WorldWideScience

Sample records for alkaline earth lanthanide

  1. Modifying the size and shape of monodisperse bifunctional alkaline-earth fluoride nanocrystals through lanthanide doping.

    Science.gov (United States)

    Chen, Daqin; Yu, Yunlong; Huang, Feng; Huang, Ping; Yang, Anping; Wang, Yuansheng

    2010-07-28

    In this communication, a simple route for modifying the uneven size and shape of alkaline-earth fluoride nanophases to monodisperse ultrasmall nanospheres through lanthanide doping is offered. These nanospheres are found to exhibit bifunctionality, i.e., tunable upconversion emissions as well as proper paramagnetism, making them potentially applicable in the biological field. The synthesis strategy, which involves doping of an impurity with a different valence than the cation in the nanophase, might be useful for controlling the solution growth of some technologically important nanomaterials.

  2. Quantum mechanics and molecular dynamics simulations of complexation of alkaline-earth and lanthanide cations by poly-amino-carboxylate ligands

    International Nuclear Information System (INIS)

    Durand, S.

    1999-01-01

    Molecular dynamics (MD) simulations on lanthanide(III) and alkaline-earth(II) complexes with poly-amino-carboxylates (ethylene-diamino-tetra-acetate EDTA 4- , ethylene-diamino-tri-acetate-acetic acid EDTA(H) 3- , tetra-aza-cyclo-dodecane-tetra-acetate DOTA 4- , methylene-imidine-acetate MIDA 2- ) are reported. First, a consistent set of Lennard-Jones parameters for La 3+ , Eu 3+ and Lu 3+ cations has been derived from free energy calculations in aqueous solution. Observed differences in hydration free energies, coordination distances and hydration numbers are reproduced. Then, the solution structures of 1:1 complexes of alkaline-earth and/or lanthanide cations with EDTA 4- , EDTA(H) 3- , DOTA 4- and 1:2 complexes of lanthanide cations with MIDA 2- were studied by MD in water. In addition, free energy calculations were performed to study, for each ligand, the relative thermodynamic stabilities of complexes with Ca 2+ vs Sr 2+ and vs Ba 2+ on the one hand, and with La 3+ vs Eu 3+ and vs Lu 3+ on the other hand. Model does not take into account explicitly polarization and charge transfer. However, the results qualitatively agree with experimental complexation data (structure and selectivities). (author)

  3. Quantum mechanics and molecular dynamics simulations of complexation of alkaline-earth and lanthanide cations by poly-amino-carboxylate ligands; Simulations par mecanique quantique et dynamique moleculaire de la complexation de cations alcalino-terreux et lanthanides par des ligands polyaminocarboxylates

    Energy Technology Data Exchange (ETDEWEB)

    Durand, S

    1999-07-01

    Molecular dynamics (MD) simulations on lanthanide(III) and alkaline-earth(II) complexes with poly-amino-carboxylates (ethylene-diamino-tetra-acetate EDTA{sup 4-}, ethylene-diamino-tri-acetate-acetic acid EDTA(H){sup 3-}, tetra-aza-cyclo-dodecane-tetra-acetate DOTA{sup 4-}, methylene-imidine-acetate MIDA{sup 2-}) are reported. First, a consistent set of Lennard-Jones parameters for La{sup 3+}, Eu{sup 3+} and Lu{sup 3+} cations has been derived from free energy calculations in aqueous solution. Observed differences in hydration free energies, coordination distances and hydration numbers are reproduced. Then, the solution structures of 1:1 complexes of alkaline-earth and/or lanthanide cations with EDTA{sup 4-}, EDTA(H){sup 3-}, DOTA{sup 4-} and 1:2 complexes of lanthanide cations with MIDA{sup 2-} were studied by MD in water. In addition, free energy calculations were performed to study, for each ligand, the relative thermodynamic stabilities of complexes with Ca{sup 2+} vs Sr{sup 2+} and vs Ba{sup 2+} on the one hand, and with La{sup 3+} vs Eu{sup 3+} and vs Lu{sup 3+} on the other hand. Model does not take into account explicitly polarization and charge transfer. However, the results qualitatively agree with experimental complexation data (structure and selectivities). (author)

  4. Diagnostic study about lanthanides (rare earths)

    International Nuclear Information System (INIS)

    Ribeiro, G.F.

    1985-01-01

    The world situation of rare earths (lanthanides) is evaluated, and a comparison of the Brazilian situation in respect to other countries is established, concerning the following aspects: geology of mineral deposits; main sources, uses, reserves and production; their consumption, prices and state-of-art of geological researches and industrial processes for physical and chemical separation / concentration of these elements. (C.L.B.) [pt

  5. Viscosity of Molten Alkaline-Earth Fluorides

    Science.gov (United States)

    Takeda, Osamu; Hoshino, Yosuke; Anbo, Yusuke; Yanagase, Kei-ichi; Aono, Masahiro; Sato, Yuzuru

    2015-04-01

    The viscosities of molten alkaline-earth fluorides were measured using the oscillating crucible method, which is especially suitable for measuring molten salts with low viscosity. The results showed a good Arrhenius linearity over a wide temperature range. The measured viscosities and activation energies increased in the following order: . Judging by the charge density, the viscosity of alkaline-earth fluorides should increase from molten to . However, the results indicate a different tendency, which may be explained by a Coulomb force that is very strong. The low viscosity of can be attributed to a decreased cohesive force, due to a partial loss of the Coulomb force caused by a higher charge density of the material. The viscosities were also compared to those of molten alkali fluorides and alkaline-earth chlorides. The viscosities of molten alkaline-earth fluorides were higher than those of molten alkali fluorides and alkaline-earth chlorides. The viscosity determined in this study was compared to literature values and showed a reasonable value in the relatively low-viscosity region.

  6. Alkaline earth filled nickel skutterudite antimonide thermoelectrics

    Science.gov (United States)

    Singh, David Joseph

    2013-07-16

    A thermoelectric material including a body centered cubic filled skutterudite having the formula A.sub.xFe.sub.yNi.sub.zSb.sub.12, where A is an alkaline earth element, x is no more than approximately 1.0, and the sum of y and z is approximately equal to 4.0. The alkaline earth element includes guest atoms selected from the group consisting of Be, Mb, Ca, Sr, Ba, Ra and combinations thereof. The filled skutterudite is shown to have properties suitable for a wide variety of thermoelectric applications.

  7. Alkaline earth metal catalysts for asymmetric reactions.

    Science.gov (United States)

    Kobayashi, Shū; Yamashita, Yasuhiro

    2011-01-18

    The group 2 alkaline earth metals calcium (Ca), strontium (Sr), and barium (Ba) are among the most common elements on Earth, abundant in both the sea and the Earth's crust. Although they are familiar in our daily lives, their application to organic synthesis has, so far, been limited. Some particularly useful properties of these elements include (i) low electronegativity, (ii) a stable oxidation state of +2, meaning that they can potentially form two covalent bonds with anions, and (iii) the ability to occupy a variety of coordination sites due to their large ionic radius. Furthermore, the alkaline earth metals, found between the group 1 and group 3 elements, show mild but significant Lewis acidity, which can be harnessed to control coordinative molecules via a Lewis acid-base interaction. Taken together, these characteristics make the metals Ca, Sr, and Ba very promising components of highly functionalized acid-base catalysts. In this Account, we describe the development of chiral alkaline earth metal catalysts for asymmetric carbon-carbon bond-forming reactions. Recently prepared chiral alkaline earth metal complexes have shown high diastereo- and enantioselectivities in fundamental and important chemical transformations. We chose chiral bisoxazoline (Box) derivatives bearing a methylene tether as a ligand for chiral modification. These molecules are very useful because they can covalently coordinate to alkaline earth metals in a bidentate fashion through deprotonation of the tether portion. It was found that chiral calcium-Box complexes could successfully promote catalytic asymmetric 1,4-addition and [3 + 2] cycloaddition reactions with high diastereo- and enantioselectivities. Both the calcium-Box complexes and chiral strontium-bis-sulfonamide and chiral barium-BINOLate complexes could catalyze asymmetric 1,4-addition reactions with high enantioselectivities. Furthermore, we designed a calcium-neutral coordinative ligand complex as a new type of chiral alkaline

  8. Optical properties of alkaline earth borate glasses

    African Journals Online (AJOL)

    user

    applications in the field of optical fibers, optoelectronic devices; radiation shields, surgical lasers and their glass ceramic counter parts have wide range of applications (Rajasree et al., 2011; Sharma et al., 2007, Limkitjaroenporn et al., 2010). Boric acid. (H3BO3) form stable glasses with alkaline earth oxides (R= MgO, CaO, ...

  9. Alkaline and alkaline earth metal phosphate halides and phosphors

    Science.gov (United States)

    Lyons, Robert Joseph; Setlur, Anant Achyut; Cleaver, Robert John

    2012-11-13

    Compounds, phosphor materials and apparatus related to nacaphite family of materials are presented. Potassium and rubidium based nacaphite family compounds and phosphors designed by doping divalent rare earth elements in the sites of alkaline earth metals in the nacaphite material families are descried. An apparatus comprising the phosphors based on the nacaphite family materials are presented herein. The compounds presented is of formula A.sub.2B.sub.1-yR.sub.yPO.sub.4X where the elements A, B, R, X and suffix y are defined such that A is potassium, rubidium, or a combination of potassium and rubidium and B is calcium, strontium, barium, or a combination of any of calcium, strontium and barium. X is fluorine, chlorine, or a combination of fluorine and chlorine, R is europium, samarium, ytterbium, or a combination of any of europium, samarium, and ytterbium, and y ranges from 0 to about 0.1.

  10. Photolysis of alkaline-earth nitrates

    Science.gov (United States)

    Kriger, L. D.; Miklin, M. B.; Dyagileva, E. P.; Anan'ev, V. A.

    2013-02-01

    Peroxynitrite and nitrite ions are the diamagnetic products of photolysis (with light at a wavelength of 253.7 nm) of alkaline-earth nitrates; the paramagnetic products and hydrogen peroxide were not found. The structural water in alkaline-earth nitrate crystals did not affect the qualitative composition of the photodecomposition products. The quantum yield of nitrite ions was 0.0012, 0.0038, 0.0078, and 0.0091 quanta-1 and that of peroxynitrite ions was 0.0070, 0.0107, 0.0286, and 0.0407 quanta-1 for Sr(NO3)2, Ba(NO3)2, Ca(NO3)2 · 4H2O, and Mg(NO3)2 · 6H2O, respectively.

  11. Oxidation catalysts on alkaline earth supports

    Science.gov (United States)

    Mohajeri, Nahid

    2017-03-21

    An oxidation catalyst includes a support including particles of an alkaline earth salt, and first particles including a palladium compound on the support. The oxidation catalyst can also include precious metal group (PMG) metal particles in addition to the first particles intermixed together on the support. A gas permeable polymer that provides a continuous phase can completely encapsulate the particles and the support. The oxidation catalyst may be used as a gas sensor, where the first particles are chemochromic particles.

  12. The pressure induced B1-B2 phase transition of alkaline halides and alkaline earth chalcogenides. A first principles investigation

    International Nuclear Information System (INIS)

    Potzel, Oliver; Taubmann, Gerhard

    2011-01-01

    In this work, we considered the pressure induced B1-B2 phase transition of AB compounds. The DFT calculations were carried out for 11 alkaline halides, 11 alkaline earth chalcogenides and the lanthanide pnictide CeP. For both the B1 and the B2 structures of each compound, the energy was calculated as a function of the cell volume. The transition pressure, the bulk moduli and their pressure derivatives were obtained from the corresponding equations of state. The transition path of the Buerger mechanism was described using roots of the transition matrix. We correlated the computed enthalpies of activation to some structure defining properties of the compounds. A fair correlation to Pearsons hardness of the ions was observed. -- Graphical abstract: Pressure induced transition from the B1 structure (left) via the transition state (middle) to the B2 structure (right). Display Omitted Highlights: → Pressure induced phase transitions in AB compounds were considered. → Alkaline halides and alkaline earth chalcogenides were treated. → DFT calculations with periodic boundary conditions were applied. → The transition path was described by roots of the transition matrix. → The enthalpy of activation was calculated for numerous compounds.

  13. 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

  14. Retention of alkaline earth elements in man

    International Nuclear Information System (INIS)

    Newton, D.

    1990-06-01

    The data on human metabolism and long-term retention of alkaline earth elements ( 133 Ba injected into six healthy male volunteers at age 25-81 y and 45 Ca and 85 Sr received by one healthy male volunteer) are presented. Excreta were collected for 2-3 weeks after injection of the tracer into an antecubital vein. Activity in urine, ashed faeces and early samples of blood plasma was determined by gamma-ray scintillation spectrometry. Whole body retention has been assessed through serial measurements of body radioactivity. The injected 133 Ba apparently became mainly skeletal within several days, much earlier than predicted by the ICRP model. The whole-body retention at 32 d ranged from 5 to 14%, the rate of loss correlating with the excretory plasma clearance rate. No age-related trends were identified in the metabolism of Ca and Sr. 2 refs, 2 figs

  15. Americium/Lanthanide Separations in Alkaline Solutions for Advanced Nuclear Fuel Cycles

    Energy Technology Data Exchange (ETDEWEB)

    Goff, George S. [Los Alamos National Laboratory; Long, Kristy Marie [Los Alamos National Laboratory; Reilly, Sean D. [Los Alamos National Laboratory; Jarvinen, Gordon D. [Los Alamos National Laboratory; Runde, Wolfgang H. [Los Alamos National Laboratory

    2012-06-11

    Project goals: Can used nuclear fuel be partitioned by dissolution in alkaline aqueous solution to give a solution of uranium, neptunium, plutonium, americium and curium and a filterable solid containing nearly all of the lanthanide fission products and certain other fission products? What is the chemistry of Am/Cm/Ln in oxidative carbonate solutions? Can higher oxidation states of Am be stabilized and exploited? Conclusions: Am(VI) is kinetically stable in 0.5-2.0 M carbonate solutions for hours. Aliquat 336 in toluene has been successfully shown to extract U(VI) and Pu(VI) from carbonate solutions. (Stepanov et al 2011). Higher carbonate concentration gives lower D, SF{sub U/Eu} for = 4 in 1 M K{sub 2}CO{sub 3}. Experiments with Am(VI) were unsuccessful due to reduction by the organics. Multiple sources of reducing organics...more optimization. Reduction experiments of Am(VI) in dodecane/octanol/Aliquat 336 show that after 5 minutes of contact, only 30-40% of the Am(VI) has been reduced. Long enough to perform an extraction. Shorter contact times, lower T, and lower Aliquat 336 concentration still did not result in any significant extraction of Am. Anion exchange experiments using a strong base anion exchanger show uptake of U(VI) with minimal uptake of Nd(III). Experiments with Am(VI) indicate Am sorption with a Kd of 9 (10 minute contact) but sorption mechanism is not yet understood. SF{sub U/Nd} for = 7 and SF{sub U/Eu} for = 19 after 24 hours in 1 M K{sub 2}CO{sub 3}.

  16. The mechanism of radiolysis of alkaline-earth nitrates

    Science.gov (United States)

    Anan'ev, V.; Kriger, L.; Miklin, M.

    2015-04-01

    The formation of peroxynitrite and nitrite in crystalline alkaline-earth nitrates under γ-irradiation at 310 K by optical reflectance spectroscopy has been studied. The radiolysis of Sr(NO3)2 and Ba(NO3)2 results in nitrite and peroxynitrite, Mg(NO3)2·6H2O and Ca(NO3)2·4H2O - nitrite. The mechanism for nitrite and peroxynitrite formation under γ-irradiation of crystalline alkaline-earth nitrates has been discussed.

  17. Spectrum Estimation of Density Operators with Alkaline-Earth Atoms

    Science.gov (United States)

    Beverland, Michael E.; Haah, Jeongwan; Alagic, Gorjan; Campbell, Gretchen K.; Rey, Ana Maria; Gorshkov, Alexey V.

    2018-01-01

    We show that Ramsey spectroscopy of fermionic alkaline-earth atoms in a square-well trap provides an efficient and accurate estimate for the eigenspectrum of a density matrix whose n copies are stored in the nuclear spins of n such atoms. This spectrum estimation is enabled by the high symmetry of the interaction Hamiltonian, dictated, in turn, by the decoupling of the nuclear spin from the electrons and by the shape of the square-well trap. Practical performance of this procedure and its potential applications to quantum computing and time keeping with alkaline-earth atoms are discussed.

  18. Upconversion studies in rare earth ions-doped lanthanide materials

    Indian Academy of Sciences (India)

    2014-02-08

    Feb 8, 2014 ... for direct vision applications. There are many applications of rare earth-doped materials. [1,2]. Er3+ ion has low photon absorption coefficient at around 976 nm. The 976 nm laser excitation wavelength is cheaply available and absorption of this wavelength in water is also low. Therefore, many researchers ...

  19. Synthesis of monomeric and polymeric alkali and alkaline earth ...

    Indian Academy of Sciences (India)

    5, September 2014, pp. 1463–1475. c Indian Academy of Sciences. Synthesis of monomeric and polymeric alkali and alkaline earth metal complexes using a phosphinoselenoic amide ligand in metal coordination sphere. JAYEETA BHATTACHARJEE, RAVI K KOTTALANKA, HARINATH ADIMULAM and TARUN K PANDA.

  20. Spectroscopic characterization of manganese-doped alkaline earth

    Indian Academy of Sciences (India)

    The intensity and frequency variations for the characteristic phosphate group vibrations have been correlated with the changes of the structural units present in these glasses. Depolymerization of the phosphate chains in all the glasses is observed with replacement of alkaline earth content by spectroscopic studies.

  1. Optical properties of alkaline earth borate glasses | Rao ...

    African Journals Online (AJOL)

    Borate glasses containing fixed concentrations of heavy metal oxides (MO= ZnO, PbO, TeO2, Bi2O3) and alkaline earth oxides (R= Mg, Ca, Sr, Ba) are prepared by melt quenching technique. The optical band gap values are estimated from the optical absorption spectra using absorption spectrum fitting (ASF) method.

  2. Spectroscopic characterization of manganese-doped alkaline earth ...

    Indian Academy of Sciences (India)

    Alkaline earth lead zinc phosphate glasses doped with Mn(II) are characterized by spectroscopic techniques like X-ray diffraction (XRD), UV–visible, differential scanning calorimetry (DSC), electron paramagnetic resonance (EPR), Fourier transform infrared (FTIR) and Raman. Optical absorption spectrum exhibits four ...

  3. Structural variations in layered alkaline earth metal cyclohexyl ...

    Indian Academy of Sciences (India)

    Administrator

    because of the entrance of the guest molecules between the layers, there will be a change in the interlayer distance (Alberti 1978). Although M(IV) organo-phos- phonates are well documented, the chemistry of M(II) organophosphonates especially the alkaline earth metal organophosphonates has been explored marginally ...

  4. Synthesis and infrared spectra of alkaline earth metal carbonates ...

    Indian Academy of Sciences (India)

    Unknown

    investigations deal with the synthesis and characteriza- tion of complexes of urea with transition metals (Penland et al 1957; Schafer and Curran 1966; Barbier and Hugel. 1974, 1977; Srivastava and Aravindakshan 1983). How- ever, studies on the nature of the reaction of urea with alkaline earth metals are very rare and ...

  5. Alkaline-earth metal phenylphosphonates and their intercalation chemistry

    Czech Academy of Sciences Publication Activity Database

    Melánová, Klára; Beneš, L.; Svoboda, J.; Zima, Vítězslav; Pospíšil, M.; Kovář, P.

    2018-01-01

    Roč. 47, č. 9 (2018), s. 2867-2880 ISSN 1477-9226 R&D Projects: GA ČR(CZ) GA17-10639S Institutional support: RVO:61389013 Keywords : intercalation * layered compounds * alkaline-earth metal phenylphosphonates Subject RIV: CA - Inorganic Chemistry OBOR OECD: Inorganic and nuclear chemistry Impact factor: 4.029, year: 2016

  6. Effects of Mixed Alkaline Earth Oxides in Potash Silicate Glass ...

    African Journals Online (AJOL)

    The aim of this work is to investigate the effects of mixed alkaline earth oxide in potash silicate glasses with regards to their physical properties. More recently; there has been an increase in the demand for light weight glasses which retains their physical and chemical properties for both domestic and industrial applications.

  7. Temperature Dependence of Mineral Solubility in Water. Part 2. Alkaline and Alkaline Earth Bromides

    Science.gov (United States)

    Krumgalz, B. S.

    2018-03-01

    Databases of alkaline and alkaline earth bromide solubilities in water at various temperatures were created using experimental data from publications over about the last two centuries. Statistical critical evaluation of the created databases was produced since there were enough independent data sources to justify such evaluation. The reliable experimental data were adequately described by polynomial expressions over various temperature ranges. Using the Pitzer approach for ionic activity and osmotic coefficients, the thermodynamic solubility products for the discussed bromide minerals have been calculated at various temperature intervals and also represented by polynomial expressions.

  8. Distribution of lanthanides in the aquatic environment of a rare earths processing plant

    International Nuclear Information System (INIS)

    Radhakrishnan, Sujata; Paul, A.C.

    1997-01-01

    During the chemical processing of monazite to separate rare earths from thorium liquid effluents are generated which after treatment are discharged to Periyar river. Distribution of lanthanide elements such as La, Ce, Nd, Pr and Sm have been investigated in Periyar river. The concentrations of these elements in the river at the industrial zone show enhancement by factors ranging from 4 to 8. The concentration factors in the river sediment is of the order of 10 4 . The mass median diameter work out to 10 μm in the sediment at the industrial zone. Water hyacinth concentrates the elements in its roots. 4 refs., 3 tabs., 1 fig

  9. 40 CFR 721.4668 - Hydrated alkaline earth metal salts of metalloid oxyanions.

    Science.gov (United States)

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Hydrated alkaline earth metal salts of... Specific Chemical Substances § 721.4668 Hydrated alkaline earth metal salts of metalloid oxyanions. (a... hydrated alkaline earth metal salts of metalloid oxyanions (PMN P-94-1557) is subject to reporting under...

  10. Bose-Einstein condensation of alkaline earth atoms: ;{40}Ca.

    Science.gov (United States)

    Kraft, Sebastian; Vogt, Felix; Appel, Oliver; Riehle, Fritz; Sterr, Uwe

    2009-09-25

    We have achieved Bose-Einstein condensation of ;{40}Ca, the first for an alkaline earth element. The influence of elastic and inelastic collisions associated with the large ground-state s-wave scattering length of ;{40}Ca was measured. From these findings, an optimized loading and cooling scheme was developed that allowed us to condense about 2 x 10;{4} atoms after laser cooling in a two-stage magneto-optical trap and subsequent forced evaporation in a crossed dipole trap within less than 3 s. The condensation of an alkaline earth element opens novel opportunities for precision measurements on the narrow intercombination lines as well as investigations of molecular states at the ;{1}S-;{3}P asymptotes.

  11. Alkaline-earth metal compounds. Oddities and applications

    International Nuclear Information System (INIS)

    Harder, Sjoerd

    2013-01-01

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

  12. Neutral alkaline-metal and alkaline-earth-metal derivatives of imidazole and benzimidazole.

    Science.gov (United States)

    Blanco, Fernando; Lloyd, David G; Alkorta, Ibon; Elguero, José

    2014-06-12

    A theoretical study of the minima and connecting transition states of the neutral complexes formed by alkaline-metal and alkaline-earth-metal derivatives of imidazolate and benzimidazolate anions has been carried out using B3LYP/6-31+G(d,p), B3LYP/6-311+G(3df,2p), and G3B3 methods. Two and three nondegenerated minima and two and four TS structures have been identified for imidazole and benzimidazole derivatives, respectively. The most stable minima of the alkaline-metal derivatives of both systems correspond to the metal interacting with the imidazole ring, whereas in the alkaline-earth-metal derivatives, the preferred minima depend on the substituent. A remarkable feature of some minima is the fact that some of the metal-aromatic interactions follow the classical π-cation pattern, even though the global structure corresponds to a neutral salt, constituting a class of noncovalent interaction of great interest in the chemistry of aromatic and heterocyclic complexes. A CSD search has confirmed that the two bonding modes, N-σ and π, are present in the solid phase. The π mode has been analyzed by comparison with other azoles.

  13. Defect structure of cubic solid solutions of alkaline earth and rare earth fluorides

    NARCIS (Netherlands)

    DenHartog, HW

    1996-01-01

    In this paper we will consider the disorder in some cubic solid solutions consisting of one of the alkaline earth fluorides and one of the rare earth fluorides. This is an attractive group of model materials, because these materials have a rather simple overall cubic structure. We will discuss the

  14. Modelling the crystallisation of alkaline earth boroaluminosilicate glass ceramics

    DEFF Research Database (Denmark)

    Svenson, Mouritz Nolsøe; Agersted, Karsten; Holm, Paul Martin

    2014-01-01

    To investigate the potential use of a thermochemical software package (FactSage 6.2), in the design of alkaline earth boroaluminosilicate glass ceramics, experimental and modelled results on four glass ceramics were compared. Initially large discrepancies were found. These are described and related...... for the topology of multicomponent melts, before accurate prediction of phase relations within boron-containing glass ceramics can be obtained....

  15. Preparation process of an yttrium (or one rare earth), one alkaline earth metal, copper and oxygen superconductive compound

    International Nuclear Information System (INIS)

    Michel, C.; Pham Ai-Qooc; Raveau, B.

    1991-01-01

    The present invention describes the fabrication at atmospheric pressure of a compound based on yttrium (or a rare earth), one alkaline earth metal, copper, and oxygen so as to get a high-tc superconductor material. 2 refs

  16. Recent advances in rare earth doped alkali-alkaline earth borates for solid state lighting applications

    Science.gov (United States)

    Verma, Shefali; Verma, Kartikey; Kumar, Deepak; Chaudhary, Babulal; Som, Sudipta; Sharma, Vishal; Kumar, Vijay; Swart, Hendrik C.

    2018-04-01

    As a novel class of inorganic phosphor, the alkali-alkaline earth borate phosphors have gained huge attention due to their charming applications in solid-state lighting (SSL) and display devices. The current research drive shows that phosphors based on the alkali-alkaline earth borates have transformed the science and technology due to their high transparency over a broad spectral range, their flexibility in structure and durability for mechanical and high-laser applications. Recent advances in various aspects of rare-earth (RE) doped borate based phosphors and their utilizations in SSL and light emitting diodes are summarized in this review article. Moreover, the present status and upcoming scenario of RE-doped borate phosphors were reviewed in general along with the proper credential from the existing literature. It is believed that this review is a sole compilation of crucial information about the RE-doped borate phosphors in a single platform.

  17. Individual activity coefficients of single ionic species of alkaline earth halogenides, alkaline earth perchlorates, and uranyl perchlorate at 25 0C in aqueous solutions

    International Nuclear Information System (INIS)

    Ferse, A.

    1981-01-01

    The individual activity coefficients of the single ionic species of alkaline-earth haloides, alkaline earth perchlorates and uranylic perchlorate, resp., at 25 0 C in aqueous solution are calculated and presented up to the concentration of about m = 4 mol/kg. The individual activity coefficients of the alkaline-earth ions pass mostly as a function of the concentration through a steep minimum and decrease from Mg 2+ to Ba 2+ . The individual activity coefficients of the anions pass generally as a function of the concentration through a marked flat minimum, but they increase - the complex perchlorate ions excepted - only a little above 1. (author)

  18. Potassium salts of fatty acids as precipitating agents of alkaline earth metal ions

    International Nuclear Information System (INIS)

    Skrylev, L.D.; Sin'kova, L.A.

    1977-01-01

    Regularities have been studied of precipitation of ions of alkaline-earth elements with caprilate, pelargonate, caprinate, undecanate, laurate, tridecanate, myristate, pentadecanate, palmitate, and stearate of potassium. It has been shown that completeness of precipitation of metal ions is determined by the nature of alkaline-earth metal and potassium salt as well as by pH value and temperature of the solution. The study of temperature dependence of soaps of alkaline-earth metals makes it possible to calculate the heats of dissolution of laurates of alkaline-earth metals, and a change in entropy and free energy

  19. On the crystal chemistry of alkaline earth- and rare earth-oxocobaltates

    Energy Technology Data Exchange (ETDEWEB)

    Mueller-Buschbaum, Hanskarl [Institut fuer Anorganische Chemie, Christian-Alberts-Universitaet Kiel (Germany)

    2013-12-15

    A review on the crystal chemistry of oxocobaltates of alkaline earth and rare earth metals is presented according to the formula of the compounds, based on increasing metal and oxygen content. The well-known structures of perowskites and K{sub 2}NiF{sub 4}-type compounds and their higher homologues have been ignored and cross-referred to older publications. Cobalt shows mainly the oxidation states Co{sup 2+} and Co{sup 3+}. In many cases it exhibits integer valences like Co{sup 2.28+}, Co{sup 2.5+}, Co{sup 2.54+}, Co{sup 2.8+}, Co{sup 3.5}, and Co{sup 3.6+}, referred in the ICSD database. The dominant coordination polyhedra are CoO{sub 4}-tetrahedra and CoO{sub 6}-oktahedra. In two cases a trigonal prismatic CoO{sub 6}-coordination is observed. Composition, crystal structure, and oxidation state of cobalt often depend on the preparation conditions. In contrast to the alkaline oxides, the alkaline earth and rare earth oxides used for preparations are less reactive. Therefore the necessary reaction temperatures are much higher. In these cases single crystals for X-ray investigation were prepared by plasma-burner and CO{sub 2}-LASER techniques. (Copyright copyright 2013 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  20. Bioadsorption of Rare Earth Elements through Cell Surface Display of Lanthanide Binding Tags.

    Science.gov (United States)

    Park, Dan M; Reed, David W; Yung, Mimi C; Eslamimanesh, Ali; Lencka, Malgorzata M; Anderko, Andrzej; Fujita, Yoshiko; Riman, Richard E; Navrotsky, Alexandra; Jiao, Yongqin

    2016-03-01

    With the increasing demand for rare earth elements (REEs) in many emerging clean energy technologies, there is an urgent need for the development of new approaches for efficient REE extraction and recovery. As a step toward this goal, we genetically engineered the aerobic bacterium Caulobacter crescentus for REE adsorption through high-density cell surface display of lanthanide binding tags (LBTs) on its S-layer. The LBT-displayed strains exhibited enhanced adsorption of REEs compared to cells lacking LBT, high specificity for REEs, and an adsorption preference for REEs with small atomic radii. Adsorbed Tb(3+) could be effectively recovered using citrate, consistent with thermodynamic speciation calculations that predicted strong complexation of Tb(3+) by citrate. No reduction in Tb(3+) adsorption capacity was observed following citrate elution, enabling consecutive adsorption/desorption cycles. The LBT-displayed strain was effective for extracting REEs from the acid leachate of core samples collected at a prospective rare earth mine. Our collective results demonstrate a rapid, efficient, and reversible process for REE adsorption with potential industrial application for REE enrichment and separation.

  1. Lanthanide amidinates and guanidinates: from laboratory curiosities to efficient homogeneous catalysts and precursors for rare-earth oxide thin films.

    Science.gov (United States)

    Edelmann, Frank T

    2009-08-01

    For decades, the organometallic chemistry of the rare earth elements was largely dominated by the cyclopentadienyl ligand and its ring-substituted derivatives. A hot topic in current organolanthanide chemistry is the search for alternative ligand sets which are able to satisfy the coordination requirements of the large lanthanide cations. Among the most successful approaches in this field is the use of amidinate ligands of the general type [RC(NR')(2)](-) (R = H, alkyl, aryl; R' = alkyl, cycloalkyl, aryl, SiMe(3)) which can be regarded as steric cyclopentadienyl equivalents. Closely related are the guanidinate anions of the general type [R(2)NC(NR')(2)](-) (R = alkyl, SiMe(3); R' = alkyl, cycloalkyl, aryl, SiMe(3)). Two amidinate or guanidinate ligands can coordinate to a lanthanide ion to form a metallocene-like coordination environment which allows the isolation and characterization of stable though very reactive amide, alkyl, and hydride species. Mono- and trisubstituted lanthanide amidinate and guanidinate complexes are also readily available. Various rare earth amidinates and guanidinates have turned out to be very efficient homogeneous catalysts e.g. for ring-opening polymerization reactions. Moreover, certain alkyl-substituted lanthanide tris(amidinates) and tris(guanidinates) were found to be highly volatile and could thus be promising precursors for ALD (= Atomic Layer Deposition) and MOCVD (= Metal-Organic Chemical Vapor Deposition) processes in materials science and nanotechnology. This tutorial review covers the success story of lanthanide amidinates and guanidinates and their transition from mere laboratory curiosities to efficient homogeneous catalysts as well as ALD and MOCVD precursors.

  2. Reaction cross section calculation of some alkaline earth elements

    Science.gov (United States)

    Tel, Eyyup; Kavun, Yusuf; Sarpün, Ismail Hakki

    2017-09-01

    Reaction cross section knowledge is crucial to application nuclear physics such as medical imaging, radiation shielding and material evaluations. Nuclear reaction codes can be used if the experimental data are unavailable or are improbably to be produced because of the experimental trouble. In this study, there action cross sections of some target alkaline earth elements have been calculated by using pre-equilibrium and equilibrium nuclear reaction models for nucleon induced reactions. While these calculations, the Hybrid Model, the Geometry Dependent Hybrid Model, the Full Exciton Model, the Cascade Exciton Model for pre-equilibrium reactions and the Weisskopf-Ewing Model for equilibrium reactions have been used. The calculated cross sections have been discussed and compared with the experimental data taken from Experimental Nuclear Reaction Data library.

  3. Determination of lanthanides in rare earths concentrates by emission optical spectrography

    International Nuclear Information System (INIS)

    Friedmann, R.; Lordello, A.R.; Abrao, A.

    1978-01-01

    A spectrochemical method has been developed for the determination of Y, Pr, Sm, Eu, Gd and Dy in purified lanthanum oxide; Y, La, Nd, Sm, Gd and Dy in purified cerium oxide and Y, La, Sm, Eu, Gd and Dy in purified neodymium oxide. The technique consists of an almost total consumption of the sample in a 17 ampere direct current arc. The rare earth oxides are mixed with an equal amount by weight of spectrographic graphite and the electrodes are arced in an argon (80%)-oxygen (20%) atmosphere, inside a specially desingned chamber, to suppress cyanogen bands. The concentration ranges are approximatelly 0.002 - 2%, depending on the matrix and the elements to be analysed. The presicion, accuracy and acceptability of the method are calculated for all elements. The total error values are approximately in the range of 18-48%. The method was developed for quality control of the individual fractions held by pulsed and ion exchange columns in the lanthanide separations, in the Chemical Engineering Centre, Atomic Energy Institute, Sao Paulo [pt

  4. Daily intakes of alkaline earth metals in Japanese males

    International Nuclear Information System (INIS)

    Shiraishi, Kunio; Yamamoto, Masayoshi; Ueno, Kaoru

    1994-01-01

    Diet samples were collected for two duplicate portion studies and one market basket study. 226 Ra in the diet samples was determined by alpha spectrometry and daily intake was estimated as 23 mBq (0.62 pCi) per person. Other alkaline earth metals were determined by inductively coupled plasma atomic-emission spectrometry. Average mineral intakes of calcium, magnesium, strontium, and barium were 0.55 g, 0.21 g, 2.3 mg, and 0.39 mg, respectively. Element ratios magnesium:calcium 0.38, strontium:calcium 4.2 x 10 -3 barium:calcium 7.1 X 10 -4 , and Ra:calcium 1.1 x 10 -12 were found in the diet; these compared with element ratios in Japanese vertebrae of magnesium:calcium 0.011, strontium:calcium 3.1 x 10 -4 , barium:calcium 2.7 x 10 -5 , and radium:calcium 2.6 x 10 -14 . Observed ratios, defined as the element ratio in bone divided by the respective element intake ratio in Japanese males, were as follows: 226 Ra 0.02, magnesium 0.03, strontium 0.07, and barium 0.04

  5. SEPARATION OF EUROPIUM FROM OTHER LANTHANIDE RAE EARTHS BY SOLVENT EXTRACTION

    Science.gov (United States)

    Peppard, D.F.; Horwitz, E.P.; Mason, G.W.

    1963-02-12

    This patent deals with a process of separating europium from other lanthanides present in aqueous hydrochloric or sulfuric acid solutions. The europium is selectively reduced to the divalent state with a divalent chromium salt formed in situ from chromium(III) salt plus zinc amalgam. The other trivalent lanthanides are then extracted away from the divalent europium with a nitrogen-flushed phosphoric acid ester or a phosphonic acid ester. (AEC)

  6. When VSEPR fails: experimental and theoretical investigations of the behavior of alkaline-earth-metal acetylides.

    Science.gov (United States)

    Guino-o, Marites A; Alexander, Jacob S; McKee, Michael L; Hope, Håkon; Englich, Ulrich B; Ruhlandt-Senge, Karin

    2009-11-09

    The synthesis, structural, and spectral characterization as well as a theoretical study of a family of alkaline-earth-metal acetylides provides insights into synthetic access and the structural and bonding characteristics of this group of highly reactive compounds. Based on our earlier communication that reported unusual geometry for a family of triphenylsilyl-substituted alkaline-earth-metal acetylides, we herein present our studies on an expanded family of target derivatives, providing experimental and theoretical data to offer new insights into the intensively debated theme of structural chemistry in heavy alkaline-earth-metal chemistry.

  7. On the capacity to the complexing of alkaline earth metal and magnesium chromates

    International Nuclear Information System (INIS)

    Orekhov, O.L.

    1978-01-01

    Considered is the capacity to the complexing of magnesium chromates and alkaline earth metal chromates with ammonium chromates in aqueous solutions. It has been established that the complexing of alkaline earth metal and magnesium chromates is effected by a nature of initial salts as well as their solubilities and the presence of crystallization water. Capacity of magnesium ions and alkaline rare earth metals to the complexing decreases in a series of Mg-Ca-Sr-Ba. Ca complexes exceed magnesium derivatives in respect of stability

  8. The electronic structure of rare-earth luminescent centre in alkaline-earth sulphides

    International Nuclear Information System (INIS)

    Zheng Qingqi; Pan Wei; Huang Maichun; He Xiaoguang

    1988-09-01

    The cluster method is used to investigate the electronic structure of rare-earth Eu 2+ and Ce 3+ doped SrS and CaS alkaline-earth sulphides in the local density theory regime. The ground state is obtained self-consistently by the DV-X α method, while the transition state theory is used to calculate the excited states. The energy difference between ground state and excited state is 2.95 eV (420 nm) for CaS:Eu is in good agreement with the experimental data of 430 nm for the absorption peak in SrS:Cu. The composition of ground state and excited state is also calculated which can give information about the EL excitation mechanism. (author). 7 refs, 4 figs, 3 tabs

  9. Electromigration in molten salts and application to isotopic separation of alkaline and alkaline-earth elements

    International Nuclear Information System (INIS)

    Menes, F.

    1969-01-01

    The separation of the isotopes of the alkaline-earth elements has been studied using counter-current electromigration in molten bromides. The conditions under which the cathode operates as a bromine electrode for the highest possible currents have been examined. For the separation of calcium, it has been necessary to use a stable CaBr 2 - (CaBr 2 + KBr) 'chain'. In the case of barium and strontium, it was possible to employ the pure bromides. Enrichment factors of the order of 10 for 48 Ca and of the order of 1.5 for the rare isotopes of barium and strontium have been obtained. In the case of magnesium the method is slightly more difficult to apply because of material loss due to the relatively high vapour pressure of the salt requiring the use of electrolyte chains, MgBr 2 - CeBr 3 . A study has been made that has led to a larger-scale application of the method. These are essentially the inhibition of reversible operation of the cathode by traces of water, limiting the intensity which can be tolerated; evacuation of the heat produced by the Joule effect, in the absence of which the separation efficiency is reduced by thermal gradients; corrosion of the materials by molten salts at high temperature. Several cells capable of treating a few kilograms of substance have been put into operation; none of these has lasted long enough to produce a satisfactory enrichment. The method is thus limited actually to yields of the order of a few grams. (author) [fr

  10. Release characteristics of alkali and alkaline earth metallic species during biomass pyrolysis and steam gasification process.

    Science.gov (United States)

    Long, Jiang; Song, Hu; Jun, Xiang; Sheng, Su; Lun-Shi, Sun; Kai, Xu; Yao, Yao

    2012-07-01

    Investigating the release characteristics of alkali and alkaline earth metallic species (AAEMs) is of potential interest because of AAEM's possible useful service as catalysts in biomass thermal conversion. In this study, three kinds of typical Chinese biomass were selected to pyrolyse and their chars were subsequently steam gasified in a designed quartz fixed-bed reactor to investigate the release characteristics of alkali and alkaline earth metallic species (AAEMs). The results indicate that 53-76% of alkali metal and 27-40% of alkaline earth metal release in pyrolysis process, as well as 12-34% of alkali metal and 12-16% of alkaline earth metal evaporate in char gasification process, and temperature is not the only factor to impact AAEMs emission. The releasing characteristics of AAEMs during pyrolysis and char gasification process of three kinds of biomass were discussed in this paper. Copyright © 2012 Elsevier Ltd. All rights reserved.

  11. Desorption of acetone from alkaline-earth exchanged Y zeolite after propane selective oxidation

    NARCIS (Netherlands)

    Xu, J.; Mojet, Barbara; van Ommen, J.G.; Lefferts, Leonardus

    2004-01-01

    The desorption of products from a series of alkaline-earth exchanged Y zeolites after room-temperature propane selective oxidation was investigated by in situ infrared and mass spectroscopy. The intermediate product, isopropylhydroperoxide (IHP), did not desorb during

  12. The application of extraction chromatography for analysis of alkali and alkaline earth uranates

    International Nuclear Information System (INIS)

    Tomazic, B.; Cukovic, M.

    1978-01-01

    A method for rapid analysis of alkali and alkaline earth uranates is proposed. The method is based on the use of an HDEHP extraction chromatographic column, which makes possible quantitative separations of alkaline earth ions from macroamounts of uranium(VI). Composition of alkaline earth uranates, based on regression analysis, are presented. The results, which show that under the given experimental conditions alkaline earth triuranates precipitate, are in good agreement with previous data from same laboratory. In addition the HDEHP extraction chromatographic column can be suggested as a tool for separation of representative fission products from irradiated uranium for the purpose of determination of the burn-up factor of nuclear reactor materials. (T.G.)

  13. When VSEPR Fails: Experimental and Theoretical Investigations of the Behavior of Alkaline-Earth-Metal Acetylides

    OpenAIRE

    Guino-o, Marites A.; Alexander, Jacob S.; McKee, Michael L.; Hope, Håkon; Englich, Ulrich B.; Ruhlandt-Senge, Karin

    2009-01-01

    The synthesis, structural, and spectral characterization as well as a theoretical study of a family of alkaline-earth-metal acetylides provides insights into synthetic access and the structural and bonding characteristics of this group of highly reactive compounds. Based on our earlier communication that reported unusual geometry for a family of triphenylsilyl-substituted alkaline-earth-metal acetylides, we herein present our studies on an expanded family of target derivatives, providing expe...

  14. Mass-spectrometric investigation of thermal dissociation of alkaline earth metal monophosphates

    International Nuclear Information System (INIS)

    Lopatin, S.I.; Semenov, G.A.

    1989-01-01

    By the Knudsen effusion method with mass-spectrometric analysis of vapour phase, processes of thermal dissociation of Mg, Ca, Sr and Ba monophosphates have been studied. It is shown that vapour composition over alkaline-earth metal monophoshates depends on the compsition of condensed phase and volatility of alkaline-earth metal oxides. Dependences of partial pressures of vapour components on the temperature and duration of the experiment are given

  15. Study of alkaline-earth element complexes in anhydrous acetic acid

    International Nuclear Information System (INIS)

    Petit, N.

    1968-10-01

    We have studied the complexes of alkaline-earth elements in anhydrous acetic acid. Using glass-electrode potentiometry we have studied the titration of alkaline earth acetates with perchloric acid which is the strongest acid in anhydrous acetic acid. These titrations have shown that the basic strength of these acetates increases as follows: Mg 4 ); the mixed acetate-acid sulfate complex of barium: Ba (OAc)(HSO 4 ); the mixed acetate-chloride of barium: Ba (OAc)(Cl). (author) [fr

  16. Tuning the activity of Pt alloy electrocatalysts by means of the lanthanide contraction

    DEFF Research Database (Denmark)

    Escribano, Maria Escudero; Malacrida, Paolo; Hansen, Martin Hangaard

    2016-01-01

    The high platinum loadings required to compensate for the slow kinetics of the oxygen reduction reaction (ORR) impede the widespread uptake of low-temperature fuel cells in automotive vehicles. We have studied the ORR on eight platinum (Pt)–lanthanide and Pt-alkaline earth electrodes, Pt5M, where...

  17. Thermochemistry of the alkali metal and alkaline earth-actinide complex oxides

    International Nuclear Information System (INIS)

    Fuger, J.

    1985-01-01

    After a brief discussion of the various techniques used for the preparation of actinide complex oxides, the present status of the thermochemistry of these compounds is reviewed. Perovskite-related compounds are especially considered as thermodynamic data are available for compounds of several actinides and/or several alkali and alkaline earth metals. The stabilities of the complex oxides are discussed with respect to the parent binary oxides and to the aqueous ions; trends as a function of the size and the alkali or the alkaline earth cation are presented. Suggestions for synthesis of some analogous compounds with heavier actinides are also discussed. (orig./RK)

  18. Structural biology of the lanthanides-mining rare earths in the Protein Data Bank.

    Science.gov (United States)

    Djinovic-Carugo, Kristina; Carugo, Oliviero

    2015-02-01

    With its about 100,000 three-dimensional structures, the Protein Data Bank is a copious source of information: it contains also some hundreds of structures of macromolecules complexed with lanthanide cations, which are examined here. These cations, which are found in a wide variety of protein types, were introduced to determine the structures, by exploiting their anomalous dispersion (in crystallographic studies, where they are also used as crystallization additives) or the paramagnetic pseudocontact shifts (in NMR analyses). The coordination numbers in the first coordination sphere are very variable, though they tend to be close to those that are observed in small molecules or in water solution. The coordination polyhedra are also quite variable as it can be expected for large cations. Interestingly, lanthanide cations are frequently observed in packing bridges between symmetry equivalent molecules in crystals, where they tend to form polynuclear complexes, with up to seven cations bridged by water/hydroxide ligands. Copyright © 2014 Elsevier Inc. All rights reserved.

  19. Modelling the crystallisation of alkaline earth boroaluminosilicate glass ceramics

    DEFF Research Database (Denmark)

    Svenson, Mouritz Nolsøe; Agersted, Karsten; Holm, Paul Martin

    2014-01-01

    -empirical optimisation of boron and alkali/alkali earth oxide activities in the liquid oxide solution, significantly improved fits between modelled and experimental results were obtained. Based on these results, it is suggested that more precise descriptions of higher order interactions need to be addressed, to account...

  20. The alkali and alkaline earth metal doped ZnO nanotubes: DFT studies

    International Nuclear Information System (INIS)

    Peyghan, Ali Ahmadi; Noei, Maziar

    2014-01-01

    Doping of several alkali and alkaline earth metals into sidewall of an armchair ZnO nanotube has been investigated by employing the density functional theory in terms of energetic, geometric, and electronic properties. It has been found that doping processes of the alkali and alkaline metals are endothermic and exothermic, respectively. Based on the results, contrary to the alkaline metal doping, the electronic properties of the tube are much more sensitive to alkali metal doping so that it is transformed from intrinsic semiconductor with HOMO–LUMO energy gap of 3.77 eV to an extrinsic semiconductor with the energy gap of ∼1.11–1.95 eV. The doping of alkali and alkaline metals increases and decreases the work function of the tube, respectively, which may influence the electron emission from the tube surface

  1. Depolarizing collisions with hydrogen: Neutral and singly ionized alkaline earths

    Energy Technology Data Exchange (ETDEWEB)

    Manso Sainz, Rafael; Ramos, Andrés Asensio; Bueno, Javier Trujillo [Instituto de Astrofísica de Canarias, Vía Láctea s/n, E-38205 La Laguna, Tenerife (Spain); Roncero, Octavio; Sanz-Sanz, Cristina [Instituto de Física Fundamental (IFF-CSIC), CSIC, Serrano 123, E-28006 Madrid (Spain); Aguado, Alfredo, E-mail: octavio.roncero@csic.es [Departamento de Química Física, Unidad Asociada UAM-CSIC, Facultad de Ciencias M-14, Universidad Autónoma de Madrid, E-28049 Madrid (Spain)

    2014-06-20

    Depolarizing collisions are elastic or quasielastic collisions that equalize the populations and destroy the coherence between the magnetic sublevels of atomic levels. In astrophysical plasmas, the main depolarizing collider is neutral hydrogen. We consider depolarizing rates on the lowest levels of neutral and singly ionized alkali earths Mg I, Sr I, Ba I, Mg II, Ca II, and Ba II, due to collisions with H°. We compute ab initio potential curves of the atom-H° system and solve the quantum mechanical dynamics. From the scattering amplitudes, we calculate the depolarizing rates for Maxwellian distributions of colliders at temperatures T ≤ 10,000 K. A comparative analysis of our results and previous calculations in the literature is completed. We discuss the effect of these rates on the formation of scattering polarization patterns of resonant lines of alkali earths in the solar atmosphere, and their effect on Hanle effect diagnostics of solar magnetic fields.

  2. Vibrational spectra of double rare earth alkaline metal metaphosphates

    International Nuclear Information System (INIS)

    Madij, V.A.; Krasilov, Yu.I.; Kizel', V.A.; Denisov, Yu.V.; Chudinova, N.N.; Vinogradova, N.V.

    1978-01-01

    Joint analysis of the Raman and infrared absorption spectra, as well as X-ray structural data for binary metaphosphates, suggest a cyclic structure of the anion in RbEu(PO 3 ) 4 and a chain structure of the anions in HEu(PO 3 ) 4 and LiEu(PO 3 ) 4 . Spectroscopic criteria are proposed for distinguishing between cyclic and chain structures in binary metaphosphates of rare earth elements and alkali metals

  3. Use of polysulfides of alkali and alkaline-earth metals to obtain highly dispersed sulfur

    International Nuclear Information System (INIS)

    Massalimov, I.A.; Vikhareva, I.N.; Kireeva, M.S.

    2008-01-01

    Possibilities of obtaining polysulfides of alkali and alkaline earth metals (M is Na, K, Ca, Sr, Ba) in aqueous solutions were considered. The composition of the polysulfides and their concentration in solutions were found. The efficiencies of application of highly dispersed sulfur, produced from calcium polysulfide, and colloid sulfur as a fungicide were compared [ru

  4. Light shifts and magic wavelengths for heavy alkaline earth elements : Ba and Ra

    NARCIS (Netherlands)

    Dammalapati, U.; Santra, B.; Willmann, L.

    2012-01-01

    In this paper, we investigate light shifts of heavy alkaline earth elements barium (Ba) and radium (Ra), which are interesting for optical lattice clocks and for permanent electric dipole moment searches. Detailed knowledge is required in the design of efficient loading of atoms from a

  5. Molecular dynamics of liquid alkaline-earth metals near the melting ...

    Indian Academy of Sciences (India)

    Results of the studies of the properties like binding energy, the pair distribution function (), the structure factor (), specific heat at constant volume, velocity autocorrelation function (VACF), radial distribution function, self-diffusion coefficient and coordination number of alkaline-earth metals (Be, Mg, Ca, Sr and Ba) near ...

  6. Computer simulation studies of ternary uranate phases with alkali and alkaline-earth metals: Pt. 1

    International Nuclear Information System (INIS)

    Ball, R.G.J.

    1992-01-01

    Solid-state computer simulation techniques have been used to study the alkali and alkaline-earth metal MUO 3 uranate phases. These compounds display an interesting gradation in their structures which, it is shown, is accompanied by a variation in their intrinsic defect chemistry. For example, in the alkali-metal series, LiUO 3 adopts the lithium niobate structure and lithium Frenkel disorder dominates whereas KUO 3 and RbUO 3 adopt regular perovskite structures with Schottky defects being dominant. For the alkaline-earth metal compounds, both the calculations and experiment show that only SrUO 3 and BaUO 3 are stable with respect to the binary oxides. Both of these phases adopt the GdFeO 3 distorted perovskite structure and both have anti-site defects as the dominant intrinsic disorder. The tendency for anti-site disorder is also seen in the oxidation behaviour of these compounds. The calculations suggest that the oxidation will occur through the formation of a secondary UO 2 fluorite phase by the movement of alkaline-earth ions onto uranium sites, leaving behind M vacancies. The calculated energies for such oxidation processes are particularly favourable. The solution of alkaline-earth oxide, M 11 O, in M 11 UO 3 is shown to occur via a mechanism in which the M 11 ions substitute onto both the M 11 and U sublattices. (author)

  7. Formation of H- by charge transfer in alkaline-earth vapors

    International Nuclear Information System (INIS)

    Schlachter, A.S.; Morgan, T.J.

