also for uranyl complexation by nitrates and for the decrease in the concentration of the free L4- ligand in the aqueous phase, due to its protonation, bonding in the uranyl complex and the distribution between the two liquid phases. The unusually strong dependence of the D values on the acidity, found in the experiment, could hardly be explained as due to L4- protonation merely. Three hypotheses were experimentally tested, striving to interpret the data in terms of additional extraction to the organic phase of ion associates of protonated TODGA cation with either partly protonated anionic L4- ligands or anionic UO22+ complexes with NO3 - or L4-. None of them has been confirmed. The analysis of the results, based on the formal correction of free ligand concentrations, points to the formation of 1 : 1 and 1 : 2 uranyl - SO3-Ph-BTP complexes in the aqueous phase. The conditional formation constant of the 1:1 complex has been determined, logßL,1 = 2.95 ± 0.15.

  19. Synthesized research report in the second mid-term research phase. Mizunami Underground Research Laboratory project, Horonobe Underground Research Laboratory project and geo-stability project (Translated document)

    International Nuclear Information System (INIS)

    Hama, Katsuhiro; Sasao, Eiji; Iwatsuki, Teruki; Onoe, Hironori; Sato, Toshinori; Yasue, Kenichi; Asamori, Koichi; Niwa, Masakazu; Osawa, Hideaki; Nagae, Isako; Natsuyama, Ryoko; Fujita, Tomoo; Sasamoto, Hiroshi; Matsuoka, Toshiyuki; Takeda, Masaki; Aoyagi, Kazuhei; Nakayama, Masashi; Miyakawa, Kazuya; Ito, Hiroaki; Ohyama, Takuya; Senba, Takeshi; Amano, Kenji

    2016-08-01

    We have synthesized the research results from the Mizunami/Horonobe Underground Research Laboratories (URLs) and geo-stability projects in the second mid-term research phase. This report can be used as a technical basis for the Nuclear Waste Management Organization of Japan/Regulator at each decision point from siting to beginning of disposal (Principal Investigation to Detailed Investigation Phase). High-quality construction techniques and field investigation methods have been developed and implemented, which will be directly applicable to the National Disposal Program (together with general assessments of hazardous natural events and processes). Acquisition of technical knowledge on decisions of partial backfilling and final closure from actual field experiments in the Mizunami/Horonobe URLs will be crucial as the main theme for the next phases. (author)

  20. Adsorption of uranyl in SiO2 porous glass

    International Nuclear Information System (INIS)

    Benedetto, F. E.; Prado, M. O.

    2013-01-01

    Vitreous SiO 2 porous matrices can be used in many applications involving the uptake of chemical species on its solid surface. In this work, vitreous silica sponges were prepared from a sodium borosilicate glass manufactured in our laboratory. The product obtained was then separated into phases with subsequent leaching of the soluble phase rich in B and Na. The resulting porous matrices have a specific surface of 35 m2/gr. Adsorption of uranyl ions onto the SiO 2 porous surface was studied to evaluate the use of this material as a filter for treatment of uranium containing water. The effects of contact time, adsorbent mass and equilibrium concentration of solution were studied. The porous adsorbent exhibits a pseudo-second-order kinetic behavior. The sponges with adsorbed uranium were thermally sealed as a way of U immobilization. Retention of uranium was confirmed during the matrix sealing by TGA. Uranium concentration before and after adsorption tests were made by means of ICP-OES. For uranium concentration of 800 ppm, 72 hours contact time and pH of 3.5, the amount of uranium adsorbed was 21.06 ± 0.02 mg U per gram of vitreous porous SiO 2 . (author)

  1. Complexes of uranyl nitrate with 2,6-pyridinedicarboxamides: synthesis, crystal structure, and DFT study

    Energy Technology Data Exchange (ETDEWEB)

    Alyapyshev, Mikhail; Babain, Vasiliy [ITMO University, 49, Kronverksky pr., 197101, St. Petersburg (Russian Federation); ThreeArc Mining Ltd., 5, Stary Tolmachevskiy per., 115184, Moscow (Russian Federation); Tkachenko, Lyudmila; Lumpov, Alexander [Khlopin Radium Institute, 28, 2nd Murinskiy pr., 194021, St. Petersburg (Russian Federation); Gurzhiy, Vladislav; Zolotarev, Andrey; Dar' in, Dmitriy [St. Petersburg State University, 7-9, Universitetskaya nab., 199034, St. Petersburg (Russian Federation); Ustynyuk, Yuriy; Gloriozov, Igor [M.V. Lomonosov Moscow State University, 119991, Moscow (Russian Federation); Paulenova, Alena [Department of Nuclear Engineering, Oregon State University, Corvallis, OR (United States)

    2017-05-04

    Two complexes of uranyl nitrate with N,N,N',N'-tetrabutyl-2,6-pyridinedicarboxamide (TBuDPA) and N,N'-diethyl-N,N'-diphenyl-2,6-pyridinedicarboxamide (EtPhDPA) were synthesized and studied. The complex of tetraalkyl-2,6-pyridinedicarboxamide with metal nitrate was synthesized for the first time. XRD analysis revealed the different type of complexation: a 1:1 metal:ligand complex for EtPhDPA and complex with polymeric structure for TBuDPA. The quantum chemical calculations (DFT) confirm that both ligands form the most stable complexes that match the minimal values pre-organization energy of the ligands. (copyright 2017 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  2. Radiolysis studies of uranyl nitrate solution in nitric acid medium

    International Nuclear Information System (INIS)

    Siri, Sandra; Mondino, Angel V.

    2005-01-01

    The radiolysis of acidic uranyl nitrate solutions was investigated using Co-60 gamma radiation. Hydrogen peroxide was determined as a function of increasing dose. The UV-vis absorption spectra of the irradiated solutions were measured and the spectral changes were analyzed. The increasing dose increases the absorbance intensities, possibly by an increment in nitrate concentration produced by radiolysis, which can originate the formation of different uranyl complexes in solution. (author)

  3. Thermodynamics of dehydration process of uranyl nitrate pentahydrate of thorium

    International Nuclear Information System (INIS)

    Khamidov, F.A.; Mirsaidov, I.U.; Nazarov, K.M.; Nasriddinov, S.K.; Badalov, A.B.

    2010-01-01

    Present article is devoted to thermodynamics of dehydration process of uranyl nitrate pentahydrate of thorium. The results of researches of dehydration process of uranyl nitrate pentahydrate of thorium Th(NO 3 ) 4 ·5H 2 O were considered. The researches were carried out by means of tensimeter method with membrane zero-manometer under equilibrium conditions and at 300-450 K temperature ranges. The thermodynamic characteristics of dehydration process of initial crystalline hydrate was defined.

  4. Uranyl phosphate mineral in Gapyeong area

    International Nuclear Information System (INIS)

    Chung, S.J.

    1980-01-01

    An uranyl phosphate crystal from Gapeong area is studied by means of single crystal x-ray diffraction and electron microscopic qualitative analysis of chemical contents. The crystal is identified as meta-ankoleite which has a unit cell of super structure with a=b=6.99 A, c=17.69 A and space group P4 2 22. There exists some indication in the total fluorescent spectrum of the sample that potassium may be partially substituted by calcium. The chemical formula of this meta-ankoleite may be expressed by Ksub(1-2x)Casub(x)(UO 2 PO 4 ) (H 2 O)sub(3-x). (Author)

  5. Glutathione attenuates uranyl toxicity in Lactococcus lactis

    International Nuclear Information System (INIS)

    Fahmy, Karim; Oertel, Jana; Solioz, M.

    2017-01-01

    We investigated the role of intracellular glutathione (GSH), which in a large number of taxa plays a role in the protection against the toxicity of heavy metals. Anaerobically grown Lactococcus lactis containing an inducible GSH synthesis pathway was used as a model organism allowing the study of GSH-dependent uranyl detoxification without interference from additional reactive oxygen species. Microcalorimetric measurements of the metabolic heat showed that intracellular GSH attenuates the toxicity of uranium at a concentration in the range of 10-150 μM. Isothermal titration calorimetry revealed the endothermic binding of U(VI) to the carboxyl group(s) of GSH. The data indicate that the primary detoxifying mechanism is the intracellular sequestration of carboxyl-coordinated U(VI) into an insoluble complex with GSH.

  6. Glutathione attenuates uranyl toxicity in Lactococcus lactis

    Energy Technology Data Exchange (ETDEWEB)

    Fahmy, Karim; Oertel, Jana [Helmholtz-Zentrum Dresden-Rossendorf e.V., Dresden (Germany). Biophysics; Obeid, M. [Technische Univ. Dresden (Germany); Solioz, M. [Bern Univ. (Switzerland)

    2017-06-01

    We investigated the role of intracellular glutathione (GSH), which in a large number of taxa plays a role in the protection against the toxicity of heavy metals. Anaerobically grown Lactococcus lactis containing an inducible GSH synthesis pathway was used as a model organism allowing the study of GSH-dependent uranyl detoxification without interference from additional reactive oxygen species. Microcalorimetric measurements of the metabolic heat showed that intracellular GSH attenuates the toxicity of uranium at a concentration in the range of 10-150 μM. Isothermal titration calorimetry revealed the endothermic binding of U(VI) to the carboxyl group(s) of GSH. The data indicate that the primary detoxifying mechanism is the intracellular sequestration of carboxyl-coordinated U(VI) into an insoluble complex with GSH.

  7. Uranyl-organic hybrids designed from hydroxyphosphonate

    Energy Technology Data Exchange (ETDEWEB)

    Adelani, Pius O.; Cook, Nathaniel D. [Department of Civil and Environmental Engineering and Earth Sciences, University of Notre Dame, Notre Dame, IN (United States); Martinez, Nicholas A. [Department of Chemistry and Biochemistry, University of Notre Dame, Notre Dame, IN (United States); Burns, Peter C. [Department of Civil and Environmental Engineering and Earth Sciences, University of Notre Dame, Notre Dame, IN (United States); Department of Chemistry and Biochemistry, University of Notre Dame, Notre Dame, IN (United States)

    2015-01-15

    A series of phosphonate-based uranyl-organic hybrids has been assembled based on the reaction of uranyl cations with 2,5-dihydroxy-1,4-benzenediphosphonic acid in the presence of a variety of alkali metal and organoammonium cations: K[(UO{sub 2}){sub 2}F{sub 2}{H_0_._5O_3PC_6H_2(OH)_2PO_3H_0_._5}](H{sub 2}O){sub 2} (1), Cs[(UO{sub 2}){sub 2}{H_0_._7_5O_3PC_6H_2(OH)_2PO_3H_0_._7_5}](H{sub 2}O){sub 4}.2H{sub 2}O (2), [(CH{sub 3}){sub 4}N]{sub 2}[UO{sub 2}{HO_3PC_6H_2(OH)_2PO_3H}{sub 2}] (3), [(CH{sub 3}CH{sub 2}){sub 4}N][UO{sub 2}F{HO_3PC_6H_2(OH)_2PO_3H}] (4), and [(CH{sub 3}CH{sub 2}){sub 2}N(CH{sub 3}){sub 2}][UO{sub 2}F{HO_3PC_6H_2(OH)_2PO_3H}] (5). In compounds 1, 4, and 5, chains of UO{sub 5}F{sub 2} pentagonal bipyramids are linked by the hydroxyphosphonate moiety into three-dimensional frameworks, and compound 4 is isostructural with 5. However, the structures of 2 and 3 are composed of monomeric UO{sub 7} pentagonal bipyramids assembled to form layered structural units. Additional steric influences from the -OH groups appended on the diphosphonate species play a vital role in directing the structure topologies. (Copyright copyright 2015 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  8. Uranyl-organic hybrids designed from hydroxyphosphonate

    International Nuclear Information System (INIS)

    Adelani, Pius O.; Cook, Nathaniel D.; Martinez, Nicholas A.; Burns, Peter C.

    2015-01-01

    A series of phosphonate-based uranyl-organic hybrids has been assembled based on the reaction of uranyl cations with 2,5-dihydroxy-1,4-benzenediphosphonic acid in the presence of a variety of alkali metal and organoammonium cations: K[(UO 2 ) 2 F 2 {H 0.5 O 3 PC 6 H 2 (OH) 2 PO 3 H 0.5 }](H 2 O) 2 (1), Cs[(UO 2 ) 2 {H 0.75 O 3 PC 6 H 2 (OH) 2 PO 3 H 0.75 }](H 2 O) 4 .2H 2 O (2), [(CH 3 ) 4 N] 2 [UO 2 {HO 3 PC 6 H 2 (OH) 2 PO 3 H} 2 ] (3), [(CH 3 CH 2 ) 4 N][UO 2 F{HO 3 PC 6 H 2 (OH) 2 PO 3 H}] (4), and [(CH 3 CH 2 ) 2 N(CH 3 ) 2 ][UO 2 F{HO 3 PC 6 H 2 (OH) 2 PO 3 H}] (5). In compounds 1, 4, and 5, chains of UO 5 F 2 pentagonal bipyramids are linked by the hydroxyphosphonate moiety into three-dimensional frameworks, and compound 4 is isostructural with 5. However, the structures of 2 and 3 are composed of monomeric UO 7 pentagonal bipyramids assembled to form layered structural units. Additional steric influences from the -OH groups appended on the diphosphonate species play a vital role in directing the structure topologies. (Copyright copyright 2015 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  9. Magnetic response of polycrystalline YBaCo{sub 4}O{sub 7+δ} synthesized through the physical and chemical route: The role of phase inhomogeneities

    Energy Technology Data Exchange (ETDEWEB)

    Vallejos, E. [Universidad de Nariño, Centro de Materiales Avanzados, Torobajo, Pasto (Colombia); Galeano, V.; Gómez, L.; Izquierdo, J.L.; Montoya, J.F. [Universidad Nacional de Colombia, Campus Medellín, Departamento de Física, Laboratorio de Materiales Cerámicos y Vítreos, A.A. 568 Medellín (Colombia); Mera, J.; Córdoba, C. [Universidad de Nariño, Centro de Materiales Avanzados, Torobajo, Pasto (Colombia); Gómez, A. [Universidad Nacional de Colombia, Campus Medellín, Facultad de Minas, Laboratorio de caracterización de materiales, A.A. 568 Medellín (Colombia); Paucar, C. [Universidad Nacional de Colombia, Campus Medellín, Departamento de Física, Laboratorio de Materiales Cerámicos y Vítreos, A.A. 568 Medellín (Colombia); Morán, O., E-mail: omoranc@unal.edu.co [Universidad Nacional de Colombia, Campus Medellín, Departamento de Física, Laboratorio de Materiales Cerámicos y Vítreos, A.A. 568 Medellín (Colombia)

    2014-06-01

    Polycrystalline YBaCo{sub 4}O{sub 7+δ} samples were obtained through a standard solid state reaction, and their structural, morphological, electrical, and magnetic properties are carefully studied. The X-ray powder diffraction (XRD) patterns showed reflections of a pure hexagonal structure (space group P6{sub 3}mc) with lattice parameters being very close to those reported in the literature. Although XRD analysis showed that the main phase present is 114, the presence of secondary phases could not be ruled out based solely on the XRD characterization. Indeed, sensitive SQUID magnetic measurements showed that the samples were affected by very small quantities of the 112 phase (YBaCo{sub 2}O{sub 5.5}), which typically manifests itself through a conspicuous increase in the magnetization at∼300 K. The results achieved corroborated the predictions concerning the difficulty of stabilizing the 114 phase when synthesized via the standard solid-state reaction. With this in mind, we next attempted to obtain the compound with improved phase purity. In so doing, the YBaCo{sub 4}O{sub 7+δ} compound was synthesized through a wet chemistry method based on a citrates route. The XRD patterns recorded for these samples revealed well-defined peaks corresponding to a pure hexagonal structure. More interestingly, SQUID measurements show no sign of features in the M(T) curve at temperatures as low as∼80 K. This result was consistent with the magnetic behavior observed in YBaCo{sub 4}O{sub 7+δ} single-crystals. At temperatures below∼80 K, a clear feature was observed which seemed to correlate with a transition into an antiferromagnetic state. Isothermal magnetization recorded at 70 K showed that field-induced effects manifested themselves through the appearance of a ferromagnetic-like component. This ferromagnetic component may arise from spin canting of the underlying antiferromagnetic state or through field-induced structural transition (at least at local scale). Although a

  10. Magnetic response of polycrystalline YBaCo4O7+δ synthesized through the physical and chemical route: The role of phase inhomogeneities

    International Nuclear Information System (INIS)

    Vallejos, E.; Galeano, V.; Gómez, L.; Izquierdo, J.L.; Montoya, J.F.; Mera, J.; Córdoba, C.; Gómez, A.; Paucar, C.; Morán, O.

    2014-01-01

    Polycrystalline YBaCo 4 O 7+δ samples were obtained through a standard solid state reaction, and their structural, morphological, electrical, and magnetic properties are carefully studied. The X-ray powder diffraction (XRD) patterns showed reflections of a pure hexagonal structure (space group P6 3 mc) with lattice parameters being very close to those reported in the literature. Although XRD analysis showed that the main phase present is 114, the presence of secondary phases could not be ruled out based solely on the XRD characterization. Indeed, sensitive SQUID magnetic measurements showed that the samples were affected by very small quantities of the 112 phase (YBaCo 2 O 5.5 ), which typically manifests itself through a conspicuous increase in the magnetization at∼300 K. The results achieved corroborated the predictions concerning the difficulty of stabilizing the 114 phase when synthesized via the standard solid-state reaction. With this in mind, we next attempted to obtain the compound with improved phase purity. In so doing, the YBaCo 4 O 7+δ compound was synthesized through a wet chemistry method based on a citrates route. The XRD patterns recorded for these samples revealed well-defined peaks corresponding to a pure hexagonal structure. More interestingly, SQUID measurements show no sign of features in the M(T) curve at temperatures as low as∼80 K. This result was consistent with the magnetic behavior observed in YBaCo 4 O 7+δ single-crystals. At temperatures below∼80 K, a clear feature was observed which seemed to correlate with a transition into an antiferromagnetic state. Isothermal magnetization recorded at 70 K showed that field-induced effects manifested themselves through the appearance of a ferromagnetic-like component. This ferromagnetic component may arise from spin canting of the underlying antiferromagnetic state or through field-induced structural transition (at least at local scale). Although a definitive interpretation of the in

  11. Probing the influence of N-donor capping ligands on supramolecular assembly in molecular uranyl materials

    Energy Technology Data Exchange (ETDEWEB)

    Carter, Korey P.; Kalaj, Mark; Cahill, Christopher L. [Department of Chemistry, The George Washington University, Washington, DC (United States)

    2016-01-15

    The syntheses and crystal structures of six new compounds containing the UO{sub 2}{sup 2+} cation, 3,5-dichlorobenzoic acid, and a chelating N-donor [2,2'-bipyridine (bipy), 1,10-phenanthroline (phen), 4,7-dimethyl-1,10-phenanthroline (dimethylphen), 2,2{sup '}:6{sup '},2''-terpyridine (terpy), 4{sup '}-chloro-2,2{sup '}:6{sup '},2''-terpyridine (Cl-terpy), or 2,4,6-tris(2-pyridyl)-s-triazine (TPTZ)] are reported. Single-crystal X-ray diffraction analysis of these materials enabled the exploration of the structural relationship between the benzoic acids and the chelating N-donor as well as providing a platform to evaluate the effects of ligand choice on uranyl hydrolysis and subsequent oligomerization. At an unadjusted pH (ca. 3), a mix of uranyl monomers and dimers are observed, dimer formation resulting from both bridging carboxylate linkers and hydroxo bridges. Assembly by halogen- and hydrogen-bonding interactions as well as π-π interactions was observed depending on the experimental conditions utilized. Further, spectroscopic characterization (both vibrational and luminescence) of complexes 1, 4, and 5 to explore the effects of the electron-donating ability of the capping ligand on the corresponding uranyl luminescence and vibrational spectra suggests that there is a relationship between the observed bathochromic shifts and the electron-donating ability of the capping ligands. (Copyright copyright 2015 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  12. Probing the influence of N-donor capping ligands on supramolecular assembly in molecular uranyl materials

    International Nuclear Information System (INIS)

    Carter, Korey P.; Kalaj, Mark; Cahill, Christopher L.

    2016-01-01

    The syntheses and crystal structures of six new compounds containing the UO 2 2+ cation, 3,5-dichlorobenzoic acid, and a chelating N-donor [2,2'-bipyridine (bipy), 1,10-phenanthroline (phen), 4,7-dimethyl-1,10-phenanthroline (dimethylphen), 2,2 ' :6 ' ,2''-terpyridine (terpy), 4 ' -chloro-2,2 ' :6 ' ,2''-terpyridine (Cl-terpy), or 2,4,6-tris(2-pyridyl)-s-triazine (TPTZ)] are reported. Single-crystal X-ray diffraction analysis of these materials enabled the exploration of the structural relationship between the benzoic acids and the chelating N-donor as well as providing a platform to evaluate the effects of ligand choice on uranyl hydrolysis and subsequent oligomerization. At an unadjusted pH (ca. 3), a mix of uranyl monomers and dimers are observed, dimer formation resulting from both bridging carboxylate linkers and hydroxo bridges. Assembly by halogen- and hydrogen-bonding interactions as well as π-π interactions was observed depending on the experimental conditions utilized. Further, spectroscopic characterization (both vibrational and luminescence) of complexes 1, 4, and 5 to explore the effects of the electron-donating ability of the capping ligand on the corresponding uranyl luminescence and vibrational spectra suggests that there is a relationship between the observed bathochromic shifts and the electron-donating ability of the capping ligands. (Copyright copyright 2015 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  13. Characterization of Cr-rich Cr-Sb multilayer films: Syntheses of a new metastable phase using modulated elemental reactants

    International Nuclear Information System (INIS)

    Regus, Matthias; Mankovsky, Sergiy; Polesya, Svitlana; Kuhn, Gerhard; Ditto, Jeffrey; Schürmann, Ulrich; Jacquot, Alexandre; Bartholomé, Kilian; Näther, Christian; Winkler, Markus; König, Jan D.; Böttner, Harald; Kienle, Lorenz; Johnson, David C.; Ebert, Hubert; Bensch, Wolfgang

    2015-01-01

    The new metastable compound Cr 1+x Sb with x up to 0.6 has been prepared via a thin film approach using modulated elemental reactants and investigated by in-situ X-ray reflectivity, X-ray diffraction, differential scanning calorimetry, energy dispersive X-ray analysis as well as transmission electron microscopy and atomic force microscopy. The new Cr-rich antimonide crystallizes in a structure related to the Ni 2 In-type structure, where the crystallographic position (1/3, 2/3, 3/4) is partially occupied by excess Cr. The elemental layers of the pristine material interdiffused significantly before Cr 1+x Sb crystallized. A change in the activation energy was observed for the diffusion process when crystal growth starts. First-principles electronic structure calculations provide insight into the structural stability, magnetic properties and resistivity of Cr 1+x Sb. - Graphical abstract: 1 amorphous multilayered film 2 interdiffused amorphous film 3 metastable crystalline phase 4 thermodynamic stable phase (and by-product). - Highlights: • Interdiffusion of amorphous Cr and Sb occurs before crystallization. • Crystallization of a new metastable phase Cr 1.6 Sb in Ni 2 In-type structure. • The new Cr-rich phase shows half-metallic behavior

  14. Kinetic of liquid-liquid extraction for uranyl nitrate and actinides (III) and lanthanides (III) nitrates by amide extractants

    International Nuclear Information System (INIS)

    Toulemonde, V.; CEA Centre d'Etudes de la Vallee du Rhone, 30 -Marcoule

    1995-01-01

    The kinetics of liquid-liquid extraction by amide extractants have been investigated for uranyl nitrate (monoamide extractants), actinides (III) and lanthanides (III) nitrates (diamide extractants). The transfer of the metallic species from the aqueous phase to the organic phase was studied using two experimental devices: ARMOLLEX (Argonne Modified Lewis cell for Liquid Liquid Extraction) and RSC (Rotating Stabilized Cell). The main conclusions are: for the extraction of uranyl nitrate by DEHDMBA monoamide, the rate-controlling step is the complexation of the species at the interface of the two liquids. Thus, an absorption-desorption (according to Langmuir theory) reaction mechanism was proposed; for the extraction of actinides (III) and lanthanides (III) nitrates in nitric acid media by DMDBTDMA diamide, the kinetic is also limited by interfacial reactions. The behavior of Americium and Europium is very similar as fare as their reaction kinetics are concerned. (author)

  15. Tetragonal-cubic phase boundary in nanocrystalline ZrO2-Y2O3 solid solutions synthesized by gel-combustion

    International Nuclear Information System (INIS)

    Fabregas, Ismael O.; Craievich, Aldo F.; Fantini, Marcia C.A.; Millen, Ricardo P.; Temperini, Marcia L.A.; Lamas, Diego G.

    2011-01-01

    Research highlights: → Gel-combustion synthesis yields compositionally homogeneous, single-phased ZrO 2 -Y 2 O 3 nanopowders, that exhibit the presence at room temperature of three different phases depending on Y 2 O 3 content, namely two tetragonal forms (t' and t'') and the cubic phase. → Phase identification can be achieved by synchrotron XPD (SXPD) and Raman spectroscopy since the tetragonal forms and the cubic phase can be distinguished by these techniques. → The crystallographic features of ZrO 2 -Y 2 O 3 nanopowders were determined by SXPD. They are similar to those reported by Yashima and coworkers for compositionally homogeneous materials containing larger (micro)crystals. However, the lattice parameters are slightly different and the axial ratios c/a of our t' samples are smaller than those reported by these authors. → Compositional t'/t'' and t''/cubic phase boundaries are located at (9 ± 1) and (10.5 ± 0.5) mol% Y 2 O 3 , respectively. → For the whole series of nanocrystalline ZrO 2 -Y 2 O 3 solid solutions studied in the present work, no evidences of the presence of a mixture of phases - as reported by Yashima and coworkers for microcrystalline solid solutions - were detected. - Abstract: By means of synchrotron X-ray powder diffraction (SXPD) and Raman spectroscopy, we have detected, in a series of nanocrystalline and compositionally homogeneous ZrO 2 -Y 2 O 3 solid solutions, the presence at room temperature of three different phases depending on Y 2 O 3 content, namely two tetragonal forms and the cubic phase. The studied materials, with average crystallite sizes within the range 7-10 nm, were synthesized by a nitrate-citrate gel-combustion process. The crystal structure of these phases was also investigated by SXPD. The results presented here indicate that the studied nanocrystalline ZrO 2 -Y 2 O 3 solid solutions exhibit the same phases reported in the literature for compositionally homogeneous materials containing larger (micro

  16. Methods to synthesize NiPt bimetallic nanoparticles by a reversed-phase microemulsion, deposition of NiPt bimetallic nanoparticles on a support, and application of the supported catalyst for CO.sub.2 reforming of methane

    KAUST Repository

    Biausque, Gregory

    2015-04-28

    Methods to synthesize NiPt bimetallic nanoparticles by a reversed-phase microemulsion, deposition of NiPt bimetallic nanoparticles on a support, and application of the supported catalyst for CO.sub.2 reforming of methane

  17. Magnetic phase diagram of S r2 -xL axIr O4 synthesized by mechanical alloying

    Science.gov (United States)

    Horigane, K.; Fujii, M.; Okabe, H.; Kobayashi, K.; Horie, R.; Ishii, H.; Liao, Y. F.; Kubozono, Y.; Koda, A.; Kadono, R.; Akimitsu, J.

    2018-02-01

    We report the crystal structure and physical properties of S r2 -xL axIr O4 synthesized by mechanical alloying. The magnetic transition temperature TN and electrical resistivity decreased with increasing La doping, consistent with previous studies involving single-crystalline samples. We also identified the relationship between TN and tetragonal distortion (c /a ) in this system. This result suggests that the magnetism of the Sr214 system is strongly correlated with its crystal structure. Zero-field muon spin rotation/relaxation studies revealed that short-range antiferromagnetic ordering is realized in S r1.9L a0.1Ir O4 ; also, the spin-glass state is stabilized in the low-temperature region. The Ir moment estimated from the longitudinal field μSR results is 0.045 μB , ten times smaller than that of S r2Ir O4 (˜0.4 μB ), indicating that electrons are introduced into the Ir atoms.

  18. Structural and electrical properties of different vanadium oxide phases in thin film form synthesized using pulsed laser deposition

    Science.gov (United States)

    Majid, S. S.; Shukla, D. K.; Rahman, F.; Choudhary, R. J.; Phase, D. M.

    2015-06-01

    We present here the structural and electrical properties of the thin films of V2O3 (Vanadium sesquioxide) and V5O9. Both these oxide phases, V2O3 and V5O9, have beenachieved on (001) orientedSi substrate using the V2O5 target by optimizing the deposition parameters using pulsed laser deposition technique (PLD).Deposited films were characterized by X-ray diffraction(XRD)and four probe temperature dependent resistivity measurements. XRD studies reveal the V2O3 and V5O9 phases and the amount of strain present in both these films. The temperature dependency of electrical resistivity confirmed the characteristic metal-insulator transitions (MIT) for both the films, V2O3 and V5O9.

  19. Study on the transport behavior of uranyl nitrate in aqueous and non-aqueous systems

    International Nuclear Information System (INIS)

    Roesel, B.

    1985-01-01

    The analytical ultracentrifuge has proven itself through diffusion measurements to be well suited for studying radioactive compounds. In the framework of this paper the extent to which the UV and schlieren optics of an analytical ultracentrifuge can be used for extraction-kinetic tests was tested. With this method there is also the possibility of determining the distribution coefficients right at the phase boundary. The results show the good possibility of application of the absorption and schlieren optics to the study of the transport behavior of uranyl nitrate in practice oriented solutions. (orig.) [de

  20. Effect of n-octanol on -uranyl extraction by tri-n-octylammonium sulfate

    International Nuclear Information System (INIS)

    Ochkin, A.V.; Kudrov, A.N.

    1984-01-01

    The effect of n-octanol on the extraction of uranyl sulfate by solutions of tri-n-octylamine sulfate in benzene has been studied. With the increase of alcohol concentration the coefficient of uranium distribution passes through the maximum. At low alcohol concentrations a decrease in water content in the organic phase is observed. It is shown that the increase in ammonium salt activity in replacement of part of hydrate At high alcohol concentration the decrease in uranium distribution coefficients is observed, which is related to TOA sulfate solvation by alcohol

  1. Efficient tetracycline adsorption and photocatalytic degradation of rhodamine B by uranyl coordination polymer

    Science.gov (United States)

    Ren, Ya-Nan; Xu, Wei; Zhou, Lin-Xia; Zheng, Yue-Qing

    2017-07-01

    Two mixed uranyl-cadmium malonate coordination polymers [(UO2)2Cd(H-bipy)2(mal)4(H2O)2]·4H2O 1 and [(UO2)Cd(bipy)(mal)2]·H2O 2 (H2mal = malonic acid, bipy =4,4‧-bipyridine) have been synthesized in room temperature. Compound 1 represents a one-dimensional (1D) chain assembly of Cd(II) ions, uranyl centers and malonate ligands. Compound 2 exhibits a two-dimensional (2D) 2D +2D → 3D polycatenated framework based on inclined interlocked 2D 44 sql grids. The two compounds have been characterized by elemental analysis, IR and UV-vis spectroscopy, thermal analysis, powder X-ray diffraction and photoluminescence spectroscopy. And the ferroelectric property of 2 also has been studied. Moreover, compound 2 exhibits good photocatalytic activity for dye degradation under UV light and is excellent adsorbent for removing tetracycline antibiotics in the aqueous solution.

  2. Structural and electrical properties of different vanadium oxide phases in thin film form synthesized using pulsed laser deposition

    Energy Technology Data Exchange (ETDEWEB)

    Majid, S. S., E-mail: suhailphy276@gmail.com; Rahman, F. [Department of Physics, Aligarh Muslim University, Aligarh-202002 (India); Shukla, D. K.; Choudhary, R. J.; Phase, D. M. [UGC-DAE Consortium for Scientific Research, Indore-452001 (India)

    2015-06-24

    We present here the structural and electrical properties of the thin films of V{sub 2}O{sub 3} (Vanadium sesquioxide) and V{sub 5}O{sub 9}. Both these oxide phases, V{sub 2}O{sub 3} and V{sub 5}O{sub 9}, have beenachieved on (001) orientedSi substrate using the V{sub 2}O{sub 5} target by optimizing the deposition parameters using pulsed laser deposition technique (PLD).Deposited films were characterized by X-ray diffraction(XRD)and four probe temperature dependent resistivity measurements. XRD studies reveal the V{sub 2}O{sub 3} and V{sub 5}O{sub 9} phases and the amount of strain present in both these films. The temperature dependency of electrical resistivity confirmed the characteristic metal-insulator transitions (MIT) for both the films, V{sub 2}O{sub 3} and V{sub 5}O{sub 9}.

  3. Syntheses and modulations in the chromatin contents of histones H1/sup o/ and H1 during G1 and S phases in Chinese hamsters cells

    International Nuclear Information System (INIS)

    D'Anna, J.A.; Gurley, L.R.; Tobey, R.A.

    1982-01-01

    Flow cytometry, conventional autoradiography, and autoradiography employing high concentrations of high specific activity [ 3 H]thymidine indicate that (1) treatment of Chinese hamster ovary (line CHO) cells with butyrate truly blocks cells in G 1 and (2) cells blocked in G 1 by isoleucine deprivation remain blocked in G 1 when they are released into complete medium containing butyrate. Measurements of H1/sup o/ content relative to core histones and H1/sup o/:H1 ratios indicate that H1/sup o/ is enhanced somewhat in G 1 cells arrested by isoleucine deprivation; however, (1) treatment with butyrate greatly increases the H1/sup o/ content in G 1 -blocked cells, and (2) the enhancement is very sensitive to butyrate concentration. Measurements of relative histone contents in the isolated chromatin of synchronized cultures also suggest that the acid-soluble content of histone H1 (relative to core histones) becomes greatly depleted in the isolated chromatin when synchronized cells are blocked in early S phase by sequential use of isoleucine deprivation and hydroxyurea blockade. We also have measured [ 3 H]lysine incorporation, various protein ratios, and relative rates of deposition of newly synthesized H1/sup o/, H1, and H4 onto chromatin during G 1 and S in the absence of butyrate. The results suggest a dynamic picture of chromatin organization in which (1) newly synthesized histone H1/sup o/ binds to chromatin during traverse of G 1 and S phases and (2) histone H1 dissociates from (or becomes loosely bound to) chromatin during prolonged early S-phase block with hydroxyurea

  4. G1- and S-phase syntheses of histones H1 and H1o in mitotically selected CHO cells: utilization of high-performance liquid chromatography

    International Nuclear Information System (INIS)

    D'Anna, J.A.; Thayer, M.M.; Tobey, R.A.; Gurley, L.R.

    1985-01-01

    The authors have employed high-performance liquid chromatography (HPLC) to investigate the syntheses of histones H1 and H1o as synchronized cells traverse from mitosis to S phase. Chinese hamster (line CHO) cells were synchronized by mitotic selection, and, at appropriate times, they were pulse labeled for 1 h with [ 3 H]lysine. Histones H1 and H1o were extracted by blending radiolabeled and carrier cells directly in 0.83 M HC1O 4 ; the total HC1O 4 -soluble, Cl 3 CCO 2 H-precipitable proteins were then separated by a modification of an HPLC system employing three mu Bondapak reversed-phase columns. These procedures (1) produce minimally perturbed populations of synchronized proliferating cells and (2) maximize the recovery of radiolabeled histones during isolation and analysis. Measurements of rates of synthesis indicate that the rate of H1 synthesis increases as cells traverse from early to mid G1; as cells enter S phase, the rate of H1 synthesis increases an additional congruent to 22-fold and is proportional to the number of S-phase cells. In contrast to H1, the rate of H1o synthesis is nearly constant throughout G1. As cells progress into S phase, the rate of H1o synthesis increases so that it also appears to be proportional to the number of S-phase cells. Except for the first 1-2 h after mitotic selection, these results are similar to those obtained when cells are synchronized in G1 with the isoleucine deprivation procedure

  5. Uranyl ion transport across tri-n-butyl phosphate/n-dodecane liquid membranes

    International Nuclear Information System (INIS)

    Shukla, J.P.; Misra, S.K.

    1991-01-01

    Carrier-facilitated transport of uranium (VI) against its concentration gradient from aqueous nitrate acidic solutions across organic bulk liquid membranes (BLM) and supported liquid membranes (SLM) containing TBP as the mobile carrier and n-dodecane as the membrane solvent was investigated. Extremely dilute uranyl nitrate solutions in about 2.5 M nitric acid generally constituted as the source phase. Uranyl transport appreciably increased with both stirring of the receiving phase and the carrier concentration in the organic membrane, while enhanced acidity of the strip side adversely affected the partioning of the cation into this phase. Among the several reagents tested, diluted ammonium carbonate (∼1M) solutions served efficiently as the stripant. Besides Accurel polypropylene (PP) film as the solid support for SLM, some silicon flat-sheet membranes with different inorganic fillers like silica, calcium silicate, calcium carbonate, chromium oxide, zinc oxide etc. and teflon membranes transported about 70% of uranium in nearly 7-8 hr employing 1 M ammonium carbonate as the strippant. Specifically, 30% TBP supported on Accurel flat-sheet supports transfered better than 70% of uranium from moderate acid feeds (2.5M) under similar conditions. Membranes supporting Aliquat-336, TLA, TOPO etc. yielded somewhat poor uranium recoveries. The feed : strip volume ratio showed an inverse relationship to the fraction of cation transported. (author). 9 refs., 2 tab s

  6. Solid state and aqueous behavior of uranyl peroxide cage clusters

    Science.gov (United States)

    Pellegrini, Kristi Lynn

    Uranyl peroxide cage clusters include a large family of more than 50 published clusters of a variety of sizes, which can incorporate various ligands including pyrophosphate and oxalate. Previous studies have reported that uranyl clusters can be used as a method to separate uranium from a solid matrix, with potential applications in reprocessing of irradiated nuclear fuel. Because of the potential applications of these novel structures in an advanced nuclear fuel cycle and their likely presence in areas of contamination, it is important to understand their behavior in both solid state and aqueous systems, including complex environments where other ions are present. In this thesis, I examine the aqueous behavior of U24Pp 12, as well as aqueous cluster systems with added mono-, di-, and trivalent cations. The resulting solutions were analyzed using dynamic light scattering and ultra-small angle X-ray scattering to evaluate the species in solution. Precipitates of these systems were analyzed using powder X-ray diffraction, X-ray fluorescence spectrometry, and Raman spectroscopy. The results of these analyses demonstrate the importance of cation size, charge, and concentration of added cations on the aqueous behavior of uranium macroions. Specifically, aggregates of various sizes and shapes form rapidly upon addition of cations, and in some cases these aggregates appear to precipitate into an X-ray amorphous material that still contains U24Pp12 clusters. In addition, I probe aggregation of U24Pp12 and U60, another uranyl peroxide cage cluster, in mixed solvent water-alcohol systems. The aggregation of uranyl clusters in water-alcohol systems is a result of hydrogen bonding with polar organic molecules and the reduction of the dielectric constant of the system. Studies of aggregation of uranyl clusters also allow for comparison between the newer uranyl polyoxometalate family and century-old transition metal polyoxometalates. To complement the solution studies of uranyl

  7. Simplified recovery process of Ralstonia solanacearum-synthesized polyhydroxyalkanoates via chemical extraction complemented by liquid-liquid phase separation

    Directory of Open Access Journals (Sweden)

    Karine L. Macagnan

    Full Text Available Poly (3-hydroxybutyrate (P(3HB is the most studied thermoplastic biopolymer belonging to the polyhydroxyalkanoate (PHA family, the main features of which include rapid biodegradability and biocompatibility. The bioplastic recovery process is an important step during production and can directly influence the characteristics of PHAs. However, more efficient methods for the production of P(3HB are necessary to make it economically viable. The aim of the present study was to improve the standard, chloroform-based, extraction step for the recovery of P(3HB. The polymer was produced using a Ralstonia solanacearum strain. The following parameters were improved in the recovery process: heating time, separation method (filtration or liquid-liquid phase separation, biomass state (fresh or dry cell concentrate and the solvent:biomass ratio. By improving the chemical extraction of P(3HB we recovered 98% of the cumulative polymer and reduced the heating time by 75%. Furthermore, we improved the separation process and developed an extraction solution that was faster and more economical.

  8. Design and analysis of an energy-efficient O-QPSK coherent IR-UWB transceiver with a 0.52° RMS phase-noise fractional synthesizer

    Science.gov (United States)

    Ying, Yutong; Lin, Fujiang; Bai, Xuefei

    2018-03-01

    This paper explores an energy-efficient pulsed ultra-wideband (UWB) radio-frequency (RF) front-end chip fabricated in 0.18-μm CMOS technology, including a transmitter, receiver, and fractional synthesizer. The transmitter adopts a digital offset quadrature phase-shift keying (O-QPSK) modulator and passive direct-phase multiplexing technology, which are energy- and hardware-efficient, to enhance the data rate for a given spectrum. A passive mixer and a capacitor cross-coupled (CCC) source-follower driving amplifier (DA) are also designed for the transmitter to further reduce the low power consumption. For the receiver, a power-aware low-noise amplifier (LNA) and a quadrature mixer are applied. The LNA adopts a CCC boost common-gate amplifier as the input stage, and its current is reused for the second stage to save power. The mixer uses a shared amplification stage for the following passive IQ mixer. Phase noise suppression of the phase-locked loop (PLL) is achieved by utilizing an even-harmonics-nulled series-coupled quadrature oscillator (QVCO) and an in-band noise-aware charge pump (CP) design. The transceiver achieves a measured data rate of 0.8 Gbps with power consumption of 16 mW and 31.5 mW for the transmitter and the receiver, respectively. The optimized integrated phase noise of the PLL is 0.52° at 4.025 GHz. Project supported by the National Science and Technology Major Project of China (No. 2011ZX03004-002-01).

  9. Significant enhancement of the quantum yield of CdTe nanocrystals synthesized in aqueous phase by controlling the pH and concentrations of precursor solutions

    International Nuclear Information System (INIS)

    Li Liang; Qian Huifeng; Fang Nenghu; Ren Jicun

    2006-01-01

    In this paper, we systematically investigated the aqueous synthesis conditions of CdTe nanocrystals (QDs), and found that the pH value and the concentrations of precursors significantly affected the photoluminescence quantum yield (QY) of CdTe QDs. When the concentration of precursors (Cd) was 1.25 mM, and the pH of Cd precursors solution was about 8.0, CdTe QDs with high QY up to 40-67% were successfully prepared in aqueous phase. Moreover, these high luminescent QDs showed excellent stabilities in aqueous phases, and their luminescence was nearly independent of the pH of the colloid solution. The XPS and XRD characterizations implied that the high luminescence of the QDs synthesized at lower pH was possibly attributed to the formation of the thicker shell (cadmium-3-mercaptopropionic acid complexes) on particles surface, which not only decreased the traps on QDs surface, but also acted as a steric barrier to control the kinetics of QDs growth and led to the formation of a better surface structure. Our modification of conventional aqueous synthesis dramatically improved the QY of the prepared CdTe QDs, and it will become an attractive alternative to the synthesis of QDs in organic phase

  10. Synthesizing A Phase Changing Bistable Electroactive Polymer And Silver Nanoparticles Coated Fabric As A Resistive Heating Element

    Science.gov (United States)

    Ren, Zhi

    Transducer technologies that convert energy from one form to another (e.g. electrical energy to mechanical energy or thermal energy and vise versa) are considered as the basic building blocks of robots and wearable electronics, two of the rapidly emerging technologies that impact our daily life. With an emphasis on developing the essential smart materials, this dissertation focuses on two specific transducer technologies, bistable large-strain electro-mechanical actuation and resistive Joule heating, in pursuit of refreshable Braille electronic displays and wearable thermal management element, respectively. Dielectric elastomers (DEs) have been intensively studied for their promising ability to mimic human muscles in providing efficient electro-mechanical actuation. They exhibit a unique combination of properties, including large strain, fast response, high energy density, mechanical compliancy, lightweight, and low cost. However, the softness of the DE materials, which is a prerequisite for electrically induced large actuation strain, has been hindering their application in adaptive structures. In these applications such as braille displays, a certain amount of mechanical support is necessary in addition to large strains for the device or system to function. Bistable electroactive polymers (BSEP) that leverage the electrically induced large-strain actuation of DE actuators and the bi-stable rigid-to-rigid deformation of shape memory polymers are innovated to provide large electrical actuation strain in their rubbery state and fix the deformation by cooling down to room temperature to incorporate mechanical rigidity. BSEP materials that can suppress electromechanical instability and exhibit stable mechanical properties in the rubbery state are desired. A bimodal BSEP material with a glass transition temperature right above room temperature has been synthesized employing simple UV curing process. The BSEP has a large storage modulus over 1GPa at room temperature

  11. Uranyl Sulfate Nanotubules Templated by N-phenylglycine

    Directory of Open Access Journals (Sweden)

    Oleg I. Siidra

    2018-04-01

    Full Text Available The synthesis, structure, and infrared spectroscopy properties of the new organically templated uranyl sulfate Na(phgH+7[(UO26(SO410](H2O3.5 (1, obtained at room temperature by evaporation from aqueous solution, are reported. Its structure contains unique uranyl sulfate [(UO26(SO410]8− nanotubules templated by protonated N-phenylglycine (C6H5NH2CH2COOH+. Their internal diameter is 1.4 nm. Each of the nanotubules is built from uranyl sulfate rings sharing common SO4 tetrahedra. The template plays an important role in the formation of the complex structure of 1. The aromatic rings are stacked parallel to each other due to the effect of π–π interaction with their side chains extending into the gaps between the nanotubules.

  12. Complexation of uranyl(VI) by aqueous orthosilicic acid

    International Nuclear Information System (INIS)

    Jensen, M.P.; Choppin, G.R.

    1998-01-01

    The complexation reaction of uranyl(VI) with orthosilicic acid, Si(OH) 4 , was studied by spectrophotometry in aqueous solutions of 0.1 M NaClO 4 using competitive complexation with pyrocatechol violet to measure log K 1 for the reaction UO 2 2+ + Si(OH) 4 UO 2 (OSi(OH) 3 ) + + H + . The value of log K 1 = -2.92 ± 0.06 obtained was used to estimate uranyl speciation in groundwater that contained only silicic and carbonic acids. The results of these speciation calculations indicate that the formation of UO 2 (OSi(OH) 3 ) + is greatest at pH 6 and that UO 2 (OSi(OH) 3 ) + comprises less than 50% of the uranyl species in groundwater that is undersaturated with respect to amorphous silica. (orig.)

  13. Biogeochemical changes induced in uranium mining waste pile samples by uranyl nitrate treatments under anaerobic conditions.

    Science.gov (United States)

    Geissler, A; Merroun, M; Geipel, G; Reuther, H; Selenska-Pobell, S

    2009-06-01

    Response of the subsurface soil bacterial community of a uranium mining waste pile to treatments with uranyl nitrate over different periods of time was studied under anaerobic conditions. The fate of the added U(VI) without supplementation with electron donors was investigated as well. By using 16S rRNA gene retrieval, we demonstrated that incubation with uranyl nitrate for 4 weeks resulted in a strong reduction in and even disappearance of some of the most predominant bacterial groups of the original sample. Instead, a strong proliferation of denitrifying and uranium-resistant populations of Rahnella spp. from Gammaproteobacteria and of Firmicutes occurred. After longer incubations for 14 weeks with uranyl nitrate, bacterial diversity increased and populations intrinsic to the untreated samples such as Bacteroidetes and Deltaproteobacteria propagated and replaced the above-mentioned uranium-resistant groups. This indicated that U(VI) was immobilized. Mössbauer spectroscopic analysis revealed an increased Fe(III) reduction by increasing the incubation time from four to 14 weeks. This result signified that Fe(III) was used as an electron acceptor by the bacterial community established at the later stages of the treatment. X-ray absorption spectroscopic analysis demonstrated that no detectable amounts of U(VI) were reduced to U(IV) in the time frames of the performed experiments. The reason for this observation is possibly due to the low level of electron donors in the studied oligotrophic environment. Time-resolved laser-induced fluorescence spectroscopic analysis demonstrated that most of the added U(VI) was bound by organic or inorganic phosphate phases both of biotic origin.

  14. Electronic structure and properties of uranyl compounds. Problems of electron-donor conception

    International Nuclear Information System (INIS)

    Glebov, V.A.

    1982-01-01

    Comparison of the series of the ligand mutual substitution in the uranyl compounds with the ligand series of d-elements and with the uranyl ''covalent model'', is made. The data on ionization potentials of the ligand higher valent levels and on the structure of some uranyl nitrate compounds are considered. It is concluded that the mechanism of the ligand effect on the properties of uranyl grouping is more complex, than it is supposed in the traditional representations on the nature of electron-donor interactions in the uranyl compounds

  15. Uranyl peroxide enhanced nuclear fuel corrosion in seawater.

    Science.gov (United States)

    Armstrong, Christopher R; Nyman, May; Shvareva, Tatiana; Sigmon, Ginger E; Burns, Peter C; Navrotsky, Alexandra

    2012-02-07

    The Fukushima-Daiichi nuclear accident brought together compromised irradiated fuel and large amounts of seawater in a high radiation field. Based on newly acquired thermochemical data for a series of uranyl peroxide compounds containing charge-balancing alkali cations, here we show that nanoscale cage clusters containing as many as 60 uranyl ions, bonded through peroxide and hydroxide bridges, are likely to form in solution or as precipitates under such conditions. These species will enhance the corrosion of the damaged fuel and, being thermodynamically stable and kinetically persistent in the absence of peroxide, they can potentially transport uranium over long distances.

  16. The interaction of uranyl ions with inorganic pyrophosphatase from baker's yeast

    International Nuclear Information System (INIS)

    Bienwald, B.; Heitmann, P.

    1978-01-01

    The interaction of uranyl ions with inorganic pyrophosphatase from baker's yeast was investigated by measurement of their effect on the protein fluorescence. Fluorescence titrations of the native enzyme with uranyl nitrate show that there is a specific binding of uranyl ions to the enzyme. It was deduced that each subunit of the enzyme binds one uranyl ion. The binding constant was estimated to be in the order of 10 7 M -1 . The enzyme which contains a small number of chemically modified carboxyl groups was not able to bind uranyl ions specifically. The modification of carboxyl groups was carried out by use of a water soluble carbodiimide and the nucleophilic reagent N-(2,4-dinitro-phenyl)-hexamethylenediamine. The substrate analogue calcium pyrophosphate displaced the uranyl ions from their binding sites at the enzyme From the results it is concluded that carboxyl groups of the active site are the ligands for the binding of uranyl ions. (author)

  17. Effect of metal-ion-to-fuel ratio on the phase formation of bioceramic phosphates synthesized by self-propagating combustion

    Directory of Open Access Journals (Sweden)

    Swamiappan Sasikumar and Rajagopalan Vijayaraghavan

    2008-01-01

    Full Text Available Synthetic calcium hydroxyapatite (HAP, Ca10 (PO46 (OH2 is a well-known bioceramic material used in orthopedic and dental applications because of its excellent biocompatibility and bone-bonding ability due to its structural and compositional similarity to human bone. Here we report, for the first time, the synthesis of HAP by combustion employing tartaric acid as a fuel. Calcium nitrate is used as the source of calcium and diammonium hydrogen phosphate serves as the source of phosphate ions. Reaction processing parameters such as the pH, fuel-oxidant ratio and autoignition temperature are controlled and monitored. The products were characterized by powder x-ray diffraction, which revealed the formation of a hexagonal hydroxyapatite phase. Fourier transform infrared spectroscopy (FT-IR spectra showed that the substitution of a carbonate ion occurs at the phosphate site. The morphology of the particles was imaged by scanning electron microscopy, which also revealed that the particles are of submicron size. Thermal analysis showed that the phase formation takes place at the time of combustion. Surface area and porosity analysis showed that the surface area is high and that the pores are of nanometer size. The mean grain size of the HAP powder, determined by the Debye–Scherrer formula, is in the range 20–30 nm. Chemical analyses to determine the Ca : P atomic ratio in synthesized ceramics were performed, and it was found to be 1 : 1.66.

  18. Effect of metal-ion-to-fuel ratio on the phase formation of bioceramic phosphates synthesized by self-propagating combustion

    Science.gov (United States)

    Sasikumar, Swamiappan; Vijayaraghavan, Rajagopalan

    2008-07-01

    Synthetic calcium hydroxyapatite (HAP, Ca10 (PO4)6 (OH)2) is a well-known bioceramic material used in orthopedic and dental applications because of its excellent biocompatibility and bone-bonding ability due to its structural and compositional similarity to human bone. Here we report, for the first time, the synthesis of HAP by combustion employing tartaric acid as a fuel. Calcium nitrate is used as the source of calcium and diammonium hydrogen phosphate serves as the source of phosphate ions. Reaction processing parameters such as the pH, fuel-oxidant ratio and autoignition temperature are controlled and monitored. The products were characterized by powder x-ray diffraction, which revealed the formation of a hexagonal hydroxyapatite phase. Fourier transform infrared spectroscopy (FT-IR) spectra showed that the substitution of a carbonate ion occurs at the phosphate site. The morphology of the particles was imaged by scanning electron microscopy, which also revealed that the particles are of submicron size. Thermal analysis showed that the phase formation takes place at the time of combustion. Surface area and porosity analysis showed that the surface area is high and that the pores are of nanometer size. The mean grain size of the HAP powder, determined by the Debye-Scherrer formula, is in the range 20-30 nm. Chemical analyses to determine the Ca : P atomic ratio in synthesized ceramics were performed, and it was found to be 1 : 1.66.

  19. Solubility of sulfoxide complexes of uranyl chlorides and uranyl nitrates in hydrocarbons

    International Nuclear Information System (INIS)

    Murinov, Yu.I.; Kurochkin, A.V.; Nikitin, Yu.E.

    1983-01-01

    Solubility of uranylnitrate and uranylchloride complexes with sulfoxides of different structure in hydrocarbons of different types at 15 deg C has been studied. Solubility of the complexes with DHSO in hydrocarbons in the temperature range 0-20 deg C is determined. Thermodynamic functions of the complexes dissolution are calculated. It is shown that solubility of uranyl salt complexes depends considerably on the structure of ligand hydrocarbon radicals, and especially on the number of ''available'' methylene groups and varies from 5x10 -7 to 0.5 mol parts. A connection between the number of available methylene groups of ligands in the complexes with solubility spread of the complex in the given set of organic solvents is detected. Analysis of the thermodynamics of the complexes dissolution has shown that entropy constituent makes the determining contribution to the interaction. Complex-hydrocarbon interactions are accompanied by a strong braking of both rotational and translational movements of hydrocarbon melecules

  20. Synthesis of pyrimidine carboxamide derivatives catalyzed by uranyl ...

    African Journals Online (AJOL)

    carboxamides using UO2(NO3)2.6H2O catalyst under conventional and microwave irradiation. The synthesis of dihydropyrimidine using uranyl nitrate had shown many advantages such as easy work up, shorter reaction times and higher yields ...

  1. Can uranyl complexes encapsulate to carbon nanotubes? A ...

    Indian Academy of Sciences (India)

    However, upon functionalizing (at the hub carbon) the C36 cork, the binding affinity of [UO₂(FM)3]¹⁻ is larger inside the CNT due to favorable hydrogen bonding interactions with the uranyl oxygens. Our findings are consistent with the experimental observations which will help to design novel nanomaterials for nuclear ...

  2. Synthesis, structural investigation and kinetic studies of uranyl (VI ...

    Indian Academy of Sciences (India)

    Uranyl schiff base complexes; kinetic study; X-ray crystallography; kinetics of thermal decomposition; cyclic voltammetry. ... Chemistry Department, College of Sciences, Shiraz University, Shiraz 71454, I. R. Iran; Institute of Physics ASCR, v.v.i, Na Slovance 2, 182 21 Praha, Czech Republic; Department of Chemistry, Faculty ...