    1983-10-01

    Progress on the study of H - formation by charge transfer in alkaline-earth vapors is reported. The H - equilibrium yield in strontium vapor reaches a maximum of 50% at an energy of 250 eV/amu, which is the highest H - yield reported to date

  8. Coordination Chemistry of Alkali and Alkaline-Earth Cations with Macrocyclic Ligands.

    Science.gov (United States)

    Dietrich, Bernard

    1985-01-01

    Discusses: (l) alkali and alkaline-earth cations in biology (considering naturally occurring lonophores, their X-ray structures, and physiochemical studies); (2) synthetic complexing agents for groups IA and IIA; and (3) ion transport across membranes (examining neutral macrobicyclic ligands as metal cation carriers, transport by anionic carriers,…

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

    African Journals Online (AJOL)

    eobe

    2 DEPARTMENT OF MECHANICAL ENGINEERING, UNIVERSITY OF UYO,UYO, AKWA-IBOM STATE, NIGERIA. E-mail address mail address mail addresses: 1 oyeahama1@yahoo.com, 2 memetie@yahoo.com. ABSTRACT. The aim of this work is to investigate the effects of mixed alkaline earth oxide. The aim of this work ...

  10. Syntheses, structure and properties of Alkaline-earth metal salts of 4 ...

    Indian Academy of Sciences (India)

    The synthesis, crystal structure, spectral characteristics and thermal properties of alkaline-earth metal salts of 4-nitrophenylacetic acid (4-npaH) .... Isothermal weight loss studies were performed in a temperature controlled furnace. TG-DTA study ... resulted in the dissolu- tion of MCO3. Filtration followed by slow evaporation ...

  11. Propane selective oxidation on alkaline earth exchanged zeolite Y: room temperature in situ IR study

    NARCIS (Netherlands)

    Xu, J.; Mojet, Barbara; van Ommen, J.G.; Lefferts, Leonardus

    2003-01-01

    The effect of zeolite Y ion-exchanged with a series of alkaline-earth cations on selective propane oxidation at room temperature was studied with in situ infrared spectroscopy. Isopropylhydroperoxide was observed as a reaction intermediate and can be decomposed into acetone and water. Contrary to

  12. Doping of graphite by an alkaline-earth metal to reduce the work function

    NARCIS (Netherlands)

    Baturin, AS; Nikolski, KN; Knyazev, AI; Tchesov, RG; Sheshin, EP

    2004-01-01

    A technique for reducing the work function of a field-emission graphite cathode by doping it by an alkaline-earth metal (barium) is suggested. A model of formation of a barium monolayer on the cathode surface is proposed. Field-emission tests show that the operating voltage of the doped cathode is

  13. Alkaline-earth metal phosphonocarboxylates: synthesis, structures, chirality, and luminescence properties

    Czech Academy of Sciences Publication Activity Database

    Zima, Vítězslav; Raja, D. S.; Lee, Y. S.; Chang, T. G.; Wu, Ch. Y.; Hu, Ch. Ch.; Lee, K. R.; Lai, J. Y.; Yeh, J. M.; Lin, Ch. H.

    2013-01-01

    Roč. 42, č. 43 (2013), s. 15332-15342 ISSN 1477-9226 Grant - others:AV ČR(CZ) M200501202 Program:M Institutional support: RVO:61389013 Keywords : coordination polymers * phosphonates * alkaline-earth Subject RIV: CA - Inorganic Chemistry Impact factor: 4.097, year: 2013

  14. A study on equilibrium and kinetics of ion exchange of alkaline earth ...

    Indian Academy of Sciences (India)

    Unknown

    A study on equilibrium and kinetics of ion exchange of alkaline earth metals using an inorganic cation exchanger – zirconium titanium phosphate. AMIN JIGNASA, THAKKAR RAKESH and CHUDASAMA UMA*. Applied Chemistry Department, Faculty of Technology and Engineering, MS University of Baroda,. Vadodara 390 ...

  15. Environmental effects on fatigue of alkaline earth aluminosilicate glass with varying fictive temperature

    DEFF Research Database (Denmark)

    Striepe, Simon; Deubener, Joachim; Smedskjær, Morten Mattrup

    2013-01-01

    The influence of relative humidity on microhardness, stress intensity, crack resistance, and sub-critical crack growth of an alkaline earth aluminosilicate glass has been studied by Vickers indentation. Quenched and annealed glasses with a wide range of fictive temperatures (ΔTf ≈ 130 K) are comp...

  16. A Kinetic Insight into the Activation of n -Octane with Alkaline-Earth ...

    African Journals Online (AJOL)

    Alkaline-earth metal hydroxyapatites are prepared by the co-precipitation method and characterized using XRD, ICP,NH3-TPD, SEM-EDX, TEM and N2 physisorption analysis. The metal present in the hydroxyapatite influences the acidity of the catalyst. Oxidative dehydrogenation reactions carried out in a continuous flow ...

  17. The Kvanefjeld rare earth and uranium deposits in the llimaussaq alkaline complex (Greenland)

    International Nuclear Information System (INIS)

    Lagny, Ph.

    2012-01-01

    Presentation of the Kvanefjeld deposit in Greenland, a new rare earth deposit that will be in production in a near future, and which is included in the llimaussaq alkaline complex located at the southern end of Greenland. Apart from the fact that it contains considerable amounts of rare earths and uranium, the main interest of this deposit is that its ore includes a relatively high part of heavy rare earths which are particularly searched for by a large number of industrial applications. The geology of the deposit is detailed and commented

  18. The Lanthanide Contraction Revisited

    Energy Technology Data Exchange (ETDEWEB)

    Seitz, Michael; Oliver, Allen G.; Raymond, Kenneth N.

    2007-04-19

    A complete, isostructural series of lanthanide complexes (except Pm) with the ligand TREN-1,2-HOIQO has been synthesized and structurally characterized by means of single-crystal X-ray analysis. All complexes are 1D-polymeric species in the solid state, with the lanthanide being in an eight-coordinate, distorted trigonal-dodecahedral environment with a donor set of eight unique oxygen atoms. This series constitutes the first complete set of isostructural lanthanide complexes with a ligand of denticity greater than two. The geometric arrangement of the chelating moieties slightly deviates across the lanthanide series, as analyzed by a shape parameter metric based on the comparison of the dihedral angles along all edges of the coordination polyhedron. The apparent lanthanide contraction in the individual Ln-O bond lengths deviates considerably from the expected quadratic decrease that was found previously in a number of complexes with ligands of low denticity. The sum of all bond lengths around the trivalent metal cation, however, is more regular, showing an almost ideal quadratic behavior across the entire series. The quadratic nature of the lanthanide contraction is derived theoretically from Slater's model for the calculation of ionic radii. In addition, the sum of all distances along the edges of the coordination polyhedron show exactly the same quadratic dependency as the Ln-X bond lengths. The universal validity of this coordination sphere contraction, concomitant with the quadratic decrease in Ln-X bond lengths, was confirmed by reexamination of four other, previously published, almost complete series of lanthanide complexes. Due to the importance of multidentate ligands for the chelation of rare-earth metals, this result provides a significant advance for the prediction and rationalization of the geometric features of the corresponding lanthanide complexes, with great potential impact for all aspects of lanthanide coordination.

  19. Alkali or alkaline earth metal promoted catalyst and a process for methanol synthesis using alkali or alkaline earth metals as promoters

    Science.gov (United States)

    Tierney, John W.; Wender, Irving; Palekar, Vishwesh M.

    1995-01-01

    The present invention relates to a novel route for the synthesis of methanol, and more specifically to the production of methanol by contacting synthesis gas under relatively mild conditions in a slurry phase with a heterogeneous catalyst comprising reduced copper chromite impregnated with an alkali or alkaline earth metal. There is thus no need to add a separate alkali or alkaline earth compound. The present invention allows the synthesis of methanol to occur in the temperature range of approximately 100.degree.-160.degree. C. and the pressure range of 40-65 atm. The process produces methanol with up to 90% syngas conversion per pass and up to 95% methanol selectivity. The only major by-product is a small amount of easily separated methyl formate. Very small amounts of water, carbon dioxide and dimethyl ether are also produced. The present catalyst combination also is capable of tolerating fluctuations in the H.sub.2 /CO ratio without major deleterious effect on the reaction rate. Furthermore, carbon dioxide and water are also tolerated without substantial catalyst deactivation.

  20. The Lanthanide Contraction beyond Coordination Chemistry.

    Science.gov (United States)

    Ferru, Geoffroy; Reinhart, Benjamin; Bera, Mrinal K; Olvera de la Cruz, Monica; Qiao, Baofu; Ellis, Ross J

    2016-05-10

    The lanthanide contraction is conceptualized traditionally through coordination chemistry. Here we break this mold in a structural study of lanthanide ions dissolved in an amphiphilic liquid. The lanthanide contraction perturbs the weak interactions between molecular aggregates that drive mesoscale assembly and emergent behavior. The weak interactions correlate with lanthanide ion transport properties, suggesting new strategies for rare-earth separation that exploit forces outside of the coordination sphere. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. Effect of the kind of alkaline and rare earth ions on the structure of a glass rich in earth

    International Nuclear Information System (INIS)

    Quintas, Arnaud; Caurant, Daniel; Majerus, Odile; Lenoir, Marion; Dussossoy, Jean-Luc; Charpentier, Thibault; Neuville, Daniel R.; Gervais, C.

    2006-01-01

    In the framework of a structural study of a nuclear wastes containment glass of type alumino borosilicate and rich in rare earths, the influence of the kind of alkaline or rare earth ions is analyzed. For that, two glasses series have been prepared in which the Na + ion (respectively Ca 2+ ions) present in the standard composition is totally substituted by another alkaline ion Li + , K + , Rb + or Cs + (respectively another rare earth ion Mg 2+ , Sr 2+ or Ba 2+ ). These glasses, analyzed by optical absorption, Raman and 27 Al or 11 B NMR spectroscopies have revealed the strong impact of the kind of the modifying ion as well as the structure of the vitreous lattice (variation of the ratio BO 3 /BO 4 and local variations of the polymerization degree) than the local surroundings of the rare earth (decrease of the covalency degree of the bond Nd-O with the increase of the field force of the modifying ion). (O.M.)

  2. Theoretical study of Ce2+ cubic centres in alkaline earth fluoride crystals

    International Nuclear Information System (INIS)

    Popov, N.; Mysovsky, A.; Shendrik, R.; Radzhabov, E.

    2016-01-01

    In this paper we present theoretical study of Ce 2+ impurity centres in alkaline earth fluoride crystals (CaF 2 , SrF 2 ). Only cubic configurations of centres were considered. Electronic levels and related properties were studied using CASSCF/CASPT2 approach within embedded-cluster formalism including scalar relativistic corrections and spin-orbital interaction. Calculated absorption spectra for Ce 2+ in CaF 2 and SrF 2 are in good agreement with experimental data. For both crystals the ground state of Ce 2+ ion has predominantly 4f 1 5d 1 singlet character. - Highlights: • Ab inito study of Ce 2+ impurity centres in alkaline earth fluoride crystals. • Calculated Ce 2+ ground state in CaF 2 and SrF 2 is predominantly 4f 1 5d 1 singlet. • Calculated absorption spectra are in good agreement width experimental data.

  3. IUPAC-NIST Solubility Data Series. 95. Alkaline Earth Carbonates in Aqueous Systems. Part 2. Ca

    International Nuclear Information System (INIS)

    De Visscher, Alex; Vanderdeelen, Jan

    2012-01-01

    The alkaline earth carbonates are an important class of minerals. This article is part of a volume in the IUPAC-NIST Solubility Data Series that compiles and critically evaluates solubility data of the alkaline earth carbonates in water and in simple aqueous electrolyte solutions. Part 1 outlined the procedure adopted in this volume, and presented the beryllium and magnesium carbonates. Part 2, the current paper, compiles and critically evaluates the solubility data of calcium carbonate. The chemical forms included are the anhydrous CaCO 3 types calcite, aragonite, and vaterite, the monohydrate monohydrocalcite (CaCO 3 · H 2 O), the hexahydrate ikaite (CaCO 3 ·6H 2 O), and an amorphous form. The data were analyzed with two model variants, and thermodynamic data of each form consistent with each of the models and with the CODATA key values for thermodynamics are presented.

  4. Properties of the triplet metastable states of the alkaline-earth-metal atoms

    International Nuclear Information System (INIS)

    Mitroy, J.; Bromley, M.W.J.

    2004-01-01

    The static and dynamic properties of the alkaline-earth-metal atoms in their metastable state are computed in a configuration interaction approach with a semiempirical model potential for the core. Among the properties determined are the scalar and tensor polarizabilities, the quadrupole moment, some of the oscillator strengths, and the dispersion coefficients of the van der Waals interaction. A simple method for including the effect of the core on the dispersion parameters is described

  5. Long-range interactions between alkali and alkaline-earth atoms

    International Nuclear Information System (INIS)

    Jiang Jun; Cheng Yongjun; Mitroy, J

    2013-01-01

    Dispersion coefficients between the alkali metal atoms (Li–Rb) and alkaline-earth metal atoms (Be–Sr) are evaluated using matrix elements computed from frozen core configuration interaction calculations. Besides dispersion coefficients with both atoms in their respective ground states, dispersion coefficients are also given for the case where one atom is in its ground state and the other atom is in a low-lying excited state. (paper)

  6. Influence of alkali and alkaline earth ions on the O-alkylation of the ...

    Indian Academy of Sciences (India)

    WINTEC

    Influence of alkali and alkaline earth ions on the O-alkylation of the lower rim phenolic-OH groups of p-tert-butyl-calix[4]arene to result in amide-pendants: Template action of K. + and the structure of. K. + bound tetra-amide derivative crystallized with a p-tert-butyl- calix[4]arene anion. AMJAD ALI,1,3 CHEBROLU P RAO1,* ...

  7. Alkaline-earth metal bicarbonates as lixiviants for uranium (VI) under CO2 sparging

    International Nuclear Information System (INIS)

    Vaziri, F.; White, D.A.

    1989-01-01

    In recent years it has become apparent that uranium is significantly soluble in solutions of alkaline-earth metal bicarbonates -particularly those of magnesium and calcium. A system has been proposed by previous authors in which milled uranium ore is leached in a medium to which an oxidizing agent, the metal hydroxide and CO 2 are added. The alkaline-earth metal hydroxides are much more readily soluble in this medium than the corresponding carbonates. Magnesium and calcium bicarbonates are quite soluble in aqueous media at neutral or nearly neutral pH. The pH determines the relative quantities of bicarbonate and carbonate ions in the system. Even if the pH is quite low, small amounts of carbonate ion are present that can complex with the uranyl ion to produce anionic uranyl complexes. Both UO 2 (CO 3 ) 2 2- and UO 2 (CO 3 ) 3 4- complexes are known and both have a very high stability constant. Despite the appearance of several patents on the use of alkaline-earth metal ions in carbonate media as uranium lixiviants, little theoretical or experimental work on the system has been published. In view of the potential of these systems for cheap, large-scale dissolution of uranium the present contribution will discuss the theory behind this method and provide some experimental data to verify the theoretical treatment. (author)

  8. Effects of alkaline earth metal ion complexation on amino acid zwitterion stability: Results from infrared action spectroscopy

    NARCIS (Netherlands)

    Bush, M. F.; Oomens, J.; Saykally, R. J.; Williams, E. R.

    2008-01-01

    The structures of isolated alkaline earth metal cationized amino acids are investigated using infrared multiple photon dissociation (IRMPD) spectroscopy and theory. These results indicate that arginine, glutamine, proline, serine, and valine all adopt zwitterionic structures when complexed with

  9. Secret lanthanides.

    Science.gov (United States)

    Sturza, C M

    2014-09-15

    Lanthanides are a group of 15 chemical elements which, together with their salts, have come to be used in the last decade as homoeopathic remedies. The effective introduction of lanthanides and their salts into the clinical use, as homoeopathic remedies was based on the idea of Jan Scholten, MD to relate their physicochemical properties shown in the periodic table of elements to their homoeopathic potential. The lanthanides and their salts were prepared as homoeopathic remedies by Pharmacist Robert Münz.

  10. Alkaline earth-based coordination polymers derived from a cyclotriphosphazene-functionalized hexacarboxylate

    International Nuclear Information System (INIS)

    Ling, Yajing; Bai, Dongjie; Feng, Yunlong; He, Yabing

    2016-01-01

    Combination of hexakis(4-carboxylatephenoxy)cyclotriphosphazene with alkaline earth ions of increasing ionic radii (Mg 2+ , Ca 2+ and Ba 2+ ) under different solvothermal conditions yielded three new coordination polymers, and their crystal structures were determined by single-crystal X-ray diffraction analysis. The magnesium compound displays a three dimensional (3D) network structure constructed from the deprotonated ligand and the secondary building block Mg(COO) 4 , which can be rationalized as a (4,6)-connected topological net with the Schläfli symbol of (4 4 ·6 2 ) 3 (4 9 ·6 6 ) 2 . The calcium compound consists of 1D infinite “Ca-O” inorganic chains connected by the deprotonated ligands to from a 3D framework. The barium compound exhibits a 3D framework in which 1D “Ba-O” inorganic chains are connected together by the deprotonated organic linkers. Due to the semi-rigid nature, the ligand adopts distinctly different conformations in the three compounds. The metal ions’ influence exerted on the final structure of the resulting coordination polymers is also discussed. When the radii of alkaline earth ions increases descending down the group from Mg(II) to Ba(II), the coordination number becomes larger and more versatile: from 6 in the magnesium compound, to 6,7 and 10 in the calcium compound, and to 8 and 9 in the barium compound, thus substantially influencing the resulting final framework structures. Also, the photophysical properties were investigated systematically, revealing that the three compounds are photoluminscent in the solid state at room temperature. This work demonstrates that although the multiplicity of conformation in the hexacarboxylate ligand based on the inorganic scaffold cyclotriphosphazene makes it difficult to predict how this ligand will form extended network, but provides unique opportunities for the formation of diverse inorganic-organic hybrids exhibiting rich structural topologies. - Graphical abstract: Three alkaline

  11. Alkaline earth-based coordination polymers derived from a cyclotriphosphazene-functionalized hexacarboxylate

    Energy Technology Data Exchange (ETDEWEB)

    Ling, Yajing; Bai, Dongjie; Feng, Yunlong; He, Yabing, E-mail: heyabing@zjnu.cn

    2016-10-15

    Combination of hexakis(4-carboxylatephenoxy)cyclotriphosphazene with alkaline earth ions of increasing ionic radii (Mg{sup 2+}, Ca{sup 2+} and Ba{sup 2+}) under different solvothermal conditions yielded three new coordination polymers, and their crystal structures were determined by single-crystal X-ray diffraction analysis. The magnesium compound displays a three dimensional (3D) network structure constructed from the deprotonated ligand and the secondary building block Mg(COO){sub 4}, which can be rationalized as a (4,6)-connected topological net with the Schläfli symbol of (4{sup 4}·6{sup 2}){sub 3}(4{sup 9}·6{sup 6}){sub 2}. The calcium compound consists of 1D infinite “Ca-O” inorganic chains connected by the deprotonated ligands to from a 3D framework. The barium compound exhibits a 3D framework in which 1D “Ba-O” inorganic chains are connected together by the deprotonated organic linkers. Due to the semi-rigid nature, the ligand adopts distinctly different conformations in the three compounds. The metal ions’ influence exerted on the final structure of the resulting coordination polymers is also discussed. When the radii of alkaline earth ions increases descending down the group from Mg(II) to Ba(II), the coordination number becomes larger and more versatile: from 6 in the magnesium compound, to 6,7 and 10 in the calcium compound, and to 8 and 9 in the barium compound, thus substantially influencing the resulting final framework structures. Also, the photophysical properties were investigated systematically, revealing that the three compounds are photoluminscent in the solid state at room temperature. This work demonstrates that although the multiplicity of conformation in the hexacarboxylate ligand based on the inorganic scaffold cyclotriphosphazene makes it difficult to predict how this ligand will form extended network, but provides unique opportunities for the formation of diverse inorganic-organic hybrids exhibiting rich structural

  12. Kinetics of the mechanochemical synthesis of alkaline-earth metal amides

    Science.gov (United States)

    Garroni, Sebastiano; Takacs, Laszlo; Leng, Haiyan; Delogu, Francesco

    2014-07-01

    A phenomenological framework is developed to model the kinetics of the formation of alkaline-earth metal amides by the ball milling induced reaction of their hydrides with gaseous ammonia. It is shown that the exponential character of the kinetic curves is modulated by the increase of the total volume of the powder inside the reactor due to the substantially larger molar volume of the products compared to the reactants. It is claimed that the volume of powder effectively processed during each collision connects the transformation rate to the physical and chemical processes underlying the mechanochemical transformations.

  13. Calculation of the electronic structure and contact hyperfine parameters of interstitial hydrogen in alkaline - earth fluorides

    International Nuclear Information System (INIS)

    Oliveira, L.E.M.C. de.

    1976-01-01

    The electronic structure of the interstitial hydrogen atom in alkaline-earth fluorides has been studied using the self-consistent-field multiple-scattering Xα method. In the calculations a cluster constituted by the hydrogen atom and its first anion and cation neighbors has been used. The contact parameters with the proton and the fluorine nuclei have been evaluated. The agreement obtained with the experimental results is in general good and indicates that this method is also appropriate to study defects in ionic crystals. (author) [pt

  14. Novel Extraction Process Of Rare Earth Elements From NdFeB Powders Via Alkaline Treatment

    Directory of Open Access Journals (Sweden)

    Chung K.W.

    2015-06-01

    Full Text Available The alkaline treatment of NdFeB powders in NaOH solution at various equivalent amounts of NaOH at 100°C was performed. The resultant powders were then leached in 0.5M H2SO4 solution at 25°C for 2 minutes. At 5 equivalents of NaOH, neodymium in NdFeB powders was partially transformed to neodymium hydroxide. The transformation of neodymium to neodymium hydroxide actually occurred at 10 equivalents of NaOH and was facilitated by increasing the equivalent of NaOH from 10 to 30. In addition, iron was partially transformed to magnetite during the alkaline treatment, which was also promoted at a higher equivalent of NaOH. The leaching yield of neodymium from alkaline-treated powders was increased with an increasing equivalent of NaOH up to 10; however, it slightly decreased with the equivalent NaOH of over 10. The leaching yield of iron was inversely proportional to that of rare earth elements. NdFeB powders treated at 10 equivalents of NaOH showed a maximum leaching yield of neodymium and dysprosium of 91.6% and 94.6%, respectively, and the lowest leaching yield of iron of 24.2%, resulting in the highest selective leaching efficiency of 69.4%.

  15. Health Effects of Alkaline Diet and Water, Reduction of Digestive-tract Bacterial Load, and Earthing.

    Science.gov (United States)

    Mousa, Haider Abdul-Lateef

    2016-04-01

    In the article, the author discusses the issue of chronic, low-grade acidosis that is thought to be brought about primarily by 2 factors: (1) advancing age, with a consequent decline in renal function; and (2) diet. An acid-forming diet can induce low-grade metabolic acidosis, which causes very small decreases in blood pH and plasma bicarbonate (HCO3-) that remain within the range considered to be normal. However, if the duration of the acidosis is prolonged or chronically present, even a low degree of acidosis can become significant. This article reviews supporting evidence in the literature that has shown that consumption of abundant alkaline-forming foods can result in improvement in bone mineral density (BMD) and muscle mass, protection from chronic illnesses, reduced tumor-cell invasion and metastasis, and effective excretion of toxins from the body. In addition, a large number of studies showing the benefits of alkaline water (mineral water) have revealed that people consuming water with a high level of total dissolved solids (TDS) (ie, with a high mineral content) have shown a lower incidence of coronary heart disease (CHD), cardiovascular disease (CVD), and cancer and lower total mortality rates. Consumption of alkaline water also may prevent osteoporosis and protect pancreatic beta cells with its antioxidant effects. In addition, this article discusses the literature that shows that reducing digestive-tract bacterial load can play an important role in increasing blood alkalinity toward the normal upper limit. That change occurs through good oral hygiene, flossing of teeth, perfect chewing of food, and bowel evacuation as soon as possible. Finally, the author reviews the literature that shows that earthing (ie, the direct contact of the human body with the earth) can supply a current of plentiful electrons. Earthing has been shown to reduce acute and chronic inflammation, blood glucose in patients with diabetes, red blood cell (RBC) aggregation, and blood

  16. Synthesis and luminescence of Eu2+-doped alkaline-earth apatites for application in white LED

    International Nuclear Information System (INIS)

    Zhang Xinguo; Zhang Jilin; Huang Jinqing; Tang Xueping; Gong Menglian

    2010-01-01

    A series of Eu 2+ -doped alkaline-earth apatites (alkaline-earth=Ca, Sr and Ba) were synthesized by a solid state reaction method with excess chlorides, and the effect of the used excess chlorides on the luminescent property of the synthesized products was discussed. Photoluminescence measurements showed that Eu 2+ -doped calcium apatite exhibited intensely blue wide-band emission peaking at 457 nm under near UV excitation among the Eu 2+ -doped Ca, Sr and Ba apatites. Blue and white LEDs were successfully fabricated by pre-coating the calcium apatite phosphors onto ∼395 nm-emitting InGaN chips. The CIE coordinates, color temperature, luminous efficacy and rendering index value of the fabricated white LED are (0.3432, 0.3234), 4969 K, 8 lm/W and 80, respectively. The results indicate that the Eu 2+ -activated calcium apatite phosphor is a promising candidate as a blue component for fabrication of near UV-based white LEDs.

  17. Modelling three-dimensional-quench cooling for alkaline-earth atoms

    CERN Document Server

    Mehlstaeubler, T E; Douillet, A; Rehbein, N; Rasel, E M; Ertmer, W

    2003-01-01

    Quench cooling is a promising technique to reach ultra-cold temperatures in alkaline-earth atoms by Doppler cooling on ultra-narrow transitions. The principles of quench cooling are derived from an effective two-level system with a linewidth adjustable by the quenching laser. A tunable linewidth reconciles the contradictory requirements of a fast cooling rate and a high velocity selectivity at high and low temperatures, respectively. In this paper, we investigate the efficiency of quench cooling in alkaline-earth systems. We present a one-dimensional analytical description of the quenching process. Cooling and trapping in three dimensions is studied with semi-classical Monte Carlo simulations. Our results for magnesium indicate a loading efficiency of up to 40% of pre-cooled atoms at 2 mK into a QuenchMOT. Final temperatures of 9 mu K and an increase in phase-space density by almost five orders of magnitude are observed in the simulations.

  18. Tensorial analysis of the long-range interaction between metastable alkaline-earth-metal atoms

    International Nuclear Information System (INIS)

    Santra, Robin; Greene, Chris H.

    2003-01-01

    Alkaline-earth-metal atoms in their lowest (nsnp) 3 P 2 state are exceptionally long lived and can be trapped magnetically. The nonspherical atomic structure leads to anisotropic long-range interactions between two metastable alkaline-earth-metal atoms. The anisotropy affects the rotational motion of the diatomic system and couples states of different rotational quantum numbers. This paper develops a tensorial decomposition of the most important long-range interaction operators, and a systematic inclusion of molecular rotations, in the presence of an external magnetic field. This analysis illuminates the nature of the coupling between the various degrees of freedom. The consequences are illustrated by application to a system of practical interest: metastable 88 Sr. Using atomic parameters determined in a nearly ab initio calculation, we compute adiabatic potential-energy curves. The anisotropic interatomic interaction, in combination with the applied magnetic field, is demonstrated to induce the formation of a long-range molecular potential well. This curve correlates to two fully polarized, low-field seeking atoms in a rotational s-wave state. The coupling among molecular rotational states controls the existence of the potential well, and its properties vary as a function of magnetic-field strength, thus allowing the scattering length in this state to be tuned. The scattering length of metastable 88 Sr displays a resonance at a field of 339 G

  19. Endonuclease active site plasticity allows DNA cleavage with diverse alkaline Earth and transition metal ions.

    Science.gov (United States)

    Vasu, Kommireddy; Saravanan, Matheshwaran; Nagaraja, Valakunja

    2011-09-16

    A majority of enzymes show a high degree of specificity toward a particular metal ion in their catalytic reaction. However, Type II restriction endonuclease (REase) R.KpnI, which is the first member of the HNH superfamily of REases, exhibits extraordinary diversity in metal ion dependent DNA cleavage. Several alkaline earth and transition group metal ions induce high fidelity and promiscuous cleavage or inhibition depending upon their concentration. The metal ions having different ionic radii and co-ordination geometries readily replace each other from the enzyme's active site, revealing its plasticity. Ability of R.KpnI to cleave DNA with both alkaline earth and transition group metal ions having varied ionic radii could imply utilization of different catalytic site(s). However, mutation of the invariant His residue of the HNH motif caused abolition of the enzyme activity with all of the cofactors, indicating that the enzyme follows a single metal ion catalytic mechanism for DNA cleavage. Indispensability of His in nucleophile activation together with broad cofactor tolerance of the enzyme indicates electrostatic stabilization function of metal ions during catalysis. Nevertheless, a second metal ion is recruited at higher concentrations to either induce promiscuity or inhibit the DNA cleavage. Regulation of the endonuclease activity and fidelity by a second metal ion binding is a unique feature of R.KpnI among REases and HNH nucleases. The active site plasticity of R.KpnI opens up avenues for redesigning cofactor specificities and generation of mutants specific to a particular metal ion.

  20. Optical absorption, fluorescence and thermoluminescence of CaF2 single crystals doped with lanthanide rare earth ions

    International Nuclear Information System (INIS)

    Otani, Choyu

    1979-01-01

    Optical Absorption (OA) , Fluorescence (FL) and Thermoluminescence (TL) experiments were carried out in X-irradiated CaF 2 crystals doped with most of the Lanthanide Rare Earth (RE) ions, Yttrium, and with both RE ions Dysprosium and Terbium. All optical Absorption and Fluorescence measurements as well as optical bleaching and X-irradiation were performed at RT while the TL measurements were done i n the RT- 800K range. Every RE-doped specimen has been fully characterized by its OA and FL bands due to the RE ion-electronic transitions. Most of the RE ions which substitutes for a Ca 2+ ion in the CaF 2 lattice is in the trivial state, being reduced to the divalent state by X-irradiation. The TL results for X-irradiated CaF 2 :Tb , CaF 2 :Dy and CaF 2 :Ho specimens show that the mechanism proposed f o r the 4K-300K TL processing these crystals is also valid for the 300K - 800K temperature range. The photochromic (PC) effect in X-irradiated Tb-doped CaF 2 crystals upon thermal and optical bleaching has been detected. Optical experiments in CaF 2 :Tb,Dy show that the observed PC effect is due to photo switched reversibility of an electron between two states, the thermally stable original state and the ionized stat PC - e - -> PC + , Tb 3+ e - -. Tb 2+ . The regeneration of the OA bands is achieved thermally (-100 deg C) and optically (λ Vis >400nm) with further UV blenching. A detailed analysis of the OA spectra of CaF 2 :Tb crystals X=irradiated and thermally as well as optically bleached show that besides the photo switching, electron-hole recombination occurs leading to a decrease in the overall OA spectrum. The OA bands due to PC-, PC + and Tb 2+ - transitions have been identified by means of Optical Absorption Differential Analysis. Further studies of Photochromic color centers in CaF 2 :Tb crystals show that some of the OA bands detected i the 15Kcm -1 - 20Kcm -1 spectral region are due to hole centers. The TL emissions peaks resulting from the thermal

  1. Relations between structure and material properties in earth alkaline silicate basing phosphors; Struktureigenschaftsbeziehungen in Erdalkalisilikat basierenden Leuchtstoffen

    Energy Technology Data Exchange (ETDEWEB)

    Hempel, Wolfgang

    2008-03-19

    This work is basing on the relation between structure and luminescence of Eu{sup 2+} doped Earth-Alkaline-Silicates. After an overview of Earth-Alkaline-Silicates silicates with an additional cation (Li{sup +}, Al{sup 3+}) and an additional anion (Cl{sup -}, N{sup 3-}) are examined in chapter 4 and 5. Basing on this data an relation between structural influence - like ion-radii, anion and coordination polyeder - and phosphor luminescence is set up. The ability of using as an industrial phosphor is made in the final chapter. (orig.)

  2. Methanol synthesis using a catalyst combination of alkali or alkaline earth salts and reduced copper chromite

    Science.gov (United States)

    Tierney, John W.; Wender, Irving; Palekar, Vishwesh M.

    1995-01-01

    The present invention relates to a novel route for the synthesis of methanol, and more specifically to the production of methanol by contacting synthesis gas under relatively mild conditions in a slurry phase with a catalyst combination comprising reduced copper chromite and basic alkali salts or alkaline earth salts. The present invention allows the synthesis of methanol to occur in the temperature range of approximately 100.degree.-160.degree. C. and the pressure range of 40-65 atm. The process produces methanol with up to 90% syngas conversion per pass and up to 95% methanol selectivity. The only major by-product is a small amount of easily separated methyl formate. Very small amounts of water, carbon dioxide and dimethyl ether are also produced. The present catalyst combination also is capable of tolerating fluctuations in the H.sub.2 /CO ratio without major deleterious effect on the reaction rate. Furthermore, carbon dioxide and water are also tolerated without substantial catalyst deactivation.

  3. Crystal and defect chemistry influences on band gap trends in alkaline earth perovskites

    International Nuclear Information System (INIS)

    Lee, Soonil; Woodford, William H.; Randall, Clive A.

    2008-01-01

    A number of perovskites with A-site alkaline earth chemistries being Ca, Sr, and Ba, and tetravalent cations including Ce, Zr, and Ti are measured for optical band gap and found to vary systematically with tolerance factor and lattice volume within limits defined by the chemistry of the octahedral site. This paper also focuses on the BaTiO 3 system, considering equilibrated nonstoichiometries, and determines the changes in band gap with respect to Ba/Ti ratios. It was found that the optical band gap changes in the solid solution regime and is invariant in the second phase regions, as would be expected. In the cases of Ba/Ti 1.0 stoichiometries, there is a distinct Urbach tail and the trend with lattice volume no longer holds. It is inferred that the V Ti q prime-2V O partial Schottky complex controls the band gap trend with Ba-rich nonstoichiometries

  4. Role of elastic deformation in determining the mixed alkaline earth effect of hardness in silicate glasses

    DEFF Research Database (Denmark)

    Kjeldsen, Jonas; Smedskjær, Morten Mattrup; Potuzak, M.

    2015-01-01

    show that the mixed alkaline earth effect manifests itself as deviations from linearity in shear modulus, Poisson’s ratio, glass transition temperature, liquid fragility index, hardness, volume of densification, and volume of plastic flow. We find no correlation between the elastic part......Glasses deform permanently as a result of indentation and the total resistance to deformation consists of three individual resistances, i.e., those to elastic deformation, densification, and plastic flow. The link between Vickers hardness and the resistances to densification and plastic flow has...... been investigated previously, but the link between the resistance to elastic deformation and hardness has not yet been studied. In this work, we investigate the link between elastic deformation during indentation and Vickers hardness in a series of mixed magnesium-barium boroaluminosilicate glasses. We...

  5. Raman and Rietveld structural characterization of sintered alkaline earth doped ceria

    Energy Technology Data Exchange (ETDEWEB)

    Siqueira Junior, Jose Marcio; Brum Malta, Luiz Fernando; Garrido, Francisco M.S. [Departamento de Quimica Inorganica, Instituto de Quimica, Universidade Federal do Rio de Janeiro, Av. Athos da Silveira Ramos, 149, Centro de Tecnologia, Bloco A, room 632, CEP 68563, 21941-909 Rio de Janeiro, RJ (Brazil); Ogasawara, Tsuneharu [Programa de Engenharia Metalurgica e de Materiais, Coordenacao dos Programas de Pos - Graduacao de Engenharia, Centro de Tecnologia, Universidade Federal do Rio de Janeiro, Ilha do Fundao, CEP 68505, 21941-972 Rio de Janeiro, RJ (Brazil); Medeiros, Marta Eloisa, E-mail: chico@iq.ufrj.br [Departamento de Quimica Inorganica, Instituto de Quimica, Universidade Federal do Rio de Janeiro, Av. Athos da Silveira Ramos, 149, Centro de Tecnologia, Bloco A, room 632, CEP 68563, 21941-909 Rio de Janeiro, RJ (Brazil)

    2012-08-15

    Nanocrystalline calcium and strontium singly doped ceria and co-doped ceria materials for solid electrolytes were prepared via a hydrothermal route. The effect of the hydrothermal treatment time on the solid solution composition was evaluated. Sr doped ceria was the most difficult to form, due to the Sr{sup 2+} large ionic radius. The small crystal size (12-16 nm) of powders allowed sintering into dense ceramic pellets at 1350 Degree-Sign C for 5 h. Raman spectroscopy evidenced a great lattice distortion for Sr doped and co-doped ceria materials, explaining the deterioration of the electrical properties for these ceramics. Besides that, a second phase was detected for Sr doped ceria pellet by using X-ray powder diffraction and Rietveld refinement of XRD data. Impedance measurements showed that Ca-doped ceria behaves as the best ionic conductor ({sigma}{sub g} 390 Degree-Sign C = 1.0 Multiplication-Sign 10{sup -3} S cm{sup -1}) since the nominal composition was achieved; on the other hand, Sr doped ceria performed as resistive materials since Sr incorporation into ceria lattice was critical. These results enhance the close interlace between electrical performance and chemical composition of alkaline earth doped ceria. -- Highlights: Black-Right-Pointing-Pointer Hydrothermally synthesized calcium doped ceria nanoparticles. Black-Right-Pointing-Pointer Incorporation of alkaline earth dopant into ceria lattice. Black-Right-Pointing-Pointer Raman and Rietveld structural characterization. Black-Right-Pointing-Pointer Calcium doped ceria ceramic pellets with high ionic conductivity. Black-Right-Pointing-Pointer Problems associated with the Sr{sup 2+} incorporation into ceria lattice.

  6. Adsorption of alkali, alkaline-earth, and 3d transition metal atoms on silicene

    Science.gov (United States)

    Sahin, H.; Peeters, F. M.

    2013-02-01

    The adsorption characteristics of alkali, alkaline-earth, and transition metal adatoms on silicene, a graphene-like monolayer structure of silicon are analyzed by means of first-principles calculations. In contrast to graphene, interaction between the metal atoms and the silicene surface is quite strong due to its highly reactive buckled hexagonal structure. In addition to structural properties, we also calculate the electronic band dispersion, net magnetic moment, charge transfer, work function, and dipole moment of the metal adsorbed silicene sheets. Alkali metals, Li, Na, and K, adsorb to hollow sites without any lattice distortion. As a consequence of the significant charge transfer from alkalis to silicene, metalization of silicene takes place. Trends directly related to atomic size, adsorption height, work function, and dipole moment of the silicene/alkali adatom system are also revealed. We found that the adsorption of alkaline-earth metals on silicene is entirely different from their adsorption on graphene. The adsorption of Be, Mg, and Ca turns silicene into a narrow gap semiconductor. Adsorption characteristics of eight transition metals Ti, V, Cr, Mn, Fe, Co, Mo, and W are also investigated. As a result of their partially occupied d orbital, transition metals show diverse structural, electronic, and magnetic properties. Upon the adsorption of transition metals, depending on the adatom type and atomic radius, the system can exhibit metal, half-metal, and semiconducting behavior. For all metal adsorbates, the direction of the charge transfer is from adsorbate to silicene, because of its high surface reactivity. Our results indicate that the reactive crystal structure of silicene provides a rich playground for functionalization at nanoscale.

  7. Alkaline earth-based coordination polymers derived from a cyclotriphosphazene-functionalized hexacarboxylate

    Science.gov (United States)

    Ling, Yajing; Bai, Dongjie; Feng, Yunlong; He, Yabing

    2016-10-01

    Combination of hexakis(4-carboxylatephenoxy)cyclotriphosphazene with alkaline earth ions of increasing ionic radii (Mg2+, Ca2+ and Ba2+) under different solvothermal conditions yielded three new coordination polymers, and their crystal structures were determined by single-crystal X-ray diffraction analysis. The magnesium compound displays a three dimensional (3D) network structure constructed from the deprotonated ligand and the secondary building block Mg(COO)4, which can be rationalized as a (4,6)-connected topological net with the Schläfli symbol of (44·62)3(49·66)2. The calcium compound consists of 1D infinite "Ca-O" inorganic chains connected by the deprotonated ligands to from a 3D framework. The barium compound exhibits a 3D framework in which 1D "Ba-O" inorganic chains are connected together by the deprotonated organic linkers. Due to the semi-rigid nature, the ligand adopts distinctly different conformations in the three compounds. The metal ions' influence exerted on the final structure of the resulting coordination polymers is also discussed. When the radii of alkaline earth ions increases descending down the group from Mg(II) to Ba(II), the coordination number becomes larger and more versatile: from 6 in the magnesium compound, to 6,7 and 10 in the calcium compound, and to 8 and 9 in the barium compound, thus substantially influencing the resulting final framework structures. Also, the photophysical properties were investigated systematically, revealing that the three compounds are photoluminscent in the solid state at room temperature. This work demonstrates that although the multiplicity of conformation in the hexacarboxylate ligand based on the inorganic scaffold cyclotriphosphazene makes it difficult to predict how this ligand will form extended network, but provides unique opportunities for the formation of diverse inorganic-organic hybrids exhibiting rich structural topologies.

  8. The heterogeneous reactions of silica, titania and zirconia with alkaline-earth metal oxides in metal chloride melts - to form alkaline-earth metal silicates titanates and zirconates. 1

    International Nuclear Information System (INIS)

    Packter, A.; Zaidi, S.A.

    1982-01-01

    The solubility versus temperature phase diagrams, for calcium, strontium and barium oxide (silicate and titanate) solutions in the metal chloride melts at 800 to 1400 0 C, have been analysed. The alkaline-earth metal oxide solutions are binary mixtures with solvate formation and the liquid phases probably contain [O . 4 MCl 2 ] 2- , [O . MCl 2 ] 2- and O 2- anions. The alkaline-earth metal metsilicate solutions are non-ideal binary mixtures and the liquid phases probably contain mainly Si 3 O 9 6- anions: the orthosilicate solutions probably contain [SiO 4 . MCl 2 ] 4- and SiO 4 4- anions. The alkaline-earth metal titanate solutions are ideal binary mixtures upto titanate mole fraction 0.3-0.6 and the liquid phases probably contain only TiO 3 2- anions. The overall ionic equilibria, occurring in the liquid phases during the chemical reactions of silica (and titania) with alkaline-earth metal oxides in metal chloride melts in this temperature range, were thence assessed. (author)

  9. Luminescence properties of lanthanide doped alkaline earth chlorides under (V)UV and X-ray excitation

    Energy Technology Data Exchange (ETDEWEB)

    Zych, Aleksander, E-mail: a.k.zych@uu.nl [CMI, Debye Institute for NanoMaterials Science, Utrecht University, Princetonplein 1, 3508TA Utrecht (Netherlands); Leferink op Reinink, Anke; Eerden, Koen van der; Mello Donega, Celso de; Meijerink, Andries [CMI, Debye Institute for NanoMaterials Science, Utrecht University, Princetonplein 1, 3508TA Utrecht (Netherlands)

    2011-03-31

    Research highlights: > Fast d-f luminescence from Ce{sup 3+} and Pr{sup 3+} doped SrCl{sub 2} and BaCl{sub 2} has been observed. > Radiative lifetime of 26 ns for Ce{sup 3+} and 13 ns for Pr{sup 3+}d-f emission in SrCl{sub 2} has been measured. > Radiative lifetime of 19 ns for Ce{sup 3+} and 10 ns for Pr{sup 3+}d-f emission in BaCl{sub 2} has been measured. - Abstract: The photoluminescence and radioluminescence of Ce{sup 3+}, Pr{sup 3+} and Nd{sup 3+} in SrCl{sub 2} and BaCl{sub 2} are reported and discussed in relation to application as a (fast) scintillator material. The Ce{sup 3+} doped materials exhibit the typical fast cerium d-f emission (358, 382 nm in SrCl{sub 2} and 350, 375 nm in BaCl{sub 2}) both under synchrotron and ionizing radiation excitations. A weak afterglow is observed. For Pr{sup 3+} a very fast d-f emission is observed in SrCl{sub 2} (250, 263, 300 and 328 nm, {tau} = 13 ns) and BaCl{sub 2} (260, 288 and 315 nm, {tau} = 10 ns), but only under direct f-d excitation. No d-f luminescence is observed for Pr{sup 3+} under X-ray excitation. The absence of d-f emission is explained by the energy of the host lattice emission which is too low for energy transfer to the high energy fd states of Pr{sup 3+} (230 nm in SrCl{sub 2} and 235 nm in BaCl{sub 2}). The neodymium doped chlorides do not show d-f luminescence.

  10. Selective oxidation of methanol to hydrogen over gold catalysts promoted by alkaline-earth-metal and lanthanum oxides

    NARCIS (Netherlands)

    Hereijgers, B.P.C.; Weckhuysen, B.M.

    2009-01-01

    A series of alumina-supported gold catalysts was investigated for the CO-free production of hydrogen by partial oxidation of methanol. The addition of alkaline-earth metal oxide promoters resulted in a significant improvement of the catalytic performance. The methanol conversion was ca. 85 % with

  11. Long-range interactions of excited He atoms with the alkaline earth atoms Mg, Ca, and Sr

    KAUST Repository

    Zhang, J.-Y.

    2013-04-05

    Dispersion coefficients for the long-range interactions of the first four excited states of He, i.e., He(2 1, 3 S) and He(2 1, 3 P), with the low-lying states of the alkaline earth atoms Mg, Ca, and Sr are calculated by summing over the reduced matrix elements of multipole transition operators.

  12. Enhanced NO2 abatement by alkaline-earth modified g-C3N4 nanocomposites for efficient air purification

    Science.gov (United States)

    Papailias, Ilias; Todorova, Nadia; Giannakopoulou, Tatiana; Karapati, Sofia; Boukos, Nikos; Dimotikali, Dimitra; Trapalis, Christos

    2018-02-01

    The emission of nitrogen dioxide (NO2) is a major problem encountered in photocatalytic NOx removal for air purification. Although the oxidation of nitric oxide (NO) has been extensively studied, the elimination of NO2 byproduct is still in preliminary stage. In this work, alkaline-earth modified graphitic carbon nitride (g-C3N4) is proposed for efficient NOx removal by minimizing the emission of NO2 during the NO oxidation process. The novel photocatalysts were synthesized by annealing mixtures of melamine and various alkaline-earth acetates (magnesium, calcium and barium acetate) at 550 °C for 3 h. The specific surface area of the photocatalysts varied between 4.65 and 11.81 m2/g. The formation of MgO, CaCO3 and BaCO3 was demonstrated by XPS and FT-IR analyses. The initial concentration of each alkaline-earth precursor was 5 and 10 wt%, while the final metal concentration in the nanocomposites was in the range of 7.19-22.39 wt%. The modified photocatalysts showed slightly reduced NO oxidation ability. However, the overall air quality was significantly improved by restraining the NO2 emission. The results were related to the basic character of the nanocomposites due to the presence of alkaline-earths and their enhanced NO2 adsorption capability.

  13. Studies on the determination of trace amounts of nitrogen along with alkali and alkaline earth elements in uranium based samples by ion-chromatography (IC)

    International Nuclear Information System (INIS)

    Verma, Poonam; Rastogi, R.K.; Ramakumar, K.L.

    2006-12-01

    Present report describes an ion chromatography (IC) method with suppressed conductivity detection for the determination of traces of nitrogen along with alkali and alkaline earth elements in uranium based nuclear fuels. Method was developed to determine nitrogen as NH 4 + along with alkali and alkaline earth cations by IC using a cation exchange column. (author)

  14. Physical and spectroscopic studies of Cr{sup 3+} doped mixed alkaline earth oxide borate glasses

    Energy Technology Data Exchange (ETDEWEB)

    Samdani, E-mail: samdanimohd82@gmail.com [Department of Engineering, Salalah College of Technology, Salalah (Oman); Ramadevudu, G. [Department of Physics, Vasavi College of Engineering, Ibrahimbagh, Hyderabad 500031, Telangana (India); Chary, M. Narasimha; Shareefuddin, Md. [Department of Physics, Osmania University, Hyderabad 500007, Telangana (India)

    2017-01-15

    A series of mixed alkaline earth oxide glasses xMgO-(30-x)BaO-69.8B{sub 2}O{sub 3}-0.2Cr{sub 2}O{sub 3} were prepared and studied using electron paramagnetic resonance (EPR), optical absorption, Raman spectroscopy and photoluminescence experimental techniques. The optical absorption spectra revealed the characteristic octahedral symmetry of Cr{sup 3+}ions through three broad band transitions {sup 4}A{sub 2g}(F)→ {sup 4}T{sub 2g}(F), {sup 4}A{sub 2g}(F)→ {sup 4}T{sub 1g}(F), and {sup 4}A{sub 2g}(F)→ {sup 2}T{sub 1g}(P). The crystal field (Dq) and Racah parameters (B and C), the optical band gap and Urbach energies of the glass samples were also reported along with the physical properties like density and molar volume. In the EPR spectra three resonance signals corresponding to Cr3+ ions were observed. A broad signal with g = 5.110 was observed which belongs to the isolated Cr3+ centers localized in the strongly distorted octahedral (rhombic) sites of the glass network, a narrow signal (g = 1.960) corresponding to the Cr{sup 3+} centers in the weekly distorted (cubic) sites of the glass network, and a third very broad signal (g = 2.210) was also observed corresponding to Cr{sup 3+}- Cr{sup 3+} paired centers coupled by magnetic dipolar interaction. Another resonance signal with effective value g ≈ 4.220 was attributed to Fe{sup 3+} ions impurity. The number of spins (N) participating in the resonance and susceptibility (χ) values at room temperature were reported and their values varied in a non-linear manner with the composition exhibiting mixed oxide effect. The estimated molecular bonding coefficients (α) values indicated stronger ionic contribution. The Raman spectral investigations were carried out. The Photoluminescence spectra bands near 690 and 750 nm correspond to the Cr{sup 3+} centers in high and low field sites respectively. - Highlights: • Spectroscopic studies were made on alkaline earth borate glasses. • Three resonance signals

  15. Formation of H a - hydrogen centers upon additive coloration of alkaline-earth fluoride crystals

    Science.gov (United States)

    Radzhabov, E. A.; Egranov, A. V.; Shendrik, R. Yu.

    2017-06-01

    The mechanism of coloration of alkaline-earth fluoride crystals CaF2, SrF2, and BaF2 in calcium vapors in an autoclave with a cold zone is studied. It was found that the pressure in the autoclave upon constant evacuation by a vacuum pump within the temperature range of 500-800°C increases due to evaporation of metal calcium. In addition to the optical-absorption bands of color centers in the additively colored undoped crystals or to the bands of divalent ions in the crystals doped with rare-earth Sm, Yb, and Tm elements, there appear intense bands in the vacuum ultraviolet region at 7.7, 7.0, and 6.025 eV in CaF2, SrF2, and BaF2, respectively. These bands belong to the Ha - hydrogen centers. The formation of hydrogen centers is also confirmed by the appearance of the EPR signal of interstitial hydrogen atoms after X-ray irradiation of the additively colored crystals. Grinding of the outer edges of the colored crystals leads to a decrease in the hydrogen absorption-band intensity with depth to complete disappearance. The rate of hydrogen penetration inside the crystal is lower than the corresponding rate of color centers (anion vacancies) by a factor of tens. The visible color density of the outer regions of the hydrogen-containing crystals is several times lower than that of the inner region due to the competition between the color centers and hydrogen centers.

  16. Alkaline-earth metal (Mg) polynitrides at high pressure as possible high-energy materials.

    Science.gov (United States)

    Wei, Shuli; Li, Da; Liu, Zhao; Li, Xin; Tian, Fubo; Duan, Defang; Liu, Bingbing; Cui, Tian

    2017-03-29

    The high-pressure structural evolutionary behaviors of magnesium polynitrides were studied up to 100 GPa using first-principles calculations. Using the unbiased structure searching method, five stable chemical stoichiometries of magnesium polynitrides (MgN, Mg 2 N 3 , MgN 2 , MgN 3 , and MgN 4 ) were theoretically predicted at high pressures. The predicted MgN x compounds contain a rich variety of polynitrogen forms ranging from charged molecules (one-dimensional bent molecules N 3 , planar triangle N 4 to benzene-like rings N 6 ) to extended polymeric chains (N ∞ ). To the best of our knowledge, this is the first time that stable bent molecules N 3 , planar triangle N 4 , and polymeric chains (N ∞ ) were predicted in alkaline-earth metal polynitrides. The decomposition of P1[combining macron]-MgN 3 and P1[combining macron]-MgN 4 are expected to be highly exothermic, releasing an energy of approximately 2.83 kJ g -1 and 2.01 kJ g -1 , respectively. Furthermore, P1[combining macron]-MgN 4 can be synthesized at several GPa. The results of the present study suggest that it is possible to obtain energetic polynitrogen in main-group nitrides under high pressure.

  17. Nitridomanganates of alkaline-earth metals. Synthesis, structure, and physical properties

    Energy Technology Data Exchange (ETDEWEB)

    Ovchinnikov, Alexander

    2016-12-02

    The main goal of the present work was the synthesis of alkaline-earth nitridomanganates (AE{sub x}Mn{sub y}N{sub z}) with extended anionic structures and the characterization of their electronic and magnetic properties. Up to now, only compounds with isolated nitridomanganate anions have been reported in the discussed ternary systems. A systematic exploratory synthesis, employing high-temperature treatment of AE nitrides and Mn under controlled N2 pressure, yielded more than ten new nitridomanganates. Their crystal structures contain anionic building blocks of different dimensionalities, ranging from isolated species to three-dimensional frameworks. In general, the formation of Mn-rich compositions was found to be driven by the emergence of Mn-Mn interactions, which creates a link between nitridometalates and transition-metal-rich binary nitrides. The obtained nitridomanganates display a plethora of interesting phenomena, such as large spin-orbit coupling, magnetic frustration, quenching of magnetism due to Mn-Mn interactions, and metal-insulator transition.

  18. Surface fractal dimensions and textural properties of mesoporous alkaline-earth hydroxyapatites

    Energy Technology Data Exchange (ETDEWEB)

    Vilchis-Granados, J. [Instituto Nacional de Investigaciones Nucleares, Departamento de Química, A.P. 18-1027, Col. Escandón, Delegación Miguel Hidalgo, C.P. 11801, México, DF (Mexico); Universidad Autónoma del Estado de México, Facultad de Química, Av. Paseo Colón esquina con Paseo Tollocan s/n Toluca, México (Mexico); Granados-Correa, F., E-mail: francisco.granados@inin.gob.mx [Instituto Nacional de Investigaciones Nucleares, Departamento de Química, A.P. 18-1027, Col. Escandón, Delegación Miguel Hidalgo, C.P. 11801, México, DF (Mexico); Barrera-Díaz, C.E. [Universidad Autónoma del Estado de México, Facultad de Química, Av. Paseo Colón esquina con Paseo Tollocan s/n Toluca, México (Mexico)

    2013-08-15

    This work examines the surface fractal dimensions (D{sub f}) and textural properties of three different alkaline-earth hydroxyapatites. Calcium, strontium and barium hydroxyapatite compounds were successfully synthesized via chemical precipitation method and characterized using X-ray diffraction, scanning electron microscopy, energy dispersive X-ray spectrometry, Fourier transform infrared spectroscopy, and N{sub 2}-physisorption measurements. Surface fractal dimensions were determined using single N{sub 2}-adsorption/desorption isotherms method to quantify the irregular surface of as-prepared compounds. The obtained materials were also characterized through their surface hydroxyl group content, determined by the mass titration method. It was found that the D{sub f} values for the three materials covered the range of 0.77 ± 0.04–2.33 ± 0.11; these results indicated that the materials tend to have smooth surfaces, except the irregular surface of barium hydroxyapatite. Moreover, regarding the synthesized calcium hydroxyapatite exhibited better textural properties compared with the synthesized strontium and barium hydroxyapatites for adsorbent purposes. However, barium hydroxyapatite shows irregular surface, indicating a high population of active sites across the surface, in comparison with the others studied hydroxyapatites. Finally, the results showed a linear correlation between the surface hydroxyl group content at the external surface of materials and their surface fractal dimensions.

  19. Alkaline earth metal and samarium co-doped ceria as efficient electrolytes

    Science.gov (United States)

    Ali, Amjad; Raza, Rizwan; Kaleem Ullah, M.; Rafique, Asia; Wang, Baoyuan; Zhu, Bin

    2018-01-01

    Co-doped ceramic electrolytes M0.1Sm0.1Ce0.8O2-δ (M = Ba, Ca, Mg, and Sr) were synthesized via co-precipitation. The focus of this study was to highlight the effects of alkaline earth metals in doped ceria on the microstructure, densification, conductivity, and performance. The ionic conductivity comparisons of prepared electrolytes in the air atmosphere were studied. It has been observed that Ca0.1Sm0.1Ce0.8O2-δ shows the highest conductivity of 0.124 Scm-1 at 650 °C and a lower activation energy of 0.48 eV. The cell shows a maximum power density of 630 mW cm-2 at 650 °C using hydrogen fuel. The enhancement in conductivity and performance was due to increasing the oxygen vacancies in the ceria lattice with the increasing dopant concentration. The bandgap was calculated from UV-Vis data, which shows a red shift when compared with pure ceria. The average crystallite size is in the range of 37-49 nm. DFT was used to analyze the co-doping structure, and the calculated lattice parameter was compared with the experimental lattice parameter.

  20. Emission properties of Ce-doped alkaline earth borate glasses for scintillator applications

    Science.gov (United States)

    Torimoto, Aya; Masai, Hirokazu; Okada, Go; Kawaguchi, Noriaki; Yanagida, Takayuki

    2017-11-01

    We investigate the photoluminescence (PL) and X-ray-induced luminescence properties of 0.1 mol% Ce-doped MO-B2O3 (M = Ca, Sr, and Ba) glasses. We also determine the Ce3+/(Ce3++Ce4+) ratio by X-ray absorption near-edge structure analyses. The emission intensities of PL, X-ray scintillation, and thermally stimulated luminescence (TSL) depend on the host glass composition. The order of the PL intensity from highest to lowest is as follows: Ca-substituted glass, Ba-substituted glass, and Sr-substituted glass. Our results suggest that the optical absorption edge and quantum yield (QY) are influenced by the local coordination state of Ce3+, which, in turn, is likely to be affected by the optical basicity. The order of the X-ray scintillation intensity from highest to lowest is reverse of that of the PL intensity. This is probably because the interaction probability of X-rays with matter depends on the effective atomic number of the material and the effective atomic number has a stronger influence on the scintillation intensity than does the QY. Though the TSL glow curves reveal that the density and energy depth of the trap sites depend on the substituted alkaline earth oxides, we are unable to correlate the electron spin resonance (ESR) spectra with the TSL results. Therefore, it is considered that the ESR active sites are not responsible for the TSL in these systems.

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

    Energy Technology Data Exchange (ETDEWEB)

    Srinivas, G., E-mail: srinu123g@gmail.com; Ramesh, B.; Shareefuddin, Md.; Chary, M. N.; Sayanna, R. [Department of Physics, Osmania University, Hyderabad, Telangana, India. (India)

    2016-05-06

    The mixed alkali and alkaline earth oxide borate glass with the composition xK{sub 2}O - (25-x) Li{sub 2}O-12.5BaO-12.5MgO-50B{sub 2}O{sub 3} (x = 0, 5, 10, 15, 20 and 25mol %) and doped with 1mol% CuO were prepared by the melt quenching technique. From the optical absorption spectra the optical band gap, electronic polarizability(α{sub 0}2-), interaction parameter (A), theoretical and experimental optical basicity (Λ) values were evaluated. From the Electron Paramagnetic Resonance (EPR) spectral data the number of spins (N) and susceptibility (χ) were evaluated. The values of (α{sub 0}2-), and (Λ) increases with increasing of K{sub 2}O content and electronic polarizability and interaction parameter show opposite behaviuor which may be due to the creation of non-bridging oxygens and expansion of borate network. The reciprocal of susceptibility (1/χ) and spin concentration (N) as a function of K{sub 2}O content, varied nonlinearly which may be due to creation of non-bridging oxygens in the present glass system. This may be attributed to mixed alkali effect (MAE).

  2. Non-stoichiometry, Compensation and Disorder in Hybrid MBE-grown Alkaline Earth Stannate

    Science.gov (United States)

    Wang, Tianqi; Prakash, Abhinav; Nunn, William; Haugstad, Greg; Jalan, Bharat

    Alkaline earth stannate has recently been of significant interest for transparent conducting oxide and power electronic applications owing to its wide band gap and high conductivity. In this talk, we will present a novel hybrid molecular beam epitaxy approach utilizing elemental solid source for Ba and Sr, a chemical precursor source for Sn and a rf plasma source for oxygen, for the growth of BaSnO3 and SrSnO3 films on (001) SrTiO3 and (110) GdScO3 substrates. High-resolution x-ray diffraction and reflection high-energy electron diffraction revealed single phase, epitaxial films and a layer-by-layer growth mode, respectively. Films' cation stoichiometry was determined using high energy Rutherford backscattering spectrometry. Using temperature dependent electronic transport measurements of films with varying cation stoichiometry, we will discuss how cation stoichiometry, charge compensation and structural disorder influence the metal-to-insulator transition, electron density, and mobility in La-doped BaSnO3 and SrSnO3 films. worked supported by NSF.

  3. Rare-earth organic frameworks involving three types of architecture tuned by the lanthanide contraction effect: hydrothermal syntheses, structures and luminescence.

    Science.gov (United States)

    Deng, Zhao-Peng; Kang, Wei; Huo, Li-Hua; Zhao, Hui; Gao, Shan

    2010-07-21

    The first example of rare-earth organic frameworks with 3-aminopyrazine-2-carboxylic acid (Hapca) was synthesized under hydrothermal conditions and characterized by elemental analysis, IR, PL, TG, powder and single-crystal X-ray diffraction. These ten complexes exhibit three different structure types with decreasing lanthanide radii: [La(apca)(3)](n) () for type I, {[Ln(apca)(ox)(H(2)O)(2)].H(2)O}(n) (Ln = Pr (2), Nd (3), ox = oxalate) for type II, and [Ln(2)(apca)(4)(OH)(2)(H(2)O)(2)](n) (Ln = Sm (4), Eu (5), Gd (6), Tb (7), Dy (8), Er (9), Y (10)) for type III. The structure of type I consists of 1D "snowflake" chains along a-axis, which are further interconnected by hydrogen bonds to produce a 3D sra net topology containing infinite (-C-O-La-)(n) rod-shaped SBU. Type II has 2D Ln-apca-ox 4(4)-net, in which a planar udud water tetramers (H(2)O)(4) are formed by coordinated and free water molecules. Type III also comprises of 2D 4(4)-layer network constructed from Ln-apca-OH. The structure diversity is mainly caused by the variation of coordinated ligand and lanthanide contraction effect. Remarkably, the oxalate in type II was in situ synthesized from 3-aminopyrazine-2-carboxylic acid through an oxidation-hydrolysis reaction. The luminescent investigations reveal that complex exhibits strong blue emission and complex exhibits characteristic luminescence of Eu(3+).

  4. Driving force for the hydration of the swelling clays: Case of montmorillonites saturated with alkaline-earth cations

    International Nuclear Information System (INIS)

    Salles, Fabrice; Douillard, Jean-Marc; Gaudin, Cedric; Prelot, Benedicte; Zajac, Jerzy; Bildstein, Olivier; Van Damme, Henri

    2013-01-01

    Important structural modifications occur in swelling clays upon water adsorption. The multi-scale evolution of the swelling clay structure is usually evidenced by various experimental techniques. However, the driving force behind such phenomena is still not thoroughly understood. It appears strongly dependent on the nature of the interlayer cation. In the case of montmorillonites saturated with alkaline cations, it was inferred that the compensating cation or the layer surface could control the hydration process and thus the opening of the interlayer space, depending on the nature of the interlayer cation. In the present study, emphasis is put on the impact of divalent alkaline-earth cations compensating the layer charge in montmorillonites. Since no experimental technique offers the possibility of directly determining the hydration contributions related to interlayer cations and layer surfaces, an approach based on the combination of electrostatic calculations and immersion data is developed here, as already validated in the case of montmorillonites saturated by alkaline cations. This methodology allows to estimate the hydration energy for divalent interlayer cations and therefore to shed a new light on the driving force for hydration process occurring in montmorillonites saturated with alkaline-earth cations. Firstly, the surface energy values obtained from the electrostatic calculations based on the Electronegativity Equalization Method vary from 450 mJ m -2 for Mg-montmorillonite to 1100 mJ m -2 for Ba-montmorillonite. Secondly, considering both the hydration energy for cations and layer surfaces, the driving force for the hydration of alkaline-earth saturated montmorillonites can be attributed to the interlayer cation in the case of Mg-, Ca-, Sr-montmorillonites and to the interlayer surface in the case of Ba-montmorillonites. These results explain the differences in behaviour upon water adsorption as a function of the nature of the interlayer cation, thereby

  5. Optimizing the performance of bandpass photon detectors for inverse photoemission: Transmission of alkaline earth fluoride window crystals

    International Nuclear Information System (INIS)

    Thiede, Christian; Schmidt, Anke B.; Donath, Markus

    2015-01-01

    Bandpass photon detectors are widely used in inverse photoemission in the isochromat mode at energies in the vacuum-ultraviolet spectral range. The energy bandpass of gas-filled counters is usually formed by the ionization threshold of the counting gas as high-pass filter and the transmission cutoff of an alkaline earth fluoride window as low-pass filter. The transmission characteristics of the window have, therefore, a crucial impact on the detector performance. We present transmission measurements in the vacuum-ultraviolet spectral range for alkaline earth fluoride window crystals in the vicinity of the transmission cutoff as a function of crystal purity, surface finish, surface contamination, temperature, and thickness. Our findings reveal that the transmission characteristics of the window crystal and, thus, the detector performance depend critically on these window parameters

  6. Effect of alkaline earth metal and magnesium cations on cadmium extraction from chloride solutions by tributyl phosphate

    International Nuclear Information System (INIS)

    Prokuev, V.A.; Belousov, E.A.

    1985-01-01

    At 298 K thermodynamic constants of cadmium (2) extraction from chloride solutions of magnesium, calcium, strontium and barium by tributyl phosphate are calculated. It is established, that logarithm of the thermodynamic extraction constant is in a linear dependence from the change in the cation hydration enthalpy in agqueous solution. It is shown, that activity coefficient of neutral complex CdVCl 2 differs from one, and it is the higher the more stable the complex is in alkaline earth metal chloride solutions

  7. Extraction process of U from its ores using solutions of alkaline earth carbonates and bicarbonates in presence of carbon dioxide

    International Nuclear Information System (INIS)

    Floreancig, Antoine; Schuffenecker, Robert.

    1976-01-01

    A process is described for extracting uranium from its ores, either directly in the ore deposit or after such ore bodies have been taken from the ground, comprising an oxidation-leaching stage followed by a recovery stage. The characteristic of this process is that in the leaching process, carbonate and bicarbonate solutions of an alkaline-earth metal are used under a pressure of carbon dioxide between zero and 60 bars and at a temperature of zero to 100 0 C [fr

  8. Are concentrations of alkaline earth elements in maternal hair associated with risk of neural tube defects?

    Science.gov (United States)

    Li, Zhenjiang; Wang, Bin; Huo, Wenhua; Liu, Yingying; Zhu, Yibing; Xie, Jing; Li, Zhiwen; Ren, Aiguo

    2017-12-31

    The relationship between maternal intake of alkaline earth elements (AEEs) during the period of neural tube closure and the risk of neural tube defects (NTDs) is still unclear. We propose that AEE deficiency during the early period of pregnancy is associated with an elevated risk of NTDs in the offspring. In this study, we recruited 191 women with NTD-affected pregnancies (cases) and 261 women who delivered healthy infants (controls). The concentrations of four AEEs (Ca, Mg, Sr, Ba) in maternal hair sections that grew during early pregnancy were analyzed. Information on the dietary habits of the mothers was also collected by questionnaire. Higher concentrations of the four AEEs in hair had protective effects against the risk of total NTDs, with odds ratios with 95% confidence interval (comparing groups separated by each median level) of 0.44 (0.28-0.68) for Mg, 0.56 (0.36-0.87) for Ca, 0.45 (0.28-0.70) for Sr, and 0.41 (0.26-0.65) for Ba. Significant negative dose-response trends were identified for the relationships between the four AEE concentrations in maternal hair and the risks of anencephaly and spina bifida, but not for encephalocele. The frequencies of maternal consumption of fresh green vegetables, fresh fruit, and meat or fish were positively correlated with the concentrations of AEEs in hair. We concluded that the maternal intake of AEEs may play an important role in preventing NTD formation in offspring, and that this intake is related to maternal dietary habits of consuming fresh green vegetables, fresh fruit, and fish or meat. Copyright © 2017 Elsevier B.V. All rights reserved.

  9. Isosteric heat of water adsorption and desorption in homoionic alkaline-earth montmorillonites

    Science.gov (United States)

    Belhocine, M.; Haouzi, A.; Bassou, G.; Phou, T.; Maurin, D.; Bantignies, J. L.; Henn, F.

    2018-02-01

    The aim of the present work is to study by means of thermodynamic measurements and Infrared spectroscopy, the effect of the interlayer cations on the adsorption-desorption of water in the case of a montmorillonite exchanged with alkaline-earth metals. For the first time, the net isosteric heat of water adsorption and desorption is determined from isotherms recorded at three temperatures. The net isosteric heat is a very useful parameter for getting more insights into the sorption mechanism since it provides information about the sorption energy evolution which can be complementary to that obtained from structural or gravimetric measurements. The homoionic montmorillonite samples are prepared from purification and cationic exchanged in aqueous solution of the raw material, i.e. the reference SWy-2 Wyoming material. XRD at the dry state and elemental chemical analysis confirm that the treatment does not deteriorate the clay structure and yield the expected homoionic composition. The sorption isotherms measured at various temperatures show that the nature of the interlayer, i.e. exchangeable, cation changes the adsorbed/desorbed amount of water molecules for a given water relative pressure. The total amount of water adsorbed at P/P∘ = 0.5 follows the cation sequence Ca ∼ Mg>Ba while the sorption isosteric heats follow a slightly different sequence, i.e. Ca > Mg>Ba. This discrepancy between the adsorption and desorption heat is due to the higher irreversibility of water sorption process in the Ca exchanged montmorillonite. Finally, analysis of the IR spectra recorded at room temperature and under a primary vacuum reveals that the amount of adsorbed water follows the same sequence as that of the isosteric heat of adsorption and shows the coexistence of liquid-like and solid-like water confined in the interlayer space.

  10. Survey of the class of isovalent antiperovskite alkaline-earth pnictide compounds

    Science.gov (United States)

    Goh, Wen Fong; Pickett, Warren E.

    2018-01-01

    The few reported members of the antiperovskite structure class A e3P nAP nB of alkaline-earth (A e =Ca , Sr, Ba) pnictide (P n =N , P, As, Sb, Bi) compounds are all based on the B -site anion P nB=N . All can be categorized as narrow-gap semiconductors, making them of interest for several reasons. Because chemical reasoning suggests that more members of this class may be stable, we provide here a density functional theory (DFT)-based survey of this entire class of 3 ×5 ×5 compounds. We determine first the relative energetic stability of the distribution of pairs of P n ions in the A and B sites of the structure, finding that the B site always favors the small pnictogen anion. The trends of the calculated energy gaps versus the A e cation and P n anions are determined, and we study effects of spin-orbit coupling as well as two types of gap corrections to the conventional DFT electronic spectrum. Because there have been suggestions that this class harbors topological insulating phases, we have given this possibility attention and found that energy gap corrections indicate the cubic structures will provide at most a few topological insulators. Structural instability is addressed by calculating phonon dispersion curves for a few compounds, with one outcome being that distorted structures should be investigated further for thermoelectric and topological character. Examples of the interplay between spin-orbit coupling and strain on the topological nature are provided. A case study of Ca3BiP including the effect of strain illustrates how a topological semimetal can be transformed into a topological insulator and Dirac semimetal.

  11. Microstructure and creep behavior of magnesium-aluminum alloys containing alkaline and rare earth additions

    Science.gov (United States)

    Saddock, Nicholas David

    In the past few decades governmental regulation and consumer demands have lead the automotive companies towards vehicle lightweighting. Powertrain components offer significant potential for vehicle weight reductions. Recently, magnesium alloys have shown promise for use in powertrain applications where creep has been a limiting factor. These systems are Mg-Al based, with alkaline earth or rare earth additions. The solidification, microstructure, and creep behavior of a series of Mg-4 Al- 4 X:(Ca, Ce, La, and Sr) alloys and a commercially developed AXJ530 (Mg--5 Al--3 Ca--0.15 Sr) alloy (by wt%) have been investigated. The order of decreasing freezing range of the five alloys was: AX44, AXJ530, AJ44, ALa44 and ACe44. All alloys exhibited a solid solution primary alpha-Mg phase surrounded by an interdendritic region of Mg and intermetallic(s). The primary phase was composed of grains approximately an order of magnitude larger than the cellular structure. All alloys were permanent mold cast directly to creep specimens and AXJ530 specimens were provided in die-cast form. The tensile creep behavior was investigated at 175 °C for stresses ranging from 40 to 100 MPa. The order of decreasing creep resistance was: die-cast AXJ530 and permanent mold cast AXJ530, AX44, AJ44, ALa44 and ACe44. Grain size, solute concentration, and matrix precipitates were the most significant microstructural features that influenced the creep resistance. Decreases in grain size or increases in solute concentration, both Al and the ternary addition, lowered the minimum creep rate. In the Mg-Al-Ca alloys, finely distributed Al2Ca precipitates in the matrix also improved the creep resistance by a factor of ten over the same alloy with coarse precipitates. The morphology of the eutectic region was distinct between alloys but did not contribute to difference in creep behavior. Creep strain distribution for the Mg-Al-Ca alloys developed heterogeneously on the scale of the alpha-Mg grains. As

  12. A gravimetric method for the determination of oxygen in uranium oxides and ternary uranium oxides by addition of alkaline earth compounds

    International Nuclear Information System (INIS)

    Fujino, Takeo; Tagawa, Hiroaki; Adachi, Takeo; Hashitani, Hiroshi

    1978-01-01

    A simple gravimetric determination of oxygen in uranium oxides and ternary uranium oxides is described. In alkaline earth uranates which are formed by heating in air at 800-1100 0 C, uranium is in the hexavalent state over certain continuous ranges of alkaline earth-to-uranium ratios. Thus, if an alkaline earth uranate or a compound containing an alkaline earth element, e.g. MgO, is mixed with the oxide sample and heated in air under suitable conditions, oxygen can be determined from the weight change before and after the reaction. The standard deviation of the O:U ratio for a UOsub(2+x) test sample is +-0.0008-0.001, if a correction is applied for atmospheric moisture absorbed during mixing. (Auth.)

  13. IUPAC-NIST Solubility Data Series. 100. Rare Earth Metal Fluorides in Water and Aqueous Systems. Part 3. Heavy Lanthanides (Gd–Lu)

    Energy Technology Data Exchange (ETDEWEB)

    Mioduski, Tomasz [Institute of Nuclear Chemistry and Technology, 03195 Warszawa (Poland); Gumiński, Cezary, E-mail: cegie@chem.uw.edu.pl [Department of Chemistry, University of Warsaw, 02093 Warszawa (Poland); Zeng, Dewen, E-mail: dewen-zeng@hotmail.com [College of Chemistry and Chemical Engineering, Central South University, Changsha 410083 (China)

    2015-06-15

    This is the third part of the volume devoted to solubility data for the rare earth metal (REM) fluorides in water and in aqueous ternary and multicomponent systems. It covers experimental results of trivalent fluorides of Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu (so-called heavy lanthanides), since no quantitative data on solubilities of TbF{sub 4} and YbF{sub 2} (the most stable compounds at these valencies) are available. The related literature has been covered through the end of 2014. Compilations of all available papers with the solubility data are introduced for each REM fluoride with a corresponding critical evaluation. Every such assessment contains a collection of all solubility results in aqueous solution, a selection of suggested solubility data, a solubility equation, and a brief discussion of the multicomponent systems. Only simple fluorides (no complexes or double salts) are treated as the input substances in this report. General features of the systems, such as nature of the equilibrium solid phases, solubility as a function of temperature, influence of ionic strength, solution pH, mixed solvent medium on the solubility, quality of the solubility results, and the solubility as a function of REM atomic number, have already been presented in Part 1 of the volume.

  14. Theoretical consideration of metabolic and histomorphometric data for alkaline earth and actinide distribution dynamics in the beagle skeleton

    International Nuclear Information System (INIS)

    Parks, N.J.

    1989-01-01

    The beagle has been used for thirty years as a putative model for human skeletal dynamics in terms of metabolic behaviour and response to in situ radiation insults. The partitioned clearance model (PCM) is a bone by bone description of radionuclide redistribution in the beagle skeleton after the end of exposure to 226 Ra by eight semi-monthly injections at 435-535 days or by continuous ingestion of 90 Sr from in utero to 540 days. The PCM describes both the clearance of radium after deposition on surfaces following injection and the clearance of 90 Sr after uniform deposition in the skeleton as a function of Ca mass. The PCM relates the metabolically determined time-zero deposition fraction (% A) per skeletal component to the calcium fraction (%Ca) per component. The ratio of these two fractions is defined as an estimator of relative 'surface',S, in PCM for the alkaline earths (ae). A comparison is made of 'surface' as defined, in PCM, by activity fraction per mass fraction in a given skeletal component for bone seeking alkaline earths (S ae ), to similarly defined 'surface' (S act ) for injected plutonium citrate. For inhaled soluble plutonium nitrate that translocates to bone, the S act values are very similar to the S ae values for injected radium. The physiochemical determinants of Pu deposition in bone after inhalation appear to be similar to those for alkaline earths. Histomorphometric data from actual bone surfaces marked in vivo with fluorescent labels given to a juvenile dog and then 13 years later give direct evidence that actinides not removed metabolically may never be removed by remodelling processes. (author)

  15. Novel alkaline earth copper germanates with ferro and antiferromagnetic S=1/2 chains

    Energy Technology Data Exchange (ETDEWEB)

    Brandao, Paula [CICECO, Universidade de Aveiro, 3810-193 Aveiro (Portugal); Reis, Mario S. [Instituto de Fisica, Universidade Federal Fluminense, Av. Gal. Milton Tavares de Souza s/n, 24210-346 Niteroi-RJ (Brazil); Gai, Zheng [Center for Nanophase Materials Sciences, Oak Ridge National Laboratory Oak Ridge, TN 37831-6487 (United States); Santos, Antonio M. dos, E-mail: dossantosam@ornl.gov [Quantum Condensed Matter Division, Neutron Sciences Directorate, Oak Ridge National Laboratory Oak Ridge, TN 37831-6460 (United States)

    2013-02-15

    Two new alkaline earth copper(II) germanates were hydrothermally synthesized: CaCuGeO{sub 4}{center_dot}H{sub 2}O (1) and BaCu{sub 2}Ge{sub 3}O{sub 9}{center_dot}H{sub 2}O (2), and their structures determined by single crystal X-ray diffraction. Compound (1) crystallizes in space group P2{sub 1}/c with a=5.1320(2) Angstrom-Sign , b=16.1637(5) Angstrom-Sign , c=5.4818(2) Angstrom-Sign , {beta}=102.609(2) Degree-Sign , V=443.76(3) Angstrom-Sign {sup 3} and Z=4. This copper germanate contains layers of composition [CuGeO{sub 4}]{sub {infinity}}{sup 2-} comprising CuO{sub 4} square planes and GeO{sub 4} tetrahedra with calcium and water molecules in the inter-layer space. Compound (2) crystallizes in the Cmcm space group with a=5.5593(3) Angstrom-Sign , b=10.8606(9) Angstrom-Sign , c=13.5409(8) Angstrom-Sign , V=817.56(9) Angstrom-Sign {sup 3} and Z=4. This structure contains GeO{sub 6} and CuO{sub 6} octahedra as well as GeO{sub 4} tetrahedra, forming a three-dimensional network of interconnecting six-membered ring channels. The magnetic susceptibility for both samples can be interpreted as S=1/2 chains, in agreement with the copper topology observed in the crystal structure. The susceptibility of (1) exhibits a Bonner-Fisher type behavior, resulting from antiferromagnetic intra-chain interactions without three-dimensional ordering down to 5 K-the lowest measured temperature. This observation, together with the absence of super-exchange paths between the copper chains, make this system particularly promising for the study of low dimensional magnetism. The magnetic properties of (2) show a very weak ferromagnetic near-neighbor interaction along the chain. In this compound a peak the {chi}T plot seems to indicate the onset of interchain antiferromagentic correlations. However, no ordering temperature is detected in the susceptibility data. - Graphical abstract: Copper chains present in CaCuGeO{sub 4}{center_dot}H{sub 2}O and BaCu{sub 2}Ge{sub 3}O{sub 9}{center

  16. Use of EDTA for potentiometric back titration of rare earths and analysis of their mixtures

    International Nuclear Information System (INIS)

    Zayed, M.A.; Rizk, M.S.; Khalifa, H.; Omer, W.F.

    1987-01-01

    Advantage was taken of the stoichiometric reaction between mercury(II), rare earths, alkaline earths, heavy metal ions and EDTA in urotropine buffered media to determine rare earths by back-titration of excess EDTA in the course of estimating a variety of lanthanides or analysing their binary mixture with one of the alkaline earth metals by selective control of pH; or analysing their binary mixtures with heavy metals using fluoride as a good masking agent for rare earths; or analysing their ternary mixtures with both heavy and alkaline earth metals in two steps, one by selective control of pH and the other by masking of rare earths with fluoride at lower pH to estimate the heavy metal. The procedures given are simple, rapid and extremely reliable. 19 refs. (author)

  17. Modelling the liquid-liquid extraction of nitric acid and lanthanide nitrates by tributylphosphate. Study of the influence of the aqueous phase composition on the selectivity of rare earth separation

    International Nuclear Information System (INIS)

    Mokili, Bandombele

    1992-01-01

    This research thesis reports the application of advances in the modelling of liquid-liquid extraction to a quantitative processing of the selectivity of separations. It is here applied to the extraction-based separation of lanthanide nitrates by using the tributylphosphate (TBP) in nitric environment as this system is interesting for industrial applications in hydro-metallurgy of rare earths as well as in the processing of irradiated nuclear fuels. Experimental data are acquired and then used in the Mikulin-Sergievskii-Dannus model. Complete modelling is thus obtained which allowed the complex problem of extraction of nitric acid and of lanthanide to be addressed, and the existence of a hybrid solvate to be supported. A mathematical expression of the separation factor of two lanthanides is proposed and used to highlight its influencing parameters, i.e. water activity in the aqueous phase, and the rate of the effective extraction constants of the two elements to be separated. Experimental observations are thus interpreted. The selection of optimal separation conditions is thus justified, and, in some cases, the system selectivity can be predicted [fr

  18. Scalable Synthesis of Carbon-Supported Platinum–Lanthanide and −Rare-Earth Alloys for Oxygen Reduction

    DEFF Research Database (Denmark)

    Roy, Claudie; Knudsen, Brian P.; Pedersen, Christoffer M.

    2018-01-01

    the thermodynamics relevant for the reduction conditions of the rare earths to form alloys with platinum. We show how the tolerance for water and oxygen severely limits the synthesis parameters and how under certain conditions the thermal reduction of YCl3 with H2 is possible from 500 °C. From the insight gained, we...... an improved mass activity in comparison to the unmodified catalyst,proving the viability of the method. Initial work based on thermodynamic equilibrium calculations on reduction time show promise in controlling the phase formed by tuning the parameters of time, temperature, and gas composition....

  19. Study of conformational and acid-base properties of norbadione A and pulvinic derivatives: Consequences on their complexation properties of alkaline and alkaline earth cations

    International Nuclear Information System (INIS)

    Kuad, P.

    2006-01-01

    This work deals with the study of norbadione A, a pigment extracted from mushrooms and known to complex cesium cations. The study of the acid-base properties of norbadione A has allowed to determine the relative acidity of the seven protonable functions of the molecule and to reveal a reversible isomerization of the double exocyclic bond of the pulvinic moieties. The observed change of configuration is induced by a hydrogen bond of the H-O-H type and by electrostatic interactions. Moreover, the microscopic protonation mechanism of the norbadione A has been analyzed, considering three different study media where the acid-base properties of the norbadione A are compared. In the presence of 0.15 mol.l -1 of NaCl, it has been observed a remarkable cooperativity in the protonation of the enol groups. At last, the use of different analytical methods (NMR, potentiometry and calorimetry) has allowed to study the complexing properties of the norbadione A towards cesium and other alkaline and rare earth cations. (O.M.)

  20. Isolation of radioactive strontium from natural samples. Separation of strontium from alkaline and alkaline earth elements by means of mixed solvent anion exchange

    International Nuclear Information System (INIS)

    Grahek, Z.; Kosutic, K.; Lulic, S.; Kvastek, K.; Eskinja, I.

    1999-01-01

    This paper presents the results of studies which led to the procedures for the chromatographic separation of radioactive strontium from alkaline, earth-alkaline and other elements in natural samples, on columns filled with strong base anion exchangers using alcoholic solutions of nitric acid as eluents. It has been shown that potassium, caesium, calcium, barium, yttrium and strontium can be adsorbed on strong base anion exchangers of the Dowex and Amberlite type, which contain the quaternary ammonium group with nitrate as counter-ion, from solutions of nitric acid in alcohol. Adsorption strength increases in the order methanol 3 in methanol, while they are adsorbed from ethanol and propanol. The adsorption strength is influenced by the polarity of alcohol, by the concentration of nitrate and by pH. The strength with which strontium adsorbs on the exchangers increases in the interval from 0 to 0.25M NH 4 NO 3 in methanol, after which it starts to decrease. Strontium adsorbs to the exchangers from the alcoholic solution of ammonium nitrate twice as strongly as from the alcoholic solution of nitric acid, while a fraction of water in pure alcohol exceeding 10% prevents adsorption. In the mixture of alcohol and nitric acid, the adsorption strength for calcium and strontium increases with the increase of the volume fraction of alcohol with a lower dielectric constant. The rate and strength of adsorption of ions on the exchanger also increase in the series 0.25M HNO 3 in methanol 3 in ethanol 3 in 1-propanol for each individual ion, as well as in the Ca 3 in methanol, 0.25M HNO 3 in ethanol and 0.25M HNO 3 in propanol. Separation is also possible from alcohol mixtures. Strontium separation is most difficult from calcium, while the efficiency of separation increases with a decrease of the polarity of the used alcohol or alcohol mixture. The first group elements of the periodic table are not separated from each other in this way, while the elements of the second group are

  1. Extraction of uranium from alkaline medium by organic extractants

    International Nuclear Information System (INIS)

    El - nadi, Y.A.M.

    1996-01-01

    A recent possible route for treatment of small amounts of neutron irradiated uranium from alkaline medium was addressed. This have some advantages related to the isolation of many troublesome fission products which forms insoluble carbonates or hydroxides upon alkaline carbonate dissolution of uranium oxide. In alkaline solution containing sodium carbonate and hydroxide, hexavalent uranium is expected to be dissolved in solution whereby most of the fission products transition elements exemplified by zirconium and niobium as well as trivalent lanthanides and actinides will be precipitated. Therefore, in this medium the solution will contain mainly alkali and alkaline earth metal such as Cs + and Sr 2+ and anionic fission products such as pertechnetates and antimonates, Which can be easily separted from uranium. Therefore, The present thesis is directed to investigate the following; 1 - solubility of uranium oxide in alkaline medium consists of sodium carbonate and sodium hydroxide in presence of oxidizing agent. 2 - Extraction of uranium from the aforementioned alkaline medium by immiscible organic diluent containing different amine extractants. 3 - Extraction behaviour of uranium by the macroporous anion exchanger, amberlite IRA - 410, from alkaline solution

  2. Colorimetric and bare-eye detection of alkaline earth metal ions based on the aggregation of silver nanoparticles functionalized with thioglycolic acid

    International Nuclear Information System (INIS)

    Wu, Xiaoyan; Tang, Wanxin; Hou, Cong; Zhang, Chao; Zhu, Ningning

    2014-01-01

    We describe a simple and rapid method for colorimetric and bare-eye detection of the alkaline earth metal ions Mg(II), Ca(II), Sr(II) and Ba(II) based on the use of silver nanoparticles (AgNPs) functionalized with thioglycolic acid (TGA). The TGA ligand was self-assembled onto the AgNPs to form a probe that undergoes a color change from yellow to orange or red on exposure to the alkaline earth ions. It is presumed that the color change is a result of the aggregation of the AgNPs caused by the interaction of the bivalent ions with the carboxy groups on the AgNPs. The color change can be used for bare-eye and colorimetric determination of the alkaline earth metal ions, for example to rapidly determine water hardness. (author)

  3. Oxidation behavior of Cr(III) during thermal treatment of chromium hydroxide in the presence of alkali and alkaline earth metal chlorides.

    Science.gov (United States)

    Mao, Linqiang; Gao, Bingying; Deng, Ning; Liu, Lu; Cui, Hao

    2016-02-01

    The oxidation behavior of Cr(III) during the thermal treatment of chromium hydroxide in the presence of alkali and alkaline earth metal chlorides (NaCl, KCl, MgCl2, and CaCl2) was investigated. The amounts of Cr(III) oxidized at various temperatures and heating times were determined, and the Cr-containing species in the residues were characterized. During the transformation of chromium hydroxide to Cr2O3 at 300 °C approximately 5% of the Cr(III) was oxidized to form intermediate compounds containing Cr(VI) (i.e., CrO3), but these intermediates were reduced to Cr2O3 when the temperature was above 400 °C. Alkali and alkaline earth metals significantly promoted the oxidation of Cr(III) during the thermal drying process. Two pathways were involved in the influences the alkali and alkaline earth metals had on the formation of Cr(VI). In pathway I, the alkali and alkaline earth metals were found to act as electron transfer agents and to interfere with the dehydration process, causing more intermediate Cr(VI)-containing compounds (which were identified as being CrO3 and Cr5O12) to be formed. The reduction of intermediate compounds to Cr2O3 was also found to be hindered in pathway I. In pathway II, the alkali and alkaline earth metals were found to contribute to the oxidation of Cr(III) to form chromates. The results showed that the presence of alkali and alkaline earth metals significantly increases the degree to which Cr(III) is oxidized during the thermal drying of chromium-containing sludge. Copyright © 2015 Elsevier Ltd. All rights reserved.

  4. Environmental Characteristics of Carbonatite and Alkaline Intrusion-related Rare Earth Element (REE) Deposits

    Science.gov (United States)

    Seal, R. R., II; Piatak, N. M.

    2017-12-01

    Carbonatites and alkaline intrusions are important sources of REEs. Environmental risks related to these deposit types have been assessed through literature review and evaluation of the geochemical properties of representative samples of mill tailings and their leachates. The main ore mineral in carbonatite deposits is bastnasite [(Ce,La)(CO3)F], which is found with dolomite and calcite ( 65 %), barite (20 - 25 %), plus a number of minor accessory minerals including sulfides such as galena and pyrite. Generally, alkaline intrusion-related REE deposits either occur in layered complexes or with dikes and veins cutting alkaline intrusions. Such intrusions have a more diverse group of REE ore minerals that include fluorcarbonates, oxides, silicates, and phosphates. Ore also can include minor calcite and iron (Fe), lead (Pb), and zinc (Zn) sulfides. The acid-generating potential of both deposit types is low because of a predominance of carbonate minerals in the carbonatite deposits, the presence of feldspars and minor calcite in alkaline intrusion-related deposits, and to only minor to trace occurrence of potentially acid-generating sulfide minerals. Both deposit types, however, are produced by igneous and hydrothermal processes that enrich high-field strength, incompatible elements, which typically are excluded from common rock-forming minerals. Elements such as yttrium (Y), niobium Nb), zirconium (Zr), hafnium (Hf), tungsten (W), titanium (Ti), tantalum (Ta), scandium (Sc), thorium (Th), and uranium (U) can be characteristic of these deposits and may be of environmental concern. Most of these elements, including the REEs, but with the exception of U, have low solubilities in water at the near-neutral pH values expected around these deposits. Mill tailings from carbonatite deposits can exceed residential soil and sediment criteria for Pb, and leachates from mill tailings can exceed drinking water guidelines for Pb. The greatest environmental challenges, however, are

  5. Evaluation of complexing agents and column temperature in ion chromatographic separation of alkali metals, alkaline earth metals and transition metals ion

    International Nuclear Information System (INIS)

    Kelkar, Anoop; Pandey, Ashish; Name, Anil B.; Das, D.K.; Behere, P.G.; Mohd Afzal

    2015-01-01

    The aim of ion chromatography method development is the resolution of all metal ions of interests. Resolution can be improved by changing the selectivity. Selectivity in chromatography can be altered by changes in mobile phase (eg eluent type, eluent strength) or through changes in stationary phase. Temperature has been used in altering the selectivity of particularly in reversed phase liquid chromatography and ion exchange chromatography. Present paper describe the retention behaviour of alkali metals, alkaline earth metals and transition metal ions on a silica based carboxylate function group containing analyte column. Alkali metals, alkaline earth metals and transition metal ions were detected by ion conductivity and UV-VIS detectors respectively

  6. Distribution behavior of uranium, neptunium, rare-earth elements ( Y, La, Ce, Nd, Sm, Eu, Gd) and alkaline-earth metals (Sr,Ba) between molten LiClKCI eutectic salt and liquid cadmium or bismuth

    Science.gov (United States)

    Kurata, M.; Sakamura, Y.; Hijikata, T.; Kinoshita, K.

    1995-12-01

    Distribution coefficients of uranium neptunium, eight rare-earth elements (Y, La, Ce, Pr, Nd, Sm, Eu and Gd) and two alkaline-earth metals (Sr and Ba) between molten LiCl-KCI eutectic salt and either liquid cadmium or bismuth were measured at 773 K. Separation factors of trivalent rare-earth elements to uranium or neptunium in the LiCl-KCl/Bi system were by one or two orders of magnitude larger than those in the LiCl-KCl/Cd system. On the contrary, the separation factors of alkaline-earth metals and divalent rare-earth elements to trivalent rare-earth elements were by one or two orders of magnitude smaller in the LiCl-KCl/Bi system.

  7. Distribution behavior of uranium, neptunium, rare-earth elements (Y, La, Ce, Nd, Sm, Eu, Gd) and alkaline-earth metals (Sr,Ba) between molten LiCl-KCl eutectic salt and liquid cadmium or bismuth

    International Nuclear Information System (INIS)

    Kurata, M.; Sakamura, Y.; Hijikata, T.; Kinoshita, K.

    1995-01-01

    Distribution coefficients of uranium neptunium, eight rare-earth elements (Y, La, Ce, Pr, Nd, Sm, Eu and Gd) and two alkaline-earth metals (Sr and Ba) between molten LiCl-KCl eutectic salt and either liquid cadmium or bismuth were measured at 773 K. Separation factors of trivalent rare-earth elements to uranium or neptunium in the LiCl-KCl/Bi system were by one or two orders of magnitude larger than those in the LiCl-KCl/Cd system. On the contrary, the separation factors of alkaline-earth metals and divalent rare-earth elements to trivalent rare-earth elements were by one or two orders of magnitude smaller in the LiCl-KCl/Bi system. (orig.)

  8. Alkaline earth lead and tin compounds Ae2 Pb, Ae2 Sn, Ae =Ca,Sr,Ba, as thermoelectric materials

    Science.gov (United States)

    Parker, David; Singh, David

    2014-03-01

    We present a detailed theoretical study of three alkaline earth compounds Ca2Pb, Sr2Pb and Ba2Pb, which have undergone little previous study, calculating electronic band structures and Boltzmann transport and bulk moduli using density functional theory. We also study the corresponding tin compounds Ca2Sn, Sr2Sn and Ba2Sn. We find that these are all narrow band gap semiconductors with an electronic structure favorable for thermoelectric performance, with substantial thermopowers for the lead compounds at temperature ranges from 300 to 800 K. For the lead compounds, we further find very low calculated bulk moduli - roughly half of the values for the lead chalcogenides, suggestive of soft phonons and hence low lattice thermal conductivity. All these facts indicate that these materials merit experimental investigation as potential high performance thermoelectrics. We find good potential for thermoelectric performance in the environmentally friendly stannide materials, particularly at high temperature.

  9. Alkaline earth lead and tin compounds Ae2Pb, Ae2Sn, Ae = Ca, Sr, Ba, as thermoelectric materials

    Directory of Open Access Journals (Sweden)

    David Parker and David J Singh

    2013-01-01

    Full Text Available We present a detailed theoretical study of three alkaline earth compounds Ca2Pb, Sr2Pb and Ba2Pb, which have undergone little previous study, calculating electronic band structures and Boltzmann transport and bulk moduli using density functional theory. We also study the corresponding tin compounds Ca2Sn, Sr2Sn and Ba2Sn. We find that these are all narrow band gap semiconductors with an electronic structure favorable for thermoelectric performance, with substantial thermopowers for the lead compounds at temperature ranges from 300 to 800 K. For the lead compounds, we further find very low calculated bulk moduli—roughly half of the values for the lead chalcogenides, suggestive of soft phonons and hence low lattice thermal conductivity. All these facts indicate that these materials merit experimental investigation as potential high performance thermoelectrics. We find good potential for thermoelectric performance in the environmentally friendly stannide materials, particularly at high temperature.

  10. Methanol synthesis using a catalyst combination of alkali or alkaline earth salts and reduced copper chromite for methanol synthesis

    Science.gov (United States)

    Tierney, John W.; Wender, Irving; Palekar, Vishwesh M.

    1993-01-01

    The present invention relates to a novel route for the synthesis of methanol, and more specifically to the production of methanol by contacting synthesis gas under relatively mild conditions in a slurry phase with a catalyst combination comprising reduced copper chromite and basic alkali salts or alkaline earth salts. The present invention allows the synthesis of methanol to occur in the temperature range of approximately 100.degree.-160.degree. C. and the pressure range of 40-65 atm. The process produces methanol with up to 90% syngas conversion per pass and up to 95% methanol selectivity. The only major by-product is a small amount of easily separated methyl formate. Very small amounts of water, carbon dioxide and dimethyl ether are also produced. The present catalyst combination also is capable of tolerating fluctuations in the H.sub.2 /CO ratio without major deleterious effect on the reaction rate. Furthermore, carbon dioxide and water are also tolerated without substantial catalyst deactivation.

  11. Physical and optical absorption studies of Fe{sup 3+} - ions doped lithium borate glasses containing certain alkaline earths

    Energy Technology Data Exchange (ETDEWEB)

    Bhogi, Ashok [VNR Vignana Jyothi Institute of Engineering and Technology, Hyderabad, Telangana (India); Kumar, R. Vijaya [School of Physics, University of Hyderabad, Hyderabad, Telangana (India); Kistaiah, P., E-mail: pkistaiah@yahoo.com [Department of Physics, Osmania University, Hyderabad, Telangana (India)

    2016-05-23

    Iron ion doped lithium borate glasses with the composition 15RO-25Li{sub 2}O-59B{sub 2}O{sub 3}-1Fe{sub 2}O{sub 3} (where R= Ca, Sr and Ba) have been prepared by the conventional melt quenching technique and characterized to investigate the physical and optical properties using XRD, density, molar volume and UV-Visible spectroscopy. The optical absorption spectra exhibit a band at around 460 nm which is assigned to {sup 6}A{sub 1g}(S) → 4E{sub g} (G) of Fe{sup 3+} ions with distorted octahedral symmetry. From ultraviolet absorption edges, the optical band gap and Urbach energies have been evaluated. The effect of alkaline earths on these properties is discussed.

  12. Quantum mechanical study of molecular collisions at ultra-low energy: applications to alkali and alkaline-earth systems

    International Nuclear Information System (INIS)

    Quemener, G.

    2006-10-01

    In order to investigate the collisional processes which occur during the formation of molecular Bose-Einstein condensates, a time-independent quantum mechanical formalism, based on hyperspherical coordinates, has been applied to the study of atom-diatom dynamics at ultra-low energies. We present theoretical results for three alkali systems, each composed of lithium, sodium or potassium atoms, and for an alkaline-earth system composed of calcium atoms. We also study dynamics at large and positive atom-atom scattering length. Evidence for the suppression of inelastic processes in a fermionic system is given, as well as a linear relation between the atom-diatom scattering length and the atom-atom scattering length. (author)

  13. Semiempirical calculation of van der Waals coefficients for alkali-metal and alkaline-earth-metal atoms

    International Nuclear Information System (INIS)

    Mitroy, J.; Bromley, M.W.J.

    2003-01-01

    The van der Waals coefficients, C 6 , C 8 , and C 10 for the alkali-metal (Li, Na, K, and Rb) and alkaline-earth-metal (Be, Mg, Ca, and Sr) atoms are estimated by a combination of ab initio and semiempirical methods. Polarizabilities and atom-wall coefficients are given as a diagnostic check, and the lowest order nonadiabatic dispersion coefficient, D 8 and the three-body coefficient, C 9 are also presented. The dispersion coefficients are in agreement with the available relativistic many-body perturbation theory calculations. The contribution from the core was included by using constrained sum rules involving the core polarizability and Hartree-Fock expectation values to estimate the f-value distribution

  14. The retention of 226Ra in human soft tissue and bone; implications for the ICRP 20 alkaline earth model

    International Nuclear Information System (INIS)

    Schlenker, R.A.; Keane, A.T.; Holtzman, R.B.

    1982-01-01

    The ICRP model of alkaline earth metabolism was adjusted to fit data on the 226 Ra content of 87 samples of soft tissue from 17 persons who received radium by injection or ingestion 5 days to 53 yr before measurement. The fitted functions indicate that soft tissue retention rises to 58% of the whole body retention at 18 days after single intake, and then falls steadily reaching 33% at 100 days and 6% at 1000 days. The model also fitted data on bone retention in 5 persons 8-467 days after injection. For both types of tissue, the new functions differ substantially from those originally published. The adjustments improve or do not significantly reduce the model's ability to fit other radium data. (author)

  15. Coprecipitation of rare earths in systems of three heterovalent ions with sulfates of alkali and alkaline-earth metals

    International Nuclear Information System (INIS)

    Bobrik, V.M.

    1977-01-01

    Co-precipitation of rare earth elements (REE) in milligram amounts (3x10 -3 -3x10 -1 M) with alkali earth (AEE) sulfates in presence of alkali metal ions has been studied, the AEE:REE ratios between the co-precipitator and a REE (up to 50:1) the latter can be co-precipitated quantitatively in presence of corresponding alkali metals linked with the AEE in the Periodic table by a diagonal, i.e. in presence of sodium in co-precipitation with calcium sulfate, potassium with strontium sulfate and rubidium with barium sulfate. Co-precipitation with sulfates of sodium and calcium occurs at temperatures above 85 deg C and presumably involves calcium semihydrate. In presence of an alkali metal REE co-precipitation with AEE becomes isomorphic, i.e. at different AEE:REE ratios the co-precipitation coefficient remains constant. In presence of corresponding alkali metals the decrease in effectiveness of co-precipitation with AEE in the La-Lu series is more pronounced

  16. Sign Changes in the Electric Dipole Moment of Excited States in Rubidium-Alkaline Earth Diatomic Molecules

    Science.gov (United States)

    Pototschnig, Johann V.; Lackner, Florian; Hauser, Andreas W.; Ernst, Wolfgang E.