  3. Structure and dynamics of aqueous solution of uranyl ions

    International Nuclear Information System (INIS)

    Chopra, Manish; Choudhury, Niharendu

    2014-01-01

    The present work describes a molecular dynamics simulation study of structure and dynamics of aqueous solution of uranyl ions in water. Structural properties of the system in terms of radial distribution functions and dynamical characteristics as obtained through velocity autocorrelation function and mean square displacements have been analyzed. The results for radial distribution functions show the oxygen of water to form the first solvation shell at 2.4 Å around the uranium atom, whereas the hydrogen atoms of water are distributed around the uranium atom with the major peak at around 3.0 Å. Analyses of transport behaviors of ions and water through MSD indicates that the diffusion of the uranyl ion is much less as compared to that of the water molecules. It is also observed that the dynamical behavior of water molecules gets modified due to the presence of uranyl ion. The effect of increase in concentration of uranyl ions on the structure and dynamics of water molecules is also studied

  4. Multi-scale modelling of uranyl chloride solutions

    Energy Technology Data Exchange (ETDEWEB)

    Nguyen, Thanh-Nghi; Duvail, Magali, E-mail: magali.duvail@icsm.fr; Villard, Arnaud; Dufrêche, Jean-François, E-mail: jean-francois.dufreche@univ-montp2.fr [Institut de Chimie Séparative de Marcoule (ICSM), UMR 5257, CEA-CNRS-Université Montpellier 2-ENSCM, Site de Marcoule, Bâtiment 426, BP 17171, F-30207 Bagnols-sur-Cèze Cedex (France); Molina, John Jairo [Fukui Institute for Fundamental Chemistry, Kyoto University, Takano-Nishihiraki-cho 34-4, Sakyo-ku, Kyoto 606-8103 (Japan); Guilbaud, Philippe [CEA/DEN/DRCP/SMCS/LILA, Marcoule, F-30207 Bagnols-sur-Cèze Cedex (France)

    2015-01-14

    Classical molecular dynamics simulations with explicit polarization have been successfully used to determine the structural and thermodynamic properties of binary aqueous solutions of uranyl chloride (UO{sub 2}Cl{sub 2}). Concentrated aqueous solutions of uranyl chloride have been studied to determine the hydration properties and the ion-ion interactions. The bond distances and the coordination number of the hydrated uranyl are in good agreement with available experimental data. Two stable positions of chloride in the second hydration shell of uranyl have been identified. The UO{sub 2}{sup 2+}-Cl{sup −} association constants have also been calculated using a multi-scale approach. First, the ion-ion potential averaged over the solvent configurations at infinite dilution (McMillan-Mayer potential) was calculated to establish the dissociation/association processes of UO{sub 2}{sup 2+}-Cl{sup −} ion pairs in aqueous solution. Then, the association constant was calculated from this potential. The value we obtained for the association constant is in good agreement with the experimental result (K{sub UO{sub 2Cl{sup +}}} = 1.48 l mol{sup −1}), but the resulting activity coefficient appears to be too low at molar concentration.

  5. Studying of the dehydration process of uranyl nitrate hexahydrate (Unh)

    International Nuclear Information System (INIS)

    Badalov, A.; Kamalov, J.J.; Homidov, B.J.; Mirsaidov, I.U.; Eshbekov, N.R.

    2005-01-01

    By the tensimeteric method is studying the dehydration process of uranyl nitrate hexahydrate (Unh). It is shown, that the temperature interval 300-400 K in equilibrium conditions the dehydration process of Unh runs in three stages. According to the equations of dependence of saturated steam pressure from temperature, the thermodynamic characteristics of each stage of the dehydration process of Unh are calculated

  6. Synthesis of pyrimidine carboxamide derivatives catalyzed by uranyl

    African Journals Online (AJOL)

    2014-09-02

    (Received September 2, 2014; revised January 1, 2016). ABSTRACT. An efficient and simple method was developed for the synthesis pyrimidine-5-carboxamides using. UO2(NO3)2.6H2O catalyst under conventional and microwave irradiation. The synthesis of dihydropyrimidine using uranyl nitrate had shown many ...

  7. Colorimetric peroxidase mimetic assay for uranyl detection in sea water

    KAUST Repository

    Zhang, Dingyuan

    2015-03-04

    Uranyl (UO2 2+) is a form of uranium in aqueous solution that represents the greatest risk to human health because of its bioavailability. Different sensing techniques have been used with very sensitive detection limits especially the recently reported uranyl-specific DNAzymes systems. However, to the best of our knowledge, few efficient detection methods have been reported for uranyl sensing in seawater. Herein, gold nanoclusters (AuNCs) are employed in an efficient spectroscopic method to detect uranyl ion (UO2 2+) with a detection limit of 1.86 ÎM. In the absence of UO2 2+, the BSA-stabilized AuNCs (BSA-AuNCs) showed an intrinsic peroxidase-like activity. In the presence of UO2 2+, this activity can be efficiently restrained. The preliminary quenching mechanism and selectivity of UO2 2+ was also investigated and compared with other ions. This design strategy could be useful in understanding the binding affinity of protein-stabilized AuNCs to UO2 2+ and consequently prompt the recycling of UO2 2+ from seawater.

  8. Weathering of natural uranyl oxide hydrates: Schoepite polytypes and dehydration effects

    International Nuclear Information System (INIS)

    Finch, R.J.; Miller, M.L.; Ewing, R.C.

    1992-01-01

    Partial dehydration of schoepite, UO 3 x2H 2 O, is reported to produce three discrete schoepite polytypes with characteristic unit cell parameters, but this has not been confirmed. The loss of structural water from the schoepite interlayer results in progressive modification to the structure; expansion parallel to schoepite cleavage planes, and extensive fracturing. Dehydration of schoepite commences at grain boundaries and progresses inward until the entire grain is converted to dehydrated schoepite, UO 3 x0.8H 2 O. The volume decrease associated with dehydration results in expanded grain boundaries. These gaps can provide pathways for the access of groundwater, and uranyl silicates and uranyl carbonates have precipitated within these gaps, replacing both schoepite and dehydrated schoepite. Schoepite, however, is not observed to re-precipitate where in contact with dehydrated schoepite. Thus, while the formation of schoepite early during the corrosion of uraninite may be favored, schoepite is not a long-term solubility limiting phase for oxidized uranium in natural ground waters containing dissolved silica or carbonate. (orig.)

  9. The energy landscape of uranyl-peroxide species

    Energy Technology Data Exchange (ETDEWEB)

    Tiferet, Eitan [Peter A. Rock Thermochemistry Laboratory, University of California, Davis, CA (United States); Nuclear Research Center - Negev, Be' er-Sheva (Israel); Gil, Adria; Bo, Carles [Institute of Chemical Research of Catalonia (ICIQ), Tarragona (Spain); Departament de Quimica Fisica i Inorganica, Universitat Rovira i Virgil, Tarragona (Spain); Shvareva, Tatiana Y.; Navrotsky, Alexandra [Peter A. Rock Thermochemistry Laboratory, University of California, Davis, CA (United States); Nyman, May [Department of Chemistry, Oregon State University, Corvallis, OR (United States)

    2014-03-24

    Nanoscale uranyl peroxide clusters containing UO{sub 2}{sup 2+} groups bonded through peroxide bridges to form polynuclear molecular species (polyoxometalates) exist both in solution and in the solid state. There is an extensive family of clusters containing 28 uranium atoms (U{sub 28} clusters), with an encapsulated anion in the center, for example, [UO{sub 2}(O{sub 2}){sub 3-x}(OH){sub x}{sup 4-}], [Nb(O{sub 2}){sub 4}{sup 3-}], or [Ta(O{sub 2}){sub 4}{sup 3-}]. The negative charge of these clusters is balanced by alkali ions, both encapsulated, and located exterior to the cluster. The present study reports measurement of enthalpy of formation for two such U{sub 28} compounds, one of which is uranyl centered and the other is peroxotantalate centered. The [Ta(O{sub 2}){sub 4}]-centered U{sub 28} capsule is energetically more stable than the [(UO{sub 2})(O{sub 2}){sub 3}]-centered capsule. These data, along with our prior studies on other uranyl-peroxide solids, are used to explore the energy landscape and define thermochemical trends in alkali-uranyl-peroxide systems. It was suggested that the energetic role of charge-balancing alkali ions and their electrostatic interactions with the negatively charged uranyl-peroxide species is the dominant factor in defining energetic stability. These experimental data were supported by DFT calculations, which agree that the [Ta(O{sub 2}){sub 4}]-centered U{sub 28} capsule is more stable than the uranyl-centered capsule. Moreover, the relative stability is controlled by the interactions of the encapsulated alkalis with the encapsulated anion. Thus, the role of alkali-anion interactions was shown to be important at all length scales of uranyl-peroxide species: in both comparing clusters to clusters; and clusters to monomers or extended solids. (copyright 2014 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  10. Luminescent properties of [UO{sub 2}(TFA){sub 2}(DMSO){sub 3}], a promising material for sensing and monitoring the uranyl ion

    Energy Technology Data Exchange (ETDEWEB)

    Martin-Ramos, Pablo; Silva, Manuela Ramos; Silva, Pedro S. Pereira da [Centro de Fisica da Universidade de Coimbra (CFisUC), Department of Physics, Universidade de Coimbra (Portugal); Costa, Ana L.; Melo, J. Sergio Seixas de [Centro de Quimica de Coimbra, Department of Chemistry, Universidade de Coimbra (Portugal); Pereira, Laura C.J. [Centro de Ciencias e Tecnologias Nucleares, Instituto Superior Tecnico, Universidade de Lisboa, Bobadela LRS (Portugal); Martin-Gil, Jesus, E-mail: pmr@unizar.es [Advanced Materials Laboratory, Escuela Tecnica Superior de Ingenierias Agrarias, University of Valladolid, Palencia (Spain)

    2016-03-15

    An uranyl complex [UO{sub 2}(TFA){sub 2}(DMSO){sub 3}] (TFA=deprotonated trifluoroacetic acid; DMSO=dimethyl sulfoxide) has been successfully synthesized by reacting UO{sub 2}(CH{sub 3}COO){sub 2} ·H{sub 2} O with one equivalent of (CF{sub 3} CO){sub 2} O and DMSO. The complex has been characterized by single-crystal X-ray diffraction, X-ray powder diffraction, elemental analysis, FTIR spectroscopy, thermal analysis and absorption and emission spectroscopies. The spectroscopic properties of the material make it suitable for its application in the sensing and monitoring of uranyl in the PUREX process. (author)

  11. Photo-catalytic activity of Plasmonic Ag@AgCl nanoparticles (synthesized via a green route) for the effective degradation of Victoria Blue B from aqueous phase.

    Science.gov (United States)

    Devi, Th Babita; Begum, Shamima; Ahmaruzzaman, M

    2016-07-01

    This study reports a green process for the fabrication of Ag@AgCl (silver@silver chloride) nanoparticles by using Aquilaria agallocha (AA) leaves juice without using any external reagents. The effect of various reaction parameters, such as reaction temperature, reaction time and concentration of Aquilaria agallocha leaves juice in the formation of nanoparticles have also been investigated. From the FTIR spectra of leaves juice and phytochemicals test, it was found that flavonoids present in the leaves are responsible for the reduction of Ag(+) ions to Ag(0) species and leads to the formation of Ag@AgCl NPs. The synthesized Ag@AgCl NPs were utilized for the removal of toxic and hazardous dyes, such as Victoria Blue B from aqueous phase. Approximately, 99.46% degradation of Victoria Blue B dye were observed with Ag@AgCl NPs. Furthermore, the photocatalytic activity of the Ag@AgCl nanoparticles was unchanged after 5cycles of operation. Copyright © 2016 Elsevier B.V. All rights reserved.

  12. Pure, single phase, high crystalline, chamfered-edge zeolite 4A synthesized from coal fly ash for use as a builder in detergents

    International Nuclear Information System (INIS)

    Hui, K.S.; Chao, C.Y.H.

    2006-01-01

    Single phase chamfered-edge zeolite 4A samples in pure form with a high crystallinity were synthesized by applying step-change of synthesis temperature during hydrothermal treatment of coal fly ash. The calcium binding capacity of these zeolite 4A samples (prepared from coal fly ash) and the commercial detergent grade zeolite 4A were tested for usage as a detergent builder. The results show that these zeolite 4A samples behaved similarly as the commercial one in removing calcium ions during the washing cycle. Moreover, from the leaching tests (evaluation of toxicological safety), the results show that these zeolite 4A samples leached the same elements (Sb, As, Se and Tl) as the commercial one with the concentrations in the same order of magnitude. This shows that the toxicological effect of the coal fly ash converted zeolite 4A was not worse than that of the commercial sample. Finally, economic and environmental aspects of converting coal fly ash to useful products were discussed

  13. A metal-free route to synthesize pure-phase 3C-SiC with excellent optical and magnetic properties

    Science.gov (United States)

    Liu, S.; Wang, J. G.

    2017-11-01

    Large amount of pure-phase 3C-SiC particles were synthesized via microwave heating, without using any metal catalyst. Ball-milling pre-treatment was employed to enhance reaction activity of raw materials prior to the microwave heating process. The morphology, microstructure of the SiC products were characterized by scanning electron microscope (SEM), X-ray diffraction (XRD), and transmission electron microscope (TEM). As the result of SEM, the SiC particles have diameters of 500–2000 nm and smooth surface. TEM image shows that some of the micro-sized SiC particles are composed of agglomerate nano-particles with diameters of 50–200 nm. Photoluminescence and magnetic properties of the SiC products were measured by fluorescence spectrophotometer and vibrating sample magnetometer (VSM), respectively. Ultra-violet emission from the 3C-SiC products can be detected under excitation wavelength of 240 nm. Without any contribution from the magnetic metal ions, the SiC particles can exhibit ferromagnetic properties around room temperature with saturation magnetization (Ms) of 0.9 emu/g, approximately. The excellent optical and magnetic properties of SiC may mainly be attributed to the point defects.

  14. Sulfate-Centered Sodium-Icosahedron-Templated Uranyl Peroxide Phosphate Cages with Uranyl Bridged by μ-η1:η2Peroxide.

    Science.gov (United States)

    Qiu, Jie; Spano, Tyler L; Dembowski, Mateusz; Kokot, Alex M; Szymanowski, Jennifer E S; Burns, Peter C

    2017-02-20

    Two novel hybrid uranyl peroxide phosphate cage clusters, designated U 20 P 6 and U 20 P 12 , contain peroxide bridges between uranyl in an unusual μ-η 1 :η 2 configuration, as well as the common μ-η 2 :η 2 configuration. These appear to be the only high-nuclearity metal peroxide complexes containing μ-η 1 :η 2 peroxide bridges, and they are unique among uranyl peroxide cages. Both clusters contain 20 uranyl polyhedra, and U 20 P 6 and U 20 P 12 contain 6 and 12 phosphate tetrahedra, respectively. The 20 uranyl polyhedra in both cages are arranged on the vertices of distorted topological dodecahedrons (20 vertex fullerenes). Each cage is completed by phosphate tetrahedra and is templated by a sulfate-centered Na 12 cluster with the Na cations defining a regular convex isocahedron. Whereas μ-η 2 :η 2 peroxides are essential features of uranyl peroxide cages, where they form equatorial edges of uranyl hexagonal bipyramids, the μ-η 1 :η 2 peroxide groups in U 20 P 6 and U 20 P 12 are associated with strong distortions of the uranyl polyhedra. Formation of U 20 P 6 and U 20 P 12 is a further demonstration of the pliable nature of uranyl polyhedra, which contributes to the tremendous topological variability of uranyl compounds. Despite the unusual structure and highly distorted polyhedral geometries of U 20 P 6 , small-angle X-ray scattering and Raman spectra suggest its stability in the aqueous solution and solid state.

  15. The study of kinetics of uranyl nitrate extraction and reextraction, di-n-butylphosphoric acid reextraction in the flow mixer in the system aqueous solutions - tri-n-butyl phosphate in diluent

    International Nuclear Information System (INIS)

    Shchepetil'nikov, N.N.; Timofeev, A.N.; Kharitonov, V.V.

    1992-01-01

    Kinetics of uranyl nitrate and HNO 3 extraction and reextraction in a flow-type mixer for the system 30 vol.% TBP in extractant dearomatized diluent (EDD) was studied. Kinetics of dibutylphosphate acid reextraction was considered and the influence of uranium and zirconium presence on the process was investigated. It is shown that in laboratory mixer of continuous action in case of phase contact duration of 1 min. in system 30 % solution of TBP in EDD extraction sufficiently similar to equilibrium extraction of uranyl nitrate and nitric acid during their extraction and reextraction is achieved

  16. Critical experiments on low enriched uranyl nitrate solution with STACY

    International Nuclear Information System (INIS)

    Miyoshi, Yoshinori

    1996-01-01

    As the STACY started steady operations, systematic criticality data on low enriched uranyl nitrate solution system could be accumulated. Main experimental parameters for the cylindrical tank of 60 cm in diameter were uranium concentration and the reflector condition. Basic data on a simple geometry will be helpful for the validation of the standard criticality safety codes, and for evaluating the safety margin included in the criticality designs. Experiments on the reactivity effects of structural materials such as borated concrete and polyethylene are on schedule next year as the second series of experiments using 10 wt% enriched uranyl solution. Furthermore, neutron interacting experiments with two slab tanks will be performed to investigate the fundamental properties of neutron interaction effects between core tanks. These data will be useful for making more reasonable calculation models and for evaluating the safety margin in the criticality designs for the multiple unit system. (J.P.N.)

  17. New chemistry of the uranyl ion in non aqueous media

    International Nuclear Information System (INIS)

    Siffredi, G.

    2008-12-01

    This work deals with new aspects of the chemistry of the uranyl(VI) ion {UO 2 } 2+ in anhydrous polar organic solvents such as the activation of the reputedly inert U-O yl bond and the controlled reduction of this species which represent a particularly active field of research that attracts much attention for both its fundamental aspects and applications. Treatment of uranyl(VI) compounds UO 2 X' 2 (X' = I, OTf, Cl) with Me 3 SiX (X = Cl, Br, I) reagents, in various anhydrous polar organic solvents, has been first considered. In most cases, reduction into tetravalent species with complete de-oxygenation of the uranyl {UO 2 } 2+ ion is observed. The reaction is particularly efficient in acetonitrile where the tetravalent [UX 4 (MeCN) 4 ] complexes, which are useful precursors in uranium chemistry, are isolated. In the course of these reactions, the influence of the solvent, the nature of X' and X in the UO 2 X' 2 precursor and the Me 3 SiX reagent are pointed out. Reaction of the uranyl(VI) UO 2 X 2 (X = I, Cl, OTf, NO 3 ) precursors with the anionic MC 5 R 5 (M = K, R = H, Me; M= Li, R = Me; M= Tl, R = H) reagents did not lead to the organometallic [(η 5 -C 5 R 5 ) n UO 2 X 2-n ] species (n = 1, 2) but to pentavalent uranyl(V) complexes. This method is a facile and rapid route towards the formation of stable pentavalent uranyl which offers promising sources for further U(V) chemical developments and for fundamental and applied interests. Their structure is strongly dependent on the nature of the solvent, the additional ligands X and of the M + cation. In pyridine, the {UO 2 (py) 5 } + ion appears to be an ubiquitous and a quite stable entity. The coordinating properties of the basic oxo groups, which coordinate easily to M + ions (M= Li, K, Tl), favour structural diversity with formation of hetero-polymetallic complexes such as [{UO 2 (py) 5 }{MX(py) 2 }] (M= Li, X I), [{UO 2 (py) 5 }{MX 2 (py) 2 }] ∞ (M= K, Tl, X= OTf; M= K, X= I), [{UO 2 (py) 5 }(M 2 X 3 )]

  18. Development of the process for production of UO2 powder by atomization of uranyl nitrate

    International Nuclear Information System (INIS)

    Oliveira Lainetti, P.E. de.

    1991-01-01

    A method of direct conversion of uranyl nitrate hexahydrate (UNH) solution to ceramic grade uranium dioxide powders by thermal denitration in a furnace that combines atomization nozzle and a gas stirred bed is described. The main purpose of this work is to show that this alternative process is technically viable, specially if the recovery of the scrap generated in the nuclear fuel pellet production is required, without further generation of new liquid wastes. The steps for the development of the denitration unit as well as the characteristics of the final powders are described. Powder production experiments have been carried out for different atomization gas pressures and furnace upper section temperatures. Determination of impurity content, specific surface area, particle size and pore size distribution, density, U content, and O/U rate of uranium dioxide powders have been done; phase identification and morphology studies have also been performed. Sintered pellets have been studied by hydrostatic density determination and microstructure analyses. (author)

  19. Crystal structure of the uranyl-oxide mineral rameauite

    Czech Academy of Sciences Publication Activity Database

    Plášil, Jakub; Škoda, R.; Čejka, J.; Bourgoin, V.; Boulliard, J.C.

    2016-01-01

    Roč. 28, č. 5 (2016), s. 959-967 ISSN 0935-1221 R&D Projects: GA MŠk LO1603 EU Projects: European Commission(XE) CZ.2.16/3.1.00/24510 Institutional support: RVO:68378271 Keywords : rameauite * uranyl-oxide hydroxy-hydrate * crystal structure * Raman spectrum Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 1.362, year: 2016

  20. Structural determination of some uranyl compounds by vibrational spectroscopy

    International Nuclear Information System (INIS)

    Rodriguez S, A.; Martinez Q, E.

    1990-07-01

    The vibrational spectra of different uranyl compounds has been studied and of it spectral information has been used the fundamental asymmetric vibrational frequency, to determine the length and constant bond force U=O by means of the combination of the concept of absorbed energy and the mathematical expression of Badger modified by Jones. It is intended a factor that simplifies the mathematical treatment and the results are compared with the values obtained for other methods. (Author)

  1. Safe use and waste disposal of uranyl acetate

    International Nuclear Information System (INIS)

    Sanchez, A.; Calvo, S.; Caparros, G.; Gallego, E.; Rascon, J.; Valladares, M.C.

    2006-01-01

    Radioactive labelled molecules are widely used in Biological Research Centres. The most common radioisotopes are: 32 P, 33 P, 35 S, 3 H, 14 C, 125 I and 45 Ca.Due to the inherent risk in the manipulation of these radiation unsealed sources, in these radioactive installations there are established radiological protection programs to reduce this potential risk and the professional exposure in the manipulation and in the radioactive waste generated. In these Biological Research Centres we used techniques with other radioactive products less used, that we must to control. It is the case of the use of uranyl acetate. Uranyl acetate is a uranium salt used in the preparation of samples for analysis in the electron microscope. Although the amounts used are relatively small, both the chemical and radiological toxicities of these compounds are significant and require working whit that some cautions, with the main emphasis on avoiding the possibility of inhalation of fine particulates or vapours. Due to changes in the Spanish regulations for this product, it was necessary to establish a specific control program in its manipulation. The purpose of this work is the accomplishment of specific protocols for the acquisition, manipulation, contamination measurements, inspections of the work zone and waste management, in order to minimize the risks in the manipulation of uranyl acetate,as well as apply the knowledge and use of specific norms for working with this product. (authors)

  2. Variable Denticity in Carboxylate Binding to the Uranyl Coordination Complexes

    International Nuclear Information System (INIS)

    Groenewold, G.S.; De Jong, Wibe A.; Oomens, Jos; Van Stipdonk, Michael J.

    2010-01-01

    Tris-carboxylate complexes of the uranyl (UO2)2+ cation with acetate and benzoate were generated using electrospray ionization mass spectrometry, and then isolated in a Fourier transformion cyclotron resonance mass spectrometer. Wavelength-selective infrared multiple photon dissociation (IRMPD) of the tris-acetatouranyl anion resulted in a redox elimination of an acetate radical, which was used to generate an IR spectrum that consisted of six prominent absorption bands. These were interpreted with the aid of density functional theory calculations in terms of symmetric and antisymmetric -CO2 stretches of both the monodentate and bidentate acetate, CH3 bending and umbrella vibrations, and a uranyl O-U-O asymmetric stretch. The comparison of the calculated and measured IR spectra indicated that the tris-acetate complex contained two acetate ligands bound in a bidentate fashion, while the third acetate was monodentate. In similar fashion, the tris-benzoate uranyl anion was formed and photodissociated by loss of a benzoate radical, enabling measurement of the infrared spectrum that was in close agreement with that calculated for a structure containing one monodentate, and two bidentate benzoate ligands.

  3. Design of one evaporation system for uranyl nitrate solution

    International Nuclear Information System (INIS)

    Mancilla Romero, R.J.

    1975-01-01

    The authors propose an instant evaporation system with recirculation of the concentrated solution to raise the concentration from 50 to 1500 g of uranium per litre of solution. The capacity of the plant is to be 14.1 kg of uranium per hour. The main equipment used in the system is as follows: 1. Ring-type heat exchanger, for increasing the temperature of the mixture of fresh and recirculated solution from 80 to 115 0 C; 2. Separation tank, in which instant evaporation is carried out. The absolute pressure inside the tank will be 500 mmHg, with steam separation from a concentrated (78.5 wt.%) uranyl nitrate solution; 3. Desuperheater-condenser of horizontal tubular type for condensing water vapour and recovering any uranyl nitrate that may have been entrained; 4. Storage tank for the concentrate, with a capacity for one day's normal operation, and a heating coil to prevent crystallization of the concentrated solution; 5. Two storage tanks for feed and condensate with capacity for one day's normal operation; 6. Supporting structure for the above components. Virtually all equipment in contact with the uranyl nitrate solution will be made of 304 stainless steel. Saturated steam at 143.3 0 C will be required. The cost of the proposed system is $543 030.00. (author)

  4. Safe use and waste disposal of uranyl acetate

    Energy Technology Data Exchange (ETDEWEB)

    Sanchez, A.; Calvo, S.; Caparros, G.; Gallego, E.; Rascon, J.; Valladares, M.C. [Centro de Biologia Molecular, Madrid (Spain)

    2006-07-01

    Radioactive labelled molecules are widely used in Biological Research Centres. The most common radioisotopes are: {sup 32}P,{sup 33}P, {sup 35}S,{sup 3}H,{sup 14}C,{sup 125}I and {sup 45}Ca.Due to the inherent risk in the manipulation of these radiation unsealed sources, in these radioactive installations there are established radiological protection programs to reduce this potential risk and the professional exposure in the manipulation and in the radioactive waste generated. In these Biological Research Centres we used techniques with other radioactive products less used, that we must to control. It is the case of the use of uranyl acetate. Uranyl acetate is a uranium salt used in the preparation of samples for analysis in the electron microscope. Although the amounts used are relatively small, both the chemical and radiological toxicities of these compounds are significant and require working whit that some cautions, with the main emphasis on avoiding the possibility of inhalation of fine particulates or vapours. Due to changes in the Spanish regulations for this product, it was necessary to establish a specific control program in its manipulation. The purpose of this work is the accomplishment of specific protocols for the acquisition, manipulation, contamination measurements, inspections of the work zone and waste management, in order to minimize the risks in the manipulation of uranyl acetate,as well as apply the knowledge and use of specific norms for working with this product. (authors)

  5. A family of uranyl-aromatic dicarboxylate (pht-, ipa-, tpa-) framework hybrid materials: photoluminescence, surface photovoltage and dye adsorption.

    Science.gov (United States)

    Gao, Xue; Wang, Che; Shi, Zhong-Feng; Song, Jian; Bai, Feng-Ying; Wang, Ji-Xiao; Xing, Yong-Heng

    2015-07-07

    Four uranyl complexes [(UO2)(pht)H2O]·H2O (pht = phthalic acid) (1), (UO2)2(Hipa)4(H2O)2 (Hipa = isophthalic acid) (2), (UO2)(tpa)(DMF)2 (tpa = terephthalic acid) (3) and (UO2)(box)2 (box = benzoic acid) (4) were synthesized by the reaction of UO2(CH3COO)2·2H2O as the metal source and phthalic acid, isophthalic acid, terephthalic acid or benzoic acid as the ligand. They were characterized by elemental analyses, IR, UV-Vis, XRD, single crystal X-ray diffraction analysis and thermal gravimetric analysis. The structural analysis reveals that complex 1 exhibits a one-dimensional chain structure constructed by the building unit [(UO2)2(pht)4(H2O)2] and further extends the chain into a 2D supramolecular architecture by hydrogen bonding interactions. Complex 2 is a discrete [(UO2)2(Hipa)4(H2O)2] structure, and by the hydrogen bonding interaction, forms a 3D supramolecular structure. In complexes 3 and 4, adjacent uranyl polyhedra form a 1D chain through bridging terephthalic acid and benzoic acid, respectively. In order to extend their functional properties, their photoluminescence, surface photovoltage and dye adsorption properties have been studied.

  6. Functional polyterthiophene-appended uranyl-salophen complex: electropolymerization and ion-selective response for monohydrogen phosphate.

    Science.gov (United States)

    Kim, Junghwan; Kang, Dong Min; Shin, Sung Chul; Choi, Myong Yong; Kim, Jineun; Lee, Shim Sung; Kim, Jae Sang

    2008-04-28

    We have synthesized a bis(terthiophene)-appended uranyl-salophen complex, comprising N,N'-bis[4-(5,2':5',2''-terthiophen-3'-yl)salicylidene]-1,2-ethanediamine-uranyl complexes (TUS), and used it as a monomer for the electrochemical polymerizations (poly-TUS) on glassy carbon surfaces to prepare functionalized conducting polymer (CP) films. The poly-TUS films prepared from propylene carbonate/0.1 M tetrabutyl ammonium perchlorate (TBAP) on a glassy carbon electrode have both the functionality of ion-to-electron transducers (solid contact) and Lewis-acidic binding sites for a monohydrogen phosphate (MHP) ion-selective electrode (ISE). The CP/poly-TUS sensor showed a linear range between 1.0 x 10(-1) and 1.0 x 10(-4.5) M with a near-Nernstian behavior (-30.4 mV decade(-1)) at a pH of 8.2. The detection limit of the electrode was 10(-5.0) M and the response time was improved (polyvinyl chloride (PVC) liquid membrane with or without tridodecylmethylammonium chloride (TDMACl) as an additive was also constructed and its performance as an MHP-ISE were studied. The superior selectivity and sensitivity of the CP/poly-TUS sensor enabled the direct measurement of MHP in a wide variety of applications.

  7. Catalytic one-electron reduction of uranyl(VI) to Group 1 uranyl(V) complexes via Al(III) coordination

    OpenAIRE

    Zegke, Markus; Nichol, Gary S; Arnold, Polly L; Love, Jason B

    2015-01-01

    Reactions between the uranyl(vi) Pacman complex [(UO2)(py)(H2L)] of the Schiff-base polypyrrolic macrocycle L and Tebbe's reagent or DIBAL result in the first selective reductive functionalisation of the uranyl oxo by Al to form [(py)(R2AlOUO)(py)(H2L)] (R = Me or (i)Bu). The clean displacement of the oxo-coordinated Al(iii) by Group 1 cations has enabled the development of a one-pot, DIBAL-catalysed reduction of the U(vi) uranyl complexes to a series of new, mono-oxo alkali-metal-functionali...

  8. Uranyl ion sorption mechanisms on titanium oxide: a multi-scale approach

    International Nuclear Information System (INIS)

    Vandenborre, J.; Drot, R.; Simoni, E.; Dong, W.; Du, J.; Dossot, M.; Humbert, B.; Ehrhardt, J.J.

    2005-01-01

    Full text of publication follows: Radionuclides retention mechanisms onto mineral phases is of primary importance for nuclear waste management. The aim of the presented study is to demonstrate that it is possible to predict the retention properties of a methodological powdery substrate from the study of its natural crystallographic orientations. Among the radionuclides of interest, U(VI) can be seen as a model of the radionuclides oxo-cations. The substrate under study is the titanium oxide (TiO 2 ). In fact, rutile can be found as powder and also as manufactured single crystal which allows to study the retention processes on perfectly known crystallographic planes. Since the repartition of the different crystallographic orientations are known for the powder, the results obtained for the single crystals can directly be used to account for the powder retention properties. By using combined spectroscopic techniques such as TRLFS, XPS, DRIFT and SHG, it is possible to determine the nature of the reactive surface sites and also the surface species. XPS and TRLFS measurements allowed to determine that two same uranyl surface species were formed on titania (110) and (001). Only, the relative intensities of these species vary with the surface coverage. Atomic Force Microscopy was carried out to verify that no surface precipitation occurs for the higher surface coverages. Moreover, these analysis have also evidenced that the U(VI) sorption is homogeneous. These observations were corroborated by SHG experiments (mainly for (001)) which have also shown that the sorption occurs, in a first step, onto preferential surface symmetry axis. For rutile powder, the preferential crystallographic orientations are (110), (100) and (101) in the ratio 60/20/20. TRLFS and XPS experiments have shown that two uranyl surface species are formed whatever the pH value ranged from 1 to 5. The spectroscopic characteristics of these species are the same as the ones observed on (110) and (001

  9. Synthesis and complexation properties towards uranyl cation of carboxylic acid derivatives of p-tert-butyl-calix[6]arene

    International Nuclear Information System (INIS)

    Souane, R.

    2005-03-01

    In the fuel reprocessing plants radioactive metals, and more particularly, uranium in UO 2 2+ form in the various installations, have many varied physico-chemical forms and there is a risk of exposure and internal contamination in the nuclear industry. It is necessary to exert a medical control to ensure the protection of the health of the workers. This medical control is done by dosing uranyl cation in the urine of the exposed people. This work forms part of this context. Indeed, we prepared a ligand able to complex the ion uranyl and which is also to be grafted on a solid support. In the family of calixarenes, the calix[6]arenes functionalized by three or four carboxylic functions were selected like chelating molecules of the ion uranyl. The properties of complexation of these calixarenes were studied by potentiometry in methanol, under these conditions balances of protonation and complexation were determined and the constant partners were obtained using the Hyperquad program. We synthesized tri-carboxylic calix[6]arenes comprising of the groupings nitro (NO 2 ) in para position of phenol in order to see the influence of a substitution in para position on the complexation. We also synthesized calix[6]arenes tetra-carboxylic in order to show the role of an additional carboxylic acid grouping. The potentiometric study determined thermodynamic parameters of protonation and complexation of carboxylic calix[6]arenes. The results of the complexation highlighted which complex UO 2 L corresponding to the ligand para-tert-butyl-calix[6]arene tetra-acid is more stable than that corresponding to the ligand mono-nitro calix[6]arene tri-acid (ΔlogΒ110 = 4.3), and than the effect of the groupings nitro in para position has low influence on the complexation of UO 2 2+ . This makes it possible to consider as possible the grafting of the calix[6]arenes which one knows the behaviour of trapping. To this end we synthesized the ligand 23. (author)

  10. SERS detection of uranyl using functionalized gold nanostars promoted by nanoparticle shape and size.

    Science.gov (United States)

    Lu, Grace; Forbes, Tori Z; Haes, Amanda J

    2016-08-15

    The radius of curvature of gold (Au) nanostar tips but not the overall particle dimensions can be used for understanding the large and quantitative surface-enhanced Raman scattering (SERS) signal of the uranyl (UO2)(2+) moiety. The engineered roughness of the Au nanostar architecture and the distance between the gold surface and uranyl cations are promoted using carboxylic acid terminated alkanethiols containing 2, 5, and 10 methylene groups. By systematically varying the self-assembled monolayer (SAM) thickness with these molecules, the localized surface plasmon resonance (LSPR) spectral properties are used to quantify the SAM layer thickness and to promote uranyl coordination to the Au nanostars in neutral aqueous solutions. Successful uranyl detection is demonstrated for all three functionalized Au nanostar samples as indicated by enhanced signals and red-shifts in the symmetric U(vi)-O stretch. Quantitative uranyl detection is achieved by evaluating the integrated area of these bands in the uranyl fingerprint window. By varying the concentration of uranyl, similar free energies of adsorption are observed for the three carboxylic acid terminated functionalized Au nanostar samples indicating similar coordination to uranyl, but the SERS signals scale inversely with the alkanethiol layer thickness. This distance dependence follows previously established models assuming that roughness features associated with the radius of curvature of the tips are considered. These results indicate that SERS signals using functionalized Au nanostar substrates can provide quantitative detection of small molecules and that the tip architecture plays an important role in understanding the resulting SERS intensities.

  11. Mineralization enrichment of uranyl mineral in mid-low temperature hydrothermal of Shuanghuajiang uranium deposit

    International Nuclear Information System (INIS)

    Fang Shiyi; Liang Yongdong; Tao Zhijun; Chen Weifeng

    2009-01-01

    Based on field examination and mineral study by X-ray powder diffraction, electronic probe and back scatter electronic image, uranium mineral in Shuanghuajiang uranium deposit are analyzed and the mineral are divided into two classes: uranyl phosphate and uranyl silicate. After studying the forming condition of these uranylminerals, the deposit fall into low temperature hydrothermal genesis. The metallogenic model is hence established. (authors)

  12. A protein engineered to bind uranyl selectively and with femtomolar affinity

    Science.gov (United States)

    Zhou, Lu; Bosscher, Mike; Zhang, Changsheng; Özçubukçu, Salih; Zhang, Liang; Zhang, Wen; Li, Charles J.; Liu, Jianzhao; Jensen, Mark P.; Lai, Luhua; He, Chuan

    2014-03-01

    Uranyl (UO22+), the predominant aerobic form of uranium, is present in the ocean at a concentration of ~3.2 parts per 109 (13.7 nM) however, the successful enrichment of uranyl from this vast resource has been limited by the high concentrations of metal ions of similar size and charge, which makes it difficult to design a binding motif that is selective for uranyl. Here we report the design and rational development of a uranyl-binding protein using a computational screening process in the initial search for potential uranyl-binding sites. The engineered protein is thermally stable and offers very high affinity and selectivity for uranyl with a Kd of 7.4 femtomolar (fM) and >10,000-fold selectivity over other metal ions. We also demonstrated that the uranyl-binding protein can repeatedly sequester 30-60% of the uranyl in synthetic sea water. The chemical strategy employed here may be applied to engineer other selective metal-binding proteins for biotechnology and remediation applications.

  13. Production and Characterization of Desmalonichrome Relative Binding Affinity for Uranyl Ions in Relation to Other Siderophores

    Energy Technology Data Exchange (ETDEWEB)

    Mo, Kai-For; Dai, Ziyu; Wunschel, David S.

    2016-06-24

    Siderophores are Fe binding secondary metabolites that have been investigated for their uranium binding properties. Much of the previous work has focused on characterizing hydroxamate types of siderophores, such as desferrioxamine B, for their uranyl binding affinity. Carboxylate forms of these metabolites hold potential to be more efficient chelators of uranyl, yet they have not been widely studied and are more difficult to obtain. Desmalonichrome is a carboxylate siderophore which is not commercially available and so was obtained from the ascomycete fungus Fusarium oxysporum cultivated under Fe depleted conditions. The relative affinity for uranyl binding of desmalonichrome was investigated using a competitive analysis of binding affinities between uranyl acetate and different concentrations of iron(III) chloride using electrospray ionization mass spectrometry (ESI-MS). In addition to desmalonichrome, three other siderophores, including two hydroxamates (desferrioxamine B and desferrichrome) and one carboxylate (desferrichrome A) were studied to understand their relative affinities for the uranyl ion at two pH values. The binding affinities of hydroxymate siderophores to uranyl ion were found to decrease to a greater degree at lower pH as the concentration of Fe (III) ion increases. On the other hand, lowering pH has little impact on the binding affinities between carboxylate siderophores and uranyl ion. Desmalonichrome was shown to have the greatest relative affinity for uranyl at any pH and Fe(III) concentration. These results suggest that acidic functional groups in the ligands are critical for strong chelation with uranium at lower pH.

  14. A surface structural model for ferrihydrite II: Adsorption of uranyl and carbonate

    NARCIS (Netherlands)

    Hiemstra, T.; Riemsdijk, van W.H.; Rossberg, A.; Ulrich, K.

    2009-01-01

    The adsorption of uranyl (UO22+) on ferrihydrite has been evaluated with the charge distribution (CD) model for systems covering a very large range of conditions, i.e. pH, ionic strength, CO2 pressure, U(VI) concentration, and loading. Modeling suggests that uranyl forms bidentate inner sphere

  15. Widely tunable THz synthesizer

    Science.gov (United States)

    Hindle, F.; Mouret, G.; Eliet, S.; Guinet, M.; Cuisset, A.; Bocquet, R.; Yasui, T.; Rovera, D.

    2011-09-01

    The generation of cw-THz radiation by photomixing is particularly suited to the high resolution spectroscopy of gases; nevertheless, until recently, it has suffered from a lack of frequency metrology. Frequency combs are a powerful tool that can transfer microwave frequency standards to optical frequencies and a single comb has permitted accurate (10-8) THz frequency synthesis with a limited tuning range. A THz synthesizer composed of three extended cavity laser diodes phase locked to a frequency comb has been constructed and its utility for high resolution gas phase spectroscopy demonstrated. The third laser diode allows a larger tuning range of up to 300 MHz to be achieved without the need for large frequency excursions, while the frequency comb provides a versatile link to be established from any traceable microwave frequency standard. The use of a single frequency comb as a reference for all of the cw-lasers eliminates the dependency of synthesized frequency on the carrier envelope offset frequency. This greatly simplifies the frequency comb stabilization requirements and leads to a reduced instrument complexity.

  16. The effect of humic acid on uranyl sorption onto bentonite at trace uranium levels.

    Science.gov (United States)

    Ivanov, Peter; Griffiths, Tamara; Bryan, Nick D; Bozhikov, Gospodin; Dmitriev, Serguei

    2012-11-01

    The effect of humic acid (HA) on U(VI) sorption on bentonite was studied in batch experiments at room temperature and ambient atmosphere at a (237)U(VI) concentration of 8.4 × 10(-11) M and HA concentration of 100 mg L(-1). The distribution of U(VI) between the liquid and solid phases was studied as a function of pH and ionic strength both in the absence and presence of HA. It was shown that the uranyl sorption on bentonite is strongly dependent on pH and the presence of humics, and the effect of the addition order was negligible. In the absence of HA an enhancement in the uptake with increasing pH was observed and a sharp sorption edge was found to take place between pH 3.2 and 4.2. The presence of HA slightly increases uranium(VI) sorption at low pH and curtails it at moderate pH, compared to the absence of HA. In the basic pH range for both the presence and absence of HA the sorption of uranium is significantly reduced, which could be attributed to the formation of soluble uranyl carbonate complexes. The influence of ionic strength on U(VI) and HA uptake by bentonite were investigated in the range of 0.01-1.0 M, and while there was an enhancement in the sorption of humic acid with increasing ionic strength, no significant effect of the ionic strength on the U(VI) sorption was observed in both the absence and presence of HA.

  17. Potential remediation approach for uranium-contaminated groundwaters through potassium uranyl vanadate precipitation

    Energy Technology Data Exchange (ETDEWEB)

    Tokunaga, T.K.; Kim, Y.; Wan, J.

    2009-06-01

    Methods for remediating groundwaters contaminated with uranium (U) through precipitation under oxidizing conditions are needed because bioreduction-based approaches require indefinite supply of electron donor. Although strategies based on precipitation of some phosphate minerals within the (meta)autunite group have been considered for this purpose, thermodynamic calculations for K- and Ca-uranyl phopsphates, meta-ankoleite and autunite, predict that U concentrations will exceed the Maximum Contaminant Level (MCL = 0.13 {micro}M for U) at any pH and pCO{sub 2}, unless phosphate is maintained at much higher concentrations than the sub-{micro}M levels typically found in groundwaters. We hypothesized that potassium uranyl vanadate will control U(VI) concentrations below regulatory levels in slightly acidic to neutral solutions based on thermodynamic data available for carnotite, K{sub 2}(UO{sub 2}){sub 2}V{sub 2}O8. The calculations indicate that maintaining U concentrations below the MCL through precipitation of carnotite will be sustainable in some oxidizing waters having pH in the range of 5.5 to 7, even when dissolution of this solid phase becomes the sole supply of sub-{micro}M levels of V. Batch experiments were conducted in solutions at pH 6.0 and 7.8, chosen because of their very different predicted extents of U(VI) removal. Conditions were identified where U concentrations dropped below its MCL within 1 to 5 days of contact with oxidizing solutions containing 0.2 to 10 mM K, and 0.1 to 20 {micro}M V(V). This method may also have application in extracting (mining) U and V from groundwaters where they both occur at elevated concentrations.

  18. Quantification of uranyl in presence of citric acid; Cuantificacion de uranilo en presencia de acido citrico

    Energy Technology Data Exchange (ETDEWEB)

    Garcia G, N.; Barrera D, C.E. [UAEM, Facultad de Quimica, 50000 Toluca, Estado de Mexico (Mexico); Ordonez R, E. [ININ, 52750 La Marquesa, Estado de Mexico (Mexico)]. e-mail: nidgg@yahoo.com.mx

    2007-07-01

    To determine the influence that has the organic matter of the soil on the uranyl sorption on some solids is necessary to have a detection technique and quantification of uranyl that it is reliable and sufficiently quick in the obtaining of results. For that in this work, it intends to carry out the uranyl quantification in presence of citric acid modifying the Fluorescence induced by UV-Vis radiation technique. Since the uranyl ion is very sensitive to the medium that contains it, (speciation, pH, ionic forces, etc.) it was necessary to develop an analysis technique that stands out the fluorescence of uranyl ion avoiding the out one that produce the organic acids. (Author)

  19. A Phosphorylation Tag for Uranyl Mediated Protein Purification and Photo Assisted Tag Removal

    DEFF Research Database (Denmark)

    Zhang, Qiang; Jørgensen, Thomas. J. D.; Nielsen, Peter E

    2014-01-01

    of enzymes available for this purpose. In the present study, we demonstrate the utility of the divalent uranyl ion in a new procedure for protein purification and tag removal. By employment of a GFP (green florescence protein) recombinant protein we show that uranyl binding to a phosphorylated C-terminal tag......Most protein purification procedures include an affinity tag fused to either the N or C-terminal end of the protein of interest as well as a procedure for tag removal. Tag removal is not straightforward and especially tag removal from the C-terminal end is a challenge due to the characteristics...... enables target protein purification from an E. coli extract by immobilized uranyl affinity chromatography. Subsequently, the tag can be efficiently removed by UV-irradiation assisted uranyl photocleavage. We therefore suggest that the divalent uranyl ion (UO22+) may provide a dual function in protein...

  20. Kinetic of liquid-liquid extraction for uranyl nitrate and actinides (III) and lanthanides (III) nitrates by amide extractants; Cinetique d`extraction liquide-liquide du nitrate d`uranyle et des nitrates d`actinides (III) et de lanthanides (III) par des extractants a fonction amide

    Energy Technology Data Exchange (ETDEWEB)

    Toulemonde, V. [CEA Centre d`Etudes Nucleaires de Saclay, 91 -Gif-sur-Yvette (France)]|[CEA Centre d`Etudes de la Vallee du Rhone, 30 -Marcoule (France). Dept. d`Exploitation du Retraitement et de Demantelement

    1995-12-20

    The kinetics of liquid-liquid extraction by amide extractants have been investigated for uranyl nitrate (monoamide extractants), actinides (III) and lanthanides (III) nitrates (diamide extractants). The transfer of the metallic species from the aqueous phase to the organic phase was studied using two experimental devices: ARMOLLEX (Argonne Modified Lewis cell for Liquid Liquid Extraction) and RSC (Rotating Stabilized Cell). The main conclusions are: for the extraction of uranyl nitrate by DEHDMBA monoamide, the rate-controlling step is the complexation of the species at the interface of the two liquids. Thus, an absorption-desorption (according to Langmuir theory) reaction mechanism was proposed; for the extraction of actinides (III) and lanthanides (III) nitrates in nitric acid media by DMDBTDMA diamide, the kinetic is also limited by interfacial reactions. The behavior of Americium and Europium is very similar as fare as their reaction kinetics are concerned. (author). 89 refs.

  1. Liquid-liquid extraction kinetics of uranyl nitrate and actinides (III)-lanthanides nitrates by extractants with amide function

    International Nuclear Information System (INIS)

    Toulemonde, V.

    1995-01-01

    Nowadays, the most important part of electric power is generated by fission energy. But spent fuels have then to be reprocessed. The production of these reprocessed materials separately and with a high purity level is done according to a liquid-liquid extraction process (Purex process) with the use of tributyl phosphate as solvent. Optimization studies concerning the extracting agent have been undertaken. This work gives the results obtained for the uranyl nitrate and the actinides (III)-lanthanides (III) nitrates extraction by extractants with amide function (monoamide for U(VI) and diamide for actinides (III) and lanthanides (III)). The extraction kinetics have been studied in the case of a metallic specie transfer from the aqueous phase towards the organic phase. The experiments show that the nitrates extraction kinetics is limited by the complexation chemical reaction of the species at the interface between the two liquids. An adsorption-desorption interfacial reactional mechanism (Langmuir theory) is proposed for the uranyl nitrate. (O.M.)

  2. The system uranyl nitrate-dietyl ether-water. Extraction by water in spray and packed columns from uranyl nitrate-either solutions; El sistema nitrato de uranilo-eter dietilico-agua, extraccion de nitrato de uranilo con agua a partir de disoluciones etereas en columnas de pulverizacion y de relleno

    Energy Technology Data Exchange (ETDEWEB)

    Perez Luina, A.; Gutierrez Jodra, L.

    1960-07-01

    This paper is a continuation of the one published in Chemical Engineering Progress. Symposium Series, 50, n. 12, 127 (1954). New runs for spray columns, are given and other concentrations in uranyl nitrate for the packed columns. New correlations for the overall H.T.U. are also given. The individual H.T.U. have been grapycally calculated and show that the film resistances have similar values, being independent of the concentration of the ether phase. (Author) 24 refs.

  3. Photoluminescence Study of the Photoinduced Phase Separation in Mixed-Halide Hybrid Perovskite CH3NH3Pb(BrxI1-x)3 Crystals Synthesized via a Solvothermal Method.

    Science.gov (United States)

    Zhang, Baohua; Guo, Fuqiang; Xue, Junjun; Yang, Lianhong; Zhao, Yafei; Ge, Mei; Cai, Qing; Liu, Bin; Xie, Zili; Chen, Dunjun; Lu, Hai; Zhang, Rong; Zheng, Youdou

    2017-12-18

    We systematically synthesized mixed-halide hybrid perovskite CH 3 NH 3 Pb(Br x I 1-x ) 3 (0 ≤ x ≤ 1) crystals in the full composition range by a solvothermal method. The as-synthesized crystals retained cuboid shapes, and the crystalline structure transitioned from the tetragonal phase to the cubic phase with an increasing Br-ion content. The photoluminescence (PL) of CH 3 NH 3 Pb(Br x I 1-x ) 3 crystals exhibited a continuous variation from red (768 nm) to green (549 nm) with increasing the volume ratio of HBr (V HBr %), corresponding to a variation in the bandgap from 1.61 eV to 2.26 eV. Moreover, the bandgap of the crystals changed nonlinearly as a quadratic function of x with a bowing parameter of 0.53 eV. Notably, the CH 3 NH 3 Pb(Br x I 1-x ) 3 (0.4 ≤ x ≤ 0.6) crystals exhibited obvious phase separation by prolonged illumination. The cause for the phase separation was attributed to the formation of small clusters enriched in lower-band-gap, iodide-rich and higher-band-gap, bromide-rich domains, which induced localized strain to promote halide phase separation. We also clarified the relationship between the PL features and the band structures of the crystals.

  4. Comparing uranyl sorption complexes on soil and reference clays

    International Nuclear Information System (INIS)

    Chisholm-Brause, C.J.; Berg, J.M.; Conradson, S.D.; Morris, D.E.; McKinley, J.P.; Zachara, J.M.

    1993-01-01

    Clay minerals and other components in natural soils may play a key role in limiting the mobility of uranium in the environment through the formation of sorption complexes. Reference clays are frequently used as models to study sorption processes because they have well-known chemical and physical properties, but they may differ chemically and morphologically from clays derived from natural soils. Therefore, inferences based on reference clay data have been questioned. The authors have used luminescence and x-ray absorption spectroscopies to characterize the sorption complexes of aqueous uranyl (UO 2 2+ ) species on two soil smectites from the Kenoma and Ringold formations, and compared these results to those obtained on reference smectite clays. The pH dependence of uptake suggests that the ratio of sorption on amphoteric edge sites is greater for the soil smectites than for reference clays such as Wyoming montmorillonite (SWy-1). The luminescence spectra for uranyl sorbed to the soil clays are very similar to those for uranyl sorbed principally to the edge sites of SWy-1. This observation supports the solution data suggesting that adsorption to amphoteric sites is a more important mechanism for soil clays. However, the spectral data indicate that the sorption complexes on natural and reference clays are quite similar. Furthermore, as with the reference clays, the authors have found that the chemistry of the solution plays a greater role in defining the sorption complex than does the clay matrix. Thus, if differences in surface properties are adequately taken into account, the reference clays may serve as useful analogs for soil clays in investigations of metal-ion sorption

  5. Determination of free nitric acid in uranyl nitrate solution

    International Nuclear Information System (INIS)

    Mayankutty, P.C.; Ravi, S.; Nadkarni, M.N.

    1981-01-01

    Potentiometric titration of uranyl nitrate solution with sodium hydroxide exhibits two peaks. The first peak characterises the following reaction, UO 2 (C 2 O 4 )+NaOH Na[UO 2 (C 2 O 4 )(OH)]. This reaction, indicating the partial hydrolysis of uranyl oxalate complex, appears to be complete at pH9. If the titration is carried out to this end-point pH, the total alkali consumed can be equated to the sum of uranium content and the free acidity present in the sample volume. Based on this, a method was standardised to determine the free acidity in uranyl nitrate solution. The sample, taken in a solution of potassium oxalate previously adjusted to pH9, is titrated to this pH with standard sodium hydroxide. The free acidity in the sample can be computed by subtracting the alkali reacted with uranium from the total alkali consumed. Analyses of several synthetic samples containing uranium and nitric acid in a wide range of combinations indicate that the free acidity can be accurately determined by this method, if uranium concentration in the sample is known. The results are compared to those obtained by two other widely used methods, viz., (i) titration of pH7 in the presence of neutral potassium oxalate to suppress hydrolysis and (ii) separation of hydrolyzable ions on a cationic resin and alkali titration of the free acid released. The advantages of and the precision obtained with the present method over the above two methods are discussed. (author)

  6. Biosolubilization of uranyl ions in uranium ores by hydrophyte plants

    International Nuclear Information System (INIS)

    Cecal, Alexandru; Calmoi, Rodica; Melniciuc-Puica, Nicoleta

    2006-01-01

    This paper investigated the bioleaching of uranyl ions from uranium ores, in aqueous medium by hydrophyte plants: Lemna minor, Azolla caroliniana and Elodea canadensis under different experimental conditions. The oxidation of U(IV) to U(VI) species was done by the atomic oxygen generated in the photosynthesis process by the aquatic plants in the solution above uranium ores. Under identical experimental conditions, the capacity of bioleaching of uranium ores decreases according to the following series: Lemna minor > Elodea canadensis > Azolla caroliniana. The results of IR spectra suggest the possible use of Lemna minor and Elodea canadensis as a biological decontaminant of uranium containing wastewaters. (author)

  7. Study of diamagnetism in uranyl complexes of some Schiff bases

    International Nuclear Information System (INIS)

    Dodwad, S.S.; Sawant, A.S.

    1992-01-01

    Uranyl complexes of Schiff bases obtained by condensing salicylaldehyde with aromatic amines have been isolated and characterised. The complexes have the formula M (LH) 2 (NO 3 ) 2 where M = UO 2 and LH = Schiff base. The magnetic susceptibilities of these complexes have been measured on a Gouy balance. These values have been compared with the computed ones. The percentage deviation between the observed and computed values of molar magnetic susceptibilities clearly show that they are outside experimental error and therefore significant. These deviations have been discussed in the light of VanVleck's, equation for molar susceptibility of polyatomic molecule. (author). 3 refs., 1 tab

  8. The quenching of excited uranyl ion by d6 metallocenes

    International Nuclear Information System (INIS)

    Traverso, O.; Rossi, R.; Magon, L.; Cinquantini, A.; Kemp, T.

    1978-01-01

    Quenching constants Ksub(Q) of uranyl luminescence by d 6 metallocenes of Fe, Ru, and Os have been obtained both from luminescence intensity and lifetime measurements. The values of log 10 Ksub(Q) are correlated with the oxidant potentials of metallocenes, in accordance with an electron-transfer mechanism. This scheme is supported by photoreaction studies, where the formation of either the rather elusive [UO 2 ] + ion or (in the case of osmocene solutions) uranium(IV) species has been observed: in the case of ferrocene solutions, ferricenium ion is also produced. (author)

  9. EXAFS investigations of the interaction of humic acids and model compounds with uranyl cations in solid complexes

    International Nuclear Information System (INIS)

    Denecke, M.A.; Reich, T.; Pompe, S.; Bubner, M.; Heise, K.H.; Nitsche, H.; Allen, P.G.; Bucher, J.J.; Edelstein, N.M.; Shuh, D.K.; Czerwinski, K.R.

    1998-01-01

    Natural humic acids, HA's, having varying amounts of their proton exchange capacities, PEC's, loaded with uranyl ions and synthetic HA loaded with 14% PEC were prepared either from solution or from suspension. The interaction of uranium with the humates was studied using U L III -edge extended X-ray absorption fine structure, EXAFS, and infrared, IR, spectroscopy. IR results indicate a direct complexation of the uranyl ions onto the HA's. The spectral positions of the asymmetric and symmetric IR stretching frequencies for COO - in the complex suggest monodentate coordination of HA carboxylate groups onto the uranyl cation. In all samples studied, the EXAFS analysis yielded axial uranium-oxygen distances of 1.77-1.78 A and five oxygen atoms in the plane equatorial to the uranyl unit at distances of 2.37-2.39 A. The bond distances determined from the EXAFS are the same, within the experimental error, for both synthetic and two different natural uranyl humates, for samples with large loadings and samples with relatively low uranyl loadings, as well as for dry and wet paste samples. Comparison of the EXAFS from the uranyl humates with that observed for two crystalline uranyl carboxylate complexes indicates that the HA carboxylate groups act predominantly as monodentate ligands when bound to the uranyl unit. Additional, neutral ligands must also be coordinated to the uranyl ion in order to satisfy the uranyl cation coordination number determined as 5 ± 0.7. (orig.)