    2015-06-01

    In a recent series of combined experimental and theoretical studies we investigated the ground state and several excited states of the Rb-alkaline earth molecules RbSr and RbCa. The group of alkali-alkaline earth (AK-AKE) molecules has drawn attention for applications in ultracold molecular physics and the measurement of fundamental constants due to their large permanent electric and magnetic dipole moments in the ground state. These properties should allow for an easy manipulation of the molecules and simulations of spin models in optical lattices. In our studies we found that the permanent electric dipole moment points in different directions for certain electronically excited states, and changes the sign in some cases as a function of bond length. We summarize our results, give possible causes for the measured trends in terms of molecular orbital theory and extrapolate the tendencies to other combinations of AK and AKE - elements. F. Lackner, G. Krois, T. Buchsteiner, J. V. Pototschnig, and W. E. Ernst, Phys. Rev. Lett., 2014, 113, 153001; G. Krois, F. Lackner, J. V. Pototschnig, T. Buchsteiner, and W. E. Ernst, Phys. Chem. Chem. Phys., 2014, 16, 22373; J. V. Pototschnig, G. Krois, F. Lackner, and W. E. Ernst, J. Chem. Phys., 2014, 141, 234309 J. V. Pototschnig, G. Krois, F. Lackner, and W. E. Ernst, J. Mol. Spectrosc., in Press (2015), doi:10.1016/j.jms.2015.01.006 M. Kajita, G. Gopakumar, M. Abe, and M. Hada, J. Mol. Spectrosc., 2014, 300, 99-107 A. Micheli, G. K. Brennen, and P. Zoller, Nature Physics, 2006, 2, 341-347

  17. Enhanced NH3 gas sensing performance based on electrospun alkaline-earth metals composited SnO2 nanofibers

    International Nuclear Information System (INIS)

    Xu, Shuang; Kan, Kan; Yang, Ying; Jiang, Chao; Gao, Jun; Jing, Liqiang; Shen, Peikang; Li, Li

    2015-01-01

    Highlights: • The small-sized SnO 2 (5–7 nm) were obtained by adding the alkaline-earth. • Sr-composited SnO 2 nanofibers showed uniform nanotubes structure (Sr/SnO 2 ). • Sr/SnO 2 showed an excellent sensing performance to NH 3 at room temperature. - Abstract: One-dimensional alkaline-earth metals composited SnO 2 (Ae/SnO 2 ) nanofibres were fabricated via electrospinning technique, followed by thermal treatment at 600 °C for 5 h. Transmission electron microscopy (TEM) studies showed that the nanoparticles size of Ae/SnO 2 was 5–7 nm, which was smaller than the pristine SnO 2 nanorods attached by 20 nm nanoparticles. Moreover, Sr/SnO 2 nanocomposites showed uniform nanotubes structure with the wall thickness of about 30 nm, in which all the nanoparticles were connected to their neighbors by necks. The Sr/SnO 2 nanotubes exhibited an excellent sensing response toward NH 3 gas at room temperature, lower detection limit (10 ppm), faster response time (6 s towards 2000 ppm∼16 s towards 10 ppm) and better reversibility compared to the pristine SnO 2 nanorods. The enhanced sensor performances were attributed to the higher conductivity of the Sr/SnO 2 . Mott–Schottky plots (M–S) and electrochemical impedance spectroscopy (EIS) measurements indicated that the carrier density of Sr/SnO 2 nanotubes was 3 fold of that pristine SnO 2

  18. Influence of alkali and alkaline earth elements on the uptake of radionuclides by Pleurototus eryngii fruit bodies

    Energy Technology Data Exchange (ETDEWEB)

    Guillen, J., E-mail: fguillen@unex.es [LARUEX, Dpt. Applied Physics, Faculty of Veterinary Science, University of Extremadura, Avda. Universidad, s/n, 10071 Caceres (Spain); Baeza, A.; Salas, A. [LARUEX, Dpt. Applied Physics, Faculty of Veterinary Science, University of Extremadura, Avda. Universidad, s/n, 10071 Caceres (Spain)

    2012-04-15

    In the literature, there are many data available on radionuclide contents and their transfer to different species of mushrooms. There are some variables, however, which affect the transfer but are very difficult to observe in collected wild mushrooms. An example is the effect of different concentrations of alkali and alkaline earth elements in the soil. Modification of these concentrations in the soil solution has traditionally been used as a countermeasure to deal with radioactively contaminated areas. In the present work, fruiting bodies of Pleurotus eryngii, a saprophytic mushroom, were grown under controlled laboratory conditions, varying the content of alkali (potassium and caesium) and alkaline earth (calcium and strontium) elements. The transfer of {sup 134}Cs, {sup 85}Sr, and {sup 60}Co (added to the cultures) and of natural {sup 210}Pb was analysed by increasing the content of each stable element considered. A significant, but nonlinear, enhancement of stable caesium and {sup 134}Cs was observed with increasing content of stable caesium in the substrate/mycelium. The transfer of {sup 85}Sr decreased with the addition of each stable cation, whereas the {sup 60}Co and {sup 210}Pb transfers were unaffected. - Highlights: Black-Right-Pointing-Pointer The addition of stable potassium did not affect the uptake of radiocaesium. Black-Right-Pointing-Pointer The addition of stable caesium increased the stable caesium and {sup 134}Cs content in the fruiting bodies of Pleurotus eryngii. Black-Right-Pointing-Pointer The addition of calcium reduced the content of calcium and {sup 85}Sr in the fruiting bodies. Black-Right-Pointing-Pointer These countermeasures did not work properly in the case of {sup 60}Co and {sup 210}Pb, no effect was observed.

  19. Cure and mechanical properties of carboxylated nitrile rubber (XNBR) vulcanized by alkaline earth metal compounds

    Science.gov (United States)

    Tulyapitak, Tulyapong

    Compounds of carboxylated nitrile rubber (XNBR) with alkaline metal oxides and hydroxide were prepared, and their cure and mechanical properties were investigated. Magnesium oxide (MgO) with different specific surface areas (45, 65, and 140 m2/g) was used. Increased specific surface area and concentration of MgO resulted in higher cure rate. Optimum stiffness, tensile strength, and ultimate strain required an equimolar amount of acidity and MgO. The effect of specific surface area on tensile properties was not significant. Crosslink density of XNBR-MgO vulcanizates increased with increased amounts of MgO. ATR-IR spectroscopy showed that neutralization occurs in two steps: (1) During mixing and storage, MgO reacts with carboxyl groups (RCOOH) to give RCOOMgOH. (2) Upon curing, these react bimolecularly to form RCOOMgOOCR and Mg(OH)2. Dynamic mechanical thermal analysis revealed an ionic transition at higher temperature, in addition to the glass transition. The ionic transition shifts to higher temperature with increasing MgO concentration. Like MgO-XNBR systems, cure rates of XNBR-calcium hydroxide (Ca(OH)2) and XNBR-barium oxide (BaO) compounds increased with increased content of curing agents. Curing by these two agents resulted in ionic crosslinks. To ensure optimum tensile properties, equimolar amounts of carboxyl groups and curing agents were required. Dynamic mechanical analysis revealed the ionic transition in these two systems. It shifted to higher temperature with increased amounts of curing agents. In contrast to MgO, Ca(OH)2, and BaO, calcium oxide (CaO) gave results similar to those for thermally cured samples. No ionic transition was observed in XNBR-CaO systems. Tensile strength of XNBR depended on the strength of ionic crosslinks, which was dependent on the size of the alkaline metal ions.

  20. Preliminary investigations on picoplankton-related precipitation of alkaline-earth metal carbonates in meso-oligotrophic lake Geneva (Switzerland

    Directory of Open Access Journals (Sweden)

    Jean-Michel Jaquet

    2013-10-01

    Full Text Available In the course of a routine water-quality survey in meso-oligotrophic lake Geneva (Switzerland, suspended matter was collected by filtration on 0.2 μm membranes in July and August 2012 at the depth of maximal chlorophyll a (Chl a concentration (2 mg m–3. Examination by scanning electron microscopy revealed the presence of numerous dark and gelatinous patches occluding the pores of the membranes, containing high numbers of picoplanktonic cells and, in places, clusters of high-reflectance smooth microspheres (1-2 μm in diameter. Their chemical composition, determined by semi-quantitative, energy-dispersive X ray spectroscopy (EDS showed magnesium (Mg, calcium (Ca, strontium (Sr and barium (Ba (alkaline earth metals to be the dominant cations. Among the anions, phosphorus (P and carbon (C were present, but only the latter is considered here (as carbonate. The microspheres were subdivided into four types represented in a Ca-Sr-Ba ternary space. All types are confined within a domain bound by Ca>45, Sr<10 and Ba<50 (in mole %. Type I, the most frequent, displays a broad variability in Ba/Ca, even within a given cluster. Types II and III are devoid of Ba, but may incorporate P. Type IV contains only Ca. The Type I composition resembles that of benstonite, a Group IIA carbonate that was recently found as intracellular granules in a cyanobacterium from alkaline lake Alchichica (Mexico.Lake Geneva microspheres are solid, featureless and embedded in a mucilage-looking substance in the vicinity of, but seemingly not inside, picoplanktonic cells morphologically similar to Chlorella and Synechococcus. In summer 2012, the macroscopic physico-chemical conditions in lake Geneva epilimnion were such as to allow precipitation of Ca but not of Sr and Ba carbonates. Favourable conditions did exist, though, in the micro-environment provided by the combination of active picoplankton and a mucilaginous envelope. Further studies are ongoing to investigate the

  1. Theoretical study on the role of surface basicity and Lewis acidity on the etherification of glycerol over alkaline earth metal oxides

    NARCIS (Netherlands)

    Calatayud, M.; Ruppert, A.M.|info:eu-repo/dai/nl/314003398; Weckhuysen, B.M.|info:eu-repo/dai/nl/285484397

    2009-01-01

    Alkaline earth metal oxides (MO) are catalytically active in the etherification of glycerol. Density Functional Theory (DFT) calculations have been used to examine the reactivity of glycerol with MO surfaces with M=Mg, Ca, Sr or Ba. More specifically, the optimum glycerol adsorption mode and the

  2. Determination of trace lanthanide impurities in nuclear grade uranium by coupled-column liquid chromatography

    Energy Technology Data Exchange (ETDEWEB)

    Lucy, C.A.; Gureli, L.; Elchuk, S. (Chalk River Lab., Ontario (Canada))

    1993-11-15

    Impurities such as Sm, Gd, Eu, and Dy will degrade the neutron economy of a nuclear reactor when present even at sub-parts-per-million levels, as a result of their high neutron absorption cross sections. Conventional determinations of lanthanide impurities in uranium require 0.5-100 g of uranium. A coupled-column chromatographic procedure has been developed which dramatically reduces the quantity of uranium required. The first column, a semipreparative reversed-phase column, removes the uranium matrix, while the second column, an analytical-scale cation exchange column, concentrates and separates the lanthanides prior to their postcolumn reaction detection with arsenazo III. The maximum loading of uranium onto the reversed-phase column is determined by the volume overload of the lanthanides rather than the concentration overload of the uranium. Using 20 mg of uranium, a detection limit of 0.02 [mu]g/g of U is achieved for Sm, Gd, Eu, and Dy with no interference from transition or alkaline earth metals present in the uranium. 39 refs., 5 figs., 2 tabs.

  3. Theoretical Studies of the Spin Hamiltonian Parameters and Local Distortions for Cu2+ in Alkaline Earth Lead Zinc Phosphate Glasses

    Science.gov (United States)

    Wang, Bo-Kun; Wu, Shao-Yi; Yuan, Zi-Yi; Liu, Zi-Xuan; Jiang, Shi-Xin; Liu, Zheng; Yao, Zi-Jian; Teng, Bao-Hua; Wu, Ming-He

    2016-08-01

    The spin Hamiltonian parameters and local structures are theoretically studied for Cu2+-doped alkaline earth lead zinc phosphate (RPPZ, R=Mg, Ca, Sr, and Ba) glasses based on the high-order perturbation calculations for a tetragonally elongated octahedral 3d9 cluster. The relative elongation ratios are found to be ρ≈3.2%, 4.4%, 4.6%, and 3.3% for R=Mg, Ca, Sr, and Ba, respectively, because of the Jahn-Teller effect. The whole decreasing crystal-field strength Dq and orbital reduction factor k from Mg to Sr are ascribed to the weakening electrostatic coulombic interactions and the increasing probability of productivity of nonbridge oxygen (and hence increasing Cu2+-O2- electron cloud admixtures) under PbO addition, respectively, with increasing alkali earth ionic radius. The anomalies (the largest Dq and the next highest k among the systems) for R=Ba are attributed to the cross linkage of this large cation in the network. The overall increasing order (Mg≤Bacontaining copper dopants.

  4. Melting curve of compressed barium carbonate from in situ ionic conductivity measurements: Implications for the melting behavior of alkaline earth carbonates in Earth's deep carbon cycle

    Science.gov (United States)

    Dong, J.; Li, J.; Zhu, F.; Li, Z.; Farawi, R.

    2017-12-01

    The whereabouts of subducted carbonates place a major constraint on the Earth's deep carbon cycle, but the fraction of carbon retained in the slab and transported into the deep mantle, compared to that released from the slab and recycled to the surface, is still under debate. Knowledge of the stability of carbonated mantle rocks is pivotal for assessing the ability of slabs to carry carbonates into the deep mantle. Determination and systematic comparison of the melting curves of alkali and alkaline earth carbonates at high pressure can help construct thermodynamic models to predict the melting behavior of complex carbonated mantle rocks. Among alkaline earth carbonates, the melting behavior of barium carbonate (BaCO3) has not been adequately understood. The reported melting point of BaCO3at 1 bar differ by nearly 800 °C and constraints on the melting curve of BaCO3 at high pressure are not available. In this study, the melting temperatures of BaCO3 were determined up to 11 GPa from in situ ionic conductivity measurements using the multi-anvil apparatus at the University of Michigan. The solid-liquid boundary at high pressure was detected on the basis of a steep rise in conductivity through the sample upon melting. The melting point of BaCO3 was found to drop from 1797 °C at 3.3 GPa to 1600 °C at 5.5 GPa and then rise with pressure to 2180 °C at 11 GPa. The observed melting depression point at 5.5 GPa corresponds to the phase transition of BaCO3 from the aragonite structure (Pmcn) to post-aragonite structure (Pmmn) at 6.3 GPa, 877 °C and 8.0 GPa, 727 °C, determined from synchrotron X-ray diffraction measurements using laser-heated DAC experiments at the Advanced Photon Source, Argonne National Laboratory. These results are also compared with ex situ falling marker experiments, and the three methods together place tight constraints on the melting curve of BaCO3 and elucidates the effect of structural phase transitions on its melting behavior.

  5. Far from equilibrium enstatite dissolution rates in alkaline solutions at earth surface conditions

    Science.gov (United States)

    Halder, Sougata; Walther, John V.

    2011-12-01

    Far from equilibrium enstatite dissolution rates both open to atmospheric CO 2 and CO 2 purged were measured as a function of solution pH from 8 to 13 in batch reactors at room temperature. Congruent dissolution was observed after an initial period of incongruent dissolution with preferential Si release from the enstatite. Steady-state dissolution rates in open to atmospheric CO 2 conditions decrease with increase in solution pH from 8 to 12 similar to the behavior reported by other investigators. Judging from the pH 13 dissolution rate, rates increase with pH above pH 12. This is thought to occur because of the increase in overall negative surface charges on enstatite as Mg surface sites become negative above pH 12.4, the pH of zero surface charge of MgO. Steady-state dissolution rates of enstatite increase above pH 10 when CO 2 was purged by performing the experiments in a N 2 atmosphere. This suggests inhibition of dissolution rates above pH 10 when experiments were open to the atmosphere. The dissolved carbonate in these solutions becomes dominantly CO 32- above pH 10.33. It is argued that CO 32- forms a >Mg 2-CO 3 complex at positively charged Mg surface sites on enstatite, resulting in stabilization of the surface Si-O bonds. Therefore, removal of solution carbonate results in an increase in dissolution rates of enstatite above pH 10. The log rate of CO 2-purged enstatite dissolution in moles per cm 2 per s as a function of increasing pH above pH 10 is equal to 0.35. This is consistent with the model of silicate mineral dissolution in the absence of surface carbonation in alkaline solutions proposed earlier in the literature.

  6. Rare Earth Elements (REE Deposits Associated with Great Plain Margin Deposits (Alkaline-Related, Southwestern United States and Eastern Mexico

    Directory of Open Access Journals (Sweden)

    Virginia T. McLemore

    2018-01-01

    Full Text Available W.G. Lindgren in 1933 first noted that a belt of alkaline-igneous rocks extends along the eastern edge of the Rocky Mountains and Basin and Range provinces from Alaska and British Columbia southward into New Mexico, Trans-Pecos Texas, and eastern Mexico and that these rocks contain relatively large quantities of important commodities such as, gold, fluorine, zirconium, rare earth elements (REE, tellurium, gallium, and other critical elements. In New Mexico, these deposits were called Great Plain Margin (GPM deposits, because this north-south belt of alkaline-igneous rocks roughly coincides with crustal thickening along the margin between the Great Plains physiographic province with the Basin and Range (including the Rio Grande rift and Rocky Mountains physiographic provinces, which extends into Trans-Pecos Texas and eastern Mexico. Since 1996, only minor exploration and development of these deposits in New Mexico, Texas, and eastern Mexico has occurred because of low commodity prices, permitting issues, and environmental concerns. However, as the current demand for gold and critical elements, such as REE and tellurium has increased, new exploration programs have encouraged additional research on the geology of these deposits. The lack of abundant quartz in these systems results in these deposits being less resistant to erosion, being covered, and not as well exposed as other types of quartz-rich deposits, therefore additional undiscovered alkaline-related gold and REE deposits are likely in these areas. Deposits of Th-REE-fluorite (±U, Nb epithermal veins and breccias are found in the several GPM districts, but typically do not contain significant gold, although trace amounts of gold are found in most GPM districts. Gold-rich deposits in these districts tend to have moderate to low REE and anomalously high tungsten and sporadic amounts of tellurium. Carbonatites are only found in New Mexico and Mexico. The diversity of igneous rocks, including

  7. Structural, optical absorption and photoluminescence spectral studies of Sm3+ ions in Alkaline-Earth Boro Tellurite glasses

    Science.gov (United States)

    Siva Rama Krishna Reddy, K.; Swapna, K.; Mahamuda, Sk.; Venkateswarlu, M.; Srinivas Prasad, M. V. V. K.; Rao, A. S.; Prakash, G. Vijaya

    2018-05-01

    Sm3+ ions doped Alkaline-Earth Boro Tellurite (AEBT) glasses were prepared by using conventional melt quenching technique and characterized using the spectroscopic techniques such as FT-IR, optical absorption, emission and decay spectral measurements to understand their utility in optoelectronic devices. From absorption spectra, the bonding parameters, nephelauxetic ratios were determined to know the nature of bonding between Sm3+ ions and its surrounding ligands. From the measured oscillator strengths, the Judd-Ofelt (J-O) intensity parameters were evaluated and in turn used to estimate various radiative parameters for the fluorescent levels of Sm3+ ions in AEBT glasses. The PL spectra of Sm3+ ions exhibit three emission bands corresponding to the transitions 4G5/2 → 6H5/2, 6H7/2 and 6H9/2 in the visible region for which the emission cross-sections and branching ratios were evaluated. The decay spectral profiles measured for 4G5/2 → 6H7/2 transition showed single exponential for lower concentration and non-exponential for higher concentration of doped rare earth ion in the as prepared glasses. Conversion of decay spectral profiles from single to non-exponential have been analyzed using Inokuti-Hirayama (I-H) model to understand the energy transfer mechanism involved in the decay process. CIE Chromaticity coordinates were measured using emission spectral data to identify the exact region of emission from the as-prepared glasses. From the evaluated radiative parameters, emission cross-sections and quantum efficiencies, it was observed that AEBT glass with 1 mol% of Sm3+ ions is more suitable for designing optoelectronic devices.

  8. Luminescence investigation of R{sup 3+}-doped alkaline earth tungstates prepared by a soft chemistry method

    Energy Technology Data Exchange (ETDEWEB)

    Barbosa, Helliomar P. [Instituto de Química, Universidade de São Paulo, São Paulo, SP (Brazil); Kai, Jiang [Pontifícia Universidade Católica do Rio de Janeiro, Departamento de Química, Rio de Janeiro, RJ, Brazil (Brazil); Silva, Ivan G.N.; Rodrigues, Lucas C.V. [Instituto de Química, Universidade de São Paulo, São Paulo, SP (Brazil); Felinto, Maria C.F.C. [Centro de Química e Meio Ambiente, Instituto de Pesquisas Energéticas e Nucleares, São Paulo, SP (Brazil); Hölsä, Jorma [Instituto de Química, Universidade de São Paulo, São Paulo, SP (Brazil); Department of Chemistry, University of Turku,FI-20014 Turku (Finland); Turku University Centre for Materials and Surfaces (MatSurf), Turku (Finland); Malta, Oscar L. [Departamento de Química Fundamental, Universidade Federal de Pernambuco, Recife, PE (Brazil); Brito, Hermi F., E-mail: hefbrito@iq.usp.br [Instituto de Química, Universidade de São Paulo, São Paulo, SP (Brazil)

    2016-02-15

    Highly luminescent rare earth (R{sup 3+}) doped alkaline-earth tungstates MWO{sub 4}:R{sup 3+} (M{sup 2+}: Ca, Sr and Ba, R{sup 3+}: Eu, Tb, Gd) were prepared with a room temperature coprecipitation method. The phosphors were characterized by X-ray powder diffraction (XPD), thermal analysis (TG), infrared absorption spectroscopy (FTIR) and UV excited photoluminescence. The as-prepared MWO{sub 4}:R{sup 3+} particles belong to the tetragonal scheelite phase, and are well crystallized and are of the average size of 16–48 nm. The excitation and emission spectra of the materials were recorded at 300 and 77 K temperatures. The luminescent materials exhibit intense red (Eu{sup 3+}) and green (Tb{sup 3+}) colors under UV excitation. The excitation spectra of the Eu{sup 3+} doped materials show broad bands arising from the ligand-to-metal charge transfer transitions (O{sup 2−}→W{sup VI} and O{sup 2−}→Eu{sup 3+}) as well as narrow bands from 4f–4f intraconfigurational transitions of Eu{sup 3+}. 4f–4f emission data of the Eu{sup 3+} and Tb{sup 3+} in the MWO{sub 4} host matrices as well as the values of emission quantum efficiencies of the {sup 5}D{sub 0} level and the 4f–4f experimental intensity parameters of Eu{sup 3+} ion are presented and discussed. - Highlights: • Highly red Europium and green Terbium doped tungstate under UV excitation. • Efficient energy transfer process from tungstate to R{sup 3+} ion. • Promising candidates for a red (Eu{sup 3+}) and green (Tb{sup 3+}) emitting phosphors. • Ligand Metal charge transfer to R{sup 3+} ion. • Charge compensation with Na{sup +}.

  9. Photocytotoxic lanthanide complexes

    Indian Academy of Sciences (India)

    The chemistry of photoactive lanthanide complexes showing biological applications is of recent origin. Photodynamic therapy (PDT) is a non-invasive treatment modality of cancer using a photosensitizer drug and light. This review primarily focuses on different aspects of the chemistry of lanthanide complexes showing ...

  10. New type of complex alkali and alkaline earth metal borates with isolated (B12O24)12) anionic group.

    Science.gov (United States)

    Wu, Hongping; Yu, Hongwei; Pan, Shilie; Jiao, Anqing; Han, Jian; Wu, Kui; Han, Shujuan; Li, Hongyi

    2014-03-28

    Compounds with isolated anionic groups often exhibit special linear and nonlinear optical properties and possess potential applications such as birefringence, second harmonic generation and stimulated Raman scattering crystals. In this paper, two new alkali and alkaline earth mixed-metal borates, Li3KB4O8 and LiNa2Sr8B12O24F6Cl, with isolated (B12O24)(12-) anionic groups have been successfully synthesized by spontaneous crystallization. Their structures were determined by single crystal X-ray diffraction and they both crystallize in the same space group, R3[combining macron]. More interestingly, further structure comparison shows that the discovered anhydrous borates with the (B12O24)(12-) groups also crystallize in the same space group R3[combining macron], which is related with the local symmetry of the (B12O24)(12-) groups. These structural features suggest that the crystal structures of the family of compounds depend more on their anionic groups. In addition, the property characterizations of the two new borates were investigated by TG-DSC, IR and UV-vis-NIR diffuse reflectance.

  11. Synthesis and Sintering Behavior of Cordierite Prepared from Multi-Component Materials Including Alkaline-Earth Minerals

    Energy Technology Data Exchange (ETDEWEB)

    Jeong, Suk-In; Kim, Nam-Il; Lee, Sang-Jin [Mokpo National University, Muan (Korea, Republic of)

    2016-10-15

    Cordierite was synthesized using multi-component materials based on a talc-alumina-clay system. The cordierite sintered at 1360 °C showed a high relative density of 98.8% and a low thermal expansion coefficient of 1.59×10{sup -}6/°C. To study the effect of adding alkaline-earth minerals on the cordierite properties, petalite, potash-feldspar, and dicalcium phosphate were added to the synthesized cordierite. In the case of 9 wt% petalite or potash-feldspar addition, the cordierite was more densified; however, the thermal expansion coefficient and the pyroplasticity index were increased. In particular, a 5 μm thick self-glazed coating was formed with the addition of 9 wt% potash-feldspar. In the case of adding dicalcium phosphate, a glass phase was formed at low temperature and gas bubbles formed at high temperature above 1320 ℃. The cordierite synthesized using multi-component materials is expected to be employed as a material for high thermal shock, dense-microstructure flameware.

  12. CO2 gasification reactivity of biomass char: catalytic influence of alkali, alkaline earth and transition metal salts.

    Science.gov (United States)

    Lahijani, Pooya; Zainal, Zainal Alimuddin; Mohamed, Abdul Rahman; Mohammadi, Maedeh

    2013-09-01

    This study investigates the influence of alkali (Na, K), alkaline earth (Ca, Mg) and transition (Fe) metal nitrates on CO2 gasification reactivity of pistachio nut shell (PNS) char. The preliminary gasification experiments were performed in thermogravimetric analyzer (TGA) and the results showed considerable improvement in carbon conversion; Na-char>Ca-char>Fe-char>K-char>Mg-char>raw char. Based on TGA studies, NaNO3 (with loadings of 3-7 wt%) was selected as the superior catalyst for further gasification studies in bench-scale reactor; the highest reactivity was devoted to 5 wt% Na loaded char. The data acquired for gasification rate of catalyzed char were fitted with several kinetic models, among which, random pore model was adopted as the best model. Based on obtained gasification rate constant and using the Arrhenius plot, activation energy of 5 wt% Na loaded char was calculated as 151.46 kJ/mol which was 53 kJ/mol lower than that of un-catalyzed char. Copyright © 2013 Elsevier Ltd. All rights reserved.

  13. Dipole polarizability of alkali-metal (Na, K, Rb)-alkaline-earth-metal (Ca, Sr) polar molecules: Prospects for alignment

    Science.gov (United States)

    Gopakumar, Geetha; Abe, Minori; Hada, Masahiko; Kajita, Masatoshi

    2014-06-01

    Electronic open-shell ground-state properties of selected alkali-metal-alkaline-earth-metal polar molecules are investigated. We determine potential energy curves of the 2Σ+ ground state at the coupled-cluster singles and doubles with partial triples (CCSD(T)) level of electron correlation. Calculated spectroscopic constants for the isotopes (23Na, 39K, 85Rb)-(40Ca, 88Sr) are compared with available theoretical and experimental results. The variation of the permanent dipole moment (PDM), average dipole polarizability, and polarizability anisotropy with internuclear distance is determined using finite-field perturbation theory at the CCSD(T) level. Owing to moderate PDM (KCa: 1.67 D, RbCa: 1.75 D, KSr: 1.27 D, RbSr: 1.41 D) and large polarizability anisotropy (KCa: 566 a.u., RbCa: 604 a.u., KSr: 574 a.u., RbSr: 615 a.u.), KCa, RbCa, KSr, and RbSr are potential candidates for alignment and orientation in combined intense laser and external static electric fields.

  14. Surface effect on the electronic and the magnetic properties of rock-salt alkaline-earth metal silicides

    International Nuclear Information System (INIS)

    Bialek, Beata; Lee, Jaeil

    2011-01-01

    An all electron ab-initio method was employed to study the electronic and the magnetic properties of the (001) surface of alkaline-earth metal silicides, CaSi, SrSi, and BaSi, in the rock-salt structure. The three compounds retain their ferromagnetic metallic properties at the surface. Due to the surface effects, the magnetism of the topmost layer is changed as compared with the bulk. This is a short-range effect. In CaSi, the magnetism of the surface layer is noticeably reduced, as compared with the bulk: magnetic moments (MMs) on both Ca and Si atoms are reduced. In SrSi (001), the polarization of electrons in the surface atoms is similar to that in the bulk atoms, and the values of MMs on the component atoms in the topmost layer do not change as much as in CaSi. In BaSi (001), the magnetic properties of Si surface atoms are enhanced slightly, and the magnetism of Ba atoms is not affected considerably by the surface effect. The calculated densities of states confirm the short-range effect of the surface on the electronic properties of the metal silicides.

  15. Transfer of alkaline earth elements in mothers' milk and doses from 45Ca, 90Sr and 226Ra

    International Nuclear Information System (INIS)

    Smith, T.J.; Phipps, A.W.; Fell, T.P.; Harrison, J.D.

    2003-01-01

    An international programme of work is currently under way to develop methods for calculating doses to infants from ingestion of radionuclides present in mothers' milk. This paper considers the special case of the alkaline earth elements. Models have been developed for 45 Ca, 90 Sr and 226 Ra and the sensitivity of results to various changes in parameter values is discussed. A complication when calculating doses from intakes of radium is that the International Commission on Radiological Protection has previously recommended that doses from decay products of radium should be calculated using element-specific biokinetic models (so-called independent biokinetics). An extension of this method to the models for breastfeeding is proposed. Preliminary estimates of the doses received by the infant for a number of maternal intake scenarios show that doses to the infant can exceed the corresponding adult dose, such as for 45 Ca (ratio = 3.1) while, in other cases such as 90 Sr, the infant dose can be a significant fraction of the adult dose. (author)

  16. Hydrogen storage property of alkali and alkaline-earth metal atoms decorated C24 fullerene: A DFT study

    Science.gov (United States)

    Zhang, Yafei; Cheng, Xinlu

    2018-04-01

    The hydrogen storage behavior of alkali and alkaline-earth metal (AM = Li, Na, K, Mg, Ca) atoms decorated C24 fullerene was investigated by using density functional theory (DFT) study. Our results indicate that the AM atoms prefer to adsorb atop the center of tetragon of C24 fullerene with the largest binding energy than other possible adsorption sites. Moreover, the hydrogen storage gravimetric density of 24H2/6Li/C24, 24H2/6Na/C24 and 36H2/6Ca/C24 configurations reaches up to 12.7 wt%, 10.1 wt% and 12 wt%, higher than the year 2020 target from the US department of energy (DOE). Also, the average adsorption energies of H2 molecules of the 24H2/6Li/C24, 24H2/6Na/C24 and 36H2/6Ca/C24 configurations are -0.198 eV/H2, -0.164 eV/H2 and -0.138 eV/H2, locate the desirable range under the physical adsorption at near ambient conditions. These findings will have important implications on designing new hydrogen storage materials in the future.

  17. 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

  18. Theoretical studies of the local structures and spin Hamiltonian parameters for Cu2+ in alkaline earth alumino borate glasses

    Science.gov (United States)

    Guo, Jia-Xing; Wu, Shao-Yi; Kuang, Min-Quan; Peng, Li; Wu, Li-Na

    2018-01-01

    The local structures and spin Hamiltonian parameters are theoretically studied for Cu2+ in alkaline earth alumino borate (XAB, X = Mg, Ca and Sr) glasses by using the perturbation calculations for tetragonally elongated octahedral 3d9 groups. The [CuO6]10‑ groups are subject to the large relative tetragonal elongation ratios of 15.4%, 13.4% and 13.0% for MgAB, CaAB and SrAB glasses, respectively, arising from the Jahn-Teller effect. The decreasing cubic field parameter Dq, orbital reduction factor k and relative elongation ratio with the increase of the radius of alkaline earth ion X from Mg to Ca or Sr are analyzed for the studied systems in a uniform way.

  19. Equilibrium mononuclear-trinuclear complex in acetonitrile solutions of copper (2) N,N'-ethylene-bis-salicylideneiminate and alkaline earth metal perchlorates

    International Nuclear Information System (INIS)

    Zheltvaj, I.I.; Siritsov, A.I.; Egorova, A.L.; Kamalov, G.L.

    1985-01-01

    Trinuclear adducts of copper (2) NN'-ethylene-bis salicylidenimi=n ate (CuES) with alkaline earth metal perchlorates are dissolved in acetonitrile with the preservation of polynuclear structure, which is confirmed by the data of vibrational and electron spectroscopy. Reversible dissociation of polynuclear adduct is detected, its scale depending on alkaline earth metal nature and increasing in the series Mg 2+ reversible M(CuES) 2 are found, the logarithms of which in the above-mentioned series of metals equal: 11.7+-0.1; 10.5+-0.1; 9.3+-0.1; 8.1+-0.1 and correlate linearly with the absorption band frequencies of the corresponding complexes. Possible reasons for the correlation are discussed

  20. Electrochemical transformations of oxygen and the defect structure of solid solutions on the basis of alkaline earth metal ortho-vanadates

    International Nuclear Information System (INIS)

    Khodos, M.Ya.; Belysheva, G.M.; Brajnina, Kh.Z.

    1986-01-01

    Effect of iso- and heterovalent substitution in the structure of alkaline earth metal ortho-vanadates and synthesis conditions, simulating the definite type of their crystal lattice disordering, on the character of potentiodynamic anodic-cathodic curves has been investigated by the method of cyclic voltammetry. Correlation between signals observed and the defect structure of oxide compounds is refined. Oxygen chemisorption is shown to be determined by concentration of nonequilibrium oxygen vacancies, which formation is accompanied by appearance of quasi-free electrons

  1. Validation of ion chromatography for the determination of transition metal ions along with alkali, alkaline earth metal elements for uranium oxide fuel

    International Nuclear Information System (INIS)

    Kelkar, Anoop; Prakash, Amrit; Afzal, Mohd.; Panakkal, J.P.

    2009-02-01

    The present report describes the use of Ion chromatography (IC) methods with spectrophotometric and direct conductivity detection for the determination of transition metal elements and alkali alkaline earth metal ions in UO 2 pellets. Transmet analytical column and Metrosep- cation 1-2 column were used for the separation of transition metal elements and alkali and alkaline earth metal elements respectively. Oxalic acid and mixture of pyridine 2,6-dicarboxylic acid (PDCA), Na 2 SO 4 and NaCl were used as mobile phase for the separation of transition metal ions and monitored after post - column reaction with 4,2-pyridylazo resorcinol (PAR) at 520nm spectrophotometrically. In the determination of alkali and alkaline earth metal ions the interference of transition metals are removed by complexing them with PDCA. Mixture of tartaric acid and PDCA employed in the separation of alkali and alkaline earth metal ions and monitored on direct conductivity detector. Mobile phase composition was optimised for the base line separation. Calibration plots of Fe 3+ , Cu 2+ , Ni 2+ , Co 2+ , Cd 2+ , Mn 2+ , Li + , Na + , K + , Mg 2+ , Ca 2+ and Sr 2+ were linear over a wide dynamic range with regression coefficient better than 0.999. Detection limit of above ions were between 5-30ppb. To prevent the overloading of the cation exchange column, uranium matrix was removed from UO 2 sample by solvent extraction with 30% TBP - TOPO/CCl 4 . Ten sintered UO2 pellets of same lot were analysed and R.S.D. ±10% was obtained. These methods were validated by analysis of ILCE standards of UO 2 . (author)

  2. Novel 2D or 3D alkaline-earth metal sulfonate-phosphonates based on [O 3S-C 2H 4-PO 3H] 2- ligand

    Science.gov (United States)

    Du, Zi-Yi; Wen, He-Rui; Xie, Yong-Rong

    2008-11-01

    Three novel alkaline-earth metal sulfonate-phosphonates based on [O 3S-C 2H 4-PO 3H] 2- ligand, namely, [Ca(O 3SC 2H 4PO 3H)(H 2O) 2] ( 1), [Sr(O 3SC 2H 4PO 3H)] ( 2) and [Ba 2(O 3SC 2H 4PO 3H) 2] ( 3), have been synthesized by hydrothermal reactions. They represent the first structurally characterized alkaline-earth metal complexes of phosphonic acid attached with a sulfonate group. The structure of compound 1 features a 2D layer based on 1D chains of [Ca 2(PO 3) 2] bridged by -CH 2-CH 2-SO 3- groups. Compounds 2 and 3 show pillar-layer architecture based on two different inorganic layers linked by -CH 2-CH 2- groups. The inorganic layer in compound 2 features a 1D chain of edge-sharing SrO 8 polyhedra whereas that in compound 3 features an edge-sharing Ba 2O 14 di-polyhedral unit which is further corner-shared with four neighboring ones. The [O 3S-C 2H 4-PO 3H] 2- ligand shows diverse coordination modes in the three alkaline-earth metal sulfonate-phosphonates.

  3. Ab initio study of the neutral and anionic alkali and alkaline earth hydroxides: Electronic structure and prospects for sympathetic cooling of OH.

    Science.gov (United States)

    Kas, Milaim; Loreau, Jérôme; Liévin, Jacques; Vaeck, Nathalie

    2017-05-21

    We have performed a systematic ab initio study on alkali and alkaline earth hydroxide neutral (MOH) and anionic (MOH - ) species where M = Li, Na, K, Rb, Cs or Be, Mg, Ca, Sr, Ba. The CCSD(T) method with extended basis sets and Dirac-Fock relativistic effective core potentials for the heavier atoms has been used to study their equilibrium geometries, interaction energies, electron affinities, electric dipole moment, and potential energy surfaces. All neutral and anionic species exhibit a linear shape with the exception of BeOH, BeOH - , and MgOH - , for which the equilibrium structure is found to be bent. Our analysis shows that the alkaline earth hydroxide anions are valence-bound whereas the alkali hydroxide anions are dipole bound. In the context of sympathetic cooling of OH - by collision with ultracold alkali and alkaline earth atoms, we investigate the 2D MOH - potential energy surfaces and the associative detachment reaction M + OH→- MOH + e - , which is the only energetically allowed reactive channel in the cold regime. We discuss the implication for the sympathetic cooling of OH - and conclude that Li and K are the best candidates for an ultracold buffer gas.

  4. Alkaline-earth elements of scalp hair and presence of hypertension in housewives: A perspective of chronic effect.

    Science.gov (United States)

    Wang, Bin; Yan, Lailai; Sun, Ying; Yan, Jingjing; Lu, Qun; Zhang, Jingxu; Li, Zhiwen

    2017-08-01

    The relationship between population intakes of alkaline-earth elements (AEEs) and hypertension risk remains under discussion. Hair AEE concentrations can indicate their intake levels into human body. Thus, we aimed to investigate an association of hair AEE concentrations with hypertension risk, and the potential effect of dietary habit on this association. We recruited 398 housewives [163 subjects with hypertension (case group) and 235 subjects without hypertension (control group)] in Shanxi Province of north China. The scalp hair grown in the recent 2 years of each subject was collected and analyzed for the four concerned AEEs [i.e. calcium (Ca), magnesium (Mg), strontium (Sr), and barium (Ba)]. Our study results revealed that median concentrations (μg/g hair) of hair AEEs in the case group were systematically lower than those in control group [i.e. 701 vs. 1271 of Ca, 55.2 vs. 88.3 of Mg, 4.60 vs. 10.4 of Sr, and 1.02 vs. 1.68 of Ba]. Lower levels of the four individual AEEs of hair were associated with an increased presence of hypertension, respectively. Moreover, hair AEE concentrations were all positively correlated with the ingestion frequencies of meat, eggs, fresh vegetables, and fruits, while negatively with that of salted vegetables. A high ingestion frequency of fresh vegetables was associated with a lower prevalence of hypertension with or without adjusting confounders, while salted vegetables revealed a reverse tend. It was concluded that low hair AEEs, as markers of their long-term dietary intake, were associated with the presence of hypertension in a rural Chinese women. Copyright © 2017 Elsevier Ltd. All rights reserved.

  5. Separation of alkali, alkaline earth and rare earth cations by liquid membranes containing macrocyclic carriers. Third progress report, September 1, 1980-April 1, 1981

    International Nuclear Information System (INIS)

    Christensen, J.J.

    1981-01-01

    The overall objective of this project is to study the use of liquid membrane systems employing macrocyclic ligand carriers in making separations among metal cations. During the third year of the project, work continued in the development of a mathematical model to describe cation transport. The model was originally developed to describe the relationship between cation transport rate (J/sub M/) and the cation-macrocycle stability constant (K). The model was tested by determining the rates of transport of alkali and alkaline earth cations through chloroform membranes containing carrier ligands where the stability constants for their reaction with cations in methanol were known. From the results, it is clear that the model correctly describes the dependence of J/sub M/ on log K. The model also correctly describes the effect of cation concentration and carrier concentration on cation transport rates, as detailed in the previous progress report. During the third year of the project, the transport model was expanded so as to apply to competitive transport of cations from mixtures of two cations in the source aqueous phase. Data were collected under these conditions and the ability of the model to predict the flux of each cation was tested. Representative data of this type are presented along with corresponding data which were obtained when each cation was transported by the same carrier from a source phase containing only that cation. Comparison of transport rates determined under the two experimental conditions indicates that the relationship between the two sets of data is complex. To date, a few of these data involving transport from binary cation mixtures have been tested against the transport model. It was found that the model correctly predicts the cation fluxes from cation mixtures. These preliminary results indicate that the transport model can successfully predict separation factors when cation mixtures are used

  6. Lanthanide single molecule magnets

    CERN Document Server

    Tang, Jinkui

    2015-01-01

    This book begins by providing basic information on single-molecule magnets (SMMs), covering the magnetism of lanthanide, the characterization and relaxation dynamics of SMMs, and advanced means of studying lanthanide SMMs. It then systematically introduces lanthanide SMMs ranging from mononuclear and dinuclear to polynuclear complexes, classifying them and highlighting those SMMs with high barrier and blocking temperatures – an approach that provides some very valuable indicators for the structural features needed to optimize the contribution of an Ising type spin to a molecular magnet. The final chapter presents some of the newest developments in the lanthanide SMM field, such as the design of multifunctional and stimuli-responsive magnetic materials as well as the anchoring and organization of the SMMs on surfaces. In addition, the crystal structure and magnetic data are clearly presented with a wealth of illustrations in each chapter, helping newcomers and experts alike to better grasp ongoing trends and...

  7. Lanthanide single molecule magnets

    Energy Technology Data Exchange (ETDEWEB)

    Tang, Jinkui; Zhang, Peng [Chinese Academy of Sciences, Changchun (China). Changchun Inst. of Applied Chemistry

    2015-10-01

    This book begins by providing basic information on single-molecule magnets (SMMs), covering the magnetism of lanthanide, the characterization and relaxation dynamics of SMMs and advanced means of studying lanthanide SMMs. It then systematically introduces lanthanide SMMs ranging from mononuclear and dinuclear to polynuclear complexes, classifying them and highlighting those SMMs with high barrier and blocking temperatures - an approach that provides some very valuable indicators for the structural features needed to optimize the contribution of an Ising type spin to a molecular magnet. The final chapter presents some of the newest developments in the lanthanide SMM field, such as the design of multifunctional and stimuli-responsive magnetic materials as well as the anchoring and organization of the SMMs on surfaces. In addition, the crystal structure and magnetic data are clearly presented with a wealth of illustrations in each chapter, helping newcomers and experts alike to better grasp ongoing trends and explore new directions.

  8. Hydroxylated derivatives of dimethoxy-1,4-benzoquinone as redox switchable earth-alkaline metal ligands and radical scavengers

    OpenAIRE

    Gulaboski, Rubin; Bogeski, Ivan; Mirceski, Valentin; Saul, Stephanie; Pasieka, Bastian; Haeri, Haleh H.; Stefova, Marina; Petreska Stanoeva, Jasmina; Mitrev, Sasa; Hoth, Markus; Kappl, Reinhard

    2013-01-01

    Benzoquinones (BQ) have important functions in many biological processes. In alkaline environments, BQs can be hydroxylated at quinoid ring proton positions. Very little is known about the chemical reaction leading to these structural transformations as well as about the properties of the obtained hydroxyl benzoquinones. We analyzed the behavior of the naturally occurring 2,6-dimethoxy-1,4-benzoquinone under alkaline conditions and show that upon substitution of methoxy-groups, poly-hydroxyl-...

  9. The synthesis and crystal structures of the first rare-earth alkaline-earth selenite chlorides MNd10(SeO3)12Cl8 (M=Ca and Sr)

    International Nuclear Information System (INIS)

    Berdonosov, P.S.; Olenev, A.V.; Dolgikh, V.A.; Lightfoot, P.

    2007-01-01

    Two new alkaline-earth Nd selenite chlorides MNd 10 (SeO 3 ) 12 Cl 8 (M=Ca, Sr) were obtained using crystal growth from alkaline-earth chloride melts in quartz tubes. These new compounds crystallize in the orthorhombic system in space group C cca (no. 68). The compounds were studied by energy dispersive X-ray spectroscopy (EDX) and X-ray diffraction. It was shown that both compounds adopt the same structure type, constructed by complex [M 11 (SeO 3 ) 12 ] 8+ slabs separated by chloride anion layers perpendicular to the longest cell parameter. The SeO 3 groups show a pyramidal shape and may be described as SeO 3 E tetrahedra. Such SeO 3 groups decorate the Nd-O skeletons forming the [M 11 (SeO 3 ) 12 ] 8+ slabs. - Graphical abstract: Two new alkaline-earth Nd selenite chlorides MNd 10 (SeO 3 ) 12 Cl 8 (M=Ca, Sr) were synthesized. These structures are constructed by [M 11 (SeO 3 ) 12 ] 8+ slabs separated by chloride anion layers

  10. Removal of toxic and alkali/alkaline earth metals during co-thermal treatment of two types of MSWI fly ashes in China.

    Science.gov (United States)

    Yu, Jie; Qiao, Yu; Jin, Limei; Ma, Chuan; Paterson, Nigel; Sun, Lushi

    2015-12-01

    This study aims to vaporize heavy metals and alkali/alkaline earth metals from two different types of fly ashes by thermal treatment method. Fly ash from a fluidized bed incinerator (HK fly ash) was mixed with one from a grate incinerator (HS fly ash) in various proportions and thermally treated under different temperatures. The melting of HS fly ash was avoided when treated with HK fly ash. Alkali/alkaline earth metals in HS fly ash served as Cl-donors to promote the vaporization of heavy metals during thermal treatment. With temperature increasing from 800 to 900°C, significant amounts of Cl, Na and K were vaporized. Up to 1000°C in air, less than 3% of Cl and Na and less than 5% of K were retained in ash. Under all conditions, Cd can be vaporized effectively. The vaporization of Pb was mildly improved when treated with HS fly ash, while the effect became less pronounced above 900°C. Alkali/alkaline earth metals can promote Cu vaporization by forming copper chlorides. Comparatively, Zn vaporization was low and only slightly improved by HS fly ash. The low vaporization of Zn could be caused by the formation of Zn2SiO4, ZnFe2O4 and ZnAl2O4. Under all conditions, less than 20% of Cr was vaporized. In a reductive atmosphere, the vaporization of Cd and Pb were as high as that in oxidative atmosphere. However, the vaporization of Zn was accelerated and that of Cu was hindered because the formation of Zn2SiO4, ZnFe2O4 and ZnAl2O4 and copper chloride was depressed in reductive atmosphere. Copyright © 2015. Published by Elsevier Ltd.

  11. Effect of the kind of alkaline and rare earth ions on the structure of a glass rich in earth; Effet de la nature des ions alcalins et alcalino-terreux sur la structure d un verre riche en terre

    Energy Technology Data Exchange (ETDEWEB)

    Quintas, Arnaud; Caurant, Daniel; Majerus, Odile [Laboratoire de Chimie Appliquee de l Etat Solide, UMR 7574, ENSCP, 11 rue Pierre et Marie Curie, 75231 Paris Cedex 05, (France); Lenoir, Marion; Dussossoy, Jean-Luc [Commissariat a l Energie Atomique, Centre d Etudes de la Vallee du Rhone, DIEC/SCDV/LEBM, 30207 Bagnols-sur-Ceze, (France); Charpentier, Thibault [Service de Chimie Moleculaire, DSM/DRECAM/CEA Saclay, 91191 Gif-sur-Yvette Cedex, (France); Neuville, Daniel R. [Laboratoire de Physique des Mineraux et des Magmas, UMR 7047-CNRS-IPGP, Universite Pierre et Marie Curie, 4 place Jussieu, 75252 Paris Cedex 05, (France); Gervais, C. [Laboratoire de Chimie de la matiere condensee, UMR7574, Universite Pierre et Marie Curie, 4 place Jussieu, F-75252 Paris Cedex 05, (France)

    2006-07-01

    In the framework of a structural study of a nuclear wastes containment glass of type alumino borosilicate and rich in rare earths, the influence of the kind of alkaline or rare earth ions is analyzed. For that, two glasses series have been prepared in which the Na{sup +} ion (respectively Ca{sup 2+} ions) present in the standard composition is totally substituted by another alkaline ion Li{sup +}, K{sup +}, Rb{sup +} or Cs{sup +} (respectively another rare earth ion Mg{sup 2+}, Sr{sup 2+} or Ba{sup 2+}). These glasses, analyzed by optical absorption, Raman and {sup 27}Al or {sup 11}B NMR spectroscopies have revealed the strong impact of the kind of the modifying ion as well as the structure of the vitreous lattice (variation of the ratio BO{sub 3}/BO{sub 4} and local variations of the polymerization degree) than the local surroundings of the rare earth (decrease of the covalency degree of the bond Nd-O with the increase of the field force of the modifying ion). (O.M.)

  12. Luminescent macrocyclic lanthanide complexes

    Science.gov (United States)

    Raymond, Kenneth N; Corneillie, Todd M; Xu, Jide

    2014-05-20

    The present invention provides a novel class of macrocyclic compounds as well as complexes formed between a metal (e.g., lanthanide) ion and the compounds of the invention. Preferred complexes exhibit high stability as well as high quantum yields of lanthanide ion luminescence in aqueous media without the need for secondary activating agents. Preferred compounds incorporate hydroxy-isophthalamide moieties within their macrocyclic structure and are characterized by surprisingly low, non-specific binding to a variety of polypeptides such as antibodies and proteins as well as high kinetic stability. These characteristics distinguish them from known, open-structured ligands.

  13. Effect of alkaline earth modifier on the optical and structural properties of Cu2+ doped phosphate glasses as a bandpass filter

    Science.gov (United States)

    Farouk, M.; Samir, A.; El Okr, M.

    2018-02-01

    Glasses of composition [16RO-3Al2O3sbnd 6CuOsbnd 20Na2Osbnd 55P2O5], where R is the alkaline earth (R = Mg, Ca, Sr and Ba mol. %), were prepared by conventional melt quenching technique. The glass samples were characterized by X-ray diffraction, infrared spectroscopy, and spectrophotometer. XRD patterns show no sharp peaks indicating the non-crystalline nature of the prepared glasses. The density and molar volume of the glass systems were determined in order to study their structures. These results revealed that addition of alkaline earth elements leads to the formation of non-bridging oxygens (NBOs) and expands (opens up) the structure. The infrared spectra were analyzed to quantify the present phosphate groups. The optical absorption spectra of Cu2+ ions show the characteristic broadband single of Cu2+ ions in octahedral symmetry. The band gap was estimated following two methodologies. The first method considers the band edge of the transmission, while the second approach relays on the estimated values of the optical constants. A decent agreement for the band gap values using the two methods was obtained.

  14. Syntheses, Vibrational Spectroscopy, and Crystal Structure Determination from X-Ray Powder Diffraction Data of Alkaline Earth Dicyanamides M[N(CN)

    Energy Technology Data Exchange (ETDEWEB)

    Juergens, Barbara; Irran, Elisabeth; Schnick, Wolfgang

    2001-03-01

    The alkaline earth dicyanamides Mg[N(CN){sub 2}]{sub 2}, Ca[N(CN){sub 2}]{sub 2}, Sr[N(CN){sub 2}]{sub 2}, and Ba[N(CN){sub 2}]{sub 2} were synthesized by ion exchange using Na[N(CN){sub 2}] and the respective nitrates or bromides as starting materials. The crystal structures were determined from X-ray powder diffractometry: Mg[N(CN){sub 2}]{sub 2}, Pnnm, Z=2, a=617.14(3), b=716.97(3), and c=740.35(5) pm; Ca[N(CN){sub 2}]{sub 2} and Sr[N(CN){sub 2}]{sub 2}, C2/c, Z=4; Ca[N(CN){sub 2}]{sub 2}, a=1244.55(3), b=607.97(1), and c=789.81(1) pm, {beta}=98.864(2){degree}; Sr[N(CN){sub 2}]{sub 2}, a=1279.63(2), b=624.756(8), and c=817.56(1) pm, {beta}=99.787(1){degree}; Ba[N(CN){sub 2}]{sub 2}, Pnma, Z=4, a=1368.68(7), b=429.07(7), and c=1226.26(2) pm. The dicyanamides consist of the respective alkaline earth cations and bent planar [N(CN){sub 2}]{sup -} ions. The structural features were correlated with vibrational spectroscopic data. The thermal behavior was studied by thermoanalytical experiments.

  15. Origin of low sodium capacity in graphite and generally weak substrate binding of Na and Mg among alkali and alkaline earth metals.

    Science.gov (United States)

    Liu, Yuanyue; Merinov, Boris V; Goddard, William A

    2016-04-05

    It is well known that graphite has a low capacity for Na but a high capacity for other alkali metals. The growing interest in alternative cation batteries beyond Li makes it particularly important to elucidate the origin of this behavior, which is not well understood. In examining this question, we find a quite general phenomenon: among the alkali and alkaline earth metals, Na and Mg generally have the weakest chemical binding to a given substrate, compared with the other elements in the same column of the periodic table. We demonstrate this with quantum mechanics calculations for a wide range of substrate materials (not limited to C) covering a variety of structures and chemical compositions. The phenomenon arises from the competition between trends in the ionization energy and the ion-substrate coupling, down the columns of the periodic table. Consequently, the cathodic voltage for Na and Mg is expected to be lower than those for other metals in the same column. This generality provides a basis for analyzing the binding of alkali and alkaline earth metal atoms over a broad range of systems.

  16. Comparative DFT study of van der Waals complexes: rare-gas dimers, alkaline-earth dimers, zinc dimer, and zinc-rare-gas dimers.

    Science.gov (United States)

    Zhao, Yan; Truhlar, Donald G

    2006-04-20

    Recent interest in the application of density functional theory prompted us to test various functionals for the van der Waals interactions in the rare-gas dimers, the alkaline-earth metal dimers, zinc dimer, and zinc-rare-gas dimers. In the present study, we report such tests for 18 DFT functionals, including both some very recent functionals and some well-established older ones. We draw the following conclusions based on the mean errors in binding energies and complex geometries: (1) B97-1 gives the best performance for predicting the geometry of rare-gas dimers, whereas M05-2X and B97-1 give the best energetics for rare-gas dimers. (2) PWB6K gives the best performance for the prediction of the geometry of the alkaline-earth metal dimers, zinc dimers, and zinc-rare-gas dimers. M05-2X gives the best energetics for the metal dimers, whereas B97-1 gives the best energetics for the zinc-rare-gas dimers. (3) The M05 functional is unique in providing good accuracy for both covalent transition-metal dimers and van der Waals metal dimers. (4) The combined mean percentage unsigned error in geometries and energetics shows that M05-2X and MPWB1K are the overall best methods for the prediction of van der Waals interactions in metal and rare-gas van der Waals dimers.

  17. Structures, Thermochemical Properties, and Bonding of Mixed Alkaline-Earth-Metal Silicon Trimers Si3M(+/0/-) with M = Be, Mg, Ca.

    Science.gov (United States)

    Hang, Tran Dieu; Hung, Huynh Minh; Nguyen, Huyen Thi; Nguyen, Minh Tho

    2015-06-18

    The ground state geometries, electronic structures, and thermochemical properties of binary alkaline-earth-metal silicon clusters Si3M with M = Be, Mg, Ca in neutral, cationic, and anionic states were investigated using quantum chemical computations. Lowest-lying isomers of the clusters were determined on the basis of the composite G4 energies. Along with total atomization energies, thermochemical parameters were determined for the first time by means of the G4 and coupled-cluster theory with complete basis set CCSD(T)/CBS approaches. The most favored equilibrium formation sequences for Si3M clusters emerge as follows: all Si3M(+/0/-) clusters are formed by attaching the M atom into the corresponding cation, neutral and anion silicon trimer Si3(+/0/-), except for the Si3Mg(+) and Si3Ca(+) where the metal cations are bound to the neutral Si3. The resulting mixed tetramers exhibit geometrical and electronic features similar to those of the pure silicon tetramer Si4(+/0/-). Electron localization function (ELF) and ring current analyses point out that the σ-aromatic character of silicon tetramer remains unchanged upon substituting one Si atom by one alkaline-earth-metal atom.

  18. Indirect ultraviolet detection of alkaline earth metal ions using an imidazolium ionic liquid as an ultraviolet absorption reagent in ion chromatography.

    Science.gov (United States)

    Liu, Yong-Qiang; Yu, Hong

    2017-04-01

    A convenient and versatile method was developed for the separation and detection of alkaline earth metal ions by ion chromatography with indirect UV detection. The chromatographic separation of Mg 2+ , Ca 2+ , and Sr 2+ was performed on a carboxylic acid base cation exchange column using imidazolium ionic liquid/acid as the mobile phase, in which the imidazolium ionic liquid acted as an UV-absorption reagent. The effects of imidazolium ionic liquids, detection wavelength, acids in the mobile phase, and column temperature on the retention of Mg 2+ , Ca 2+ , and Sr 2+ were investigated. The main factors influencing the separation and detection were the background UV absorption reagent and the concentration of hydrogen ion in ion chromatography with indirect UV detection. The successful separation and detection of Mg 2+ , Ca 2+ , and Sr 2+ within 14 min were achieved using the selected chromatographic conditions, and the detection limits (S/N = 3) were 0.06, 0.12, and 0.23 mg/L, respectively. A new separation and detection method of alkaline earth metal ions by ion chromatography with indirect UV detection was developed, and the application range of ionic liquids was expanded. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. Enhanced Electroresponse of Alkaline Earth Metal-Doped Silica/Titania Spheres by Synergetic Effect of Dispersion Stability and Dielectric Property.

    Science.gov (United States)

    Yoon, Chang-Min; Lee, Seungae; Cheong, Oug Jae; Jang, Jyongsik

    2015-09-02

    A series of alkaline earth metal-doped hollow SiO2/TiO2 spheres (EM-HST) are prepared as electrorheological (ER) materials via sonication-mediated etching method with various alkaline earth metal hydroxides as the etchant. The EM-HST spheres are assessed to determine how their hollow interior and metal-doping affects the ER activity. Both the dispersion stability and the dielectric properties of these materials are greatly enhanced by the proposed one-step etching method, which results in significant enhancement of ER activity. These improvements are attributed to increased particle mobility and interfacial polarization originating from the hollow nature of the EM-HST spheres and the effects of EM metal-doping. In particular, Ca-HST-based ER fluid exhibits ER performance which is 7.1-fold and 3.1-fold higher than those of nonhollow core/shell silica/titania (CS/ST) and undoped hollow silica/titania (HST)-based ER fluids, respectively. This study develops a versatile and simple approach to enhancing ER activity through synergetic effects arising from the combination of dispersion stability and the unique dielectric properties of hollow EM-HST spheres. In addition, the multigram scale production described in this experiment can be an excellent advantage for practical and commercial ER application.

  20. Effect of metal cation replacement on the electronic structure of metalorganic halide perovskites: Replacement of lead with alkaline-earth metals

    Science.gov (United States)

    Pazoki, Meysam; Jacobsson, T. Jesper; Hagfeldt, Anders; Boschloo, Gerrit; Edvinsson, Tomas

    2016-04-01

    Organic and inorganic lead halogen perovskites, and in particular, C H3N H3Pb I3 , have during the last years emerged as a class of highly efficient solar cell materials. Herein we introduce metalorganic halogen perovskite materials for energy-relevant applications based on alkaline-earth metals. Based on the classical notion of Goldschmidt's rules and quantum mechanical considerations, the three alkaline-earth metals, Ca, Sr, and Ba, are shown to be able to exchange lead in the perovskite structure. The three alkaline-earth perovskites, C H3N H3Ca I3,C H3N H3Sr I3 , and C H3N H3Ba I3 , as well as the reference compound, C H3N H3Pb I3 , are in this paper investigated with density functional theory (DFT) calculations, which predict these compounds to exist as stable perovskite materials, and their electronic properties are explored. A detailed analysis of the projected molecular orbital density of states and electronic band structure from DFT calculations were used for interpretation of the band-gap variations in these materials and for estimation of the effective masses of the electrons and holes. Neglecting spin-orbit effects, the band gap of MACa I3,MASr I3 , and MABa I3 were estimated to be 2.95, 3.6, and 3.3 eV, respectively, showing the relative change expected for metal cation exchange. The shifts in the conduction band (CB) edges for the alkaline-earth perovskites were quantified using scalar relativistic DFT calculations and tight-binding analysis, and were compared to the situation in the more extensively studied lead halide perovskite, C H3N H3Pb I3 , where the change in the work function of the metal is the single most important factor in tuning the CB edge and band gap. The results show that alkaline-earth-based organometallic perovskites will not work as an efficient light absorber in photovoltaic applications but instead could be applicable as charge-selective contact materials. The rather high CB edge and the wide band gap together with the large

  1. Photocytotoxic lanthanide complexes

    Indian Academy of Sciences (India)

    Ln(III) complexes are also expected to be non-toxic in dark owing to the redox stability of the Ln(III) ions thus making them suitable for cellular applications in the presence of reducing cellular glutathione. The presence of heavy lanthanide metal is likely to facilitate the ISC due to heavy atom effect thereby contributing to the ...

  2. Valencies of the lanthanides

    OpenAIRE

    Johnson, David A.; Nelson, Peter G.

    2018-01-01

    The valencies of the lanthanides vary more than was once thought. In addition to valencies associated with a half-full shell, there are valencies associated with a quarter- and three-quarter-full shell. This can be explained on the basis of Slater’s theory of many-electron atoms. The same theory explains the variation in complexing constants in the trivalent state (the “tetrad effect”). Valency in metallic and organometallic compounds is also discussed.

  3. The coordination complex structures and hydrogen bonding in the three-dimensional alkaline earth metal salts (Mg, Ca, Sr and Ba) of (4-aminophenyl)arsonic acid.

    Science.gov (United States)

    Smith, Graham; Wermuth, Urs D

    2017-01-01

    (4-Aminophenyl)arsonic acid (p-arsanilic acid) is used as an antihelminth in veterinary applications and was earlier used in the monosodium salt dihydrate form as the antisyphilitic drug atoxyl. Examples of complexes with this acid are rare. The structures of the alkaline earth metal (Mg, Ca, Sr and Ba) complexes with (4-aminophenyl)arsonic acid (p-arsanilic acid) have been determined, viz. hexaaquamagnesium bis[hydrogen (4-aminophenyl)arsonate] tetrahydrate, [Mg(H 2 O) 6 ](C 6 H 7 AsNO 3 )·4H 2 O, (I), catena-poly[[[diaquacalcium]-bis[μ 2 -hydrogen (4-aminophenyl)arsonato-κ 2 O:O']-[diaquacalcium]-bis[μ 2 -hydrogen (4-aminophenyl)arsonato-κ 2 O:O

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

    International Nuclear Information System (INIS)

    Teske, M.

    1993-01-01

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

  5. Actinide and lanthanide separation process (ALSEP)

    Science.gov (United States)

    Guelis, Artem V.

    2013-01-15

    The process of the invention is the separation of minor actinides from lanthanides in a fluid mixture comprising, fission products, lanthanides, minor actinides, rare earth elements, nitric acid and water by addition of an organic chelating aid to the fluid; extracting the fluid with a solvent comprising a first extractant, a second extractant and an organic diluent to form an organic extractant stream and an aqueous raffinate. Scrubbing the organic stream with a dicarboxylic acid and a chelating agent to form a scrubber discharge. The scrubber discharge is stripped with a simple buffering agent and a second chelating agent in the pH range of 2.5 to 6.1 to produce actinide and lanthanide streams and spent organic diluents. The first extractant is selected from bis(2-ethylhexyl)hydrogen phosphate (HDEHP) and mono(2-ethylhexyl)2-ethylhexyl phosphonate (HEH(EHP)) and the second extractant is selected from N,N,N,N-tetra-2-ethylhexyl diglycol amide (TEHDGA) and N,N,N',N'-tetraoctyl-3-oxapentanediamide (TODGA).

  6. Elastic and mechanical properties of lanthanide monoxides

    Energy Technology Data Exchange (ETDEWEB)

    Shafiq, M. [Center for Computational Materials Science, University of Malakand, Chakdara (Pakistan); Department of Physics, University of Malakand, Chakdara (Pakistan); Arif, Suneela [Department of Physics, Hazara University, Mansehra (Pakistan); Ahmad, Iftikhar, E-mail: ahma5532@gmail.com [Center for Computational Materials Science, University of Malakand, Chakdara (Pakistan); Department of Physics, University of Malakand, Chakdara (Pakistan); Asadabadi, S. Jalali [Department of Physics, Faculty of Science, University of Isfahan, Hezar Gerib Avenue, Isfahan 81744 (Iran, Islamic Republic of); Maqbool, M. [Department of Physics and Astronomy, Ball State University, Muncie, IN 47306 (United States); Rahnamaye Aliabad, H.A. [Department of Physics, Hakim Sabzevari University, Sabzevar (Iran, Islamic Republic of)

    2015-01-05

    Highlights: • Elastic, mechanical and thermal properties of rare-earth lanthanide monoxide are theoretically investigated. • Higher values of Young’s modulus indicate that these compounds are stiffer. • These compounds show anisotropic character and also show resistance against deforming force due to compressible character. • These mechanically stable materials can be effectively used for practical applications. - Abstract: In this article we communicate theoretical results of the mechanical properties of lanthanide monoxide LnO (Ln = La, Ce, Pr, Nd, Sm, Eu, Tb, Ho, Er and Yb) i.e., bulk modulus, shear modulus, Young’s modulus, anisotropic ratio, Kleinman parameters, Poisson’s ratio, Lame’s coefficients, sound velocities for shear and longitudinal waves, and Debye temperature. Cauchy pressure and B/G ratio are also investigated to explore the ductile and brittle nature of these compounds. The calculations are performed with the density functional theory based full potential linearized augmented plane waves (FP-LAPW) method. The calculated results reveal that lanthanide based monoxides are mechanically stable and possess good resistive power against elastic deformations. Therefore, these mechanically stable materials can effectively be used for practical applications. The computed DOSs shows the metallic character of these compounds. Contour plots of the electron charge densities are also computed to reveal the nature of bonding in these compounds.

  7. Syntheses and characterization of energetic compounds constructed from alkaline earth metal cations (Sr and Ba) and 1,2-bis(tetrazol-5-yl)ethane

    International Nuclear Information System (INIS)

    Xia Zhengqiang; Chen Sanping; Wei Qing; Qiao Chengfang

    2011-01-01

    Two new energetic compounds, [M(BTE)(H 2 O) 5 ] n (M=Sr(1), Ba(2)) [H 2 BTE=1,2-bis(tetrazol-5-yl)ethane], have been hydrothermally synthesized and structurally characterized. Single-crystal X-ray diffraction analyses reveal that they are isomorphous and exhibit 2D (4,4) net framework, generated by 4-connected Sr 2 (H 2 O) 10 /Ba 2 (H 2 O) 10 SBUs linked up by two independent binding modes of H 2 BTE, and the resulting 2D structure is interconnected by hydrogen-bond and strong face to face π-π stacking interactions between two tetrazole rings to lead to a 3D supramolecular architecture. DSC measurements show that they have significant catalytic effects on thermal decomposition of ammonium perchlorate. Moreover, the photoluminescence properties, thermogravimetric analyses, and flame colors of the as-prepared compounds are also investigated in this paper. - Graphical abstract: Two novel 2D isomorphous alkaline earth metal complexes were assembled by 4-connected Sr 2 (H 2 O) 10 /Ba 2 (H 2 O) 10 SBUs and two independent binding modes of H 2 BTE ligands, and the catalytic performances toward thermal decomposition of ammonium perchlorate and photoluminescent properties of them were investigated. Highlights: → Two novel alkaline earth energetic coordination polymers have been prepared.→ Both structures are layered based on 4-connected Sr 2 (H 2 O) 10 /Ba 2 (H 2 O) 10 SBUs and two distinct H 2 BTE coordination modes.→ The dehydrated products of the compounds possess good thermostability and significant catalytic effects on thermal decomposition of AP.

  8. A modelling exercise on the importance of ternary alkaline earth carbonate species of uranium(VI) in the inorganic speciation of natural waters

    International Nuclear Information System (INIS)

    Vercouter, Thomas; Reiller, Pascal E.; Ansoborlo, Eric; Février, Laureline; Gilbin, Rodolphe; Lomenech, Claire; Philippini, Violaine

    2015-01-01

    Highlights: • The U(VI) speciation in natural waters has been modelled through a modelling exercise. • The results evidence the importance of alkaline earth U(VI) carbonate complexes. • Possible solubility-controlling phases were reported and discussed. • The differences were related to the choice and reliability of thermodynamic data. • Databases need to be improved for reliable U(VI) speciation calculations. - Abstract: Predictive modelling of uranium speciation in natural waters can be achieved using equilibrium thermodynamic data and adequate speciation software. The reliability of such calculations is highly dependent on the equilibrium reactions that are considered as entry data, and the values chosen for the equilibrium constants. The working group “Speciation” of the CETAMA (Analytical methods establishment committee of the French Atomic Energy commission, CEA) has organized a modelling exercise, including four participants, in order to compare modellers’ selections of data and test thermodynamic data bases regarding the calculation of U(VI) inorganic speciation. Six different compositions of model waters were chosen so that to check the importance of ternary alkaline earth carbonate species of U(VI) on the aqueous speciation, and the possible uranium solid phases as solubility-limiting phases. The comparison of the results from the participants suggests (i) that it would be highly valuable for end-users to review thermodynamic constants of ternary carbonate species of U(VI) in a consistent way and implement them in available speciation data bases, and (ii) stresses the necessary care when using data bases to avoid biases and possible erroneous calculations

  9. Study of absorption spectra for alkali and alkaline earth metal salts in flameless atomic absorption spectrometry using a carbon tube atomizer

    International Nuclear Information System (INIS)

    Yasuda, Seiji; Kakiyama, Hitoo

    1975-01-01

    Absorption spectra of various salts such as alkali metal salts, alkaline earth dichlorides, and ammonium halides were investigated and absorptions of some molecular species produced in the carbon tube were identified. The aqueous solution (20 μl) containing 1.0 mg/ml of each salt was placed in the carbon tube atomizer and heated in a similar manner to usual flameless atomic absorption method. D 2 -lamp was used as a continuous light source and argon gas was employed as an inert sheath gas. The spectra were obtained over the range of wavelength 200 to 350 nm. When alkali halides were feeded, the absorption spectra agreed with those of alkali halide vapors. Therefore, in such cases vapors of the alkali halides were probably produced by the sublimation or vaporization in the atomizer. The spectra of alkali perchlorates were considered to be those of alkali chlorides produced by the pyrolysis of the perchlorates in the atomizer. The absorptions of alkaline earth chlorides below 250 nm were probably due to their gaseous states. Sulfur dioxide was found to be produced by the pyrolysis of alkali sulfates, bisulfates and sulfites in the atomizer, Alkali phosphates and pyrophosphates gave almost identical spectra below 300 nm. Gamma band spectrum of nitrogen monoxide was observed from 200 to 240 nm during ashing at bout 330 0 C for alkali nitrates and nitrites. Ammonia vapor was produced from ammonium halides during drying at about 170 0 C. Although the absorptions of alkali carbonates and hydroxides were almost undetectable, the same spectra as those of alkali halides were observed by the addition of ammonium halides to the solutions of alkali compounds. This shows that alkali halides are produced in the atomizer by the addition of halide ions. (auth.)

  10. Analysis and separation of lanthanide elements

    International Nuclear Information System (INIS)

    Almeida Pimentel, E. de.

    1973-01-01

    Improvements of rare earth separation by the combined use of acetic and critic acid were studied and analytical methods for determining some of the lanthanides were tryed out. Separations of the R.E. studied were favorable when citric acid (solution A) and acetic acid (solution B) were used in the proportion of 10:1 at pH=4,00. Neutron activation, spectro-photometric, polarographic, volumetric and gravimetric procedures allowed the determination of 8 R.E.; samarium, neodymium, praseodymium, lanthanum, cerium, holmium, erbium and europium

  11. Effect of the nature of alkali and alkaline-earth oxides on the structure and crystallization of an alumino-borosilicate glass developed to immobilize highly concentrated nuclear waste solutions

    International Nuclear Information System (INIS)

    Quintas, A.; Caurant, D.; Majerus, O.; Charpentier, T.; Dussossoy, J.L.

    2008-01-01

    A complex rare-earth rich alumino-borosilicate glass has been proved to be a good candidate for the immobilization of new high level radioactive wastes. A simplified seven-oxides composition of this glass was selected for this study. In this system, sodium and calcium cations were supposed in other works to simulate respectively all the other alkali (R + = Li + , Rb + , Cs + ) and alkaline-earth (R 2+ = Sr 2+ , Ba 2+ ) cations present in the complex glass composition. Moreover, neodymium or lanthanum are used here to simulate all the rare-earths and actinides occurring in waste solutions. In order to study the impact of the nature of R + and R 2+ cations on both glass structure and melt crystallization tendency during cooling, two glass series were prepared by replacing either Na + or Ca 2+ cations in the simplified glass by respectively (Li + , K + , Rb + , Cs + ) or (Mg 2+ , Sr 2+ , Ba 2+ ) cations. From these substitutions, it was established that alkali ions are preferentially involved in the charge compensation of (AlO 4 ) - entities in the glass network comparatively to alkaline-earth ions. The glass compositions containing calcium give way to the crystallization of an apatite silicate phase bearing calcium and rare-earth ions. The melt crystallization tendency during cooling strongly varies with the nature of the alkaline-earth. (authors)

  12. Rare earths and rare earth alloys electrolytic preparation process and device for this process

    International Nuclear Information System (INIS)

    Seon, F.; Barthole, G.

    1986-01-01

    Electrolysis of a molten salt of rare earth or rare earth alloy for preparation of the metal or alloy is described. The molten salt bath comprises at least a rare earth chloride, at least an alkaline or alkaline earth chloride and at least an alkaline or alkaline earth fluoride [fr

  13. Fabrication of lanthanide-doped glasses and their possible application as UV detectors

    OpenAIRE

    McKernan, Desmond C

    1990-01-01

    This work describes the preparation of lanthanide-doped glasses and examines the performance potential of these glasses as UV detectors. All presently available UV detection systems are extremely expensive and most are unstable to some degree. A number of the lanthanides fluoresce within the spectral response region of commercial photomultiplier tubes and glass is a suitable material for use in vacuum systems. Rare earth ions are readily incorporated into a glass m...

  14. Lanthanide alkyl and silyl compounds: Synthesis, reactivity and catalysts for green

    Energy Technology Data Exchange (ETDEWEB)

    Pindwal, Aradhana [Iowa State Univ., Ames, IA (United States)

    2016-01-01

    The last few decades have witnessed enormous research in the field of organometallic lanthanide chemistry. Our research group has developed a few rare earth alkyl compounds containing tris(dimethylsilyl)methyl ligand and explored their reactivity. This thesis focusses on extending the study of lanthanide alkyl and silyl compounds to develop strategies for their synthesis and explore their reactivity and role as catalysts in processes such as hydrosilylation and cross-dehydrocoupling.

  15. Neutron scattering of lanthanide materials

    International Nuclear Information System (INIS)

    Moon, R.M.; Nicklow, R.M.

    1991-01-01

    A selected review of recent neutron scattering results on lanthanide materials is presented. Topics covered include the magnetic structures of the elemental metals, magnetic superlattices, enhanced nuclear magnetism, magnetic excitations and critical scattering. (orig.)

  16. Transfer of alkaline earth elements in mothers' milk and doses from {sup 45}Ca, {sup 90}Sr and {sup 226}Ra

    Energy Technology Data Exchange (ETDEWEB)

    Smith, T.J.; Phipps, A.W.; Fell, T.P.; Harrison, J.D

    2003-07-01

    An international programme of work is currently under way to develop methods for calculating doses to infants from ingestion of radionuclides present in mothers' milk. This paper considers the special case of the alkaline earth elements. Models have been developed for {sup 45}Ca, {sup 90}Sr and {sup 226}Ra and the sensitivity of results to various changes in parameter values is discussed. A complication when calculating doses from intakes of radium is that the International Commission on Radiological Protection has previously recommended that doses from decay products of radium should be calculated using element-specific biokinetic models (so-called independent biokinetics). An extension of this method to the models for breastfeeding is proposed. Preliminary estimates of the doses received by the infant for a number of maternal intake scenarios show that doses to the infant can exceed the corresponding adult dose, such as for {sup 45}Ca (ratio = 3.1) while, in other cases such as {sup 90}Sr, the infant dose can be a significant fraction of the adult dose. (author)

  17. Thermal stability of the anionic sigma complexes of 2,4,6-trinitroanisole with the methylates of the alkaline-earth metals

    Energy Technology Data Exchange (ETDEWEB)

    Glaz, A.I.; Soldatova, T.A.; Golopolosova, T.V.; Gitis, S.S.

    1987-09-10

    The study of the stability of the 1,1-dimethoxy-2,4,6-trinitrocyclohexadienates of the alkali metals when they are heated in air showed that their temperature of decomposition and the heat effect of the process are dependent on the nature of the cation. Our study centered on the thermal decomposition of the products resulting from the addition of the methylates of calcium, strontium, and barium to 2,4,6-trinitroanisole. For a quantitative assessment of the process we used the combined methods of differential-thermal analysis and differential thermogravimetry. The anionic sigma-complexes of 2,4,6-trinitroanisole with the methylates of the alkaline-earth metals decompose on heating into the corresponding picrates; at the same time, when one passes from the calcium slat to the strontium and barium salts the decomposition temperature and the heat effect of the process show a drop which is linked to the structure both of the complexes and of the picrates forming therefrom.

  18. Hydrogen and syngas production by catalytic gasification of algal biomass (Cladophora glomerata L.) using alkali and alkaline-earth metals compounds.

    Science.gov (United States)

    Ebadi, Abdol Ghaffar; Hisoriev, Hikmat; Zarnegar, Mohammad; Ahmadi, Hamed

    2018-01-02

    The steam gasification of algal biomass (Cladophora glomerata L.) in presence of alkali and alkaline-earth metal compounds catalysts was studied to enhance the yield of syngas and reduce its tar content through cracking and reforming of condensable fractions. The commercial catalysts used include NaOH, KHCO 3 , Na 3 PO 4 and MgO. The gasification runs carried out with a research scale, biomass gasification unit, show that the NaOH has a strong potential for production of hydrogen, along with the added advantages of char converting and tar destruction, allowing enhancement of produced syngas caloric value. When the temperature increased from 700°C to 900°C, the tar content in the gas sharply decreased, while the hydrogen yield increased. Increasing steam/biomass ratio significantly increased hydrogen yield and tar destruction; however, the particle size in the range of 0.5-2.5 mm played a minor role in the process.

  19. Dipole polarizability of alkali-metal (Na, K, Rb)–alkaline-earth-metal (Ca, Sr) polar molecules: Prospects for alignment

    Energy Technology Data Exchange (ETDEWEB)

    Gopakumar, Geetha, E-mail: geetha@tmu.ac.jp; Abe, Minori; Hada, Masahiko [Department of Chemistry, Tokyo Metropolitan University, 1-1 Minami-Osawa, Hachioji, Tokyo 192-0397 (Japan); JST, CREST, 4-1-8 Honcho, Kawaguchi, Saitama 332-0012 (Japan); Kajita, Masatoshi [National Institute of Information and Communications Technology, Koganei, Tokyo 184-8795 (Japan)

    2014-06-14

    Electronic open-shell ground-state properties of selected alkali-metal–alkaline-earth-metal polar molecules are investigated. We determine potential energy curves of the {sup 2}Σ{sup +} ground state at the coupled-cluster singles and doubles with partial triples (CCSD(T)) level of electron correlation. Calculated spectroscopic constants for the isotopes ({sup 23}Na, {sup 39}K, {sup 85}Rb)–({sup 40}Ca, {sup 88}Sr) are compared with available theoretical and experimental results. The variation of the permanent dipole moment (PDM), average dipole polarizability, and polarizability anisotropy with internuclear distance is determined using finite-field perturbation theory at the CCSD(T) level. Owing to moderate PDM (KCa: 1.67 D, RbCa: 1.75 D, KSr: 1.27 D, RbSr: 1.41 D) and large polarizability anisotropy (KCa: 566 a.u., RbCa: 604 a.u., KSr: 574 a.u., RbSr: 615 a.u.), KCa, RbCa, KSr, and RbSr are potential candidates for alignment and orientation in combined intense laser and external static electric fields.

  20. The Electronic Structures and Optical Properties of Alkaline-Earth Metals Doped Anatase TiO2: A Comparative Study of Screened Hybrid Functional and Generalized Gradient Approximation

    Directory of Open Access Journals (Sweden)

    Jin-Gang Ma

    2015-08-01

    Full Text Available Alkaline-earth metallic dopant can improve the performance of anatase TiO2 in photocatalysis and solar cells. Aiming to understand doping mechanisms, the dopant formation energies, electronic structures, and optical properties for Be, Mg, Ca, Sr, and Ba doped anatase TiO2 are investigated by using density functional theory calculations with the HSE06 and PBE functionals. By combining our results with those of previous studies, the HSE06 functional provides a better description of electronic structures. The calculated formation energies indicate that the substitution of a lattice Ti with an AEM atom is energetically favorable under O-rich growth conditions. The electronic structures suggest that, AEM dopants shift the valence bands (VBs to higher energy, and the dopant-state energies for the cases of Ca, Sr, and Ba are quite higher than Fermi levels, while the Be and Mg dopants result into the spin polarized gap states near the top of VBs. The components of VBs and dopant-states support that the AEM dopants are active in inter-band transitions with lower energy excitations. As to optical properties, Ca/Sr/Ba are more effective than Be/Mg to enhance absorbance in visible region, but the Be/Mg are superior to Ca/Sr/Ba for the absorbance improvement in near-IR region.

  1. Mechanochemical synthesis, structure and properties of lead containing alkaline earth metal fluoride solid solutions MxPb1-xF2 (M = Ca, Sr, Ba)

    Science.gov (United States)

    Heise, M.; Scholz, G.; Düvel, A.; Heitjans, P.; Kemnitz, E.

    2018-03-01

    The paper deals with the mechanochemical synthesis of lead containing alkaline earth metal fluoride solid solutions MxPb1-xF2 (M = Ca, Sr, Ba) by high-energy ball milling. Several metal precursors and fluorinating agents were tested for synthesizing M0.5Pb0.5F2. Metal acetates and ammonium fluoride as precursors show the most promising results and were therefore used for the formation of MxPb1-xF2 with different metal cationic ratios. The characterization of the local fluorine coordination and the crystal structure was performed by 19F MAS NMR spectroscopy and X-ray diffraction. Additional calculations of 19F chemical shifts using the superposition model allow a deeper insight into the local structure of the compounds. The fluoride ion conductivity was followed by temperature dependent DC conductivity measurements. Significantly higher conductivities were found in comparison with those of the corresponding binary fluorides. The highest values were observed for samples with high lead content M0.25Pb0.75F2, bearing in mind the much higher conductivity of PbF2 compared to MF2.

  2. [High current microsecond pulsed hollow cathode lamp excited ionic fluorescence spectrometry of alkaline earth elements in inductively coupled plasma with a Fassel-torch].

    Science.gov (United States)

    Zhang, Shao-Yu; Gong, Zhen-Bin; Huang, Ben-Li

    2006-02-01

    High current microsecond pulsed hollow cathode lamp (HCMP-HCL) excited ionic fluorescence spectrometry (IFS) of alkaline earth elements in inductively coupled plasma (ICP) with a Fassel-torch has been investigated. In wide condition ranges only IFS was observed, whilst atomic fluorescence spectrometry (AFS) was not detectable. More intense ionic fluorescence signal was observed at lower observation heights and at lower incident RF powers. Without introduction of any reduction organic gases into the ICP, the limit of detection (LOD, 3sigma) of Ba was improved by 50-fold over that of a conventional pulsed (CP) HCL with the Baird sleeve-extended torch. For Ca and Sr, the LODs by HCMP-HCL-ICP-IFS and CP-HCL-ICP-AFS show no significant difference. Relative standard deviations were 0.6%-1.4% (0.1-0.2 microg x mL(-1), n = 10) for 5 ionic fluorescence lines. Preliminary studies showed that the intensity of ionic fluorescence could be depressed in the presence of K, Al and P.

  3. Nature of the chemical bond between metal atoms and oxide surfaces: new evidences from spin density studies of K atoms on alkaline earth oxides.

    Science.gov (United States)

    Chiesa, Mario; Giamello, Elio; Di Valentin, Cristiana; Pacchioni, Gianfranco; Sojka, Zbigniew; Van Doorslaer, Sabine

    2005-12-07

    We have studied the interaction of K atoms with the surface of polycrystalline alkaline-earth metal oxides (MgO, CaO, SrO) by means of CW- and Pulsed-EPR, UV-Vis-NIR spectroscopies and DFT cluster model calculations. The K adsorption site is proposed to be an anionic reverse corner formed at the intersection of two steps, where K binds by more than 1 eV, resulting in thermally stable species up to about 400 K. The bonding has small covalent and large polarization contributions, and the K atom remains neutral, with one unpaired electron in the valence shell. The interaction results in strong modifications of the K electronic wave function which are directly reflected by the hyperfine coupling constant, (K)a(iso). This is found to be a very efficient "probe" to measure the degree of metal-oxide interaction which directly depends on the substrate basicity. These results provide an original and general model of the early stages of the metal-support interaction in the case of ionic oxides.

  4. Commercial alkaline earth boroaluminosilicate glasses for sealing solid oxide cell stacks. Part I: Development of glass-ceramic microstructure and thermomechanical properties

    DEFF Research Database (Denmark)

    Agersted, Karsten; Balic-Zunic, Tonci

    2017-01-01

    was developed over ~1000 hours at 800°C, depends mainly on the formation of cristobalite and quartz as well as the presence of a residual glass phase. The glass ceramic sealant appears relatively stable over time, except for a slow transition of cristobalite to quartz, and can possibly show self......Sealing performance in solid oxide cell (SOC) stacks and the devitrification process of commercially available alkaline earth boroaluminosilicate glasses containing 48‐61 mol% SiO2, 18‐28 mol% CaO, 1‐7 mol% MgO, 7‐10 mol% Al2O3, 1‐11 mol% B2O3 plus minor amounts of Na2O, K2O, FeO, and TiO2 were...... investigated and quantified through analysis of phase assemblages as function of heat treatments above the glass transition temperatures using the electron microprobe and powder X‐ray diffraction. For two of these glasses devitrification behavior was compared to the devitrification behavior of similar glasses...

  5. Study of the effect hydrogen binding in the solvation of alkaline earth cations with MeOH in nitromethane using 1 H NMR technique and determination of ionic solvation number

    CERN Document Server

    Alizadeh, N

    2001-01-01

    A proton NMR method for the study of the effect hydrogen binding and determination of solvation numbers of alkaline earth cations with methanol (MeOH) in in tromethane (NM) as diluent is described. The method is based on monitoring the resonance frequency of MeOH protons as a function of MeOH to metal ion mole ratio at constant metal ion concentration. the average solvation number of cation, n, at any MeOH/ metal ion mole ration was calculated from the NMR chemical shift-mole ration data and was plotted against the mole ration values. The solvation numbers of alkaline earth cations were obtained from the limiting values of the corresponding n, vs. mole ratio plots.

  6. Study of the effect hydrogen binding in the solvation of alkaline earth cations with MeOH in nitromethane using 1 H NMR technique and determination of ionic solvation number

    International Nuclear Information System (INIS)

    Alizadeh, N.

    2001-01-01

    A proton NMR method for the study of the effect hydrogen binding and determination of solvation numbers of alkaline earth cations with methanol (MeOH) in in tromethane (NM) as diluent is described. The method is based on monitoring the resonance frequency of MeOH protons as a function of MeOH to metal ion mole ratio at constant metal ion concentration. the average solvation number of cation, n, at any MeOH/ metal ion mole ration was calculated from the NMR chemical shift-mole ration data and was plotted against the mole ration values. The solvation numbers of alkaline earth cations were obtained from the limiting values of the corresponding n, vs. mole ratio plots

  7. Effect of the nature of alkali and alkaline-earth oxides on the structure and crystallization of an alumino-borosilicate glass developed to immobilize highly concentrated nuclear waste solutions

    Energy Technology Data Exchange (ETDEWEB)

    Quintas, A.; Caurant, D.; Majerus, O. [Laboratoire de Chimie de la Matiere Condensee de Paris (UMR 7574), Ecole Nationale Superieure de Chimie de Paris - ENSCP, ParisTech, Paris, 75005 (France); Charpentier, T. [CEA Saclay, Laboratoire de Structure et Dynamique par Resonance Magnetique, DSM/DRECAM/SCM - CEA CNRS URA 331, Gif-sur-Yvette, 91191 (France); Dussossoy, J.L. [Laboratoire d' Etude de Base sur les Verres, CEA Valrho, DEN/DTCD/SCDV/LEBV, Bagnols-sur-Ceze, 30207 (France)

    2008-07-01

    A complex rare-earth rich alumino-borosilicate glass has been proved to be a good candidate for the immobilization of new high level radioactive wastes. A simplified seven-oxides composition of this glass was selected for this study. In this system, sodium and calcium cations were supposed in other works to simulate respectively all the other alkali (R{sup +} = Li{sup +}, Rb{sup +}, Cs{sup +}) and alkaline-earth (R{sup 2+} = Sr{sup 2+}, Ba{sup 2+}) cations present in the complex glass composition. Moreover, neodymium or lanthanum are used here to simulate all the rare-earths and actinides occurring in waste solutions. In order to study the impact of the nature of R{sup +} and R{sup 2+} cations on both glass structure and melt crystallization tendency during cooling, two glass series were prepared by replacing either Na{sup +} or Ca{sup 2+} cations in the simplified glass by respectively (Li{sup +}, K{sup +}, Rb{sup +}, Cs{sup +}) or (Mg{sup 2+}, Sr{sup 2+}, Ba{sup 2+}) cations. From these substitutions, it was established that alkali ions are preferentially involved in the charge compensation of (AlO{sub 4}){sup -} entities in the glass network comparatively to alkaline-earth ions. The glass compositions containing calcium give way to the crystallization of an apatite silicate phase bearing calcium and rare-earth ions. The melt crystallization tendency during cooling strongly varies with the nature of the alkaline-earth. (authors)

  8. Use of lanthanide catalysts in air electrodes

    International Nuclear Information System (INIS)

    Souza Parente, L.T. de

    1982-01-01

    A review on the lanthanide catalysts suitable for the reduction catalysis of oxygen in air electrodes is presented. The kinds of lanthanide indicated to be used as catalysts of oxygen reduction are shown. (A.R.H.) [pt

  9. Coordination of lanthanide cation to an Anderson type ...

    Indian Academy of Sciences (India)

    For correspondence lanthanide cations. In 2002, we reported a prelimi- nary result14 on “a polyoxometalate chain formed from heteropolyanion building blocks and rare earth metal ion linkers: [La(H2O)7Al(OH)6Mo6O18]n · 4nH2O”, in which we mentioned that “this material provides an opportunity to synthesize a new class ...

  10. Lanthanides separation by counter - current electrophoretic using α - hydroxyisobutyric acid

    International Nuclear Information System (INIS)

    Alleluia, I.B.

    1975-01-01

    Studies about counter-current electrophoretic separation of rare earth metal ions using α-hydroxyisobutyric acid as complexing electrolyte are discussed. La, Pr, Nd, Sm and Eu were separated and fractions with purities better than 99,9% were obtained, using neutron activation analysis. A relation between the first stability constant of the α-hydroxyisobutyrate/lanthanide complexes and their migration velocities were observed. (M.J.C.) [pt

  11. Extraction chromatography of lanthanides, ch. 8

    International Nuclear Information System (INIS)

    Siekierski, S.; Fidelis, I.

    1975-01-01

    The extraction of lanthanides by chelate formation with acidic organophosphorous extractants, by solvation of salts, and in the form of ion pairs is reviewed. The double-double effect and its significance for the lanthanide as well as the actinide separation is discussed. A short survey of the existing data on the enthalpies of lanthanide extraction and on the influence of temperature on their separation factor is given. The resolution ability of columns used for the separation of lanthanides is briefly surveyed

  12. Absorption spectroscopy of heavy alkaline earth metals Ba and Sr in rare gas matrices--CCSD(T) calculations and atomic site occupancies.

    Science.gov (United States)

    Davis, Barry M; McCaffrey, John G

    2016-01-28

    Isolation of the heavier alkaline earth metals Ba and Sr in the solid rare gases (RGs) Ar, Kr, and Xe is analysed with absorption spectroscopy and interpreted partly with the assistance of ab initio calculations of the diatomic M ⋅ RG ground state interaction potentials. The y(1)P ← a(1)S resonance transitions in the visible spectral region are used to compare the isolation conditions of these two metal atom systems and calcium. Complex absorption bands were recorded in all three metal atom systems even after extensive sample annealing. Coupled cluster calculations conducted on the ground states of the nine M ⋅ RG diatomics (M = Ca, Sr, and Ba; RG = Ar, Kr, and Xe) at the coupled cluster single, double, and non-iterative triple level of theory revealed long bond lengths (>5 Å) and shallow bound regions (rare gas dimers, with the consequence that isolation of these metal atoms in a single substitutional site of the solid rare gas is unlikely, with the possible exception of Ca/Xe. The luminescence of metal dimer bands has been recorded for Ba and Sr revealing very different behaviours. Resonance fluorescence with a lifetime of 15 ns is observed for the lowest energy transition of Sr2 while this transition is quenched in Ba2. This behaviour is consistent with the absence of vibrational structure on the dimer absorption band in Ba2 indicating lifetime broadening arising from efficient relaxation to low-lying molecular states. More extensive 2D excitation-emission data recorded for the complex site structures present on the absorption bands of the atomic Ba and Sr systems will be presented in future publications.

  13. Recovery of uranium and lanthanides

    International Nuclear Information System (INIS)

    Awadalla, F.T.; Habashi, F.

    1989-01-01

    The authors discuss how solutions containing Ca(H 2 PO 4 ) 2 -Ca(NO 3 ) 2-H2 O and Ca(H 2 PO 4 ) 2 -CaCI-H 2 O obtained by leaching phosphate rock in situ or in dumps can be treated for uranium and lanthanides recovery prior to P 2 O 5 recovery as follows: In a nitrate system, uranium is first extracted by a mixture of bis(2-ethylehexl)phosphoric acid (D2EHPA) and tributyl phosphate (TBP) in hexane followed by the extraction of the lanthanides with TBP. In a chloride system, uranium is first extracted by the same mixture, D2EHPA + TBP, followed by the extraction of lanthanides with D2EHPA in toluene

  14. Separation of lanthanides through hydroxyapatite

    International Nuclear Information System (INIS)

    Garcia M, F.G.

    2006-01-01

    With the objective of obtaining from an independent way to each one of the lanthanides 151 Pm, 161 Tb, 166 Ho and 177 Lu free of carrier and with high specific activities starting from the indirect irradiation via, it intends in this work to determine the viability of separation of the couples Nd/Pm, Dy/Ho, Gd/Tb and Yb/Lu, by means of ion exchange column chromatography, using hydroxyapatite (HAp) and fluorite like absorbent material in complexing media. It is important to mention that have registered separation studies among lanthanides of the heavy group with those of the slight group, using the same mass and, in comparison with this work, quantities different from the father were used and of the son, also, that the separation studies were carried out among neighboring lanthanides. In this investigation, it was determined the effect that its have the complexing media: KSCN, sodium tartrate, sodium citrate, EDTA and aluminon, their pH and concentration, in the adsorption of the lanthanides in both minerals, in order to determine the chromatographic conditions for separation of the couples Nd/Pm, Dy/Ho, Gd/Tb and Yb/Lu. The work consists of five chapters, in the first one they are presented a theoretical introduction of the characteristics more important of the lanthanides, the hydroxyapatite and the fluorite; in the second, it is deepened in the ion exchange, as well as the two techniques (XRD and High Vacuum Electron Microscopy) to make the characterization of LnCI 3 (Ln = Nd, Gd, Dy or Yb) synthesized. The third chapter, it describes the methodology continued in our experimental work; in the room, its are presented the obtained results of the static and dynamic method to determine the viability of separation of neighboring lanthanides; and finally, the five chapter shows the conclusions. In this study, it is concludes that the separation among neighboring lanthanides cannot be carried out in the minerals and used media; because practically these lanthanides

  15. Two novel alkaline earth coordination polymers constructed from cinnamic acid and 1,10-phenanthroline: synthesis and structural and thermal properties.

    Science.gov (United States)

    Bendjellal, Nassima; Trifa, Chahrazed; Bouacida, Sofiane; Boudaren, Chaouki; Boudraa, Mhamed; Merazig, Hocine

    2018-02-01

    In coordination chemistry and crystal engineering, many factors influence the construction of coordination polymers and the final frameworks depend greatly on the organic ligands used. The diverse coordination modes of N-donor ligands have been employed to assemble metal-organic frameworks. Carboxylic acid ligands can deprotonate completely or partially when bonding to metal ions and can also act as donors or acceptors of hydrogen bonds; they are thus good candidates for the construction of supramolecular architectures. We synthesized under reflux or hydrothermal conditions two new alkaline earth(II) complexes, namely poly[(1,10-phenanthroline-κ 2 N,N')bis(μ-3-phenylprop-2-enoato-κ 3 O,O':O)calcium(II)], [Ca(C 10 H 7 O 2 ) 2 (C 10 H 8 N 2 )] n , (1), and poly[(1,10-phenanthroline-κ 2 N,N')(μ 3 -3-phenylprop-2-enoato-κ 4 O:O,O':O')(μ-3-phenylprop-2-enoato-κ 3 O,O':O)barium(II)], [Ba(C 10 H 7 O 2 ) 2 (C 10 H 8 N 2 )] n , (2), and characterized them by FT-IR and UV-Vis spectroscopies, thermogravimetric analysis (TGA) and single-crystal X-ray diffraction analysis, as well as by powder X-ray diffraction (PXRD) analysis. Complex (1) features a chain topology of type 2,4 C4, where the Ca atoms are connected by O and N atoms, forming a distorted bicapped trigonal prismatic geometry. Complex (2) displays chains of topology type 2,3,5 C4, where the Ba atom is nine-coordinated by seven O atoms of bridging/chelating carboxylate groups from two cinnamate ligands and by two N atoms from one phenanthroline ligand, forming a distorted tricapped prismatic arrangement. Weak C-H...O hydrogen bonds and π-π stacking interactions between phenanthroline ligands are responsible to the formation of a supramolecular three-dimensional network. The thermal decompositions of (1) and (2) in the temperature range 297-1173 K revealed that they both decompose in three steps and transform to the corresponding metal oxide.

  16. Chemical composition of modern and fossil hippopotamid teeth and implications for paleoenvironmental reconstructions and enamel formation - Part 2: Alkaline earth elements as tracers of watershed hydrochemistry and provenance

    Science.gov (United States)

    Brügmann, G.; Krause, J.; Brachert, T. C.; Stoll, B.; Weis, U.; Kullmer, O.; Ssemmanda, I.; Mertz, D. F.

    2012-11-01

    This study demonstrates that alkaline earth elements in enamel of hippopotamids, in particular Ba and Sr, are tracers for water provenance and hydrochemistry in terrestrial settings. The studied specimens are permanent premolar and molar teeth found in modern and fossil lacustrine sediments of the Western Branch of the East African Rift system (Lake Kikorongo, Lake Albert, and Lake Malawi) and from modern fluvial environments of the Nile River. Concentrations in enamel vary by two orders of magnitude for Ba (120-9336 μg g-1) as well as for Sr (9-2150 μg g-1). The variations are partially induced during post-mortem alteration and during amelogenesis, but the major contribution originates ultimately from the variable water chemistry in the habitats of the hippopotamids which is controlled by the lithologies and weathering processes in the watershed areas. Amelogenesis causes a distinct distribution of MgO, Ba and Sr in modern and fossil enamel, in that element concentrations increase along profiles from the outer rim towards the enamel-dentin junction by a factor of 1.3-1.9. These elements are well correlated in single specimens, thus suggesting that their distribution is determined by a common, single process, which can be described by closed system Rayleigh crystallization of bioapatite in vivo. Enamel from most hippopotamid specimens has Sr/Ca and Ba/Ca which are typical for herbivores. However, Ba/Sr ranges from 0.1 to 3 and varies on spatial and temporal scales. Thus, Sr concentrations and Ba/Sr in enamel differentiate between habitats having basaltic mantle rocks or Archean crustal rocks as the ultimate sources of Sr and Ba. This provenance signal is modulated by climate change. In Miocene to Pleistocene enamel from the Lake Albert region, Ba/Sr decreases systematically with time from 2 to 0.5. This trend can be correlated with changes in climate from humid to arid, in vegetation from C3 to C4 biomass as well as with increasing evaporation of the lake water

  17. Surprisingly Different Reaction Behavior of Alkali and Alkaline Earth Metal Bis(trimethylsilyl)amides toward Bulky N-(2-Pyridylethyl)-N'-(2,6-diisopropylphenyl)pivalamidine.

    Science.gov (United States)

    Kalden, Diana; Oberheide, Ansgar; Loh, Claas; Görls, Helmar; Krieck, Sven; Westerhausen, Matthias

    2016-07-25

    N-(2,6-Diisopropylphenyl)-N'-(2-pyridylethyl)pivalamidine (Dipp-N=C(tBu)-N(H)-C2 H4 -Py) (1), reacts with metalation reagents of lithium, magnesium, calcium, and strontium to give the corresponding pivalamidinates [(tmeda)Li{Dipp-N=C(tBu)-N-C2 H4 -Py}] (6), [Mg{Dipp-N=C(tBu)-N-C2 H4 -Py}2 ] (3), and heteroleptic [{(Me3 Si)2 N}Ae{Dipp-N=C(tBu)-N-C2 H4 -Py}], with Ae being Ca (2 a) and Sr (2 b). In contrast to this straightforward deprotonation of the amidine units, the reaction of 1 with the bis(trimethylsilyl)amides of sodium or potassium unexpectedly leads to a β-metalation and an immediate deamidation reaction yielding [(thf)2 Na{Dipp-N=C(tBu)-N(H)}] (4 a) or [(thf)2 K{Dipp-N=C(tBu)-N(H)}] (4 b), respectively, as well as 2-vinylpyridine in both cases. The lithium derivative shows a similar reaction behavior to the alkaline earth metal congeners, underlining the diagonal relationship in the periodic table. Protonation of 4 a or the metathesis reaction of 4 b with CaI2 in tetrahydrofuran yields N-(2,6-diisopropylphenyl)pivalamidine (Dipp-N=C(tBu)-NH2 ) (5), or [(thf)4 Ca{Dipp-N=C(tBu)-N(H)}2 ] (7), respectively. The reaction of AN(SiMe3 )2 (A=Na, K) with less bulky formamidine Dipp-N=C(H)-N(H)-C2 H4 -Py (8) leads to deprotonation of the amidine functionality, and [(thf)Na{Dipp-N=C(H)-N-C2 H4 -Py}]2 (9 a) or [(thf)K{Dipp-N=C(H)-N-C2 H4 -Py}]2 (9 b), respectively, are isolated as dinuclear complexes. From these experiments it is obvious, that β-metalation/deamidation of N-(2-pyridylethyl)amidines requires bases with soft metal ions and also steric pressure. The isomeric forms of all compounds are verified by single-crystal X-ray structure analysis and are maintained in solution. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. Earth

    CERN Document Server

    Carter, Jason

    2017-01-01

    This curriculum-based, easy-to-follow book teaches young readers about Earth as one of the eight planets in our solar system in astronomical terms. With accessible text, it provides the fundamental information any student needs to begin their studies in astronomy, such as how Earth spins and revolves around the Sun, why it's uniquely suitable for life, its physical features, atmosphere, biosphere, moon, its past, future, and more. To enhance the learning experience, many of the images come directly from NASA. This straightforward title offers the fundamental information any student needs to sp

  19. Biological toxicity of lanthanide elements on algae.

    Science.gov (United States)

    Tai, Peidong; Zhao, Qing; Su, Dan; Li, Peijun; Stagnitti, Frank

    2010-08-01

    The biological toxicity of lanthanides on marine monocellular algae was investigated. The specific objective of this research was to establish the relationship between the abundance in the seawater of lanthanides and their biological toxicities on marine monocellular algae. The results showed that all single lanthanides had similar toxic effects on Skeletonema costatum. High concentrations of lanthanides (29.04+/-0.61 micromol L(-1)) resulted in 50% reduction in growth of algae compared to the controls (0 micromol L(-1)) after 96 h (96 h-EC50). The biological toxicity of 13 lanthanides on marine monocellular algae was unrelated with the abundance of different lanthanide elements in nature, and the "Harkins rule" was not appropriate for the lanthanides. A mixed solution that contained equivalent concentrations of each lanthanide element had the same inhibition effect on algae cells as each individual lanthanide element at the same total concentration. This phenomenon is unique compared to the groups of other elements in the periodic table. Hence, we speculate that the monocellular organisms might not be able to sufficiently differentiate between the almost chemically identical lanthanide elements. Copyright (c) 2010 Elsevier Ltd. All rights reserved.

  20. {sup 1}H and {sup 23}Na MAS NMR spectroscopy of cationic species in CO{sub 2} selective alkaline earth metal porous silicoaluminophosphates prepared via liquid and solid state ion exchange

    Energy Technology Data Exchange (ETDEWEB)

    Arevalo-Hidalgo, Ana G. [Department of Chemical Engineering, University of Puerto Rico-Mayagueez Campus, Mayagueez, PR 00681-9000 (Puerto Rico); Dugar, Sneha; Fu, Riqiang [National High Magnetic Field Laboratory, Florida State University, Tallahassee, FL 32310 (United States); Hernandez-Maldonado, Arturo J., E-mail: arturoj.hernandez@upr.edu [Department of Chemical Engineering, University of Puerto Rico-Mayagueez Campus, Mayagueez, PR 00681-9000 (Puerto Rico)

    2012-07-15

    The location of extraframework cations in Sr{sup 2+} and Ba{sup 2+} ion-exchanged SAPO-34 was estimated by means of {sup 1}H and {sup 23}Na MAS NMR spectroscopy and spectral deconvolution. Incorporation of the alkaline earth metal cations onto the SAPO framework was achieved via liquid state ion exchange, coupled partial detemplation/solid-state ion exchange, and combination of both techniques. MAS NMR revealed that the level of ion exchange was limited by the presence of protons and sodium cations near hexagonal prisms (site SI), which are relatively difficult to exchange with the alkaline earth metal due to steric and charge repulsion criteria. In addition, the presence of ammonium cations in the supercages facilitated the exchange of otherwise tenacious hydrogen as corroborated by unit cell compositional data as well as enhanced CO{sub 2} adsorption at low partial pressures. The extraframework ammonium species were produced from partial detemplation of the structure-directing agent employed for the SAPO-34 synthesis, tetraethylammonium. - Graphical abstract: MAS NMR was used to elucidate the position the cationic species in alkaline earth metal exchanged silicoaluminophosphates. These species played a significant role during the ion exchange process and, therefore, the materials ultimate CO{sub 2} adsorption performance. Highlights: Black-Right-Pointing-Pointer Location of extraframework Sr{sup 2+} or Ba{sup 2+} cations was estimated by means of {sup 1}H and {sup 23}Na MAS NMR. Black-Right-Pointing-Pointer Level of Sr{sup 2+} or Ba{sup 2+} ion exchange was limited by the presence of protons and sodium cations. Black-Right-Pointing-Pointer Presence of ammonium cations in the supercages facilitated the exchange. Black-Right-Pointing-Pointer Sr{sup 2+} and Ba{sup 2+} ion exchanged SAPOs are outstanding CO{sub 2} adsorbents.