  10. Substituted biurets as uranophilic ligands: A facile DMSO-induced conversion of a 1:1 into a 2:1 uranyl-ligand complex

    Energy Technology Data Exchange (ETDEWEB)

    Potts, K.T.; O' Brien, J.J.; Tham, F.S. (Rensselaer Polytechnic Inst., Troy, NY (United States))

    1990-01-01

    1,5-Bis(6-(1-ethoxycarbonyl-3-thioureido)-2-pyridindiyl)biuret and uranyl acetate gave a crystalline 1:1 uranyl-ligand complex which, on crystallization from DMSO, underwent rearrangement to a crystalline 2:1 uranyl-ligand complex and a stoichiometric amount of the uncomplexed ligand. Spectral characteristics of these ligands and their uranyl complexes together with single crystal x-ray data for the uranyl-ligand complexes are described.

  11. Synthesis, structure, and photoluminescence properties of an organically-templated uranyl selenite

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Dong-Sheng; Kuang, Han-Mao; Chen, Wen-Tong; Luo, Qiu-Yan; Sui, Yan [Institute of Applied Chemistry, School of Chemistry and Chemical Engineering, Jinggangshan University, Ji' an, Jiangxi 343009 (China)

    2015-09-15

    The organically-templated uranyl selenite, (H{sub 2}en)[(UO{sub 2})(SeO{sub 3})(HSeO{sub 3})](NO{sub 3}).0.5H{sub 2}O (1) (en = 1,2-ethylenediamine) was synthesized and characterized by elemental analyses, IR spectroscopy, TG, and single-crystal X-ray diffraction. Compound 1 crystallizes in the orthorhombic system, space group Pbca, with a = 13.170(3) Aa, b = 11.055(2) Aa, c = 18.009(4) Aa, V = 2621.8(9) Aa{sup 3}, M = 1316.19, Z = 4, D{sub cal} = 3.334 g.cm{sup -3}, μ(Mo-K{sub α}) = 17.998 mm{sup -1}, GOF = 1.059, R{sub 1} = 0.0263, wR{sub 2} = 0.0532 [I>2σ(I)]. The X-ray diffraction analysis reveals that compound 1 has a three-dimensional (3D) supramolecular structure. It contains negatively charged [UO{sub 2}(HSeO{sub 3})(SeO{sub 3})]{sup -} inorganic anion layers and is balanced by [H{sub 2}en]{sup 2+} cations and NO{sub 3}{sup -} anions located in the interlayers. Furthermore, the photoluminescence properties of 1 were investigated. (Copyright copyright 2015 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  12. Synthesis, structure, and photoluminescence properties of an organically-templated uranyl selenite

    International Nuclear Information System (INIS)

    Liu, Dong-Sheng; Kuang, Han-Mao; Chen, Wen-Tong; Luo, Qiu-Yan; Sui, Yan

    2015-01-01

    The organically-templated uranyl selenite, (H 2 en)[(UO 2 )(SeO 3 )(HSeO 3 )](NO 3 ).0.5H 2 O (1) (en = 1,2-ethylenediamine) was synthesized and characterized by elemental analyses, IR spectroscopy, TG, and single-crystal X-ray diffraction. Compound 1 crystallizes in the orthorhombic system, space group Pbca, with a = 13.170(3) Aa, b = 11.055(2) Aa, c = 18.009(4) Aa, V = 2621.8(9) Aa 3 , M = 1316.19, Z = 4, D cal = 3.334 g.cm -3 , μ(Mo-K α ) = 17.998 mm -1 , GOF = 1.059, R 1 = 0.0263, wR 2 = 0.0532 [I>2σ(I)]. The X-ray diffraction analysis reveals that compound 1 has a three-dimensional (3D) supramolecular structure. It contains negatively charged [UO 2 (HSeO 3 )(SeO 3 )] - inorganic anion layers and is balanced by [H 2 en] 2+ cations and NO 3 - anions located in the interlayers. Furthermore, the photoluminescence properties of 1 were investigated. (Copyright copyright 2015 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  13. A simple chemical route to synthesize the umangite phase of copper selenide (Cu3Se2) thin film at room temperature

    Science.gov (United States)

    Palve, Balasaheb M.; Jadkar, Sandesh R.; Pathan, Habib M.

    2017-06-01

    Copper selenide (Cu3Se2) thin films have been synthesized with Se as the precursor in aqueous solution by chemical bath deposition technique at room temperature. We have investigated the influence of the growth time ranging from 30 to 90 min on structural, optical and electrical properties of Cu3Se2 thin films. The as-grown film at 60 min exhibits a tetragonal structure and is (101) oriented. The maximum value of crystal size D = 55 nm is attained for Cu3Se2 films grown at 60 min. The Raman spectrum reveals a pronounced peak at 259 cm-1, which is assigned to vibrational (stretching) modes from the covalent Se-Se bonds. The optical band gap energy is 1.91 to 2.01 eV with growth time increased from 30 to 90 min. The scanning electron microscopy (SEM) study reveals that the grains are uniform and spread over the entire surface of the substrate of the film at 60 min. The Hall effect study reveals that the film exhibits p-type conductivity. The synthesized film showed good absorbance in the visible region which signifies that synthesized Cu3Se2 films can be suitable as a sensitized material in semiconductor sensitized solar cells.

  14. Construction of Uranyl Selective Electrode Based on Complex of Uranyl Ion with New Ligand Carboxybenzotriazole in PVC Matrix Membrane

    Science.gov (United States)

    Abu-Dalo, M. A.; Al-Rawashdeh, N. A. F.; Al-Mheidat, I. R.; Nassory, N. S.

    2015-10-01

    In the present study uranyl selective electrodes in polyvinyl chloride (PVC) matrix membrane were prepared based on a complex of uranyl ion (UO2) with carboxybenzotriazole (CBT) as ligand. The effect of the nature of plasticizer in PVC matrix were evaluated using three different plasticizers, these are dibutyl phthalate (DBP), dioctyl phthalate (DOP) and bis(2-ethylhexyl) sebacate (BHS). The results of this study indicated that the best plasticizer could be used is the DBP, which may be attributed to its lowest viscosity value compared to DOP and BHS. The electrodes with DBP as plasticizer exhibits a Nernstian response with a slope of 28.0 mV/ decade, over a wide range of concentration from 3.0×10-5-6.0×10-2 M and a detection limit of 4.0×10-6 M. It can be used in the pH range of 4.0-10.0 with a response time of less than 10 s for DBP and 25 s for both DOP and BHS. The effects of ions interferences on the electrode response were evaluated. The di- and tri-valent cations were found to interfere less than univalent cations, which was attributed to the high diffusion and the exchange rate between the univalent ions and the uranyl ion solution. The electrodes were characterized by Fourier Transform Infrared Spectroscopy (FTIR) and Scanning Electron microscopy (SEM). The results of the standard addition method were satisfactory with errors less than 7%. The developed electrode was found to be fast, sensitive and reliable indicated its potential use in measuring the uranly ion concentration in the field.

  15. Effect of the substitutional groups on the electrochemistry, kinetic of thermal decomposition and kinetic of substitution of some uranyl Schiff base complexes

    Energy Technology Data Exchange (ETDEWEB)

    Asadi, Zahra; Nasrollahi, Rahele; Ranjkeshshorkaei, Mohammad; Firuzabadi, Fahimeh Dehghani [Shiraz Univ. (Iran, Islamic Republic of). Chemistry Dept.; Dusek, Michal; Fejfarova, Karla [ASCR, Prague (Czech Republic). Inst. of Physics

    2016-05-15

    Uranyl(VI) complexes, [UO{sub 2}(X-saloph)(solvent)], where saloph denotes N,N{sup '}-bis(salicylidene)-1,2-phenylenediamine and X = NO{sub 2}, Cl, Me, H; were synthesized and characterized by 61H NMR, IR, UV-Vis spectroscopy, thermal gravimetry (TG), cyclic voltammetry, elemental analysis (C.H.N) and X-ray crystallography. X-ray crystallography of [UO{sub 2}(4-nitro-saloph)(DMF)] revealed coordination of the uranyl by the tetradentate Schiff base ligand and one solvent molecule, resulting in seven-coordinated uranium. The complex of [UO{sub 2}(4-nitro-saloph)(DMF)] was also synthesized in nano form. Transmission electron microscopy image showed nano-particles with sizes between 30 and 35 nm. The TG method and analysis of Coats-Redfern plots revealed that the kinetics of thermal decomposition of the complexes is of the first-order in all stages. The kinetics and mechanism of the exchange reaction of the coordinated solvent with tributylphosphine was investigated by spectrophotometric method. The second-order rate constants at four temperatures and the activation parameters showed an associative mechanism for all corresponding complexes with the following trend: 4-Nitro > 4-Cl > H > 4-Me. It was concluded that the steric and electronic properties of the complexes were important for the reaction rate. For analysis of anticancer properties of uranyl Schiff base complexes, cell culture and MTT assay was carried out. These results showed a reduction of jurkat cell line concentration across the complexes.

  16. Uranyl and/or rare-earth mellitates in extended organic-inorganic networks: A unique case of hetero-metallic cation-cation interaction with U-VI=O-Ln(III) bonding (Ln = Ce, Nd)

    International Nuclear Information System (INIS)

    Volkringer, Christophe; Henry, Natacha; Grandjean, Stephane; Loiseau, Thierry

    2012-01-01

    A series of uranyl and lanthanide (trivalent Ce, Nd) mellitates (mel) has been hydrothermally synthesized in aqueous solvent. Mixtures of these 4f and 5f elements also revealed the formation of a rare case of lanthanide-uranyl coordination polymers. Their structures, determined by XRD single-crystal analysis, exhibit three distinct architectures. The pure lanthanide mellitate Ln 2 (H 2 O) 6 (mel) possesses a 3D framework built up from the connection of isolated LnO 6 (H 2 O) 3 polyhedra (tri-capped trigonal prism) through the mellitate ligand. The structure of the uranyl mellitate (UO 2 ) 3 (H 2 O) 6 - (mel).11.5H 2 O is lamellar and consists of 8-fold coordinated uranium atoms linked to each other through the organic ligand giving rise to the formation of a 2D 3 6 net. The third structural type, (UO 2 ) 2 Ln(OH)(H 2 O) 3 (mel).2.5H 2 O, involves direct oxygen bondings between the lanthanide and uranyl centers, with the isolation of a hetero-metallic dinuclear motif. The 9-fold coordinated Ln cation, LnO 5 (OH)(H 2 O) 3 , is linked to the 7-fold coordinated uranyl (UO 2 )O-4(OH) (pentagonal bipyramid) via one μ 2 -hydroxo group and one μ 2 -oxo group. The latter is shared between the uranyl bonding (U=O = 1.777(4)1.779(6) angstrom) and a long Ln-O bonding (Ce-O = 2.822(4) angstrom; Nd-O = 2.792(6) angstrom). This unusual linkage is a unique illustration of the so-called cation cation interaction associating 4f and 5f metals. The dinuclear motif is then further connected through the mellitate ligand, and this generates organic inorganic layers that are linked to each other via discrete uranyl (UO 2 )O 4 units (square bipyramid), which ensure the three-dimensional cohesion of the structure. The mixed U-Ln carboxylate is thermally decomposed from 260 to 280 degrees C and then transformed into the basic uranium oxide (U 3 O 8 ) together with U-Ln oxide with the fluorite structural type ('(Ln,U)O 2 '). At 1400 degrees C, only fluorite type '(Ln,U)O 2 ' is formed with

  17. Study of the influence of the citric and oxalic acid in the uranyl sorption in ZrP2O7 for their use in contention barriers

    International Nuclear Information System (INIS)

    Garcia G, N.

    2009-01-01

    Countries which produce electricity by nuclear means, such as Mexico, need to develop a technology for that at long term safe containment of nuclear waste that are produced in nuclear power plants, for now, the arrangement of these is made by international companies, as which is extremely expensive. The most accepted proposal for the containment of radioactive waste is the Deep Geological Repository (DGR), which consists of a number of natural barriers and of engineering barriers. Currently, barriers to engineering and materials that the make up are still under study, because must meet a series of structural criteria and chemical such as high insolubility, thermal and chemical stability with ionizing radiation. The surface must have adsorbed features of ions and organic compounds dissolved in infiltration water that could penetrate for a crack in the DGR. This study focuses, as first stage, is the uranyl sorption on zirconium diphosphate in various conditions of time, concentration and ph, then evaluates the influence of citric acid and oxalic acid on the sorption of uranyl on ZrP 2 O 7 , in order to model the behaviour of alpha emitters that are dissolved by percolating water laden with salts and organic matter, that infiltrates might during catastrophic events in the DGR. It was confirmed the purity of the zirconium diphosphate because it was synthesized from sea sand with the physicochemical characterization and superficial. The proposed methodology included elemental analysis by neutron activation and X-ray emission induced by charged particles, functional group analysis with infrared spectroscopy, morphology with scanning electron microscopy, crystallinity with transmission electron microscopy and X-ray diffraction. For properties surface was determined, the specific area using Bet multipoint technique, acidity constants in the FITEQL 4.0 program, the hydration time was obtained from literature, the point of zero charge was identified with a mass titration and

  18. Understanding the bonding nature of uranyl ion and functionalized graphene: a theoretical study.

    Science.gov (United States)

    Wu, Qun-Yan; Lan, Jian-Hui; Wang, Cong-Zhi; Xiao, Cheng-Liang; Zhao, Yu-Liang; Wei, Yue-Zhou; Chai, Zhi-Fang; Shi, Wei-Qun

    2014-03-20

    Studying the bonding nature of uranyl ion and graphene oxide (GO) is very important for understanding the mechanism of the removal of uranium from radioactive wastewater with GO-based materials. We have optimized 22 complexes between uranyl ion and GO applying density functional theory (DFT) combined with quasi-relativistic small-core pseudopotentials. The studied oxygen-containing functional groups include hydroxyl, carboxyl, amido, and dimethylformamide. It is observed that the distances between uranium atoms and oxygen atoms of GO (U-OG) are shorter in the anionic GO complexes (uranyl/GO(-/2-)) compared to the neutral GO ones (uranyl/GO). The formation of hydrogen bonds in the uranyl/GO(-/2-) complexes can enhance the binding ability of anionic GO toward uranyl ions. Furthermore, the thermodynamic calculations show that the changes of the Gibbs free energies in solution are relatively more negative for complexation reactions concerning the hydroxyl and carboxyl functionalized anionic GO complexes. Therefore, both the geometries and thermodynamic energies indicate that the binding abilities of uranyl ions toward GO modified by hydroxyl and carboxyl groups are much stronger compared to those by amido and dimethylformamide groups. This study can provide insights for designing new nanomaterials that can efficiently remove radionuclides from radioactive wastewater.

  19. Surface complexation modeling of uranyl adsorption on corrensite from the Waste Isolation Pilot Plant Site

    International Nuclear Information System (INIS)

    Park, Sang-Won; Leckie, J.O.; Siegel, M.D.

    1995-09-01

    Corrensite is the dominant clay mineral in the Culebra Dolomite at the Waste Isolation Pilot Plant. The surface characteristics of corrensite, a mixed chlorite/smectite clay mineral, have been studied. Zeta potential measurements and titration experiments suggest that the corrensite surface contains a mixture of permanent charge sites on the basal plane and SiOH and AlOH sites with a net pH-dependent charge at the edge of the clay platelets. Triple-layer model parameters were determined by the double extrapolation technique for use in chemical speciation calculations of adsorption reactions using the computer program HYDRAQL. Batch adsorption studies showed that corrensite is an effective adsorbent for uranyl. The pH-dependent adsorption behavior indicates that adsorption occurs at the edge sites. Adsorption studies were also conducted in the presence of competing cations and complexing ligands. The cations did not affect uranyl adsorption in the range studied. This observation lends support to the hypothesis that uranyl adsorption occurs at the edge sites. Uranyl adsorption was significantly hindered by carbonate. It is proposed that the formation of carbonate uranyl complexes inhibits uranyl adsorption and that only the carbonate-free species adsorb to the corrensite surface. The presence of the organic complexing agents EDTA and oxine also inhibits uranyl sorption

  20. Synthesis, structure, and nonlinear optical activity of K, Rb, and Cs tris(crotonato)uranylates(VI)

    Energy Technology Data Exchange (ETDEWEB)

    Savchenkov, Anton V.; Serezhkina, Larisa B.; Pushkin, Denis V.; Serezhkin, Viktor N. [Inorganic Chemistry Department, Samara State University, 1 Ak. Pavlova st.Samara, 443011 (Russian Federation); Vologzhanina, Anna V. [Laboratory for X-ray Diffraction Studies, Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, 28 Vavilova st.Moscow, 119991 (Russian Federation); Stefanovich, Sergey Yu. [Department of Chemical Technology and New Materials, Lomonosov Moscow State University, 1 Leninskie Gory, Moscow, 119991 (Russian Federation)

    2015-05-15

    Three uranyl crotonate complexes with composition RUO{sub 2}(C{sub 3}H{sub 5}COO){sub 3} [R = K (I), Rb (II), Cs (III)] were studied using FT-IR spectroscopy and X-ray diffraction analyses. The structures of I-III are constructed of typical anionic tris(carboxylato)uranylate complexes [UO{sub 2}(C{sub 3}H{sub 5}COO){sub 3}]{sup -}. Cubic crystals of I and II have 3D framework structure, whereas triclinic crystals of III have layered structure. In the structure of III uranyl ions are nonlinear and non equal-arm due to uranyl-cation UO{sub 2}{sup 2+}-Cs{sup +} interactions. Nonlinear optical activity of noncentrosymmetric uranyl carboxylates was estimated by second harmonic generation measurements. Uranyl crotonate complexes show about twice higher SHG ability than uranyl butyrate and valerate complexes. (Copyright copyright 2015 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  1. Use of uranyl nitrate as a shift reagent in polar and inert solvents

    International Nuclear Information System (INIS)

    Nosov, B.P.

    1988-01-01

    This work examines the effect of uranyl nitrate as a shift reagent on the PMR spectra of different organic molecules in polar and inert solvents. In order to identify the coordination site of the uranyl ion, its effect on the spectra of amino acids and acetic or propionic acids in water was compared. It was found that the induced shifts of the protons in the corresponding positions of the different acids after addition of uranyl nitrate agreed to within ±0.01 ppm. When nitrogenous bases such as diethylamine and pyridine were added to solutions of the carboxylic acids with uranyl nitrate, an increase in the induced chemical shift of the resonance signals occurred. These facts suggest the coordination of the uranyl ion with the carboxyl oxygen both for acetic and propionic acids and for amino acids. The authors established that the addition of uranyl nitrate to solutions of organic compounds caused different downfield shifts of the resonance signals from the protons. In polar solvents shifts induced by uranyl nitrate in the PMR spectra of carboxylic acids occur only when nitrogenous bases are added

  2. Enhanced Adsorption and Recovery of Uranyl Ions by NikR Mutant-Displaying Yeast

    Directory of Open Access Journals (Sweden)

    Kouichi Kuroda

    2014-04-01

    Full Text Available Uranium is one of the most important metal resources, and the technology for the recovery of uranyl ions (UO22+ from aqueous solutions is required to ensure a semi-permanent supply of uranium. The NikR protein is a Ni2+-dependent transcriptional repressor of the nickel-ion uptake system in Escherichia coli, but its mutant protein (NikRm is able to selectively bind uranyl ions in the interface of the two monomers. In this study, NikRm protein with ability to adsorb uranyl ions was displayed on the cell surface of Saccharomyces cerevisiae. To perform the binding of metal ions in the interface of the two monomers, two metal-binding domains (MBDs of NikRm were tandemly fused via linker peptides and displayed on the yeast cell surface by fusion with the cell wall-anchoring domain of yeast α-agglutinin. The NikRm-MBD-displaying yeast cells with particular linker lengths showed the enhanced adsorption of uranyl ions in comparison to the control strain. By treating cells with citrate buffer (pH 4.3, the uranyl ions adsorbed on the cell surface were recovered. Our results indicate that the adsorption system by yeast cells displaying tandemly fused MBDs of NikRm is effective for simple and concentrated recovery of uranyl ions, as well as adsorption of uranyl ions.

  3. Hydrothermal Synthesis of Disulfide-Containing Uranyl Compounds. In Situ Ligand Synthesis versus Direct Assembly

    Energy Technology Data Exchange (ETDEWEB)

    Rowland, Clare E. [George Washington Univ., Washington, DC (United States); Belai, Nebebech [George Washington Univ., Washington, DC (United States); Knope, Karah E. [George Washington Univ., Washington, DC (United States); Cahill, Christopher L. [George Washington Univ., Washington, DC (United States)

    2010-01-29

    Three disulfide-containing uranyl compounds, [UO2(C7H4O2S)3]·H2O (1), [UO2(C7H4O2S)2(C7H5O2S)] (2), and [UO2(C7H4O2S)4] (3) have been hydrothermally synthesized. Both in situ disulfide bond formation from 3- and 4-mercaptobenzoic acid (C7H5O2S, MBA) to yield 3,3'- and 4,4'-dithiobisbenzoic acid (C14H8O4S2, DTBA) and direct assembly with the presynthesized dimeric ligands have been explored. While the starting materials 4-MBA and 4,4'-DTBA both yield 2 via in situ ligand synthesis and direct assembly, respectively, we observe the formation of 1 from the starting material 3-MBA via in situ ligand synthesis and of 3 from the direct assembly of the uranyl cation with 3,3'-DTBA. Concurrently with the synthesis of 1 and 2, we have observed the in situ formation of the crystalline dimeric organic species, 3,3'-DTBA, [(C7H5O2S)2] (4) and 4,4'-DTBA, [(C7H5O2S)2] (5). Herein we report the synthesis and crystallographic characterization of 1-5, as well as observations regarding the utility of product formation via direct assembly and in situ ligand synthesis.

  4. SEPARATION OF BARIUM VALUES FROM URANYL NITRATE SOLUTIONS

    Science.gov (United States)

    Tompkins, E.R.

    1959-02-24

    The separation of radioactive barium values from a uranyl nitrate solution of neutron-irradiated uranium is described. The 10 to 20% uranyl nitrate solution is passed through a flrst column of a cation exchange resin under conditions favoring the adsorption of barium and certain other cations. The loaded resin is first washed with dilute sulfuric acid to remove a portion of the other cations, and then wash with a citric acid solution at pH of 5 to 7 to recover the barium along with a lesser amount of the other cations. The PH of the resulting eluate is adjusted to about 2.3 to 3.5 and diluted prior to passing through a smaller second column of exchange resin. The loaded resin is first washed with a citric acid solution at a pH of 3 to elute undesired cations and then with citric acid solution at a pH of 6 to eluts the barium, which is substantially free of undesired cations.

  5. XAFS spectroscopic study of uranyl coordination in solids and aqueous solution

    International Nuclear Information System (INIS)

    Thompson, H.A.; Brown, G.E. Jr.; Parks, G.A.

    1997-01-01

    To evaluate the ability of X-ray absorption fine structure (XAFS) spectroscopy to elucidate the coordination environment of U 6+ at the solid-water interface, we conducted an in-depth analysis of experimental XAFS data from U 6+ solid and solution model compounds. Using the ab initio XAFS code FEFF6, we calculated phase-shift and amplitude functions for fitting experimental data. The code FEFF6 does a good job of reproducing experimental data and is particularly valuable for providing phase-shift and amplitude functions for neighboring atoms whose spectral contributions are difficult to isolate from experimental data because of overlap of Fourier transform features. In solid-phase model compounds at ambient temperature, we were able to fit spectral contributions from axial O (1.8 Angstrom), equatorial O (2.2-2.5 Angstrom), N (2.9 Angstrom), C (2.9 Angstrom), Si (3.2 Angstrom), P (3.6 Angstrom), distant 0 (4.3 Angstrom), and U (4.0, 4.3, 4.9, and 5.2 Angstrom) atoms. Contributions from N, C, Si, P, distant O, and distant U (4.9 and 5.2 Angstrom) are weak and therefore might go undetected in a sample of unknown composition. Lowering the temperature to 10 K extends detection of U neighbors to 7.0 Angstrom. The ability to detect these atoms suggests that XAFS might be capable of discerning inner-sphere U sorption at solid aluminosilicate-water interfaces. XAFS should definitely detect multinuclear U complexes and precipitates. Multiple-scattering paths are minor contributors to uranyl XAFS beyond k = 3 Angstrom -1 . Allowing shell-dependent disorder parameters (σ 2 ) to vary, we observed narrow ranges of σ 2 values for similar shells of neighboring atoms. Knowledge of these ranges is necessary to constrain the fit of XAFS spectra for unknowns. Finally, we found that structures reported in the literature for uranyl diacetate and rutherfordine are not completely correct. 50 refs., 6 figs., 2 tabs

  6. Physico-chemical study of new functionalized surfactants having thermo sensitive de-mixing behaviour: use in extraction of uranyl nitrate

    International Nuclear Information System (INIS)

    Prevost, S.

    2006-04-01

    New thermo-sensitive functionalized surfactants with metal-chelating properties have been developed and their physical-chemistry studied. They associate a polyethoxylated nonionic surfactant (CiEj) block and a amino-acid residue as a chelating group. Functionalization preserves both properties of the thermo-sensitive surfactant moiety and the chelating group, a diamide closed to uranyl ionophore.The complexing group participates to the polar head group of the surfactant, increasing the area per molecule. As a result, functionalized surfactants form spherical micelles when diluted in water, and the concentrated part of their phase diagrams exhibits structures having higher curvatures than the nonionic precursor CiEj. The structure of the uranyl - diamide complex has been elucidated by NMR and ESI-MS and is of the type UO 2 (NO 3 ) 2 .L; the associated complexation constant, which is very low, has been evaluated by 1 H NMR.A nitrate salt, LiNO 3 , is added at high concentration to improve complexation. The effect of this salt has been analyzed, and was found to be rather similar to the effect on classical CiEj. When uranyl nitrate complexation occurs, the cloud point decreases dramatically, together with the reduction of the area per head group at micelle/solution interface. This effect can be minimized by using a nonionic precursor having a larger polar head group. The functionalized surfactants have been tested in the cloud point extraction of uranyl nitrate, and have proved their efficiency. Those results demonstrate the viability of the functionalized surfactants design, with a covalent link between a thermo-sensitive surfactant block and a chelating group. (author)

  7. Ionic flotation of complexing oxyanions. Thermodynamics of uranyl complexation in a sulfuric medium. Definition of selectivity conditions of the process

    International Nuclear Information System (INIS)

    Bouzat, G.

    1987-01-01

    Oxyanion ionic flotation process with dodecylamine hydrochloride as collector is studied by investigation of flotation and filtration recovery curves, suspension turbidity, conductimetric measurements, and solubility of ionic species. The process is controlled by chemical reactions of precipitation and by adsorption of surfactant confering hydrophobic or hydrophilic surface properties to the solid phase respectively when one or two monolayers of surfactant are successively adsorbed. Equilibrium constants (in terms of activity) of the uranium (VI) complexation with sulphate oxyanions are calculated through Raman spectroscopic study of uranyl sulphate aqueous solutions. The complexation results in a shift of the symmetrical stretching vibration band of U0 2 to low wavenumbers and an increase of their cross section. The solubility curves of ionic species in the precipitation of uranyl -sulphate complexes by dodecylamine hydrochloride are modelled. The knowledge of solubility products, activity coefficients of the species and critical micellar concentration of the surfactant allow the modelling of flotation recovery curves. Temperature and collector structure modifications are studied in terms of optimization parameters and uranium extraction of mine drainage water is processed. Residual concentration of surfactant is considerably lowered by adsorption on montmorillonite

  8. Uranyl Photocleavage of Phosphopeptides Yields Truncated C-Terminally Amidated Peptide Products

    DEFF Research Database (Denmark)

    Elnegaard, Rasmus L B; Møllegaard, Niels Erik; Zhang, Qiang

    2017-01-01

    The uranyl ion (UO2(2+) ) binds phosphopeptides with high affinity, and when irradiated with UV-light, it can cleave the peptide backbone. In this study, high-accuracy tandem mass spectrometry and enzymatic assays were used to characterise the photocleavage products resulting from the uranyl phot...... challenges in green pharmaceutical chemistry....... photocleavage reaction of a tetraphosphorylated β-casein model peptide. We show that the primary photocleavage products of the uranyl-catalysed reaction are C-terminally amidated. This could be of great interest to the pharmaceutical industry, as efficient peptide amidation reactions are one of the top...

  9. Study of structural phase transformation and hysteresis behavior of inverse-spinel α-ferrite nanoparticles synthesized by co-precipitation method

    Science.gov (United States)

    Dabagh, Shadab; Chaudhary, Kashif; Haider, Zuhaib; Ali, Jalil

    2018-03-01

    Substitution of cobalt (Co2+) ions in cobalt ferrite (CoFe2O4) with copper (Cu2+) and aluminum (Al3+) ions allows variations in their electric and magnetic properties which can be optimized for specific applications. In this article, synthesis of inverse-spinel Co1-xCuxFe2-xAlxO4 (0.0 ≤ x ≤ 0.8) nanoparticles by substituting Cu2+ and Al3+ ions in CoFe2O4 via co-precipitation method is reported. By controlling copper and aluminum (Cu-Al) substituent ratio, the magnetic moment and coercivity of synthesized cobalt ferrite nanoparticles is optimized. The role of substituents on the structure, particle size, morphology, and magnetic properties of nano-crystalline ferrite is investigated. The Co1-xCuxFe2-xAlxO4 (0.0 ≤ x≤ 0.8) nanoparticles with crystallite size in the range of 23.1-26.5 nm are observed, 26.5 nm for x = 0.0-23.1 nm for x = 0.8. The inverse-spinel structure of synthesized Co1-xCuxFe2-xAlxO4 (0.0 ≤ x ≤ 0.8) nano-particles is confirmed by characteristic vibrational bands at tetrahedral and octahedral sites using Fourier transform infrared spectroscopy. A decreases in coercive field and magnetic moment is observed as Cu-Al contents are increased (x = 0.0-0.8). The positive anisotropy of synthesized particles Co1-xCuxFe2-xAlxO4 (0.0 ≤ x ≤ 0.8) is obtained in the range 1.96 × 105 J/m3 for x = 0.0 to 0.29 × 105 J/m3 for x = 0.8.

  10. Determination of total and extractable hydrogen peroxide in organic and aqueous solutions of uranyl nitrate

    International Nuclear Information System (INIS)

    Goodall, Ph.

    1999-01-01

    The development of a spectrophotometric method for the determination of hydrogen peroxide in uranyl nitrate solutions is reported. The method involves the measurement of the absorbance at 520 mm of a vanadyl peroxide species. This species was formed by the addition of a reagent consisting of vanadium (V) (50 mmol x dm -3 ) in dilute sulphuric acid (2 mol x dm -3 H 2 SO 4 ). This reagent, after dilution, was also used as an extractant for organic phase samples. The method is simple and robust and tolerant of nitric acid and U(VI). Specificity and accuracy were improved by the application of solid phase extraction techniques to remove entrained organic solvents and Pu(VI). Reverse phase solid phase extraction was used to clean-up aqueous samples or extracts which were contaminated with entrained solvent. A solid phase extraction system based upon an extraction chromatography system was used to remove Pu(IV). Detection limits of 26 μmol x dm -3 (0.88 μg x cm -3 ) or 7 μmol x dm -3 (0.24 μg x cm -3 ) for, respectively, a 1 and 4 cm path length cell were obtained. Precisions of RSD = 1.4% and 19.5% were obtained at the extremes of the calibration curve (5 mmol x dm -3 and 50 μmol x dm -3 H 2 O 2 , 1 cm cell). The introduction of the extraction and clean-up stages had a negligible effect upon the precision of the determination. The stability of an organic phase sample was tested and no loss of analyte could be discerned over a period of at least 5 days. (author)

  11. [H2bipy]2[(UO2)6Zn2(PO3OH)4(PO4)4].H2O: an open-framework uranyl zinc phosphate templated by diprotonated 4,4'-bipyridyl.

    Science.gov (United States)

    Yu, Yaqin; Zhan, Wei; Albrecht-Schmitt, Thomas E

    2008-10-06

    Under mild hydrothermal conditions, a new organically templated uranyl zinc phosphate, [H 2bipy] 2[(UO 2) 6Zn 2(PO 3OH) 4(PO 4) 4].H 2O ( UZnP-2), has been synthesized. Structural analysis reveals that UZnP-2 is constructed from UO 7 pentagonal bipyramids that are linked into edge-sharing dimers that are in turn joined together by ZnO 4 and PO 4 tetrahedra to form a three-dimensional network. Intersecting channels occur along the a, b, and c axes. These channels house the diprotonated 4,4'-bipyridyl cations and water molecules. Ion-exchange experiments demonstrate that replacement of the 4,4'-bipyridyl cations by alkali and alkaline-earth metal cations results in a rearrangement of the framework. Further characterization of UZnP-2 is provided by Raman and fluorescence spectroscopy. The latter method reveals strong emission from the uranyl moieties with characteristic fine structure.

  12. Study of structural phase transformation and hysteresis behavior of inverse-spinel α-ferrite nanoparticles synthesized by co-precipitation method

    Directory of Open Access Journals (Sweden)

    Shadab Dabagh

    2018-03-01

    Full Text Available Substitution of cobalt (Co2+ ions in cobalt ferrite (CoFe2O4 with copper (Cu2+ and aluminum (Al3+ ions allows variations in their electric and magnetic properties which can be optimized for specific applications. In this article, synthesis of inverse-spinel Co1−xCuxFe2−xAlxO4 (0.0 ≤ x ≤ 0.8 nanoparticles by substituting Cu2+ and Al3+ ions in CoFe2O4 via co-precipitation method is reported. By controlling copper and aluminum (Cu-Al substituent ratio, the magnetic moment and coercivity of synthesized cobalt ferrite nanoparticles is optimized. The role of substituents on the structure, particle size, morphology, and magnetic properties of nano-crystalline ferrite is investigated. The Co1−xCuxFe2−xAlxO4 (0.0 ≤ x≤ 0.8 nanoparticles with crystallite size in the range of 23.1–26.5 nm are observed, 26.5 nm for x = 0.0–23.1 nm for x = 0.8. The inverse-spinel structure of synthesized Co1−xCuxFe2−xAlxO4 (0.0 ≤ x ≤ 0.8 nano-particles is confirmed by characteristic vibrational bands at tetrahedral and octahedral sites using Fourier transform infrared spectroscopy. A decreases in coercive field and magnetic moment is observed as Cu-Al contents are increased (x = 0.0–0.8. The positive anisotropy of synthesized particles Co1−xCuxFe2−xAlxO4 (0.0 ≤ x ≤ 0.8 is obtained in the range 1.96 × 105 J/m3 for x = 0.0 to 0.29 × 105 J/m3 for x = 0.8. Keywords: Co-precipitation method, XRD, Spinel ferrites, VSM, TEM

  13. Charge-density matching in organic-inorganic uranyl compounds

    International Nuclear Information System (INIS)

    Krivovichev, S.V.; Krivovichev, S.V.; Tananaev, I.G.; Myasoedov, B.F.

    2007-01-01

    Single crystals of [C 10 H 26 N 2 ][(UO 2 )(SeO 4 ) 2 (H 2 O)](H 2 SeO 4 ) 0.85 (H 2 O) 2 (1), [C 10 H 26 N 2 ][(UO 2 )(SeO 4 ) 2 ] (H 2 SeO 4 ) 0.50 (H 2 O) (2), and [C 8 H 20 N] 2 [(UO 2 )(SeO 4 ) 2 (H 2 O)] (H 2 O) (3) were prepared by evaporation from aqueous solution of uranyl nitrate, selenic acid and the respective amines. The structures of the compounds have been solved by direct methods and structural models have been obtained. The structures of the compounds 1, 2, and 3 contain U and Se atoms in pentagonal bipyramidal and tetrahedral coordinations, respectively. The UO 7 and SeO 4 polyhedra polymerize by sharing common O atoms to form chains (compound 1) or sheets (compounds 2 and 3). In the structure of 1, the layers consisting of hydrogen-bonded [UO 2 (SeO 4 ) 2 (H 2 O)] 2- chains are separated by mixed organic-inorganic layers comprising from [NH 3 (CH 2 ) 10 NH 3 ] 2+ molecules, H 2 O molecules, and disordered electroneutral (H 2 SeO 4 ) groups. The structure of 2 has a similar architecture but a purely inorganic layer is represented by a fully connected [UO 2 (SeO 4 ) 2 ] 2- sheet. The structure of 3 does not contain disordered (H 2 SeO 4 ) groups but is based upon alternating [UO 2 (SeO 4 ) 2 (H 2 O)] 2- sheets and 1.5-nm-thick organic blocks consisting of positively charged protonated octylamine molecules, [NH 3 (CH 2 ) 7 CH 3 ] + . The structures may be considered as composed of anionic inorganic sheets (2D blocks) and cationic organic blocks self-organized according to competing hydrophilic-hydrophobic interactions. Analysis of the structures allows us to conclude that the charge-density matching principle is observed in uranyl compounds. In order to satisfy some basic peculiarities of uranyl (in general, actinyl) chemistry, it requires specific additional mechanisms: (a) in long-chain-amine-templated compounds, protonated amine molecules inter-digitate; (b) in long-chain-diamine-templated compounds, incorporation of acid-water interlayers into

  14. The uranyl influence on a mutation process in germ and somatic cells of mice

    International Nuclear Information System (INIS)

    Kostrova, L.N.; Mosseh, I.B.; Molofej, V.P.

    2008-01-01

    The mutagenic effect of uranyl was revealed by the chromosome rearrangement test in germ and somatic cells of mice. The effect value depended on duration of substance administration into organism. (authors)

  15. Sorption rate of uranyl ions by hyphan cellulose exchangers and by hydrated titanium dioxide

    International Nuclear Information System (INIS)

    Ambe, F.; Burba, P.; Lieser, K.H.

    1979-01-01

    Sorption of uranyl ions by the cellulose exchanger Hyphan proceeds rather fast. Two steps are observed with half-times of the order of 10 s and 2 min. The majority of the uranyl ions is bound in 1 min. Sorption of uranyl ions by titanium dioxide is a very slow process. For particle sizes between 0,1 and 0,5 mm the half-time is about 3 h and equilibrium is attained in about 1 day. The effect of stirring suspensions of inorganic sorbents like titanium dioxide in solution is investigated in detail. Sorption of uranyl ions by titanium dioxide and change in pH in solution are measured simultaneously as a function of time. (orig.) [de

  16. Critical experiments on STACY homogeneous core containing 10% enriched uranyl nitrate solution

    International Nuclear Information System (INIS)

    Miyoshi, Yoshinori; Yamamoto, Toshihiro; Tonoike, Kotaro; Yamane, Yuichi; Watanabe, Shouichi

    2003-01-01

    In order to investigate criticality properties of low enriched uranyl nitrate solution treated in the reprocessing facility for LWR fuel cycle, systematic and high precision critical experiments have been performed at the Static Experiment Critical Facility, STACY since 1995. Criticality benchmark data on 10% enriched uranyl nitrate solution for single core and multiple core systems have been accumulated using cylindrical and slab type core tanks. This paper overviews mains data and related criticality calculation results using standard criticality safety calculation code system. (author)

  17. Stability and visible absorption of glutamic acid complexes with uranyl and neodymium ions

    International Nuclear Information System (INIS)

    Petit-Ramel, M.M.; Mosoni, L.

    1982-01-01

    The stability constants of the complexes of uranyl and neodymium ions with glutanic acid are determined pH-metrically in 0.1 M NaClO 4 solution at 25 0 C. In both cases protonated complexes are formed in significant concentrations. A new MA complex is found in the uranyl glutamic acid system. In accordance with this investigation a graphical treatment of the visible spectral data gives the molar absorption coefficients of both MA and MHA species. (orig.) [de

  18. Ligand exchange in uranyl complexes in non-aqueous solutions: equilibrium properties

    International Nuclear Information System (INIS)

    Egozy, Y.; Weiss, S.

    1976-01-01

    The systems uranyl nitrate, tributylphosphate and 8-hydroxyquinoline or diphenylcarbazone were studied in chloroform, carbon tetrachloride and 1,2-dichloroethane at a number of temperatures. The nature of the complexes formed was determined and the equilibrium constants and several thermodynamic functions were measured. 8-hydroxyquinoline and diphenylcarbazone will be valuable as indicators for uranyl in kinetic studies. They are also interesting since they participate, along with tributylphosphate, in formation of synergistic complexes. (author)

  19. Giant regular polyhedra from calixarene carboxylates and uranyl

    Science.gov (United States)

    Pasquale, Sara; Sattin, Sara; Escudero-Adán, Eduardo C.; Martínez-Belmonte, Marta; de Mendoza, Javier

    2012-01-01

    Self-assembly of large multi-component systems is a common strategy for the bottom-up construction of discrete, well-defined, nanoscopic-sized cages. Icosahedral or pseudospherical viral capsids, built up from hundreds of identical proteins, constitute typical examples of the complexity attained by biological self-assembly. Chemical versions of the so-called 5 Platonic regular or 13 Archimedean semi-regular polyhedra are usually assembled combining molecular platforms with metals with commensurate coordination spheres. Here we report novel, self-assembled cages, using the conical-shaped carboxylic acid derivatives of calix[4]arene and calix[5]arene as ligands, and the uranyl cation UO22+ as a metallic counterpart, which coordinates with three carboxylates at the equatorial plane, giving rise to hexagonal bipyramidal architectures. As a result, octahedral and icosahedral anionic metallocages of nanoscopic dimensions are formed with an unusually small number of components. PMID:22510690

  20. Pilot scale for preparation of ammonium uranyl carbonate

    International Nuclear Information System (INIS)

    Santos, L.R. dos.

    1989-01-01

    The procedure adopted for obtaining Ammonium Uranyl Carbonate (AUC) from uranium hexafluoride (UF sub(6)) or aqueous solutions of uranylnitrate (UO sub(2)(NO sub(3)) sub(2)) is described in the present work. This procedure involves the precipitation of AUC in a chemical reactor by the addition of gaseous UF sub(6) or solutions of uranylnitrate to NH sub(3) and CO sub(2) gases in a solution containing ammonium bicarbonate, where pH and temperature are controlled. Details regarding the characterization and quality control methods in the preparation of AUC are presented along with their physical and chemical properties. Some informations about effluents generated during the process are presented too. An attempt is made to correlate the parameters involved in the precipitation process of AUC and their characteristics. (author)

  1. Observation of phase noise reduction in photonically synthesized sub-THz signals using a passively mode-locked laser diode and highly selective optical filtering

    DEFF Research Database (Denmark)

    Criado, A. R.; Acedo, P.; Carpintero, G.

    2012-01-01

    A Continuous Wave (CW) sub-THz photonic synthesis setup based on a single Passively Mode-Locked Laser Diode (PMLLD) acting as a monolithic Optical Frequency Comb Generator (OFCG) and highly selective optical filtering has been implemented to evaluate the phase noise performance of the generated sub...

  2. Functional polyterthiophene-appended uranyl-salophen complex: Electropolymerization and ion-selective response for monohydrogen phosphate

    International Nuclear Information System (INIS)

    Kim, Junghwan; Kang, Dong Min; Shin, Sung Chul; Choi, Myong Yong; Kim, Jineun; Lee, Shim Sung; Kim, Jae Sang

    2008-01-01

    We have synthesized a bis(terthiophene)-appended uranyl-salophen complex, comprising N,N'-bis[4-(5,2':5',2''-terthiophen-3'-yl)salicylidene] -1,2-ethanediamine-uranyl complexes (TUS), and used it as a monomer for the electrochemical polymerizations (poly-TUS) on glassy carbon surfaces to prepare functionalized conducting polymer (CP) films. The poly-TUS films prepared from propylene carbonate/0.1 M tetrabutyl ammonium perchlorate (TBAP) on a glassy carbon electrode have both the functionality of ion-to-electron transducers (solid contact) and Lewis-acidic binding sites for a monohydrogen phosphate (MHP) ion-selective electrode (ISE). The CP/poly-TUS sensor showed a linear range between 1.0 x 10 -1 and 1.0 x 10 -4.5 M with a near-Nernstian behavior (-30.4 mV decade -1 ) at a pH of 8.2. The detection limit of the electrode was 10 -5.0 M and the response time was improved (<10 s) compared to that of conventional ISEs (<20 s). For comparison, a conventional ISE (with an internal aqueous solution) based on a TUS monomer/o-nitrophenyl octylether (o-NPOE)/polyvinyl chloride (PVC) liquid membrane with or without tridodecylmethylammonium chloride (TDMACl) as an additive was also constructed and its performance as an MHP-ISE were studied. The superior selectivity and sensitivity of the CP/poly-TUS sensor enabled the direct measurement of MHP in a wide variety of applications

  3. Theoretical insights into the uranyl adsorption behavior on vanadium carbide MXene

    Science.gov (United States)

    Zhang, Yu-Juan; Zhou, Zhang-Jian; Lan, Jian-Hui; Ge, Chang-Chun; Chai, Zhi-Fang; Zhang, Peihong; Shi, Wei-Qun

    2017-12-01

    Remediation of the contamination by long-lived actinide wastes is extremely important but also challenging. Adsorption based techniques have attracted much research attention for their potential as low-cost and effective methods to reduce the radioactive waste from solution. In this work, we have investigated the adsorption behavior of uranyl species [with the general form UO2(L1)x(L2)y(L3)z, where L1, L2 and L3 stand for ligands H2O, OH and CO3, respectively] on hydroxylated vanadium carbide V2C(OH)2 MXene nanosheets using density functional theory based simulation methods We find that all studied uranyl species can stably bond to hydroxylated MXene with binding energies ranging from -3.3 to -4.6 eV, suggesting that MXenes could be effective adsorbers for uranyl ions. The strong adsorption is achieved by forming two Usbnd O bonds with the hydroxylated Mxene. In addition, the axial oxygen atoms from the uranyl ions form hydrogen bonds with the hydroxylated V2C, further strengthening the adsorption. We have also investigated the effects of F termination on the uranyl adsorption properties of V2C nanosheets. Usbnd F bonds are in general weaker than Usbnd O bonds on the adsorption site, suggesting that F terminated Mexne is less favorable for uranyl adsorption applications.

  4. Adsorption of uranyl species on hydroxylated titanium carbide nanosheet: A first-principles study

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Yu-Juan [School of Materials Science and Engineering, University of Science and Technology Beijing, 100083 Beijing (China); Laboratory of Nuclear Energy Chemistry and Key Laboratory for Biomedical Effects of Nanomaterials and Nanosafety, Institute of High Energy Physics, Chinese Academy of Sciences, 100049 Beijing (China); Lan, Jian-Hui; Wang, Lin; Wu, Qun-Yan; Wang, Cong-Zhi; Bo, Tao [Laboratory of Nuclear Energy Chemistry and Key Laboratory for Biomedical Effects of Nanomaterials and Nanosafety, Institute of High Energy Physics, Chinese Academy of Sciences, 100049 Beijing (China); Chai, Zhi-Fang [Laboratory of Nuclear Energy Chemistry and Key Laboratory for Biomedical Effects of Nanomaterials and Nanosafety, Institute of High Energy Physics, Chinese Academy of Sciences, 100049 Beijing (China); School of Radiological & Interdisciplinary Sciences and Collaborative Innovation Center of Radiation Medicine of Jiangsu Higher Education Institutions, Soochow University, 215123 Suzhou (China); Shi, Wei-Qun, E-mail: shiwq@ihep.ac.cn [Laboratory of Nuclear Energy Chemistry and Key Laboratory for Biomedical Effects of Nanomaterials and Nanosafety, Institute of High Energy Physics, Chinese Academy of Sciences, 100049 Beijing (China)

    2016-05-05

    Highlights: • Ti{sub 3}C{sub 2}(OH){sub 2} is firstly predicted to be an effective adsorbent for uranyl ions. • The bidentate coordination is energetically more favorable. • The uranyl ion prefers to bind with the deprotonated O adsorption site. • Chemical interaction and hydrogen bonds contribute to the adsorption mechanism. • The theoretical adsorption capacity can approach 595.3 mg/g. - Abstract: In this work, hydroxylated titanium carbide Ti{sub 3}C{sub 2}(OH){sub 2}, a representative of the two-dimensional transition metal carbides, has been predicted to be an effective adsorbent for uranyl ions in aqueous environments for the first time using density functional theory simulations. The calculations revealed that the uranyl ion can strongly bind with Ti{sub 3}C{sub 2}(OH){sub 2} nanosheet in aqueous solution regardless of the presence of anionic ligands such as OH{sup −}, Cl{sup −} and NO{sub 3}{sup −}. The bidentate coordination of uranyl to the surface is energetically more favorable than other adsorption configurations, and the uranyl ion prefers to bind with the deprotonated O adsorption site rather than the protonated one on the hydroxylated surface. During the adsorption process, the chemical adsorption as well as the formation of hydrogen bonds is the dominant factor.

  5. Raman spectral titration method: an informative technique for studying the complexation of uranyl with uranyl(vi)-DPA/oxalate systems as examples.

    Science.gov (United States)

    Liu, Qian; Zhang, Qianci; Yang, Suliang; Zhu, Haiqiao; Liu, Quanwei; Tian, Guoxin

    2017-10-10

    The Raman band at about 870 cm -1 originating from the symmetric stretch vibration (ν 1 ) of uranyl, UO 2 2+ , has proven to be very informative for investigating the complexation of uranyl using perchlorate or nitrate of known concentration as internal standards. The concentration of uranyl can be conveniently calculated by using the ratio of the directly read band intensities of uranyl and the added reference, ClO 4 - , with a factor of 1.72. While with NO 3 - of concentration lower than 1.8 M as the reference, a factor of 0.85 should be used. Furthermore, with added internal standards, the linear relationship between the Raman intensity and the concentration of the corresponding species is illustrated by the spectral titration of U(vi) with a very strong ligand, dipicolinic acid (DPA); and the application of a spectral titration method with Raman spectroscopy in studying the complexation of uranyl is demonstrated by the titration of U(vi) with oxalate. The stepwise changes in the Raman shift of 18, 17, and 6 cm -1 , corresponding to the three oxalate anions successively bonding to UO 2 2+ , imply that the coordination modes are different. In the 1 : 1 and 1 : 2 ratios of metal to ligand complexes, the oxalate anions bond to the uranyl ion in side-on bidentate mode, but in the 1 : 3 complex the third oxalate bonds in head-on mode, which is much weaker than the first two.

  6. Thermolysis synthesis of pure phase NiO from novel sonochemical synthesized Ni(II) nano metal-organic supramolecular architecture.

    Science.gov (United States)

    Hanifehpour, Younes; Morsali, Ali; Mirtamizdoust, Babak; Joo, Sang Woo; Soltani, Behzad

    2017-07-01

    Nano-structures of a new supramolecular coordination compound of divalent nickel with the pyrazol (pzH) containing the terminal azide anions, [Ni(pzH) 2 (N 3 ) 2 ] (1), with discrete molecular architecture (DMA) in solid state was synthesized via sonochemical method. The new nanostructure was characterized by scanning electron microscopy, X-ray powder diffraction, IR, and elemental analysis. Compound 1 was structurally characterized by single crystal X-ray diffraction and the single-crystal X-ray data shows that the coordination number of Ni (II) ions is six, (NiN 6 ), with four N-donor atoms from neutral "pzH" ligands and two N-donors from two terminal azide anions. The supramolecular features in these complexes are guided and controlled by weak directional intermolecular interactions. The structure of the title complex was optimized by density functional theory calculations. Calculated structural parameters and IR spectra for the title complex are consistent with the crystal structure. The NiO nanoparticles were obtained by thermolysis of 1 at 180°C with oleic acid as a surfactant. Copyright © 2017 Elsevier B.V. All rights reserved.

  7. Structural and Phase Changes in the System Al-Si-Ti-B, Synthesized Using the Electron-Ion-Plasma Treatment Method

    Science.gov (United States)

    Klopotov, A. A.; Petrikova, E. A.; Ivanov, Yu F.; Teresov, A. D.; Cherenda, N. N.; Uglov, V. V.; Tsvetkov, N. A.

    2017-04-01

    The results of surface modification of silumin samples of the eutectic composition using the combined method, which includes the irradiation with plasma formed during an electric explosion of the conductive material and the subsequent processing with a high-intensity pulsed electron beam, are presented. Formation of a multilayer multiphase submicron and nanoscale structure with high mechanical and tribological properties is established. The results of the structural phase analysis of the material are discussed from the standpoint of thermodynamics.

  8. Influence of uranyl speciation and iron oxides on uranium biogeochemical redox reactions

    Energy Technology Data Exchange (ETDEWEB)

    Stewart, B.D.; Amos, R.T.; Nico, P.S.; Fendorf, S.

    2010-03-15

    Uranium is a pollutant of concern to both human and ecosystem health. Uranium's redox state often dictates its partitioning between the aqueous- and solid-phases, and thus controls its dissolved concentration and, coupled with groundwater flow, its migration within the environment. In anaerobic environments, the more oxidized and mobile form of uranium (UO{sub 2}{sup 2+} and associated species) may be reduced, directly or indirectly, by microorganisms to U(IV) with subsequent precipitation of UO{sub 2}. However, various factors within soils and sediments may limit biological reduction of U(VI), inclusive of alterations in U(VI) speciation and competitive electron acceptors. Here we elucidate the impact of U(VI) speciation on the extent and rate of reduction with specific emphasis on speciation changes induced by dissolved Ca, and we examine the impact of Fe(III) (hydr)oxides (ferrihydrite, goethite and hematite) varying in free energies of formation on U reduction. The amount of uranium removed from solution during 100 h of incubation with S. putrefaciens was 77% with no Ca or ferrihydrite present but only 24% (with ferrihydrite) and 14% (no ferrihydrite) were removed for systems with 0.8 mM Ca. Imparting an important criterion on uranium reduction, goethite and hematite decrease the dissolved concentration of calcium through adsorption and thus tend to diminish the effect of calcium on uranium reduction. Dissimilatory reduction of Fe(III) and U(VI) can proceed through different enzyme pathways, even within a single organism, thus providing a potential second means by which Fe(III) bearing minerals may impact U(VI) reduction. We quantify rate coefficients for simultaneous dissimilatory reduction of Fe(III) and U(VI) in systems varying in Ca concentration (0 to 0.8 mM), and using a mathematical construct implemented with the reactive transport code MIN3P, we reveal the predominant influence of uranyl speciation, specifically the formation of uranyl

  9. Catalytic method for synthesizing hydrocarbons

    Science.gov (United States)

    Sapienza, R.S.; Sansone, M.J.; Slegeir, W.A.R.

    A method for synthesizing hydrocarbons from carbon monoxide and hydrogen by contacting said gases with a slurry of a catalyst composed of palladium or platinum and cobalt supported on a solid phase is disclosed. The catalyst is prepared by heating a heterogeneous component of the palladium or platinum deposited on the solid support in a solution of cobalt carbonyl or precursors thereof. The catalyst exhibits excellent activity, stability in air, and produces highly desirable product fractions even with dilute gaseous reactants.

  10. Nephrotoxicity of uranyl fluoride and reversibility of reval injury in the rat

    International Nuclear Information System (INIS)

    Diamond, G.L.; Gelein, R.M.; Morrow, P.E.; Panner, B.J.; Baggs, R.B.

    1987-09-01

    This study examined the severity and duration of renal injury produced in the rat from exposure to low levels of uranyl fluoride (UO 2 F 2 ). Rats received multiple i.p. injections of UO 2 F 2 (cumulative dose: 0.66 or 1.32 mg U/kg body wt). Renal injury was characterized primarily by cellular and tubular necroses of the pars recta of the proximal tubule (S 2 and S 3 ), with less severe cellular injury to the thick ascending limb of the loop of Henle and collecting tubule. The injury was apparent early in the dosing phase of the study, at a time when renal uranium levels were between 0.7 to 1.4 μg U/g, and was most severe when the renal uranium burden was between 3.4 to 5.6 μg U/g. Repair of the injury was rapid, with complete restoration within 35 days after the exposure. Associated with the injury were numerous abnormalities in kidney function, including impaired tubular reabsorption, proteinuria and enzymuria, which appeared to be temporally related, to variable degrees, to the progression of renal injury. Thus, reversible renal injury occurred in the rat at levels of uranium in kidney below the proposed threshold standard for renal injury in humans of 3 μg U/g kidney. However, renal injury preceded and outlasted functional abnormalities as assessed by urinalysis and clearance measurements. 28 refs., 35 figs., 7 tabs

  11. Sorption of strontium on uranyl peroxide: implications for a high-level nuclear waste repository.

    Science.gov (United States)

    Sureda, Rosa; Martínez-Lladó, Xavier; Rovira, Miquel; de Pablo, Joan; Casas, Ignasi; Giménez, Javier

    2010-09-15

    Strontium-90 is considered the most important radioactive isotope in the environment and one of the most frequently occurring radionuclides in groundwaters at nuclear facilities. The uranyl peroxide studtite (UO2O2 . 4H2O) has been observed to be formed in spent nuclear fuel leaching experiments and seems to have a relatively high sorption capacity for some radionuclides. In this work, the sorption of strontium onto studtite is studied as a function of time, strontium concentration in solution and pH. The main results obtained are (a) sorption is relatively fast although slower than for cesium; (b) strontium seems to be sorbed via a monolayer coverage of the studtite surface, (c) sorption has a strong dependence on ionic strength, is negligible at acidic pH, and increases at neutral to alkaline pH (almost 100% of the strontium in solution is sorbed above pH 10). These results point to uranium secondary solid phase formation on the spent nuclear fuel as an important mechanism for strontium retention in a high-level nuclear waste repository (HLNW). Copyright 2010 Elsevier B.V. All rights reserved.

  12. The transformation of uranyl oxide hydrates: The effect of dehydration on synthetic metaschoepite and its alteration to becquerelite

    International Nuclear Information System (INIS)

    Sowder, A.G.; Clark, S.B.; Fjeld, R.A.

    1999-01-01

    The U(VI) solid phases schoepite, metaschoepite, and dehydrated schoepite are important reservoirs of mobile uranium in the environment. These simple uranyl oxide hydrates result from weathering of uranium minerals and the corrosion of anthropogenic uranium solids. The authors have studied the role of hydrational water among these phases and in subsequent transformation to other secondary metal-U(VI) oxide hydrates. Synthetic metaschoepite (MS, UO 3 ·2.0H 2 O), its dehydrated phases, and its secondary alteration products were characterized using X-ray powder diffraction (XRD), scanning electron microscopy (SEM), X-ray energy dispersive spectroscopy (EDS), and high-resolution thermogravimetric analysis (HRTGA). Drying MS at 105 C resulted in the formation of a dehydrated phase (UO 3 ·0.9H 2 O) that was structurally distinct from natural dehydrated schoepite (DS, UO 3 ·0.75H 2 O) reported by others. Unlike natural DS, their dehydrated material was easily rehydrated, although crystallinity of the rehydrated phase was reduced. The rates of transformation of synthetic MS and dehydrated MS in the presence of Ca 2+ to form becquerelite (Ca[(UO 2 ) 6 O 4 (OH) 6 ]·8H 2 O) were determined. Alteration rates were significantly faster when the starting material had been dehydrated. These results are explained in the context of structural aspects of U(VI) solid phases, and the possible impact of hydration on long-term stability of U(VI) oxide hydrates in environmental systems is discussed

  13. Optical and Dielectric Properties of CuAl2O4 Films Synthesized by Solid-Phase Epitaxy

    Energy Technology Data Exchange (ETDEWEB)

    Leu, L. C. [University of Florida, Gainesville; Norton, David P. [University of Florida; Jellison Jr, Gerald Earle [ORNL; Selvamanickam, V. [SuperPower Incorporated, Schenectady, New York; Xiong, X. [SuperPower Incorporated, Schenectady, New York

    2007-01-01

    The synthesis and properties of CuAl{sub 2}O{sub 4} thin films have been examined. The CuAl{sub 2}O{sub 4} films were deposited via reactive direct current magnetron sputter using a CuAl{sub 2} target. As-deposited films were amorphous. Post-deposition annealing at high temperature in oxygen yielded solid-phase epitaxy on MgO. The film orientation was cube-on-cube epitaxy on (001) MgO single-crystal substrates. The films were transparent to visible light. The band gap of crystalline CuAl{sub 2}O{sub 4} was determined to be {approx} 4 eV using a Tauc plot from the optical transmission spectrum. The dielectric constant of the amorphous films was determined to be {approx} 20-23 at 1-100 kHz.

  14. Cryptomelane-type manganese oxide (KMn8O16) nanorods cathode materials synthesized by a rheological phase for lithium ion batteries

    Science.gov (United States)

    Zheng, Hao; Wang, Ting; Zhao, Rongfei; Chen, Jinsong; Li, Lin

    2018-01-01

    Cryotolerance-type manganese oxide (KMn8O16) nanorods were prepared for the first time by a rheological phase reaction method. The KMn8O16 samples were characterized by X-ray diffraction, scanning electron microscopy, the effects of different annealed temperatures on the morphologies and electrochemical properties of the final products were systematically investigated. The result that the annealed samples exhibit the superior electrochemical performances compared to the unannealed sample. The KMn8O16 nanorods annealed at 400 °C show the highest reversible discharge capacity (147.9 mAh/g even after 80 cycles) at current density of 50 mA/g and the best cycling stability. These results indicate that the KMn8O16 nanorods could be a promising cathode material for lithium ion batteries.

  15. 1H chemically induced dynamic nuclear polarization in the photodecomposition of uranyl carboxylates

    International Nuclear Information System (INIS)

    Rykov, S.V.; Khudyakov, I.V.; Skakovsky, E.D.; Burrows, H.D.; Formosinho, S.J.; Miguel, M. da G.M.

    1991-01-01

    Chemically induced dynamic nuclear polarization ( 1 H CIDNP) has been observed during photolysis of uranyl salts of pivalic, propionic, and acetic acids in D 2 O solution, [ 2 H 6 ]acetone, [ 2 H 4 ]methanol, or in some other solvent. The multiplet polarization of isobutene and isobutane protons has been found under photolysis of deoxygenated pivalate solution. The polarized compounds are formed in the triplet pairs of tert-butyl free radicals. 1 H Emission of the tert-butylperoxyl group and emission of 1 H from isobutene have been recorded under photolysis of air-saturated pivalate solutions. The CIDNP of butane protons stays as a multiplet. Such changes in the presence of air/oxygen have arisen apparently because of the formation of tert-butylperoxyl free radical and its reaction with tert-butyl radical products, i.e. hydroperoxide (peroxide) and isobutene. Isobutene probably forms a complex with molecular oxygen which has a very short proton relaxation time. During the photolysis of uranyl pivalate in the presence of p-benzoquinone (5 x 10 -2 -0.1 mol dm -3 ) we have not observed any CIDNP, whereas under p-benzoquinone concentrations of 10 -3 -10 -2 mol dm -3 the CIDNP from both hydroquinone and p-benzoquinone has been followed. Photolysis of uranyl propionate has led to CIDNP from butane protons. An emission from methyl group protons of a compound with an ethylperoxyl fragment in the presence of air/oxygen has been observed. The same polarization picture has arisen under interaction of photoexcited uranyl with propionic acid. During the photolysis of uranyl acetate at relatively low concentrations (10 -2 mol dm -3 ) a CIDNP very similar to that registered for uranyl propionate was recorded. The ethyl fragment is probably obtained in reactions for two methyl radicals formed from acetate with the parent uranyl acetate, namely hydrogen-atom abstraction and addition reactions. (author)

  16. Charge-density matching in organic-inorganic uranyl compounds

    Energy Technology Data Exchange (ETDEWEB)

    Krivovichev, S.V. [Saint Petersburg State Univ., Dept. of Crystallography, Faculty of Geology (Russian Federation); Krivovichev, S.V.; Tananaev, I.G.; Myasoedov, B.F. [Russian Academy of Sciences, A.N. Frumkin Institute of Physical Chemistry and Electrochemistry, Moscow (Russian Federation)

    2007-10-15

    Single crystals of [C{sub 10}H{sub 26}N{sub 2}][(UO{sub 2})(SeO{sub 4}){sub 2}(H{sub 2}O)](H{sub 2}SeO{sub 4}){sub 0.85}(H{sub 2}O){sub 2} (1), [C{sub 10}H{sub 26}N{sub 2}][(UO{sub 2})(SeO{sub 4}){sub 2}] (H{sub 2}SeO{sub 4}){sub 0.50}(H{sub 2}O) (2), and [C{sub 8}H{sub 20}N]{sub 2}[(UO{sub 2})(SeO{sub 4}){sub 2}(H{sub 2}O)] (H{sub 2}O) (3) were prepared by evaporation from aqueous solution of uranyl nitrate, selenic acid and the respective amines. The structures of the compounds have been solved by direct methods and structural models have been obtained. The structures of the compounds 1, 2, and 3 contain U and Se atoms in pentagonal bipyramidal and tetrahedral coordinations, respectively. The UO{sub 7} and SeO{sub 4} polyhedra polymerize by sharing common O atoms to form chains (compound 1) or sheets (compounds 2 and 3). In the structure of 1, the layers consisting of hydrogen-bonded [UO{sub 2}(SeO{sub 4}){sub 2}(H{sub 2}O)]{sup 2-} chains are separated by mixed organic-inorganic layers comprising from [NH{sub 3}(CH{sub 2}){sub 10}NH{sub 3}]{sup 2+} molecules, H{sub 2}O molecules, and disordered electroneutral (H{sub 2}SeO{sub 4}) groups. The structure of 2 has a similar architecture but a purely inorganic layer is represented by a fully connected [UO{sub 2}(SeO{sub 4}){sub 2}]{sup 2-} sheet. The structure of 3 does not contain disordered (H{sub 2}SeO{sub 4}) groups but is based upon alternating [UO{sub 2}(SeO{sub 4}){sub 2}(H{sub 2}O)]{sup 2-} sheets and 1.5-nm-thick organic blocks consisting of positively charged protonated octylamine molecules, [NH{sub 3}(CH{sub 2}){sub 7}CH{sub 3}]{sup +}. The structures may be considered as composed of anionic inorganic sheets (2D blocks) and cationic organic blocks self-organized according to competing hydrophilic-hydrophobic interactions. Analysis of the structures allows us to conclude that the charge-density matching principle is observed in uranyl compounds. In order to satisfy some basic peculiarities of uranyl (in

  17. Crystal structure of the uranyl-oxide mineral rameauite

    Energy Technology Data Exchange (ETDEWEB)

    Plasil, Jakub [ASCR, Prague (Czech Republic). Inst. of Physics; Skoda, Radek [Masaryk Univ., Brno (Czech Republic). Dept. of Geological Sciences; Cejka, Jiri [National Museum, Prague (Czech Republic). Dept. of Mineralogy and Petrology; Bourgoin, Vincent; Boulliard, Jean-Claude [Pierre et Marie Curie Univ., Paris (France). Association Jean Wyart, Collection des Mineraux de Jussieu

    2016-12-15

    Rameauite is a rare supergene uranyl-oxide hydroxy-hydrate mineral that forms during hydration-oxidation weathering of uraninite. On the basis of single-crystal X-ray diffraction data collected on a microfocus source, rameauite is monoclinic, space group Cc, with a = 13.9458(19), b = 14.3105(19), c = 13.8959(18) Aa, β = 118.477(14) , V = 2437.7(6) Aa{sup 3} and Z = 4, with D{sub calc} = 5.467 g cm{sup -3}. The structure of rameauite (R = 0.060 for 1698 unique observed reflections) contains sheets of the β-U{sub 3}O{sub 8} topology, with both UO{sub 6} and UO{sub 7} bipyramids, which is similar to the sheets found in spriggite, ianthinite and wyartite. The sheets alternate with the interlayer, which contains K{sup +}, Ca{sup 2+} and H{sub 2}O molecules. Interstitial cations are linked into infinite chains that extend along [10-1]. Adjacent sheets are linked through K-O, Ca-O and H-bonds. The structural formula of rameauite is K{sub 2} Ca(H{sub 2}{sup [3]}O){sub 1}(H{sub 2}{sup [5]}O){sub 4}[(UO{sub 2}) {sub 6}O{sub 6}(OH){sub 4}](H{sub 2}{sup [4]}O){sub 1}. The empirical formula obtained from the average of eight electron-microprobe analyses is (on the basi s of 6 U p.f.u.) K{sub 1.87}(Ca{sub 1.10}Sr{sub 0.04}){sub Σ1.14}[(UO 2){sub 6}O{sub 6}(OH){sub 4.15}].6H{sub 2}O. The Raman spectrum is dominate d by U.O and O.H vibrations. A discussion of related uranyl-oxide minerals is given.

  18. Controlled phase evolution and the occurrence of single domain CoFe2O4 nanoparticles synthesized by PVA assisted sol-gel method

    Science.gov (United States)

    Srinivasa Rao, K.; Ranga Nayakulu, S. V.; Chaitanya Varma, M.; Choudary, G. S. V. R. K.; Rao, K. H.

    2018-04-01

    The present investigation describes the development of cobalt ferrite nanoparticles having size less than 10 nm, by a sol-gel method using polyvinyl alcohol as chelating agent. X-ray results show all the samples, annealed above 700 °C have spinel structure. The information about phase evolution with reaction temperatures was obtained by subjecting the as-prepared powder for DSC/TGA study. High saturation magnetization of 84.63 emu/g has been observed for a particle size of 8.1 nm, a rare event reported till date. The dM/dH versus H curves suggest that the transition from single domain state to multi-domain state occurs with increasing annealing temperature and the critical size for the single domain nature of CoFe2O4 is around 6.5 nm. The estimated critical diameter for single domain particle (6.7 nm) is in good agreement with that (6.5 nm) obtained from Transmission Electron Micrographs. The highest coercivity (1645 Oe) has been found for a particle of size 6.5 nm.

  19. Microemulsion and Sol-Gel Synthesized ZrO₂-MgO Catalysts for the Liquid-Phase Dehydration of Xylose to Furfural.

    Science.gov (United States)

    Parejas, Almudena; Montes, Vicente; Hidalgo-Carrillo, Jesús; Sánchez-López, Elena; Marinas, Alberto; Urbano, Francisco J

    2017-12-18

    Two series of catalysts were prepared by sol-gel and microemulsion synthetic procedure (SG and ME, respectively). Each series includes both pure Mg and Zr solids as well as Mg-Zr mixed solids with 25%, 50% and 75% nominal Zr content. The whole set of catalysts was characterized from thermal, structural and surface chemical points of view and subsequently applied to the liquid-phase xylose dehydration to furfural. Reactions were carried out in either a high-pressure autoclave or in an atmospheric pressure multi-reactor under a biphasic (organic/water) reaction mixture. Butan-2-ol and toluene were essayed as organic solvents. Catalysts prepared by microemulsion retained part of the surfactant used in the synthetic procedure, mainly associated with the Zr part of the solid. The MgZr-SG solid presented the highest surface acidity while the Mg3Zr-SG one exhibited the highest surface basicity among mixed systems. Xylose dehydration in the high-pressure system and with toluene/water solvent mixture led to the highest furfural yield. Moreover, the yield of furfural increases with the Zr content of the catalyst. Therefore, the catalysts constituted of pure ZrO₂ (especially Zr-SG) are the most suitable to carry out the process under study although MgZr mixed solids could be also suitable for overall processes with additional reaction steps.

  20. Effect of oxidation on α″-Fe16N2 phase formation from plasma-synthesized spherical core-shell α-Fe/Al2O3 nanoparticles

    Science.gov (United States)

    Zulhijah, Rizka; Nandiyanto, Asep Bayu Dani; Ogi, Takashi; Iwaki, Toru; Nakamura, Keitaro; Okuyama, Kikuo

    2015-05-01

    The introduction of an oxidation treatment to the synthesis of spherical and core-shell α″-Fe16N2/Al2O3 nanoparticles (~62 nm) from plasma-synthesized core-shell α-Fe/Al2O3 nanoparticles has been found to result in a high yield of α″-Fe16N2 phase of up to 98%. The oxidation treatment leads the formation of a maghemite phase with open channeled structures along the c-axis, facilitating penetration of H2 and NH3 gases during the hydrogen reduction and nitridation steps. The saturation magnetization and magnetic coercivity of the core-shell α″-Fe16N2/Al2O3 magnetic nanoparticles were found to be 156 emu/g and 1450 Oe, respectively. The detailed effects of the oxidation on the formation of α″-Fe16N2 phase were investigated by characterizing the morphology (SEM, TEM and BET), elemental composition (EDX, EELS, and XAFS) and magnetic properties (Mössbauer and MSPS) of the prepared particles. The good magnetic properties obtained have the potential for future applications such as rare-earth-free magnetic materials.

  1. Low-resistivity m-plane freestanding GaN substrate with very low point-defect concentrations grown by hydride vapor phase epitaxy on a GaN seed crystal synthesized by the ammonothermal method

    Science.gov (United States)

    Kojima, Kazunobu; Tsukada, Yusuke; Furukawa, Erika; Saito, Makoto; Mikawa, Yutaka; Kubo, Shuichi; Ikeda, Hirotaka; Fujito, Kenji; Uedono, Akira; Chichibu, Shigefusa F.

    2015-09-01

    An m-plane freestanding GaN substrate satisfying both low resistivity (ρ = 8.5 × 10-3 Ω·cm) and a low point-defect concentration, being applicable to vertically conducting power-switching devices, was grown by hydride vapor phase epitaxy on a nearly bowing-free bulk GaN seed wafer synthesized by the ammonothermal method in supercritical ammonia using an acidic mineralizer. Its threading dislocation and basal-plane staking-fault densities were approximately 104 cm-2 and lower than 100 cm-1, respectively. A record-long fast-component photoluminescence lifetime of 2.07 ns at room temperature was obtained for the near-band-edge emission, reflecting a significantly low concentration of nonradiative recombination centers composed of Ga vacancies.

  2. Particular aspect of the behaviour of the uranyl ion in phosphoric medium; Aspect particulier du comportement de l'ion uranyle en milieu phosphorique

    Energy Technology Data Exchange (ETDEWEB)

    Sefiani, N.; Hlaibi, M.; Saib, N.; Azzi, M. [Faculte des Sciences Ain Chock, Lab. Interface Materiaux Environnement (LIME), Casablanca (Morocco)

    2007-07-01

    The uranium element is present at trace amounts in phosphate ores. During the production of phosphoric acid by wet way, most of the uranium passes in solution. In order to control its extraction, it is important to understand the behaviour of uranium in this phosphoric medium and to determine under which form it exists. The aim of this work is to study the speciation of the uranyl ion in a phosphoric acid medium. Preliminary tests of conductometry and viscosimetry have shown that the conductivity and the viscosity of the phosphoric medium evolve with the concentration of the uranyl ion. They have allowed to reveal a process of interaction between the metallic cation and the phosphoric acid molecule. Spectrophotometric tests based on the principle of indirect photometry detection have confirmed the interaction between this metallic cation and the phosphate specie. These tests have allowed too to determine the molar uranium/ phosphate ratio and the number of protons involved during this interaction. The influence of the acidity of the medium on the stability of the formed specie coming from the interaction between the uranyl ion and the phosphoric acid molecules has been studied too. Thus, has been established the complexation reaction corresponding to this interaction. In order to obtain more data on the possible interactions between the uranyl and phosphate species, investigations by {sup 31}P NMR and by Raman spectroscopy have been carried out. With these tests, it has been possible to confirm the results obtained by indirect photometry and to identify the nature and the structure of the uranyl complex in phosphoric acid medium. The comparison of these results with previous studies have allowed to propose a structure of the specie in solution. (O.M.)

  3. Electron microscopy studies of natural and synthetic zeolites impregnated with uranyl dioxide

    Energy Technology Data Exchange (ETDEWEB)

    Acosta, Dwight R.; T-Olguin, Maria; Solache, Marcos; Bosch, Pedro; Bulbulian, Silvia [Universidad Nacional Autonoma de Mexico, Mexico City (Mexico). Inst. de Fisica; Asomoza, Max [Instituto Nacional de Investigaciones Nucleares, Mexico City (Mexico). Dept. de Quimica Nuclear

    1995-09-01

    Full text. The use of Y zeolite and erionite to remove uranyl dioxide ions from aqueous solution is focussed on catalysis and energy transfer problems but it can be oriented to recovery uranyl dioxide ions, among other radioactive compounds. The samples impregnated with uranyl dioxide at several concentrations and contact times were studied using conventional, high resolution and scanning electron microscopy in order to detect changes as consequence of contact with a radioactive material and to verify mechanical stability of zeolites. Also X ray diffraction, thermal analysis, neutron activation were used to characterize the samples at several steps of treatment. The crystallinity of zeolites was maintained only when using dilute uranyl nitrate solution (up to 0.0100 N for y zeolite and 0.0300 N for erionite). The samples impregnated with highest nitrate concentrations partially lost their crystallinity. From selected area electron diffraction pattern, lattice parameter variations were detected and from high resolution electron microscopy localization of uranyl ions in and on zeolite structure was determined. Surface modification in zeolites was observed by scanning electron microscopy just for samples with long contact time with radioactive solutions. (author)

  4. Preparation of controlled particle size U3O8 by uranyl formate precipitation and calcination

    International Nuclear Information System (INIS)

    Johnson, D.R.

    1978-11-01

    A conceptual process flowsheet for preparation of U 3 O 8 by precipitating uranyl formate monohydrate with excess formic acid and calcining it was developed and demonstrated on a laboratory scale. The product U 3 O 8 has a particle size distribution apropriate for fabrication of U 3 O 8 -Al fuel by powder metallurgy. The U 3 O 8 particles are crystalline, do not exceed 150 μm in diameter, and have a narrow particle size distribution with most particles within the range of 44 to 150 μm. A ten-fold decontamination of uranium from low-level fission products during uranyl formate precipitation was demonstrated. Minimal variations in U 3 O 8 particle size distribution as a function of various uranyl formate precipitation conditions were observed. Preliminary tests demonstrated that calcination of uranyl formate monohydrate recovered from solution by evaporation to dryness did not produce U 3 O 8 with the desired particle size distribution. Calcination of uranyl oxalate, uranous oxalate, or uranous formate also did not produce U 3 O 8 with the appropriate particle size distribution

  5. Adsorption of uranyl ion by chelate-type adsorbent with amidoxime and amidoxime/carboxyl group

    International Nuclear Information System (INIS)

    Choi, S.H.; Choi, M.S.; Park, Y.T.; Lee, K.P.

    2002-01-01

    Complete text of publication follows. Uranium recovery from seawater is important for security of future energy supply. The main difficulty in the recovery process arises from the low concentration (∼3 ppb) of the uranyl ion in seawater, whereas other metal ions are abundantly present. Thus, development of selective adsorbents with a high adsorption rate and a large adsorption capacity is essential for the economic recovery uranyl ion. The polymeric adsorbents containing the amidoxime group are mostly promising, but information on their adsorption characterization in the presence of other abundantly metal ions such as sodium, calcium, etc. is still insufficient. In order to obtain uranium from seawater, the resins with amidoxime and amidoxime/carboxylic acid group were prepared by radiation-induced polymerization of aclylonitrile (AN) and AN/acrylic acid and by the subsequent amidoximation of cyano group of poly(AN), respectively. The resins with amidoxime and amidoxime/carboxylic acid groups were characterized by FT-IR, FT-Raman, solid state 13C-NMR, SEM, thermal (TGA/DSC) analysis, and elemental analysis, respectively. The adsorption of uranyl ion was examined. In resin with amidoxime group, the uranyl uptake increased with increasing amidoxime content. The adsorption rate of uranyl ion by resin with amidoxime/carboxylic acid was higher than that of resin with amidoxime group

  6. Kinetic studies of uranyl ion adsorption on acrylonitrile (AN) / polyethylene glycol (PEG) interpenetrating networks (IPN)

    International Nuclear Information System (INIS)

    Aycik, G.A.; Gurellier, R.

    2004-01-01

    The kinetics of the adsorption of uranyl ions on amidoximated acrylonitrile (AN)/ polyethylene glycol (PEG) interpenetrating network (IPNs) from aqueous solutions was studied as a function of time and temperature. Adsorption analyses were performed for definite uranyl ion concentrations of 1x10 -2 M and at four different temperatures as 290K, 298K, 308K and 318K. Adsorption time was increased from zero to 48 hours. Adsorption capacities of uranyl ions by PEG/AN IPNS were determined by gamma spectrometer. The results indicate that adsorption capacity increases linearly with increasing temperature. The max adsorption capacity was found as 602 mgu/g IPN at 308K. Adsorption rate was evaluated from the curve plotted of adsorption capacity versus time, for each temperature. Rate constants for uranyl ions adsorption on amidoximated ipns were calculated for 290K, 298K, 308K and 318K at the solution concentration of 1x10 -2 M . The results showed that as the temperature increases the rate constant increases exponentially too. The mean activation energy of uranyl ions adsorption was found as 34.6 kJ/mole by using arrhenius equation. (author)

  7. Densities concentrations of aqueous of uranyl nitrate solutions; densidades concentraciones de soluciones acuosas de nitrato de uranilo

    Energy Technology Data Exchange (ETDEWEB)

    Rodrigo Otero, A.; Rodriguez Hernandez, B.; Fernandez Rodriguez, L.

    1966-07-01

    The ratio density-concentration of aqueous uranyl nitrate solutions expressed as U{sub 3}O{sub 8} grams/liter, U grams/liter and hexahydrate uranyl nitrate weight percent at different temperatures, are established. Experimental values are graphically correlated and compared whit some published data. (Author) 2 refs.

  8. Quenching of excited uranyl ion during its photochemical reduction with triphenyl-phosphine : Part IV - effect of heterocyclic molecules

    International Nuclear Information System (INIS)

    Sidhu, M.S.; Bhatia, P.V.K.

    1994-01-01

    The presence of heterocyclic compounds triggers off a competition between photophysical and photochemical annihilation of excited uranyl ion during its photochemical reduction with triphenylphosphine. This competition is used to measure Stern-Volmer constant using UV visible spectrophotometer for quenching the uranyl ion luminescence with a number of heterocyclic molecules viz., pyridine, thiophene bipyridyl, tetrahydrofuran and piperidine. (author). 7 refs., 2 figs., 1 tab

  9. Reversible uranyl fluoride nephrotoxicity in the Long Evans rat

    International Nuclear Information System (INIS)

    Diamond, G.L.; Morrow, P.E.; Panner, B.J.; Gelein, R.M.; Baggs, R.B.

    1989-01-01

    Severity and duration of renal injury produced by low levels of uranyl fluoride (UO2F2) were examined in the rat. Rats received multiple ip injections of UO2F2 (cumulative dose: 0.66 or 1.32 mg U/kg body wt). Renal injury was characterized histologically by cellular and tubular necrosis of pars recta of proximal tubule (S2 and S3), with less severe cellular injury to thick ascending limb of loop of Henle and collecting tubule. Injury was evident when renal uranium levels were between 0.7 and 1.4 micrograms U/g wet kidney and was most severe when renal uranium burden was between 3.4 and 5.6 micrograms U/g. Repair of injury was rapid, with complete restoration within 35 days after exposure. Associated with injury were abnormalities in renal function, including impaired tubular reabsorption, proteinuria, and enzymuria, which appeared temporally related, to variable degrees, to progression of renal injury. Thus, reversible renal injury occurs in the rat at levels of uranium in kidney below the present Nuclear Regulatory Commission standard of 3 micrograms U/g kidney for renal injury in humans

  10. Tritium gettering from air with hydrogen uranyl phosphate

    Energy Technology Data Exchange (ETDEWEB)

    Souers, P.C.; Uribe, F.S.; Stevens, C.G.; Tsugawa, T.T.

    1985-08-01

    The managers of all tritium facilities now worry about their emissions into the atmosphere. The only method for cleaning tritium out of air is to catalyze the formation of tritiated water which is adsorbed, along with the overwhelming bulk of naturally occurring water vapor, on a zeolite molecular sieve. This method generally costs several million dollars for a small system, because of the necessary steel ducting, compressors and holding tanks. We have long had the dream of finding another getter that might be cheaper to use and would, hopefully, not make tritiated water (HTO). In a previous paper, we discovered that hydrogen uranyl phosphate (HUP, with the formula HUO/sub 2/PO/sub 4/ x 4H/sub 2/O) getters 1 ppM of tritium gas out of moist air. This makes HUP the first known ''direct'' tritium getter to work in air. However, the tritium enters a hydroxyl network within the HUP, so that it is effectively still in ''water'' form within the HUP. Worse yet, we found up to 10% tritiated water formed during the previous gettering experiments. HUP is unusual in possessing the exceptionally low vapor pressure of 0.6 torr water vapor at 298/sup 0/K. This allows HUP to be used in fairly dry environments. 14 refs., 3 figs., 2 tabs.

  11. Tritium gettering from air with hydrogen uranyl phosphate

    International Nuclear Information System (INIS)

    Souers, P.C.; Uribe, F.S.; Stevens, C.G.; Tsugawa, T.T.

    1985-08-01

    The managers of all tritium facilities now worry about their emissions into the atmosphere. The only method for cleaning tritium out of air is to catalyze the formation of tritiated water which is adsorbed, along with the overwhelming bulk of naturally occurring water vapor, on a zeolite molecular sieve. This method generally costs several million dollars for a small system, because of the necessary steel ducting, compressors and holding tanks. We have long had the dream of finding another getter that might be cheaper to use and would, hopefully, not make tritiated water (HTO). In a previous paper, we discovered that hydrogen uranyl phosphate (HUP, with the formula HUO 2 PO 4 x 4H 2 O) getters 1 ppM of tritium gas out of moist air. This makes HUP the first known ''direct'' tritium getter to work in air. However, the tritium enters a hydroxyl network within the HUP, so that it is effectively still in ''water'' form within the HUP. Worse yet, we found up to 10% tritiated water formed during the previous gettering experiments. HUP is unusual in possessing the exceptionally low vapor pressure of 0.6 torr water vapor at 298 0 K. This allows HUP to be used in fairly dry environments. 14 refs., 3 figs., 2 tabs

  12. Ultrastructural and metabolic changes in osteoblasts exposed to uranyl nitrate

    Energy Technology Data Exchange (ETDEWEB)

    Tasat, D.R. [Universidad Nacional de San Martin, Escuela de Ciencia y Tecnologia, Pcia de Bs.As. (Argentina); Universidad de Buenos Aires, Catedra de Histologia y Embriologia, Facultad de Odontologia, Buenos Aires (Argentina); Orona, N.S. [Universidad Nacional de San Martin, Escuela de Ciencia y Tecnologia, Pcia de Bs.As. (Argentina); Mandalunis, P.M. [Universidad de Buenos Aires, Catedra de Histologia y Embriologia, Facultad de Odontologia, Buenos Aires (Argentina); Cabrini, R.L. [Comision Nacional de Energia Atomica, Departamento de Radiobiologia, Buenos Aires (Argentina); Ubios, A.M. [Comision Nacional de Energia Atomica, Departamento de Radiobiologia, Buenos Aires (Argentina); Universidad de Buenos Aires, Catedra de Histologia y Embriologia, Facultad de Odontologia, Buenos Aires (Argentina)

    2007-05-15

    Exposure to uranium is an occupational hazard to workers who continually handle uranium and an environmental risk to the population at large. Since the cellular and molecular pathways of uranium toxicity in osteoblast cells are still unknown, the aim of the present work was to evaluate the adverse effects of uranyl nitrate (UN) on osteoblasts both in vivo and in vitro. Herein we studied the osteoblastic ultrastructural changes induced by UN in vivo and analyzed cell proliferation, generation of reactive oxygen species (ROS), apoptosis, and alkaline phosphatase (APh) activity in osteoblasts exposed to various UN concentrations (0.1, 1, 10, and 100 {mu}M) in vitro. Cell proliferation was quantified by means of the 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide assay, ROS was determined using the nitro blue tetrazolium test, apoptosis was morphologically determined using Hoechst 3332 and APh activity was assayed spectrophotometrically. Electron microscopy revealed that the ultrastructure of active and inactive osteoblasts exposed to uranium presented cytoplasmic and nuclear alterations. In vitro, 1-100 {mu}M UN failed to modify cell proliferation ratio and to induce apoptosis. ROS generation increased in a dose-dependent manner in all tested doses. APh activity was found to decrease in 1-100 {mu}M UN-treated cells vs. controls. Our results show that UN modifies osteoblast cell metabolism by increasing ROS generation and reducing APh activity, suggesting that ROS may play a more complex role in cell physiology than simply causing oxidative damage. (orig.)

  13. Assessment of accidental intakes of uranyl acetylacetonate (UAA)

    International Nuclear Information System (INIS)

    Fisher, D.R.; Briant, J.K.

    1993-01-01

    Uranyl acetylacetonate (UAA) is an organic complex of uranium used for military applications as a chemical catalyst in high explosives. It is prepared from depleted uranium metal (in lots of 5 kg to 7 kg) by dissolution in nitric acid, neutralization, and complexation with 2,4-pentanedione; the precipitate is dissolved in benzene and recrystallized, dried, ground, and packaged. About six workers at a small chemical company were exposed over a period of time to UAA powders during routine preparation and packaging of the uranium catalyst. The dissolution characteristics of the inhaled material were unknown and could not be determined from the published scientific literature. A 1.05-g sample of UAA powder was obtained from the responsible regulatory authority for further study to determine its chemical composition, and for dissolution in simulated lung fluid. We found the solubility of UAA to be equivalent to a mixture of 52% ICRP class D and 48% ICRP class W material. The annual limit on intake and the derived air concentration for radiological protection were estimated from this result for airborne exposure to UAA. A recycling biokinetic model was used to estimate both material-specific variations in urinary excretion rates and lung retention with time after accidental intakes. This study provides new information for evaluating future exposures to UAA

  14. An X-ray photoelectron spectroscopy study of uranyl-chitosan interaction

    Directory of Open Access Journals (Sweden)

    Veleshko Alexander N.

    2008-01-01

    Full Text Available An X-ray photoelectron spectroscopy study of uranium sorption by spherically-granulated chitosan in sulphate solutions, as well as the study of the nature of the U(VI - chitosan interaction was carried out in this work. The X-ray photoelectron spectroscopy analysis showed that the uranyl - chitosan interaction results in the formation of complexes with aminogroup nitrogen, and possibly chitin ring oxygens and free hydroxyl groups in the equatorial plane. Under the UHV in the spectrometer chamber, the uranyl-amin and uranyl-hyroxide bonds were shown to break and tetravalent uranium compounds were shown to form on the sample surface. Hydroxyl groups were shown to evaporate. The calculated DG0 = -1,3 kJ/mol can be an evidence of several concurrent processes, some of which require energy, as well as of the formation of a surface chemical compound.

  15. Activity coefficients of uranyl nitrate and nitric acid in aqueous mixtures

    Energy Technology Data Exchange (ETDEWEB)

    Ochkin, A.; Gladilov, D.; Nekhaevskiy, S.; Merkushkin, A. [D. Mendeleev University of Chemical Technology of Russia, 9 Miusskay Sqr., Moscow, 125047 (Russian Federation)

    2016-07-01

    The activity coefficients of nitric acid and uranyl nitrate in aqueous mixtures are necessary to model the extracting system H{sub 2}O-HNO{sub 3}-UO{sub 2}(NO{sub 3}){sub 2}-TBP-diluent used in the PUREX process. Three methods have been compared in this work to determine activity coefficients based on experimental data, Pitzer's equation or Zdanovskiy's rule. Acid activities have been calculated from the data of the two first methods. These results were compared with the data of the third method. Errors were about 3.3%. Activity coefficients of uranyl nitrate γ{sub U} as a function of concentration of uranyl nitrate and nitric acid were determined in 76 mixed solutions. The equation to calculate γ{sub U} is proposed. (authors)

  16. Acceptor extraction of uranyl salts with mixtures of organophosphoric acids with neutral additives

    International Nuclear Information System (INIS)

    Torgov, V.G.; Us, T.V.; Mikhajlov, V.A.; Stoyanov, Ye.S.; Drozdova, M.K.; Bogdanova, D.D.

    1988-01-01

    Uranium solvent extraction by mixtures of organophosphoric acids (HX) with neutral additives (L) (phosphine oxides, sulfoxides, tbp) excibits, along with the widely known synergic effect at low HX saturation with uranium, a new synergic effect occurring after complete HX saturation. Three types of isotherms of uranyl salt extraction by benzene solutions of HX and mixtures of HX with L were revealed. Their forms depend on superposition of cation-exchange and noncation-exchange synergic effects. Similarity of synergic effect of acid and neutral mixture components during solvent extraction from diluted and concentrated solutions of uranyl salts testified to the same nature of these two effects; both of them are determined by acceptor properties of uranium atom in monomeric UO 2 (HX 2 ) 2 and polymeric (UO 2 X 2 ) p complexes. The established reqularities were confirmed, when studying uranyl sulfate extraction by UO 2 X 2 mixture with L

  17. Engineering of specific uranyl-coordination sites in the calcium-binding motif of Calmodulin

    International Nuclear Information System (INIS)

    Beccia, M.; Pardoux, R.; Sauge-Merle, S.; Bremond, N.; Lemaire, D.; Berthomieu, C.; Delangle, P.; Guilbaud, P.

    2014-01-01

    Complete text of publication follows: Characterization of heavy metals interactions with proteins is fundamental for understanding the molecular factors and mechanisms governing ions toxicity and speciation in cells. This line of research will also help in developing new molecules able to selectively and efficiently bind toxic metal ions, which could find application for bio-detection or bioremediation purposes. We have used the regulatory calcium-binding protein Calmodulin (CaM) from A. thaliana as a structural model and, starting from it, we have designed various mutants by site-directed mutagenesis. We have analysed thermodynamics of uranyl ion binding to both sites I and II of CaM N-terminal domain and we have identified structural factors governing this interaction. Selectivity for uranyl ion has been tested by studying reactions of the investigated peptides with Ca 2+ , in the same conditions used for UO 2 2+ . Spectro-fluorimetric titrations and FTIR analysis have shown that the affinity for uranyl increases by phosphorylation of a threonine in site I, especially approaching the physiological pH, where the phospho-threonine side chain is deprotonated. Based on structural models obtained by Molecular Dynamics, we tested the effect of a two residues deletion on site I properties. We obtained an almost two orders of magnitude increase in affinity for uranyl, with a sub-nanomolar dissociation constant for the uranyl complex with the non phosphorylated peptide, and an improved uranyl/calcium selectivity. Allosteric effects depending on Ca 2+ and UO 2 2+ binding have been investigated by comparing thermodynamic parameters obtained for mutants having both sites I and II able to chelate metal ions with those of mutants consisting of just one active site

  18. Removal of uranyl ions by p-hexasulfonated calyx[6]arene acid

    Energy Technology Data Exchange (ETDEWEB)

    Popescu, Ioana-Carmen [R and D National Institute for Metals and Radioactive Resources–ICPMRR, B-dul Carol I No.70, Sector 2, Bucharest 020917 (Romania); Petru, Filip [“C.D. Nenitescu” Institute of Organic Chemistry, Splaiul Independentei 202B, Sector 6, Bucharest 71141 (Romania); Humelnicu, Ionel [“Al.I. Cuza” University of Iasi, The Faculty of Chemistry, Bd. Carol-I No. 11, Iasi 700506 (Romania); Mateescu, Marina [National R and D Institute for Chemistry and Petrochemistry, Splaiul Independenţei No. 202, Bucharest 060021 (Romania); Militaru, Ecaterina [R and D National Institute for Metals and Radioactive Resources–ICPMRR, B-dul Carol I No.70, Sector 2, Bucharest 020917 (Romania); Humelnicu, Doina, E-mail: doinah@uaic.ro [“Al.I. Cuza” University of Iasi, The Faculty of Chemistry, Bd. Carol-I No. 11, Iasi 700506 (Romania)

    2014-10-15

    Radioactive pollution is a significant threat for the people’s health. Therefore highly effective radioactive decontamination methods are required. Ion exchange, biotechnologies and phytoremediation in constructed wetlands have been used as radioactive decontamination technologies for uranium contaminated soil and water remediation. Recently, beside those classical methods the calix[n]arenic derivatives’ utilization as radioactive decontaminators has jogged attention. The present work aims to present the preliminary research results of uranyl ion sorption studies on the p-hexasulfonated calyx[6]arenic acid. The effect of temperature, contact time, sorbent amount and uranyl concentration variation on sorption efficiency was investigated. Isotherm models revealed that the sorption process fit better Langmuir isotherm.

  19. Investigation of regularities of uranyl salts complexing with neutral bases in nonaqueous media

    International Nuclear Information System (INIS)

    Kobets, L.V.; Buchikhin, E.P.

    1986-01-01

    Anhydrous uranyl chloride complexing with neutral oxygen-containing organic bases (sulfoxides, organic phosphates, phosphinates, phosphinoxides, N-oxides) in the acetone medium depending on the donor capacity of neutral molecules is discussed. The constants of 1:1 complexes dissociation are shown to detect no correlation with the donor capacity of neutral bases. At the same time stability constants of complexes increase as the donor capacity of ligands grows. But the dependence is of a complex character and is determined by the nature of neutral molecules. Estimation of uranyl chloride and 0-donor contributions into the values of stability constants and complex formation heats is given

  20. Ultrastructure changes produced by the action of uranyl acetate on the human erythrocyte in vitro

    International Nuclear Information System (INIS)

    Wyatt, J.H.

    1975-06-01

    Human erythrocytes exposed in vitro to low concentrations of uranyl ions are immediately changed in shape to stomatocytes. Electron microscope examination demonstrates that cellular damage is confined to the plasma membrane. Endocytosis of the cell membrane produces groups of inside out membrane-lined vesicles within the cell; lipid from the membrane enters the cell, giving rise to intracellular myelin figures, and breaks are seen in the cell membrane. It is proposed that the lipid fraction of the cell membrane is the primary target for damage by uranyl ions. (author)

  1. High-value utilization of egg shell to synthesize Silver and Gold-Silver core shell nanoparticles and their application for the degradation of hazardous dyes from aqueous phase-A green approach.

    Science.gov (United States)

    Sinha, Tanur; Ahmaruzzaman, M

    2015-09-01

    The common household material, egg shell of Anas platyrhynchos is utilized for the synthesis of Silver and Gold-Silver core shell nanoparticles using greener, environment friendly and economic way. The egg shell extracts were acting as a stabilizing and reducing agents. This method avoids the use of external reducing and stabilizing agents, templates and solvents. The effects of various reaction parameters, such as reaction temperature, concentration in the formation of nanoparticles have also been investigated. The compositional abundance of gelatin may be envisaged for the effective reductive as well as stabilizing potency. The mechanisms for the formation of NPs have also been presented. The synthesized Ag NPs formed were predominantly spherical in nature with an average size of particles in the range of 6-26 nm. While, Au-Ag core shell nanoparticles formed were spherical and oval shaped, within a narrow size spectrum of 9-18 nm. Both the Ag NPs Au-and Ag core shell nanoparticles showed characteristic Bragg's reflection planes of fcc structure and surface plasmon resonance at 430 nm and 365 nm, respectively. The NPs were utilized for the removal of toxic and hazardous dyes, such as Rose Bengal, Methyl Violet 6 B and Methylene Blue from aqueous phase. Approximately 98.2%, 98.4% and 97% degradations of Rose Bengal, Methyl Violet 6 B, and Methylene Blue were observed with Ag NPs, while the percentage degradation of these dyes was 97.3%, 97.6% and 96% with Au-Ag NPs, respectively. Therefore, the present study has opened up an innovative way for synthesizing Ag NPs and Au-Ag bimetallic nanostructures of different morphologies and sizes involving the utilization of egg shell extract. The high efficiency of the NPs as photocatalysts has opened a promising application for the removal of hazardous dyes from the industrial effluents. Copyright © 2015 Elsevier Inc. All rights reserved.

  2. Effect of oxidation on α″-Fe16N2 phase formation from plasma-synthesized spherical core–shell α-Fe/Al2O3 nanoparticles

    International Nuclear Information System (INIS)

    Zulhijah, Rizka; Nandiyanto, Asep Bayu Dani; Ogi, Takashi; Iwaki, Toru; Nakamura, Keitaro; Okuyama, Kikuo

    2015-01-01

    The introduction of an oxidation treatment to the synthesis of spherical and core–shell α″-Fe 16 N 2 /Al 2 O 3 nanoparticles (~62 nm) from plasma-synthesized core–shell α-Fe/Al 2 O 3 nanoparticles has been found to result in a high yield of α″-Fe 16 N 2 phase of up to 98%. The oxidation treatment leads the formation of a maghemite phase with open channeled structures along the c-axis, facilitating penetration of H 2 and NH 3 gases during the hydrogen reduction and nitridation steps. The saturation magnetization and magnetic coercivity of the core–shell α″-Fe 16 N 2 /Al 2 O 3 magnetic nanoparticles were found to be 156 emu/g and 1450 Oe, respectively. The detailed effects of the oxidation on the formation of α″-Fe 16 N 2 phase were investigated by characterizing the morphology (SEM, TEM and BET), elemental composition (EDX, EELS, and XAFS) and magnetic properties (Mössbauer and MSPS) of the prepared particles. The good magnetic properties obtained have the potential for future applications such as rare-earth-free magnetic materials. - Highlights: • High yield of α″-Fe 16 N 2 up to 98% was prepared from core–shell α-Fe/Al 2 O 3 NPs. • Introduction of oxidation improved yield of α″-Fe 16 N 2 for large size of NPs. • Oxidation forming microporous structured maghemite facilitated nitridation process. • Particle morphology changed during the nitrogen process due to atomic dislocation. • Core–shell α″-Fe 16 N 2 /Al 2 O 3 nanoparticles showed good magnetic performances

  3. Characterization of osteopontin-uranyl interaction: role of multiple phosphorylations

    International Nuclear Information System (INIS)

    Qi, Lei

    2014-01-01

    While some metals are essential for Life, other ones are only toxicants for living organisms, tolerated below well-definite concentrations. This is the case for uranium, a natural element which has no known biological function. It is a low α emitter and its chemical toxicity rather than its radiological toxicity is a subject of concern. Once in the body, this metal reaches the blood and accumulates in the bones under the action of unknown mechanisms. Uranium mainly exists in form of uranyl ion (UO 2 2+ ) in aqueous media and particularly reacts with carboxylates, phenolates and phosphates of the proteins. Previous studies have highlighted that UO 2 2+ modulates the SPP1 expression, a gene which codes for osteopontin (OPN). This highly phosphorylated glycoprotein plays an important role in bone homeostasis. This role and its biochemical properties led us to hypothesize that OPN might be a potential target of UO 2 2+ and involved in its accumulation in bones. A simple and original purification process was optimized to produce very highly purified OPN starting from human and bovine milk. Various biophysical approaches were set up and confirmed that both bovine and human OPN display very high affinity for UO 2 2+ . Moreover, the formation of stable UO 2 -protein complexes originating from structural changes was evidenced. The major role of phosphorylations, both on the OPN's affinity for UO 2 2+ and the stability of the UO 2 -protein complexes, was confirmed. These results demonstrate that OPN presents all the characteristics to be a major UO 2 2+ binding-protein in vitro, and they open new insights in the understanding of the UO 2 2+ mineralization process mechanisms. (author) [fr

  4. Rates and mechanisms of uranyl oxyhydroxide mineral dissolution

    Science.gov (United States)

    Reinoso-Maset, Estela; Steefel, Carl I.; Um, Wooyong; Chorover, Jon; O'Day, Peggy A.

    2017-06-01

    Uranyl oxyhydroxide minerals are important weathering products in uranium-contaminated surface and subsurface environments that regulate dissolved uranium (U) concentrations. However, dissolution rates for this class of minerals and associated dissolution mechanisms have not been previously reported for circumneutral pH conditions, particularly for the case of flow through porous media. In this work, the dissolution rates of K- and Na-compreignacite (K2(UO2)6O4(OH)6·8H2O and Na2(UO2)6O4(OH)6·8H2O, respectively) were measured using flow-through columns reacted with two simulated background porewater (BPW) solutions of low and high dissolved carbonate concentration (ca. 0.2 and 2.8 mmol L-1). Column materials were characterized before and after reaction with electron microscopy, bulk chemistry, and EXAFS to identify structural and chemical changes during dissolution and to obtain insight into molecular-scale processes. The reactive transport code CrunchFlow was used to calculate overall dissolution rates while accounting for fluid transport and changes in mineral volume and reactive surface area, and results were compared to steady-state dissolution rate calculations. In low carbonate BPW systems, interlayer K and Na were initially leached from both minerals, and in Na-compreignacite, K and minor divalent cations from the input solution were incorporated into the mineral structure. Results of characterization analyses suggested that after reaction both K- and Na-compreignacite resembled a disordered K-compreignacite with altered surfaces. A 10-fold increase in dissolved carbonate concentration and corresponding increase in pH (from 6.65 to 8.40) resulted in a net removal of 58-87% of total U mass from the columns, compared to importance of coupling reaction and transport processes during the quantification of mineral dissolution rates to accurately predict the fate of contaminants such as U in porous geomedia.

  5. Standard test method for isotopic analysis of hydrolyzed uranium hexafluoride and uranyl nitrate solutions by thermal ionization mass spectrometry

    CERN Document Server

    American Society for Testing and Materials. Philadelphia

    2005-01-01

    1.1 This method applies to the determination of isotopic composition in hydrolyzed nuclear grade uranium hexafluoride. It covers isotopic abundance of 235U between 0.1 and 5.0 % mass fraction, abundance of 234U between 0.0055 and 0.05 % mass fraction, and abundance of 236U between 0.0003 and 0.5 % mass fraction. This test method may be applicable to other isotopic abundance providing that corresponding standards are available. 1.2 This test method can apply to uranyl nitrate solutions. This can be achieved either by transforming the uranyl nitrate solution to a uranyl fluoride solution prior to the deposition on the filaments or directly by depositing the uranyl nitrate solution on the filaments. In the latter case, a calibration with uranyl nitrate standards must be performed. 1.3 This test method can also apply to other nuclear grade matrices (for example, uranium oxides) by providing a chemical transformation to uranyl fluoride or uranyl nitrate solution. 1.4 This standard does not purport to address al...

  6. The extraction and effect in the system uranyl nitrate-dietyl ether-water; El efecto final de la extraccion en el sistema nitrato de uranillo-eter dietilico-agua

    Energy Technology Data Exchange (ETDEWEB)

    Perez Luina, A.; Gutierrez Jodra, L.; Rius Miro, A.

    1960-07-01

    The solute transfer of uranyl nitrate from diethyl ether to water has been studied in a spray column using water as dispersed phase and a direction of extraction from ether to water. The column is 102 cm long and has a diameter of 4,7 cm. The entrances of the phases are 77 cm apart. The rates of flow of both phases have been used as variables and the concentration of the continuous phase has been determined at different heights. The curves of logarithm of concentration of the continuous phase vs. distance to interphase show the present of a drop of concentration in the entrance of the continuous phase. This depends on the rates of flow of the phases. No effect in the entrance of the dispersed phase has been found. (Author) 20 refs.

  7. Thermal Analysis of the Decomposition of Ammonium Uranyl Carbonate (AUC) in Different Atmospheres

    DEFF Research Database (Denmark)

    Hälldahl, L.; Sørensen, Ole Toft

    1979-01-01

    The intermediate products formed during thermal decomposition of ammonium uranyl carbonate (AUC) in different atmospheres, (air, helium and hydrogen) have been determined by thermal analysis, (TG, and DTA) and X-ray analysis. The endproducts observed are U3O8 and UO2 in air/He and hydrogen...

  8. Potential New Ligand Systems for Binding Uranyl Ions in Seawater Environments

    Energy Technology Data Exchange (ETDEWEB)

    Arnold, John [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)

    2014-12-13

    Work began this quarter on a new project involving a combined computational and biosynthetic approach to selective recognition of uranyl ion in aqueous solution. This project exploits the results of computational studies to discover new ligand classes. Synthetic studies will follow to generate target systems for uranyl binding and determination of binding constants. The process will be iterative, with results from computation informing synthesis, and vice versa. The theme of the ligand classes to be examined initially will be biologically based. New phosphonate-containing α-amino acid N-carboxyanhydride (NCA) monomers were used recently to prepare well-defined phosphonate-containing poly-peptides and block copolypeptides. Our first approach is to utilize these phosphate- and phosphonate-containing NCAs for the coordination of uranyl. The work includes the laboratory-scale preparation of a series of NCAs and the full thermodynamic and spectroscopic characterization of the resulting uranyl complexes. We are also evaluating the sequestering activity in different physiological and environmental conditions of these copolymers as well as their biodegradability.

  9. Unusual intramolecular CHO hydrogen bonding interaction between a sterically bulky amide and uranyl oxygen.

    Science.gov (United States)

    Kannan, Shanmugaperumal; Kumar, Mukesh; Sadhu, Biswajit; Jaccob, Madhavan; Sundararajan, Mahesh

    2017-12-12

    The selective separation of toxic heavy metals such as uranyl can be accomplished using ligands with stereognostic hydrogen bonding interactions to the uranyl oxo group, as proposed by Raymond and co-workers (T. S. Franczyk, K. R. Czerwinski and K. N. Raymond, J. Am. Chem. Soc., 1992, 114, 8138-8146). Recently, several ligands possessing this weak interaction have been proposed involving the hydrogen bonding of NH and OH based moieties with uranyl oxygen. We herein report the structurally and spectroscopically characterized CHO hydrogen bonding using a sterically bulky amide based ligand. In conjunction with experiments, electronic structure calculations are carried out to understand the structure, binding and the strength of the CHO hydrogen bonding interactions. This weak interaction is mainly due to the steric effect caused by a bulky substituent around the donor group which has direct relevance in designing novel ligands in nuclear waste management processes. Although the kinetics are very slow, the ligand is also highly selective to uranyl in the presence of other interfering ions such as lanthanides.

  10. On the retention of uranyl and thorium ions from radioactive solution on peat moss.

    Science.gov (United States)

    Humelnicu, Doina; Bulgariu, Laura; Macoveanu, Matei

    2010-02-15

    The efficiency of the radioactive uranyl and thorium ions on the peat moss from aqueous solutions has been investigated under different experimental conditions. The sorption and desorption of uranyl and thorium ions on three types (unmodified peat moss, peat moss treated with HNO(3) and peat moss treated with NaOH) of peat moss were studied by the static method. Peat moss was selected as it is available in nature, in any amount, as a cheap and accessible sorbent. Study on desorption of such ions led to the conclusion that the most favourable desorptive reagent for the uranyl ions is Na(2)CO(3) 1M while, for the thorium ions is HCl 1M. The results obtained show that the parameters here under investigation exercise a significant effect on the sorption process of the two ions. Also, the investigations performed recommend the peat moss treated with a base as a potential sorbent for the uranyl and thorium ions from a radioactive aqueous solution.

  11. Synthesis, structural investigation and kinetic studies of uranyl(VI) unsymmetrical Schiff base complexes

    Czech Academy of Sciences Publication Activity Database

    Asadi, Z.; Asadi, M.; Zeinali, A.; Ranjkeshshorkaei, M.; Fejfarová, Karla; Eigner, Václav; Dušek, Michal; Dehnokhalaji, A.

    2014-01-01

    Roč. 126, č. 6 (2014), s. 1673-1683 ISSN 0974-3626 R&D Projects: GA ČR(CZ) GAP204/11/0809 Institutional support: RVO:68378271 Keywords : uranyl schiff base complexes * kinetic study * kinetic s of thermal decomposition * X-ray crystallography * cyclic voltammetry Subject RIV: CA - Inorganic Chemistry Impact factor: 1.191, year: 2014

  12. Complexes of uranyl with N-oxides of heterocyclic amines. Electron-vibrational absorption spectra

    International Nuclear Information System (INIS)

    Jezowska-Trzebiatowska, B.; Wieczorek, M.

    1977-01-01

    A number of coordination compounds formed by uranyl chloride and nitrate with N-oxides of heterocyclic amines have been prepared and characterized by spectral measurements in the absorption region 20000-50000 cm -1 . The electrons and vibronic transitions have been determined and discussed. (author)

  13. Cyclic phosphopeptides to rationalize the role of phosphoamino acids in uranyl binding to biological targets

    Energy Technology Data Exchange (ETDEWEB)

    Starck, Matthieu; Laporte, Fanny A.; Oros, Stephane; Sisommay, Nathalie; Gathu, Vicky; Lebrun, Colette; Delangle, Pascale [INAC/SyMMES, UMR5819, Universite Grenoble Alpes, CEA, CNRS, Grenoble (France); Solari, Pier Lorenzo [Synchrotron SOLEIL, L' orme des Merisiers, Saint-Aubin, Gif-sur-Yvette (France); Creff, Gaelle; Den Auwer, Christophe [Institut de Chimie de Nice, UMR7272, Universite Cote d' Azur, Nice (France); Roques, Jerome [Institut de Physique Nucleaire d' Orsay, CNRS-IN2P3, Univ. Paris-Sud, Universite Paris-Saclay (France)

    2017-04-19

    The specific molecular interactions responsible for uranium toxicity are not yet understood. The uranyl binding sites in high-affinity target proteins have not been identified yet and the involvement of phosphoamino acids is still an important question. Short cyclic peptide sequences, with three glutamic acids and one phosphoamino acid, are used as simple models to mimic metal binding sites in phosphoproteins and to help understand the mechanisms involved in uranium toxicity. A combination of peptide design and synthesis, analytical chemistry, extended X-ray absorption fine structure (EXAFS) spectroscopy, and DFT calculations demonstrates the involvement of the phosphate group in the uranyl coordination sphere together with the three carboxylates of the glutamate moieties. The affinity constants measured with a reliable analytical competitive approach at physiological pH are significantly enhanced owing to the presence of the phosphorous moiety. These findings corroborate the importance of phosphoamino acids in uranyl binding in proteins and the relevance of considering phosphoproteins as potential uranyl targets in vivo. (copyright 2017 Wiley-VCH Verlag GmbH and Co. KGaA, Weinheim)

  14. Criticality parameters for uranyl nitrate or plutonium nitrate systems in tributyl phosphate/kerosine and water

    International Nuclear Information System (INIS)

    Weber, W.