  1. Recent Advanced in Rare Earth Chemistry: IREC (International Rare Earth Conference) 85 Held at Zurich (Switzerland) on 4-8 Mar 85.

    Science.gov (United States)

    1985-06-04

    his book on the excited states in (State University Utrecht, The Nether- rare earth compounds. Lanthanide com- lands ). He discussed the probabilities...author listed, and location. reports dealt with phase studies of metal oxides and rare earth oxides, Solution and Coordination Chemistries lanthanide ...J-levels of lanthanides in transparent European Science Notes.) media, the transition probabilities from Other papers on the topic of rare the ground

  2. Mixed ligand complexes of alkaline earth metals: Part XII. Mg(II, Ca(II, Sr(II and Ba(II complexes with 5-chlorosalicylaldehyde and salicylaldehyde or hydroxyaromatic ketones

    Directory of Open Access Journals (Sweden)

    MITHLESH AGRAWAL

    2002-04-01

    Full Text Available The reactions of alkaline earth metal chlorides with 5-chlorosalicylaldehyde and salicylaldehyde, 2-hydroxyacetophenone or 2-hydroxypropiophenone have been carried out in 1 : 1 : 1 mole ratio and the mixed ligand complexes of the type MLL’(H2O2 (where M = Mg(II, Ca(II, Sr(II and Ba(II, HL = 5-chlorosalicylaldehyde and HL’ = salicylaldehyde, 2-hydroxyacetophenone or 2-hydroxypropiophenone have been isolated. These complexes were characterized by TLC, conductance measurements, IR and 1H-NMR spectra.

  3. Magnetism in lanthanide superlattices

    DEFF Research Database (Denmark)

    Goff, J.P.; Sarthour, R.S.; McMorrow, D.F.

    2000-01-01

    Neutron diffraction studies of heavy rare-earth superlattices have revealed the stabilization of novel magnetic phases chat are not present in bulk materials. The most striking result is the propagation of the magnetic ordering through nonmagnetic spacer materials. Here we describe some recent X......-ray magnetic resonant scattering studies of light rare-earth superlattices, which illuminate the mechanism of interlayer coupling, and provide access to different areas of Physics. such as the interplay between superconductivity and magnetism. Magnetic X-ray diffraction is found to be particularly well suited...... to the study of the modulated magnetic structures in superlattices, and provides unique information on the conduction-electron spin-density wave responsible for the propagation of magnetic order. (C) 2000 Elsevier Science B.V. All rights reserved....

  4. Lanthanide croconate complexation in solution

    International Nuclear Information System (INIS)

    Choppin, G.R.; Orebaugh, E.

    1977-01-01

    The thermodynamic parameters of complexation of lanthanide cations by croconate ligands have been measured in aqueous solution using potentiometry and calorimetry. Comparison of experimental and calculated (with a modified Born equation) values of ΔG indicates the presence of aromatic pi systems in the carbon rings of the ligands in squarate, croconate and tropolonate complexes but of a nonaromatic pi system in the cyclic ether rings of kojate and maltolate complexes

  5. Biosorption of lanthanides using three kinds of seaweed biomasses

    International Nuclear Information System (INIS)

    Sakamoto, Nobuo; Wang, Yudan; Gao, Lidi; Kano, Naoki; Imaizumi, Hiroshi

    2010-01-01

    In order to evaluate the efficiency of seaweed biomass as sorbent for rare earth elements (REEs), sorption experiment from aqueous solutions containing known amount of lanthanide (La, Eu or Yb) using three kinds of Ca-loaded dried seaweeds (brown algae: Sargassum hemiphyllum, green algae: Ulva pertusa and red algae: Schizymenia dubyi) in single component system was explored. Furthermore, the sorption mechanism of these elements was investigated by applying Langmuir and Freundlich isotherm equations to the data obtained. In addition, to confirm the characteristics of the seaweed biomasses, the surface morphology of the biomass before and after metal adsorption was determined by Scanning Electron Microscope (SEM). Consequently, the following matters have been mainly clarified. (1) The morphology of Sargassum hemiphyllum and Ulva pertusa surface has hardly changed even after exposing to metals. On the other hand, the change of the surface condition on Schizymenia dubyi after adsorption was observed. (2) Adsorption isotherms using the seaweed biomass can be described by Langmuir and Freundlich isotherms satisfactorily for lanthanide. These adsorption may have occurred mainly by monolayer reaction because of better-fitting for Langmuir model. (3) The seaweed biomasses could be an efficient sorbent for REEs. Particularly, Ulva pertusa is found to be a promising biosorbent for removing La. (4) Ion-exchange process is considered to be the main mechanism responsible for the sorption of lanthanide ion onto the seaweed biomass. (author)

  6. China's rare-earth industry

    Science.gov (United States)

    Tse, Pui-Kwan

    2011-01-01

    Introduction China's dominant position as the producer of over 95 percent of the world output of rare-earth minerals and rapid increases in the consumption of rare earths owing to the emergence of new clean-energy and defense-related technologies, combined with China's decisions to restrict exports of rare earths, have resulted in heightened concerns about the future availability of rare earths. As a result, industrial countries such as Japan, the United States, and countries of the European Union face tighter supplies and higher prices for rare earths. This paper briefly reviews China's rare-earth production, consumption, and reserves and the important policies and regulations regarding the production and trade of rare earths, including recently announced export quotas. The 15 lanthanide elements-lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, and lutetium (atomic numbers 57-71)-were originally known as the rare earths from their occurrence in oxides mixtures. Recently, some researchers have included two other elements-scandium and yttrium-in their discussion of rare earths. Yttrium (atomic number 39), which lies above lanthanum in transition group III of the periodic table and has a similar 3+ ion with a noble gas core, has both atomic and ionic radii similar in size to those of terbium and dysprosium and is generally found in nature with lanthanides. Scandium (atomic number 21) has a smaller ionic radius than yttrium and the lanthanides, and its chemical behavior is intermediate between that of aluminum and the lanthanides. It is found in nature with the lanthanides and yttrium. Rare earths are used widely in high-technology and clean-energy products because they impart special properties of magnetism, luminescence, and strength. Rare earths are also used in weapon systems to obtain the same properties.

  7. Electronic structure of lanthanide scandates

    Science.gov (United States)

    Mizzi, Christopher A.; Koirala, Pratik; Marks, Laurence D.

    2018-02-01

    X-ray photoelectron spectroscopy, ultraviolet photoelectron spectroscopy, and density functional theory calculations were used to study the electronic structure of three lanthanide scandates: GdSc O3,TbSc O3 , and DySc O3 . X-ray photoelectron spectra simulated from first-principles calculations using a combination of on-site hybrid and GGA +U methods were found to be in good agreement with experimental x-ray photoelectron spectra. The hybrid method was used to model the ground state electronic structure and the GGA +U method accounted for the shift of valence state energies due to photoelectron emission via a Slater-Janak transition state approach. From these results, the lanthanide scandate valence bands were determined to be composed of Ln 4 f ,O 2 p , and Sc 3 d states, in agreement with previous work. However, contrary to previous work the minority Ln 4 f states were found to be located closer to, and in some cases at, the valence band maximum. This suggests that minority Ln 4 f electrons may play a larger role in lanthanide scandate properties than previously thought.

  8. 2. Intermetallic compounds with lanthanides

    International Nuclear Information System (INIS)

    Elemans, J.B.A.A.

    1975-01-01

    Theoretical considerations are given concerning the structures of intermetallic compounds of the lanthanides and thorium (R) on the one hand, and with Fe, Co or Ni (M) on the other. They all derive from the parent composition RM 5 with the CaCu 5 hexagonal structure. This consists of alternate layers in which the M atoms are distinguished as M 1 and M 2 . The other compounds whose structures are studied are obtained by systematic replacement of R by M, or vice versa. In the first type, every third R is replaced by two M's yielding R 2 M 17 compounds. The substitution may be truly random or structured in two ways: so that either the hexagonal structure is maintained or that it is converted into a rhombihedral one. In the second type, one M (in a M 1 position) out of every five is replaced by one R, giving rise to RM 2 compounds which form Laves phases. In the third type, the M 1 's are replaced by R's, resulting in compounds RM 3 . In the fourth type, every third M is replaced by R, yielding R 2 M 7 compounds. With M = Co and R a light lanthanide, the compounds are ferromagnets; with R yttrium, thorium, or a heavy lanthanide, they are ferrimagnets. The preparation of the compounds in an arc-melting apparatus under an Ar-atmosphere followed by annealing is described

  9. First-principles study of fission product (Xe, Cs, Sr) incorporation and segregation in alkaline earth metal oxides, HfO(2), and the MgO-HfO(2) interface.

    Science.gov (United States)

    Liu, Xiang-Yang; Uberuaga, Blas P; Sickafus, Kurt E

    2009-01-28

    In order to close the nuclear fuel cycle, advanced concepts for separating out fission products are necessary. One approach is to use a dispersion fuel form in which a fissile core is surrounded by an inert matrix that captures and immobilizes the fission products from the core. If this inert matrix can be easily separated from the fuel, via e.g. solution chemistry, the fission products can be separated from the fissile material. We examine a surrogate dispersion fuel composition, in which hafnia (HfO(2)) is a surrogate for the fissile core and alkaline earth metal oxides are used as the inert matrix. The questions of fission product incorporation in these oxides and possible segregation behavior at interfaces are considered. Density functional theory based calculations for fission product elements (Xe, Sr, and Cs) in these oxides are carried out. We find smaller incorporation energy in hafnia than in MgO for Cs and Sr, and Xe if variation of charge state is allowed. We also find that this trend is reversed or reduced for alkaline earth metal oxides with large cation sizes. Model interfacial calculations show a strong tendency of segregation from bulk MgO to MgO-HfO(2) interfaces.

  10. Lanthanide mixed ligand chelates for DNA profiling and latent fingerprint detection

    Science.gov (United States)

    Menzel, E. R.; Allred, Clay

    1997-02-01

    It is our aim to develop a universally applicable latent fingerprint detection method using lanthanide (rare-earth) complexes as a source of luminescence. Use of these lanthanide complexes offers advantages on several fronts, including benefits from large Stokes shifts, long luminescence lifetimes, narrow emissions, ability of sequential assembly of complexes, and chemical variability of the ligands. Proper exploitation of these advantages would lead to a latent fingerprint detection method superior to any currently available. These same characteristics also lend themselves to many of the problems associated with DNA processing in the forensic science context.

  11. Rare earths crystal chemistry

    International Nuclear Information System (INIS)

    Wells, A.F.

    1988-01-01

    From the viewpoint of general crystal chemistry principles and on the basis of modern data the structural chemistry of rare earth compounds in different oxidation degrees (2,3,4) is briefly presented. The change of the structure type of oxides, halides and some other compounds of rare earths, as well as the coordination number of the central atom from lanthanide ionic radius is considered

  12. A sensitive fluorescent sensor of lanthanide ions

    CERN Document Server

    Bekiari, V; Lianos, P

    2003-01-01

    A fluorescent probe bearing a diazostilbene chromophore and a benzo-15-crown-5 ether moiety is a very efficient sensor of lanthanide ions. The ligand emits strong fluorescence only in the presence of specific ions, namely lanthanide ions, while the emission wavelength is associated with a particular ion providing high sensitivity and resolution.

  13. Method of cerium separation from other lanthanides and yttrium

    International Nuclear Information System (INIS)

    Tran, Duc Hiep; Mostecky, J.

    1988-01-01

    Cerium is separated from a suspension produced during the aerial oxidation process. The suspension is subject to a cyclic process of two-stage fractional dissolution. Following the first dissolution, almost all cerium remains undissolved while 95% of the other lanthanides pass into the solution. The filtrate of the second stage of dissolution containing about 5% of ceriumm is returned for oxidation with the next batch of hydroxide mixed concentrate. Following oxidation, the two-stage fractional dissolution is repeated. This cycling provides quantitative cerium separation from other rare earth elements. (E.S.)

  14. Kinetic study of the aroxyl radical-scavenging reaction of alpha-tocopherol in methanol solution: notable effect of the alkali and alkaline earth metal salts on the reaction rates.

    Science.gov (United States)

    Ouchi, Aya; Nagaoka, Shin-ichi; Abe, Kouichi; Mukai, Kazuo

    2009-10-08

    A kinetic study of the aroxyl (ArO*) radical-scavenging reaction of alpha-tocopherol (alpha-TocH) has been performed in the presence of six kinds of alkali and alkaline earth metal salts (LiI, LiClO(4), NaI, NaClO(4), KI, and Mg(ClO(4))(2)) in methanol solution, using stopped-flow spectrophotometry. The decay rate of the ArO* for the reaction of alpha-TocH with ArO* increased linearly with increasing concentration of metal salts. The second-order rate constants (k(s)) for the reaction of alpha-TocH with ArO* increased in the order of no metal salt concentration of metal salts. For example, the k(s) values in methanol solution including 4.00 x 10(-1) M of LiI and Mg(ClO(4))(2) were 3.04 and 1.30 times larger than that in the absence of metal salts, respectively. The alkali and alkaline earth metal salts having smaller ionic radius of cation and anion and larger charge of cation gave larger rate constants (k(s)). Effects of metal cations on the UV-vis absorption spectra of the alpha-Toc* (and ArO*) radical were negligible in methanol solution, suggesting that the complex formation between the alpha-Toc* (and ArO*) radical molecule and metal cations is hindered by the hydrogen bond between radical and methanol molecules. The results indicate that the hydrogen transfer reaction of alpha-TocH proceeds via an electron transfer intermediate from alpha-TocH to ArO* radicals followed by proton transfer. Both the coordinations of metal cations to the one-electron reduced anions of ArO* (ArO: (-)) and of counteranions to the one-electron oxidized cations of alpha-TocH (alpha-TocH(+)*) may stabilize the intermediate, resulting in the acceleration of electron transfer. On the other hand, the effect of metal salts on the rate of bimolecular self-reaction (2k(d)) of the alpha-Toc* radical was not observed. The result suggests that the hydrogen transfer reaction between two alpha-Toc* radical molecules proceeds via a one-step hydrogen atom transfer mechanism rather than via an

  15. A set of alkali and alkaline-earth coordination polymers based on the ligand 2-(1H-benzotriazol-1-yl) acetic acid: Effects the radius of metal ions on structures and properties

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Jin-Hua [Department of Chemical Engineering, Shandong Provincial Key Laboratory of Fine Chemicals, Qilu University of Technology, Jinan 250353 (China); Tang, Gui-Mei, E-mail: meiguit@163.com [Department of Chemical Engineering, Shandong Provincial Key Laboratory of Fine Chemicals, Qilu University of Technology, Jinan 250353 (China); Qin, Ting-Xiao; Yan, Shi-Chen [Department of Chemical Engineering, Shandong Provincial Key Laboratory of Fine Chemicals, Qilu University of Technology, Jinan 250353 (China); Wang, Yong-Tao, E-mail: ceswyt@sohu.com [Department of Chemical Engineering, Shandong Provincial Key Laboratory of Fine Chemicals, Qilu University of Technology, Jinan 250353 (China); Cui, Yue-Zhi [Department of Chemical Engineering, Shandong Provincial Key Laboratory of Fine Chemicals, Qilu University of Technology, Jinan 250353 (China); Weng Ng, Seik [Department of Chemistry, University of Malaya, Kuala Lumpur 50603 (Malaysia)

    2014-11-15

    Four new metal coordination complexes, namely, [Na(BTA)]{sub n} (1), [K{sub 2}(BTA){sub 2}(μ{sub 2}-H{sub 2}O)]{sub n} (2), and [M(BTA){sub 2}(H{sub 2}O){sub 2}]{sub n} (M=Ca(II) and Sr(II) for 3 and 4, respectively) [BTA=2-(1H-benzotriazol-1-yl) acetic anion], have been obtained under hydrothermal condition, by reacting the different alkali and alkaline-earth metal hydroxides with HBTA. Complexes 1–4 were structurally characterized by X-ray single-crystal diffraction, EA, IR, PXRD, and thermogravimetry analysis (TGA). These complexes display low-dimensional features displaying various two-dimensional (2D) and one-dimensional (1D) coordination motifs. Complex 1 displays a 2D layer with the thickness of 1.5 nm and possesses a topologic structure of a 11 nodal net with Schläfli symbol of (3{sup 18}). Complex 2 also shows a thick 2D sheet and its topologic structure is a 9 nodes with Schläfli symbol of (3{sup 11}×4{sup 2}). Complexes 3 and 4 possess a 1D linear chain and further stack via hydrogen bonding interactions to generate a three-dimensional supramolecular architecture. These results suggest that both the coordination preferences of the metal ions and the versatile nature of this flexible ligand play a critical role in the final structures. The luminescent spectra show strong emission intensities in complexes 1–4, which display violet photoluminescence. Additionally, ferroelectric, dielectric and nonlinear optic (NLO) second-harmonic generation (SHG) properties of 2 are discussed in detail. - Graphical abstract: A set of alkali and alkaline-earth metal coordination polymers were hydrothermally synthesized by 2-(1H-benzotriazol-1-yl)acetic acid, displaying interesting topologic motifs from two-dimension to one-dimension and specific physical properties. - Highlights: • Alkali and alkaline-earth metal coordination polymers have been obtained. • The ligand 2-(1H-benzotriazol-1-yl)acetic acid has been adopted. • The two-dimensional and one

  16. Synthesis and characterisation of alkaline earth bis(diphenylphosphano)metallocene complexes and heterobimetallic alkaline earth metal/platinum(II) complexes [Ae(thf)(x)(η5-C5H4PPh2)2Pt(Me)2] (Ae = Ca, Sr, Ba).

    Science.gov (United States)

    Daniels, Daisy P; Deacon, Glen B; Harakat, Dominique; Jaroschik, Florian; Junk, Peter C

    2012-01-07

    A series of alkaline earth metallocene complexes carrying the diphenylphosphanocyclopentadienyl ligand, [Ae(L)(x)(η(5)-C(5)H(4)PPh(2))(2)] (Ae = Ca, L = thf, x = 1 (6a); Ae = Ca, L = dme, x = 1 (6b); Ae = Sr, L = thf, x = 1 (7); Ae = Ba, L = thf, x = 1 (8a); Ae = Ba, L = dme, x = 2 (8b)), were prepared by redox transmetallation/protolysis from the free metals, diphenylmercury and diphenylphosphanocyclopentadiene. These complexes were characterised using multinuclear NMR spectroscopy and two by single crystal X-ray diffraction. [Ca(dme)(η(5)-C(5)H(4)PPh(2))(2)] (6b) is a discrete neutral monomeric eight coordinate molecule in which the phosphorus atoms are not coordinated to the calcium ion and the larger barium analogue, ten-coordinate [Ba(dme)(2)(η(5)-C(5)H(4)PPh(2))(2)] (8b), has an extremely bent sandwich structure due to the two dme ligands attached to the metal. Bimetallic complexes, [Ae(thf)(x)(η(5)-C(5)H(4)PPh(2))(2)Pt(Me)(2)].(solv) (Ae = Ca, L = thf, x = 2, solv = 1.5thf (9); Ae = Sr, L = thf, x = 3, solv = 1.5thf (10); Ae = Ba, L = thf, x = 3, solv = thf (11)) were obtained by reaction of the homometallic complexes with [Pt(cod)(Me)(2)]. The crystal structures of [Ca(thf)(2)(η(5)-C(5)H(4)PPh(2))(2)Pt(Me)(2)].1.5thf (9), [Sr(thf)(3)(η(5)-C(5)H(4)PPh(2))(2)Pt(Me)(2)].1.5thf (10) and [Ba(thf)(3)(η(5)-C(5)H(4)PPh(2))(2)Pt(Me)(2)].thf (11) show the eight (calcium) and nine coordinate (strontium and barium) fragments acting as a chelating metalloligand attached to the square planar platinum through the phosphorus donor atoms. The solution chemistry of these bimetallic complexes has been investigated by NMR spectroscopy, electro-spray ionisation mass spectrometry and conductivity experiments which indicate that the bimetallic compounds persist in solution.

  17. Separation of actinides from lanthanides

    Science.gov (United States)

    Smith, Barbara F.; Jarvinen, Gordon D.; Ryan, Robert R.

    1989-01-01

    An organic extracting solution and an extraction method useful for separating elements of the actinide series of the periodic table from elements of the lanthanide series, where both are in trivalent form. The extracting solution consists of a primary ligand and a secondary ligand, preferably in an organic solvent. The primary ligand is a substituted monothio-1,3-dicarbonyl, which includes a substituted 4-acyl-2-pyrazolin-5-thione, such as 4-benzoyl-2,4-dihydro-5-methyl-2-phenyl-3H-pyrazol-3-thione (BMPPT). The secondary ligand is a substituted phosphine oxide, such as trioctylphosphine oxide (TOPO).

  18. Lanthanide-doped luminescent ionogels

    OpenAIRE

    Lunstroot, Kyra; Driesen, Kris; Nockemann, Peter; Van Hecke, Kristof; Van Meervelt, Luc; Görller-Walrand, Christiane; Binnemans, Koen; Bellayer, Séverine; Viau, Lydie; Le Bideau, Jean; Vioux, André

    2009-01-01

    Ionogels are solid oxide host networks confining at a meso-scale ionic liquids, and retaining their liquid nature. Ionogels were obtained by dissolving anthanide(III) complexes in the ionic liquid 1-hexyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, [C6mim][Tf2N], followed by confinement of the lanthanide-doped ionic liquid mixtures in the pores of a nano-porous silica network. [C6mim][Ln(tta)4], where tta is 2-thenoyltrifluoroacetonate and Ln = Nd, Sm, Eu, Ho, Er, Yb, and [choli...

  19. Quantum mechanical study of molecular collisions at ultra-low energy: applications to alkali and alkaline-earth systems; Etude quantique de collisions moleculaires a ultra-basse energie: applications aux alcalins et alcalino-terreux

    Energy Technology Data Exchange (ETDEWEB)

    Quemener, G

    2006-10-15

    In order to investigate the collisional processes which occur during the formation of molecular Bose-Einstein condensates, a time-independent quantum mechanical formalism, based on hyperspherical coordinates, has been applied to the study of atom-diatom dynamics at ultra-low energies. We present theoretical results for three alkali systems, each composed of lithium, sodium or potassium atoms, and for an alkaline-earth system composed of calcium atoms. We also study dynamics at large and positive atom-atom scattering length. Evidence for the suppression of inelastic processes in a fermionic system is given, as well as a linear relation between the atom-diatom scattering length and the atom-atom scattering length. (author)

  20. Effect of alkaline earth oxides on the physical and spectroscopic properties of Dy3+- doped Li2O-B2O3 glasses for white emitting material application

    Science.gov (United States)

    Shamshad, L.; Rooh, G.; Kirdsiri, K.; Srisittipokakun, N.; Damdee, B.; Kim, H. J.; Kaewkhao, J.

    2017-02-01

    Li2O-MO-B2O3:0.5Dy2O3 glasses mixed with four different alkaline earth modifier oxides MgO, CaO, SrO and BaO were synthesized by melt quench technique. Their physical properties like density, molar volume and refractive index were measured at room temperature and the effect of alkaline earth modifier oxides were studied. Also, optical absorption and photoluminescence spectra of these glasses have been acquired at room temperature. The Judd-Ofelt theory was effectively used to characterize these spectra and spectral intensities (ƒcal), Judd-Ofelt intensity parameters (Ω2, Ω4 and Ω6) and certain radiative properties have been determined. Radiative life-times (τR), branching ratios (βcal), and emission cross-sections (σp) and optical gain parameters (σp × τR) were calculated from the Judd-Ofelt intensity parameters and the variation in these parameters with the variation of glass matrix are discussed. Yellow/Blue (Y/B) ratio and chromacity color coordinates (x,y) are calculated from the emission spectra which indicates the white light generation from all the investigated samples. The correlated color temperature (CCT) for the studied glasses is found to be 4418 K. The fluorescence decay time (τexp) of the 4F9/2 level of Dy3+ has been measured from the decay profiles and compared with calculated lifetimes (τcal). Among all the studied glass matrices, the glass containing BaO exhibits high value of branching ratio, large emission cross-section and high optical gain parameter for 6F9/2 → 6H13 at 575 nm. The results indicates the suitability of all the studied glasses for laser action and white light generation.

  1. Kinetic study of the α-tocopherol-regeneration reaction of ubiquinol-10 in methanol and acetonitrile solutions: notable effect of the alkali and alkaline earth metal salts on the reaction rates.

    Science.gov (United States)

    Mukai, Kazuo; Oi, Masanori; Ouchi, Aya; Nagaoka, Shin-ichi

    2012-03-01

    A kinetic study of regeneration reaction of α-tocopherol (α-TocH) by ubiquinol-10 has been performed in the presence of four kinds of alkali and alkaline earth metal salts (LiClO(4), NaClO(4), NaI, and Mg(ClO(4))(2)) in methanol and acetonitrile solutions, using double-mixing stopped-flow spectrophotometry. The second-order rate constants (k(r)'s) for the reaction of α-tocopheroxyl (α-Toc•) radical with ubiquinol-10 increased and decreased notably with increasing concentrations of metal salts in methanol and acetonitrile, respectively. The k(r) values increased in the order of no metal salt NaClO(4) ~ NaI > LiClO(4) > Mg(ClO(4))(2) at the same concentration of metal salts. The metal salts having a smaller ionic radius of cation and a larger charge of cation gave a larger k(r) value in methanol, and a smaller k(r) value in acetonitrile. The effect of anion was almost negligible in both the solvents. Notable effects of metal cations on the UV-vis absorption spectrum of α-Toc• radical were observed in aprotic acetonitrile solution, suggesting complex formation between α-Toc• and metal cations. On the other hand, effects of metal cations were negligible in protic methanol, suggesting that the complex formation between α-Toc• and metal cations is hindered by the hydrogen bond between α-Toc• and methanol molecules. The difference between the reaction mechanisms in methanol and acetonitrile solutions was discussed on the basis of the results obtained. High concentrations of alkali and alkaline earth metal salts coexist with α-TocH and ubiquinol-10 in plasma, blood, and many tissues, suggesting the contribution of the metal salts to the above regeneration reaction in biological systems.

  2. Lanthanide amidinates and guanidinates in catalysis and materials science: a continuing success story.

    Science.gov (United States)

    Edelmann, Frank T

    2012-12-07

    Today the rare-earth elements play a critical role in numerous high-tech applications. This is why various areas of rare-earth chemistry are currently thriving. In organolanthanide chemistry the search for new ligand sets which are able to satisfy the coordination requirements of the large lanthanide cations continues to be a hot topic. Among the most successful approaches in this field is the use of amidinate and guanidinate ligands of the general types [RC(NR')(2)](-) (R = H, alkyl, aryl; R' = alkyl, cycloalkyl, aryl, SiMe(3)) and [R(2)NC(NR')(2)](-) (R = alkyl, SiMe(3); R' = alkyl, cycloalkyl, aryl, SiMe(3)), which can both be regarded as steric cyclopentadienyl equivalents. Mono-, di- and trisubstituted lanthanide amidinate and guanidinate complexes are all readily available. Various rare earth amidinates and guanidinates have turned out to be very efficient homogeneous catalysts e.g. for the polymerization of olefins and dienes, the ring-opening polymerization of cyclic esters or the guanylation of amines. Moreover, certain alkyl-substituted lanthanide tris(amidinates) and tris(guanidinates) were found to be highly volatile and are thus promising precursors for ALD (= atomic layer deposition) and MOCVD (= metal-organic chemical vapor deposition) processes in materials science, e.g. for the production of lanthanide nitride thin layers. This tutorial review covers the continuing success story of lanthanide amidinates and guanidinates which have undergone an astonishing transition from mere laboratory curiosities to efficient homogeneous catalysts as well as ALD and MOCVD precursors within the past 10 years.

  3. The role of lanthanides in optical materials

    Energy Technology Data Exchange (ETDEWEB)

    Weber, M.J.

    1995-05-01

    A survey is presented of the use of the lanthanides as chemical components in transmitting optical materials and as activators in materials for luminescent, electro-optic, magneto-optic, and various photosensitive applications.

  4. Complexometric titration of lanthanides and yttrium

    International Nuclear Information System (INIS)

    Ionashiro, M.; Graner, C.A.F.; Zuanon Netto, J.

    1983-01-01

    The pH variation of the solution and the ammonium acetate buffering were studied when different quantities of lanthanides and yttrium were titrated with EDTA, and xylenol orange as indicator. (Author) [pt

  5. Association of alkali and alkaline earth metal cations with radical-anions of 9-fluorenone and 9.10-anthraquinone in dimethyl formamide medium

    International Nuclear Information System (INIS)

    Karpinets, A.P.; Bezuglyj, V.D.; Svetlichnaya, T.M.

    1988-01-01

    The polarographic method is used to estimate the stability of associates formed in dimethyl formamide by the products of one-electron reduction of 9-fluorenone and 9.10-anthraquinone with cations of alkali and alkali earth metals. It is shown that the strength of 9-fluorenone and 9.10-anthraquinone radical anion associates studied increases with cation charge increase and decrease of its crystallographic radius

  6. Lanthanide Organic Framework Luminescent Thermometers.

    Science.gov (United States)

    Rocha, João; Brites, Carlos D S; Carlos, Luís D

    2016-10-10

    Metal-organic frameworks (MOFs) are excellent platforms for engineering luminescence properties as their building blocks, metal ions, linkers, and guest ions or molecules, are all potential sources of light emission. Temperature is one of the most important physical properties affecting the dynamics and viability of natural and engineered systems. Because the luminescence of certain lanthanide-bearing MOFs changes considerably with temperature, in the last few years, these materials have been explored as optical thermometers, especially in temperature sensing based on the intensity ratios of two separate electronic transitions. This review discusses the main concepts and ideas assisting the design of such ratiometric thermometers, and identifies the main challenges presented to this nascent field: develop nanothermometers for bio-applications and nanomedicine; understand the energy transfer mechanisms determining the thermal sensitivity; achieve effective primary thermometers; realize multifunctional nanothermometers; integrate Ln 3+ -based thermometers in commercial products. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. Polymerization of lanthanide acrylonitrile complexes.

    Science.gov (United States)

    el-Mossalamy, El-Sayed H; Khalil, Ahmed A

    2002-01-01

    The molecular complexes of some lanthanides scandium (Sc3+), yttrium (Y3+), lanthanum (La3+), gadolinium (Gd3+), cerium (Ce3+) and ytterbium (Yb3) have been studies in dimethyl formamide (DMF) spectrophtometrically equilibrium constants (K), molar extintion coefficient (epsilon), energy of transition (E) and free energy (delta G*) were calculated. The polymerization of acrylonitrile has been studied and investigated in the presence of Sc3+, Y3+, La3+, Gd3+, Ce3+, and Yb3+ ions. The IR spectra of the formed AN-M (III) Br3 polymer complexes show the absence of the C identical to N band and the presence of two new bands corresponding to NH2 and OH groups. Magnetic moment values and the thermal stabilities of homopolymer and the polymer complexes were studied by means of thermogravimetric analysis and the activation energies for degradation were calculated.

  8. A selective spectrophotometric determination of europium in mixtures with other lanthanides, yttrium and scandium

    International Nuclear Information System (INIS)

    Lyle, S.J.; Za'tar, N.A.

    1982-01-01

    Spectrophotometric methods are presented for the determination of 0.04-5 mg of europium in rare earth mixtures, following a group separation, or in lanthanide compounds. Europium(III) is selectively reduced on a Jones reductor to europium(II) which in turn reduces molybdophosphoric acid to a molybdenum blue. The absorbance is measured at 810 nm in aqueous solution or at 790 nm after extraction into n-amyl alcohol; optimal reaction conditions and times are reported. Other rare earth elements, and chloride, bromide, perchlorate, acetate and sulphate, are without effect when present in gram amounts but nitrate and iodide must be absent. The method is applied to the determination of europium in various lanthanide oxides and bastnaesite. (Auth.)

  9. Nonaqueous method for dissolving lanthanide and actinide metals

    International Nuclear Information System (INIS)

    Crisler, L.R.

    1975-01-01

    Lanthanide and actinide beta-diketonate complex molecular compounds are produced by reacting a beta-diketone compound with a lanthanide or actinide element in the elemental metallic state in a mixture of carbon tetrachloride and methanol

  10. Synthèse par voie hydrothermale des orthophosphates de lanthanides pour des applications optiques

    OpenAIRE

    Garrido-Hernandez, Aristeo

    2015-01-01

    Rare earth (Re) doped lanthanide orthophosphates (LnPO4) are considered like promising phosphors for optical applications. Phosphors are luminescent materials which convert certain types of energy (X-ray, ultraviolet, visible, infrared) mainly into visible light. In this research Eu3+ (europium), Ce3+ (cerium), Tb3+ (terbium), Er3+ (erbium), Tm3+ (thulium) and/or Yb3+ (ytterbium) doped LuPO4 (lutetium orthophosphate), YPO4 (yttrium orthophosphate), GdPO4 (gadolinium orthophosphate) and/or Gdx...

  11. Rare earth base superconducting composition

    International Nuclear Information System (INIS)

    Raveau, B.J.; Bourgault, D.M.; Hervieu, M.; Martin, C.Y.; Michel, C.M.A.E.; Provost, J.R.J.

    1991-01-01

    A superconductin mixed valence copper oxide with a perowskite structure is claimed. It comprises a valence 4 rare earth (Ce or Pr), an alkaline earth metal (Sr or Ba) and thallium. Chemical composition is given and synthesis is described [fr

  12. New Lanthanide Alkynylamidinates and Diiminophosphinates

    Directory of Open Access Journals (Sweden)

    Farid M. Sroor

    2015-11-01

    Full Text Available This contribution reports the synthesis and structural characterization of several new lithium and lanthanide alkynylamidinate complexes. Treatment of PhC≡CLi with N,N′-diorganocarbodiimides, R–N=C=N–R (R = iPr, Cy (cyclohexyl, in THF or diethyl ether solution afforded the lithium-propiolamidinates Li[Ph–C≡C–C(NCy2] S (1: R = iPr, S = THF; 2: R = Cy, S = THF; 3: R = Cy, S = Et2O. Single-crystal X-ray diffraction studies of 1 and 2 showed the presence of typical ladder-type dimeric structures in the solid state. Reactions of anhydrous LnCl3 (Ln = Ce, Nd, Sm or Ho with 2 in a 1:3 molar ratio in THF afforded a series of new homoleptic lanthanide tris(propiolamidinate complexes, [Ph–C≡C–C(NCy2]3Ln (4: Ln = Ce; 5: Ln = Nd; 6: Ln = Sm; 7: Ln = Ho. The products were isolated in moderate to high yields (61%–89% as brightly colored, crystalline solids. The chloro-functional neodymium(III bis(cyclopropylethynylamidinate complex [{c-C3H5–C≡C–C(NiPr2}2Ln(µ-Cl(THF]2 (8 was prepared from NdCl3 and two equiv. of Li[c-C3H5–C≡C–C(NiPr2] in THF and structurally characterized. A new monomeric Ce(III-diiminophosphinate complex, [Ph2P(NSiMe32]2Ce(µ-Cl2Li(THF2 (9, has also been synthesized in a similar manner from CeCl3 and two equiv. of Li[Ph2P(NSiMe32]. Structurally, this complex resembles the well-known “ate” complexes (C5Me52Ln(µ-Cl2Li(THF2. Attempts to oxidize compound 9 using trityl chloride or phenyliodine(III dichloride did not lead to an isolable cerium(IV species.

  13. Improvement to a production process of rare earth hydroxide by treatment of ores containing rare earth phosphates

    International Nuclear Information System (INIS)

    Fabre, F.; Lambert, A.; Tognet, J.P.

    1987-01-01

    Ore is treated by an aqueous solution of alkaline metal hydroxide and solid rare earth hydroxides are separated. For recycling the alkaline hydroxide after concentration the alkaline metal phosphate is crystallized and then alkaline earth metal hydroxide is added to avoid silicates concentration in the recycled solution [fr

  14. Lanthanide-Dependent Regulation of Methanol Oxidation Systems in Methylobacterium extorquens AM1 and Their Contribution to Methanol Growth.

    Science.gov (United States)

    Vu, Huong N; Subuyuj, Gabriel A; Vijayakumar, Srividhya; Good, Nathan M; Martinez-Gomez, N Cecilia; Skovran, Elizabeth

    2016-04-01

    , our data suggest that M. extorquens AM1 has a mechanism to regulate which MeDH is transcribed, depending on the presence or absence of lanthanides. While the mechanism controlling differential regulation is not yet understood, further research into how methylotrophs obtain and use lanthanides will facilitate their cultivation in the laboratory and their use as a biomining and biorecycling strategy for recovery of these commercially valuable rare-earth elements. Copyright © 2016, American Society for Microbiology. All Rights Reserved.

  15. RARE EARTH ELEMENTS: A REVIEW OF PRODUCTION, PROCESSING, RECYCLING, AND ASSOCIATED ENVIRONMENTAL ISSUES

    Science.gov (United States)

    Rare earth elements (REEs) are a group of 15 chemical elements in the periodic table, specifically the lanthanides. Two other elements, scandium and yttrium, have a similar physiochemistry to the lanthanides, are commonly found in the same mineral assemblages, and are often refe...

  16. Phase equilibria and thermodynamic properties of oxide systems on the basis of rare earth, alkaline earth and 3d-transition (Mn, Fe, Co metals. A short overview of

    Directory of Open Access Journals (Sweden)

    V. A. Cherepanov

    2015-12-01

    Full Text Available Review is dedicated studies of phase equilibria in the systems based on rare earth elements and 3d transition metals. It’s highlighted several structural families of these compounds and is shown that many were found interesting properties for practical application, such as high conductivity up to the superconducting state, magnetic properties, catalytic activity of the processes of afterburning of exhaust gases, the high mobility in the oxygen sublattice and more.

  17. 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.

  18. Magmatic age of rare-earth element and zirconium mineralisation at the Norra Kärr alkaline complex, southern Sweden, determined by U-Pb and Lu-Hf isotope analyses of metasomatic zircon and eudialyte

    Science.gov (United States)

    Sjöqvist, Axel S. L.; Cornell, David H.; Andersen, Tom; Christensson, Ulf I.; Berg, Johan T.

    2017-12-01

    The agpaitic Norra Kärr alkaline complex in southern Sweden is rich in heavy rare-earth elements and zirconium. Despite generally containing high concentrations of Zr, agpaitic rocks sensu stricto are devoid of igneous zircon. During the late stages of magmatic activity at Norra Kärr, metasomatic Na- and F-rich fluids transporting Zr complexes caused fenitisation (syn-magmatic alkali metasomatism) of the granitic wall rocks, which formed new metasomatic zircon. Fenite zircon was dated by LA-MC-ICP-MS with the U-Pb method at 1.49 ± 0.01 Ga, while the unaltered country rock granite was dated at 1.79 ± 0.01 Ga. Zircon in the fenites exhibits εHf + 6.58 ± 0.36 at 1.49 Ga; significantly above the expected value for Svecofennian crust at that time (ca. - 5 ± 2), but identical, within error, of that measured in eudialyte from Norra Kärr. This suggests a common source of Hf for fenite zircon and eudialyte from Norra Kärr, which isotopically strengthens the genetic link between fenite and nepheline syenite. The 1.49 Ga age dates not only the fenitisation, but also the relatively small agpaitic intrusion, which caused the fenitisation. This also dates the origin of the rare-earth element and Zr ore within the agpaitic nepheline syenite, which probably formed from an evolved magma derived from the mantle. A few zircon xenocrysts, which survived in the agpaitic nepheline syenite magma, may indicate the presence of an Archaean component in the basement.

  19. Alkaline sorbent injection for mercury control

    Science.gov (United States)

    Madden, Deborah A.; Holmes, Michael J.

    2002-01-01

    A mercury removal system for removing mercury from combustion flue gases is provided in which alkaline sorbents at generally extremely low stoichiometric molar ratios of alkaline earth or an alkali metal to sulfur of less than 1.0 are injected into a power plant system at one or more locations to remove at least between about 40% and 60% of the mercury content from combustion flue gases. Small amounts of alkaline sorbents are injected into the flue gas stream at a relatively low rate. A particulate filter is used to remove mercury-containing particles downstream of each injection point used in the power plant system.

  20. Gaussian basis sets for use in correlated molecular calculations. XI. Pseudopotential-based and all-electron relativistic basis sets for alkali metal (K-Fr) and alkaline earth (Ca-Ra) elements

    Science.gov (United States)

    Hill, J. Grant; Peterson, Kirk A.

    2017-12-01

    New correlation consistent basis sets based on pseudopotential (PP) Hamiltonians have been developed from double- to quintuple-zeta quality for the late alkali (K-Fr) and alkaline earth (Ca-Ra) metals. These are accompanied by new all-electron basis sets of double- to quadruple-zeta quality that have been contracted for use with both Douglas-Kroll-Hess (DKH) and eXact 2-Component (X2C) scalar relativistic Hamiltonians. Sets for valence correlation (ms), cc-pVnZ-PP and cc-pVnZ-(DK,DK3/X2C), in addition to outer-core correlation [valence + (m-1)sp], cc-p(w)CVnZ-PP and cc-pwCVnZ-(DK,DK3/X2C), are reported. The -PP sets have been developed for use with small-core PPs [I. S. Lim et al., J. Chem. Phys. 122, 104103 (2005) and I. S. Lim et al., J. Chem. Phys. 124, 034107 (2006)], while the all-electron sets utilized second-order DKH Hamiltonians for 4s and 5s elements and third-order DKH for 6s and 7s. The accuracy of the basis sets is assessed through benchmark calculations at the coupled-cluster level of theory for both atomic and molecular properties. Not surprisingly, it is found that outer-core correlation is vital for accurate calculation of the thermodynamic and spectroscopic properties of diatomic molecules containing these elements.

  1. Gaussian basis sets for use in correlated molecular calculations. XI. Pseudopotential-based and all-electron relativistic basis sets for alkali metal (K-Fr) and alkaline earth (Ca-Ra) elements.

    Science.gov (United States)

    Hill, J Grant; Peterson, Kirk A

    2017-12-28

    New correlation consistent basis sets based on pseudopotential (PP) Hamiltonians have been developed from double- to quintuple-zeta quality for the late alkali (K-Fr) and alkaline earth (Ca-Ra) metals. These are accompanied by new all-electron basis sets of double- to quadruple-zeta quality that have been contracted for use with both Douglas-Kroll-Hess (DKH) and eXact 2-Component (X2C) scalar relativistic Hamiltonians. Sets for valence correlation (ms), cc-pVnZ-PP and cc-pVnZ-(DK,DK3/X2C), in addition to outer-core correlation [valence + (m-1)sp], cc-p(w)CVnZ-PP and cc-pwCVnZ-(DK,DK3/X2C), are reported. The -PP sets have been developed for use with small-core PPs [I. S. Lim et al., J. Chem. Phys. 122, 104103 (2005) and I. S. Lim et al., J. Chem. Phys. 124, 034107 (2006)], while the all-electron sets utilized second-order DKH Hamiltonians for 4s and 5s elements and third-order DKH for 6s and 7s. The accuracy of the basis sets is assessed through benchmark calculations at the coupled-cluster level of theory for both atomic and molecular properties. Not surprisingly, it is found that outer-core correlation is vital for accurate calculation of the thermodynamic and spectroscopic properties of diatomic molecules containing these elements.

  2. High hydrogen loading of thin palladium wires through alkaline earth carbonates' precipitation on the cathodic surface - evidence of a new phase in the Pd-H system

    Energy Technology Data Exchange (ETDEWEB)

    Celani, F.; Spallone, A.; Di Gioacchino, D. [Istituto Nazionale di Fisica Nucleare, Laboratori Nazionali di Frascati, Frascati, RM (Italy); Marini, P.; Di Stefano, V.; Nakamura, M. [EURESYS, Rome (Italy); Pace, S. [Salerno Univ., Salerno (Italy). Dept. of Physics, Istituto Nazionale per la Fisica della Materia; Mancini, A. [ORIM S.r.l., Piediripa, MC (Italy); Tripodi, P. [Stanford Research Institut International, Stanford, CA (United States)

    2000-07-01

    A new protocol for the electrolytic loading of hydrogen (H) in thin palladium (Pd) wires has been developed. In order to increase the cathodic overvoltage, which is known to be the main parameter capable to enhance the electrolytic H loading of Pd, the catalytic action of the Pd surface versus H-H recombination has been strongly reduced by precipitation of a thin layer of alkaline-earth carbonates on the cathode. A set of electrolytes has been employed, containing small amounts of hydrochloric or sulfuric acid and strontium or calcium ions. The H loading has been continuously evaluated through ac measurements of the Pd wire resistance. Uncommonly low resistivity values, leading to an estimate of exceptionally high H loading, have been observed. Evidence of the existence of a new phase in the very high H content region of the Pd-H system has been inferred on the basis of the determination of the temperature coefficient of the electrical resistivity. Mainly for this purpose a thin layer of Hg was galvanically deposed on the cathodic surface, in order to prevent any H deloading during the measurements. The results have been fully reproduced in other 2 well equipped and experienced Laboratories (Italy, USA).

  3. Vibronic transitions in the alkali-metal (Li, Na, K, Rb) - alkaline-earth-metal (Ca, Sr) series: A systematic analysis of de-excitation mechanisms based on the graphical mapping of Frank-Condon integrals

    Science.gov (United States)

    Pototschnig, Johann V.; Meyer, Ralf; Hauser, Andreas W.; Ernst, Wolfgang E.

    2017-02-01

    Research on ultracold molecules has seen a growing interest recently in the context of high-resolution spectroscopy and quantum computation. After forming weakly bound molecules from atoms in cold collisions, the preparation of molecules in low vibrational levels of the ground state is experimentally challenging, and typically achieved by population transfer using excited electronic states. Accurate potential energy surfaces are needed for a correct description of processes such as the coherent de-excitation from the highest and therefore weakly bound vibrational levels in the electronic ground state via couplings to electronically excited states. This paper is dedicated to the vibrational analysis of potentially relevant electronically excited states in the alkali-metal (Li, Na, K, Rb)- alkaline-earth metal (Ca,Sr) diatomic series. Graphical maps of Frank-Condon overlap integrals are presented for all molecules of the group. By comparison to overlap graphics produced for idealized potential surfaces, we judge the usability of the selected states for future experiments on laser-enhanced molecular formation from mixtures of quantum degenerate gases.

  4. Study of conformational and acid-base properties of norbadione A and pulvinic derivatives: Consequences on their complexation properties of alkaline and alkaline earth cations; Etude des proprietes conformationnelles et acido-basiques de la norbadione A et de derives pulviniques: consequences sur leurs proprietes complexantes de cations alcalins et alcalino-terreux

    Energy Technology Data Exchange (ETDEWEB)

    Kuad, P

    2006-01-15

    This work deals with the study of norbadione A, a pigment extracted from mushrooms and known to complex cesium cations. The study of the acid-base properties of norbadione A has allowed to determine the relative acidity of the seven protonable functions of the molecule and to reveal a reversible isomerization of the double exocyclic bond of the pulvinic moieties. The observed change of configuration is induced by a hydrogen bond of the H-O-H type and by electrostatic interactions. Moreover, the microscopic protonation mechanism of the norbadione A has been analyzed, considering three different study media where the acid-base properties of the norbadione A are compared. In the presence of 0.15 mol.l{sup -1} of NaCl, it has been observed a remarkable cooperativity in the protonation of the enol groups. At last, the use of different analytical methods (NMR, potentiometry and calorimetry) has allowed to study the complexing properties of the norbadione A towards cesium and other alkaline and rare earth cations. (O.M.)

  5. Lanthanides in the frame of Molecular Magnetism

    Directory of Open Access Journals (Sweden)

    Gatteschi D.

    2014-07-01

    Full Text Available Molecular magnetism is producing new types of materials which cover up to date aspects of basic science together with possible applications. This article highlights recent results from the point of view of lanthanides which are now intensively used to produce single molecule magnets, single chain and single ion magnets. After a short introduction reminding the main steps of development of molecular magnetism, the basic properties of lanthanides will be covered highlighting important features which are enhanced by the electronic structure of lanthanides, like spin frustration and chirality, anisotropy and non collinear axes in zero and one dimensional materials. A paragraph of conclusions will discuss what has been done and theperspectives to be expected.

  6. Curvature of the Lanthanide Contraction: An Explanation

    Energy Technology Data Exchange (ETDEWEB)

    Raymond, Kenneth; Wellman, Daniel; Sgarlata, Carmelo; Hill, Aru

    2009-12-21

    A number of studies have shown that for isostructural series of the lanthanides (elements La through Lu), a plot of equivalent metal-ligand bond lengths versus atomic number differs significantly from linearity and can be better fit as a quadratic equation. However, for hydrogen type wave functions, it is the inverse of the average distance of the electron from the nucleus (an estimate of size) that varies linearly with effective nuclear charge. This generates an apparent quadratic dependence of radius with atomic number. Plotting the inverse of lanthanide ion radii (the observed distance minus the ligand size) as a function of effective nuclear charge gives very good linear fits for a variety of lanthanide complexes and materials. Parameters obtained from this fit are in excellent agreement with the calculated Slater shielding constant, k.

  7. Separations of actinides, lanthanides and other metals

    Science.gov (United States)

    Smith, Barbara F.; Jarvinen, Gordon D.; Ensor, Dale D.

    1995-01-01

    An organic extracting solution comprised of a bis(acylpyrazolone or a substituted bis(acylpyrazolone) and an extraction method useful for separating certain elements of the actinide series of the periodic table having a valence of four from one other, and also from one or more of the substances in a group consisting of hexavalent actinides, trivalent actinides, trivalent lanthanides, trivalent iron, trivalent aluminum, divalent metals, and monovalent metals and also from one or more of the substances in a group consisting of hexavalent actinides, trivalent actinides, trivalent lanthanides, trivalent iron, trivalent aluminum, divalent metals, and monovalent metals and also useful for separating hexavalent actinides from one or more of the substances in a group consisting of trivalent actinides, trivalent lanthanides, trivalent iron, trivalent aluminum, divalent metals, and monovalent metals.

  8. Taking advantage of luminescent lanthanide ions.

    Science.gov (United States)

    Bünzli, Jean-Claude G; Piguet, Claude

    2005-12-01

    Lanthanide ions possess fascinating optical properties and their discovery, first industrial uses and present high technological applications are largely governed by their interaction with light. Lighting devices (economical luminescent lamps, light emitting diodes), television and computer displays, optical fibres, optical amplifiers, lasers, as well as responsive luminescent stains for biomedical analysis, medical diagnosis, and cell imaging rely heavily on lanthanide ions. This critical review has been tailored for a broad audience of chemists, biochemists and materials scientists; the basics of lanthanide photophysics are highlighted together with the synthetic strategies used to insert these ions into mono- and polymetallic molecular edifices. Recent advances in NIR-emitting materials, including liquid crystals, and in the control of luminescent properties in polymetallic assemblies are also presented. (210 references.).

  9. Lanthanides in molecular magnetism: old tools in a new field.

    Science.gov (United States)

    Sorace, Lorenzo; Benelli, Cristiano; Gatteschi, Dante

    2011-06-01

    In this tutorial review we discuss some basic aspects concerning the magnetic properties of rare-earth ions, which are currently the subject of a renovated interest in the field of molecular magnetism, after the discovery that slow relaxation of the magnetization at liquid nitrogen temperature can occur in mononuclear complexes of these ions. Focusing on Dy(III) derivatives a tutorial discussion is given of the relation of the crystal field parameters, which determine the anisotropy of these systems and consequently their interesting magnetic properties, with the geometry of the coordination sphere around the lanthanide centre and with the pattern of f orbitals. The problem of systems of low point symmetry is also addressed by showing how detailed single crystal investigation, coupled to more sophisticated calculation procedures, is an absolute necessity to obtain meaningful structure-property relationships in these systems.

  10. Optimization of the radio lanthanides separation device

    International Nuclear Information System (INIS)

    Vera T, A. L.