    1985-01-01

    This report presents the calculated values of smallest critical masses and volumina and neutron physical parameters for uranyl nitrate (3, 4, 5% U-235) or plutonium nitrate (5% Pu-240), each in a 30 per cent solution of tributyl phosphate (TBP)/kerosine. For the corresponding nitrate-water solutions, newly calculated results are presented together with a revised solution density model. A comparison of the data shows to what extent the criticality of nitrate-TBP/kerosine systems can be assessed on the basis of nitrate-water parameters, revealing that such data can be applied to uranyl nitrate/water systems, taking into account that the smallest critical mass of uranyl nitrate-TBP/kerosine systems, up to a 5 p.c. U-235 enrichment, is by 4.5 p.c. at the most smaller than that of UNH-water solutions. Plutonium nitrate (5% Pu-240) in the TBP/kerosine solution will have a smallest critical mass of up to 7 p.c. smaller, as compared with the water data. The suitability of the computing methods and cross-sections used is verified by recalculating experiments carried out to determine the lowest critical enrichment of uranyl nitrate. The calculated results are well in agreement with experimental data. The lowest critical enrichment is calculated to be 2.10 p.c. in the isotope U-235. (orig.) [de

  15. Study of the mechanism and kinetics of the reduction of uranyl ions in phosphoric acid solutions

    International Nuclear Information System (INIS)

    El Kacemi, K.; Tyburce, B.; Belcadi, S.

    1982-01-01

    The electrochemical reduction of uranyl ions in 0.1 to 9 M phosphoric acid has been investigated by polarography, cyclic voltammetry, chronopotentiometry and potentiostatic coulometry. In concentrated phosphoric acid solutions (H 3 PO 4 3 PO 4 concentrations. So, when the concentration of U(VI) increases and/or that of H 3 PO 4 reduces, the system becomes reversible. (author)

  16. Modeling of critical experiments employing Raschig rings in uranyl nitrate solution

    International Nuclear Information System (INIS)

    Tanner, J.E.

    1989-01-01

    Four critical experiments employing borated glass rings in concentrated uranyl nitrate solution yielded k eff higher by 0. 04 when modeled with a flux-weighted, homogenized cross section set than when modeled with discrete rings. k eff varied by 0.014 for a 10% boron uncertainty and by up to 0.04 for a 10% packing fraction uncertainty

  17. Kinetics of thermal decomposition and kinetics of substitution reaction of nano uranyl Schiff base complexes

    Czech Academy of Sciences Publication Activity Database

    Asadi, Z.; Zeinali, A.; Dušek, Michal; Eigner, Václav

    2014-01-01

    Roč. 46, č. 12 (2014), s. 718-729 ISSN 0538-8066 R&D Projects: GA ČR(CZ) GAP204/11/0809 Institutional support: RVO:68378271 Keywords : uranyl * Schiff base * kinetics * anticancer activity Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 1.517, year: 2014

  18. Effects of maleic acid and uranyl on mercurial diuresis in dogs

    Energy Technology Data Exchange (ETDEWEB)

    Nigrovic, V.; Koechel, D.A.; Cafruny, E.J.

    1973-01-01

    The effects of two nephrotoxic agents were studied in anesthetized dogs undergoing mercurial diuresis. One of the agents, uranyl, accumulates in the kidneys when administered as the acetate salt but does not readily react with sulfhydryl groups. In acute experiments uranyl acetate in doses up to 5 ..mu..mol/kg produced no change in the urinary excretion of sodium or chloride. Uranyl acetate given before the injection of mercury(II) did not reduce the diuretic response to inorganic mercury. The other compound, maleic acid, accumulates in the kidneys and also reacts readily with sulfhydryl groups. The administration of small doses of maleic acid did not change the excretion of sodium but it decreased the excretion of chloride. The administration of maleic acid either before or after the administration of mercury completely abolished the diuretic response. The inhibition occurred without significant changes in urinary pH. Diuretic responses to ethacrynic acid, furosemide, hydrochlorothiazide or acetazolamide were preserved in maleate-treated dogs. Both the lack of any effect of uranyl on mercurial diuresis and the specific inhibition of mercurial diuresis by maleic acid support the presently accepted view that the renal diuretic receptor for mercury(II) has at least one sulfhydryl binding site. Although the inhibition is ascribed to competition between mercury(II) and maleate for binding on the receptor, it is conceivable that the reduction in urinary chloride excretion produced by maleate may be responsible, in part, for refractoriness to mercury(II).

  19. A note on the molecular water content in uranyl carbonate mineral andersonite

    Czech Academy of Sciences Publication Activity Database

    Plášil, Jakub; Čejka, J.

    2015-01-01

    Roč. 60, č. 3 (2015), s. 181-187 ISSN 1802-6222 R&D Projects: GA ČR GP13-31276P Institutional support: RVO:68378271 Keywords : andersonite * uranyl carbonate * crystal structure * molecular water Subject RIV: DB - Geology ; Mineralogy Impact factor: 1.326, year: 2015

  20. Identification of Uranyl Surface Complexes an Ferrihydrite: Advanced EXAFS Data Analysis and CD-MUSIC Modeling

    NARCIS (Netherlands)

    Rossberg, A.; Ulrich, K.U.; Weiss, S.; Tsushima, S.; Hiemstra, T.; Scheinost, A.C.

    2009-01-01

    Previous spectroscopic research suggested that uranium(VI) adsorption to iron oxides is dominated by ternary uranyl-carbonato surface complexes across an unexpectedly wide pH range. Formation of such complexes would have a significant impact on the sorption behavior and mobility of uranium in

  1. Application of the NICADonnan model for proton, copper and uranyl binding to humic acid

    NARCIS (Netherlands)

    Saito, T.; Nagasaki, S.; Tanaka, S.; Koopal, L.K.

    2004-01-01

    Humic acids are natural organic materials that play an important role in the migration of heavy metal and actinide ions in aquatic and soil systems. In the present study, the binding of protons, copper ions and uranyl ions to the purified Aldrich humic acid (PAHA) is investigated and the results are

  2. Inhibition Mechanism of Uranyl Reduction Induced by Calcium-Carbonato Complexes

    Science.gov (United States)

    Jones, M. E.; Bargar, J.; Fendorf, S. E.

    2015-12-01

    Uranium mobility in the subsurface is controlled by the redox state and chemical speciation, generally as minimally soluble U(IV) or soluble U(VI) species. In the presence of even low carbonate concentrations the uranyl-carbonato complex quickly becomes the dominant aqueous species; they are, in fact, the primary aqueous species in most groundwaters. Calcium in groundwater leads to ternary calcium-uranyl-carbonato complexes that limit the rate and extent of U(VI) reduction. This decrease in reduction rate has been attributed to surface processes, thermodynamic limitations, and kinetic factors. Here we present a new mechanism for the inhibition of ferrous iron reduction of uranyl-carbonato species in the presence of calcium. A series of experiments under variable Ca conditions were preformed to determine the role of Ca in the inhibition of U reduction by ferrous iron. Calcium ions in the Ca2UO2(CO3)3 complex sterically prevent the interaction of Fe(II) with U(VI), in turn preventing the Fe(II)-U(VI) distance required for electron transfer. The mechanism described here helps to predict U redox transformations in suboxic environments and clarifies the role of Ca in the fate and mobility of U. Electrochemical measurements further show the decrease of the U(VI) to U(V) redox potential of the uranyl-carbonato complex with decreasing pH suggesting the first electron transfer is critical determining the rate and extent of uranium reduction.

  3. Kinetic investigation of uranyl-uranophile complexation. 1. Macrocyclic kinetic effect and macrocyclic protection effect

    International Nuclear Information System (INIS)

    Tabushi, I.; Yoshizawa, A.

    1986-01-01

    Equilibria and rates of ligand-exchange reactions between uranyl tricarbonate and dithiocarbamates and between uranyl tris-(dithiocarbamates) and carbonate were studied under a variety of conditions. The dithiocarbamates used were acyclic diethyl-dithiocarbamate and macrocyclic tris(dithiocarbamate). The acyclic ligand showed a triphasic (successive three-step) equilibrium with three different equilibrium constants while the macrocyclic ligand showed a clear monophasic (one-step) equilibrium with a much larger stability constant for the dithiocarbamate-uranyl complex. The macrocyclic ligand showed the S/sub N/2-type ligand-exchange rate in the forward as well as reverse process, while the first step of the acyclic ligand-exchange reaction proceeded via the S/sub N/1-type mechanism. This kinetic macrocyclic effect on molecularity is interpreted as the result of a unique topological requirement of uranyl complexation. The macrocyclic ligand also exhibited a clear protection effect, leading to the large stability constant. 19 references, 10 figures, 2 tables

  4. Reductive metalation of the uranyl oxo-groups with main Group-, d- and f-block metals

    OpenAIRE

    Zegke, Markus

    2015-01-01

    This thesis describes the reductive functionalisation of the uranyl(VI) dication by metalation of the uranyl oxo-groups (O=UVI=O), using reductants from Group I, Group II, Group IV, Group XII and Group XIII as well as from the lanthanide and actinide series of the periodic table. Chapter 1 introduces uranium and nuclear waste, and gives an introduction into uranium(V) chemistry. It further compares the chemistry of uranyl(V) to neptunyl(V), with a specific focus on solid sta...

  5. Effect of sonochemical synthesized TiO2 nanoparticles and coagulation bath temperature on morphology, thermal stability and pure water flux of asymmetric cellulose acetate membranes prepared via phase inversion method

    Directory of Open Access Journals (Sweden)

    Abedini Reza

    2012-01-01

    Full Text Available In this study, asymmetric pure CA and CA/ TiO2 composite membranes were prepared via phase inversion by dispersing TiO2 nanopaticles in the CA casting solutions induced by immersion precipitation in water coagulation bath. TiO2 nanoparticles, which were synthesized by the sonochemical method, were added into the casting solution with different concentrations. Effects of TiO2 nanoparticles concentration (0 wt. %, 5wt.%, 10wt.%, 15wt.%, 20wt.% and 25wt.% and coagulation bath temperature (CBT= 25°C, 50°C and 75°C on morphology, thermal stability and pure water flux (PWF of the prepared membranes were studied and discussed. Increasing TiO2 concentration in the casting solution film along with higher CBT resulted in increasing the membrane thickness, water content (WC, membrane porosity and pure water flux (PWF, also these changes facilitate macrovoids formation. Thermal gravimetric analysis (TGA shows that thermal stability of the composite membranes were improved by the addition of TiO2 nanopaticles. Also TGA results indicated that increasing CBT in each TiO2 concentration leads to the decreasing of decomposition temperature (Td of hybrid membranes.

  6. Partitioning of uranyl between ferrihydrite and humic substances at acidic and circum-neutral pH

    Science.gov (United States)

    Dublet, Gabrielle; Lezama Pacheco, Juan; Bargar, John R.; Fendorf, Scott; Kumar, Naresh; Lowry, Gregory V.; Brown, Gordon E.

    2017-10-01

    As part of a larger study of the reactivity and mobility of uranyl (U(VI)O22+) cations in subsurface environments containing natural organic matter (NOM) and hydrous ferric oxides, we have examined the effect of reference humic and fulvic substances on the sorption of uranyl on 2-line ferrihydrite (Fh), a common, naturally occurring nano-Fe(III)-hydroxide. Uranyl was reacted with Fh at pH 4.6 and 7.0 in the presence and absence of Elliott Soil Humic Acid (ESHA) (0-835 ppm) or Suwanee River Fulvic Acid (SRFA) (0-955 ppm). No evidence was found for reduction of uranyl by either form of NOM after 24 h of exposure. The following three size fractions were considered in this study: (1) ≥0.2 μm (Fh-NOM aggregates), (2) 0.02-0.2 μm (dispersed Fh nanoparticles and NOM macro-molecules), and (3) <0.02 μm (dissolved). The extent to which U(VI) is sorbed in aggregates or dispersed as colloids was assessed by comparing U, Fe, and NOM concentrations in these three size fractions. Partitioning of uranyl between Fh and NOM was determined in size fraction (1) using X-ray absorption spectroscopy (XAS). Uranyl sorption on Fh-NOM aggregates was affected by the presence of NOM in different ways depending on pH and type of NOM (ESHA vs. SRFA). The presence of ESHA in the uranyl-Fh-NOM ternary system at pH 4.6 enhanced uranyl uptake more than the presence of SRFA. In contrast, neither form of NOM affected uranyl sorption at pH 7.0 over most of the NOM concentration range examined (0-500 ppm); at the highest NOM concentrations (500-955 ppm) uranyl uptake in the aggregates was slightly inhibited at pH 7.0, which is interpreted as being due to the dispersion of Fh aggregates. XAS at the U LIII-edge was used to characterize molecular-level changes in uranyl complexation as a result of sorption to the Fh-NOM aggregates. In the absence of NOM, uranyl formed dominantly inner-sphere, mononuclear, bidentate sorption complexes on Fh. However, when NOM concentration was increased at pH 4.6, the

  7. Corrosion evaluation of uranyl nitrate solution evaporator and denitrator in Tokai reprocessing plant

    International Nuclear Information System (INIS)

    Yamanaka, Atsushi; Hashimoto, Kowa; Uchida, Toyomi; Shirato, Yoji; Isozaki, Toshihiko; Nakamura, Yoshinobu

    2011-01-01

    The Tokai reprocessing plant (TRP) adopted the PUREX method in 1977 and has reprocessed spent nuclear fuel of 1140 tHM (tons of heavy metals) since then. The reprocessing equipment suffers from various corrosion phenomena because of high nitric acidity, solution ion concentrations, such as uranium, plutonium, and fission products, and temperature. Therefore, considering corrosion performance in such a severe environment, stainless steels, titanium steel, and so forth were employed as corrosion resistant materials. The severity of the corrosive environment depends on the nitric acid concentration and the temperature of the solution, and uranium in the solution reportedly does not significantly affect the corrosion of stainless steels and controls the corrosion rates of titanium steel. The TRP equipment that handles uranyl nitrate solution operates at a low nitric acid concentration and has not experienced corrosion problems until now. However, there is a report that corrosion rates of some stainless steels increase in proportion to rising uranium concentrations. The equipment that handles the uranyl nitrate solution in the TRP includes the evaporators, which concentrate uranyl nitrate to a maximum concentration of about 1000 gU/L (grams of uranium per liter), and the denitrator, where uranyl nitrate is converted to UO 3 powder at about 320degC. These equipments are therefore required to grasp the degree of the progress of corrosion to handle high-temperature and high-concentration uranyl nitrate. The evaluation of this equipment on the basis of thickness measurement confirmed only minor corrosion and indicated that the equipment would be fully adequate for future operation. (author)

  8. Observation of Radiolytic Field Alteration of the Uranyl Cation in Bicarbonate Solution

    Energy Technology Data Exchange (ETDEWEB)

    Snow, Lanee A.; McNamara, Bruce K.; Sinkov, Sergey I.; Cho, Herman M.; Friese, Judah I.

    2006-12-01

    In previous work we demonstrated that radiolysis of uranyl tris carbonate in near neutral pH to alkaline carbonate solutions, could be followed by 13C NMR. Radiolysis of the complex produced novel uranyl peroxo carbonate solution state species, whose structures depended on the pH and radiolytic dose rate. In this work, we investigate speciation of the uranyl carbonate trimer which is predominant in bicarbonate solution near pH 5.9. We observe radiolytically derived speciation to different mixed peroxy carbonate species than seen in the higher pH solutions. Auto radiolysis of uranium (VI) carbonate solutions between pH 5.9 and 7.2 is shown to alter the uranium speciation over relatively short periods of time and was followed by 13C NMR and visible spectrophotometry, using dissolved 233(UO2)3(CO3)6 6- both as the radiolysis source (D= 14.9 Gy/hr) and as a trap for the newly formed hydrogen peroxide. Direct addition of hydrogen peroxide to solutions of the uranyl-carbonate trimer is shown to reproduce the 13 C NMR signatures of the complexe(s) formed by radiolysis, but additionally a variety of new complexes are revealed. Ratios of H2O2/trimer < 1.5 produced a uranyl peroxo carbonate adduct, that is shown to be common to the radiolytically produced species. Ratios of H2O2/ trimer >1 resulted in formation of stable higher order peroxo carbonate complexes. The 13C NMR signatures and visible spectra of these complexes are described here. Rigorous characterization of the species is an ongoing effort.

  9. Liquid-liquid extraction kinetics of uranyl nitrate and actinides (III)-lanthanides nitrates by extractants with amide function; Cinetique d`extraction liquide-liquide du nitrate d`uranyle et des nitrates d`actinides (III) et de lanthanides (III) par des extractants a fonction amide

    Energy Technology Data Exchange (ETDEWEB)

    Toulemonde, V.

    1995-12-20

    Nowadays, the most important part of electric power is generated by fission energy. But spent fuels have then to be reprocessed. The production of these reprocessed materials separately and with a high purity level is done according to a liquid-liquid extraction process (Purex process) with the use of tributyl phosphate as solvent. Optimization studies concerning the extracting agent have been undertaken. This work gives the results obtained for the uranyl nitrate and the actinides (III)-lanthanides (III) nitrates extraction by extractants with amide function (monoamide for U(VI) and diamide for actinides (III) and lanthanides (III)). The extraction kinetics have been studied in the case of a metallic specie transfer from the aqueous phase towards the organic phase. The experiments show that the nitrates extraction kinetics is limited by the complexation chemical reaction of the species at the interface between the two liquids. An adsorption-desorption interfacial reactional mechanism (Langmuir theory) is proposed for the uranyl nitrate. (O.M.). 89 refs.

  10. Cytotoxicity of Nanoliposomal Cisplatin Coated with Synthesized ...

    African Journals Online (AJOL)

    Methods: Synthesized methoxypolyethylene glycol (mPEG) propionaldehyde was characterized by 1H- nuclear magnetic resonance (1H-NMR) and Fourier transform infrared spectroscopy (FTIR) and used as coating agent for the preparation of liposomal nanodrug formulation by reverse phase evaporation method.

  11. Reactive transport of uranyl: fixation mode on silica and goethite; experiments in columns and closed reactors; simulations

    International Nuclear Information System (INIS)

    Gabriel, U.

    1998-01-01

    Uranium contaminated areas are found in mine waste disposal sites, former military areas, etc. The present study focuses on the identification or mechanisms which may lead contaminated soils to become a sudden potential threat to surface and ground waters. Mechanisms were studied on model material at two levels. On the molecular scale, the complexation of uranyl at trace metal concentrations was investigated with amorphous silica. Complexation is shown to occur via the formation of surface complexes, characterised by different time-resolved laser-induced luminescence spectra and life times and stoichiometry. On the macro-scale the transport behaviour of uranyl in a cristobalite-goethite-carbonate-uranyl system was investigated with laboratory column and batch experiments. Uranium mobility was found to be controlled by the interaction between physical transport and a reversible, rate-controlled, fixation reaction. Sorption was shown to be an ensemble of competing solution and surface complexation reactions, leading to an apparent non-linear (Langmuir-like) adsorption isotherm. Finally the impact of a sudden change in background geochemistry was studied. Conditions leading to a dramatic mobilization of uranium from mildly contaminated systems were experimentally identified. Maximal uranyl concentration are controlled by the total extractable uranyl in the system and limited by uranyl solubility. Evolution of the background geochemical conditions is thus an important part of contaminated sites risk assessment. (author)

  12. Isolation of a star-shaped uranium(V/VI) cluster from the anaerobic photochemical reduction of uranyl(VI)

    International Nuclear Information System (INIS)

    Chatelain, Lucile; White, Sarah; Scopelliti, Rosario; Mazzanti, Marinella

    2016-01-01

    Actinide oxo clusters are an important class of compounds due to their impact on actinide migration in the environment. The photolytic reduction of uranyl(VI) has potential application in catalysis and spent nuclear fuel reprocessing, but the intermediate species involved in this reduction have not yet been elucidated. Here we show that the photolysis of partially hydrated uranyl(VI) in anaerobic conditions leads to the reduction of uranyl(VI), and to the incorporation of the resulting U V species into the stable mixed-valent star-shaped U VI /U V oxo cluster [U(UO 2 ) 5 (μ 3 -O) 5 (PhCOO) 5 (Py) 7 ]. This cluster is only the second example of a U VI /U V cluster and the first one associating uranyl groups to a non-uranyl(V) center. The U V center in 1 is stable, while the reaction of uranyl(V) iodide with potassium benzoate leads to immediate disproportionation and formation of the U 12 IV U 4 V O 24 cluster {[K(Py) 2 ] 2 [K(Py)] 2 [U 16 O 24 (PhCOO) 24 (Py) 2 ]}.

  13. Production of U3O8 by uranyl formate precipitation and calcination in a full-scale pilot facility

    International Nuclear Information System (INIS)

    Kendrick, L.S.; Wilson, W.A.; Mosley, W.C.

    1984-08-01

    The uranyl formate process for the production of U 3 O 8 with a controlled particle size has been extensively studied on a laboratory scale. Based on this study, a pilot-scale facility (the Uranyl Formate Facility) was built to investigate the key steps of the process on a larger scale. These steps were the precipitation of a uranyl formate monohydrate salt and the calcination of this salt to U 3 O 8 . Tests of the facility and process were conducted at conditions recommended by the laboratory-scale studies for a full-scale production facility. These tests demonstrated that U 3 O 8 of the required particle size for the PM process can be produced on a plant scale by the calcination of uranyl formate crystals. The performance of the U 3 O 8 produced by the uranyl formate process in fuel tube fabrication was also investigated. Small-scale extrusion tests of U 3 O 8 -Al cores which used the U 3 O 8 produced in the Uranyl Formate Facility were conducted. These tests demonstrated that the U 3 O 8 quality was satisfactory for the PM process

  14. Determination of the stability of the uranyl ion sipped in τ-hydrogen phosphate of zirconium in sodic form

    International Nuclear Information System (INIS)

    Ordonez R, E.; Fernandez V, S.M.; Drot, R.; Simoni, E.

    2005-01-01

    The stability of the uranyl sipped in the zirconium τ-hydrogen phosphate in sodic form (τ-NaZrP), was carried out characterizing the complexes formed by Laser spectroscopy in the visible region and by X-ray photoelectron spectroscopy. The material was prepared by a new synthesis technique working in nitrogen atmosphere and to low temperatures. The sorption of the uranyl ion was made in acid media with concentrations of 10 -4 and 10 -5 of uranyl nitrate and with ion forces of 0.1 and 0.5 M of NaClO 4 . The spectra of induced fluorescence with laser (TRLFS) show that the uranyl is fixed in very acid media in three well differentiated species, to pH less acid, the specie of long half life disappears and are only those of short half life. The results of the binding energy obtained by XPS indicate that the binding energy of the uranyl confer it a stable character to the complex formed in the τ-NaZP, that makes to this material appropriate to retain to the uranyl in solution to high ion forces and in acid media. (Author)

  15. Isolation of a star-shaped uranium(V/VI) cluster from the anaerobic photochemical reduction of uranyl(VI)

    Energy Technology Data Exchange (ETDEWEB)

    Chatelain, Lucile; White, Sarah; Scopelliti, Rosario; Mazzanti, Marinella [Ecole Polytechnique Federale de Lausanne (EPFL) (Switzerland). Inst. de Sciences et Ingenierie Chimiques

    2016-11-07

    Actinide oxo clusters are an important class of compounds due to their impact on actinide migration in the environment. The photolytic reduction of uranyl(VI) has potential application in catalysis and spent nuclear fuel reprocessing, but the intermediate species involved in this reduction have not yet been elucidated. Here we show that the photolysis of partially hydrated uranyl(VI) in anaerobic conditions leads to the reduction of uranyl(VI), and to the incorporation of the resulting U{sup V} species into the stable mixed-valent star-shaped U{sup VI}/U{sup V} oxo cluster [U(UO{sub 2}){sub 5}(μ{sub 3}-O){sub 5}(PhCOO){sub 5}(Py){sub 7}]. This cluster is only the second example of a U{sup VI}/U{sup V} cluster and the first one associating uranyl groups to a non-uranyl(V) center. The U{sup V} center in 1 is stable, while the reaction of uranyl(V) iodide with potassium benzoate leads to immediate disproportionation and formation of the U{sub 12}{sup IV}U{sub 4}{sup V}O{sub 24} cluster {[K(Py)_2]_2[K(Py)]_2[U_1_6O_2_4(PhCOO)_2_4(Py)_2]}.

  16. Explaining Synthesized Software

    Science.gov (United States)

    VanBaalen, Jeffrey; Robinson, Peter; Lowry, Michael; Pressburger, Thomas; Lau, Sonie (Technical Monitor)

    1998-01-01

    Motivated by NASA's need for high-assurance software, NASA Ames' Amphion project has developed a generic program generation system based on deductive synthesis. Amphion has a number of advantages, such as the ability to develop a new synthesis system simply by writing a declarative domain theory. However, as a practical matter, the validation of the domain theory for such a system is problematic because the link between generated programs and the domain theory is complex. As a result, when generated programs do not behave as expected, it is difficult to isolate the cause, whether it be an incorrect problem specification or an error in the domain theory. This paper describes a tool we are developing that provides formal traceability between specifications and generated code for deductive synthesis systems. It is based on extensive instrumentation of the refutation-based theorem prover used to synthesize programs. It takes augmented proof structures and abstracts them to provide explanations of the relation between a specification, a domain theory, and synthesized code. In generating these explanations, the tool exploits the structure of Amphion domain theories, so the end user is not confronted with the intricacies of raw proof traces. This tool is crucial for the validation of domain theories as well as being important in everyday use of the code synthesis system. It plays an important role in validation because when generated programs exhibit incorrect behavior, it provides the links that can be traced to identify errors in specifications or domain theory. It plays an important role in the everyday use of the synthesis system by explaining to users what parts of a specification or of the domain theory contribute to what pieces of a generated program. Comments are inserted into the synthesized code that document these explanations.

  17. Thermodynamic study of uranyl sorption onto lanthanum monophosphate (LaPO4) and magnetite (Fe3O4)

    International Nuclear Information System (INIS)

    Felix, Olivia

    2012-01-01

    The migration of radio-toxic elements in the geosphere is mainly regulated by chemical parameters which control the partitioning of the elements between mineral phases and aqueous solutions. Variation in temperature may affect the retention properties of a mineral surface and requires a careful investigation in order to understand the radionuclides behavior in the geosphere. In this way, the interaction mechanisms between uranium(VI) and two minerals (LaPO 4 and Fe 3 O 4 ) have been studied. In a first step, the monazite (LaPO 4 ) has been chosen as methodological solid in order to clearly define all the different stages needed to completely characterize the influence of temperature on the sorption phenomena. To reach that goal, three media, more or less complexants towards aqueous uranyl and the mineral surface, have been considered. Physico-chemical as well as surface acid-base properties of the solid surface have been studied by considering three electrolytes (NaClO 4 , NaNO 3 and Na 2 SO 4 ) and temperatures ranged from 25 C to 95 C. The point of zero charge has been found to be identical for perchlorate and nitrate media (pH PZC =2.1) but it was found to be one pK unit higher for the sulfate medium indicating a sorption of the background electrolyte ions. The reaction heats associated to the hydration of the solid have been measured by using microcalorimetry and the nature of the reactive surface sites has been determined by carrying out Time-Resolved Laser-Induced Fluorescence Spectroscopy (TRLFS). On the basis of these experimental constraints, the titration curves obtained for the monazite suspensions were fitted by using the Constant Capacitance Model and the 1-pK model was preferred to characterize the surface charge evolution, due to the limited number of adjustable parameters. The surface protonation constants being determined, the behavior of U(VI) towards the monazite surface in the three electrolytes has been investigated. On the basis of both U

  18. Uranyl complexes as scaffolding or spacers for cucurbit[6]uril molecules in homo- and heterometallic species, including a uranyl-lanthanide complex

    Energy Technology Data Exchange (ETDEWEB)

    Thuery, Pierre [NIMBE, CEA, CNRS, Universite Paris-Saclay, CEA Saclay, Gif-sur-Yvette (France)

    2017-06-16

    The reaction of uranyl nitrate with cucurbit[6]uril (CB6) and carboxylic or sulfonic ligands under hydrothermal conditions and in the presence of additional metal cations (K{sup I} or Ce{sup III}) or cosolvents provided four complexes, which were crystallographically characterized. The compound [(UO{sub 2}){sub 2}K{sub 2}(CB6)(adc){sub 2}(NO{sub 3}){sub 2}(H{sub 2}O){sub 2}].5H{sub 2}O (1), where H{sub 2}adc is 1,3-adamantanedicarboxylic acid, crystallizes in the form of a central K{sub 2}(CB6){sup 2+} column surrounded by two one-dimensional (1D) polymeric UO{sub 2}(adc)(NO{sub 3}){sup -} chains attached to the column by nitrate bridges, with a perfect match of the repeat lengths in the two subunits. The longer 1,3-adamantanediacetic acid (H{sub 2}adac) gives the complex [(UO{sub 2}){sub 2}(adac){sub 2}(HCOOH){sub 2}].CB6.6H{sub 2}O (2), in which the 1D uranyl-containing polymer and columns of CB6 molecules form a layered arrangement held by weak CH..O hydrogen bonds. The complex formed with the dipotassium salt of methanedisulfonic acid (K{sub 2}mds), [(UO{sub 2}){sub 2}K{sub 2}(CB6)(mds){sub 2}(OH){sub 2}(H{sub 2}O){sub 8}].4H{sub 2}O (3), is a 1D polymer, in which K{sub 2}(CB6){sup 2+} units are connected to one another by doubly hydroxide-bridged uranyl dimers in which the disulfonates are terminal, chelating ligands; connection between the two subunits is solely through potassium oxo-bonding to uranyl. The complex [(UO{sub 2}){sub 2}Ce{sub 2}(CB6)(C{sub 2}O{sub 4}){sub 3}(NO{sub 3}){sub 4}(H{sub 2}O){sub 6}].2H{sub 2}O (4) is a 1D polymer containing bridging oxalate ligands formed in situ, in which CB6 is coordinated to the lanthanide cations only; one nitrate ligand and one water ligand, hydrogen-bonded to each other, are included in the CB6 cavity, with the possible occurrence of interactions between nitrate oxygen atoms and ureido carbon atoms. (copyright 2017 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  19. Interaction of uranyl ions with snake venom proteins from Lachesis muta muta

    International Nuclear Information System (INIS)

    MacCordick, H.J.; Taghva, F.

    1997-01-01

    The reaction product of uranyl nitrate with whole-protein Bushmaster snake venom in nitrate buffer at pH 3.5 has been studied. The maximum uptake of uranium was 291 μmol U x g -1 of venom. The infrared spectrum of the product showed an asymmetric O-U-O vibration at 921 cm -1 typical of complex formation with the uranyl ion. Stability measurements with the UO 2 2+ -protein complex in neutral medium indicated moderate hydrolytic stability, with 14% dissociation after 16 hours at 0 deg C. Neutron irradiation and desorption studies with a 235 U-labelled complex showed that generated fission products such as lanthanides and barium were readily lixiviated at pH 7, whereas Ru and Zr were highly retained by the protein substrate. (author)

  20. Thermometric titration of a free acid and of uranyl in spent fuel element solutions

    International Nuclear Information System (INIS)

    Zamek, M.; Strafelda, F.

    1975-01-01

    A method was elaborated of determining nitric acid in the presence of uranyl nitrate in both aqueous and non-aqueous solutions using a pyridine aqueous solution as a titration agent, and of determining excess uranyl after a hydrogen peroxide addition by a further titration using the same agent. Even a hundred-fold excess of magnesium did not disturb the titration. The method is used in operating solution analyses in the extraction fuel reprocessing in the presence of a small amount of plutonium and of fission products. The reproducibility and accuracy of the method varied in the order of tens to units per cent depending on the concentration of components to be determined. The procedure is applicable for test volumes ranging between 0.1 and 10 ml in concentrations of 1 to 10 -3 M. (author)

  1. Biosensing for the Environment and Defence: Aqueous Uranyl Detection Using Bacterial Surface Layer Proteins

    Directory of Open Access Journals (Sweden)

    David J.R. Conroy

    2010-05-01

    Full Text Available The fabrication of novel uranyl (UO22+ binding protein based sensors is reported. The new biosensor responds to picomolar levels of aqueous uranyl ions within minutes using Lysinibacillus sphaericus JG-A12 S-layer protein tethered to gold electrodes. In comparison to traditional self assembled monolayer based biosensors the porous bioconjugated layer gave greater stability, longer electrode life span and a denser protein layer. Biosensors responded specifically to UO22+ ions and showed minor interference from Ni2+, Cs+, Cd2+ and Co2+. Chemical modification of JG-A12 protein phosphate and carboxyl groups prevented UO22+ binding, showing that both moieties are involved in the recognition to UO22+.

  2. Determination of small amounts of nitric acid in the presence of large amounts of uranium (VI) and extraction of nitric acid into TBP solutions highly loaded with uranyl nitrate

    International Nuclear Information System (INIS)

    Kolarik, Z.; Schuler, R.

    1982-10-01

    A new method for the determination of small amounts of nitric acid in the presence of large amounts of uranium(VI) was elaborated. The method is based on the precipitation of uranium(VI) as iodate and subsequent alkalimetric titration of the acid in the supernatant. The extraction of nitric acid and uranium(VI) with 30% TBP in dodecane was studied at high loading of the organic phase with uranyl nitrate and at 25, 40 and 60 0 C. The results are compared with available published data on the extraction of nitric acid under similar conditions. (orig.) [de

  3. Removal of toxic uranium from synthetic nuclear power reactor effluents using uranyl ion imprinted polymer particles.

    Science.gov (United States)

    Preetha, Chandrika Ravindran; Gladis, Joseph Mary; Rao, Talasila Prasada; Venkateswaran, Gopala

    2006-05-01

    Major quantities of uranium find use as nuclear fuel in nuclear power reactors. In view of the extreme toxicity of uranium and consequent stringent limits fixed by WHO and various national governments, it is essential to remove uranium from nuclear power reactor effluents before discharge into environment. Ion imprinted polymer (IIP) materials have traditionally been used for the recovery of uranium from dilute aqueous solutions prior to detection or from seawater. We now describe the use of IIP materials for selective removal of uranium from a typical synthetic nuclear power reactor effluent. The IIP materials were prepared for uranyl ion (imprint ion) by forming binary salicylaldoxime (SALO) or 4-vinylpyridine (VP) or ternary SALO-VP complexes in 2-methoxyethanol (porogen) and copolymerizing in the presence of styrene (monomer), divinylbenzene (cross-linking monomer), and 2,2'-azobisisobutyronitrile (initiator). The resulting materials were then ground and sieved to obtain unleached polymer particles. Leached IIP particles were obtained by leaching the imprint ions with 6.0 M HCl. Control polymer particles were also prepared analogously without the imprint ion. The IIP particles obtained with ternary complex alone gave quantitative removal of uranyl ion in the pH range 3.5-5.0 with as low as 0.08 g. The retention capacity of uranyl IIP particles was found to be 98.50 mg/g of polymer. The present study successfully demonstrates the feasibility of removing uranyl ions selectively in the range 5 microg - 300 mg present in 500 mL of synthetic nuclear power reactor effluent containing a host of other inorganic species.

  4. A bibliographical review on the radiolysis of uranyl nitrate solutions in nitric acid medium

    International Nuclear Information System (INIS)

    Siri, Sandra; Mondino, Angel V.

    2004-01-01

    A bibliographical study on the effects of ionizing radiation on uranyl nitrate solutions in nitric acid medium was performed, and the state of knowledge on this subject is presented. The main experimental and theoretical results on water, nitric acid and uranium solutions radiolysis are reviewed and critically evaluated. This paper provides a collection of references as an aid to the development of practical applications, and to stimulate new research on fundamental processes in these systems. (author) [es

  5. Synthesis, X-ray crystallography, spectroscopy, electrochemistry, thermal and kinetic study of uranyl Schiff base complexes

    Czech Academy of Sciences Publication Activity Database

    Asadi, Z.; Golzard, F.; Eigner, Václav; Dušek, Michal

    2013-01-01

    Roč. 66, č. 20 (2013), s. 3629-3646 ISSN 0095-8972 R&D Projects: GA ČR(CZ) GAP204/11/0809 Institutional support: RVO:68378271 Keywords : X-ray crystallography * uranyl Schiff base complex * kinetics of thermal decomposition * cyclic voltammetry * kinetics and mechanism Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 2.224, year: 2013

  6. Crystal structure of the (REE)–uranyl carbonate mineral shabaite-(Nd)

    Czech Academy of Sciences Publication Activity Database

    Plášil, Jakub; Škoda, R.

    2017-01-01

    Roč. 62, č. 2 (2017), s. 97-105 ISSN 1802-6222 R&D Projects: GA MŠk LO1603 EU Projects: European Commission(XE) CZ.2.16/3.1.00/24510 Institutional support: RVO:68378271 Keywords : shabaite-(Nd) * uranyl carbonate * rare -earth elements * crystal structure * mineral evolution Subject RIV: DB - Geology ; Mineralogy OBOR OECD: Geology Impact factor: 0.609, year: 2016

  7. Novel two-dimensional uranyl-organic assemblages in the citrate and D(-)-citramalate families

    International Nuclear Information System (INIS)

    Thuery, P.

    2008-01-01

    Uranyl nitrate reacts with D(-)-citramalic acid (H(3)citml) under mild hydrothermal conditions to give the two-dimensional polymer [UO 2 (Hcitml)] 1, in which each ligand chelates one metal atom through its hydroxyl and alpha- carboxylate groups and binds to three others in monodentate fashion. The resulting neutral layers display isolated uranyl pentagonal bipyramidal polyhedra. Whereas citric acid (H(4)cit) has been shown previously to give various three- and mono-dimensional uranyl organic assemblages, complexation under hydrothermal conditions in the presence of either NaOH/NEt 4 Cl or pyridine yields the complexes [NEt 4 ] 2 [(UO 2 ) 3 (cit) 2 (H 2 O) 2 ]· 2H 2 O 2 and [Hpy] 2 )[(UO 2 ) 3 (cit)(Hcit)(OH)] 3, respectively, which both crystallize as two- dimensional frameworks. The layers are either planar and separated by the counter ions in 2 or corrugated and hydrogen bonded to one another in 3. In both 2 and 3, [UO 2 (cit)] 2 4- dimeric subunits with edge-sharing pentagonal bipyramidal uranium coordination polyhedra are present but, in both cases and in contrast with previous structures containing [UO 2 (Hcit)] 2 2- dimers, the carboxylate group not involved in the dimer formation is coordinated to another uranyl unit, which is part of either a centrosymmetric hexagonal bipyramidal bis-aquated group or a different, [(UO 2 ) 2 (Hcit)(OH)] dimer. These examples of two- dimensional assemblages further illustrate the variety of architectures which can be obtained with citric and related acids and the important structure-directing effects of the counter ions. (author)

  8. Stability and kinetics of uranyl ion complexation by macrocycles in propylene carbonate

    International Nuclear Information System (INIS)

    Fux, P.

    1984-06-01

    A thermodynamic study of uranyl ion complexes formation with different macrocyclic ligands was realized in propylene carbonate as solvent using spectrophotometric and potentiometric techniques. Formation kinetics of two UO 2 complexes: a crown ether (18C6) and a coronand (22) was studied by spectrophotometry in propylene carbonate with addition of tetraethylammonium chlorate 0.1M at 25 0 C. Possible structures of complexes in solution are discussed [fr

  9. Crystal structure of the (REE)-uranyl carbonate mineral kamotoite-(Y)

    Czech Academy of Sciences Publication Activity Database

    Plášil, Jakub; Petříček, Václav

    2017-01-01

    Roč. 81, č. 3 (2017), s. 653-660 ISSN 0026-461X R&D Projects: GA MŠk LO1603 EU Projects: European Commission(XE) CZ.2.16/3.1.00/24510 Institutional support: RVO:68378271 Keywords : kamotoite-(Y) * uranyl carbonate * rare-earth elements * crystal structure Subject RIV: DB - Geology ; Mineralogy OBOR OECD: Geology Impact factor: 1.285, year: 2016

  10. Selectivity in Ligand Binding to Uranyl Compounds: A Synthetic, Structural, Thermodynamic and Computational Study

    Energy Technology Data Exchange (ETDEWEB)

    Arnold, John [Univ. of California, Berkeley, CA (United States)

    2017-12-06

    The uranyl cation (UO22+) is the most abundant form of uranium on the planet. It is estimated that 4.5 billion tons of uranium in this form exist in sea water. The ability to bind and extract the uranyl cation from aqueous solution while separating it from other elements would provide a limitless source of nuclear fuel. A large body of research concerns the selective recognition and extraction of uranyl. A stable molecule, the cation has a linear O=U=O geometry. The short U-O bonds (1.78 Å) arise from the combination of uranium 5f/6d and oxygen 2p orbitals. Due to the oxygen moieties being multiply bonded, these sites were not thought to be basic enough for Lewis acidic coordination to be a viable approach to sequestration. We believe that the goal of developing a practical system for uranium separation from seawater will not be attained without new insights into our existing fundamental knowledge of actinide chemistry. We posit that detailed studies of the kinetic and thermodynamic factors that influence interactions between f-elements and ligands with a range of donor atoms is essential to any major advance in this important area. The goal of this research is thus to broaden the coordination chemistry of the uranyl ion by studying new ligand systems via synthetic, structural, thermodynamic and computational methods. We anticipate that this fundamental science will find use beyond actinide separation technologies in areas such as nuclear waste remediation and nuclear materials.

  11. Spectrophotometric investigation of uranyl interaction with orthosilicic acid and polymeric silicon acids in aqueous solutions

    International Nuclear Information System (INIS)

    Yusov, A.B.; Fedoseev, A.M.

    2005-01-01

    Interaction of uranyl ion with orthosilicic acid and polymeric silicic acids is investigated using spectrophotometry. Equilibrium constant of UO 2 2+ + Si(OH) 4 = UO 2 OSi(OH) 3 + + H + reaction is lg K=-2.56±0.09 in solutions with ionic strength I=0.1-0.2. Stability constant of UO 2 OSi(OH) 3 + complex is determined [ru

  12. Engaging the Terminal: Promoting Halogen Bonding Interactions with Uranyl Oxo Atoms.

    Science.gov (United States)

    Carter, Korey P; Kalaj, Mark; Surbella, Robert G; Ducati, Lucas C; Autschbach, Jochen; Cahill, Christopher L

    2017-11-02

    Engaging the nominally terminal oxo atoms of the linear uranyl (UO 2 2+ ) cation in non-covalent interactions represents both a significant challenge and opportunity within the field of actinide hybrid materials. An approach has been developed for promoting oxo atom participation in a range of non-covalent interactions, through judicious choice of electron donating equatorial ligands and appropriately polarizable halogen-donor atoms. As such, a family of uranyl hybrid materials was generated based on a combination of 2,5-dihalobenzoic acid and aromatic, chelating N-donor ligands. Delineation of criteria for oxo participation in halogen bonding interactions has been achieved by preparing materials containing 2,5-dichloro- (25diClBA) and 2,5-dibromobenzoic acid (25diBrBA) coupled with 2,2'-bipyridine (bipy) (1 and 2), 1,10-phenanthroline (phen) (3-5), 2,2':6',2''-terpyridine (terpy) (6-8), or 4'-chloro-2,2':6',2''-terpyridine (Cl-terpy) (9-10), which have been characterized through single crystal X-ray diffraction, Raman, Infrared (IR), and luminescence spectroscopy, as well as through density functional calculations of electrostatic potentials. Looking comprehensively, these results are compared with recently published analogues featuring 2,5-diiodobenzoic acid which indicate that although inclusion of a capping ligand in the uranyl first coordination sphere is important, it is the polarizability of the selected halogen atom that ultimately drives halogen bonding interactions with the uranyl oxo atoms. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  13. Method for synthesizing HMX

    Science.gov (United States)

    McGuire, Raymond R.; Coon, Clifford L.; Harrar, Jackson E.; Pearson, Richard K.

    1984-01-01

    A method and apparatus for electrochemically synthesizing N.sub.2 O.sub.5 cludes oxidizing a solution of N.sub.2 O.sub.4 /HNO.sub.3 at an anode, while maintaining a controlled potential between the N.sub.2 O.sub.4 /HNO.sub.3 solution and the anode. A potential of about 1.35 to 2.0 V vs. SCE is preferred, while a potential of about 1.80 V vs. SCE is most preferred. Thereafter, the N.sub.2 O.sub.5 is reacted with either 1.5-diacetyl-3,7-dinitro-1,3,5,7-tetraazacyclooctane (DADN) or 1,3,5,7-tetraacetyl-1,3,5,7-tetraazacyclooctane (TAT) to form cyclotetramethylenetetraamine (HMX).

  14. A relativistic density functional study of uranyl hydrolysis and complexation by carboxylic acids in aqueous solution

    Energy Technology Data Exchange (ETDEWEB)

    Ray, Rupashree Shyama

    2009-02-10

    In this work, the complexation of uranium in its most stable oxidation state VI in aqueous solution was studied computationally, within the framework of density functional (DF) theory. The thesis is divided into the following parts: Chapter 2 briefly summarizes the relevant general aspects of actinide chemistry and then focuses on actinide environmental chemistry. Experimental results on hydrolysis, actinide complexation by carboxylic acids, and humic substances are presented to establish a background for the subsequent discussion. Chapter 3 describes the computational method used in this work and the relevant features of the parallel quantum chemistry code PARAGAUSS employed. First, the most relevant basics of the applied density functional approach are presented focusing on relativistic effects. Then, the treatment of solvent effects, essential for an adequate modeling of actinide species in aqueous solution, will be introduced. At the end of this chapter, computational parameters and procedures will be summarized. Chapter 4 presents the computational results including a comparison to available experimental data. In the beginning, the mononuclear hydrolysis product of UO{sub 2}{sup 2+}, [UO{sub 2}OH]{sup +}, will be discussed. The second part deals with actinide complexation by carboxylate ligands. First of all the coordination number for uranylacetate will be discussed with respect to implications for the complexation of actinides by humic substances followed by the uranyl complexation of aromatic carboxylic acids in comparison to earlier results for aliphatic ones. In the end, the ternary uranyl-hydroxo-acetate are discussed, as models of uranyl humate complexation at ambient condition.

  15. Renal hemodynamics in uranyl acetate-induced acute renal failure of rabbits

    International Nuclear Information System (INIS)

    Sudo, M.; Honda, N.; Hishida, A.; Nagase, M.

    1977-01-01

    The role of renal hemodynamic alterations in the curtailment of renal function was studied in rabbits with uranyl acetate-induced acute renal failure. The day following the i.v. injection of uranyl acetate (2 mg/kg of body wt), renal blood flow (RBF) and clearance of creatinine (Ccr) decreased to approximately 60 and 20% of controls, respectively. Intracortical fractional flow distribution, estimated by radioactive microsphere method, did not change. The extraction ratio of para-aminohippurate (EPAH) decreased and the renal extraction of sodium (CNa/Ccr) increased, with minimal structural change in the kidney. Urine output increased two to three times that of the control. After three days oliguria appeared despite complete recovery of RBF. The zonal flow redistributed toward the deep cortex. CCr and EPAH reached their minimums, concomitantly with tubular necrosis and intratubular casts. After seven days animals could be divided into the oliguric and diuretic groups. CCr and EPAH were higher in the diuretic group, while there was no significant difference in RBF and the flow distribution between groups. Regeneration of damaged tubular cells was found in the diuretic group but not in the oliguric group. The findings suggest the minor roles of RBF and the intracortical flow distribution, and a fundamental role of back leakage of filtrate across damaged tubular epithelium in the maintenance of reduced CCR and urine output during the oliguric stage in rabbits with uranyl acetate-induced renal failure

  16. Complexes of vanadyl and uranyl ions with the chelating groups of humic matter

    International Nuclear Information System (INIS)

    Goncalves, M.L.S.; Mota, A.M.

    1987-01-01

    The uranyl and vanadyl complexes formed with salicylic, phthalic and 3,4-dihydroxybenzoic acids have been studied by potentiometry in order to determine the stability constants of the Msub(m) Lsub(n) species formed in solution, and the constants for hydrolysis and polymeric complexes, at 25.0 0 , in 0.10, 0.40 and 0.70M sodium perchlorate. MINIQUAD was used in process the data to find the best models for the species in solution, and calculate the formation constants. The uranyl-salicylic acid sytem was also studied by spectrophotometry and the program SQUAD used to process the data obtained. The best models for these systems show that co-ordination of the uranyl ion by carboxylate groups is easier than for the vanadyl ion, whereas the vanadyl ion seems to form more stable complexes with phenolate groups. Both oxo-cations seem to tend to hydrolyse rather than form complexes when the L:M ratios are greater than unity. Although the change in the constants with ionic strength is small, the activity coefficients of the salicylate and phthalate species have been calculated at ionic strengths 0.40 and 0.70M, along with the interaction parameters with Na + , from the stability constants found for the species ML and H 2 L, according to the Bronsted-Guggenheim expression. (author)

  17. On synergistic effects in uranyl sulfate extraction by mixtures of organophosphoric acids with oil sulfoxides

    International Nuclear Information System (INIS)

    Torgov, V.G.; Us, T.V.

    1987-01-01

    Extraction properties of mixtures of organophosphoric acids (HX) of different compositions (di-2-ethylhexyldithiophosphoric (D2EHDTPA), di-2-ethylhexylphosphoric (D2EHPA), amyl-2-ethylhexylphosphonic (A2EHPA) and diheptylphosphinic (DHPA)) with oil sulfoxides (B) with respect to uranyl sulfate in an iodide range of its concentrations were compared. The presence of cation-exchange (at low HX saturations) and noncation-exchange (after HX saturations) synergistic effects was established. Their nature is the same one and is related with urabium atom acceptor ability in acid and neutral uranyl salts to add B and UO 2 SO 4 xB respectively. HX are arranged in the following series with respect to synergistic effect: D2EHDTPA > D2EHPA > A2EHPA > DHPA. The series is opposite to the stability series of intracomplexes (IC) of HX with uranyl. A quantitative description of the process of UO 2 SO 4 xB addition to IC was given and corresponding extraction constants were determined

  18. Mechanistic study of the interaction of uranyl ions with zirconium oxide and zirconium silicate

    International Nuclear Information System (INIS)

    Lomenech, C.

    2002-04-01

    This work deals with structural and thermodynamic studies of the sorption of uranyl species on zircon and zirconia. After determination of the specific areas, of the pH of the isoelectric points, and of the sorption site numbers, thermodynamic data were obtained using alpha spectrometry, for different uranyl concentrations, different background electrolytes (NaClO 4 or KNO 3 ) and different ionic strengths. The structural identification of the surface complexes and sorption sites was carried out using several spectroscopies: XPS spectroscopy allowed a determination of the nature of the sorption sites (≡Zr-O- on zirconia and ≡Si-O- on zircon). Whereas fluorescence decay measurements gave the number of surface species, the combined use of XPS spectroscopy and laser spectro-fluorimetry enabled us to correlate differences in bonding energies and emission wavelengths with differences in the nature of the background electrolyte or in the pH of sorption; DRIFT spectroscopy was a powerful tool for the determination of the presence of sorbed uranyl nitrate species. EXAFS results clearly showed a splitting of the equatorial oxygen atoms in two shells, corresponding to a polydentate, inner-sphere complex. EXAFS results also indicated strong similarities between dry samples and in situ experiments, which confirms the validity of all the spectroscopic measurements. Macroscopic thermodynamic data were then modeled using a surface complexation model (2 pK and constant capacitance models), the results of the structural study being used as constraints for the simulation code FITEQL. (author)

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

    International Nuclear Information System (INIS)

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

    2012-01-01

    Uranium compounds are widely used in the nuclear fuel cycle, military and many other diverse industrial processes. Health risks associated with uranium exposure include nephrotoxicity, cancer, respiratory, and immune disorders. Macrophages present in body tissues are the main cell type involved in the internalization of uranium particles. To better understand the pathological effects associated with depleted uranium (DU) inhalation, we examined the metabolic activity, phagocytosis, genotoxicity and inflammation on DU-exposed rat alveolar macrophages (12.5–200 μM). Stability and dissolution of DU could differ depending on the dissolvent and in turn alter its biological action. We dissolved DU in sodium bicarbonate (NaHCO 3 100 mM) and in what we consider a more physiological vehicle resembling human internal media: sodium chloride (NaCl 0.9%). We demonstrate that uranyl nitrate in NaCl solubilizes, enters the cell, and elicits its cytotoxic effect similarly to when it is diluted in NaHCO 3 . We show that irrespective of the dissolvent employed, uranyl nitrate impairs cell metabolism, and at low doses induces both phagocytosis and generation of superoxide anion (O 2 − ). At high doses it provokes the secretion of TNFα and through all the range of doses tested, apoptosis. We herein suggest that at DU low doses O 2 − may act as the principal mediator of DNA damage while at higher doses the signaling pathway mediated by O 2 − may be blocked, prevailing damage to DNA by the TNFα route. The study of macrophage functions after uranyl nitrate treatment could provide insights into the pathophysiology of uranium‐related diseases. -- Highlights: ► Uranyl nitrate effect on cultured macrophages is linked to the doses and independent of its solubility. ► At low doses uranyl nitrate induces generation of superoxide anion. ► At high doses uranyl nitrate provokes secretion of TNFα. ► Uranyl nitrate induces apoptosis through all the range of doses tested.

  20. Preparative conditions and vibrational study of HUP : phase transition and conductivity mechanisms

    International Nuclear Information System (INIS)

    Thi, M.P.; Novak, A.; Colomban, Ph.

    1985-01-01

    Among solid protonic conductors HUP (H 3 OUO 2 PO 4 .3 H 2 O) exhibits very high conducting properties. Uranyl/phosphate hydrates belonging to the HUP family (HUP ; UO 2 (H 2 PO 4 ) 2 .3 H 2 O ; (U= 2 ) 3 (PO 4 ) 2 .4 H 2 O ; (UO O 2 )sub(1.43)PO 4 Hsub(0.14) 2-3.5 H 2 O) have been synthesized in different forms (crystals, powders, films, ...) and characterized by various methods: chemical analysis, DTA, TGA, SEM, X-Ray diffraction, IR and Raman spectroscopy. Morphological studies reveal the presence of various particulat es, from ultrafine powders ( 2 O washing of HUP. Infrared and Raman spectra of polycrystalline H 3 OUO 2 PO 4 .3 H 2 O (HUP) have been investigated at various temperatures between 50 K and 300 K. The most temperature-sensitive bands correspond to PO 4 and H 2 O librations; U-OPO 3 stretching and OH stretching vibrations indicate four different phases of HUP and allow to propose a phasetransition mechanism from a bidimensionnal, quasi-liquid state of a protonated species in the room-temperature phase to a fully ordered crystal below 130 K. The protonic conductivity mechanism of room- and low-temperature phases is discussed. (author)

  1. Characterization of combustion synthesized zirconia powder by UV

    Indian Academy of Sciences (India)

    . The surface acidbase properties of these samples were also investigated by indicator titration method. The catalytic activity was probed with transfer hydrogenation reaction in liquid phase. It was found that combustion synthesized zirconia did ...

  2. Spurious in PLL-DDS frequency synthesizers

    Czech Academy of Sciences Publication Activity Database

    Kroupa, Věnceslav František; Štursa, Jarmil

    2002-01-01

    Roč. 2, č. 1 (2002), s. 48-51 ISSN 1335-8243. [Digital Signal Processing and Multimedia Communications DSP-MCOM 2001 /5./. Košice, 27.11.2001-29.11.2001] R&D Projects: GA ČR GA102/00/0958 Institutional research plan: CEZ:AV0Z2067918 Keywords : frequency synthesizers * phase locked loops * direct digital synthesis Subject RIV: JA - Electronics ; Optoelectronics, Electrical Engineering

  3. Electrochemical studies on the reduction of uranyl ions in nitric acid-hydrazine media at platinum electrode

    International Nuclear Information System (INIS)

    Mishra, Satyabrata; Sini, K.; Mallika, C.; Kamachi Mudali, U.; Jagadeeswara Rao, Ch.

    2015-01-01

    Production of uranous nitrate with good conversion efficiency is one of the major steps in the aqueous reprocessing of spent fuels of nuclear reactors, as U(IV) is used for the separation of Pu from U by the selective reduction of Pu(IV) into practically non-extractable Pu(III) in aqueous streams. Electro-reduction of uranyl ions has the advantage of not introducing corrosive chemicals into the process stream. High current efficiency with maximum conversion of U(VI) to U(IV) can be achieved in continuous as well as batch mode electro-reduction, if the process is voltage-controlled rather than current controlled. As potentiostatic studies reveal the mechanism of reduction of uranyl ions in potential controlled electrolysis, the reduction behavior of uranyl ions (UO 2 2+ ) in nitric acid and nitric acid-hydrazine media were investigated by Cyclic Voltammetric (CV) and Chronopotentiometric (CP) techniques using platinum working electrode at 298 K. Heterogeneous electron transfer rate constant (ks) for uranyl reduction was estimated at a very low concentration of nitric acid (0.05 M) using Klinger and Kochi equation. Values of the diffusion coefficients were determined as a function of acidity with and without hydrazine. Reduction of uranyl ions was found to be under kinetic as well as diffusion control when the concentration of nitric acid was 0.05 M and in the absence of hydrazine. However, as the acidity of the supporting electrolyte increased, the reduction was purely under kinetic control. (author)

  4. Application of membrane LaF3 electrode in the determination of stability constants of Uranyl Fluoride complex in solution

    International Nuclear Information System (INIS)

    Muzakky; Iswani GS; Mintolo

    1996-01-01

    A membrane electrode LaF 3 has been applied in the determination of uranyl fluoride complex stability constant in solution. The determination is based on the detection of free F ion in solution as a result of hydrolysis reaction (process) of uranyl ions into the uranyl hydroxide form at low pH. The experiment results showed that there was no effect of ammonium carbonate 2 M titran, flow rate on the electrode response. The F release is optimum at pH 1. The free F ion in solution is calculated from the standard curve at pH 1, after the fluoride concentration at the same pH has been corrected. Using the plot of average number of ligand binding (n) versus minus log of free ligand (-log F) the value of β1 = 4.4, β2 = 7.48, β3=9.73, and β4 = 11.67

  5. Can Electrospray Mass Spectrometry Probe Speciation? Hydrolysis of Uranyl Nitrate Studied by Gas-Phase Methods

    Czech Academy of Sciences Publication Activity Database

    Tsierkezos, Nikos; Roithová, Jana; Schröder, Detlef; Ončák, Milan; Slavíček, Petr

    2009-01-01

    Roč. 48, č. 13 (2009), s. 6287-6296 ISSN 0020-1669 R&D Projects: GA ČR GA203/08/1487 Grant - others:GA ČR(CZ) GP203/07/P449 Institutional research plan: CEZ:AV0Z40550506; CEZ:AV0Z40400503 Keywords : collision-induced dissociation * electrodpray ionization * ion association * mass spectrometry Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 4.657, year: 2009

  6. Effect of uranyl nitrate and free acid concentration in feed solution of gelation on UO2 kernel quality

    International Nuclear Information System (INIS)

    Masduki, B.; Wardaya; Widarmoko, A.

    1996-01-01

    An investigation on the effect of uranium and free nitric acid concentration of uranyl nitrate as feed of gelation process on quality of UO 2 kernel was done.The investigation is to look for some concentration of uranyl nitrate solutions those are optimum as feed for preparation of gelled UO 3 . Uranyl nitrate solution of various concentration of uranium (450; 500; 550; 600; 650; 700 g/l) and free nitric acid of (0.9; 1.0; 1.1 N) was made into feed solutions by adding urea and HMTA with mole ratio of urea/uranium and HMTA/uranium 2.1 and 2.0. The feed solutions were changed into spherical gelled UO 3 by dropping was done to get the optimum concentrations of uranyl nitrate solutions. The gelled UO 3 was soaked and washed with 2.5% ammonia solution for 17 hours, dried at 70 o C, calcined at 350 o C for 3 hours then reduced at 850 o C for 3 hours. At every step of the steps process the colour and percentage of well product of gelled UO 3 were noticed. The density and O/U ratio of end product (UO 2 kernel) was determined, the percentage of well product of all steps process was also determined. The three factor were used to chose the optimum concentration of uranyl nitrate solution. From this investigation it was concluded that the optimum concentration of uranyl nitrate was 600 g/l uranium with free nitric acid 0,9 - 1,0 N, the percentage of well product was 97% density of 6.12 - 4.8 g/cc and O/U ratio of 2.15 - 2.06. (author)

  7. Computer simulation of uranyl uptake by the rough lipopolysaccharide membrane of Pseudomonas aeruginosa.

    Science.gov (United States)

    Lins, Roberto D; Vorpagel, Erich R; Guglielmi, Matteo; Straatsma, T P

    2008-01-01

    Heavy metal environmental contaminants cannot be destroyed but require containment, preferably in concentrated form, in a solid or immobile form for recycling or final disposal. Microorganisms are able to take up and deposit high levels of contaminant metals, including radioactive metals such as uranium and plutonium, into their cell wall. Consequently, these microbial systems are of great interest as the basis for potential environmental bioremediation technologies. The outer membranes of Gram-negative microbes are highly nonsymmetric and exhibit a significant electrostatic potential gradient across the membrane. This gradient has a significant effect on the uptake and transport of charged and dipolar compounds. However, the effectiveness of microbial systems for environmental remediation will depend strongly on specific properties that determine the uptake of targeted contaminants by a particular cell wall. To aid in the design of microbial remediation technologies, knowledge of the factors that determine the affinity of a particular bacterial outer membrane for the most common ionic species found in contaminated soils and groundwater is of great importance. Using our previously developed model for the lipopolysaccharide (LPS) membrane of Pseudomonas aeruginosa, this work presents the potentials of mean force as the estimate of the free energy profile for uptake of sodium, calcium, chloride, uranyl ions, and a water molecule by the bacterial LPS membrane. A compatible classical parameter set for uranyl has been developed and validated. Results show that the uptake of uranyl is energetically a favorable process relative to the other ions studied. At neutral pH, this nuclide is shown to be retained on the surface of the LPS membrane through chelation with the carboxyl and hydroxyl groups located in the outer core.

  8. Effect of temperature on the mechanisms of interaction between uranyl ion and zirconium oxo-phosphate

    International Nuclear Information System (INIS)

    Almazan Torres, Maria Guadalupe

    2007-01-01

    Uranium sorption onto Zr 2 O(PO 4 ) 2 has been studied between 298 K and 363 K, in 0.1 M NaClO 4 medium. Potentiometric titrations were realized to determine temperature dependency of the acid-base properties (pH pcn , acidity constants). Classical batch experiments were performed at different temperatures. The sorption experiments revealed that the uranium sorption onto Zr 2 O(PO 4 ) 2 is favoured with the temperature. Structural characterization of the surface complexes was performed by both Time-Resolved Laser-Induced Fluorescence (TRLIF) and EXAFS spectroscopy. The TRLIF measurements vs. temperature revealed two uranyl surface complexes. No influence of the temperature onto the nature surface complex was observed. The EXAFS analysis showed a splitting of the equatorial oxygen atoms in two shells, corresponding to uranyl bidentate, inner-sphere complexes. The obtained structural uranyl surface complex information was used to simulate (using a constant capacitance model) the sorption edges. The proposed complexes equilibrium model consists of the following surface complexes: (≡ZrOH) 2 UO 2 2+ and (≡PO) 2 UO 2 . Besides the stability constants for the surface complexes, the thermodynamic parameters ΔH 0 and ΔS 0 were determined using the van't Hoff equation. The enthalpy values associated to the U(VI) retention onto Zr 2 O(PO 4 ) 2 , determined by the temperature dependence of the stability constants, testify that the formation of the complex (≡PO) 2 UO 2 (55 kJ/mol) is endothermic, while no influence of the temperature was observed for the formation of the complex (≡ZrOH) 2 UO 2 2+ . The adsorption reaction of the last complex is then driven by entropy. In addition, calorimetric measurements of uranium sorption onto Zr 2 O(PO 4 ) 2 were carried out to directly quantify the enthalpy associated to the retention processes. (author)

  9. Photochemical methodologies for organic waste treatment: advanced oxidation process using uranyl ion with H2O2

    International Nuclear Information System (INIS)

    Naik, D.B.; Sarkar, S.K.; Mukherjee, T.

    2009-01-01

    Excited uranyl ion is able to degrade dyes such as thionine and methylene blue on irradiation with 254 nm/300 nm light. By adding H 2 O 2 along with uranyl ion, photodegradation takes place with visible light and also with enhanced rate. The hydroxyl radicals generated in the reoxidation of U(IV)/UO 2 + to UO 2 2+ are responsible for this enhanced degradation. The above advanced oxidation process (AOP) was applied to study the oxidation of 2-propanol to acetone. (author)

  10. Complexation of uranyl ion. I. IR spectroscopic study of the composition of precipitates in sulfate and carbonate media

    International Nuclear Information System (INIS)

    Buskina, I.A.; Stupin, N.P.; Kakhaeva, T.V.; Rodionov, V.V.; Zhukova, N.G.; Vodolazov, L.I.

    1987-01-01

    The composition of uranium(VI) complexes separated from uranyl sulfate solutions at various pH values was studied by IR spectroscopy. A difference was found in the composition of sulfate complexes separated by precipitation at pH 1.5-4.0 and 4-6. At pH above 4 desulfatization occurs, with formation of polymeric ions. At pH 7 in the presence of ammonium bicarbonate, uranyl complexes form with bidentate coordination of the CO 3 2- group

  11. Skin contamination resulting from an uranyl nitrate burn. An incident study

    International Nuclear Information System (INIS)

    Quesne, B.; Auriol, B.; Berard, P.; Chalabreysse, J.

    1993-01-01

    The authors describe the circumstances of a burn incident on hand by a mixture of diluted nitric acid and uranyl nitrate. The burn is located on the left hand fingers. After important washings uranium remains on the fingers. During about ten days, the worker is examined and the therapy is going on till the total radioactivity disappearance. Urine collection of twenty four hours is prescribed during the treatment. The whole activity is kept on the burnt skin. The quick desquamation is the elimination way of the skin retention. 6 refs., 3 figs., 4 tabs

  12. A uranyl hybrid compound designed from urea-bearing dipropionic acid

    Energy Technology Data Exchange (ETDEWEB)

    Shu, Yu-Bo; Xu, Cong; Liu, Wei-Sheng [Key Laboratory of Nonferrous Metals Chemistry and Resources Utilization of Gansu Province and State Key Laboratory of Applied Organic Chemistry, College of Chemistry and Chemical Engineering, Lanzhou University (China)

    2013-07-15

    A uranyl-urea-bearing dipropionate hybrid compound, in which the two acid groups are coordinated in different modes and the urea group serves as both a coordination functionality and a supramolecular synthon, is prepared. The effect of hydrogen-bonding interactions on the luminescence properties of the compound was explored by lifetime measurements. Thermogravimetric analyses were performed under a nitrogen atmosphere and in air. The ''uranophilicity'' of this urea-bearing ligand was examined by competition experiments in alkaline spring water. (Copyright copyright 2013 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  13. Development of ammonium uranyl carbonate reduction to uranium dioxide using fluidized bed

    International Nuclear Information System (INIS)

    Gomes, R.P.; Riella, H.G.

    1988-01-01

    Laboratory development of Ammonium Uranyl Carbonate (AUC) reduction to uranium dioxide (UO 2 ) using fluidized bed furnace technique is described. The reaction is carried out at 500-550 0 C using hydrogen, liberated from cracking of ammonia, as a reducing agent. As the AUC used is obtained from uranium hexafluoride (UF 6 ) it contains considerable amounts of fluoride ( - 500μgF - /gTCAU) as contaminant. The presence of fluoride leads to high corrosion rates and hence the fluoride concentrations is reduced by pyrohydrolisis of UO 2 . Physical and Chemical proterties of the final product (UO 2 ) obtained were characterized. (author) [pt

  14. Preparation, characterization and thermal analysis of rare earth and uranyl hydrazinecarboxylate derivatives

    International Nuclear Information System (INIS)

    Mahesh, G.V.; Ravindranathan, P.; Patil, K.C.

    1986-01-01

    Hydrazinecarboxylate derivatives of rare earth elements Ln(N 2 H 3 COO) 3 .3H 2 O (Ln=Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Yb and Y) and UO 2 (N 2 H 3 COO) 2 .N 2 H 4 .H 2 O have been prepared and characterized by chemical analysis and infrared spectra. Simultaneous TG-DTG-DTA of the rare earth complexes show that the thermal decompositions occur through carbonate and oxycarbonate intermediates to the respective oxides. The oxide formation temperatures are lower than the corresponding oxalates and acetates. The uranyl complex decomposes to U 3 O 8 as the final product of decomposition. (author)

  15. Extraction study on uranyl nitrate for energy applications

    Science.gov (United States)

    Giri, R.; Nath, G.

    2017-07-01

    Due to the ever-growing demand of energy nuclear reactor materials and the nuclear energy are now considered to be the most critical materials and source of energy for future era. Deposition of nuclear wastes in different industry, nuclear power sector are very much toxic in open environment which are hazardous to living being. There are different methods for extraction and reprocessing of these materials which are cost effective and tedious process. Ultrasonic assisted solvent extraction process is a most efficient and economical way for extraction of such type materials. The presence of third phase in mixing of extractants-diluent pair with aqueous phase imposes the problems in extraction of nuclear reactor materials. The appropriate solvent mixture in proper concentration is an important step in the solvent extraction process. Study of thermo-physical properties helps in selecting an optimum blend for extraction process. In the present work, the extraction of uranium with the binary mixture of Methyl Ethyl Ketone (MEK) and Kerosene was investigated and discussed with the variation of ultrasonic frequency for different temperatures. The result shows that the low frequency and low temperature is suitable environment for extraction. The extraction of uranium by this method is found to be a better result for extraction study in laboratory scale as well as industrial sector.

  16. Difference-Equation-Based Digital Frequency Synthesizer

    Directory of Open Access Journals (Sweden)

    Lu-Ting Ko

    2012-01-01

    Full Text Available This paper presents a novel algorithm and architecture for digital frequency synthesis (DFS. It is based on a simple difference equation. Simulation results show that the proposed DFS algorithm is preferable to the conventional phase-locked-loop frequency synthesizer and the direct digital frequency synthesizer in terms of the spurious-free dynamic range (SFDR and the peak-signal-to-noise ratio (PSNR. Specifically, the results of SFDR and PSNR are more than 186.91 dBc and 127.74 dB, respectively. Moreover, an efficient DFS architecture for VLSI implementation is also proposed, which has the advantage of saving hardware cost and power consumption.

  17. Syntheses and studies of organosilicon compounds

    Energy Technology Data Exchange (ETDEWEB)

    Xie, Ren [Iowa State Univ., Ames, IA (United States)

    1999-02-12

    The syntheses of polycarbosilanes and polysilanes as silicon carbide ceramic precursors have been active research areas in the Barton Research Group. In this thesis, the work is focused on the preparation of polycarbosilanes and polysilanes as stoichiometric silicon carbide precursor polymers. The syntheses of the precursor polymers are discussed and the conversions of these precursors to silicon carbide via pyrolysis are reported. The XRD pattern and elemental analyses of the resulting silicon carbide ceramics are presented. Silicon monoxide is an important intermediate in the production of silicon metal. The existence of silicon monoxide in gap phase has been widely accepted. In the second part of this thesis, the generation of gaseous silicon monoxide in four different reactors and the reactions of gaseous silicon monoxide towards organic compounds are discussed.

  18. Some thermodynamic and photovoltaic studies of the uranyl-uranium(IV) system

    International Nuclear Information System (INIS)

    Gayer, K.H.; Kothari, P.

    1977-01-01

    Thermochemical measurements have been made in perchloric acid medium and the following thermodynamic constants have been determined for the reaction: Usub(aq)sup(4+) + 2H 2 O → UOsub(2aq)sup(2+) + 4Hsub(aq)sup(+) + 2e - (ΔH 0 =126.23 kJ; ΔG 0 =63.18 kJ; ΔS 0 =211.53 J). Photovoltaic studies were made in acetic acid medium utilizing the following cell: Pt/UO 2 2+ , CH 3 COOH, C 2 H 5 OH//C 2 H 5 OH, CH 3 COOH/H 2 (Pt). The effect of varying uranyl ion concentration, pH and ethyl alcohol concentration on E.M.F. of this cell in the presence and absence of light has been studied. The nature of the reaction occurring in the above cell and its reversibility in the presence and absence of light has been established. A mechanism for reduction of uranyl ions in organic media in presence of light has been proposed. (author)

  19. Complexation of the uranyl ion with the aminomethylenediphosphonates MAMDP and AMDP

    International Nuclear Information System (INIS)

    Bollinger, J.E.; Roundhill, D.M.

    1994-01-01

    The use of uranium as a nuclear energy source has made it a valuable mineral resource over the past forty years. Processing uranium generally involves leaching the metal as the uranyl ion (UO 2 ) 2+ from ore, followed by solvent extraction, precipitation or batch adsorption onto ion exchange-type resins. Uranium reserves exist also in the form of UO 2 (CO 3 ) 3 4- dissolved in seawater, and although these concentrations are very low they represent globally some 4.9 x 10 9 tons. In the interest of tapping this resource efforts toward developing more efficient and selective means of UO 2 2+ ion sequestering have been underway for some time. The authors have measured the stability and protonation constants of the different complexes formed in aqueous solution between the UO 2 2+ ion and the compounds N,N'-dimethylaminomethylenebis(phosphonic acid) (MAMDP) and aminomethylenebis(phosphonic acid) (AMDP). From these data one can evaluate the potential for compounds of this type to be useful as uranyl ion sequestering agents

  20. New versatile staining reagents for biological transmission electron microscopy that substitute for uranyl acetate.

    Science.gov (United States)

    Nakakoshi, Masamichi; Nishioka, Hideo; Katayama, Eisaku

    2011-12-01

    Aqueous uranyl acetate has been extensively used as a superb staining reagent for transmission electron microscopy of biological materials. However, recent regulation of nuclear fuel material severely restricts its use even for purely scientific purposes. Since uranyl salts are hazardous due to biological toxicity and remaining radioactivity, development of safe and non-radioactive substitutes is greatly anticipated. We examined two lanthanide salts, samarium triacetate and gadolinium triacetate, and found that 1-10% solution of these reagents was safe but still possess excellent capability for staining thin sections of plastic-embedded materials of animal and plant origin. Although post-fixation with osmium tetroxide was essential for high-contrast staining, post-staining with lead citrate could be eliminated if a slow-scan CCD camera is available for observation. These lanthanide salts can also be utilized as good negative-staining reagents to study supramolecular architecture of biological macromolecules. They were not as effective as a fixative of protein assembly, reflecting the non-hazardous nature of the reagents.

  1. Establishment of a luminescence technique for the quantification of uranyl ion in a KNO3 media

    International Nuclear Information System (INIS)

    Contreras R, A.; Fernandez V, S.M.; Ordonez R, E.

    2005-01-01

    The study of the storage of high level radioactive residuals that contain uranium, it makes necessary that in the sorption studies is counted with a reliable technique and not pollutant for the quantification of this element. Presently work intends a technique for the quantification of the uranyl ion using the luminescence technique, which allows not to generate radioactive or industrial residuals. It was used a solution of uranyl nitrate in KNO 3 0.5 M media. The solutions were adjusted to a pH of 1.48+0.03. A statistical study for the analysis of the data of fluorescence, about the maximum value of the peak, total area under the curve and area under the it curves is shown, being the best correlation for the concentration curve versus maximum of the peak, adjusted with a polynomial of second grade. The study of stability of the solutions with regard to the time is reported and that the technique proposal works for the interval of concentrations among 1 x 10 -2 M and 6 x 10 -5 M. (Author)

  2. Determination of uranium in uranium metal, uranium oxides, and uranyl nitrate solutions by potentiometric titration

    International Nuclear Information System (INIS)

    Tucker, H.L.; McElhaney, R.J.

    1983-01-01

    A simple, fast method for the determination of uranium in uranium metal, uranium oxides, and uranyl nitrate solutions has been adapted from the Davies-Gray volumetric method to meet the needs of Y-12. One-gram duplicate aliquots of uranium metal or uranium oxide are dissolved in 1:1 HNO 3 and concentrated H 2 SO 4 to sulfur trioxide fumes, and then diluted to 100-mL volume. Duplicate aliquots are then weighed for analysis. For uranyl nitrate samples, duplicate aliquots containing between 50 and 150 mg of U are weighed and analyzed directly. The weighed aliquot is transferred to a Berzelius beaker; 1.5 M sulfamic acid is added, followed in order by concentrated phosphoric acid, 1 M ferrous sulfate, and (after a 30-second interval) the oxidizing reagent. After a timed 3-minute waiting period, 100 mL of the 0.1% vanadyl sulfate-sulfuric acid mixture is added. The sample is then titrated past its endpoint with standard potassium dichromate, and the endpoint is determined by second derivative techniques on a mV/weight basis

  3. New insight into the ternary complexes of uranyl carbonate in seawater.

    Science.gov (United States)

    Beccia, M R; Matara-Aho, M; Reeves, B; Roques, J; Solari, P L; Monfort, M; Moulin, C; Den Auwer, C

    2017-11-01

    Uranium is naturally present in seawater at trace levels and may in some cases be present at higher concentrations, due to anthropogenic nuclear activities. Understanding uranium speciation in seawater is thus essential for predicting and controlling its behavior in this specific environmental compartment and consequently, its possible impact on living organisms. The carbonato calcic complex Ca 2 UO 2 (CO 3 ) 3 was previously identified as the main uranium species in natural seawater, together with CaUO 2 (CO 3 ) 3 2- . In this work, we further investigate the role of the alkaline earth cation in the structure of the ternary uranyl-carbonate complexes. For this purpose, artificial seawater, free of Mg 2+ and Ca 2+ , using Sr 2+ as a spectroscopic probe was prepared. Combining TRLIF and EXAFS spectroscopy, together with DFT and theoretical thermodynamic calculations, evidence for the presence of Sr alkaline earth counter ion in the complex structure can be asserted. Furthermore, data suggest that when Ca 2+ is replaced by Sr 2+ , SrUO 2 (CO 3 ) 3 2- is the main complex in solution and it occurs with the presence of at least one monodentate carbonate in the uranyl coordination sphere. Copyright © 2017 Elsevier Ltd. All rights reserved.

  4. Thermodynamic parameters of the complexation of uranyl(VI) by diethylenetriamine in dimethyl sulfoxide

    International Nuclear Information System (INIS)

    Cassol, A.; Bernardo, P. di; Portanova, R.; Tolazzi, M.; Tomat, G.; Zanonato, P.L.

    1993-01-01

    The changes in free energy, enthalpy, and entropy for the complex formation reactions between uranyl(VI) ion and diethylenetriamine (dien) in dimethyl sulfoxide have been determined by potentiometric and calorimetric measurements at 25 C in a medium of ionic strength 0.1 mol dm -3 . The amine forms a very stable 1:1 complex which results stabilized only by the highly favourable enthalpy change. Entropy change is negative and opposes the reaction. The comparison of the thermodynamic data concerning complexation of uranyl(VI) by charged and uncharged ligands reveals that in this case (uncharged ligand) the enthalpy contribution is mainly related to the formation of the metal-ligand bonds while the entropy term might be associated with the decrease in the translational and conformational entropy occurring in the complexation of the ligand. FTIR and calorimetric measurements have been carried out to study the effect of traces of water on the equilibria in solution. It has been found that water can interfere in the complexation reaction giving rise to the formation of a dinuclear hydroxo complex in which probably two μ 2 -OH bridges link two monomer moieties. (orig.)

  5. Uranyl incorporation into calcite and aragonite: XAFS and luminescence studies

    International Nuclear Information System (INIS)

    Reeder, R.J.; Nugent, M.; Lamble, G.M.; Tait, C.D.; Morris, D.E.

    2000-01-01

    X-ray absorption, luminescence, and Raman spectroscopic studies of U(VI)-containing calcite and aragonite show that the UO 2 2+ ion, the dominant and mobile form of dissolved uranium in near-surface waters, has a disordered and apparently less stable coordination environment when incorporated into calcite in comparison to aragonite, both common polymorphs of CaCO 3 . Their findings suggest that calcite, a widely distributed authigenic mineral in soils and near-surface sediments and a principal weathering product of concrete-based containment structures, is not likely to be a suitable host for the long-term sequestration of U(VI). The more stable coordination provided by aragonite suggests that its long-term retention should be favored in this phase, until it inverts to calcite. Consequently, future remobilization of U(VI) coprecipitated with calcium carbonate minerals should not be ruled out in assessments of contaminated sites. Their observation of a similar equatorial coordination of UO 2 2+ in aragonite and the dominant aqueous species [UO 2 (CO 3 ) 3 4- ] but a different coordination in calcite indicates that a change in UO 2 2+ coordination is required for its incorporation into calcite. This may explain the observed preferential uptake of U(VI) by aragonite relative to calcite

  6. Uranyl nitrate inhibits lactate gluconeogenesis in isolated human and mouse renal proximal tubules: A 13C-NMR study

    International Nuclear Information System (INIS)

    Renault, Sophie; Faiz, Hassan; Gadet, Rudy; Ferrier, Bernard; Martin, Guy; Baverel, Gabriel; Conjard-Duplany, Agnes

    2010-01-01

    As part of a study on uranium nephrotoxicity, we investigated the effect of uranyl nitrate in isolated human and mouse kidney cortex tubules metabolizing the physiological substrate lactate. In the millimolar range, uranyl nitrate reduced lactate removal and gluconeogenesis and the cellular ATP level in a dose-dependent fashion. After incubation in phosphate-free Krebs-Henseleit medium with 5 mM L-[1- 13 C]-, or L-[2- 13 C]-, or L-[3- 13 C]lactate, substrate utilization and product formation were measured by enzymatic and NMR spectroscopic methods. In the presence of 3 mM uranyl nitrate, glucose production and the intracellular ATP content were significantly reduced in both human and mouse tubules. Combination of enzymatic and NMR measurements with a mathematical model of lactate metabolism revealed an inhibition of fluxes through lactate dehydrogenase and the gluconeogenic enzymes in the presence of 3 mM uranyl nitrate; in human and mouse tubules, fluxes were lowered by 20% and 14% (lactate dehydrogenase), 27% and 32% (pyruvate carboxylase), 35% and 36% (phosphoenolpyruvate carboxykinase), and 39% and 45% (glucose-6-phosphatase), respectively. These results indicate that natural uranium is an inhibitor of renal lactate gluconeogenesis in both humans and mice.

  7. Treatment of uranyl nitrate and flouride solutions; Tratamiento de soluciones que contienen nitrato de uranilo y fluoruros

    Energy Technology Data Exchange (ETDEWEB)

    Rodrigo Otero, A.; Rodrigo Vilaseca, F.; Morales Calvo, G.

    1977-07-01

    A theoretical study on the fluoride complexes contained in uranyl and aluminium solutions has been carried out. Likewise concentration limits and Duhring diagrams for those solutions have been experimentally established. As a result, the optimum operation conditions for concentration by evaporation in the treatment plant, have been deduced. (Author) 12 refs.

  8. Crystal structure of lead uranyl carbonate mineral widenmannite: Precession electron-diffraction and synchrotron powder-diffraction study

    Czech Academy of Sciences Publication Activity Database

    Plášil, J.; Palatinus, L.; Rohlíček, J.; Houdková, L.; Klementová, Mariana; Goliáš, V.; Škácha, P.

    2014-01-01

    Roč. 99, 2-3 (2014), s. 276-282 ISSN 0003-004X Institutional support: RVO:61388980 Keywords : Widenmannite * uranyl bicarbonate * crystal structure * precession electron diffraction * synchrotron powder diffraction Subject RIV: CA - Inorganic Chemistry Impact factor: 1.964, year: 2014

  9. Mechanochemistry of the 5f-element compounds. Part 3. Mechanochemically stimulated formation of nitrosyl uranyl nitrate

    International Nuclear Information System (INIS)

    Kovacheva, P.; Minkova, N.; Todorovsky, D.; Radev, D.

    2007-01-01

    The effect of the mechanical treatment of UO 2 (NO 3 ) 2 x 6H 2 O in a planetary ball mill in air and as a suspension in toluene has been studied. The Xray diffractometry results strongly suggest that part of the mechanoactivated material is transformed in nitrosyl uranyl nitrate. (author)

  10. Determination of the dissociation constants of some organic complexing agents and stability constants of their uranyl complexes by spectrophotometry

    International Nuclear Information System (INIS)

    1989-01-01

    The dissociation constants of the weak acids derived from quinizarin (1,4-dihydroxy anthraquinone); QMF (2-(2-fury l methyl)), QMPH (2-(2-phenyl methyl)) and QMN (2-(2-naphthyl methyl)) quinizarin were determined. The stability constants of uranyl complexes with the above mentioned ligands were investigated by: 1. The molar-ratio method. 2. Computer program

  11. Annual report of STACY in 1995. 600mm diameter cylindrical core and 10% enriched uranyl nitrate solution

    International Nuclear Information System (INIS)

    Sono, Hiroki; Onodera, Seiji; Hirose, Hideyuki

    1997-03-01

    STACY, a critical assembly for static criticality safety experiments in NUCEF, had achieved the first criticality on February 23, 1995, with a 600mm diameter cylindrical core tank and 10% enriched uranyl nitrate solution. Since then, 56 experiments were performed with various conditions of fuel concentration and reflecting conditions: bare and water. Operation data of STACY in 1995 are summarized in this report. (author)

  12. SYNTHESES, SPECTROSCOPIC AND MAGNETIC PROPERTIES ...

    African Journals Online (AJOL)

    Preferred Customer

    SYNTHESES, SPECTROSCOPIC AND MAGNETIC PROPERTIES OF. POLYSTYRENE-ANCHORED COORDINATION COMPOUNDS OF. THIAZOLIDINONE. Dinesh Kumar1, Amit Kumar2* and Durga Dass3. 1Department of Chemistry, National Institute of Technology, Kurukshetra 136119, Haryana,. India. 2Department of ...

  13. Fully automated parallel oligonucleotide synthesizer

    Czech Academy of Sciences Publication Activity Database

    Lebl, M.; Burger, Ch.; Ellman, B.; Heiner, D.; Ibrahim, G.; Jones, A.; Nibbe, M.; Thompson, J.; Mudra, Petr; Pokorný, Vít; Poncar, Pavel; Ženíšek, Karel

    2001-01-01

    Roč. 66, č. 8 (2001), s. 1299-1314 ISSN 0010-0765 Institutional research plan: CEZ:AV0Z4055905 Keywords : automated oligonucleotide synthesizer Subject RIV: CC - Organic Chemistry Impact factor: 0.778, year: 2001

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

    Energy Technology Data Exchange (ETDEWEB)

    Orona, N.S. [School of Science and Technology, National University of General Martín, Avda Gral Paz 5445 (1650) San Martín, Buenos Aires (Argentina); Tasat, D.R., E-mail: deborah.tasat@unsam.edu.ar [School of Science and Technology, National University of General Martín, Avda Gral Paz 5445 (1650) San Martín, Buenos Aires (Argentina); School of Dentistry, University of Buenos Aires, M. T. de Alvear 2142 (1122), Buenos Aires (Argentina)

    2012-06-15

    Uranium compounds are widely used in the nuclear fuel cycle, military and many other diverse industrial processes. Health risks associated with uranium exposure include nephrotoxicity, cancer, respiratory, and immune disorders. Macrophages present in body tissues are the main cell type involved in the internalization of uranium particles. To better understand the pathological effects associated with depleted uranium (DU) inhalation, we examined the metabolic activity, phagocytosis, genotoxicity and inflammation on DU-exposed rat alveolar macrophages (12.5–200 μM). Stability and dissolution of DU could differ depending on the dissolvent and in turn alter its biological action. We dissolved DU in sodium bicarbonate (NaHCO{sub 3} 100 mM) and in what we consider a more physiological vehicle resembling human internal media: sodium chloride (NaCl 0.9%). We demonstrate that uranyl nitrate in NaCl solubilizes, enters the cell, and elicits its cytotoxic effect similarly to when it is diluted in NaHCO{sub 3}. We show that irrespective of the dissolvent employed, uranyl nitrate impairs cell metabolism, and at low doses induces both phagocytosis and generation of superoxide anion (O{sub 2}{sup −}). At high doses it provokes the secretion of TNFα and through all the range of doses tested, apoptosis. We herein suggest that at DU low doses O{sub 2}{sup −} may act as the principal mediator of DNA damage while at higher doses the signaling pathway mediated by O{sub 2}{sup −} may be blocked, prevailing damage to DNA by the TNFα route. The study of macrophage functions after uranyl nitrate treatment could provide insights into the pathophysiology of uranium‐related diseases. -- Highlights: ► Uranyl nitrate effect on cultured macrophages is linked to the doses and independent of its solubility. ► At low doses uranyl nitrate induces generation of superoxide anion. ► At high doses uranyl nitrate provokes secretion of TNFα. ► Uranyl nitrate induces apoptosis through

  15. FEBEX: Full-Scale engineered barriers experiment in crystalline host-rock: preoperational phase. Synthesized report; FEBEX: experimento de barreras de ingenieria a gran escala en rocas cristalinas: etapa preoperacional. Informe de sintesis

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    1997-07-01

    The FEBEX project is being cofinanced by the EC under contract F 14WCT950006. In addition to the EC, seven partners from three countries of the EU. (France, Germany, and Spain) as well as one from EFTA (Switzerland) are participating in the project. ENRESA is the coordinating partner with NAGRA assisting in coordinating some aspects. The project consists of two large-scale tests and a series of complimentary laboratory tests. The work is being executed by the following organizations: CIEMAT, AITEMIN, UP-DIT (CIMNE), ULC, CSIC-Zaidin, and UPM (SPAIN) ANDRA and G.3S (FRANCE) GRS (GERMANY). This report includes a synthesized description of the experiment from its conception through the installation of the two large-scale tests (from the middle of 1994 to the beginning of 1997, preoperation stage). The experiment is described in detail in a series of specific reports. (Author)

  16. Structure and Bonding in Uranyl(VI) Peroxide and Crown Ether Complexes; Comparison of Quantum Chemical and Experimental Data.

    Science.gov (United States)

    Vallet, Valérie; Grenthe, Ingmar

    2017-12-18

    The structure, chemical bonding, and thermodynamics of alkali ions in M[12-crown-4] + , M[15-crown-5] + , and M[18-crown-6] + , M[UO 2 (O 2 )(OH 2 ) 2 ] + 4,5 , and M[UO 2 (O 2 )(OH)(OH 2 )] n 1-n (n = 4, 5) complexes have been explored by using quantum chemical (QC) calculations at the ab initio level. The chemical bonding has been studied in the gas phase in order to eliminate solvent effects. QTAIM analysis demonstrates features that are very similar in all complexes and typical for electrostatic M-O bonds, but with the M-O bonds in the uranyl peroxide systems about 20 kJ mol -1 stronger than in the corresponding crown ether complexes. The regular decrease in bond strength with increasing M-O bond distance is consistent with predominantly electrostatic contributions. Energy decomposition of the reaction energies in the gas phase and solvent demonstrates that the predominant component of the total attractive (ΔE elec + ΔE orb ) energy contribution is the electrostatic component. There are no steric constraints for coordination of large cations to small rings, because the M + ions are located outside the ring plane, [O n ], formed by the oxygen donors in the ligands; coordination of ions smaller than the ligand cavity results in longer than normal M-O distances or in a change in the number of bonds, both resulting in weaker complexes. The Gibbs energies, enthalpies, and entropies of reaction calculated using the conductor-like screening model, COSMO, to account for solvent effects deviate significantly from experimental values in water, while those in acetonitrile are in much better agreement. Factors that might affect the selectivity are discussed, but our conclusion is that present QC methods are not accurate enough to describe the rather small differences in selectivity, which only amount to 5-10 kJ mol -1 . We can, however, conclude on the basis of QC and experimental data that M[crown ether] + complexes in the strongly coordinating water solvent are of

  17. A new uranyl phosphate sheet in the crystal structure of furongite

    Energy Technology Data Exchange (ETDEWEB)

    Dal Bo, Fabrice; Hatert, Frederic [Liege Univ. (Belgium). Lab. de Mineralogie; Philippo, Simon [Musee National d' Historie Naturelle, Luxembourg (Luxembourg). Section Mineralogie

    2017-06-15

    The crystal structure of furongite, Al{sub 4}[(UO{sub 2}){sub 4}(PO{sub 4}){sub 6}](OH){sub 2}(H{sub 2}O){sub 19.5}, from the Kobokobo pegmatite, Kivu, Democratic Republic of Congo, was solved for the first time. Furongite is triclinic, the space group P anti 1, Z=2, a = 12.1685(8), b = 14.1579(6), c = 17.7884(6) Aa, α = 79.822(3), β = 77.637(4), γ = 67.293(2) , and V = 2746.2(2)Aa{sup 3}. The crystal structure was refined from single crystal X-ray diffraction data to R{sub 1} = 0.0733 for 7716 unique observed reflections, and to wR{sub 2} = 0.2081 for all 12,538 unique reflections. The structure of furongite contains infinite uranyl phosphate sheets of composition [(UO{sub 2}){sub 4}(PO{sub 4}){sub 6}]{sup 10-} which are parallel to (1 0 1). The sheets are constituted by UrO{sub 5} pentagonal bipyramids and PO{sub 4} tetrahedra which share edges and vertices, and adjacent sheets are linked by a dense network of hydrogen bonds. Running through the sheets and connected mainly to the free apical oxygen atom of PO4 tetrahedra are Al octahedra connected together to form remarkable Al{sub 2}O{sub 5}(OH)(H{sub 2}O){sub 5} and Al{sub 4}O{sub 8}(OH){sub 2}(H{sub 2}O){sub 10} clusters. These Al clusters are only bonded to one sheet, and do not connect two adjacent sheets together. The topology of the uranyl phosphate sheets is related to the uranophane anion topology, and can be described as a new geometrical isomer of the uranophane group. Furongite is the first uranyl phosphate reported in nature with a U:P ratio of 2:3.

  18. Hydrothermal syntheses and crystal structure of NH

    International Nuclear Information System (INIS)

    Kang, Z. J.; Wang, Y. X.; You, F. T.; Lin, J. H.

    2001-01-01

    Ammonium rare earth fluorides NH(sub 4)Ln(sub 3)F(sub 10) (Ln=Dy, Ho, Y, Er, Tm) were synthesized by a hydrothermal method. Two polymorphs, of the hexagonal(beta)-KYb(sub 3)F(sub 10) and the cubic(gamma)-KYb(sub 3)F(sub 10) structure types, were formed under hydrothermal conditions for most of the rare earth fluorides except NH(sub 4)Dy(sub 3)F(sub 10), for which only the cubic -phase was obtained. The crystal structures of MLn(sub 3)F(sub 10) (M=alkaline metal, NH(sup+4) and Ln=rare earth) show a strong correlation to the ratio of ionic radii (R(sub M)/R(sub Ln)), which has been expressed in a structure phase diagram of the ionic radii of univalent and rare earth cations

  19. Analysis of uranyl in solution through the formation of luminescent complexes; Analisis de uranilo en solucion mediante la formacion de complejos luminiscentes

    Energy Technology Data Exchange (ETDEWEB)

    Garcia G, N.; Ordonez R, E.; Barrera D, C.E. [ININ, 52750 La Marquesa, Estado de Mexico (Mexico)

    2008-07-01

    The luminescence is one of the techniques used to determine the speciation of those complex that forms the uranyl in the solid-liquid interphase of distinct zirconium phosphates, also has the advantage that it allows to carry out its quantification at mid of high ion forces, because it has been demonstrated that this detection technique and quantification is reliable and sufficiently quick in the obtaining of results. For it that in this work, the quantification of the uranyl is presented by means of a luminescent complex with the aim of phosphates that avoid the fluorescence signal extinction, then the uranyl ion is very sensitive to the medium that contains it (pH, ion force, concentration, etc.) for what was necessary to establish the analysis conditions of the uranyl ion without signal lost, in inferior concentrations to 1X10{sup -3} M at mid of sodium perchlorate 0.5 M. (Author)

  20. Contribution to the study of uranyl salts in butyl phosphate solutions; Contribution a l'etude des solutions de sels d'uranyle dans les phosphates butyliques

    Energy Technology Data Exchange (ETDEWEB)

    Coulon, A. [Commissariat a l' Energie Atomique, Fontenay-aux-Roses (France). Centre d' Etudes Nucleaires

    1965-06-01

    A spectroscopic study in the normal infrared region and involving the following associations: tri-alkyl phosphates (tri-butyl, tri-ethyl, tri-methyl), uranyl salts (nitrate, chloride, acetate) has confirmed the existence of an interaction between the phosphoryl group and the uranium atom, as shown by a movement of absorption band for the valency P = 0 from {approx} 1270 cm{sup -1} to {approx} 1180 cm{sup -1}. A study of the preparation, analysis and spectroscopy of the solids obtained by the precipitation of uranyl salts by acid butyl phosphates has been carried out. By infrared spectrophotometry it has been shown that the tri-butyl and di-butyl phosphates are associated in non-polar diluents even before the uranium is introduced. The extraction of uranyl salts from acid aqueous solutions by a diluted mixture of tri-butyl and di-butyl phosphates proceeds by different mechanisms according to the nature of the ion (nitrate or chloride). (author) [French] Une etude spectroscopique dans l'infrarouge moyen portant sur les associations: - phosphates trialcoyliques (tributylique - triethylique - trimethylique) - sels d'uranyle (nitrate, chlorure, acetate) a confirme l'existence d'une interaction entre le groupement phosphoryle et l'atome d'uranium, se manifestant par un deplacement de la bande d'absorption de la vibration de valence P = 0 de {approx} 1270 cm{sup -1} a {approx} 1180 cm{sup -1}. Une etude preparative, analytique et spectroscopique des solides obtenus par precipitation de sels d'uranyle par les phosphates butyliques acides a ete effectuee. La spectrophotomerie infrarouge met en evidence l'association, anterieure a toute introduction d'uranium, des phosphates tributylique et dibutylique dans des diluants non polaires. L'extraction de sels d'uranyle, d'une solution aqueuse acide par un melange dilue de phosphates tributylique et dibutylique, s'effectue suivant des processus differents a la

  1. Determination of the extractive capacity of para-tert butyl calix[8]arene octa-phosphinoylated towards uranyl ions from an aqueous-acidic-salty medium

    International Nuclear Information System (INIS)

    Serrano V, E. C.

    2011-01-01

    The extraction properties of octa-phosphinoylated para-tert butyl calix[8]arene (prepared in the laboratory) in chloroform towards uranyl ions from an aqueous-acidic-salty medium (HNO 3 -3.5 NaNO 3 ) containing uranyl nitrate salt, was investigated. Two spectroscopic techniques UV/Vis and Luminescence were used for this study. The latter permitted analyze the fluorescence from the uranyl ions influenced by the surrounding medium. Both permitted to learn about the power of this calixarene as extractant towards the mentioned ions. Its extraction ability or capability using this calixarene at 5.91 x 10 -4 M towards the uranyl ions was 400% as determined by UV/Vis while fluorescence revealed 100% of uranyl ion extraction. A closed analysis of the results obtained by using these techniques revealed that the stoichiometry of the main extracted species was 1calixarene:2 uranyl ions. The loading capacity of the calixarene ligand towards the uranyl ions was also investigated using both techniques. UV/Vis resulted to be inadequate for quantifying exactly the loading capacity of the calixarene whereas luminescence was excellent indeed, using a 5.91 x 10 -4 M calixarene concentration, its loading capacity was 0.157 M of free uranyl ions from 0.161 M of uranyl ions present in the aqueous-acidic-salty medium. The extracts from the ability and capacity studies were concentrated to dryness, purified and the dried extracts were analyzed by infrared and neutron activation analysis. By these techniques it was demonstrated that during the extraction of the uranyl ions by the calixarene ligand they form thermodynamically and kinetically stable complexes, since in the solid state, the 1:2, calixarene; uranyl ions stoichiometry was kept with the minimum formula: (UO 2 ) 2 B 8 bL 8 (NO 3 ) 4 (H 2 O) 4 CHCl 3 (CH 3 OH) 3 the methanol molecules come from its purification. It is proposed that B 8 bL 8 calixarene in chloroform medium is a good extractant for the treatment of nuclear wastes or

  2. The structure of monomeric and dimeric uranyl adsorption complexes on gibbsite: A combined DFT and EXAFS study

    Science.gov (United States)

    Hattori, Tatsuya; Saito, Takumi; Ishida, Keisuke; Scheinost, Andreas C.; Tsuneda, Takao; Nagasaki, Shinya; Tanaka, Satoru

    2009-10-01

    We investigated the structure of uranyl sorption complexes on gibbsite (pH 5.6-9.7) by two independent methods, density functional theory (DFT) calculations and extended X-ray absorption fine structure (EXAFS) spectroscopy at the U-L III edge. To model the gibbsite surface with DFT, we tested two Al (hydr)oxide clusters, a dimer and a hexamer. Based on polarization, structure, and relaxation energies during geometry optimization, the hexamer cluster was found to be the more appropriate model. An additional advantage of the hexamer model is that it represents both edges and basal faces of gibbsite. The DFT calculations of (monomeric) uranyl sorption complexes show an energetic preference for the corner-sharing versus the edge-sharing configuration on gibbsite edges. The energy difference is so small, however, that possibly both surface species may coexist. In contrast to the edge sites, sorption to basal sites was energetically not favorable. EXAFS spectroscopy revealed in all investigated samples the same interatomic distances of the uranyl coordination environment ( R ≈ 1.80 Å, R ≈ 2.40 Å), and towards the gibbsite surface ( RU-O ≈ 2.87 Å, RU-Al ≈ 3.38 Å). In addition, two U-U distances were observed, 3.92 Å at pH 9.7 and 4.30 Å at pH 5.6, both with coordination numbers of ˜1. The short U-U distance is close to that of the aqueous uranyl hydroxo dimer, UO 2(OH) 2, reported as 3.875 Å in the literature, but significantly longer than that of aqueous trimers (3.81-3.82 Å), suggesting sorption of uranyl dimers at alkaline pH. The longer U-U distance (4.30 Å) at acidic pH, however, is not in line with known aqueous uranyl polymer complexes. Based on the EXAFS findings we further refined dimeric surface complexes with DFT. We propose two structural models: in the acidic region, the observed long U-U distance can be explained with a distortion of the uranyl dimer to form both a corner-sharing and an edge-sharing linkage to neighboring Al octahedra

  3. Voltammetry of uranyl chloride in the LiCl - KCl eutectic

    International Nuclear Information System (INIS)

    Fondanaiche, J.C.

    1965-01-01

    Spent UO 2 - PuO 2 fuels can be reprocessed in a molten salt media. Uranium dioxide can easily be dissolved as UO 2 Cl 2 in a molten salt bath using chlorine gas. A study of quantitative analysis of an uranyl chloride solution in the LiCl-KCl eutectic at 400 C has been performed here using voltammetry (a large area-graphite indicator electrode has been employed). The precision which is obtained is around 6 per cent for concentrations below 10 -2 M. Precision decreases slightly for more concentrated solutions. The study of polarization curves allowed to give a reduction mechanism for the UO 2 ++ ion. For dilute solutions, this reduction proceeds through the UO 2 + ion. But interpretation of current-potential curves is made difficult by the dismutation reaction of the UO 2 ion and by the fact that the surface of the indicator electrode is not renewed. (author) [fr

  4. Modelling of uranyl nitrate and nitric acid extraction in diluted TBP using Chem-Unifac

    Energy Technology Data Exchange (ETDEWEB)

    Hanna, M.; Rat, B. [CEA/VALRHO - site de Marcoule, Dept. de Recherche en Retraitement et en Vitrification, DRRV, 30 - Marcoule (France)

    2000-07-01

    Chem-UNIFAC model is applied to TBP/dodecane/water/UO{sub 2}(NO{sub 3}){sub 2} and TBP/dodecane/water/HNO{sub 3} systems, following our previous studies on TBP/diluent (alkane, HCCl{sub 3}, CCl{sub 4}) and TBP/diluent/water/salting out agent (same diluents) systems. New Chem-UNIFAC parameters for TBP/water pair are calculated and an unique set of parameters is proposed to describe the TBP/dodecane/water/UO{sub 2}(NO{sub 3}){sub 2} system, for a wide range of TBP/diluent volume proportions (10%, 30%, 50%, 100%) and a wide range of uranyl nitrate aqueous concentration. Nitric acid and water extraction in TBP/dodecane/water/HNO{sub 3} is also calculated and an improvement is found in the description of the corresponding isotherms. (authors)

  5. Conversion of ammonium uranyl carbonate to UO2 in a fluidized bed

    International Nuclear Information System (INIS)

    Zhao Jun; Qiu Lufu; Zhong Xing; Xu Heqing

    1989-11-01

    The conversion of AUC (Ammonium Uranyl Carbonate) to UO 2 was studied in a fluidized bed of 60 mm inner diameter based on the thermodynamics and kinetics data of decomposition-reduction of AUC. The influence of the reaction temperature, composition of fluidization gas and fluidization velocity on conversion were investigated by using N 2 , Ar and circulation gas (mixing gas of H 2 and CO obtained from the exhaust gas of the decomposition of AUC by catalyst crack-conversion) as the fluidization gas. The throughput is up to the high levels (3.32 kg(wet)/h·L) by using circulation gas or mixing of circulation gas and Ar (< 21%) as the fluidization gas when the reaction temperature exceeds 570 deg C

  6. Study of process parameters for reducing ammonium uranyl carbonate to uranium dioxide in fluidized bed furnace

    International Nuclear Information System (INIS)

    Leitao Junior, C.B.

    1992-01-01

    This work consists of studying the process parameters of AUC (ammonium uranyl carbonate) to U O 2 (uranium dioxide) reduction, with good physical and chemical characteristics, in fluidized bed. Initially, it was performed U O 2 cold fluidization experiments with an acrylic column. Afterward, it was done AUC to U O 2 reduction experiments, in which the process parameters influence in the granulometry, specific surface area, porosity and fluoride amount on the U O 2 powder produced were studied. As a last step, it was done compacting and sintering tests of U O 2 pellets in order to appreciate the U O 2 powder performance, obtained by fluidized bed, in the fuel pellets fabrication. (author)

  7. Clinico-biochemical studies on acute toxic nephropathy in goats due to uranyl nitrate

    Energy Technology Data Exchange (ETDEWEB)

    Dash, P.K.; Joshi, H.C.

    1989-02-01

    Acute toxic nephropathy was produced in 6 healthy goats by injecting intravenously 1% uranyl nitrate (UN) (15 mg/kg body weight). The early painful clinical signs simulating shock progressed with subnormal temperature, slow-shallow respiration and arrhythmic pulse followed by death due to respiratory failure within 96 to 120 hr. All the affected goats had normocytic normochromic anemia, leucocytosis, neutrophilia with left shift eosinopenia, decreased monocytes and presence of 1-2% reticulocytes in the peripheral blood smears. On blood chemical analysis, a uniform and continuous rise was seen in serum creatinine with a concomitant daily increase of serum urea and uric acid. Simultaneous analysis of urine indicated polyuria leading to oliguria, acidic pH, albuminuria, glycosuria with presence of neutrophils, RBC's, epithelial and fatty casts, increase of triple phosphate, and cystine crystals reflecting acute damage of kidneys in the affected goats.

  8. Processing of uranyl nitrate hexahydrate (UNH) at DOE's Fernald Site: Success and pitfalls

    International Nuclear Information System (INIS)

    Luken, D.W.; Brettschneider, D.J.; Heck, R.P. III; White, C.A.

    1996-01-01

    After 36 years of operation, uranium production at the Department of Energy Fernald Environmental Management Project (FEMP) was halted in 1989. Uranyl Nitrate Hexahydrate (UNH) had been produced during the uranium refining. In June 1991, DOE determined the UNH to be a mixed hazardous waste under the Resource Conservation and Recovery Act. A UNH Neutralization Project began processing UNH stored in stainless steel tanks located in various areas within the Fernald Plant 2/3 Complex. It was discovered that the valves, flanges, and other fittings of the UNH storage tanks were leaking. This made processing the UNH a high priority and Comprehensive, Environmental, Response, Compensation, and Liability Act Removal Action No. 20, Stabilization of UNH Inventories, was initiated. This report presents the successes and pitfalls of the cleanup of UNH

  9. Density functional theory investigations on the binding modes of amidoximes with uranyl ions.

    Science.gov (United States)

    Yang, Chuting; Pei, Shuqi; Chen, Baihua; Ye, Lina; Yu, Haizhu; Hu, Sheng

    2016-02-21

    Density functional theory (DFT) calculations have been carried out to examine the relative facilities of different coordination modes of aromatic amidoximes (AOs) with UO2(NO3)2. Various η(1)-, η(2)- and chelated κ(2)-coordination modes of the possible neutral AO, tautomerized neutral (TAO, with the hydroxylic hydrogen transferring to the oximic nitrogen atom) and anionic amidoxime (AAO, formed by the deprotonation of AO) were examined. The results indicate that η(1)-O of the TAO and η(1)-O/η(2)-NO of AAO are the most plausible coordination modes. Three types of uranyl complexes, i.e. UO2(NO3)2(TAO)(AAO), UO2(NO3)2(AAO)2 and UO2(EtOH)2(AAO)2 are the predominant binding structures. The good consistency between the calculation results and the experimental observations verifies the proposed conclusions.

  10. Extraction of uranyl nitrate from aqueous solution by dicyclohexyl-18-crown-6

    International Nuclear Information System (INIS)

    Kojima, Takashi; Ohno, Fumiaki; Fukutomi, Hiroshi

    1981-01-01

    The extraction of uranyl nitrate from aqueous solution by dicyclohexyl-18-crown-6(DCC) in cyclohexane, toluene, benzene, chlorobenzene and nitrobenzene has been studied in varying the concentrations of DCC and uranyl nitrate. The extraction equilibria have been discussed in detail based on the law of mass action, and it has been found that the extractions in cyclohexane, toluene and benzene are represented by the equation 2 DCC(org) + UO 2 2+ (aq) + 2 NO 3 - (aq) = (DCC) 2 UO 2 (NO 3 ) 2 (org), and the extraction in chlorobenzene is described by the equations DCC(org) + UO 2 2+ (aq) + 2NO 3 - (aq) = DCC UO 2 (NO 3 ) 2 (org) and 2DCC(org) + UO 2 2+ (aq) + 2NO 3 - (aq) = (DCC) 2 UO 2 (NO 3 ) 2 (org), and the extraction in nitrobenzene is expressed by the equations DCC(org) + UO 2 2+ (aq) + 2NO 3 - (aq) = DCC UO 2 (NO 3 ) 2 (org), 2DCC(org) + UO 2 2+ (aq) + 2NO 3 - (aq) = (DCC) 2 UO 2 (NO 3 ) 2 (org) and DCC UO 2 (NO 3 ) 2 (org) = DCC UO 2 NO 3 + (org) + NO 3 - (org). The equilibrium constants of the reaction 2DCC(org) + UO 2 2+ (aq) + 2NO 3 - (aq) = (DCC) 2 UO 2 (NO 3 ) 2 (org) increase in the order of cyclohexane < toluene < benzene < chlorobenzene < nitrobenzene. The enthalpy and entropy changes for the extraction reactions into benzene and nitrobenzene were determined from the change of the extraction equilibrium constants with temperature. (author)

  11. Stereognostic coordination chemistry. 1. The design and synthesis of chelators for the uranyl ion

    International Nuclear Information System (INIS)

    Franczyk, T.S.; Czerwinski, K.R.; Raymond, K.N.