    2009-01-01

    At present, cancer is a major cause of mortality in our country, therefore, its prevention, diagnosis and treatment are vital to health systems. The cancer treatment and other diseases, from monoclonal antibodies, peptides, or amino macro aggregates marked with beta particle emitting radionuclides, is a highly promising field. The radioactive lanthanides: Pm, Tb, Ho, and Lu are beta emitters, which possess nuclear and chemical properties, which have shown their feasibility as radioisotopes of radiotherapeutic use. However, these radioisotopes are not available commercially in this connection, the Research Laboratory of Radioactive Materials of the National Institute of Nuclear Research, has developed the methodology of production of these radioisotopes and based on this work is designed, constructed and installed the radio lanthanides separation device for the radioisotopes production routinely. This device is part of the cell, , which has and auxiliary air service, an extraction system and is protected with a 10 cm of lead shielding. The radio lanthanides separation device is manual and easy to handle. The main function of this equipment is the radio lanthanides separation from extractive chromatography through packed columns with a commercial resin (Ln SPS) and coated on the top and bottom by fiberglass. The radio lanthanides separation device comprises a main carrousel where the separation columns and elution containers are mounted. It also has a system of open irradiation vials, carrier samples for columns and glassware. This paper presents a detailed description of the radio lanthanides separation device and its management, which allows the radioisotopes production Pm, Tb, Ho, and Lu from the separation of its parents Nd, Dy, Gd, and Yb respectively. (Author)

  11. Shear viscosity coefficient of liquid lanthanides

    Energy Technology Data Exchange (ETDEWEB)

    Patel, H. P., E-mail: patel.harshal2@gmail.com; Thakor, P. B., E-mail: pbthakore@rediffmail.com; Prajapati, A. V., E-mail: anand0prajapati@gmail.com [Department of Physics, Veer Narmad South Gujarat University, Surat 395 007, Gujarat (India); Sonvane, Y. A., E-mail: yas@ashd.svnit.ac.in [Department of Applied Physics, S. V. National Institute of Technology, Surat 395 007, Gujarat (India)

    2015-05-15

    Present paper deals with the computation of shear viscosity coefficient (η) of liquid lanthanides. The effective pair potential v(r) is calculated through our newly constructed model potential. The Pair distribution function g(r) is calculated from PYHS reference system. To see the influence of local field correction function, Hartree (H), Tailor (T) and Sarkar et al (S) local field correction function are used. Present results are compared with available experimental as well as theoretical data. Lastly, we found that our newly constructed model potential successfully explains the shear viscosity coefficient (η) of liquid lanthanides.

  12. Studies of Lanthanide Transport in Metallic Fuel

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Jinsuo; Taylor, Christopher

    2018-04-02

    Metallic nuclear fuels were tested in fast reactor programs and performed well. However, metallic fuels have shown the phenomenon of FCCI that are due to deleterious reactions between lanthanide fission products and cladding material. As the burnup is increased, lanthanide fission products that contact with the cladding could react with cladding constituents such as iron and chrome. These reactions produce higher-melting intermetallic compounds and low-melting alloys, and weaken the mechanical integrity. The lanthanide interaction with clad in metallic fuels is recognized as a long-term, high-burnup cause of the clad failures. Therefore, one of the key concerns of using metallic fuels is the redistribution of lanthanide fission products and migration to the fuel surface. It is believed that lanthanide migration is in part due to the thermal gradient between the center and the fuel-cladding interface, but also largely in part due to the low solubility of lanthanides within the uranium-based metal fuel. PIE of EBR-II fuels shows that lanthanides precipitate directly and do not dissolve to an appreciable extent in the fuel matrix. Based on the PIE data from EBR-II, a recent study recommended a so-called “liquid-like” transport mechanism for lanthanides and certain other species. The liquid-like transport model readily accounts for redistribution of Ln, noble metal fission products, and cladding components in the fuel matrix. According to the novel mechanism, fission products can transport as solutes in liquid metals, such as liquid cesium or liquid cesium–sodium, and on pore surfaces and fracture surfaces for metals near their melting temperatures. Transport in such solutions is expected to be much more rapid than solid-state diffusion. The mechanism could explain the Ln migration to the fuel slug peripheral surface and their deposition with a sludge-like form. Lanthanides have high solubility in liquid cesium but have low solubility in liquid sodium. As a

  13. Separation of individual lanthanides through the combined techniques of urea fractionated homogeneous precipitation and ion exchange

    International Nuclear Information System (INIS)

    Umeda, K.; Abrao, A.

    1975-01-01

    The separation of individual lanthanides, especially Ce, Nd, Pr, Sm and La, from a rare earth chlorides concentrate by the industrial processing of monazite sand is made. To reach this goal the homogeneous fractional precipitation and ion exchange techniques were combined. Using the rare earths concentrate depleted in Cerium, fractions enriched in Nd, Pr and Sm, and one final filtrate enriched in La were obtained, by the hydrolysis of urea. The separation of individual lanthanides (Ns, Pr, Sm and La) was accomplished using two strong cationic ion exchanger columns, the second with Cu(II) as retaining ion, and EDTA-NH 4 solution buffered with acetic acid as eluant. The annoy problem of precipitation into the column during the RE elution was solved. The difficult EDTA and Cu(II) recovery was the precipitation of Cu 2 S and disruption of CU-EDTA complex by hydrolysis of thiourea. The combination of both techniques allowed the preparation of individual lanthanides as Nd, Pr and La with 99% and Sm with 90% purity

  14. RI and Target recovery system of Lanthanides

    Energy Technology Data Exchange (ETDEWEB)

    Choi, K. H.; Park, U. J.; Jung, S. H.; Kim, J. B.; Moon, J. H.; Nam, S. S.; Jang, K. D. [Korea Atomic Energy Research Institute, Daejeon (Korea, Republic of)

    2015-10-15

    Separation of adjacent lanthanides is complicated process to obtain pure target nuclide. Several papers have reported that the ionic character change of lanthanides with appropriate chelating agents can isolate the target lanthanides. These specific agents to the metal ion are called as complexing agents including-HIBA, tartaric acid, mandelic acid, lactic acid etc. Radioisotope research division of KAERI has developed separating technique for target lanthanides, total 20mg scale, by using complexing agents and ion-pairing agents in cold state. The reactor-produced radiolanthanides have been pivotal for development of therapeutic radiopharmaceuticals. Some radiolanthanides show excellent theranostic effects in that they have proper Let (Linear Energy Transfer) to induce apoptosis for cancer treatment and gamma ray to use as a tracer for cancer diagnosis. This system was designed for automated separation of the (n,γ) reaction product. Especially, we are focused on getting the carrier free Ho-166 which is the first attempt at KAERI. Even though we have already developed to produce c.a Ho-166(carrier added form), we did not try to develop to produce carrier free Ho-166 since the separating process is difficult as well as production process follows double (n,γ) reaction. After HANARO is re-operated, we are schedule to produce n.c.a Ho by using this recovery system.

  15. Analysis of lanthanide π-complexes containing N, P, and As atoms

    International Nuclear Information System (INIS)

    Blatova, O.A.; Blatov, V.A.; Serezhkin, V.N.

    2003-01-01

    On the basis of samples made up by 92 π-complexes of the composition LnC n H m Q k (Ln = Sc, Y, lanthanides; Q = N, P, As) influence of nature, oxidation state and coordination number of the central Ln atom, as well as of nature of Q atoms on characteristics of the rare-earth atoms range of action, were analyzed. Influence of steric factors on stability of complex groupings and on the presence/absence of intracomplex interactions in Ln...H structure of the complexes considered was studied. A number of regularities in crystal structure of the complexes studied, which had been previously ascertained for π-complexes of lanthanides featuring another stoichiometric composition, was confirmed [ru

  16. Rare-earth elements

    Science.gov (United States)

    Van Gosen, Bradley S.; Verplanck, Philip L.; Seal, Robert R.; Long, Keith R.; Gambogi, Joseph; Schulz, Klaus J.; DeYoung,, John H.; Seal, Robert R.; Bradley, Dwight C.

    2017-12-19

    The rare-earth elements (REEs) are 15 elements that range in atomic number from 57 (lanthanum) to 71 (lutetium); they are commonly referred to as the “lanthanides.” Yttrium (atomic number 39) is also commonly regarded as an REE because it shares chemical and physical similarities and has affinities with the lanthanides. Although REEs are not rare in terms of average crustal abundance, the concentrated deposits of REEs are limited in number.Because of their unusual physical and chemical properties, the REEs have diverse defense, energy, industrial, and military technology applications. The glass industry is the leading consumer of REE raw materials, which are used for glass polishing and as additives that provide color and special optical properties to the glass. Lanthanum-based catalysts are used in petroleum refining, and cerium-based catalysts are used in automotive catalytic converters. The use of REEs in magnets is a rapidly increasing application. Neodymium-iron-boron magnets, which are the strongest known type of magnets, are used when space and weight are restrictions. Nickel-metal hydride batteries use anodes made of a lanthanum-based alloys.China, which has led the world production of REEs for decades, accounted for more than 90 percent of global production and supply, on average, during the past decade. Citing a need to retain its limited REE resources to meet domestic requirements as well as concerns about the environmental effects of mining, China began placing restrictions on the supply of REEs in 2010 through the imposition of quotas, licenses, and taxes. As a result, the global rare-earth industry has increased its stockpiling of REEs; explored for deposits outside of China; and promoted new efforts to conserve, recycle, and substitute for REEs. New mine production began at Mount Weld in Western Australia, and numerous other exploration and development projects noted in this chapter are ongoing throughout the world.The REE-bearing minerals are

  17. Gas-Phase Reactions of Hydrated Alkaline Earth Metal Ions, M2+ (H2O)n (M = Mg, Ca, Sr, Ba and n = 4–7), With Benzene

    Science.gov (United States)

    Rodriguez-Cruz, Sandra E.; Williams, Evan R.

    2005-01-01

    Gas-phase reactions of hydrated divalent alkaline earth metal ions and benzene were investigated by electrospray ionization Fourier-transform mass spectrometry. Rate constants for solvent-exchange reactions were determined as a function of hydration extent for Mg2+, Ca2+, Sr2+, and Ba2+ clusters containing four to seven water molecules each. All of the strontium and barium clusters react quickly with benzene. Barium reacts slightly faster than the corresponding strontium cluster with the same number of water molecules attached. For calcium, clusters with four and five water molecules react quickly, whereas those with six and seven water molecules do not. Magnesium with four water molecules reacts quickly, but not when five through seven water molecules are attached. The slow reactivity observed for some of these clusters indicates that the cation–π interaction between the metal ion and benzene is partially screened by the surrounding water molecules. The reactivity of magnesium with seven water molecules is intermediate that of the hexa- and pentahydrate and the tetrahydrate. This result is consistent with the seventh water molecule being in the outer shell and much more weakly bound. The unusual trend in reactivity observed for magnesium may be due to the presence of mixed shell structures observed previously. These results are the first to provide information about the relative importance of cation–π interactions in divalent metal ions as a function of metal hydration extent. Such studies should also provide a model and some insight into the relative binding affinities of divalent metal ions to aromatic residues on peptides and proteins. PMID:11281600

  18. Gas-phase reactions of hydrated alkaline earth metal ions, M2+ (H2O)n (M = Mg, Ca, Sr, Ba and n = 4-7), with benzene.

    Science.gov (United States)

    Rodriguez-Cruz, S E; Williams, E R

    2001-03-01

    Gas-phase reactions of hydrated divalent alkaline earth metal ions and benzene were investigated by electrospray ionization Fourier-transform mass spectrometry. Rate constants for solvent-exchange reactions were determined as a function of hydration extent for Mg2+, Ca2+, Sr2+, and Ba2+ clusters containing four to seven water molecules each. All of the strontium and barium clusters react quickly with benzene. Barium reacts slightly faster than the corresponding strontium cluster with the same number of water molecules attached. For calcium, clusters with four and five water molecules react quickly, whereas those with six and seven water molecules do not. Magnesium with four water molecules reacts quickly, but not when five through seven water molecules are attached. The slow reactivity observed for some of these clusters indicates that the cation-pi interaction between the metal ion and benzene is partially screened by the surrounding water molecules. The reactivity of magnesium with seven water molecules is intermediate that of the hexa- and pentahydrate and the tetrahydrate. This result is consistent with the seventh water molecule being in the outer shell and much more weakly bound. The unusual trend in reactivity observed for magnesium may be due to the presence of mixed shell structures observed previously. These results are the first to provide information about the relative importance of cation-pi interactions in divalent metal ions as a function of metal hydration extent. Such studies should also provide a model and some insight into the relative binding affinities of divalent metal ions to aromatic residues on peptides and proteins.

  19. Preparation of lanthanide arylphosphonates and crystal structures of lanthanum phenyl- and benzylphosphonates

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Ren-Chang; Zhang, Y.; Hu, Hengliang; Frausto, R.R.; Clearfield, A. (Texas A M Univ., College Station, TX (United States))

    A series of phenyl- and benzylphosphonates of the lanthanide elements has been prepared. In the lanthanum system single crystals have been obtained and the crystal structures determined. Lanthanum phenylphosphate, La(O[sub 3]PC[sub 6]H[sub 5])(HO[sub 3]PC[sub 6]H[sub 5]), triclinic, space group. The structure is a layered one in which the lanthanum atoms are eight-coordinate. Both phosphonate groups chelate the metal atom. One oxygen of each chelate ring then bridges to an adjacent La atom, while the third oxygen bridges to lanthanum at right angles to the bridging of the chelating oxygens. The phenyl rings protrude into the interlamellar space but are disordered. This disorder arises because the true unit cell has a doubled c axis. Thus, the phenyl rings in any one row are parallel to each other in the a-axis direction but are inclined to each other in adjacent rows in the c-axis direction at angle of 58[degrees]. A short hydrogen bond (2.41 [angstrom] O-O distance) is present within the layers. La(O[sub 3]PCH[sub 2]C[sub 6]H[sub 5])(HO[sub 3]PCH[sub 2]C[sub 6]HJ[sub 5])[center dot]2H[sub 2]O is orthorhombic, space group Pbcn. This structure is also a layered one with 8-fold coordination about the lanthanum atom. There are six phosphonate and two water oxygens in the La coordination sphere in a distorted dodecahedral arrangement. One phosphonate group chelates the lanthanum, while the remaining oxygen bridges to an adjacent La atom. One of the chelating oxygens also bonds to an adjacent lanthanum atom. The second phosphonate group bridges across two La atoms with two of its oxygens, while the third bonds to hydrogen. This acid proton and the water molecules form an extensive system of intralayer hydrogen bonds. A second type of rare-earth phosphonate of composition Ln[sub 2](O[sub 3]PC[sub 6]H[sub 5])[sub 3] was prepared in slightly alkaline media. 35 refs., 6 figs., 8 tabs.

  20. Alkaline earth stannates: The next silicon?

    Directory of Open Access Journals (Sweden)

    Sohrab Ismail-Beigi

    2015-06-01

    Full Text Available Semiconductor materials are being used in an increasingly diverse array of applications, with new device concepts being proposed each year for solar cells, flat-panel displays, sensors, memory, and spin transport. This rapid progress of invention outpaces the development of new semiconductor materials with the required properties and performance. In many applications, high carrier mobility at room temperature is required in addition to specific functional properties critical to the device concept. We review recent developments on high mobility stannate perovskite oxide materials and devices.

  1. Optical properties of alkaline earth borate glasses

    African Journals Online (AJOL)

    user

    of RO oxides in the glass matrix is small and therefore no significant structural changes might have occurred in the glass network. Urbach's energy refers to the width of the tails of localized states in the forbidden gap of a disordered material. According to. Urbach's rule, optical absorption coefficient near the absorption edge ...

  2. Thermodynamic properties of alkaline earth metal oxides

    International Nuclear Information System (INIS)

    Chekhovskoj, V.Ya.; Irgashov, Kh.

    1990-01-01

    Analysis of the known experimental data on enthalpy and heat capacity of CaO, SrO, BaO and RaO above 300 K is performed. New results of experimental study: enthalpy and heat capacity in solid and liquid states of BaO up to 2500 K, SrO up to 3000 K, CaO - up to 3100 K, as well as melting points, melting heats and entropies, heat capacity of melts and formation energy of anion and cation vacancy pair are presented. For Ra evaluations of temperature, melting heat and entropy, melt heat capacity, Debye point and formation energy of anion and cation vacancy pairs are made. On the basis of high-temperature data on enthalpy and low-temperature literature data on heat capacity the tables of thermodynamic functions in the range of 0-2500 K for BaO, 0-1300 K for SrO and 0-3128 K for CaO are calculated

  3. Electrical Resistivity of Alkaline Earth Elements.

    Science.gov (United States)

    1976-12-01

    34Conduction in Amorphous Mg-Bi and Mg-Sb Alloys," J. Non-Cryst. Solids 2(3), 278-83, 1970. (E75407) ... .m.. 78 40. Rorschach , H. E. and Herlin, M...Constants and Some Mathematical Functions, Thirteenth Edition, John Wiley and Sons, Inc., New York, p. 92, 1966. 91. Landolt, H. I., "Numerical Values and

  4. Rare earth sulfates

    International Nuclear Information System (INIS)

    Komissarova, L.N.; Shatskij, V.M.; Pokrovskij, A.N.; Chizhov, S.M.; Bal'kina, T.I.; Suponitskij, Yu.L.

    1986-01-01

    Results of experimental works on the study of synthesis conditions, structure and physico-chemical properties of rare earth, scandium and yttrium sulfates, have been generalized. Phase diagrams of solubility and fusibility, thermodynamic and crystallochemical characteristics, thermal stability of hydrates and anhydrous sulfates of rare earths, including normal, double (with cations of alkali and alkaline-earth metals), ternary and anion-mixed sulfates of rare earths, as well as their adducts, are considered. The state of ions of rare earths, scandium and yttrium in aqueous sulfuric acid solutions is discussed. Data on the use of rare earth sulfates are given

  5. Upconversion studies in rare earth ions-doped lanthanide materials

    Indian Academy of Sciences (India)

    2014-02-08

    Feb 8, 2014 ... Home; Journals; Pramana – Journal of Physics; Volume 82; Issue 2 ... Department of Ceramic Engineering, IIT-BHU, Varanasi 221 005, India; Department of Applied Physics, Indian School of Mines, Dhanbad 826 004, India; Lasers and Spectroscopy Laboratory, Department of Physics, Banaras Hindu ...

  6. Upconversion studies in rare earth ions-doped lanthanide materials

    Indian Academy of Sciences (India)

    2014-02-08

    Feb 8, 2014 ... In our work we have used oxide and fluoride compounds of lanthanum and cerium for doping of Er3+/Yb3+ and measured the upconversion emission in visible region. 2. Sample preparation. 2.1 Oxide sample preparation. The urea combustion method was used for synthesis of the phosphor material.

  7. Systemic analysis of thermodynamic properties of lanthanide halides

    International Nuclear Information System (INIS)

    Mirsaidov, U.; Badalov, A.; Marufi, V.K.

    1992-01-01

    System analysis of thermodynamic characteristics of lanthanide halides was carried out. A method making allowances for the influence of spin and orbital moments of momentum of the main states of lanthanide trivalent ions in their natural series was employed. Unknown in literature thermodynamic values were calculated and corrected for certain compounds. The character of lanthanide halide thermodynamic parameter change depending on ordinal number of the metals was ascertained. Pronouncement of tetrad-effect in series of compounds considered was pointed out

  8. New class of Preyssler-lanthanide complexes with modified and extended structures tuned by the lanthanide contraction effect.

    Science.gov (United States)

    Qin, Chao; Song, Xue-Zhi; Su, Sheng-Qun; Dang, Song; Feng, Jing; Song, Shu-Yan; Hao, Zhao-Min; Zhang, Hong-Jie

    2012-02-28

    A family of polyoxometalate compounds based on Preyssler anions and lanthanide cations, K(5)Na(5)[{Pr(4)(H(2)O)(12)(pydc)(4)}{Na(H(2)O)P(5)W(30)O(110)}]·46H(2)O (1, H(2)pydc = pyridine-2,6-dicarboxylic acid), Na(7)[{Pr(4)(H(2)O)(20)(pydc)(2)(Ac)}{Na(H(2)O)P(5)W(30)O(110)}]·23H(2)O (2), and Na(10)H(2) [{Ln(2)(H(2)O)(10)(pydc)(2)}{Na(H(2)O)P(5)W(30)O(110)}]·XH(2)O (Ln = Sm 3, Eu 4, Gd 5; X = 11 for 3 and 5, 13 for 4), have been synthesized and characterized by elemental analysis and single crystal X-ray diffraction. Compound 1 exhibits a two-dimensional honeycomb layer which is built up from unique {Pr(4)} metallacycles and Preyssler anions. Remarkably, the strong involvement of the sodium countercations leads to the formation of a unique three-dimensional open architecture with one-dimensional channels. The 2D grid layer of compound 2 is constructed by the longest currently known rare-earth metal clusters {Pr(8)} and Preyssler anions. Isostructural compounds 3, 4, and 5, obtained by introduction of the intermediate lanthanide ions into the above reaction system, exhibit bisupporting [{Ln(2)(H(2)O)(10)(pydc)(2)}{Na(H(2)O)P(5)W(30)O(110)}](12-) polyoxometalate cluster structures. The magnetic properties of compounds 1 and 2 and the luminescent properties of compounds 3 and 4 are discussed in this paper.

  9. Ultrasmall lanthanide oxide nanoparticles for biomedical imaging and therapy

    CERN Document Server

    Lee, Gang Ho

    2014-01-01

    Most books discuss general and broad topics regarding molecular imagings. However, Ultrasmall Lanthanide Oxide Nanoparticles for Biomedical Imaging and Therapy, will mainly focus on lanthanide oxide nanoparticles for molecular imaging and therapeutics. Multi-modal imaging capabilities will discussed, along with up-converting FI by using lanthanide oxide nanoparticles. The synthesis will cover polyol synthesis of lanthanide oxide nanoparticles, Surface coatings with biocompatible and hydrophilic ligands will be discussed and TEM images and dynamic light scattering (DLS) patterns will be

  10. Lanthanide doped strontium-barium cesium halide scintillators

    Science.gov (United States)

    Bizarri, Gregory; Bourret-Courchesne, Edith; Derenzo, Stephen E.; Borade, Ramesh B.; Gundiah, Gautam; Yan, Zewu; Hanrahan, Stephen M.; Chaudhry, Anurag; Canning, Andrew

    2015-06-09

    The present invention provides for a composition comprising an inorganic scintillator comprising an optionally lanthanide-doped strontium-barium, optionally cesium, halide, useful for detecting nuclear material.

  11. Hybrid materials based on lanthanide organic complexes: a review.

    Science.gov (United States)

    Feng, Jing; Zhang, Hongjie

    2013-01-07

    A great deal of research has been carried out on lanthanide organic complex-based organic-inorganic hybrid materials in the last decade. This critical review begins with a formulation of the fundamentals of lanthanide organic complex luminescence, and presents various current designed ideas, synthetic routes, luminescence behaviors and potentials of the latest advanced (a) sol-gel materials, (b) mesoporous materials, (c) titania materials, (d) ionic liquids and ionogels, (e) polymers, and (f) bifunctional magnetic-optical composites based on lanthanide organic complexes. Finally, challenges and opportunities for further improvement of organic-inorganic hybrid luminescent materials based on lanthanide organic complexes will be discussed.

  12. Structural and thermodynamic study of rare earth(III) complexation by poly-hydroxylated carboxylic acids: synthesis of new extractants and outlook for the extraction of these cations; Etude structurale et thermodynamique de la complexation de lanthanides (III) par des acides carboxyliques polyhydroxyles: synthese de nouveaux extractants et perspectives pour l'extraction de ces cations

    Energy Technology Data Exchange (ETDEWEB)

    Aury, S

    2002-12-15

    The aim of this work is: to improve the knowledge on the binding sites of the poly-hydroxylated carboxylic acids with the trivalent lanthanide(III) ions by comparing them to gluconic acid (previously studied) and to molecules with different configuration and with a variable number of OH functions (threonic acid, glyceric acid, 2-hydroxy-butanoic acid, 3-hydroxy-butanoic acid). To find the best complexing agent among different acids (aldonic acids, aldaric acids, di-hydroxybenzoic acids) (determination of the set of complexes and their stability constants by potentiometry, NMR and UV-Visible spectroscopy). To synthesize hydrophobic monoamides from one lactone form of saccharic acid, to study their complexing power and their capacity to extract the trivalent lanthanide(III) ions. (author)

  13. Rare earths as a future resource

    International Nuclear Information System (INIS)

    Cornell, D.H.

    1988-01-01

    The fourteen rare earth or lanthanide elements have recently emerged as an important natural resource because of the rapidly growing demand in the electronic, chemical and metallurgical industries. The Symposium on rare earth elements as a future resource presented a multidisciplinary review of rare earth chemistry, geology, beneficiation, industrial applications and marketing. Papers by experts in many fields were presented on the following topics: chemical properties of the rare earth elements; the analysis of rare earth elements and minerals; beneficiation and extraction of rare earth elements; economic geochemistry and mineralogy of rare earths; present industrial uses of rare earth elements; the role of rare earth elements in high-temperature superconductors; the technical application of high-temperature superconductors; supply and demand for rare earth products - now and in the future, and the geology of rare earth deposits

  14. Lanthanide (III) complexes of N-arylthioureas

    International Nuclear Information System (INIS)

    Kalyani, S.A.; Murty, A.S.R.; Tembe, G.L.

    1999-01-01

    Lanthanide (III) complexes of the general formula, [LnX 3-m (Ptu) n ] X m .2H 2 O and [LnX 3-. m(o/m/p-Totu) n ]X m .2H O [where, Ln = Pr, Nd, Sm, Eu, Dy, Ho, Er, Yb, Y; X = NO 3 , Cl; Ptu = N-phenylthiourea, Totu = tolythiourea; m = 0, 1 and n = 3,4] have been isolated and characterized. A few complexes are 1:1 electrolytes while others are non-electrolytic in nature. Sulphur of the ligands takes part in coordination to the central metal ion. The electronic spectra have been analysed and spectral parameters calculated. Higher coordination number of six, seven and eight exhibited by some of the complexes is the characteristic feature of lanthanides. (author)

  15. Plutonium alteration phases from lanthanide borosilicate glass

    International Nuclear Information System (INIS)

    Fortner, J.A.; Mertz, C.J.; Chamberlain, D.C.; Bates, J.K.

    1997-01-01

    A prototype lanthanide borosilicate (LaBS) glass containing 10 mass % plutonium was reacted with water vapor at 200 C for periods of 14 to 56 days. These tests, while not designed to replicate specific conditions that may be found in a potential geologic repository (e.g., Yucca Mountain), have been shown to accelerate alteration phase formation. The surfaces of the glass samples, along with alteration phases, were examined with a transmission electron microscope (TEM). Tests of 14 days produced macroscopic (∼ 20 microm) crystallites of a plutonium-lanthanide silicate. An extensive alteration layer was found on the glass surface containing amorphous aluminosilicate layered with bands of a cryptocrystalline plutonium silicate. After 56 days of testing, additional alteration phases were formed, including a strontium lanthanide oxide phase. One of the options for disposal of surplus plutonium, particularly for impure residues that may be unfit for production of MOX fuel, is vitrification followed by geologic disposal. Since geologic disposal requires a passive system to isolate the radiotoxic elements from the biosphere, it is important to understand the possible corrosion mechanisms of the waste form

  16. Chemical composition of modern and fossil hippopotamid teeth and implications for paleoenvironmental reconstructions and enamel formation – Part 2: Alkaline earth elements as tracers of watershed hydrochemistry and provenance

    Directory of Open Access Journals (Sweden)

    I. Ssemmanda

    2012-11-01

    Full Text Available This study demonstrates that alkaline earth elements in enamel of hippopotamids, in particular Ba and Sr, are tracers for water provenance and hydrochemistry in terrestrial settings. The studied specimens are permanent premolar and molar teeth found in modern and fossil lacustrine sediments of the Western Branch of the East African Rift system (Lake Kikorongo, Lake Albert, and Lake Malawi and from modern fluvial environments of the Nile River. Concentrations in enamel vary by two orders of magnitude for Ba (120–9336 μg g−1 as well as for Sr (9–2150 μg g−1. The variations are partially induced during post-mortem alteration and during amelogenesis, but the major contribution originates ultimately from the variable water chemistry in the habitats of the hippopotamids which is controlled by the lithologies and weathering processes in the watershed areas. Amelogenesis causes a distinct distribution of MgO, Ba and Sr in modern and fossil enamel, in that element concentrations increase along profiles from the outer rim towards the enamel–dentin junction by a factor of 1.3–1.9. These elements are well correlated in single specimens, thus suggesting that their distribution is determined by a common, single process, which can be described by closed system Rayleigh crystallization of bioapatite in vivo. Enamel from most hippopotamid specimens has Sr/Ca and Ba/Ca which are typical for herbivores. However, Ba/Sr ranges from 0.1 to 3 and varies on spatial and temporal scales. Thus, Sr concentrations and Ba/Sr in enamel differentiate between habitats having basaltic mantle rocks or Archean crustal rocks as the ultimate sources of Sr and Ba. This provenance signal is modulated by climate change. In Miocene to Pleistocene enamel from the Lake Albert region, Ba/Sr decreases systematically with time from 2 to 0.5. This trend can be correlated with changes in climate from humid to arid, in vegetation from C3 to C4 biomass as well as with increasing

  17. Decomposition kinetics of alkaline earth carbonates by integral approximation method Cinética de decomposição de carbonatos de terra alcalina pelo método de aproximação integral

    Directory of Open Access Journals (Sweden)

    S. Maitra

    2008-09-01

    Full Text Available The decomposition kinetics of four synthetic alkaline earth metal carbonates (MgCO3, CaCO3, SrCO3 and BaCO3 was studied under non-isothermal conditions from thermo-gravimetric measurements as compared to. The integral approximation method of Coats and Redfern was used to determine the kinetic parameters for the decomposition processes. The decomposition reactions followed mostly first order kinetics and the activation energy of the decomposition reactions increased with the increase in the molecular mass of the carbonates. The change in enthalpy for the decomposition processes was also calculated and compared with the activation energies for the decomposition processes. The activation energy of the decomposition process for all the carbonates was higher than the enthalpy of the reaction excepting SrCO3.A cinética de decomposição de quatro carbonatos sintéticos de metais de terra alcalina (MgCO3, CaCO3, SrCO3 e BaCO3 foi estudada sob condições não isotérmicas por meio de medidas de termogravimétricas e feita sua comparação. O método de aproximação integral de Coats e Redfern foi usado para determinar os parâmetros cinéticos dos processos de decomposição. As reações de decomposição seguiram principalmente cinética de primeira ordem e a energia de ativação para as reações de decomposição aumentou com o aumento da massa molecular dos carbonatos. A variação na entalpia para os processos de decomposição foi também calculada e comparada com as energias de ativação. A energia de ativação dos processos de decomposição de todos os carbonatos foi maior que a entalpia da reação excepto para SrCO3.

  18. Anodes for alkaline electrolysis

    Science.gov (United States)

    Soloveichik, Grigorii Lev [Latham, NY

    2011-02-01

    A method of making an anode for alkaline electrolysis cells includes adsorption of precursor material on a carbonaceous material, conversion of the precursor material to hydroxide form and conversion of precursor material from hydroxide form to oxy-hydroxide form within the alkaline electrolysis cell.

  19. Alkaline "Permanent" Paper.

    Science.gov (United States)

    Pacey, Antony

    1991-01-01

    Discussion of paper manufacturing processes and their effects on library materials focuses on the promotion of alkaline "permanent" paper, with less acid, by Canadian library preservation specialists. Standards for paper acidity are explained; advantages of alkaline paper are described, including decreased manufacturing costs; and…

  20. Electrodeposition of alkali and alkali-earth metals on liquid lead cathodes in molten salts

    Energy Technology Data Exchange (ETDEWEB)

    Caravaca, C.; De Cordoba, G. [CIEMAT/DE/DFN/URAA. Avda. Complutense, 22. 28040 Madrid (Spain)

    2008-07-01

    Pyrochemical processing of spent nuclear fuel leads to the dissolution as chlorides of fission products (FPs) that have to be removed in order to recycle the salt. Precipitation technique have been tested for the removal of these FPs in the LiCl-KCl, salt selected as reference, with different results. Salt decontamination from lanthanides can be easily achieved as solid precipitates of oxychlorides or single phosphates; however, for the alkaline and alkaline-earth metals this technique is not suitable. Within the EUROPART project (VI FP of the EC), a new route that consist of the electrodeposition of these FP on a liquid lead cathode (LLC) has been considered, including the Li and K constituting the electrolyte. First results obtained with Sr and Cs are presented herein. Although according to the thermodynamic potential values, the electrodeposition order on LLC is Ba, Sr, Li, K and Cs, during our experiments it was not possible to distinguish the electrochemical signals corresponding to the individual elements. (authors)

  1. Improved method for extracting lanthanides and actinides from acid solutions

    Science.gov (United States)

    Horwitz, E.P.; Kalina, D.G.; Kaplan, L.; Mason, G.W.

    1983-07-26

    A process for the recovery of actinide and lanthanide values from aqueous acidic solutions uses a new series of neutral bi-functional extractants, the alkyl(phenyl)-N,N-dialkylcarbamoylmethylphosphine oxides. The process is suitable for the separation of actinide and lanthanide values from fission product values found together in high-level nuclear reprocessing waste solutions.

  2. Lanthanide ions as spectral converters for solar cells

    NARCIS (Netherlands)

    van der Ende, B.M.; Aarts, L.; Meijerink, A.

    2009-01-01

    The use of lanthanide ions to convert photons to different, more useful, wavelengths is well-known from a wide range of applications (e.g. fluorescent tubes, lasers, white light LEDs). Recently, a new potential application has emerged: the use of lanthanide ions for spectral conversion in solar

  3. Luminescent lanthanide reporters: new concepts for use in bioanalytical applications.

    Science.gov (United States)

    Vuojola, Johanna; Soukka, Tero

    2014-01-23

    Lanthanides represent the chemical elements from lanthanum to lutetium. They intrinsically exhibit some very exciting photophysical properties, which can be further enhanced by incorporating the lanthanide ion into organic or inorganic sensitizing structures. A very popular approach is to conjugate the lanthanide ion to an organic chromophore structure forming lanthanide chelates. Another approach, which has quickly gained interest, is to incorporate the lanthanide ions into nanoparticle structures, thus attaining improved specific activity and a large surface area for biomolecule immobilization. Lanthanide-based reporters, when properly shielded from the quenching effects of water, usually express strong luminescence emission, multiple narrow emission lines covering a wide wavelength range, and exceptionally long excited state lifetimes enabling time-gated luminescence detection. Because of these properties, lanthanide-based reporters have found widespread applications in various fields of life. This review focuses on the field of bioanalytical applications. Luminescent lanthanide reporters and assay formats utilizing these reporters pave the way for increasingly sensitive, simple, and easily automated bioanalytical applications.

  4. Luminescent lanthanide reporters: new concepts for use in bioanalytical applications

    International Nuclear Information System (INIS)

    Vuojola, Johanna; Soukka, Tero

    2014-01-01

    Lanthanides represent the chemical elements from lanthanum to lutetium. They intrinsically exhibit some very exciting photophysical properties, which can be further enhanced by incorporating the lanthanide ion into organic or inorganic sensitizing structures. A very popular approach is to conjugate the lanthanide ion to an organic chromophore structure forming lanthanide chelates. Another approach, which has quickly gained interest, is to incorporate the lanthanide ions into nanoparticle structures, thus attaining improved specific activity and a large surface area for biomolecule immobilization. Lanthanide-based reporters, when properly shielded from the quenching effects of water, usually express strong luminescence emission, multiple narrow emission lines covering a wide wavelength range, and exceptionally long excited state lifetimes enabling time-gated luminescence detection. Because of these properties, lanthanide-based reporters have found widespread applications in various fields of life. This review focuses on the field of bioanalytical applications. Luminescent lanthanide reporters and assay formats utilizing these reporters pave the way for increasingly sensitive, simple, and easily automated bioanalytical applications. (topical review)

  5. Separation and estimation of lanthanides using high performance liquid chromatography

    International Nuclear Information System (INIS)

    Datta, Arpita; Sivaraman, N.; Vasudeva Rao, P.R.

    2012-01-01

    The separation efficiency of individual lanthanides depends on the stability constant of the metal-ligand complex. Therefore, stability constant data of lanthanide complexes is important in the development of high performance separation procedures. The dynamic ion exchange HPLC technique was employed at our laboratory to estimate the stability constant of lanthanides with various complexing agents. In these studies, the retention times as well as capacity factors of lanthanides and some actinides were measured as a function of CSA, complexing agent concentrations and mobile phase pH. From these studies, a correlation has been established between capacity factor of a metal ion, concentrations of ion-pairing reagent and complexing agent with the stability constant of lanthanide complex

  6. Leaching and Group Separation of Lanthanides from Phosphogypsum

    International Nuclear Information System (INIS)

    El-Reefy, S.A.; Nayl, A.A.; Aly, H.F.

    2008-01-01

    Phosphogypsum (PG) is obtained as a by-product solid waste as a result of decomposition of phosphate ores with H 2 SO 4 solution for production of phosphoric acid. Lanthanides content in PG produced from Sebaiya ore is found to be about 0.022%. Leaching of total lanthanides from this PG has been studied and optimized. Maximum leaching of lanthanides 76 % was obtained using a mixture of 2-3 M nitric acid and 0.8 M calcium nitrate. Purification of lanthanides from the leached solution was carried out by both solvent extraction and ion exchange processes. The efficiency of lanthanides recovered by solvent extraction using TBP was 93 % whereby the efficiency using ion exchange chromatography was 98%. A flow sheet for the two processes is given

  7. Experimental solubility measurements of lanthanides in liquid alkalis

    Science.gov (United States)

    Isler, Jeremy; Zhang, Jinsuo; Mariani, Robert; Unal, Cetin

    2017-11-01

    In metallic nuclear fuel, lanthanide fission products play a crucial role in the fuel burnup-limiting phenomena of fuel cladding-chemical interaction (FCCI). The lanthanides have been hypothesized to transport by a 'liquid-like' mechanism out of the metallic fuel to the fuel peripheral to cause FCCI. By liquid fission product cesium and liquid bond sodium, the lanthanides are transported to the peripheral of the fuel through the porosity of the fuel. This work investigates the interaction between the lanthanides and the alkali metals by experimentally measuring the solubility of lanthanides within liquid sodium, and neodymium in liquid cesium and mixtures of cesium and sodium. The temperature dependence of the solubility is experimentally determined within an inert environment. In addition, the dependence of the solubility on the alkali metal concentration in liquid mixtures of cesium and sodium was examined. In quantifying the solubility, the fundamental understanding of this transport mechanism can be better determined.

  8. Luminescent lanthanide complexes as analytical tools in anion sensing, pH indication and protein recognition.

    Science.gov (United States)

    Shinoda, Satoshi; Tsukube, Hiroshi

    2011-02-07

    Although lanthanide complexes are recently used in luminescence labeling of bio-targets, this review focuses on sensing profiles of synthetic and biological lanthanide complexes. Rational design and combinatorial screening approaches toward synthetic lanthanide complexes applicable as luminescent sensing materials are described. Iron-carrying transferrin and ferritin proteins further form lanthanide complexes working as pH indicators and protein recognition reagents.

  9. Detection scheme for bioassays based on 2,6-pyridinedicarboxylic acid derivatives and enzyme-amplified lanthanide luminescence

    Energy Technology Data Exchange (ETDEWEB)

    Steinkamp, Tanja [Department of Chemical Analysis, MESA Institute for Nanotechnology, University of Twente, P.O. Box 217, 7500 AE Enschede (Netherlands); Karst, Uwe [Department of Chemical Analysis, MESA Institute for Nanotechnology, University of Twente, P.O. Box 217, 7500 AE Enschede (Netherlands)]. E-mail: u.karst@utwente.nl

    2004-11-15

    2,6-Pyridinedicarboxylic acid (PDC) and its derivatives are introduced as a new sensitizer system for enzyme-amplified lanthanide luminescence (EALL), a detection scheme for bioassays, which combines enzymatic amplification with time-resolved luminescence measurements of lanthanide chelates. Various PDC esters have been synthesized as esterase substrates that are cleaved to PDC in the presence of the enzyme. PDC forms luminescent complexes with Tb(III) or Eu(III), and the evaluation of the reaction is used for the selective and sensitive detection of esterases. For an esterase from hog liver a limit of detection of 10{sup -3} u/mL (equivalent to 10{sup -9} mol/L) and a limit of quantification of 3 x 10{sup -3} u/mL (equivalent to 3 x 10{sup -9} mol/L) could be achieved. As a second model reaction, xanthine oxidase (XOD) catalyzes the oxidation of 2,6-pyridinedicarboxaldehyde to PDC. Here, the limit of detection was 3 x 10{sup -3} u/mL and the limit of quantification 10{sup -2} u/mL for XOD from microorganisms. Major advantage of the tridentate PDC ligand is the possibility to perform all steps of the assay within or close to the physiological pH range, while the established EALL schemes based on bidentate salicylates or bisphenols have to be carried out at strongly alkaline pH to ensure sufficient complexation with the lanthanides.

  10. IR and Raman spectroscopic studies of sol–gel derived alkaline ...

    Indian Academy of Sciences (India)

    The extent of network depolymerization in the porous glass is higher at the same content of alkaline earth oxide compared to the bulk glass. ... ral properties. Silicate glasses that contain calcium and phos- phorus are known to ... guration of silica glasses modified by alkaline earth oxides. (MgO, CaO) prepared by the sol–gel ...

  11. Separation device of radio lanthanides (DISER)

    International Nuclear Information System (INIS)

    Vera T, A.L.; Monroy G, F.; Vazquez M, J.C.; Jimenez B, F.

    2008-01-01

    At the present time the cancer is one of the main causes of mortality in our country, therefore, its prevention, diagnostic and treatment is of vital importance for those health systems. The treatment of the cancer and other illnesses, starting from monoclonal antibodies, peptides, macro aggregates or marked aminoacids with beta particles emitting radioisotopes, it is an extremely promising field. The radioactive lanthanides: Promethium 149, Terbium 161, Holmium 166 and Lutetium 177 are beta emitting (β), which possess nuclear and chemical properties that have shown their feasibility like radioisotopes of radiotherapeutic use. However, these radioisotopes are not commercially available; to this respect, the Radioactive Materials Research Laboratory (LIMR) of the National Institute of Nuclear Research (ININ), it has developed the methodology of production of these radioisotopes and based on these works, there is designed, built and mounted the Radio lanthanides Separation Device (DISER) able to carry out the radioisotopes production in a routine way. This device is content in a cell that has an auxiliary air service, an extraction system and it is protected with a lead armor-plating of 10 cm. The DISER it is manual and easy of managing. The main function of this equipment is the radio lanthanides separation starting from the extractive chromatography by means of packed columns with a commercial resin (LnSPS) and recovered in the superior and inferior part by fiber glass. The DISER is composed by a main carrousel where the separation columns and the elution recipients are mounted. Also counts with an opening system of irradiation vials, port samples for columns and glass material. The present work presents a detailed description of the DISER, as well as its handling that allows to produce the radioisotopes Promethium-149, Terbium-161, Holmium-166 and Lutetium-177 starting from the separation of its parent elements Neodymium-149, Gadolinium-161, Dysprosium-166 and

  12. Alkaline battery operational methodology

    Science.gov (United States)

    Sholklapper, Tal; Gallaway, Joshua; Steingart, Daniel; Ingale, Nilesh; Nyce, Michael

    2016-08-16

    Methods of using specific operational charge and discharge parameters to extend the life of alkaline batteries are disclosed. The methods can be used with any commercial primary or secondary alkaline battery, as well as with newer alkaline battery designs, including batteries with flowing electrolyte. The methods include cycling batteries within a narrow operating voltage window, with minimum and maximum cut-off voltages that are set based on battery characteristics and environmental conditions. The narrow voltage window decreases available capacity but allows the batteries to be cycled for hundreds or thousands of times.

  13. Crystal structures and thermal decomposition of permanganates AE[MnO{sub 4}]{sub 2} . n H{sub 2}O with the heavy alkaline earth elements (AE=Ca, Sr and Ba)

    Energy Technology Data Exchange (ETDEWEB)

    Henning, Harald; Bauchert, Joerg M.; Conrad, Maurice; Schleid, Thomas [Stuttgart Univ. (Germany). Inst. fuer Anorganische Chemie

    2017-10-01

    Reexamination of the syntheses and crystal structures as well as studies of the thermal decomposition of the heavy alkaline earth metal permanganates Ca[MnO{sub 4}]{sub 2} . 4 H{sub 2}O, Sr[MnO{sub 4}]{sub 2} . 3 H{sub 2}O and Ba[MnO{sub 4}]{sub 2} are the focus of this work. As an alternative to the very inelegant Muthmann method, established for the synthesis of Ba[MnO{sub 4}]{sub 2} a long time ago, we employed a cation-exchange column loaded with Ba{sup 2+} cations and passed through an aqueous potassium-permanganate solution. We later used this alternative also with strontium- and calcium-loaded columns and all the compounds synthesized this way were indistinguishable from the products of the established methods. Ca[MnO{sub 4}]{sub 2} . 4 H{sub 2}O exhibiting [CaO{sub 8}] polyhedra crystallizes in the orthorhombic space group Pccn with the lattice parameters a=1397.15(9), b=554.06(4) and c=1338.97(9) pm with Z=4, whereas Sr[MnO{sub 4}]{sub 2} . 3 H{sub 2}O with [SrO{sub 10}] polyhedra adopts the cubic space group P2{sub 1}3 with a=964.19(7) pm and Z=4. So the harder the AE{sup 2+} cation, the higher its demand for hydration in aqueous solution. Consequently, the crystal structure of Ba[MnO{sub 4}]{sub 2} in the orthorhombic space group Fddd with a=742.36(5), b=1191.23(7) and c=1477.14(9) pm with Z=8 lacks any crystal water, but contains [BaO{sub 12}] polyhedra. During the thermal decomposition of Ca[MnO{sub 4}]{sub 2} . 4 H{sub 2}O, the compound expels up to two water molecules of hydration, before the crystal structure collapses after the loss of the third H{sub 2}O molecule at 157 C. The crystal structure of Sr[MnO{sub 4}]{sub 2} . 3 H{sub 2}O breaks down after the expulsion of the third water molecule as well, but this already occurs at 148 C. For both the calcium and the strontium permanganate samples, orthobixbyite-type α-Mn{sub 2}O{sub 3} and the oxomanganates(III,IV) AEMn{sub 3}O{sub 6} (AE=Ca and Sr) remain as final decomposition products at 800 C

  14. Structure and Magnetic Properties of Lanthanide Nanocrystals

    Energy Technology Data Exchange (ETDEWEB)

    Dickerson, James Henry [Vanderbilt Univ., Nashville, TN (United States)

    2014-06-01

    We have had considerable success on this project, particularly in the understanding of the relationship between nanostructure and magnetic properties in lanthanide nanocrystals. We also have successfully facilitated the doctoral degrees of Dr. Suseela Somarajan, in the Department of Physics and Astronomy, and Dr. Melissa Harrison, in the Materials Science Program. The following passages summarize the various accomplishments that were featured in 9 publications that were generated based on support from this grant. We thank the Department of Energy for their generous support of our research efforts in this area of materials science, magnetism, and electron microscopy.

  15. Complexes of Lapachol and Lawsone with Lanthanides.

    Science.gov (United States)

    Genovese, Salvatore; Taddeo, Vito Alessandro; Epifano, Francesco; Fiorito, Serena

    2015-11-01

    Naturally occurring 2-hydroxy-1,4-naphthoquinones are well known to form readily stable complexes with transition metals. In this short communication we describe for the first time the synthesis and preliminary data about structural characterization of complexes between two naturally widespread 2-hydroxy-1,4-naphthoquinones, namely lapachol (1) and lawsone (2), with selected lanthanides like lanthanum, gadolinium, and ytterbium. When tested as cytotoxic compounds, such complexes exhibited an activity that was either higher or equal to that of the parent naphthoquinone.

  16. Lanthanide Organophosphate Spiro Polymers: Synthesis, Structure, and Magnetocaloric Effect in the Gadolinium Polymer.

    Science.gov (United States)

    Gupta, Sandeep K; Bhat, Gulzar A; Murugavel, Ramaswamy

    2017-08-07

    Spirocyclic lanthanide organophosphate polymers, {[Ln(dipp)(dippH)(CH 3 OH)(H 2 O) 2 ](CH 3 OH) 2 } n [Ln = La (1), Ce (2), Pr (3), Nd (4), Sm (5), Eu (6), Gd (7), Tb (8), Dy (9), Ho (10), Er (11)], have been prepared from the reaction of Ln(NO 3 ) 3 ·xH 2 O with sterically hindered 2,6-diisopropylphenyl phosphate (dippH 2 ) using aqueous NaOH as the base. The one-dimensional chainlike lanthanide (III) organophosphate coordination polymers have been characterized with the aid of analytical and spectroscopic methods. The single crystal structure determination of polymers (2-5 and 7-11) reveals that in these compounds the hydrophobic organic groups of the phosphate provide a protective coating for the inorganic lanthanide phosphate polymeric chain. The encapsulation of inorganic lanthanide phosphate core, which has very low solubility product, within the organic groups assists in the facile crystallization of the polymers. The di- and monoanionic organophosphate ligands dipp 2- and dippH - display [2.111] and [2.110] binding modes, respectively, in 2-5 and 7. However, they exhibit only [2.110] binding mode in the case of 8-11. This results in the formation of two different types of polymers. While the lighter rare-earth metal ions in 2-5 and 7 display eight coordinate biaugmented trigonal prismatic geometry, the heavier rare-earth metal ions in 9-11 exhibit a seven coordinate capped trigonal prismatic environment. The Tb(III) ion in 8 displays distorted pentagonal bipyramidal geometry. Magnetic studies reveal the presence of weak antiferromagnetic interactions between the Ln(III) ions through the organophosphate ligand. The isotropic Gd(III) polymer 7 exhibits a maximum entropy change of 17.83 J kg -1 K -1 for a field change of 7.0 T at 2.5 K, which is significant considering the high molecular weight of the organophosphate ligand. These polymers represent the first family of any structurally characterized rare-earth organophosphate polymers derived from monoesters

  17. Uranium in alkaline rocks

    International Nuclear Information System (INIS)

    Murphy, M.; Wollenberg, H.; Strisower, B.; Bowman, H.; Flexser, S.; Carmichael, I.

    1978-04-01

    Geologic and geochemical criteria were developed for the occurrence of economic uranium deposits in alkaline igneous rocks. A literature search, a limited chemical analytical program, and visits to three prominent alkaline-rock localities (Ilimaussaq, Greenland; Pocos de Caldas, Brazil; and Powderhorn, Colorado) were made to establish criteria to determine if a site had some uranium resource potential. From the literature, four alkaline-intrusive occurrences of differing character were identified as type-localities for uranium mineralization, and the important aspects of these localities were described. These characteristics were used to categorize and evaluate U.S. occurrences. The literature search disclosed 69 U.S. sites, encompassing nepheline syenite, alkaline granite, and carbonatite. It was possible to compare two-thirds of these sites to the type localities. A ranking system identified ten of the sites as most likely to have uranium resource potential

  18. Uranium in alkaline rocks

    Energy Technology Data Exchange (ETDEWEB)

    Murphy, M.; Wollenberg, H.; Strisower, B.; Bowman, H.; Flexser, S.; Carmichael, I.

    1978-04-01

    Geologic and geochemical criteria were developed for the occurrence of economic uranium deposits in alkaline igneous rocks. A literature search, a limited chemical analytical program, and visits to three prominent alkaline-rock localities (Ilimaussaq, Greenland; Pocos de Caldas, Brazil; and Powderhorn, Colorado) were made to establish criteria to determine if a site had some uranium resource potential. From the literature, four alkaline-intrusive occurrences of differing character were identified as type-localities for uranium mineralization, and the important aspects of these localities were described. These characteristics were used to categorize and evaluate U.S. occurrences. The literature search disclosed 69 U.S. sites, encompassing nepheline syenite, alkaline granite, and carbonatite. It was possible to compare two-thirds of these sites to the type localities. A ranking system identified ten of the sites as most likely to have uranium resource potential.

  19. Spectral studies of Lanthanide interactions with membrane surfaces

    Energy Technology Data Exchange (ETDEWEB)

    Karukstis, K.K.; Kao, M.Y.; Savin, D.A.; Bittker, R.A.; Kaphengst, K.J.; Emetarom, C.M.; Naito, N.R.; Takamoto, D.Y. [Harvey Mudd College, Claremont, CA (United States)

    1995-03-23

    We have monitored the interactions of the series of trivalent lanthanide cations with the thylakoid membrane surface of spinach chloroplasts using two complementary spectral techniques. Measurements of the fluorescence emission of the extrinsic probe 2-p-toluidinonaphthalene-6-sulfonate (TNS) and the absorbance of the intrinsic chromophore chlorophyll provide two sensitive means of characterizing the dependence of the cation-membrane interaction on the nature of the cation. In these systems, added lanthanide cations adsorb onto the membrane surface to neutralize exposed segments of membrane-embedded protein complexes. The lanthanide-induced charge neutralization increases the proximity of added TNS anion to the membrane surface as evidenced by variations in the TNS fluorescence level and wavelength of maximum emission. Our results reveal a strong dependence of TNS fluorescence parameters on both lanthanide size and total orbital angular momentum L value. Lanthanides with greater charge density (small size and/or low L value) enhance the TNS fluorescence level to a greater extent. A possible origin for the lanthanide-dependent TNS fluorescence levels is suggested in terms of a heterogeneity in the number and type of TNS binding sites. The data are consistent with the proposal that larger lanthanides with smaller enthalpies of hydration induce more significant membrane appression. 59 refs., 9 figs., 2 tabs.

  20. Lanthanide (III) complexes of 2-(N-salicylideneamino)-4-phenylthiazole

    International Nuclear Information System (INIS)

    Sasidharan, G.N.; Mohanan, K.; Lakshmi Prabha, A.N.