    1992-01-01

    A new approach to the molecular recognition of metal oxo cations is introduced based on a ligand design strategy that provides at least one hydrogen bond donor for interaction with oxo group(s) as well as conventional electron pair donor ligands for coordination to the metal center. This concept of stereognostic coordination of oxo metal ions is exemplified in the design of four tripodal ligands-tris[2-(2-carboxyphenoxy)ethyl]amine[NEB],tris[3-(2-carboxyphenoxy)propyl]amine[NPB], tris[3-(2-carboxynaphthyl-3-oxy)propyl]amine [NPN], and tris[3-(2-carboxy=4octadecylphenoxy)propyl]amine[NPodB] - for sequestration of the uranyl ion. The ligands NEB, NPB, and NPN form 1:1 complexes with UO 2 2+ . The bidentate coordination of carboxyl groups of these compounds is indicated by the infrared spectra, which offer some support for the presence of a hydrogen bond to the uranyl group. Mass spectral data corroborate CPK model predictions that more than five intervening atoms between the tertiary nitrogen atom and the carboxylate groups are required for metal ion incorporation and monomeric complex formation. Solvent extractions of aqueous UO 2 2+ into chloroform solutions of the ligands have shown them to be powerful extractants. In the case of the very hydrophobic ligand NPodB the stoichiometry of the complexation reaction is shown to be 1:1 UO 2 /ligand complex formed by the release of 3 protons. The extraction is quantitative at pH 2.5, and an effective extraction coefficient of about 10 11 is estimated for neutral aqueous solutions of UO 2 2+ . 81 refs., 13 figs., 2 tabs

  12. Isolation of Uranyl Dicyanamide Complexes from N-Donor Ionic Liquids.

    Science.gov (United States)

    Kelley, Steven P; Rogers, Robin D

    2015-11-02

    An ionic liquid (IL) approach for soft-donor f-element chemistry has been demonstrated by the isolation of several new uranyl dicyanamide complexes through reactions of UO2(NO3)2·6H2O with dicyanamide ([N(CN)2](-))-containing ILs. The [N(CN)2](-) ions are able to rapidly substitute uranium's O-donor ligands, as evidenced by single-crystal X-ray diffraction studies on two anhydrous adducts of UO2(NO3)2 with [N(CN)2](-) ILs as well as by IR and NMR spectroscopic studies on solutions of UO2(NO3)2 in these ILs. By contrast, the slow reaction of UO2(OAc)2·2H2O with a nitrile-functionalized imidazolium dicyanamide IL in solvent and the reaction of UO2(NO3)2·6H2O with NaN(CN)2 at elevated temperature resulted in irreversible hydrolysis. The reaction of UO2SO4 with [N(CN)2](-) ions in an acidified aqueous solution resulted in the crystallization of a [UO2](2+) complex with biuret, a N(CN)2](-) hydrolysis product. [N(CN)2](-) ions in the form of ILs react rapidly with [UO2](2+) at room temperature, allowing ligand substitution with [N(CN)2](-) to out-compete the slower hydrolysis reaction, enabling the isolation of uranyl dicyanamide complexes and challenging assumptions regarding the affinity of uranium for O-donors.

  13. Comprehensive analysis of the renal transcriptional response to acute uranyl nitrate exposure

    Directory of Open Access Journals (Sweden)

    Argiles Angel

    2006-01-01

    Full Text Available Abstract Background Chemical and radiological toxicities related to uranium acute exposure have been widely studied in nuclear fuel workers and military personnel. It is well known that uranyl nitrate induces acute renal failure (ARF. However, the mechanisms of this metal-induced injury are not well defined at the molecular level. Results Renal function and histology were assessed in mice receiving uranyl nitrate (UN(+ and controls (UN(-. To identify the genomic response to uranium exposure, serial analysis gene expression (SAGE of the kidney was performed in both groups. Over 43,000 mRNA SAGE tags were sequenced. A selection of the differentially expressed transcripts was confirmed by real-time quantitative PCR and Western blotting. UN(+ animals developed renal failure and displayed the characteristic histological lesions of UN nephropathy. Of the >14,500 unique tags identified in both libraries, 224 had a modified expression level; they are known to participate in inflammation, ion transport, signal transduction, oxidative stress, apoptosis, metabolism, and catabolism. Several genes that were identified had not previously been evaluated within the context of toxic ARF such as translationally controlled tumor protein, insulin like growth factor binding protein 7 and ribosomal protein S29, all apoptosis related genes. Conclusion We report a comprehensive description of the UN induced modifications in gene expression levels, including the identification of genes previously unrelated to ARF. The study of these genes and the metabolisms they control should improve our understanding of toxic ARF and enlighten on the molecular targets for potential therapeutic interventions.

  14. X-ray Absorption Spectroscopy Identifies Calcium-Uranyl-Carbonate Complexes at Environmental Concentrations

    International Nuclear Information System (INIS)

    Kelly, Shelly D.; Kemner, Kenneth M.; Brooks, Scott C.

    2007-01-01

    Current research on bioremediation of uranium-contaminated groundwater focuses on supplying indigenous metal-reducing bacteria with the appropriate metabolic requirements to induce microbiological reduction of soluble uranium(VI) to poorly soluble uranium(IV). Recent studies of uranium(VI) bioreduction in the presence of environmentally relevant levels of calcium revealed limited and slowed uranium(VI) reduction and the formation of a Ca-UO2-CO3 complex. However, the stoichiometry of the complex is poorly defined and may be complicated by the presence of a Na-UO2-CO3 complex. Such a complex might exist even at high calcium concentrations, as some UO2-CO3 complexes will still be present. The number of calcium and/or sodium atoms coordinated to a uranyl carbonate complex will determine the net charge of the complex. Such a change in aqueous speciation of uranium(VI) in calcareous groundwater may affect the fate and transport properties of uranium. In this paper, we present the results from X-ray absorption fine structure (XAFS) measurements of a series of solutions containing 50 lM uranium(VI) and 30 mM sodium bicarbonate, with various calcium concentrations of 0-5 mM. Use of the data series reduces the uncertainty in the number of calcium atoms bound to the UO2-CO3 complex to approximately 0.6 and enables spectroscopic identification of the Na-UO2-CO3 complex. At nearly neutral pH values, the numbers of sodium and calcium atoms bound to the uranyl triscarbonate species are found to depend on the calcium concentration, as predicted by speciation calculations

  15. [UO{sub 2}Cl{sub 2}(phen){sub 2}], a simple uranium(VI) compound with a significantly bent uranyl unit (phen=1,10-phenanthroline)

    Energy Technology Data Exchange (ETDEWEB)

    Schoene, Sebastian; Radoske, Thomas; Maerz, Juliane; Stumpf, Thorsten; Patzschke, Michael; Ikeda-Ohno, Atsushi [Helmholtz-Zentrum Dresden-Rossendorf (HZDR), Institute of Resource Ecology, Dresden (Germany)

    2017-10-04

    A simple synthesis based on UO{sub 2}Cl{sub 2}.n H{sub 2}O and 1,10-phenanthroline (phen) resulted in the formation of a new uranyl(VI) complex [UO{sub 2}Cl{sub 2}(phen){sub 2}] (1), revealing a unique dodecadeltahedron coordination geometry around the uranium center with significant bending of the robust linear arrangement of the uranyl (O-U-O) unit. Quantum chemical calculations on complex 1 indicated that the weak but distinct interactions between the uranyl oxygens and the adjacent hydrogens of phen molecules play an important role in forming the dodecadeltahedron geometry that fits to the crystal structure of 1, resulting in the bending the uranyl unit. The uranyl oxygens in 1 are anticipated to be activated as compared with those in other linear uranyl(VI) compounds. (copyright 2017 Wiley-VCH Verlag GmbH and Co. KGaA, Weinheim)

  16. Effect of the temperature and oxalic acid in the uranyl sorption in zircon; Efecto de la temperatura y acido oxalico en la sorcion de uranilo en circon

    Energy Technology Data Exchange (ETDEWEB)

    Ordonez R, E.; Almazan T, M. G.; Garcia G, N. [ININ, Departamento de Quimica, Carretera Mexico-Toluca s/n, 52750 Ocoyoacac, Estado de Mexico (Mexico); Hernandez O, R., E-mail: eduardo.ordonez@inin.gob.mx [Instituto Tecnologico de Veracruz, Ingenieria Quimica, Miguel Angel de Quevedo No. 2779, 91860 Veracruz (Mexico)

    2012-10-15

    In this work the results of the temperature effect study are presented on uranyl solutions adsorbed on zirconium silicate (ZrSiO{sub 4}) and also on the compounds formed in surface with oxalic acid. The adsorption isotherms of uranyl on hydrated zircon with NaClO{sub 4} 0.5 M, show an increase of the uranyl sorption efficiency when increasing the temperature from 20 to 4 C with a sudden descent in this efficiency when changing the temperature at 60 C. The uranyl sorption efficiency increases to hydrate the zircon with a solution of oxalic acid 0.1 M, maintaining the same tendency regarding to the temperatures of the sorption in medium NaClO{sub 4} 0.5 M. The complex formation in the zircon surface with organic acids of low molecular weight increases the fixation of the uranyl in solution due to the formation of ternary systems, in the order Zircon/A. Organic/Uranyl, without altering their response to the temperature. (Author)

  17. Phase structure and luminescence properties of Eu3+-doped TiO2 nanocrystals synthesized by Ar/O2 radio frequency thermal plasma oxidation of liquid precursor mists.

    Science.gov (United States)

    Li, Ji-Guang; Wang, Xiaohui; Watanabe, Kenji; Ishigaki, Takamasa

    2006-01-26

    Eu3+-doped TiO2 luminescent nanocrystals have been synthesized in this work via Ar/O2 thermal plasma oxidizing mists of liquid precursors containing titanium tetra-n-butoxide and europium(III) nitrate, with varied O2 input in the plasma sheath (10-90 L/min) and Eu3+ addition in the precursor solution (Eu/(Ti + Eu) = 0-5 atom%). The resultant nanopowders are mixtures of the anatase (30-36 nm) and rutile (64-83 nm) polymorphs in the studied range, but the rutile fraction increases steadily at a higher Eu3+ addition, as revealed by X-ray diffraction (XRD) and Raman spectroscopy, because of the creation of oxygen vacancies in the TiO2 gas clusters by substitutional Eu3+ doping. The amount of Eu3+ that can be doped into a TiO2 lattice was limited up to 0.5 atom%, above which Eu2Ti2O7 pyrochlore was formed in the final products. High resolution transmission electron microscopy (HRTEM) observation indicates that the particles are dense and have sizes ranging from several nanometers up to 180 nm. Efficient nonradiative energy transfer from the TiO2 host to Eu3+ ions, which was seldom reported in the wet-chemically derived nanoparticles or thin films of the current system, was confirmed by combined studies of excitation, UV-vis (ultraviolet-visible), and PL (photoluminescence) spectroscopy. As a consequence of this, bright red emissions were observed from the plasma-generated nanopowders either by exciting the TiO2 host with UV light shorter than 405 nm or by directly exciting Eu3+ at a wavelength beyond the absorption edge (405 nm) of TiO2.

  18. Information Retrieval for Ecological Syntheses

    Science.gov (United States)

    Bayliss, Helen R.; Beyer, Fiona R.

    2015-01-01

    Research syntheses are increasingly being conducted within the fields of ecology and environmental management. Information retrieval is crucial in any synthesis in identifying data for inclusion whilst potentially reducing biases in the dataset gathered, yet the nature of ecological information provides several challenges when compared with…

  19. Phase contrast image synthesis

    DEFF Research Database (Denmark)

    Glückstad, J.

    1996-01-01

    A new method is presented for synthesizing arbitrary intensity patterns based on phase contrast imaging. The concept is grounded on an extension of the Zernike phase contrast method into the domain of full range [0; 2 pi] phase modulation. By controlling the average value of the input phase funct...... function and by choosing appropriate phase retardation at the phase contrast filter, a pure phase to intensity imaging is accomplished. The method presented is also directly applicable in dark field image synthesis....

  20. Development and validation of mathematical methods for the evaluation of spectroscopic data of uranyl (VI) hxdrolysis; Entwicklung und Validierung mathematischer Methoden zur Auswertung spektroskopischer Daten der Uranyl(VI)-Hydrolyse

    Energy Technology Data Exchange (ETDEWEB)

    Drobot, Bjoern

    2016-08-18

    The availability of metals in the biosphere is determined by the chemical state. Spectroscopic methods are appropriate for the analysis of speciation - the problem is the data processing. In the frame of the thesis the use of the software PARAFAC was used to analyze the excitation spectra of uranyl (VI) hydrolysis. It was shown that modern mathematical tools are essential for the data processing. The range of applicability covers deprotonation processes up to complex biochemical processes.

  1. Uranium (VI) chemistry at the interface solution/minerals (quartz and aluminium hydroxide): experiments and spectroscopic investigations of the uranyl surface species; Chimie de l'uranium (VI) a l'interface solution/mineraux (quartz et hydroxyde d'aluminium): experiences et caracterisations spectroscopiques

    Energy Technology Data Exchange (ETDEWEB)

    Froideval, A.

    2004-09-15

    This study deals with the understanding of the uranyl chemistry at the 0.1 M NaNO{sub 3} solution/mineral (quartz and aluminium hydroxide) interface. The aims are:(i) to identify and to characterize the different uranyl surface species (mononuclear, polynuclear complexes and/or precipitates...), i.e. the coordination environments of sorbed/precipitated uranyl ions, by using X-ray photoelectron spectroscopy (XPS), extended X-ray absorption fine structure (EXAFS) and time-resolved laser-induced fluorescence spectroscopy (TRLFS), and;(ii) to investigate the influence of pH, initial uranyl aqueous concentration and hydroxyl ligand concentration on the uranyl surface speciation. Our study on the speciation of uranyl ions at the quartz surface (i) confirms the formation of uranyl polynuclear/oligomers on quartz from moderate (1 {mu}mol/m{sup 2}) to high (26 {mu}mol/m{sup 2}) uranyl surface concentrations and (ii) show that theses polynuclear species coexist with uranyl mononuclear surface species over a pH range {approx_equal} 5-8.5 and a wide range of initial uranyl concentration o f the solutions (10-100 {mu}M). The uranyl concentration of these surface species depends on pH and on the initial uranyl aqueous concentration. Hydrate (surface-) precipitates and/or adsorbed polynuclear species and monomeric uranyl surface complexes are formed on aluminium hydroxide. Uranyl mononuclear complexes are predominant at acidic pH, as well as uranyl in solution or on the surface. Besides mononuclear species, precipitates and/or adsorbed polynuclear species are predominantly formed at neutral pH values on aluminium hydroxide. A main contribution of our investigations is that precipitation and/or adsorption of polynuclear species seem to occur at low uranyl surface concentrations (0.01-0.4 {mu}mol/m{sup 2}). The uranyl surface speciation is mainly dependent on the pH and the aluminol ligand concentration. (author)

  2. Mechanistic study of the interaction of uranyl ions with zirconium oxide and zirconium silicate; Etude mecanistique de l'interaction des ions uranyle avec l'oxyde et le silicate de zirconium

    Energy Technology Data Exchange (ETDEWEB)

    Lomenech, C

    2002-04-01

    This work deals with structural and thermodynamic studies of the sorption of uranyl species on zircon and zirconia. After determination of the specific areas, of the pH of the isoelectric points, and of the sorption site numbers, thermodynamic data were obtained using alpha spectrometry, for different uranyl concentrations, different background electrolytes (NaClO{sub 4} or KNO{sub 3}) and different ionic strengths. The structural identification of the surface complexes and sorption sites was carried out using several spectroscopies: XPS spectroscopy allowed a determination of the nature of the sorption sites ({identical_to}Zr-O- on zirconia and {identical_to}Si-O- on zircon). Whereas fluorescence decay measurements gave the number of surface species, the combined use of XPS spectroscopy and laser spectro-fluorimetry enabled us to correlate differences in bonding energies and emission wavelengths with differences in the nature of the background electrolyte or in the pH of sorption; DRIFT spectroscopy was a powerful tool for the determination of the presence of sorbed uranyl nitrate species. EXAFS results clearly showed a splitting of the equatorial oxygen atoms in two shells, corresponding to a polydentate, inner-sphere complex. EXAFS results also indicated strong similarities between dry samples and in situ experiments, which confirms the validity of all the spectroscopic measurements. Macroscopic thermodynamic data were then modeled using a surface complexation model (2 pK and constant capacitance models), the results of the structural study being used as constraints for the simulation code FITEQL. (author)

  3. Determination of halogens, silicon, phosphorus, carbon, sulfur, tributyl phosphate and of free acid in uranyl nitrate solutions

    International Nuclear Information System (INIS)

    Chu Van Vinh

    2003-01-01

    High-purity uranium compounds are widely used in nuclear field in the form of uranyl nitrate or uranium oxides. In production of uranium material the estimation and the control of products quality is necessary and very important. Halogens was separated from uranium compounds by steam distillation and they were later determined by high performance liquid chromatography (HPLC) for Cl - , Br - , I - ions. Br - was also determined by spectrophotometric and iodide by the individual pulse polarography. Silicon and phosphorus in uranyl nitrate solutions were determined by the photometric method. Sulfur was determined as sulfate form by the measurement of turbidity by the titrimetry. TBP in kerosene and free acid in aqueous solution were determined by the titration. (author)

  4. Effect of crystal size on purity of uranyl nitrate hexahydrate crystalline particles grown in nitric acid medium (orig.)

    International Nuclear Information System (INIS)

    Nakahara, M.; Nomura, K.

    2012-01-01

    Crystal washing experiments were carried out using a uranyl nitrate solution in order to confirm the effect of uranyl nitrate hexahydrate (UNH) crystalline particle size on the removal of liquid impurities. The UNH crystal was immersed in a Ce solution and was washed for removing the mother liquor on the surface of the UNH crystals. Larger UNH crystals were advantageous for increasing the decontamination factors (DFs) of liquid impurities. The large crystal size reduced the specific surface area of the crystals which in turn decreased the adhesion of liquid impurities on the surface of the crystals. Therefore, high DFs of liquid impurities were achieved before and after washing. In the crystallization experiments, the DFs of metals for the UNH crystal were evaluated using a dissolver solution derived from irradiated fast neutron reactor core fuel. The UNH crystal size did not affect the decontamination of solid impurities such as Ba and Np even after crystal washing in the U crystallization experiments. (orig.)

  5. Determination by vibrational spectra of the strength and the bond length of atoms U and O in uranyl complexes

    International Nuclear Information System (INIS)

    Rodriguez S, A.; Martinez Q, E.

    1996-01-01

    The vibrational spectra of different uranyl compounds were studied. The wave number was related to the harmonic oscillator model and to the mathematical expression of Badger as modified by Jones, to determine the strength and the bond length of atoms U and O in UO 2 2+ . A mathematical simplification develop by us is proposed and its results compared with values obtained by other methods. (Author)

  6. Topologically and geometrically flexible structural units in seven new organically templated uranyl selenates and selenite-selenates

    Science.gov (United States)

    Gurzhiy, Vladislav V.; Kovrugin, Vadim M.; Tyumentseva, Olga S.; Mikhaylenko, Pavel A.; Krivovichev, Sergey V.; Tananaev, Ivan G.

    2015-09-01

    Single crystals of seven novel uranyl oxysalts of selenium with protonated methylamine molecules, [C2H8N]2[(UO2)(SeO4)2(H2O)] (I), [C2H8N]2[(UO2)2(SeO4)3(H2O)] (II), [C4H15N3][H3O]0.5[(UO2)2(SeO4)2.93(SeO3)0.07(H2O)](NO3)0.5 (III), [C2H8N]3[H5O2][(UO2)2(SeO4)3(H2O)2]2(H2O)5 (IV), [C2H8N]2[H3O][(UO2)3(SeO4)4(HSeO3)(H2O)](H2SeO3)0.2 (V), [C4H12N]3[H3O][(UO2)3(SeO4)5(H2O)] (VI), and [C2H8N]3(C2H7N)[(UO2)3(SeO4)4(HSeO3)(H2O)] (VII) have been prepared by isothermal evaporation from aqueous solutions. Their crystal structures have been solved by direct methods and their uranyl selenate and selenite-selenate units investigated using black-and-white graphs from the viewpoints of topology of interpolyhedral linkages and isomeric variations. The crystal structure of IV is based upon complex layers with unique topology, which has not been observed previously in uranyl selenates. Investigations of the statistics and local distribution of the U-Obr-Se bond angles demonstrates that shorter angles associate with undulations, whereas larger angles correspond to planar areas of the uranyl selenite layers.

  7. Bioactive nanocrystalline wollastonite synthesized by sol–gel ...

    Indian Academy of Sciences (India)

    The sol–gel combustion method was employed to synthesize the nanocrystalline wollastonite by taking the raw eggshell powder as a calcium source and TEOS as a source of silicate. Glycine was used as a reductant or fuel and nitrate ions present in metal nitrate acts as an oxidizer. The phase purity of the wollastonite was ...

  8. Effect of diluent on extraction of uranyl nitrate from nitric acid solution by tri-n-octylamine

    International Nuclear Information System (INIS)

    Kojima, Takashi; Ukon, Toshiaki; Fukutomi, Hiroshi

    1979-01-01

    The distribution ratios in the extraction equilibriums of uranylnitrate from 3 M HNO 3 by tri-n-octylamine (TOA) nitrate salt in nitrobenzene, chlorobenzene, benzene, toluene, cyclohexane, nitrobenzene-benzene and benzene-cylohexane mixtures have been determined in varying the concentrations of uranyl nitrate and TOA nitrate salt. The extraction mechanisms have been discussed in detail based on the law of mass action. It has been concluded that the extractions of uranyl nitrate by TOA nitrate salt in nitrobenzene, 74% nitrobenzene-benzene and 49% nitrobenzene-benzene mixture are represented by the equation TOAHNO 3 (org) + UO 2 2+ (aq) + 2 NO 3 - (aq) = TOAHUO 2 (NO 3 - ) 3 (org), while the extractions of uranyl nitrate by TOA nitrate salt in chlorobenzene, benzene, toluene, cyclohexane, benzene-cyclohexane mixtures and 24% nitrobenzene-benzene mixture are represented by the equation 2 TOAHNO 3 (org) + UO 2 2+ (aq) + 2 NO 3 - (aq) = TOAHUO 2 (NO 3 ) 3 TOAHNO 3 (org). In the latter the extraction equilibrium constants increase in the order of chlorobenzene < benzene < toluene < cyclohexane and with decreasing of the volume fraction of benzene in benzene-cyclohexane mixtures. The effects of diluent have been discussed in detail on the basis of the Hildebrand-Scatchard theory of regular solutions. (author)

  9. A simple solution-phase approach to synthesize high quality ternary AgInSe2 and band gap tunable quaternary AgIn(S1-xSe x)2 nanocrystals

    KAUST Repository

    Bai, Tianyu

    2014-01-01

    A facile solution-phase route for the preparation of AgInSe2 nanocrystals was developed by using silver nitrate, indium stearate, and oleylamine-selenium (OAm-Se) as precursors. The evolution process of the AgInSe2 nanocrystals is discussed in detail and different reaction conditions all have a great impact on the growth and morphology of the nanocrystals. Alloyed AgIn(S1-xSex)2 nanocrystals with controlled composition across the entire range (0 ≤ x ≤ 1) was also successfully prepared by modulating the S/Se reactant mole ratio. X-ray diffraction (XRD), energy dispersive X-ray (EDX), X-ray photoelectron spectroscopy (XPS) and transmission electron microscopy (TEM) were used to confirm that the alloyed AgIn(S1-xSex)2 nanocrystals are homogeneous. The UV-vis absorption spectra revealed that the band gap energies of the alloyed AgIn(S1-xSex)2 nanocrystals could be continuously tuned by increasing the Se content. © The Royal Society of Chemistry 2014.

  10. Oxo-functionalization and reduction of the uranyl ion through lanthanide-element bond homolysis: synthetic, structural, and bonding analysis of a series of singly reduced uranyl-rare earth 5f1-4f(n) complexes.

    Science.gov (United States)

    Arnold, Polly L; Hollis, Emmalina; Nichol, Gary S; Love, Jason B; Griveau, Jean-Christophe; Caciuffo, Roberto; Magnani, Nicola; Maron, Laurent; Castro, Ludovic; Yahia, Ahmed; Odoh, Samuel O; Schreckenbach, Georg

    2013-03-13

    The heterobimetallic complexes [{UO2Ln(py)2(L)}2], combining a singly reduced uranyl cation and a rare-earth trication in a binucleating polypyrrole Schiff-base macrocycle (Pacman) and bridged through a uranyl oxo-group, have been prepared for Ln = Sc, Y, Ce, Sm, Eu, Gd, Dy, Er, Yb, and Lu. These compounds are formed by the single-electron reduction of the Pacman uranyl complex [UO2(py)(H2L)] by the rare-earth complexes Ln(III)(A)3 (A = N(SiMe3)2, OC6H3Bu(t)2-2,6) via homolysis of a Ln-A bond. The complexes are dimeric through mutual uranyl exo-oxo coordination but can be cleaved to form the trimetallic, monouranyl "ate" complexes [(py)3LiOUO(μ-X)Ln(py)(L)] by the addition of lithium halides. X-ray crystallographic structural characterization of many examples reveals very similar features for monomeric and dimeric series, the dimers containing an asymmetric U2O2 diamond core with shorter uranyl U═O distances than in the monomeric complexes. The synthesis by Ln(III)-A homolysis allows [5f(1)-4f(n)]2 and Li[5f(1)-4f(n)] complexes with oxo-bridged metal cations to be made for all possible 4f(n) configurations. Variable-temperature SQUID magnetometry and IR, NIR, and EPR spectroscopies on the complexes are utilized to provide a basis for the better understanding of the electronic structure of f-block complexes and their f-electron exchange interactions. Furthermore, the structures, calculated by restricted-core or all-electron methods, are compared along with the proposed mechanism of formation of the complexes. A strong antiferromagnetic coupling between the metal centers, mediated by the oxo groups, exists in the U(V)Sm(III) monomer, whereas the dimeric U(V)Dy(III) complex was found to show magnetic bistability at 3 K, a property required for the development of single-molecule magnets.

  11. An empirical method for calculating thermodynamic parameters for U(6) phases, applications to performance assessment calculations

    International Nuclear Information System (INIS)

    Ewing, R.C.; Chen, F.; Clark, S.B.

    2002-01-01

    Uranyl minerals form by oxidation and alteration of uraninite, UO 2+x , and the UO 2 in used nuclear fuels. The thermodynamic database for these phases is extremely limited. However, the Gibbs free energies and enthalpies for uranyl phases may be estimated based on a method that sums polyhedral contributions. The molar contributions of the structural components to Δ f G m 0 and Δ f H m 0 are derived by multiple regression using the thermodynamic data of phases for which the crystal structures are known. In comparison with experimentally determined values, the average residuals associated with the predicted Δ f G m 0 and Δ f H m 0 for the uranyl phases used in the model are 0.08 and 0.10%, respectively. There is also good agreement between the predicted mineral stability relations and field occurrences, thus providing confidence in this method for the estimation of Δ f G m 0 and Δ f H m 0 of the U(VI) phases. This approach provides a means of generating estimated thermodynamic data for performance assessment calcination and a basic for making bounding calcination of phase stabilities and solubilities. (author)

  12. Method of synthesizing tungsten nanoparticles

    Science.gov (United States)

    Thoma, Steven G; Anderson, Travis M

    2013-02-12

    A method to synthesize tungsten nanoparticles has been developed that enables synthesis of nanometer-scale, monodisperse particles that can be stabilized only by tetrahydrofuran. The method can be used at room temperature, is scalable, and the product concentrated by standard means. Since no additives or stabilizing surfactants are required, this method is particularly well suited for producing tungsten nanoparticles for dispersion in polymers. If complete dispersion is achieved due to the size of the nanoparticles, then the optical properties of the polymer can be largely maintained.

  13. Zinc Oxide Nano crystals Synthesized by Quenching Technique

    International Nuclear Information System (INIS)

    Norhayati Abu Bakar; Akrajas Ali Umar; Muhamad Mat Salleh; Muhammad Yahya

    2011-01-01

    This paper reports an attempt to synthesize non toxic zinc oxide (ZnO) nano crystals using a simple quenching technique. The hot zinc oxide powder was quenched in hexane solution to obtain ZnO nano crystals. As the result, diameter size of the synthesized ZnO is 200 nm. It was also exhibited a good crystalline with wurtzite phase. The nano crystals properties of ZnO were revealed from good absorbance and green luminescence under UV exposure. This may be related with oxygen vacancy ionization during the annealing process. (author)

  14. Chemical, mass spectrometric, spectrochemical, nuclear, and radiochemical analysis of nuclear-grade uranyl nitrate solutions

    Energy Technology Data Exchange (ETDEWEB)

    1981-01-01

    The standard covers analytical procedures to determine compliance of nuclear-grade uranyl nitrate solution to specifications. The following methods are described in detail: uranium by ferrous sulfate reduction-potassium dichromate titrimetry and by ignition gravimetry; specific gravity by pycnometry; free acid by oxalate complexation; thorium by the Arsenazo(III) (photometric) method; chromium by the diphenylcarbazide (photometric) method; molybdenum by the thiocyanate (photometric) method; halogens separation by steam distillation; fluorine by specific ion electrode; halogen distillate analysis: chloride, bromide and iodide by amperometric microtitrimetry; bromine by the fluorescein (photometric) method; sulfate sulfur by (photometric) turbidimetry; phosphorus by the molybdenum blue (photometric) method; silicon by the molybdenum blue (photometric) method; carbon by persulfate oxidation-acid titrimetry; nonvolatile impurities by spectrography; volatile impurities by rotating-disk spark spectrography; boron by emission spectrography; impurity elements by spark source mass spectrography; isotopic composition by multiple filament surface-ionization mass spectrometry; uranium-232 by alpha spectrometry; total alpha activity by direct alpha counting; fission product activity by beta and gamma counting; entrained organic matter by infrared spectrophotometry. (JMT)

  15. Transient behavior of 10% enriched uranyl nitrate solution at criticality accident

    International Nuclear Information System (INIS)

    Ogawa, Kazuhiko; Nakajima, Ken; Ohno, Akio; Sakuraba, Koichi; Aizawa, Eiju; Morita Toshio

    1999-01-01

    Japan Atomic Energy Research Institute has started the supercritical experiment program using a 10% enriched uranyl nitrate solution focusing on safety research in reprocessing plants with the Transient Criticality Experiments Facility (TRACY) in the Nuclear Fuel Cycle Safety Engineering Research Facility (NUCEF). The purpose of the TRACY program is to obtain data both on nuclear and thermal-fluidic transient characteristics and on the confinement capabilities of radioactive materials in a postulated criticality accident in reprocessing plants. In the experiment, fuel composition, reactivity insertion method, reactivity insertion rate, total insertion reactivity and initial power can be varied for the experiment parameters. In the supercritical experiment, excess reactivity can be inserted up to 3dollars by withdrawal of a transient rod continuous feed of the solution fuel to the TRACY core tank. In the transient experiment with step reactivity insertion of 2.9dollars, peak power and peak pressure of the core obtained 1400 MW and 0.85 MPa, respectively. In this paper, we will present the outline of TRACY, the power and core pressure behavior changing the insertion reactivities with step reactivity insertion, and the peak power changing the reactivity insertion rate and initial power level with ramp reactivity insertion. (author)

  16. Critical Parameters of Complex Geometry Intersecting Cylinders Containing Uranyl Nitrate Solution

    Energy Technology Data Exchange (ETDEWEB)

    Rothe, Robert Emil; Briggs, Joseph Blair

    1999-06-01

    About three dozen previously unreported critical configurations are presented for very complex geometries filled with high concentration enriched uranyl nitrate solution. These geometries resemble a tall, thin Central Column (or trunk of a "tree") having long, thin arms (or "branches") extending up to four directions off the column. Arms are equally spaced from one another in vertical planes; and that spacing ranges from arms in contact to quite wide spacings. Both the Central Column and the many different arms are critically safe by themselves when each, alone, is filled with fissile solution; but, in combination, criticality occurs due to the interactions between arms and the column. Such neutronic interactions formed the principal focus of this study. While these results are fresh to the nuclear criticality safety industry and to those seeking novel experiments against which to validate computer codes, the experiments, themselves, are not recent. Over 100 experiments were performed at the Rocky Flats Critical Mass Laboratory between September, 1967, and February of the following year.

  17. Critical Parameters of Complex Geometries of Intersecting Cylinders Containing Uranyl Nitrate Solution

    Energy Technology Data Exchange (ETDEWEB)

    J. B. Briggs (INEEL POC); R. E. Rothe

    1999-06-14

    About three dozen previously unreported critical configurations are presented for very complex geometries filled with high concentration enriched uranyl nitrate solution. These geometries resemble a tall, thin Central Column (or trunk of a ''tree'') having long, thin arms (or ''branches'') extending up to four directions off the column. Arms are equally spaced from one another in vertical planes, and that spacing ranges from arms in contact to quite wide spacings. Both the Central Column and the many different arms are critically safe by themselves with each, alone, is filled with fissile solution; but, in combination, criticality occurs due to the interactions between arms and the column. Such neutronic interactions formed the principal focus of this study. While these results are fresh to the nuclear criticality safety industry and to those seeking novel experiments against which to validate computer codes, the experiments, themselves, are not recent. Over 100 experiments were performed at the Rocky Flats Critical Mass Laboratory between September, 1967, and February of the following year.

  18. Thermal decomposition study of uranyl nitrate and cerium hydroxide in a spray dryer

    International Nuclear Information System (INIS)

    Silva Wildhagen, G.R. da.

    1993-05-01

    A study, in a spray dryer system based on drying and thermal decomposition of uranyl nitrate solutions aiming the production of uranium trioxide adequate for the use in posterior steps of reduction and hydro fluorination in nuclear fuel cycle; and cerium hydroxide suspensions for the production of cerium oxide with high surface area is presented. Thus, the project and construction of a countercurrent spray dryer was elaborated for capacity of 10 Kg U O 3 /h and 3,5 k Ce O 2 /h. The methodology used in these experiments consisted in the analysis of several parameters (concentration and flow rate of the feed, atomization pressure and inlet temperature of the dryer) over the physical and chemical properties of the products. Using the obtained results, with the help of a mathematical model, it was developed the project of a continuous pilot unity for the production of uranium trioxide or cerium oxide, with capacity of 20 Kg U O 3 /h or 10 Kg Ce O 2 /h, respectively. (author)

  19. Highly sensitive detection of ionizing radiations by a photoluminescent uranyl organic framework

    Energy Technology Data Exchange (ETDEWEB)

    Xie, Jian; Wang, Yaxing; Liu, Wei; Yin, Xuemiao; Chen, Lanhua; Diwu, Juan; Chai, Zhifang; Wang, Shuao [School for Radiological and interdisciplinary Sciences (RAD-X) and Collaborative Innovation Center of Radiation Medicine of Jiangsu Higher Education Institutions, Soochow University, Suzhou (China); Zou, Youming [High Magnetic Field Laboratory, Chinese Academy of Sciences, Hefei, Anhui (China); Albrecht-Schmitt, Thomas E. [Department of Chemistry and Biochemistry, Florida State University, Tallahassee, FL (United States); Liu, Guokui [Chemical Sciences and Engineering Division, Argonne National Laboratory, Argonne, IL (United States)

    2017-06-19

    Precise detection of low-dose X- and γ-radiations remains a challenge and is particularly important for studying biological effects under low-dose ionizing radiation, safety control in medical radiation treatment, survey of environmental radiation background, and monitoring cosmic radiations. We report here a photoluminescent uranium organic framework, whose photoluminescence intensity can be accurately correlated with the exposure dose of X- or γ-radiations. This allows for precise and instant detection of ionizing radiations down to the level of 10{sup -4} Gy, representing a significant improvement on the detection limit of approximately two orders of magnitude, compared to other chemical dosimeters reported up to now. The electron paramagnetic resonance analysis suggests that with the exposure to radiations, the carbonyl double bonds break affording oxo-radicals that can be stabilized within the conjugated uranium oxalate-carboxylate sheet. This gives rise to a substantially enhanced equatorial bonding of the uranyl(VI) ions as elucidated by the single-crystal structure of the γ-ray irradiated material, and subsequently leads to a very effective photoluminescence quenching through phonon-assisted relaxation. The quenched sample can be easily recovered by heating, enabling recycled detection for multiple runs. (copyright 2017 Wiley-VCH Verlag GmbH and Co. KGaA, Weinheim)

  20. Long-term kinetics of uranyl desorption from sediments under advective conditions

    Science.gov (United States)

    Shang, Jianying; Liu, Chongxuan; Wang, Zheming; Zachara, John

    2014-02-01

    Long-term (>4 months) column experiments were performed to investigate the kinetics of uranyl (U(VI)) desorption in sediments collected from the Integrated Field Research Challenge site at the U.S. Department of Energy Hanford 300 Area. The experimental results were used to evaluate alternative multirate surface complexation reaction (MRSCR) approaches to describe the short and long-term kinetics of U(VI) desorption under flow conditions. The surface complexation reaction (SCR) stoichiometry and equilibrium constants and multirate parameters in the MRSCR models were independently characterized in batch and stirred flow-cell reactors. MRSCR models that were either additively constructed using the MRSCRs for individual size fractions, or composite in nature, could effectively describe short-term U(VI) desorption under flow conditions. The long-term desorption results, however, revealed that using the labile U concentration measured by carbonate extraction underestimated desorbable U(VI) and the long-term rate of U(VI) desorption. This study also found that the gravel size fraction (2-8 mm), which is typically treated as nonreactive in modeling U(VI) reactive transport because of low external surface area, can have an important effect on the U(VI) desorption in the sediment. This study demonstrates an approach to effectively extrapolate U(VI) desorption kinetics for field-scale application and identifies important parameters and uncertainties affecting model predictions.

  1. High temperature interaction studies on equimolar nitrate mixture of uranyl nitrate hexahydrate and gadolinium nitrate hexahydrate

    International Nuclear Information System (INIS)

    Kalekar, Bhupesh B.; Raje, Naina; Reddy, A.V.R.

    2015-01-01

    Rare earths including gadolinium form a sizeable fraction of the fission products in the nuclear fission of fissile material in the reactor. These fission products can interact with uranium dioxide fuel and can form various compounds which can alter the thermal behavior of the fuel. The mixed oxide formed due to the high temperature interactions of mixture of uranyl nitrate hexahydrate (UNH) and gadolinium nitrate hexahydrate (GdNH) has been studied using thermal and X- ray diffraction techniques. The equimolar mixture of UNH and GdNH was prepared by mixing the weighed amount of individual nitrates and grinding gently with mortar and pestle. Thermogravimetry (TG) measurements were carried out by separately heating 100 mg of mixture and individual nitrates at heating rate of 10°C min -1 using Netzsch thermal analyzer (Model No.: STA 409 PC Luxx) in high purity nitrogen atmosphere with a flow rate of 120 mL min -1 . The XRD measurement was carried out on a Philips X-ray diffractometer (Model PW1710) using nickel-filtered Cu-Kα radiation

  2. Temperature effects on the interaction mechanisms between the europium (III) and uranyl ions and zirconium diphosphate

    International Nuclear Information System (INIS)

    Finck, N.

    2006-10-01

    Temperature should remain higher than 25 C in the near field environment of a nuclear waste repository for thousands years. In this context, the aim of this work is to study the temperature influence on the interaction mechanisms between europium (III) and uranyl ions and zirconium diphosphate, as well as the influence of a complexing medium (nitrate) on the sorption of the lanthanide. The experimental definition of the equilibria was achieved by combining a structural investigation with the macroscopic sorption data. Surface complexes were characterized at all temperatures (25 C to 90 C) by TRLFS experiments carried out on dry and in situ samples using an oven. This characterization was completed by XPS experiments carried out at 25 C on samples prepared at 25 C and 90 C. The reaction constants (surface hydration and cations sorption) were obtained by simulating the experimental data with the constant capacitance surface complexation model. The reaction constants temperature dependency allowed one to characterize thermodynamically the different reactions by application of the van't Hoff relation. The validity of this law was tested by performing microcalorimetric measurements of the sorption heat for both cations. (author)

  3. The toxicity of uranyl nitrate on primary brain cell culture of L. Hoevenii

    International Nuclear Information System (INIS)

    Ismail Bahari; Fauziah Mohd Noor

    1995-01-01

    In Malaysia, uranium is indirectly being concentrated by mining and petroleum industries that have no relevance to its use. Concentration of uranium and the production of TENORM may give rise to radiological risk to workers and the environment. A study was conducted to determine the toxicity of a uranium compound, uranyl nitrate. For this purpose a primary brain cell culture derived from L. hoevenii was used. The nature of uranil nitrate toxicity was determined by comparing with the effects induced by mitomycin C and gamma radiation. The toxicity of these agents were measured by observing changes in Unschedule DNA Synthesis (UDS) and the induction of micronucleus. Result from the study showed that UO sub 2 sup 2+ is UDS positive and is toxic to the primary brain cells of L. hoevenii. It gives a response profile that is almost similar to that induced by gamma radiation and mitomycin C. We believed that a low concentration, UO sub 2 sup 2+ acts as a chemo toxic agent rather than as an ionising radiation. At higher concentration the toxicity of UO sub 2 sup 2+ comes from both its chemo toxic and radiation effects. Results of this study also show the ability of the primary culture to carry out repair on its DNA damaged by the UDS positive agents

  4. A low-power CMOS frequency synthesizer for GPS receivers

    International Nuclear Information System (INIS)

    Yu Yunfeng; Xiao Shimao; Zhuang Haixiao; Ma Chengyan; Ye Tianchun; Yue Jianlian

    2010-01-01

    A low-power frequency synthesizer for GPS/Galileo L1/E1 band receivers implemented in a 0.18 μm CMOS process is introduced. By adding clock-controlled transistors at latch outputs to reduce the time constant at sensing time, the working frequency of the high-speed source-coupled logic prescaler supplying quadrature local oscillator signals has been increased, compared with traditional prescalers. Measurement results show that this synthesizer achieves an in-band phase noise of -87 dBc/Hz at 15 kHz offset, with spurs less than -65 dBc. The whole synthesizer consumes 6 mA in the case of a 1.8 V supply, and its core area is 0.6 mm 2 . (semiconductor integrated circuits)

  5. Uranyl citrate dimers as guests in a copper-bipyridine framework: a novel hetero-metallic inorganic-organic hybrid compound

    International Nuclear Information System (INIS)

    Thuery, P.

    2007-01-01

    Reaction of uranyl nitrate with citric acid (H 4 cit) in the presence of copper(II) bis(tri-fluoro-methane-sulfonate) and 4,4'-bipyridine (bipy) under hydrothermal conditions gave the mixed complex[Cu(bipy) 2 (H 2 O) 2 ][UO 2 (Hcit)(H 2 O)] 2 .5H 2 O, in which di-anionic uranyl citrate dimers are incorporated in the interlayer spaces of the [Cu(bipy) 2 (H 2 O) 2 ] n 2n+ square grid assemblage. An extended hydrogen bonding network links the uranyl complex units together and also to the grid framework, resulting in the formation of a 3-D assemblage held by weak interactions. (author)

  6. Study of ligand exchange kinetics in uranyl complexes with neutral organic phosphorus compounds accordipg to deactivation of excited states in aqueous solutions

    International Nuclear Information System (INIS)

    Yakshin, V.V.; Khokhlova, N.L.; Kazakov, V.P.; Afonichev, D.D.

    1983-01-01

    To study kinetic regularities of ligand exchange in aqueous solutions the photoluminescence method, based on the study of deactivation process of uranyl fluorescence, is used. It is found that introduction of neutral organophosphoric ligands to solutions of UO 2 2+ ions results in effective quenching of uranyl luminescence. Taking into account the intensity decrease of photoluminescence and life-time of UO 2 2+ in the excited state, caused by the change of ligand concentration in solution, the quenching constants, corresponding to substitution rate constants in coordination sphere of uranyl, are found. It is shown that the interaction studied obeys the rule of free energies linearity. Quantitative processing of the results using the least square method permitted to obtain linear equations, connecting ligand exchange constants with the ligand electron structure. The correlation equations found can be used to forecast the rate constants of ligand exchange of considerable number of neutral organophosphoric ligands

  7. Dehydration of the Uranyl Peroxide Studtite, [UO22-O2)(H2O)2]·2H2O, Affords a Drastic Change in the Electronic Structure: A Combined X-ray Spectroscopic and Theoretical Analysis

    Energy Technology Data Exchange (ETDEWEB)

    Vitova, Tonya [Institute for Nuclear Waste Disposal (INE), Hermann-von-Helmholtz-Platz 1, D-76344 Eggenstein-Leopoldshafen, Germany; Pidchenko, Ivan [Institute for Nuclear Waste Disposal (INE), Hermann-von-Helmholtz-Platz 1, D-76344 Eggenstein-Leopoldshafen, Germany; Biswas, Saptarshi [School; Beridze, George [Institute of Energy and Climate Research,; JARA High-Performance Computing, Schinkelstrasse 2, 52062 Aachen, Germany; Dunne, Peter W. [School; Schild, Dieter [Institute for Nuclear Waste Disposal (INE), Hermann-von-Helmholtz-Platz 1, D-76344 Eggenstein-Leopoldshafen, Germany; Wang, Zheming [Pacific Northwest National Laboratory, MSIN K8-96, P.O. Box 999, Richland, Washington 99352, United States; Kowalski, Piotr M. [Institute of Energy and Climate Research,; JARA High-Performance Computing, Schinkelstrasse 2, 52062 Aachen, Germany; Baker, Robert J. [School

    2018-02-05

    The dehydration of studtite, [UO2(2-O2)(H2O)2]·2H2O, to metastudtite, [UO2(2-O2)(H2O)2], uranyl peroxide minerals that are major oxidative alteration phases of UO2 under conditions of geological storage, has been studied using X-ray photoelectron spectroscopy (XPS) and X-ray absorption spectroscopy. XPS of the U 4f region shows small but significant differences between studtite and metastudtite, with the 4f binding energy of studtite the highest reported for a uranyl mineral studied by this technique. Further information on the changes in the electronic structure was elucidated using U M4-edge High Energy Resolution XANES (HR-XANES) spectroscopy, which directly probes f-orbital states. The transition from the 3d to the 5f* orbital is sensitive to variations of the U=Oaxial bond length and to changes in the bond covalency. We report evidences that the covalence in the uranyl fragment decreases upon dehydration. Photoluminescence spectroscopy at near liquid helium temperatures reveals significant spectral differences between the two materials, correlating with the X-ray spectroscopy results. A theoretical investigation has been conducted on the structures of both studtite and metastudtite and benchmarked to the HR-XANES spectra. These illustrate the sensitivity of the 3d to the 5f * transition towards U=Oaxial bond variation.

  8. Rapid hydrothermal route to synthesize cubic-phase gadolinium ...

    Indian Academy of Sciences (India)

    Furthermore, ∼ plot of the nanorod system (pH = 10.8) exhibited slight departure from the ideal superparamagnetic behaviour, with low remanence and coercive field values. The exploitation of one-dimensional Gd2O3 nanorods have immense potential in the production of advanced contrast agents, smart drives and ...

  9. Designing the Ideal Uranyl Ligand: a Sterically-Induced Speciation Change in Complexes with Thiophene-Bridged Bis(3-hydroxy-N-methylpyridin-2-one)

    Energy Technology Data Exchange (ETDEWEB)

    Szigethy, Geza; Raymond, Kenneth N.

    2009-09-11

    Structural characterization of a mononuclear uranyl complex with a tetradentate, thiophene-linked bis(3-hydroxy-N-methylpyridin-2-one) ligand reveals the most planar coordination geometry yet observed with this ligand class. The introduction of ethylsulfanyl groups onto the thiophene linker disrupts this planar, conjugated ligand arrangement, resulting in the formation of dimeric (UO{sub 2}){sub 2}L{sub 2} species in which each ligand spans two uranyl centers. Relative energy calculations reveal that this tendency toward dimer formation is the result of steric interference between ethylsulfanyl substituents and linking amides.

  10. Synthese de champs sonores adaptative

    Science.gov (United States)

    Gauthier, Philippe-Aubert

    La reproduction de champs acoustiques est une approche physique au probleme technologique de la spatialisation sonore. Cette these concerne l'aspect physique de la reproduction de champs acoustiques. L'objectif principal est l'amelioration de la reproduction de champs acoustiques par "synthese de champs acoustiques" ("Wave Field Synthesis", WFS), une approche connue, basee sur des hypotheses de champ libre, a l'aide du controle actif par l'ajout de capteurs de l'erreur de reproduction et d'une boucle fermee. Un premier chapitre technique (chapitre 4) expose les resultats d'appreciation objective de la WFS par simulations et mesures experimentales. L'effet indesirable de la salle de reproduction sur les qualites objectives de la WFS fut illustre. Une premiere question de recherche fut ensuite abordee (chapitre 5), a savoir s'il est possible de reproduire des champs progressifs en salle dans un paradigme physique de controle actif: cette possibilite fut prouvee. L'approche technique privilegiee, "synthese de champs adaptative" ("Adaptive Wave Field Synthesis" [AWFS]), fut definie, puis simulee (chapitre 6). Cette approche d'AWFS comporte une originalite en controle actif et en reproduction de champs acoustiques: la fonction cout quadratique representant la minimisation des erreurs de reproduction inclut une regularisation de Tikhonov avec solution a priori qui vient de la WFS. L'etude de l'AWFS a l'aide de la decomposition en valeurs singulieres (chapitre 7) a permis de comprendre les mecanismes propres a l'AWFS. C'est la deuxieme principale originalite de la these. L'algorithme FXLMS (LMS et reference filtree) est modifie pour l'AWFS (chapitre 8). Le decouplage du systeme par decomposition en valeurs singulieres est illustre dans le domaine du traitement de signal et l'AWFS basee sur le controle independant des modes de rayonnement est simulee (chapitre 8). Ce qui constitue la troisieme originalite principale de cette these. Ces simulations du traitement de signal

  11. Isoreticular MOFs functionalized in the pore wall by different organic groups for high-performance removal of uranyl ions

    International Nuclear Information System (INIS)

    Li Li Song; Chao Chen; Ning Zhang; Feng Luo; Shu Yun Huang; Ling Ling Wang

    2016-01-01

    We report the studies of uranyl adsorption on a series of isoreticular Metal–organic frameworks (MOFs) with the same 3D framework decorated by different organic groups in the pore wall. Scanning electron microscope and energy dispersive X-ray spectroscopy indicated that the sorbents were capable of encaging uranium from aqueous solution. Typical adsorption isotherms (Langmuir, Freundlich) studies showed different mechanism of sorption process and kinetic studies described different sorption behavior of the MOF materials, which were due to the different functional groups. Finally, two MOFs were successfully employed to extract U(VI) ions from simulated seawater. (author)

  12. Photobehavior of aqueous uranyl ion and photo-oxygenation of isobutane using light from the visible region

    International Nuclear Information System (INIS)

    Bergfeldt, T.M.; Waltz, W.L.; Xu, X; Sedlak, P.; Dreyer, U.; Mockel, H.; Lilie, J.; Stephenson, J.W.

    2003-01-01

    The photochemical and photophysical behavior of the aqueous uranyl ion [UO 2 (H 2 O) 5 ] 2+ has been studied under the influence of visible light and with added perchloric acid over the range of 0.01-4 M. In the presence of 2-methylpropane (isobutane), photo-oxygenation of isobutane occurs to yield, as the major product, 2-methyl-2-propanol (tert-butyl alcohol) along with lesser amounts of 2-methyl-2-propene (isobutene) and other C1-C8 products. The quantum yield for formation of tert-butyl alcohol is independent of light intensity at the irradiation wavelength of 415 nm and of uranyl concentration, but it increases from 0.016 ± 0.001 at 0.01 M HC1O 4 (pH 2) to 0.13 ± 0.01 at 4 M HC1O 4 . The emission spectrum from the electronically excited uranyl ion and the associated quantum yields have been measured in the presence and absence of isobutane, as a function of added perchloric acid. While in both cases the shape of the spectrum remains invariant, the quantum yields increase with increasing perchloric acid concentration. The strong dependence on added perchloric acid is interpreted within the context of the presence and interconversion of two electronically excited species, an acid form, *[UO 2 (H 2 O) 5 ] 2+ , and a base form, *[UO 2 (H 2 O) n (OH)] + . It is proposed that both forms react with isobutane to give a tert-butyl radical, and that oxidation of coordinated aqua ligands occur, the latter generating a hydroxyl radical whose reaction with isobutane rapidly leads also to a tert-butyl radical. The reaction of this alkyl radical with ground-state [UO 2 (H 2 O) 5 ] 2+ then gives rise to the stable tert-butyl alcohol product and reduced forms of uranyl ion. Based upon the values of the quantum yields and of excited-state lifetime measurements reported in the literature, a comprehensive mechanism has been developed in a quantitative manner to provide calculated values of the rate constants for the individual mechanistic steps. The calculated rate constants

  13. Zirconia silicate modified with phytic acid (IP6) and its effect on uranyl sorption

    International Nuclear Information System (INIS)

    Escalante G, D. C.

    2016-01-01

    In this work the sorption capacity of uranyl ions on zirconium silicate (ZrSiO 4 ) extracted from sea sand of Baja California Sur was studied, the effect of phytic acid (IP6) accompanied by a perchlorate salt of sodium (NaClO 4 ) on the surface of the mineral. In the first stage, ZrSiO 4 was obtained from sea sand by extraction using hydrofluoric acid, the purified and hydrated material was later characterized by instrumental techniques such as X-ray diffraction to determine its purity and crystallinity. The ZrSiO 4 -purified, ZrSiO 4 /NaClO 4 and ZrSiO 4 /IP6 were studied by physicochemical and surface characterization. By scanning electron microscopy was observed that ZrSiO 4 initially is formed by flat structures, however, when it is hydrated with NaClO 4 the formation of particles on the material exists, whereas when the IP6 is added the crystals on the surface are elongated forming structures geometric shapes. This modification on the surface of the ZrSiO 4 was corroborated by atomic force microscopy where significant changes were observed in the topography of the purified and hydrated material. By Fourier transform infrared spectroscopy is identifies the presence of functional groups from hydration with IP6 and NaClO 4 on the surface of SrSiO 4 . Characterization of surface properties was performed by determining the surface area of the purified ZrSiO 4 , SrSiO 4 /NaClO 4 and ZrSiO 4 /IP6 systems using the Bet multipoint and fractal dimension technique; the hydration time, zero loading point was evaluated by means of a bulk titration and surface site density (Ds). The fluorescence and phosphorescence techniques allowed determining the optimum hydration point and the uranium species sorbed on the surface of the ZrSiO 4 as in the systems hydrated with IP6 and with NaClO 4 . This technique provided relevant information about the speciation and complex formation of IP6 with uranyl ions on the surface of ZrSiO 4 . Sorption isotherms and kinetics were prepared by

  14. Spark plasma sintering of hydrothermally synthesized bismuth ferrite

    Directory of Open Access Journals (Sweden)

    Zorica Branković

    2016-12-01

    Full Text Available Bismuth ferrite, BiFeO3 (BFO, powder was synthesized by hydrothermal method from Bi(NO33·5 H2O and Fe(NO33·9 H2O as precursors. The synthesized powder was further sintered using spark plasma sintering (SPS. The sintering conditions were optimized in order to achieve high density, minimal amount of secondary phases and improved ferroelectric and magnetic properties. The optimal structure and properties were achieved after spark plasma sintering at 630 °C for 20 min, under uniaxial pressure of 90 MPa. The composition, microstructure, ferroelectric and magnetic properties of the SPS samples were characterized and compared to those of conventionally sintered ceramics obtained from the same powder. Although the samples sintered using conventional method showed slightly lower amount of secondary phases, the spark plasma sintered samples exhibited favourable microstructure and better ferroelectric properties.

  15. Early effects of uranyl nitrate on respiration and K+ transport in rabbit proximal tubule

    International Nuclear Information System (INIS)

    Brady, H.R.; Kone, B.C.; Brenner, R.M.; Gullans, S.R.

    1989-01-01

    The mechanisms by which uranyl nitrate (UN) is toxic to the proximal tubule are incompletely understood. To define these further we studied potassium (K+) transport and oxygen consumption (QO2) in rabbit proximal tubule suspensions in vitro immediately after exposure to UN using extracellular O2- and K+-sensitive electrodes. UN caused a cumulative dose-dependent inhibition of proximal tubule QO2, with a threshold concentration of 5 x 10(-5) M. Kinetic analysis suggested two patterns of cell injury: a higher affinity inhibition of QO2 with a Ki of 5 x 10(-4) M, and a lower affinity inhibition of QO2 with a Ki of 10 mM. QO2 was studied in detail in the presence of these Ki concentrations of UN to define the initial cellular events. The results indicated that different cellular processes displayed different sensitivities to UN. At submillimolar concentrations UN caused progressive selective inhibition of ouabain-insensitive QO2 (15% inhibition at 2 minutes). Ouabain-sensitive QO2 and nystatin-stimulated QO2 were not affected, suggesting that Na+,K+-ATPase activity and its coupling to mitochondrial ATP synthesis were intact. Direct measurement of proximal tubule net K+ flux confirmed that Na+,K+-ATPase activity was unchanged. Similarly, UN did not inhibit basal (state 4) or ADP-stimulated (state 3) mitochondrial QO2 in digitonin-permeabilized tubules, confirming that the mitochondria were intact. In contrast, higher concentrations of UN (greater than or equal to 1 mM) caused rapid inhibition of QO2 and net K+ efflux, due to inhibition of Na+,K+-ATPase activity and mitochondrial injury

  16. Absorption and biokinetics of U in rats following an oral administration of uranyl nitrate solution

    Energy Technology Data Exchange (ETDEWEB)

    La Touche, Y.D.; Willis, D.L.; Dawydiak, O.I.

    1987-08-01

    The absorption of U within the male Wistar rat was determined following oral gavage with uranyl nitrate solutions at seven different dosages. Gavage levels ranged from 0.003 to 45 mg U per kilogram body weight. Uranium tissue burdens were determined at 0.25, 0.5, 1, 2, 4, 8, 24, 48, 96 and 240 h following gavage. Blood, kidney, liver and bone were analyzed for U content using neutron activation followed by delayed neutron counting. Uranium rapidly localized in the kidneys and bone following ingestion. Bone was found to be the primary tissue of deposition. Skeletal and kidney burdens closely paralleled each other from 15 min to 10 d after oral gavage. Uranium burdens in the blood reached a maximum within 30 min but declined rapidly thereafter. Burdens of all tissues were well correlated with each other and with dosage at all dose levels. Equations relating body burdens with blood levels were developed and found to be useful for predicting body burdens for the initial 8 h following gavage. Gastrointestinal absorption (f1) was 0.6-2.8% over the range of U administered. Movement of U through the GI tract was assessed at two dosages. The transit time of U through the GI tract was approximately 48 h. Uranium loss from the stomach was described as a power function of time. The maximum value in the small intestine was attained within 2 h, and thereafter its rapid loss was linear up to 8 h. A minor residual loss component from the small intestine was evident beyond 8 h post-gavage.

  17. Effects of sulfate ligand on uranyl carbonato surface species on ferrihydrite surfaces

    Science.gov (United States)

    Arai, Yuji; Fuller, C.C.

    2012-01-01

    Understanding uranium (U) sorption processes in permeable reactive barriers (PRB) are critical in modeling reactive transport for evaluating PRB performance at the Fry Canyon demonstration site in Utah, USA. To gain insight into the U sequestration mechanism in the amorphous ferric oxyhydroxide (AFO)-coated gravel PRB, U(VI) sorption processes on ferrihydrite surfaces were studied in 0.01 M Na2SO4 solutions to simulate the major chemical composition of U-contaminatedgroundwater (i.e., [SO42-]~13 mM L-1) at the site. Uranyl sorption was greater at pH 7.5 than that at pH 4 in both air- and 2% pCO2-equilibrated systems. While there were negligible effects of sulfate ligands on the pH-dependent U(VI) sorption (<24 h) in both systems, X-ray absorption spectroscopy (XAS) analysis showed sulfate ligand associated U(VI) surface species at the ferrihydrite–water interface. In air-equilibrated systems, binary and mono-sulfate U(VI) ternary surface species co-existed at pH 5.43. At pH 6.55–7.83, a mixture of mono-sulfate and bis-carbonato U(VI) ternary surface species became more important. At 2% pCO2, there was no contribution of sulfate ligands on the U(VI) ternary surface species. Instead, a mixture of bis-carbonato inner-sphere (38%) and tris-carbonato outer-sphere U(VI) ternary surface species (62%) was found at pH 7.62. The study suggests that the competitive ligand (bicarbonate and sulfate) coordination on U(VI) surface species might be important in evaluating the U solid-state speciation in the AFO PRB at the study site where pCO2 fluctuates between 1 and 2 pCO2%.

  18. Tailored super magnetic nanoparticles synthesized via template free hydrothermal technique

    Science.gov (United States)

    Attallah, Olivia A.; Girgis, E.; Abdel-Mottaleb, Mohamed M. S. A.

    2016-01-01

    Magnetite nanoparticles of controlled shape and dimensions were synthesized using a modified hydrothermal technique. The influence of different synthesis conditions on the shape, size (length and diameter), structure and magnetic properties of the prepared nanoparticles is presented. The mineral phases, the morphologies, size distribution of the resulting magnetic nanoparticles and their magnetic properties were characterized using different characterization methods. We designed magnetite nanoparticles with different morphologies (nanospheres, nanorods, nanocubes and hexagons) and with improved saturation magnetization reaching 90 emu/g.

  19. Analysis of Periodic Errors for Synthesized-Reference-Wave Holography

    Directory of Open Access Journals (Sweden)

    V. Schejbal

    2009-12-01

    Full Text Available Synthesized-reference-wave holographic techniques offer relatively simple and cost-effective measurement of antenna radiation characteristics and reconstruction of complex aperture fields using near-field intensity-pattern measurement. These methods allow utilization of advantages of methods for probe compensations for amplitude and phasing near-field measurements for the planar and cylindrical scanning including accuracy analyses. The paper analyzes periodic errors, which can be created during scanning, using both theoretical results and numerical simulations.

  20. Study of the changes in composition of ammonium diuranate with progress of precipitation, and study of the properties of ammonium diuranate and its subsequent products produced from both uranyl nitrate and uranyl fluoride solutions

    Energy Technology Data Exchange (ETDEWEB)

    Manna, Subhankar; Kumar, Raj; Satpati, Santosh K.; Roy, Saswati B. [Bhabha Atomic Research Centre, Trombay, Mumbai (India); Joshi, Jyeshtharaj B. [Dept. of Chemical Engineering, Institute of Chemical Technology, Mumbai (India)

    2017-04-15

    Uranium metal used for fabrication of fuel for research reactors in India is generally produced by magnesio-thermic reduction of UF{sub 4}. Performance of magnesio-thermic reaction and recovery and quality of uranium largely depends on properties of UF{sub 4}. As ammonium diuranate (ADU) is first product in powder form in the process flow-sheet, properties of UF{sub 4} depend on properties of ADU. ADU is generally produced from uranyl nitrate solution (UNS) for natural uranium metal production and from uranyl fluoride solution (UFS) for low enriched uranium metal production. In present paper, ADU has been produced via both the routes. Variation of uranium recovery and crystal structure and composition of ADU with progress in precipitation reaction has been studied with special attention on first appearance of the precipitate Further, ADU produced by two routes have been calcined to UO{sub 3}, then reduced to UO{sub 2} and hydroflorinated to UF{sub 4}. Effect of two different process routes of ADU precipitation on the characteristics of ADU, UO{sub 3}, UO{sub 2} and UF{sub 4} were studied here.

  1. Study of the changes in composition of ammonium diuranate with progress of precipitation, and study of the properties of ammonium diuranate and its subsequent products produced from both uranyl nitrate and uranyl fluoride solutions

    International Nuclear Information System (INIS)

    Manna, Subhankar; Kumar, Raj; Satpati, Santosh K.; Roy, Saswati B.; Joshi, Jyeshtharaj B.

    2017-01-01

    Uranium metal used for fabrication of fuel for research reactors in India is generally produced by magnesio-thermic reduction of UF 4 . Performance of magnesio-thermic reaction and recovery and quality of uranium largely depends on properties of UF 4 . As ammonium diuranate (ADU) is first product in powder form in the process flow-sheet, properties of UF 4 depend on properties of ADU. ADU is generally produced from uranyl nitrate solution (UNS) for natural uranium metal production and from uranyl fluoride solution (UFS) for low enriched uranium metal production. In present paper, ADU has been produced via both the routes. Variation of uranium recovery and crystal structure and composition of ADU with progress in precipitation reaction has been studied with special attention on first appearance of the precipitate Further, ADU produced by two routes have been calcined to UO 3 , then reduced to UO 2 and hydroflorinated to UF 4 . Effect of two different process routes of ADU precipitation on the characteristics of ADU, UO 3 , UO 2 and UF 4 were studied here

  2. Study of the Changes in Composition of Ammonium Diuranate with Progress of Precipitation, and Study of the Properties of Ammonium Diuranate and its Subsequent Products Produced from both Uranyl Nitrate and Uranyl Fluoride Solutions

    Directory of Open Access Journals (Sweden)

    Subhankar Manna

    2017-04-01

    Full Text Available Uranium metal used for fabrication of fuel for research reactors in India is generally produced by magnesio-thermic reduction of UF4. Performance of magnesio-thermic reaction and recovery and quality of uranium largely depends on properties of UF4. As ammonium diuranate (ADU is first product in powder form in the process flow-sheet, properties of UF4 depend on properties of ADU. ADU is generally produced from uranyl nitrate solution (UNS for natural uranium metal production and from uranyl fluoride solution (UFS for low enriched uranium metal production. In present paper, ADU has been produced via both the routes. Variation of uranium recovery and crystal structure and composition of ADU with progress in precipitation reaction has been studied with special attention on first appearance of the precipitate Further, ADU produced by two routes have been calcined to UO3, then reduced to UO2 and hydroflorinated to UF4. Effect of two different process routes of ADU precipitation on the characteristics of ADU, UO3, UO2 and UF4 were studied here.

  3. Calculation of concentration profiles and their experimental verification with a pulsed sieve-plate column and the reactive material system of uranyl nitrate, nitric acid/tributyl phosphate, kerosine

    International Nuclear Information System (INIS)

    Ihle, E.

    1985-01-01

    The present study is concerned with the calculation of stationary and non-stationary concentration profiles as well as with the starting and disturbance behaviour of a pulsed sieve-plate extraction column. It investigates into the material system HNO 3 /uranyl nitrate in water with 30 per cent by volume of tributyl phosphate in kerosine. During the measurements of the concentration profiles for HNO 3 transition, which were effected in the direction of extraction and reextraction, it was shown that the concentration profiles measured in the mixer-settler range, in spite of a sixfold enlargement of the specific heat transfer area, do not differ essentially from those measured in the dispersion range. During the measurements of concentration profiles for HNO 3 /uranium transition, which were effected in the direction of coextraction and co-reextraction only for mixer-settler range, it was discovered that with increasing phase ratios, there is a depletion of the uranium concentration in the aqueous phase. If the phase ratio is further raised, it is the nitric acid, and not the uranium, that is depleted. (orig./PW) [de

  4. Self-assembly of a 3d-5f trinuclear single-molecule magnet from a pentavalent uranyl complex

    International Nuclear Information System (INIS)

    Chatelain, Lucile; Pecaut, Jacques; Walsh, James P.S.; Tuna, Floriana; Mazzanti, Marinella

    2014-01-01

    Mixed-metal uranium compounds are very attractive candidates in the design of single-molecule magnets (SMMs), but only one 3d-5f hetero-polymetallic SMM containing a uranium center is known. Herein, we report two trimeric heterodimetallic 3d-5f complexes self-assembled by cation-cation interactions between a uranyl(V) complex and a TPA-capped M II complex (M=Mn (1), Cd (2); TPA=tris(2-pyridylmethyl)amine). The metal centers were strategically chosen to promote the formation of discrete molecules rather than extended chains. Compound 1, which contains an almost linear {Mn-O=U=O-Mn} core, exhibits SMM behavior with a relaxation barrier of 81±0.5 K - the highest reported for a mono-uranium system - arising from intramolecular Mn-U exchange interactions combined with the high Ising anisotropy of the uranyl(V) moiety. Compound 1 also exhibits an open magnetic hysteresis loop at temperatures less than 3 K, with a significant coercive field of 1.9 T at 1.8 K.

  5. Self-assembly of a 3d-5f trinuclear single-molecule magnet from a pentavalent uranyl complex

    Energy Technology Data Exchange (ETDEWEB)

    Chatelain, Lucile; Pecaut, Jacques [CEA-Grenoble (France). Lab. de Reconnaissance Ionique et Chimie de Coordination SCIB; Walsh, James P.S.; Tuna, Floriana [Manchester Univ. (United Kingdom). School of Chemistry and Photon Science Inst.; Mazzanti, Marinella [Ecole Polytechnique Federale de Lausanne (EPFL) (Switzerland). Inst. de Sciences et Ingenierie Chimiques

    2014-12-01

    Mixed-metal uranium compounds are very attractive candidates in the design of single-molecule magnets (SMMs), but only one 3d-5f hetero-polymetallic SMM containing a uranium center is known. Herein, we report two trimeric heterodimetallic 3d-5f complexes self-assembled by cation-cation interactions between a uranyl(V) complex and a TPA-capped M{sup II} complex (M=Mn (1), Cd (2); TPA=tris(2-pyridylmethyl)amine). The metal centers were strategically chosen to promote the formation of discrete molecules rather than extended chains. Compound 1, which contains an almost linear {Mn-O=U=O-Mn} core, exhibits SMM behavior with a relaxation barrier of 81±0.5 K - the highest reported for a mono-uranium system - arising from intramolecular Mn-U exchange interactions combined with the high Ising anisotropy of the uranyl(V) moiety. Compound 1 also exhibits an open magnetic hysteresis loop at temperatures less than 3 K, with a significant coercive field of 1.9 T at 1.8 K.

  6. The radiation induced chemistry of uranyl cation in aqueous carbonate –bicarbonate solutions as followed by NMR spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    McNamara, Bruce K.; Snow, Lanee A.; Soderquist, Chuck Z.; Sinkov, Sergei I.; Cho, Herman M.; Friese, Judah I.

    2006-05-01

    Alpha radiation induced formation of hydrogen peroxide in carbonate ?bicarbonate media was followed by 13C NMR using dissolved [233UO2(13CO3)3]4- as the alpha source (Dalpha= 12.1 Gy/hr). Between the pH region between 5.9 and 11.6 hydrogen peroxide causes a varied speciation of the uranyl carbonates that is a function of the uranium, carbonate and the hydrogen peroxide concentrations. It is shown that the speciation of the peroxy carbonates (or other species) formed in solution by titration with hydrogen peroxide are common to those formed by hydrogen peroxide generated by radiolysis. The radiolysis experiment was carried out above pH = 9.96 to minimize the loss of 13CO2 over a 2800 hr period. Radiolytic generation of hydrogen peroxide was followed by formation of a uranyl peroxy carbonate complex and complex formation accelerated for about 1200 hours. Complex formation was observed to terminate at a concentration between 1x10-4 and 5x10-4 M. It is assumed that either a steady state H2O2 production rate was established in solution or that some limiting feature of the experiment was responsible for slowing the yield of product.

  7. Role of N-Donor Sterics on the Coordination Environment and Dimensionality of Uranyl Thiophenedicarboxylate Coordination Polymers

    Energy Technology Data Exchange (ETDEWEB)

    Thangavelu, Sonia G. [Department; Butcher, Ray J. [Department; Cahill, Christopher L. [Department

    2015-06-09

    Thiophene 2,5-dicarboxylic acid (TDC) was reacted with uranyl acetate dihydrate and one (or none) of six N-donor chelating ligands (2,2'-bipyridine (BPY), 4,4'-dimethyl-2,2'-bipyridine (4-MeBPY), 5,5'-dimethyl-2,2'-bipyridine (5-MeBPY), 6,6'-dimethyl-2,2'-bipyridine (6-MeBPY), 4,4',6,6'-tetramethyl-2,2'-bipyridine (4,6-MeBPY), and tetrakis(2-pyridyl)pyrazine (TPPZ) to result in the crystallization of seven uranyl coordination polymers, which were characterized by their crystal structures and luminescence properties. The seven coordination polymers, Na2[(UO2)2(C6H2O4S)3]·4H2O (1), [(UO2)4(C6H2O4S)5(C10H8N2)2]·C10H10N2·3H2O (2), [(UO2)(C6H2O4S)(C12H12N3)] (3), [(UO2)(C6H2O4S)(C12H12N3)]·H2O (4), [(UO2)2(C6H2O4S)3]·(C12H14N2)·5H2O (5), [(UO2)3(CH3CO2)(C6H2O4S)4](C14H17N2)3·(C14H16N2)·H2O (6), and [(UO2)2(C6H2O4S)3](C24H18N6) (7), consist of either uranyl hexagonal bipyramidal or pentagonal bipyramidal coordination geometries. In all structures, structural variations in the local and global structures of 1–7 are influenced by the positions (or number) of methyl groups or pyridyl rings on the N-donor species, thus resulting in a wide diversity of structures ranging from single chains, double chains, or 2-D sheets. Direct coordination of N-donor ligands to uranyl centers is observed in the chain structures of 2–4 using BPY, 4-MeBPY, and 5-MeBPY, whereas the N-donor species participate as guests (as either neutral or charge balancing species) in the chain and sheet structures of 5–7 using 6-MeBPY, 4,6-MeBPY, and TPPZ, respectively. Compound 1 is the only structure that does not contain any N-donor ligands and thus crystallizes as a 2-D interpenetrating sheet. The luminescent properties of 1–7 are influenced by the direct coordination or noncoordination of N-donor species to uranyl centers. Compounds 2–4 exhibit typical UO22+ emission upon direct coordination of N-donors, but its absence is observed in 1

  8. Programme of air surveillance and health 9 towns. Synthesis review. Surveillance of effects on the health in relation with air pollution in urban area. Phase 2; Programme de surveillance Air et Sante 9 villes. Revue de synthese. Surveillance des effets sur la sante lies a la pollution atmospherique en milieu urbain. Phase 2

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    2002-06-15

    The InVS published its first results on the Nine-City Air and Health Surveillance Programme (PSAS-9) in March 1999. This phase I pointed out that it was possible for various specialists in the field of air pollution and health to gather around a common set of problems. They also found a link between the daily variations of all the urban air pollution indicators and the total, cardio-vascular and respiratory mortality which, based on French data, contributed to strengthen scientific knowledge in this field. Today's report presents the results of phase Il of the PSAS-9 programme which essentially aimed at assessing the short-term exposure-risk relationships between pollution indicators and hospital admission indicators. This second phase also allowed to confirm the results of phase I on the short-term effect of air pollution on mortality thanks to longer periods of study. Exploratory analysis using new indicators and sensitivity analysis on the pertinence of results were also conducted. Finally, methodological tools were developed in order to optimise data collection and statistical modelization. All these results enabled the quantification of the short-term health impact of air pollution on the PSAS-9 cities. PSAS-9 is now an ongoing epidemiological surveillance programme on the effects of urban air pollution on health, providing information tools to decision-makers and the general population. (author)

  9. Perception of Paralinguistic Traits in Synthesized Voices

    DEFF Research Database (Denmark)

    Baird, Alice Emily; Hasse Jørgensen, Stina; Parada-Cabaleiro, Emilia

    the paralinguistic traits of the synthesized voice. Using a corpus of 13 synthesized voices, constructed from acoustic concatenative speech synthesis, we assessed the response of 23 listeners from differing cultural backgrounds. Evaluating if the perception shifts from the known ground–truths, we asked listeners......Along with the rise of artificial intelligence and the internet-of-things, synthesized voices are now common in daily–life, providing us with guidance, assistance, and even companionship. From formant to concatenative synthesis, the synthesized voice continues to be defined by the same traits we...

  10. Alwilkinsite-(Y), a new rare-earth uranyl sulfate mineral from the Blue Lizard mine, San Juan County, Utah, USA

    Czech Academy of Sciences Publication Activity Database

    Kampf, A.R.; Plášil, Jakub; Čejka, J.; Marty, J.; Škoda, R.; Lapčák, L.

    2017-01-01

    Roč. 81, č. 4 (2017), s. 895-907 ISSN 0026-461X R&D Projects: GA ČR GP13-31276P Institutional support: RVO:68378271 Keywords : Alwilkinsite-(Y) * new mineral * uranyl sulfate * crystal structure * Blue Lizard mine * Utah * USA Subject RIV: DB - Geology ; Mineralogy OBOR OECD: Geology Impact factor: 1.285, year: 2016

  11. Uranium and thorium phosphate based matrices; syntheses, characterizations and lixiviation

    International Nuclear Information System (INIS)

    Dacheux, N.

    1995-03-01

    In the framework of the search for a ceramic material usable in the radioactive waste storage, uranium and thorium phosphates have been investigated. Their experimental synthesis conditions have been entirely reviewed, they lead to the preparation of four new compounds: U(UO 2 )(PO 4 ) 2 , U 2 O(PO 4 ) 2 , UC1PO 4 ,H 2 O, and Th 4 (PO 4 ) 4 , U 2 O 3 P 2 O 7 and Th 3 (PO 4 ) 4 . Characterization by several techniques (X-rays and neutron powder diffractions, UV-Visible and Infra-red spectroscopies, XPS,...) were performed. The ab initio structure determination of U(UO 2 )(PO 4 ) 2 has been achieved by X-rays and refined by neutron diffractions. Through its physico-chemical analysis, we found that this compound was a new mixed valence uranium phosphate in which U 4+ and UO 2 2+ ions are ordered in pairs along parallel chains according to a new type of arrangement. Reaction mechanism, starting from UC1PO 4 , 4H 2 O and based on redox processes of uranium in solid state was set up. From two main matrices U(UO 2 )(PO 4 ) 2 and Th 4 (PO 4 ) 4 P 2 O 7 , solid solutions were studied. They consist of replacement of U(IV) by Th(IV) and reversely. The leaching tests on pure, loaded and doped matrices were performed in terms of storage time, pH of solutions, and determined by the use of solids labelled with 230 U or by the measurement of uranyl concentration by Laser-Induced Time-Resolved Spectrofluorometry. Average concentration of uranium in the liquid phase is around 10 -4 M to 10 -6 M. Taking into account the very low solubilities of the studied phosphate ceramics, we estimated their chemical performances promising as an answer to the important nuclear waste problem, if we compare them to the glasses used at the present time. (author). 47 figs., 23 tabs., 6 appendixes

  12. Effect of temperature on the mechanisms of interaction between uranyl ion and zirconium oxo-phosphate; Effet de la temperature sur les mechanismes d'interaction entre l'ion uranyle et l'oxophosphate de zirconium

    Energy Technology Data Exchange (ETDEWEB)

    Almazan Torres, Maria Guadalupe [Universite de Paris XI Orsay, Orsay (France)

    2007-07-01

    Uranium sorption onto Zr{sub 2}O(PO{sub 4}){sub 2} has been studied between 298 K and 363 K, in 0.1 M NaClO{sub 4} medium. Potentiometric titrations were realized to determine temperature dependency of the acid-base properties (pH{sub pcn}, acidity constants). Classical batch experiments were performed at different temperatures. The sorption experiments revealed that the uranium sorption onto Zr{sub 2}O(PO{sub 4}){sub 2} is favoured with the temperature. Structural characterization of the surface complexes was performed by both Time-Resolved Laser-Induced Fluorescence (TRLIF) and EXAFS spectroscopy. The TRLIF measurements vs. temperature revealed two uranyl surface complexes. No influence of the temperature onto the nature surface complex was observed. The EXAFS analysis showed a splitting of the equatorial oxygen atoms in two shells, corresponding to uranyl bidentate, inner-sphere complexes. The obtained structural uranyl surface complex information was used to simulate (using a constant capacitance model) the sorption edges. The proposed complexes equilibrium model consists of the following surface complexes: ({identical_to}ZrOH){sub 2}UO{sub 2}{sup 2+} and ({identical_to}PO){sub 2}UO{sub 2}. Besides the stability constants for the surface complexes, the thermodynamic parameters {delta}H{sup 0} and {delta}S{sup 0} were determined using the van't Hoff equation. The enthalpy values associated to the U(VI) retention onto Zr{sub 2}O(PO{sub 4}){sub 2}, determined by the temperature dependence of the stability constants, testify that the formation of the complex ({identical_to}PO){sub 2}UO{sub 2} (55 kJ/mol) is endothermic, while no influence of the temperature was observed for the formation of the complex ({identical_to}ZrOH){sub 2}UO{sub 2}{sup 2+}. The adsorption reaction of the last complex is then driven by entropy. In addition, calorimetric measurements of uranium sorption onto Zr{sub 2}O(PO{sub 4}){sub 2} were carried out to directly quantify the enthalpy

  13. Vibrational Spectroscopy of Mass-Selected [UO?(ligand)n]?? Complexes in the Gas Phase: Comparison with Theory

    International Nuclear Information System (INIS)

    Groenewold, G S.; Gianotto, Anita K.; Cossel, Kevin C.; Van Stipdonk, Michael J.; Moore, David T.; Polfer, Nick; Oomens, Jos; De Jong, Wibe A.; Visscher, Luuk

    2006-01-01

    The gas-phase infrared spectra of discrete uranyl ([UO?]??) complexes ligated with acetone and/or acetonitrile were used to evaluate systematic trends of ligation on the position of the O=U=O stretch, and to enable rigorous comparison with the results of computational studies. Ionic uranyl complexes isolated in a Fourier transform ion cyclotron resonance mass spectrometer were fragmented via infrared multiphoton dissociation using a free electron laser scanned over the mid-IR wavelengths. The asymmetric O=U=O stretching frequency was measured at 1017 cm?? for [UO?(CH?COCH?)?]?? and was systematically red shifted to 1000 and 988 cm?? by the addition of a third and fourth acetone ligand, respectively, which was consistent with increased donation of electron density to the uranium center in complexes with higher coordination number. The values generated computationally using LDA, B3LYP, and ZORA-PW91 were in good agreement with experimental measurements. In contrast to the uranyl frequency shifts, the carbonyl frequencies of the acetone ligands were progressively blue shifted as the number of ligands increased from 2 to 4, and approached that of free acetone. This observation was consistent with the formation of weaker noncovalent bonds between uranium and the carbonyl oxygen as the extent of ligation increases. Similar trends were observed for [UO?(CH?CN)n]?? complexes, although the magnitude of the red shift in the uranyl frequency upon addition of more acetonitrile ligands was smaller than for acetone, consistent with the more modest nucleophilic nature of acetonitrile. This conclusion was confirmed by the uranyl stretching frequencies measured for mixed acetone/acetonitrile complexes, which showed that substitution of one acetone for one acetonitrile produced a modest red shift of 3 to 6 cm??

  14. Composites comprising biologically-synthesized nanomaterials

    Science.gov (United States)

    Curran, Seamus; Dias, Sampath; Blau, Werner; Wang, Jun; Oremland, Ronald S; Baesman, Shaun

    2013-04-30

    The present disclosure describes composite materials containing a polymer material and a nanoscale material dispersed in the polymer material. The nanoscale materials may be biologically synthesized, such as tellurium nanorods synthesized by Bacillus selenitireducens. Composite materials of the present disclosure may have optical limiting properties and find use in optical limiting devices.

  15. Perception of Paralinguistic Traits in Synthesized Voices

    DEFF Research Database (Denmark)

    Baird, Alice Emily; Hasse Jørgensen, Stina; Parada-Cabaleiro, Emilia

    2017-01-01

    Along with the rise of artificial intelligence and the internet-of-things, synthesized voices are now common in daily–life, providing us with guidance, assistance, and even companionship. From formant to concatenative synthesis, the synthesized voice continues to be defined by the same traits we...

  16. Physical characterization and reactivity of the uranyl peroxide [UO2(η(2)-O2)(H2O)2]·2H2O: implications for storage of spent nuclear fuels.

    Science.gov (United States)

    Mallon, Colm; Walshe, Aurora; Forster, Robert J; Keyes, Tia E; Baker, Robert J

    2012-08-06

    The unusual uranyl peroxide studtite, [UO(2)(η(2)-O(2))(H(2)O)(2)]·2H(2)O, is a phase alteration product of spent nuclear fuel and has been characterized by solid-state cyclic voltammetry. The voltammogram exhibits two reduction waves that have been assigned to the U(VI/V) redox couple at -0.74 V and to the U(V/IV) redox couple at -1.10 V. This potential shows some dependence upon the identity of the cation of the supporting electrolyte, where cations with larger ionic radii exhibit more cathodic reduction potentials. Raman spectroelectrochemistry indicated that exhaustive reduction at either potential result in a product that does not contain peroxide linkers and is likely to be UO(2). On the basis of the reduction potentials, the unusual behavior of neptunium in the presence of studtite can be rationalized. Furthermore, the oxidation of other species relevant to the long-term storage of nuclear fuel, namely, iodine and iodide, has been explored. The phase altered product should therefore be considered as electrochemically noninnocent. Radiotracer studies with (241)Am show that it does not interact with studtite so mobility will not be retarded in repositories. Finally, a large difference in band gap energies between studtite and its dehydrated congener metastudtite has been determined from the electronic absorption spectra.

  17. A new approach to synthesize supported ruthenium phosphides for hydrodesulfurization

    International Nuclear Information System (INIS)

    Wang, Qingfang; Wang, Zhiqiang; Yin, Xiaoqian; Zhou, Linxi; Zhang, Minghui

    2016-01-01

    Highlights: • We bring out a new method to synthesize noble metal phosphides at low temperature. • Both RuP and Ru 2 P were synthesized using triphenylphosphine as phosphorus sources. • Ru 2 P was the better active phase for HDS than RuP and metal Ru. • RuP/SiO 2 prepared by new method had better HDS activity to that by TPR method. - Abstract: Supported noble metal ruthenium phosphides were synthesized by one-step H 2 -thermal treatment method using triphenylphosphine (TPP) as phosphorus sources at low temperatures. Two phosphides RuP and Ru 2 P can be prepared by this method via varying the molar ratio of metal salt and TPP. The as-prepared phosphides were characterized by X-ray powder diffraction (XRD), low-temperature N 2 adsorption, CO chemisorption and transmission electronic microscopy (TEM). The supported ruthenium phosphides prepared by new method and conventional method together with contradistinctive metallic ruthenium were evaluated in hydrodesulfurization (HDS) of dibenzothiophene (DBT). The catalytic results showed that metal-rich Ru 2 P was the better active phase for HDS than RuP and metal Ru. Besides this, ruthenium phosphide catalyst prepared by new method exhibited superior HDS activity to that prepared by conventional method.

  18. A new approach to synthesize supported ruthenium phosphides for hydrodesulfurization

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Qingfang [Tianjin Key Laboratory of Water Environment and Resources, Tianjin Normal University, Tianjin 300387 (China); Key Laboratory of Advanced Energy Materials Chemistry (MOE), Collaborative Innovation Center of Chemical Science and Engineering (Tianjin), College of Chemistry, Nankai University, Tianjin 300071 (China); Wang, Zhiqiang [Tianjin Key Laboratory of Water Environment and Resources, Tianjin Normal University, Tianjin 300387 (China); Yin, Xiaoqian; Zhou, Linxi [Key Laboratory of Advanced Energy Materials Chemistry (MOE), Collaborative Innovation Center of Chemical Science and Engineering (Tianjin), College of Chemistry, Nankai University, Tianjin 300071 (China); Zhang, Minghui, E-mail: zhangmh@nankai.edu.cn [Key Laboratory of Advanced Energy Materials Chemistry (MOE), Collaborative Innovation Center of Chemical Science and Engineering (Tianjin), College of Chemistry, Nankai University, Tianjin 300071 (China); College of Chemistry and Environmental Science, Kashgar University, Kashgar 844006 (China)

    2016-02-15

    Highlights: • We bring out a new method to synthesize noble metal phosphides at low temperature. • Both RuP and Ru{sub 2}P were synthesized using triphenylphosphine as phosphorus sources. • Ru{sub 2}P was the better active phase for HDS than RuP and metal Ru. • RuP/SiO{sub 2} prepared by new method had better HDS activity to that by TPR method. - Abstract: Supported noble metal ruthenium phosphides were synthesized by one-step H{sub 2}-thermal treatment method using triphenylphosphine (TPP) as phosphorus sources at low temperatures. Two phosphides RuP and Ru{sub 2}P can be prepared by this method via varying the molar ratio of metal salt and TPP. The as-prepared phosphides were characterized by X-ray powder diffraction (XRD), low-temperature N{sub 2} adsorption, CO chemisorption and transmission electronic microscopy (TEM). The supported ruthenium phosphides prepared by new method and conventional method together with contradistinctive metallic ruthenium were evaluated in hydrodesulfurization (HDS) of dibenzothiophene (DBT). The catalytic results showed that metal-rich Ru{sub 2}P was the better active phase for HDS than RuP and metal Ru. Besides this, ruthenium phosphide catalyst prepared by new method exhibited superior HDS activity to that prepared by conventional method.

  19. A spectroscopic study of uranyl speciation in chloride-bearing solutions at temperatures up to 250 °C

    Science.gov (United States)

    Migdisov, A. A.; Boukhalfa, H.; Timofeev, A.; Runde, W.; Roback, R.; Williams-Jones, A. E.

    2018-02-01

    The speciation of U in NaCl-bearing solutions at temperatures up to 250 °C and concentrations of NaCl up to 1.5 m has been investigated using an in situ spectroscopic technique. The recorded spectra permit us to identify the species present in the solutions as UO22+, UO2Cl+, and UO2Cl2°. UO2Cl3- is also likely present at high temperatures and NaCl concentrations, but concentrations of this species are insufficient for derivation of the formation constants. No evidence was found for species of higher ligand (Cl-) number. Thermodynamic stability constants derived for these species show fair agreement with published data for 25 °C, but differ significantly from those predicted by an earlier high-temperature study (Dargent et al., 2013), which suggested that UO2Cl42- and UO2Cl53- contribute significantly to the mass balance of uranyl chloride complexes, especially at high temperature. In contrast, our data suggest that the main uranyl-chloride complex present in aqueous solutions at T > 150 °C and concentrations of NaCl relevant to natural hydrothermal systems is UO2Cl2°. The values of the logarithms of thermodynamic formation constants (β) for the reaction UO22+ + Cl- = UO2Cl+ are 0.02, 0.25, 0.55, 1.09, 1.59, and 2.28 derived at 25, 50, 100, 150, 200, and 250 °C, respectively. For the reaction UO22+ + 2Cl- = UO2Cl2° the values of log β derived at these temperatures are 0.4, 0.58, 0.74, 1.44, 2.18, and 3.42. Values of the formation constant estimated for uranyl-chloride species predict the high concentrations of U observed by Richard et al. (2011) in fluid inclusions of the giant McArthur River unconformity-type uranium deposit.

  20. Structural and magnetic properties of mechanochemically synthesized nanosized yttrium titanate

    Directory of Open Access Journals (Sweden)

    Barudžija Tanja

    2012-01-01

    Full Text Available Nanosized perovskite YTiO3 with the mean crystallite size of 18 nm was synthesized for the first time by mechanochemical treatment. The mechanochemical solid state reaction between commercial Y2O3 powder and mechanochemically synthesized TiO powder in molar ratio 0.5:1 was completed for 3 h in a high-energy planetary ball mill in argon atmosphere. The heating in vacuum at 1150 °C for 12 h transforms nanosized YTiO3 to a well-crystallized single-phase perovskite YTiO3. Both samples were characterized by X-ray diffraction (XRD and thermogravimetric (TGA/DTA analyses, as well as superconducting quantum interference device magnetometer (SQUID measurements.

  1. Radiation chemistry of cis-syn-cis dicyclohexano-18-crown-6 (DCH18C6): Acidity and uranyl nitrate dependence

    Energy Technology Data Exchange (ETDEWEB)

    Draye, Micheline [Laboratoire de Chimie Moleculaire et Environnement (EA1651), Universite de Savoie-Polytech' Savoie, Campus Scientifique, 73376 Le Bourget du Lac Cedex (France)], E-mail: micheline.draye@univ-savoie.fr; Favre-Reguillon, Alain [Laboratoire de Chimie Organique (UMR7084), Conservatoire National des Arts et Metiers, 2 rue conte, 75003 Paris (France); Faure, Rene [Laboratoire des sciences analytiques, UMR CNRS 5180, Universite Claude Bernard, Lyon 1, 43 boulevard du 11 Novembre 1918, 69622 Villeurbanne Cedex (France); Lemaire, Marc [Laboratoire de Catalyse et Synthese Organique, UMR CNRS 5246, Institut de Chimie et Biochimie Moleculaires et Supramoleculaires, Universite Lyon 1 CPE, 43 boulevard du 11 novembre 1918, Villeurbanne 69622 (France)

    2008-05-15

    The cis-syn-cis isomer of dicyclohexano-18-crown-6 (DCH18C6) has been shown to be an efficient extractant able to perform the separation of Pu(IV) and U(VI) from fission products and then the separation of Pu(IV) from U(VI) without valence exchange as required in the PUREX process. This macrocycle was irradiated in nitric acid with a {sup 137}Cs {gamma} source to study its radiation chemical stability. Radiation chemical yields (G) were determined by gas chromatography. The results show that the presence of uranyl nitrate has a strong influence on DCH18C6 radiation chemical stability. Indeed, the presence of this template ion increases the macrocycle stability by promoting fragments recombination.

  2. Spectrophotometric and potentiometric study of uranyl hydrolysis in perchlorate medium. Is derivative spectrophotometry suitable for search of the chemical model?

    International Nuclear Information System (INIS)

    Lubal, P.; Havel, J.

    1997-01-01

    Uranyl hydrolysis (I = 3.00 mol dm -3 NaClO 4 , T = 298.15 K) was studied by potentiometry and spectrophotometry. Numerical analysis of experimental data yielded the logarithmic values of hydrolytic constants for (UO 2 ) p (OH) q (2p-q) species with (p, q) indices: (2, 2) - 6.24 ± 0.02, (3, 5) - 16.80 ± 0.04, and (3, 4) - 12.8 ± 0.1 (potentiometry) and (2, 2) - 6.13 ± 0.02, (3, 5) - 16.81 ± 0.02, and (32, 4) - 12.57 ± 0.02 (average values obtained by derivative spectrophotometry from the first to the fourth order). The spectra of hydrolytic species were deconvoluted and the use of derivative spectrophotometry in equilibria studies has been discussed. (authors)

  3. Uranyl Ion Complexes with Long-Chain Aliphatic α,ω-Dicarboxylates and 3d-Block Metal Counterions.

    Science.gov (United States)

    Thuéry, Pierre; Harrowfield, Jack

    2016-03-07

    Twelve new complexes were obtained from reaction of uranyl ions with the aliphatic dicarboxylic acids HOOC-(CH2)n-2-COOH (H2Cn; n = 7-10 and 12) under solvo-hydrothermal conditions, in the presence of 3d-block metal ions (Mn(2+), Fe(3+), Co(2+), Ni(2+), and Cu(2+)) and 2,2'-bipyridine (bipy) or 1,10-phenanthroline (phen). In contrast to previously reported triple-stranded helicates obtained with C9(2-) and C12(2-), all these complexes crystallize as polymeric one-dimensional (1D) or two-dimensional (2D) species. [Fe(bipy)3][(UO2)2(C7)3]·3H2O (1), [Cu(phen)2]2[(UO2)3(C7)4(H2O)2]·2H2O (2), and [Cu(bipy)2]2[(UO2)2(C9)3] (6), in which the 3d cation was reduced in situ, are 1D ladderlike polymers displaying tetra- or hexanuclear rings, of sufficient width to encompass two counterions in 2 and 6. The three complexes [Co(phen)3][(UO2)3(C8)3(O)]·H2O (3), [Ni(phen)3][(UO2)3(C8)3(O)]·H2O (4) and [Co(phen)3][(UO2)3(C9)3(O)]·H2O (5) contain bis(μ3-oxo)-bridged tetranuclear secondary building units, and they crystallize as deeply furrowed 2D assemblies. Depending on the nature of the counterion, C10(2-) gives [Ni(bipy)3][(UO2)2(C10)3]·2H2O (7), a 2D network displaying elongated decanuclear rings containing the counterions, or [Mn(phen)3][(UO2)2(C10)3]·6H2O (8), [Co(phen)3][(UO2)2(C10)3]·7H2O (9), and [Ni(phen)3][(UO2)2(C10)3]·7H2O (10), which consist of 2D assemblies with honeycomb topology; the hexanuclear rings in 8-10 are chairlike and occupied by one counterion and two uranyl groups from neighboring layers. Two complexes of the ligand with the longest chain, C12(2-), are reported. [UO2(C12)(bipy)] (11) is a neutral 1D species in which bipy chelates the uranyl ion and plays an important role in the packing through π-stacking interactions. Two polymeric units, 1D and 2D, coexist in the complex [Ni(bipy)3][(UO2)2(C12)3][UO2(C12)(H2O)2]·H2O (12); the 2D network has the honeycomb topology, but the hexanuclear rings are markedly convoluted, with local features akin to

  4. Determination of the water content in tetra-ammonium uranyl tricarbonate by the Karl Fischer reagent method

    International Nuclear Information System (INIS)

    Sisti, C.; Grigoletto, T.

    1990-08-01

    Two methods are compared for the determination of water content in tetra-ammonium uranyl tricarbonate by the Karl Fischer reagent method. In the first method it is Known that the carbonate reacts stoichiometrically with the iodine content of the Karl Fischer reagent in the same way it reacts with the water (mole of apparent H 2 O per mole of carbonate is produced). In this case, the carbonate content in the sample is determined and a suitable correction is applied to take into account the apparent water results. In the second method it is performed an extraction of the moisture by adding methanol to the sample in an independent flask. After the decantation, an aliquot of the clear supernatant methanol is taken for the determination of water content by the Karl Fischer reagent method. (author) [pt

  5. Standard test methods for chemical, mass spectrometric, spectrochemical, nuclear, and radiochemical analysis of nuclear-grade uranyl nitrate solutions

    CERN Document Server

    American Society for Testing and Materials. Philadelphia

    1999-01-01

    1.1 These test methods cover procedures for the chemical, mass spectrometric, spectrochemical, nuclear, and radiochemical analysis of nuclear-grade uranyl nitrate solution to determine compliance with specifications. 1.2 The analytical procedures appear in the following order: Sections Determination of Uranium 7 Specific Gravity by Pycnometry 15-20 Free Acid by Oxalate Complexation 21-27 Determination of Thorium 28 Determination of Chromium 29 Determination of Molybdenum 30 Halogens Separation by Steam Distillation 31-35 Fluoride by Specific Ion Electrode 36-42 Halogen Distillate Analysis: Chloride, Bromide, and Iodide by Amperometric Microtitrimetry 43 Determination of Chloride and Bromide 44 Determination of Sulfur by X-Ray Fluorescence 45 Sulfate Sulfur by (Photometric) Turbidimetry 46 Phosphorus by the Molybdenum Blue (Photometric) Method 54-61 Silicon by the Molybdenum Blue (Photometric) Method 62-69 Carbon by Persulfate Oxidation-Acid Titrimetry 70 Conversion to U3O8 71-74 Boron by ...

  6. Design and Construction of Experiment for Direct Electron Irradiation of Uranyl Sulfate Solution: Bubble Formation and Thermal Hydraulics Studies

    Energy Technology Data Exchange (ETDEWEB)

    Chemerisov, Sergey [Argonne National Lab. (ANL), Argonne, IL (United States); Gromov, Roman [Argonne National Lab. (ANL), Argonne, IL (United States); Makarashvili, Vakho [Argonne National Lab. (ANL), Argonne, IL (United States); Heltemes, Thad [Argonne National Lab. (ANL), Argonne, IL (United States); Sun, Zaijing [Argonne National Lab. (ANL), Argonne, IL (United States); Wardle, Kent E. [Argonne National Lab. (ANL), Argonne, IL (United States); Bailey, James [Argonne National Lab. (ANL), Argonne, IL (United States); Quigley, Kevin [Argonne National Lab. (ANL), Argonne, IL (United States); Stepinski, Dominique [Argonne National Lab. (ANL), Argonne, IL (United States); Vandegrift, George [Argonne National Lab. (ANL), Argonne, IL (United States)

    2014-10-01

    Argonne is assisting SHINE Medical Technologies in developing SHINE, a system for producing fission-product 99Mo using a D/T-accelerator to produce fission in a non-critical target solution of aqueous uranyl sulfate. We have developed an experimental setup for studying thermal-hydraulics and bubble formation in the uranyl sulfate solution to simulate conditions expected in the SHINE target solution during irradiation. A direct electron beam from the linac accelerator will be used to irradiate a 20 L solution (sector of the solution vessel). Because the solution will undergo radiolytic decomposition, we will be able to study bubble formation and dynamics and effects of convection and temperature on bubble behavior. These experiments will serve as a verification/ validation tool for the thermal-hydraulic model. Utilization of the direct electron beam for irradiation allows homogeneous heating of a large solution volume and simplifies observation of the bubble dynamics simultaneously with thermal-hydraulic data collection, which will complement data collected during operation of the miniSHINE experiment. Irradiation will be conducted using a 30-40 MeV electron beam from the high-power linac accelerator. The total electron-beam power will be 20 kW, which will yield a power density on the order of 1 kW/L. The solution volume will be cooled on the front and back surfaces and central tube to mimic the geometry of the proposed SHINE solution vessel. Also, multiple thermocouples will be inserted into the solution vessel to map thermal profiles. The experimental design is now complete, and installation and testing are in progress.

  7. Determination of the stability of the uranyl ion sipped in {tau}-hydrogen phosphate of zirconium in sodic form; Determinacion de la estabilidad del ion uranilo sorbido en {tau}-hidrogenofosfato de zirconio en forma sodica

    Energy Technology Data Exchange (ETDEWEB)

    Ordonez R, E.; Fernandez V, S.M. [ININ, 52045 Ocoyoacac, Estado de Mexico (Mexico); Drot, R.; Simoni, E. [Universite de Paris-Sud-XI, Institut de Physique Nucleaire d' Orsay, Groupe de radiochimie, Bat. 100, 91406 Orsay (France)]. e-mail: edo@nuclear.inin.mx

    2005-07-01

    The stability of the uranyl sipped in the zirconium {tau}-hydrogen phosphate in sodic form ({tau}-NaZrP), was carried out characterizing the complexes formed by Laser spectroscopy in the visible region and by X-ray photoelectron spectroscopy. The material was prepared by a new synthesis technique working in nitrogen atmosphere and to low temperatures. The sorption of the uranyl ion was made in acid media with concentrations of 10{sup -4} and 10{sup -5} of uranyl nitrate and with ion forces of 0.1 and 0.5 M of NaClO{sub 4}. The spectra of induced fluorescence with laser (TRLFS) show that the uranyl is fixed in very acid media in three well differentiated species, to pH less acid, the specie of long half life disappears and are only those of short half life. The results of the binding energy obtained by XPS indicate that the binding energy of the uranyl confer it a stable character to the complex formed in the {tau}-NaZP, that makes to this material appropriate to retain to the uranyl in solution to high ion forces and in acid media. (Author)

  8. Syntheses, molecular and crystalline architectures, and ...

    Indian Academy of Sciences (India)

    Syntheses, molecular and crystalline architectures, and luminescence behaviour of terephthalate bridged heptacoordinated dinuclear lead(II) complexes containing a pentadentate N-donor Schiff base. SUBHASIS ROYa, SOMNATH CHOUBEYa, SUMITAVA KHANa, KISHALAY BHARa,. PARTHA MITRAb and BARINDRA ...

  9. Synthese en chemotherapeutisch onderzoek van sulfanilamidopyrimidinen

    NARCIS (Netherlands)

    Grevenstuk, Anton Bernard

    1942-01-01

    In order to investigate the influence of substitution in the pyrimidine nucleous on the activity of the three isomeric sulfanilamidopyrimidines (2, 5 and 6), a number of substituted sulfanilamidopyrimidines were synthesized and tested on chemotherapeutic activity. ... Zie: Summary

  10. CAMAC programmable-control frequency synthesizer

    International Nuclear Information System (INIS)

    Yumaguzin, T.Kh.; Vyazovkin, D.E.; Nazirov, Eh.P.; Tuktarov, R.F.

    1989-01-01

    Synthesizer allows to set frequency with 0.015% accuracy and to scan it with variable step. Frequency controlled divider with further summing-up of divided frequency with fundamental one is used in synthesizer, and it has allowed to use digit of the input code and to obtain 3-4 MHz frequency range. Variation of operation flowsheet in the other frequency range is possible. K-155 and K-531 series microcircuits were used during development

  11. Raman assisted lightwave synthesized frequency sweeper

    DEFF Research Database (Denmark)

    Pedersen, Anders Tegtmeier; Rottwitt, Karsten

    2010-01-01

    We present a Lightwave Synthesized Frequency Sweeper comprising a Raman amplifier for loss compensation. The generated pulse train contains 123 pulses and has a flat signal level as well as a low noise level.......We present a Lightwave Synthesized Frequency Sweeper comprising a Raman amplifier for loss compensation. The generated pulse train contains 123 pulses and has a flat signal level as well as a low noise level....

  12. Psychoacoustic Analysis of Synthesized Jet Noise

    Science.gov (United States)

    Okcu, Selen; Rathsam, Jonathan; Rizzi, Stephen A.

    2013-01-01

    An aircraft noise synthesis capability is being developed so the annoyance caused by proposed aircraft can be assessed during the design stage. To make synthesized signals as realistic as possible, high fidelity simulation is required for source (e.g., engine noise, airframe noise), propagation and receiver effects. This psychoacoustic study tests whether the jet noise component of synthesized aircraft engine noise can be made more realistic using a low frequency oscillator (LFO) technique to simulate fluctuations in level observed in recordings. Jet noise predictions are commonly made in the frequency domain based on models of time-averaged empirical data. The synthesis process involves conversion of the frequency domain prediction into an audible pressure time history. However, because the predictions are time-invariant, the synthesized sound lacks fluctuations observed in recordings. Such fluctuations are hypothesized to be perceptually important. To introduce time-varying characteristics into jet noise synthesis, a method has been developed that modulates measured or predicted 1/3-octave band levels with a (<20Hz) LFO. The LFO characteristics are determined through analysis of laboratory jet noise recordings. For the aft emission angle, results indicate that signals synthesized using a generic LFO are perceived as more similar to recordings than those using no LFO, and signals synthesized with an angle-specific LFO are more similar to recordings than those synthesized with a generic LFO.

  13. Mechanical characterization of hotplate synthesized vanadium oxide nanobelts

    International Nuclear Information System (INIS)

    Zhu Yanwu; Zhang Yousheng; Dai Ling; Cheong, Fook-Chiong; Tan, Vincent; Sow, Chorng-Haur; Lim, Chwee-Teck

    2010-01-01

    Vanadium oxide nanobelts have been synthesized on Si or SiN substrates by simply heating vanadium foils on a hotplate. As-grown nanobelts were characterized as V 2 O 5 .nH 2 O (0.3 2 O 5 phase and a polycrystalline structure was observed. The Young's modulus of the annealed nanobelts showed more consistent values at an average of 28.9 GPa, lower than the calculated modulus of bulk α-V 2 O 5 at 68 GPa.

  14. Analysis and simulations of a frequency synthesizer with internal and external noise sources

    Directory of Open Access Journals (Sweden)

    G. S. Sangha

    2006-01-01

    Full Text Available In this paper, a novel technique to analyse the noise behaviour of a second-order-PLL based synthesizer is demonstrated. Its non-linear behaviour is analyzed with independent noise-sources introduced at different points of the circuit. Phase plane trajectories will be used to demonstrate that noise sources at different locations in the loop produce qualitatively different contributions to the output signal of the synthesizer.

  15. Modification of Lime Mortars with Synthesized Aluminosilicates

    Science.gov (United States)

    Loganina, Valentina I.; Sadovnikova, Marija E.; Jezierski, Walery; Małaszkiewicz, Dorota

    2017-10-01

    The increasing attention for restoration of buildings of historical and architectural importance has increased the interest for lime-based binders, which could be applied for manufacturing repair mortars and plasters compatible with historical heritage. Different additives, admixtures or fibers may be incorporated to improve mechanical and thermal features of such materials. In this study synthesized aluminosilicates (SA) were applied as an additive for lime mortar. The technology of synthesis consisted in the deposition of aluminosilicates from a sodium liquid glass by the aluminum sulphate Al2(SO4)3. The goal of this investigation was developing a new method of aluminosilicates synthesis from a sodium liquid glass and using this new material as a component for a lime mortar. Aluminosilicates were precipitated from the solution of aluminum sulphate Al2(SO)3 and sodium silicate. SA were then used as an additive to calcareous compositions and their influence was tested. Mortars were prepared with commercial air lime and siliceous river sand. Air lime binder was replaced by 5 and 10 wt.% of SA. Calcareous composition specimens were formed at water/lime ratio 1.0. The following analyses were made: grain size distribution of SA, X-ray diffraction analysis (XRD), sorption properties, plastic strength and compressive strength of lime mortars. XRD pattern of the SA shows the presence of thenardite, gibbsite and amorphous phase represented by aggregate of nano-size cristobalite-like crystallites. Application of SA leads to increase of compressive strength after 90 days of hardening by 28% and 53% at SA content 5 and 10% respectively comparing to specimens without this additive. Contents of chemically bound lime in the reference specimens after 28 days of hardening in air-dry conditions was 46.5%, while in specimens modified with SA contained 50.0-55.3% of bound lime depending on filtrate pH. This testifies to high activity of calcareous composition. The new blended lime

  16. Luminescence of uranyl ion complexed with 2,6-pyridine dicarboxylic acid as ligand in acetonitrile medium. Observation of co-luminescence

    Energy Technology Data Exchange (ETDEWEB)

    Maji, Siuli; Kumar, Satendra; Sankaran, Kannan [Indira Ghandi Centre for Atomic Research, Tamil Nadu (India). Materials Chemistry Div.

    2017-10-01

    Luminescence from UO{sub 2}{sup 2+} (uranyl ion) complexed with 2,6-pyridine dicarboxylic acid (PDA) has been studied using acetonitrile (MeCN) as solvent between pH 1.0 and 6.0. The enhancement in luminescence intensity because of sensitization by PDA in the non-aqueous environment provided by the MeCN is found to be one order better than in aqueous medium. The luminescence is further enhanced by about four times following the addition of Y{sup 3+}; a process known as co-luminescence. This is the first study on co-luminescence of uranyl ion in its PDA complex. Lifetime studies indicate the presence of two species having different micro-environments. Formations of both intra and inter molecular complexes are believed to be responsible for enhancement due to co-luminescence.

  17. Enhanced effects of nonisotopic hafnium chloride in methanol as a substitute for uranyl acetate in TEM contrast of ultrastructure of fungal and plant cells.

    Science.gov (United States)

    Ikeda, Ken-Ichi; Inoue, Kanako; Kanematsu, Satoko; Horiuchi, Yoshitaka; Park, Pyoyun

    2011-09-01

    This ultrastructural study showed that nonisotopic methanolic hafnium chloride and aqueous lead solution was an excellent new electron stain for enhancing TEM contrasts of fungal and plant cell structures. The ultrastructural definition provided by the new stain was often superior to that provided by conventional staining with uranyl acetate and lead. Definition of fine ultrastructure was also supported by quantitative data on TEM contrast ratios of organelles and components in fungal and plant cells. In particular, polysaccharides, which were localized in cell walls, glycogen particles, starch grains, and plant Golgi vesicle components, were much more reactive to the new stain than to the conventional one. The new nonisotopic stain is useful for enhancing the contrast of ultrastructure in biological tissues and is a safer alternative to uranyl acetate. Copyright © 2010 Wiley-Liss, Inc.

  18. Synthesis, characterization and solubility of alkaline earth uranyl carbonates M2[UO2(CO3)3].xH20; M: Mg, Ca, Sr, Ba

    International Nuclear Information System (INIS)

    Amayri, S.

    2002-11-01

    The release and dispersion of uranium from closed uranium mining sites and the resulting uranium contamination of the natural environment of such sites is a major problem examined in this dissertation. Knowledge of the pollution pathways and processes is indispensable for an assessment of the radiological implications for the human population, to be taken into account in the planning of site rehabilitation work. The formation of secondary uranium minerals may contribute to an immobilization of the uranium, but it is possible as well that such secondary uranium minerals will release uranium. A major task of this dissertation therefore was to examine the conditions of formation of alkaline earth uranyl carbonates in the context of their natural occurrence as observed at some sites, and to answer the question of whether hitherto unknown alkaline earth uranyl carbonates may form in the natural environment, and ought to be taken into account as new source terms. (orig./CB) [de

  19. Ion exchange reactions of n-butylamine intercalates of tin(IV) hydrogen phosphate and hydrogen uranyl phosphate with cobalt(III) complexes

    International Nuclear Information System (INIS)

    Pozas-Tormo, R.; Moreno-Real, L.; Martinez-Lara, M.; Rodriguez-Castellon, E.

    1986-01-01

    The ion exchange reactions of n-butylamine intercalates of tin(IV) hydrogen phosphate and hydrogen uranyl phosphate towards carbonatotetraamminecobalt(III), chloropentaamminecobalt(III), and hexamminecobalt(III) have been investigated. Independent of the complex cation charges, the amounts of Co(III) complex exchanged by the n-butylamine intercalate of tin(IV) hydrogen phosphate are practically the same. With the n-butylamine intercalate of hydrogen uranyl phosphate, the ionic exchange was completed and the composition was fixed by the exchanged Co(III) complex. The layer charge densities of these phosphates justify the different ionic exchange behaviour observed towards the large complex cations. All the products were characterized by chemical analysis, X-ray diffractory, infrared spectroscopy, diffuse reflectance spectroscopy, and thermal analysis

  20. Methods for estimating the enthalpy of formation of inorganic compounds; thermochemical and crystallographic investigations of uranyl salts of group VI elements

    International Nuclear Information System (INIS)

    Brandenburg, N.P.

    1978-01-01

    The first part of this thesis is concerned with parameter methods for estimating the standard enthalpy of formation, ΔH 0 sub(f), of inorganic compounds. In this type of method the estimate is a function of parameters, assigned to cation and anion, respectively. The usefulness of a new estimation method is illustrated in the case of uranyl sulphide. In the second part of this thesis crystallographic and thermochemical properties of uranyl salts of group VI elements are described. Crystal structures are given for β-UO 2 SO 4 , UO 2 SeO 3 , and α-UO 2 SeO 4 . Thermochemical measurements have been restricted to the determination of ΔH 0 sub(f)(UO 2 SO 3 ) and ΔH 0 sub(f)(UO 2 TeO 3 ) by means of isoperibol solution calorimetry. (Auth.)