    2002-01-01

    Lanthanide(III) complexes of 2-(N-salicylideneamino)-4- phenylthiazole (HSAT) have been synthesised and characterised by elemental, analytical, thermogravimetric, molar conductance, UV- visible, IR and NMR spectral data. The ligand coordinates to the lanthanide(III) ion in a tridentate fashion without deprotonation, giving complexes of the type [Ln(HSAT) 2 (NO 3 ) 3 ] and [Ln(HSAT) 2 (H 2 0) 3 Cl 3 ]. The spectral data reveal that the ligand is bonded to the lanthanide ion through azomethine nitrogen, ring nitrogen and phenolic oxygen without deprotonation. The nitrate group acts in a bidentate fashion. The ligand and the metal complexes exhibit antibacterial and antifungal activities. (author)

  1. Lanthanide-doped upconverting phosphors for bioassay and therapy

    Science.gov (United States)

    Guo, Huichen; Sun, Shiqi

    2012-10-01

    Lanthanide-doped fluorescent materials have gained increasing attention in recent years due to their unique luminescence properties which have led to their use in wide-ranging fields including those of biological applications. Aside from being used as agents for in vivo imaging, lanthanide-doped fluorescent materials also present many advantages for use in bioassays and therapy. In this review, we summarize the applications of lanthanide-doped up-converting phosphors (UCPs) in protein and gene detection, as well as in photodynamic and gene therapy in recent years, and outline their future potential in biological applications. The current report could serve as a reference for researchers in relevant fields.

  2. Liquidus temperature and chemical durability of selected glasses to immobilize rare earth oxides waste

    Science.gov (United States)

    Mohd Fadzil, Syazwani; Hrma, Pavel; Schweiger, Michael J.; Riley, Brian J.

    2015-10-01

    Pyroprocessing is are processing method for managing and reusing used nuclear fuel (UNF) by dissolving it in an electrorefiner with a molten alkali or alkaline earth chloride salt mixture while avoiding wet reprocessing. Pyroprocessing UNF with a LiCl-KCl eutectic salt releases the fission products from the fuel and generates a variety of metallic and salt-based species, including rare earth (RE) chlorides. If the RE-chlorides are converted to oxides, borosilicate glass is a prime candidate for their immobilization because of its durability and ability to dissolve almost any RE waste component into the glass matrix at high loadings. Crystallization that occurs in waste glasses as the waste loading increases may complicate glass processing and affect the product quality. This work compares three types of borosilicate glasses in terms of liquidus temperature (TL): the International Simple Glass designed by the International Working Group, sodium borosilicate glass developed by Korea Hydro and Nuclear Power, and the lanthanide aluminoborosilicate (LABS) glass established in the United States. The LABS glass allows the highest waste loadings (over 50 mass% RE2O3) while possessing an acceptable chemical durability.

  3. Chemistry of Selected Core Samples, Concentrate, Tailings, and Tailings Pond Waters: Pea Ridge Iron (-Lanthanide-Gold) Deposit, Washington County, Missouri

    Science.gov (United States)

    Grauch, Richard I.; Verplanck, Philip L.; Seeger, Cheryl M.; Budahn, James R.; Van Gosen, Bradley S.

    2010-01-01

    The Minerals at Risk and for Emerging Technologies Project of the U.S. Geological Survey (USGS) Mineral Resources Program is examining potential sources of lanthanide elements (rare earth elements) as part of its objective to provide up-to-date geologic information regarding mineral commodities likely to have increased demand in the near term. As part of the examination effort, a short visit was made to the Pea Ridge iron (-lanthanide-gold) deposit, Washington County, Missouri in October 2008. The deposit, currently owned by Wings Enterprises, Inc. of St. Louis, Missouri (Wings), contains concentrations of lanthanides that may be economic as a primary product or as a byproduct of iron ore production. This report tabulates the results of chemical analyses of the Pea Ridge samples and compares rare earth elements contents for world class lanthanide deposits with those of the Pea Ridge deposit. The data presented for the Pea Ridge deposit are preliminary and include some company data that have not been verified by the USGS or by the Missouri Department of Natural Resources, Division of Geology and Land Survey (DGLS), Geological Survey Program (MGS). The inclusion of company data is for comparative purposes only and does not imply an endorsement by either the USGS or MGS.

  4. Exploring the effect of remote substituents and solution structure on the luminescence of three lanthanide complexes

    Energy Technology Data Exchange (ETDEWEB)

    Tropiano, Manuel; Blackburn, Octavia A.; Tilney, James A.; Hill, Leila R. [Chemistry Research Laboratory, University of Oxford, 12 Mansfield Road, Oxford OX1 3TA (United Kingdom); Just Sørensen, Thomas, E-mail: TJS@chem.ku.dk [Chemistry Research Laboratory, University of Oxford, 12 Mansfield Road, Oxford OX1 3TA (United Kingdom); Nano-Science Center and Department of Chemistry, University of Copenhagen, Universitetsparken 5, 2100 København Ø (Denmark); Faulkner, Stephen, E-mail: stephen.faulkner@chem.ox.ac.uk [Chemistry Research Laboratory, University of Oxford, 12 Mansfield Road, Oxford OX1 3TA (United Kingdom)

    2015-11-15

    Sensitized luminescence from trivalent lanthanide ions relies on an appropriate energy match between the sensitizer’s excited state (triplet or singlet) and the lanthanide excited state manifold, and also an efficient mechanism of energy transfer between the two. Here, the effect of remote substituents on the luminescence properties of a series of related lanthanide complexes has been investigated. The sensitized lanthanide centered emission is not invariably found to occur following excitation of all chromophores in all systems, and it is shown that only the most structurally congested of the systems investigated exhibited pronounced solvatochromism. - Highlights: • Effect of remote substituents and self-assembly on lanthanide luminescence. • Molecular structure rather than chromophore density defines lanthanide sensitization. • Kimura's and Horrocks' approach to determine lanthanide solvation is revisited. • Solvent alters sensitization pathways in multinuclear lanthanide complexes. • Increasing chromophore density may reduce lanthanide luminescence.

  5. Alkaline phosphatase: an overview.

    Science.gov (United States)

    Sharma, Ujjawal; Pal, Deeksha; Prasad, Rajendra

    2014-07-01

    Alkaline phosphatase (ALP; E.C.3.I.3.1.) is an ubiquitous membrane-bound glycoprotein that catalyzes the hydrolysis of phosphate monoesters at basic pH values. Alkaline phosphatase is divided into four isozymes depending upon the site of tissue expression that are Intestinal ALP, Placental ALP, Germ cell ALP and tissue nonspecific alkaline phosphatase or liver/bone/kidney (L/B/K) ALP. The intestinal and placental ALP loci are located near the end of long arm of chromosome 2 and L/B/K ALP is located near the end of the short arm of chromosome 1. Although ALPs are present in many mammalian tissues and have been studied for the last several years still little is known about them. The bone isoenzyme may be involved in mammalian bone calcification and the intestinal isoenzyme is thought to play a role in the transport of phosphate into epithelial cells of the intestine. In this review, we tried to provide an overview about the various forms, structure and functions of alkaline phosphatase with special focus on liver/bone/kidney alkaline phosphatase.

  6. Fragment molecular orbital method for studying lanthanide interactions with proteins

    Energy Technology Data Exchange (ETDEWEB)

    Tsushima, Satoru [Helmholtz-Zentrum Dresden-Rossendorf e.V., Dresden (Germany). Biophysics; Komeiji, Y. [National Institute of Advanced Industrial Science and Technology (AIST), Tsukuba (Japan); Mochizuki, Y. [Rikkyo Univ., Tokyo (Japan)

    2017-06-01

    The binding affinity of the calcium-binding protein calmodulin towards Eu{sup 3+} was studied as a model for lanthanide protein interactions in the large family of ''EF-hand'' calcium-binding proteins.

  7. Lanthanides migration and immobilization in U-Zr nuclear fuels

    Energy Technology Data Exchange (ETDEWEB)

    Bozzolo, G., E-mail: guille_bozzolo@yahoo.com [Argonne National Laboratory, 9700 S. Cass Ave, Argonne, IL 60439 (United States); Hofman, G.L.; Yacout, A.M. [Argonne National Laboratory, 9700 S. Cass Ave, Argonne, IL 60439 (United States); Mosca, H.O. [Gerencia de Investigaciones y Aplicaciones, CNEA, Av. Gral Paz 1499, B165KNA, San Martin, Buenos Aires (Argentina)

    2012-06-15

    Redistribution of lanthanides fission products during irradiation and migration to the surface of U-Zr based metallic fuels is a concern due to their interaction with the cladding. The existing remedy for preventing this effect is the introduction of diffusion barriers on the cladding inner surface or by adding thermodynamically stable compound-forming elements to the fuel. Exploring this second option, in this work atomistic modeling with the Bozzolo-Ferrante-Smith (BFS) method for alloys is used to study the formation of lanthanide-rich precipitates in U-Zr fuel and the segregation patterns of all constituents to the surface. Surface energies for all elements were computed and, together with the underlying concepts of the computational methodology and large scale simulations, the migration of lanthanides to the surface region in U-Zr fuels is explained. The role of additions to the fuel such as In, Ga, and Tl for immobilization of lanthanides is discussed.

  8. Lanthanide-doped luminescent nanomaterials from fundamentals to bioapplications

    CERN Document Server

    Chen, Xueyuan; Tu, Datao

    2014-01-01

    Lanthanide-Doped Luminescent Nanomaterials reviews the latest advances in the development of lanthanide-doped luminescent inorganic nanoparticles for potential bioapplications. This book covers the chemical and physical fundamentals of these nanoparticles, such as the controlled synthesis methodology, surface modification chemistry, optical physics, and their promising applications in diverse bioassays, with an emphasis on heterogeneous and homogeneous in-vitro biodetection of tumor biomarkers. This book is intended for those readers who are interested in systematically understanding the materials design strategy, optical behavior of lanthanide ions, and practical bioapplications of lanthanide nanoparticles. It primarily focuses on the interdisciplinary frontiers in chemistry, physics and biological aspects of luminescent nanomaterials. All chapters were written by scientists active in this field and for a broad audience, providing both beginners and advanced researchers with comprehensive information on the ...

  9. Some high coordination compounds of lanthanides(III) derived from ...

    African Journals Online (AJOL)

    isonicotinamidosalicyaldimine. Ram K. Agarwal, Himanshu Agarwal. Abstract. A new series of lanthanide(III) nitrates, isothiocyanates and perchlorates coordination complexes of N-isonicotinamidosalicyaldimine (INH-SAL) with the general composition ...

  10. Luminescent lanthanide nanomaterials: an emerging tool for theranostic applications.

    Science.gov (United States)

    Ranjan, Shashi; Jayakumar, Muthu Kumara Gnanasammandhan; Zhang, Yong

    2015-05-01

    Lanthanide materials have been gaining popularity for use in various theranostic applications, primarily due to their unique optical properties such as narrow emission bands, multiple emission wavelengths, emission tunability, long fluorescence lifetime and large Stokes shift. Apart from these, some lanthanide materials also exhibit magnetic and light-up conversion properties. Such nanomaterials have been used for a wide range of applications ranging from detection of biomarkers, in vitro and in vivo imaging to therapeutic applications. Recently, combined modalities of lanthanide nanomaterials for simultaneous detection/imaging and delivery of therapeutic agents (termed 'theranostics') have been explored. The various advantages and disadvantages of using lanthanide nanomaterials as theranostic agents and potential areas for future development have been discussed in this review.

  11. Chromatographic behavior of carbonate complexes of lanthanides and of thorium in alumina

    International Nuclear Information System (INIS)

    Tomida, E.K.

    1977-01-01

    The chromatographic behavior of some rare earth elements and thorium on alumina is studied in order to evaluate the possibility of separation from concentration of trace rare earths from high-purity thorium compounds. The effect of some factors on complex thorium carbonate formation and the extent of thorium solubility in sodium and potassium carbonate solutions investigated. The sorption of rare earth elements and thoriuum on alumina from alkali carbonate solution is observed, despite the reports that alumina acts as a cation exchanger in alkali media and that thorium and rare earths form stable anionic carbonate complexes. The formation of these elements between alumina and potassium carbonate solutions is studied as a function of pH, carbonate concentration and metal ion concentration. Also the elution of rare earths from alumina is studied and the best results are obtained with mineral acids and EDTA plus alkali carbonate solutions. The effect of some parameters as column aging, mixed solvents, column treatment with organic solvents, temperature, aluant concentration is investigated. Attempting to understand this sorption mechanism, some experiments with strongly basic anion exchanger and cation exchangers of strongly acid and weakly acid type are accomplished. It is observed that there are significant differences, in some conditions, between the behavior of rare earths and of thorium, pointing our the possibility of separation of one lanthanide from others and of these from thorium [pt

  12. Advanced alkaline water electrolysis

    International Nuclear Information System (INIS)

    Marini, Stefania; Salvi, Paolo; Nelli, Paolo; Pesenti, Rachele; Villa, Marco; Berrettoni, Mario; Zangari, Giovanni; Kiros, Yohannes

    2012-01-01

    A short review on the fundamental and technological issues relevant to water electrolysis in alkaline and proton exchange membrane (PEM) devices is given. Due to price and limited availability of the platinum group metal (PGM) catalysts they currently employ, PEM electrolyzers have scant possibilities of being employed in large-scale hydrogen production. The importance and recent advancements in the development of catalysts without PGMs are poised to benefit more the field of alkaline electrolysis rather than that of PEM devices. This paper presents our original data which demonstrate that an advanced alkaline electrolyzer with performances rivaling those of PEM electrolyzers can be made without PGM and with catalysts of high stability and durability. Studies on the advantages/limitations of electrolyzers with different architectures do show how a judicious application of pressure differentials in a recirculating electrolyte scheme helps reduce mass transport limitations, increasing efficiency and power density.

  13. Fluorescence of lanthanide(III) complexes in aqueous solutions

    International Nuclear Information System (INIS)

    Elbanowski, M.; Lis, S.; Makowska, B.; Konarski, J.

    1985-01-01

    The fluorescence of lanthanide ions and of their complexes with EDTA, NTA and AA in aqueous solutions was investigated. It has been shown that the fluorescence band intensities of Sm(III), Eu(III), Gd(III), Tb(III) and Dy(III) complexes depend on the pH and the complexing agent concentration. Fluorescence measurements were used to characterise the lanthanide complexes formed and an attempt was made to interpret the results theoretically. (Author)

  14. Lanthanide extraction with 2,5-dimethyl-2-hydroxyhexanoic acid

    International Nuclear Information System (INIS)

    Miller, J.H.

    1977-12-01

    This research is concerned with the solvent extraction into chloroform of the lanthanides, using 2,5-dimethyl-2-hydroxyhexanoic acid (DMHHA). This acid is the first α-hydroxy aliphatic acid to be studied as an extracting agent for the lanthanides. The chloroform-water DMHHA partition constant was determined to be 1.0 (at 0.1 M ionic strength and 25 0 C). The acid dimerizes in chloroform with a constant of 56. The light lanthanides can be extracted into chloroform by forming complexes with the DMHHA anions. The extracted metal species is highly aggregated. This extraction has a solubility limit which increases with the addition of unionized acid. The resultant extract is also highly aggregated. At unionized acid-to-metal ratios greater than one, extractions first occur followed by the slow precipitation of the lanthanide. At the tracer level, neodymium is extracted primarily as NdA 3 (HA) 5 and (NdA 3 ) 2 (HA)/sub q/. Very small amounts of (NdA 3 ) 2 and other metal aggregates are also present. The heavy lanthanides do not extract from solutions of DMHHA and its potassium salt, but form aqueous emulsions and precipitates. In the presence of the organic soluble tetrabutylammonium ion the heavy lanthanides can be extracted, presumably as ion pairs. The stability constants of the light lanthanides and DMHHA were determined. The separation factors obtained from DMHHA extractions of the light lanthanides were also investigated and found to be comparable to those obtained employing normal aliphatic carboxylic acid

  15. Polysulfide coordination clusters of the lanthanides

    Energy Technology Data Exchange (ETDEWEB)

    Ma, Ying-Zhao; Bestgen, Sebastian; Gamer, Michael T.; Roesky, Peter W. [Institute of Inorganic Chemistry, Karlsruhe Institute of Technology, Karlsruhe (Germany); Konchenko, Sergey N. [Institute of Inorganic Chemistry, Karlsruhe Institute of Technology, Karlsruhe (Germany); Nikolaev Institute of Inorganic Chemistry, SB RAS, Novosibirsk (Russian Federation); Novosibirsk State University (Russian Federation)

    2017-10-16

    The reaction of [(DippForm){sub 2}Ln(thf){sub 2}] with an excess of elemental sulfur in toluene resulted in the formation of the trinuclear polysulfide coordination clusters [(DippForm){sub 3}Ln{sub 3}S{sub 12}] (Ln=Sm, Yb; DippForm=N,N'-bis(2,6-diisopropylphenyl)formamidinate). These are the first f element coordination clusters (Ln{sub n}S{sub x}) with a larger polysulfide unit (n and x>2). The formation of the coordination clusters can be rationalized by the reductive cleavage of S{sub 8} with divalent lanthanides. (copyright 2017 Wiley-VCH Verlag GmbH and Co. KGaA, Weinheim)

  16. [Advances of alkaline amylase production and applications].

    Science.gov (United States)

    Yang, Haiquan; Liu, Long; Li, Jianghua; Du, Guocheng; Chen, Jian

    2012-04-01

    Alkaline amylase is one of alkaline enzymes with optimum pH in the alkaline range, and it could keep stability and efficiently hydrolyze starch under alkaline conditions. Alkaline amylase finds wide applications in textile, detergent, pharmaceutical, food and other fields. Alkaline amylases could be produced by alkaliphilic microorganisms. In this work, the advances of alkaline amylase production and applications were reviewed.

  17. Determination of lanthanides by source excited energy dispersive X-ray fluorescence (EDXRF) method after preconcentration with ammonium pyrrolidine dithiocarbamate (APDC)

    Energy Technology Data Exchange (ETDEWEB)

    Orescanin, Visnja [Rudjer Boskovic Institute, Centre for Marine and Environment Research, Bijenicka cesta 54, 10002 Zagreb (Croatia)]. E-mail: vobescan@irb.hr; Mikelic, Luka [Rudjer Boskovic Institute, Centre for Marine and Environment Research, Bijenicka cesta 54, 10002 Zagreb (Croatia); Roje, Vibor [Rudjer Boskovic Institute, Centre for Marine and Environment Research, Bijenicka cesta 54, 10002 Zagreb (Croatia); Lulic, Stipe [Rudjer Boskovic Institute, Centre for Marine and Environment Research, Bijenicka cesta 54, 10002 Zagreb (Croatia)

    2006-06-16

    A new analytical procedure for determination of lanthanides in environmental samples after chemical separation from major matrix elements on DOWEX 50W-X8 resin followed by preconcentration with chelating agent ammonium pyrrolidine dithiocarbamate (APDC) and analyses of thin targets by energy dispersive X-ray fluorescence (EDXRF) method using {sup 109}Cd as the source of excitation was presented. Characteristic L{alpha} X-ray lines of the lanthanides were used for calculations of the net peak area and mass concentrations. The influence of pH value of the solution and addition of organic matter on the complexation was investigated. Percentage of recovery of each lanthanide after separation on DOWEX 50W-X8 resin was also determined. Accuracy of the method was tested on standard reference materials and real environmental samples (red mud material). For that purpose samples of standard reference materials and red mud were prepared as thick targets and directly analyzed (without the separation step) by EDXRF method using {sup 241}Am as the excitation source. In that case lanthanides concentrations were determined over their characteristic K{alpha} X-ray lines and results were compared with those obtained after separation/preconcentration step described above. Results showed that selected lanthanides made stable complexes with APDC in the alkaline medium with the maximum recovery at pH 8. The presence of organic matter slightly modified the complexation by means of somewhat higher recovery percentage at pH lower than 7 and approx. 20% lower recovery at pH higher than 7. Recovery of the elements after separation on DOWEX 50W-X8 resin and preconcentration with APDC at pH = 8 varied from 91.4% (Pr) to only 24.9% in the case of Dy. Concentrations of lanthanides measured in standard reference material and environmental samples of red mud after microwave digestion, separation on DOWEX 50W-X8 resin, preconcentration with APDC at pH = 8 and recalculation on the percentage of

  18. Determination of lanthanides by source excited energy dispersive X-ray fluorescence (EDXRF) method after preconcentration with ammonium pyrrolidine dithiocarbamate (APDC).

    Science.gov (United States)

    Orescanin, Visnja; Mikelic, Luka; Roje, Vibor; Lulic, Stipe

    2006-06-16

    A new analytical procedure for determination of lanthanides in environmental samples after chemical separation from major matrix elements on DOWEX 50W-X8 resin followed by preconcentration with chelating agent ammonium pyrrolidine dithiocarbamate (APDC) and analyses of thin targets by energy dispersive X-ray fluorescence (EDXRF) method using 109Cd as the source of excitation was presented. Characteristic Lalpha X-ray lines of the lanthanides were used for calculations of the net peak area and mass concentrations. The influence of pH value of the solution and addition of organic matter on the complexation was investigated. Percentage of recovery of each lanthanide after separation on DOWEX 50W-X8 resin was also determined. Accuracy of the method was tested on standard reference materials and real environmental samples (red mud material). For that purpose samples of standard reference materials and red mud were prepared as thick targets and directly analyzed (without the separation step) by EDXRF method using 241Am as the excitation source. In that case lanthanides concentrations were determined over their characteristic Kalpha X-ray lines and results were compared with those obtained after separation/preconcentration step described above. Results showed that selected lanthanides made stable complexes with APDC in the alkaline medium with the maximum recovery at pH=8. The presence of organic matter slightly modified the complexation by means of somewhat higher recovery percentage at pH lower than 7 and approx. 20% lower recovery at pH higher than 7. Recovery of the elements after separation on DOWEX 50W-X8 resin and preconcentration with APDC at pH=8 varied from 91.4% (Pr) to only 24.9% in the case of Dy. Concentrations of lanthanides measured in standard reference material and environmental samples of red mud after microwave digestion, separation on DOWEX 50W-X8 resin, preconcentration with APDC at pH=8 and recalculation on the percentage of recovery were in good

  19. Synthesis, characterization, and chemical bonding analysis of the lithium alkaline-earth metal gallide nitrides Li{sub 2}(Ca{sub 3}N){sub 2}[Ga{sub 4}] and Li{sub 2}(Sr{sub 3}N){sub 2}[Ga{sub 4}

    Energy Technology Data Exchange (ETDEWEB)

    Pathak, Manisha; Bobnar, Matej; Ormeci, Alim; Hoehn, Peter [Chemische Metallkunde, Max-Planck-Institut fuer Chemische Physik fester Stoffe, Dresden (Germany); Stoiber, Dominik; Niewa, Rainer [Institut fuer Anorganische Chemie, Universitaet Stuttgart (Germany); Ovchinnikov, Alexander [Chemische Metallkunde, Max-Planck-Institut fuer Chemische Physik fester Stoffe, Dresden (Germany); Department of Chemistry and Biochemistry, University of Delaware, Newark, DE (United States)

    2017-11-17

    Large single crystals of Li{sub 2}(Ca{sub 3}N){sub 2}[Ga{sub 4}] and Li{sub 2}(Sr{sub 3}N){sub 2}[Ga{sub 4}] up to several mm in size were grown from mixtures of the respective elements and binary alkaline-earth metal nitrides in reactive lithium melts employing a modified high-temperature centrifugation-aided filtration (HTCAF) technique. The main structural features of these isotypic phases are stella quadrangula building units [Ga{sub 4}]Li{sub 4/2} and octahedra (Nae{sub 6/2}), which form two independent interpenetrating networks. The phases crystallize in the η-carbide structure and represent diamagnetic small bandgap semiconductors. Real-space chemical bonding analysis indicates predominantly ionic bonding. (copyright 2017 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  20. High Resolution Fluorescence Imaging of Cancers Using Lanthanide Ion-Doped Upconverting Nanocrystals

    Directory of Open Access Journals (Sweden)

    John A. Capobianco

    2012-10-01

    Full Text Available During the last decade inorganic luminescent nanoparticles that emit visible light under near infrared (NIR excitation (in the biological window have played a relevant role for high resolution imaging of cancer. Indeed, semiconductor quantum dots (QDs and metal nanoparticles, mostly gold nanorods (GNRs, are already commercially available for this purpose. In this work we review the role which is being played by a relatively new class of nanoparticles, based on lanthanide ion doped nanocrystals, to target and image cancer cells using upconversion fluorescence microscopy. These nanoparticles are insulating nanocrystals that are usually doped with small percentages of two different rare earth (lanthanide ions: The excited donor ions (usually Yb3+ ion that absorb the NIR excitation and the acceptor ions (usually Er3+, Ho3+ or Tm3+, that are responsible for the emitted visible (or also near infrared radiation. The higher conversion efficiency of these nanoparticles in respect to those based on QDs and GNRs, as well as the almost independent excitation/emission properties from the particle size, make them particularly promising for fluorescence imaging. The different approaches of these novel nanoparticles devoted to "in vitro" and "in vivo" cancer imaging, selective targeting and treatment are examined in this review.

  1. High Resolution Fluorescence Imaging of Cancers Using Lanthanide Ion-Doped Upconverting Nanocrystals

    Energy Technology Data Exchange (ETDEWEB)

    Naccache, Rafik; Rodríguez, Emma Martín; Bogdan, Nicoleta [Department of Chemistry and Biochemistry, Concordia University, Montreal H4B 1R6 (Canada); Sanz-Rodríguez, Francisco [Departamento de Biología, Facultad de Ciencias, Universidad Autónoma de Madrid, Madrid 28049 (Spain); Cruz, Maria del Carmen Iglesias de la [Departamento de Fisiología. Facultad de Medicina, Universidad Autónoma de Madrid, Madrid 28029 (Spain); Fuente, Ángeles Juarranz de la [Departamento de Biología, Facultad de Ciencias, Universidad Autónoma de Madrid, Madrid 28049 (Spain); Vetrone, Fiorenzo [Institut National de la Recherche Scientifique-Énergie, Matériaux et Télécommunications, Université du Québec, Varennes J3X 1S2 (Canada); Jaque, Daniel; Solé, José García, E-mail: jose.garcia_sole@uam.es [Departamento de Física de Materiales, Universidad Autónoma de Madrid, Madrid 28049 (Spain); Capobianco, John A., E-mail: jose.garcia_sole@uam.es [Department of Chemistry and Biochemistry, Concordia University, Montreal H4B 1R6 (Canada)

    2012-10-22

    During the last decade inorganic luminescent nanoparticles that emit visible light under near infrared (NIR) excitation (in the biological window) have played a relevant role for high resolution imaging of cancer. Indeed, semiconductor quantum dots (QDs) and metal nanoparticles, mostly gold nanorods (GNRs), are already commercially available for this purpose. In this work we review the role which is being played by a relatively new class of nanoparticles, based on lanthanide ion doped nanocrystals, to target and image cancer cells using upconversion fluorescence microscopy. These nanoparticles are insulating nanocrystals that are usually doped with small percentages of two different rare earth (lanthanide) ions: The excited donor ions (usually Yb{sup 3+} ion) that absorb the NIR excitation and the acceptor ions (usually Er{sup 3+}, Ho{sup 3+} or Tm{sup 3+}), that are responsible for the emitted visible (or also near infrared) radiation. The higher conversion efficiency of these nanoparticles in respect to those based on QDs and GNRs, as well as the almost independent excitation/emission properties from the particle size, make them particularly promising for fluorescence imaging. The different approaches of these novel nanoparticles devoted to “in vitro” and “in vivo” cancer imaging, selective targeting and treatment are examined in this review.

  2. Trends in metallo-organic chemistry of scandium, yttrium, and the lanthanides

    International Nuclear Information System (INIS)

    Singh, A.

    1994-01-01

    Several interesting aspects of the metallo-organic chemistry of group 3 and the lanthanides have been highlighted, which include: (a) the chemistry of a few notable organolanthanide compounds, alkoxo and aryloxo derivatives derived from sterically demanding ligands, (b) new trends in the chemistry of lanthanide heterometallic alkoxides, (c) an account of zero valent organometallics of yttrium and the lanthanides, and (d) aspects of agostic interactions in the lanthanide metallo-organic compounds. (author). 49 refs

  3. Lanthanide-doped nanoparticles as the active optical medium in polymer-based devices

    NARCIS (Netherlands)

    Stouwdam, J.W.

    2004-01-01

    The luminescence of lanthanide ions in organic environment is greatly reduced compared to inorganic materials. This thesis describes the doping of the lanthanide ions in the core of inorganic nanoparticles that are soluble in organic solvents as a way to shield the lanthanide ions from the organic

  4. Spectral intensities in trivalent lanthanide systems

    Energy Technology Data Exchange (ETDEWEB)

    Acevedo, Roberto [Facultad de Ingenieria, Universidad Mayor, Avenida Manuel Montt 367, Postal code 7500994, Providencia, Santiago (Chile)], E-mail: roberto.acevedo@umayor.cl; Soto-Bubert, Andres; Bosch, Paul [Instituto de Ciencias Basicas, Facultad de Ingenieria, Universidad Diego Portales, Avenida Ejercito 441, Casilla 298-V, Santiago (Chile); Strek, Wieslaw [Institute of Low Temperature and Structure Research, Polish Academy of Sciences, Okoelna 2, 50-422 Wroclaw (Poland)

    2008-08-11

    The main goal of this research work is to rationalize the rich vibronic structure of lanthanide type crystals, such as Cs{sub 2}NaDyCl{sub 6} and Cs{sub 2}NaHoCl{sub 6}, in the space group Fm3m(O{sub h}{sup 5}). These systems are known to be highly relativistic and as a consequence, major corrections to previous model calculations should be taken into account so as to explain from a semi-quantitative viewpoint, the observed spectral intensities. We have decided to tackle this study taking special care, of both the physics and the chemistry involved with special emphasis on the theoretical model to be employed as well as, in the strategy to be followed to rationalize the available experimental data. This paper aims to advance our understanding of the intensity mechanisms, associated with observed radiative transitions, say for complex highly relativistic systems, in the solid state physics. The spectral intensities associated with superpositions (juxtapositions) of peaks and/or bands in the absortion and emission spectra are considered in detail and a preliminary working methodology is put forward with reference to the Cs{sub 2}NaDyCl{sub 6} and Cs{sub 2}NaHoCl{sub 6} crystals.

  5. High performance separation of lanthanides and actinides

    International Nuclear Information System (INIS)

    Sivaraman, N.; Vasudeva Rao, P.R.

    2011-01-01

    The major advantage of High Performance Liquid Chromatography (HPLC) is its ability to provide rapid and high performance separations. It is evident from Van Deemter curve for particle size versus resolution that packing materials with particle sizes less than 2 μm provide better resolution for high speed separations and resolving complex mixtures compared to 5 μm based supports. In the recent past, chromatographic support material using monolith has been studied extensively at our laboratory. Monolith column consists of single piece of porous, rigid material containing mesopores and micropores, which provide fast analyte mass transfer. Monolith support provides significantly higher separation efficiency than particle-packed columns. A clear advantage of monolith is that it could be operated at higher flow rates but with lower back pressure. Higher operating flow rate results in higher column permeability, which drastically reduces analysis time and provides high separation efficiency. The above developed fast separation methods were applied to assay the lanthanides and actinides from the dissolver solutions of nuclear reactor fuels

  6. Synthesis and characterization of lanthanide picrate complexes with 4-picoline-N-oxide (4-pic N O)

    International Nuclear Information System (INIS)

    Silva, E.M. da.

    1991-01-01

    The lanthanide picrate complexes with 4-picoline-N-oxide were obtained from ethanolic solutions of the hydrated lanthanide picrate and the ligand. The lanthanide content was determined by complexometric titration with EDTA. Carbon, Nitrogen and Hydrogen were determined by microanalytical procedures. Chemical analysis of the lanthanide picrate complexes are also presented. (author)

  7. Robust lanthanide emitters in polyelectrolyte thin films for photonic applications

    Science.gov (United States)

    Greenspon, Andrew S.; Marceaux, Brandt L.; Hu, Evelyn L.

    2018-02-01

    Trivalent lanthanides provide stable emission sources at wavelengths spanning the ultraviolet through the near infrared with uses in telecommunications, lighting, and biological sensing and imaging. We describe a method for incorporating an organometallic lanthanide complex within polyelectrolyte multilayers, producing uniform, optically active thin films on a variety of substrates. These films demonstrate excellent emission with narrow linewidths, stable over a period of months, even when bound to metal substrates. Utilizing different lanthanides such as europium and terbium, we are able to easily tune the resulting wavelength of emission of the thin film. These results demonstrate the suitability of this platform as a thin film emitter source for a variety of photonic applications such as waveguides, optical cavities, and sensors.

  8. Lanthanides in molecular magnetism: so fascinating, so challenging.

    Science.gov (United States)

    Luzon, Javier; Sessoli, Roberta

    2012-11-28

    Due to their usual large magnetic moments and large magnetic anisotropy lanthanide ions are investigated for the search of Single Molecule Magnets with high blocking temperature. However, the low symmetry crystal environment, the complexity of the electronic states or the non-collinearity of the magnetic anisotropy easy-axes in polynuclear systems make the rationalization of the magnetic behaviour of lanthanide based molecular systems difficult. In this perspective article we expose a methodology in which the use of additional characterization techniques, like single crystal magnetic measurements or luminescence experiments, complemented by relativistic ab initio calculations and a suitable choice of spin Hamiltonian models, can be of great help in order to overcome such difficulties, representing an essential step for the rational design of lanthanide based Single Molecule Magnets with enhanced physical properties.

  9. The electronic structure of the lanthanides and actinides, a comparison

    International Nuclear Information System (INIS)

    Edelstein, N.M.

    1998-01-01

    Full text: Optical spectra of the two f-element series (the lanthanides and actinides) are comparable in many respects. For the trivalent ions isolated in single crystals, both series exhibit rich, narrow line spectra. These data can be analysed in terms of a parametric model based on a free-ion Hamiltonian plus the addition of a crystal field Hamiltonian. For most systems the agreement between the calculated and experimental energy levels is quite good. In the actinide series there appears to be a correlation between the magnitude of the crystal field and the inadequacy of the fits. The early actinides exhibit multiple oxidation states for which there is no precedent in the lanthanide series. The parametric model mentioned earlier has been utilized for some tetravalent actinide systems with reasonably good results. A selective survey of results describing the similarities and differences of various lanthanide and actinide systems will be given

  10. Analytical separations of lanthanides and actinides by capillary electrophoresis.

    Science.gov (United States)

    Janos, Pavel

    2003-06-01

    The separation of lanthanide and actinide elements belongs to one of the most challenging tasks of the separation science, due to a great similarity in their physical and chemical properties. The electrophoretic separation can be accomplished in the presence of suitable complex-forming agents, from which alpha-hydroxyisobutyric acid (HIBA) has been used most often. In the most effective capillary electrophoretic mode--capillary zone electrophoresis (CZE)--a complete separation of lanthanide ions can be accomplished within a few minutes. Various electrophoretic methods can be relatively easily adopted for the determinations of individual lanthanide elements in certain kinds of technical materials, concentrates, precursors, etc., where the high speed and low costs of analysis characteristics of capillary electrophoresis (CE) may be advantageously exploited. Electrophoretic techniques may also be employed for speciation studies, especially for examinations of the behavior of actinides in the environment.

  11. Design of efficient electroluminescent lanthanide(III) complexes

    CERN Document Server

    You, B R; Park, N G; Kim, Y S

    2001-01-01

    The lanthanide complexes have been anticipated to exhibit high efficiency along with a narrow emission spectrum. Photoluminescence for the lanthanide complex is characterized by a high efficiency since both single and triplet excitons are involved in the luminescence process. However, the maximum external electroluminescence quantum efficiencies have exhibited values around 1% due to triplet-triplet annihilation at high current. Here, we proposed a new energy transfer mechanism to overcome triplet-triplet annihilation by the Eu complex doped into phosphorescent materials with triplet levels that were higher than single levels of the Eu complex. In order to show the feasibility of the proposed energy transfer mechanism and to obtain the optimal ligands and host material, we have calculated the effect depending on ligands as a factor that controls emission intensity in lanthanide complexes. The calculation shows that triplet state as well as singlet state of anion ligand affects on absorption efficiency indirec...

  12. Determination of stability constants of lanthanide complexes with tetracycline

    International Nuclear Information System (INIS)

    Saiki, Mitiko

    1975-01-01

    The stability constants of complexes compounds formed with tetracycline and lanthanides elements were determined for all lanthanides except promethium. The experimental procedure used was solvent extraction of the lanthanides labelled with their radioactive isotopes. It was shown that the formed complexes are mononuclear and that no hydroxo complexes or negatively charged complexes are formed in the experimental conditions of this work. Four methods of calculation were used for all complexes studied: the method of the average number of ligands, the method of limiting value, the method of two parameters and the method of weighted least squares. A comparison was made of the graphical methods with the method of least squares, showing the convenience of preceding least squares calculation by the graphical methods, in order to verify eventual mistakes of numerical data. It was shown the advantage of using radioisotopes of the elements for such a study, specially if the solvent extraction technique is used to-get the experimental data. (author)

  13. Silica-poor, mafic alkaline lavas from ocean islands and continents ...

    Indian Academy of Sciences (India)

    R. Narasimhan (Krishtel eMaging) 1461 1996 Oct 15 13:05:22

    rock major-element chemistry of silica-poor, mafic alkaline lavas with exper- ... Keywords. Silica-poor lavas; partial melting; mantle lherzolite; garnet clinopyroxenite. Proc. Indian Acad. Sci. (Earth Planet. Sci.), 113, No. 4, December 2004, pp.

  14. Analytical-scale separations of lanthanides : a review of techniques and fundamentals.

    Energy Technology Data Exchange (ETDEWEB)

    Nash, K. L.; Jensen, M. P.

    1999-10-27

    Separations chemistry is at the heart of most analytical procedures to determine the rare earth content of both man-made and naturally occurring materials. Such procedures are widely used in mineral exploration, fundamental geology and geochemistry, material science, and in the nuclear industry. Chromatographic methods that rely on aqueous solutions containing complexing agents sensitive to the lanthanide cationic radius and cation-exchange phase transfer reactions (using a variety of different solid media) have enjoyed the greatest success for these procedures. In this report, they will briefly summarize the most important methods for completing such analyses. they consider in some detail the basic aqueous (and two-phase) solution chemistry that accounts for separations that work well and offer explanations for why others are less successful.

  15. Analytical-scale separations of lanthanides : a review of techniques and fundamentals

    International Nuclear Information System (INIS)

    Nash, K. L.; Jensen, M. P.

    1999-01-01

    Separations chemistry is at the heart of most analytical procedures to determine the rare earth content of both man-made and naturally occurring materials. Such procedures are widely used in mineral exploration, fundamental geology and geochemistry, material science, and in the nuclear industry. Chromatographic methods that rely on aqueous solutions containing complexing agents sensitive to the lanthanide cationic radius and cation-exchange phase transfer reactions (using a variety of different solid media) have enjoyed the greatest success for these procedures. In this report, they will briefly summarize the most important methods for completing such analyses. they consider in some detail the basic aqueous (and two-phase) solution chemistry that accounts for separations that work well and offer explanations for why others are less successful

  16. Magnetic field alignable domains in phospholipid vesicle membranes containing lanthanides.

    Science.gov (United States)

    Beck, Paul; Liebi, Marianne; Kohlbrecher, Joachim; Ishikawa, Takashi; Rüegger, Heinz; Zepik, Helmut; Fischer, Peter; Walde, Peter; Windhab, Erich

    2010-01-14

    Magnetic fields were applied as a structuring force on phospholipid-based vesicular systems, using paramagnetic lanthanide ions as magnetic handles anchored to the vesicle membrane. Different vesicle formulations were investigated using small angle neutron scattering (SANS) in a magnetic field of up to 8 T, cryo-transmission electron microscopy (cryo-TEM), (31)P NMR spectroscopy, dynamic light scattering (DLS), and permeability measurements with a fluorescent water-soluble marker (calcein). The investigated vesicle formulations consisted usually of 80 mol % of the phospholipid 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphocholine (POPC) and 20 mol % of a chelator lipid (DMPE-DTPA; 1,2-dimyristoyl-sn-glycero-3-phosphoethanolamine-diethylenetriaminepentaacetate) with complexed lanthanide ions (Tm(3+), Dy(3+), or La(3+)), and the total lipid concentration was 15 mM. Vesicles containing the paramagnetic lanthanide Tm(3+) or Dy(3+) exhibited a temperature-dependent response to magnetic fields, which can be explained by considering the formation of lipid domains, which upon reaching a critical size become alignable in a magnetic field. The features of this "magnetic field alignable domain model" are as follows: with decreasing temperature (from 30 to 2.5 degrees C) solid domains, consisting mainly of the higher melting phospholipid (DMPE-DTPA.lanthanide), begin to form and grow in size. The domains assemble the large magnetic moments conferred by the lanthanides and orient in magnetic fields. The direction of alignment depends on the type of lanthanide used. The domains orient with their normal parallel to the magnetic field with thulium (Tm(3+)) and perpendicular with dysprosium (Dy(3+)). No magnetic field alignable domains were observed if DMPE-DTPA is replaced either by POPE-DTPA (1-palmitoyl-2-oleoyl-sn-glycero-3-phosphoethanolamine-diethylenetriamine-pentaacetate) or by DMPC (1,2-dimyristoyl-sn-glycero-3-phosphocholine).

  17. Environmental applications of lanthanide counterions bound to reverse micelles

    International Nuclear Information System (INIS)

    Warner, I.M.; Mwalupindi, A.G.; Ndou, T.T.

    1992-01-01

    The lanthanide surfactants of the formula [Ln(EHS) 3 ] [where EHS - bis(2-ethylhexyl) sulfosuccinate and Ln = Tb(III)or Eu(III)] have been synthesized from aerosol OT, and used to detect select organic analytes. This technique is based on the ability of the lanthanide ions to transform the energy absorbed by the organic compounds into a visible lanthanide ion emission via intermolecular energy transfer. When dissolved in an organic solvent, the surfactants form reverse micelles which provide molecular organization of the donor and acceptor species to come into close contact for energy transfer. An enhancement of the sensitized luminescence of the lanthanide counterions have been demonstrated in the presence of many organic analytes. The results show that a significant enhancement can be achieved by using an organic analyte containing a polar substituent. The observed efficient sensitization of the lanthanide ions is used for the determination of select organic analytes. Many of the organic analytes used are potential pollutants and carcinogens. Therefore, this procedure is more likely to provide a detection scheme to selectively analyze water for environmentally important pollutants such as polychlorobiphenyls. 1 H NMR spectroscopy has been used to establish the interaction between the organic analyte donor and lanthanide ion acceptor and then examine the relative locations of various photosensitive species present in the reverse micellar solution. This information was derived from changes in the chemical shift and resolution of both the analyte and the surfactant protons upon solubilization of the donor in the micellar solution. These data are used to estimate the average distance between the donor and the acceptor in this analytical scheme. The ability and the effectiveness of these surfactants to act as NME shift reagents is discussed

  18. Separation of lanthanides through hydroxyapatite; Separacion de lantanidos mediante hidroxiapatita

    Energy Technology Data Exchange (ETDEWEB)

    Garcia M, F.G

    2006-07-01

    With the objective of obtaining from an independent way to each one of the lanthanides {sup 151} Pm, {sup 161} Tb, {sup 166} Ho and {sup 177} Lu free of carrier and with high specific activities starting from the indirect irradiation via, it intends in this work to determine the viability of separation of the couples Nd/Pm, Dy/Ho, Gd/Tb and Yb/Lu, by means of ion exchange column chromatography, using hydroxyapatite (HAp) and fluorite like absorbent material in complexing media. It is important to mention that have registered separation studies among lanthanides of the heavy group with those of the slight group, using the same mass and, in comparison with this work, quantities different from the father were used and of the son, also, that the separation studies were carried out among neighboring lanthanides. In this investigation, it was determined the effect that its have the complexing media: KSCN, sodium tartrate, sodium citrate, EDTA and aluminon, their pH and concentration, in the adsorption of the lanthanides in both minerals, in order to determine the chromatographic conditions for separation of the couples Nd/Pm, Dy/Ho, Gd/Tb and Yb/Lu. The work consists of five chapters, in the first one they are presented a theoretical introduction of the characteristics more important of the lanthanides, the hydroxyapatite and the fluorite; in the second, it is deepened in the ion exchange, as well as the two techniques (XRD and High Vacuum Electron Microscopy) to make the characterization of LnCI{sub 3} (Ln = Nd, Gd, Dy or Yb) synthesized. The third chapter, it describes the methodology continued in our experimental work; in the room, its are presented the obtained results of the static and dynamic method to determine the viability of separation of neighboring lanthanides; and finally, the five chapter shows the conclusions. In this study, it is concludes that the separation among neighboring lanthanides cannot be carried out in the minerals and used media; because

  19. Method for extracting lanthanides and actinides from acid solutions

    Science.gov (United States)

    Horwitz, E. Philip; Kalina, Dale G.; Kaplan, Louis; Mason, George W.

    1985-01-01

    A process for the recovery of actinide and lanthanide values from aqueous acidic solutions with an organic extractant having the formula: ##STR1## where .phi. is phenyl, R.sup.1 is a straight or branched alkyl or alkoxyalkyl containing from 6 to 12 carbon atoms and R.sup.2 is an alkyl containing from 3 to 6 carbon atoms. The process is suitable for the separation of actinide and lanthanide values from fission product values found together in high level nuclear reprocessing waste solutions.

  20. Microwave synthesis of nanostructured oxide sorbents doped with lanthanides

    Energy Technology Data Exchange (ETDEWEB)

    Mitrofanov, Andrey A., E-mail: mitrofanov-a@icloud.com; Silyavka, Elena S.; Shilovskikh, Vladimir V.; Kolonitckii, Petr D.; Sukhodolov, Nikolai G.; Selyutin, Artem A., E-mail: selutin@inbox.ru [Saint Petersburg State University, 7/9, Universitetskaya nab., St. Petersburg, 199034 (Russian Federation)

    2016-06-17

    A number of nanostructured mesoporous oxide systems based on aluminum oxide, doped with lanthanide ions have been obtained in this study. Structure and morphology of oxides obtained have been examined by X-ray diffraction analysis, thermogravimetric analysis, scanning electron microscopy. The surface area of the samples was determined by the BET method. The dependence of the adsorption of insulin on synthesized oxides from the concentration was investigated. The containing of insulin in solutions after adsorption was determined by the Bradford method. The isotherms of adsorption of insulin on resulting oxide sorbents were plotted, the dependence capacity of the sorption of insulin from the lanthanide dopant was determined.

  1. Method for providing oxygen ion vacancies in lanthanide oxides

    Science.gov (United States)

    Kay, D. Alan R.; Wilson, William G.

    1989-12-05

    A method for desulfurization of fuel gases resulting from the incomplete combustion of sulfur containing hydrocarbons whereby the gases are treated with lanthanide oxides containing large numbers of oxygen-ion vacancies providing ionic porosity which enhances the ability of the lanthanide oxides to react more rapidly and completely with the sulfur in the fuel gases whereby the sulfur in such gases is reduced to low levels suitable for fuels for firing into boilers of power plants generating electricity with steam turbine driven generators, gas turbines, fuel cells and precursors for liquid fuels such as methanol and the like.

  2. The future of rare earth thin films

    International Nuclear Information System (INIS)

    Gasgnier, M.

    1986-01-01

    This paper presents some recent applications in the rare earth field and also may be, some of the future new developments of laboratory works. The field of investigations will concern only materials which contain at least one rare earth element (lanthanide series, from La to Lu, Sc and Y). After a rapid survey of the experimental procedures relative to the preparation and to the analytical characterization of thin films, technological applications in various fields of research are briefly reviewed: for polycrystalline metals (superconductors, neutron absorption, photovoltaic effect...), alloys (hydrogen storage, superconductors) and compounds (target for intense neutron sources, radiology...) and for amorphous magnetic thin films. 81 refs [fr

  3. Alkaline fuel cells applications

    Science.gov (United States)

    Kordesch, Karl; Hacker, Viktor; Gsellmann, Josef; Cifrain, Martin; Faleschini, Gottfried; Enzinger, Peter; Fankhauser, Robert; Ortner, Markus; Muhr, Michael; Aronson, Robert R.

    On the world-wide automobile market technical developments are increasingly determined by the dramatic restriction on emissions as well as the regimentation of fuel consumption by legislation. Therefore there is an increasing chance of a completely new technology breakthrough if it offers new opportunities, meeting the requirements of resource preservation and emission restrictions. Fuel cell technology offers the possibility to excel in today's motive power techniques in terms of environmental compatibility, consumer's profit, costs of maintenance and efficiency. The key question is economy. This will be decided by the costs of fuel cell systems if they are to be used as power generators for future electric vehicles. The alkaline hydrogen-air fuel cell system with circulating KOH electrolyte and low-cost catalysed carbon electrodes could be a promising alternative. Based on the experiences of Kordesch [K. Kordesch, Brennstoffbatterien, Springer, Wien, 1984, ISBN 3-387-81819-7; K. Kordesch, City car with H 2-air fuel cell and lead-battery, SAE Paper No. 719015, 6th IECEC, 1971], who operated a city car hybrid vehicle on public roads for 3 years in the early 1970s, improved air electrodes plus new variations of the bipolar stack assembly developed in Graz are investigated. Primary fuel choice will be a major issue until such time as cost-effective, on-board hydrogen storage is developed. Ammonia is an interesting option. The whole system, ammonia dissociator plus alkaline fuel cell (AFC), is characterised by a simple design and high efficiency.

  4. Rare earth metals, rare earth hydrides, and rare earth oxides as thin films

    International Nuclear Information System (INIS)

    Gasgnier, M.

    1980-01-01

    The review deals with pure rare earth materials such as rare earth metals, rare earth hydrides, and rare earth oxides as thin films. Several preparation techniques, control methods, and nature of possible contaminations of thin films are described. These films can now be produced in an extremely well-known state concerning chemical composition, structure and texture. Structural, electric, magnetic, and optical properties of thin films are studied and discussed in comparison with the bulk state. The greatest contamination of metallic rare earth thin films is caused by reaction with hydrogen or with water vapour. The compound with an f.c.c. structure is the dihydride LnH 2 (Ln = lanthanides). The oxygen contamination takes place after annealing at higher temperatures. Then there appears a compound with a b.c.c. structure which is the C-type sesquioxide C-Ln 2 O 3 . At room atmosphere dihydride light rare earth thin films are converted to hydroxide Ln(OH) 3 . For heavy rare earth thin films the oxinitride LnNsub(x)Osub(y) is observed. The LnO-type compound was never seen. The present review tries to set the stage anew for the investigations to be undertaken in the future especially through the new generations of electron microscopes

  5. Coordination of lanthanide cation to an Anderson type ...

    Indian Academy of Sciences (India)

    Home; Journals; Journal of Chemical Sciences; Volume 126; Issue 5. Coordination of lanthanide cation to an Anderson type polyoxometalate anion ... and spectroscopy. Vaddypally Shivaiah Tanmay Chatterjee Samar K Das. Special issue on Chemical Crystallography Volume 126 Issue 5 September 2014 pp 1525-1533 ...

  6. On changes in melting points of some lanthanide complexes

    International Nuclear Information System (INIS)

    Meshkova, S.B.; Poluehktov, N.S.; Korovin, Yu.V.

    1983-01-01

    An expression for calculation of melting points of complexes of trivalent lanthanide ions with account for the number of f-electrons, S orbital quantum number of the ground state and the of spin-orbit interaction energy is given. Good agreement of calculated melting points with those determined experimentally supports the consistency of the suggested conrelation

  7. Spectroscopic studies of some lanthanide(III) nitrate complexes ...

    African Journals Online (AJOL)

    ... chemical analysis, conductance, magnetic moment measurements and infrared spectra. Infrared study indicates that the ligand behaves both as neutral and ionic O donors and as neutral N donors. KEY WORDS: Lanthanide(III) complexes, Schiff base, 2,6-bis-(Salicylaldehydehydrazone)-4-chlorophenol, Infrared spectra, ...

  8. Influencing fatty acid composition of yeasts by lanthanides

    Czech Academy of Sciences Publication Activity Database

    Kolouchová, I.; Sigler, Karel; Zimola, M.; Řezanka, Tomáš; Matatková, O.; Masák, J.

    2016-01-01

    Roč. 32, č. 8 (2016), s. 126 ISSN 0959-3993 R&D Projects: GA ČR GA14-00227S Institutional support: RVO:61388971 Keywords : Fatty acids * Lanthanides * Microbial lipids Subject RIV: EE - Microbiology, Virology Impact factor: 1.658, year: 2016

  9. On the suitability of lanthanides as actinide analogs

    International Nuclear Information System (INIS)

    Raymond, Kenneth; Szigethy, Geza

    2008-01-01

    With the current level of actinide materials used in civilian power generation and the need for safe and efficient methods for the chemical separation of these species from their daughter products and for long-term storage requirements, a detailed understanding of actinide chemistry is of great importance. Due to the unique bonding properties of the f-elements, the lanthanides are commonly used as structural and chemical models for the actinides, but differences in the bonding between these 4f and 5f elements has become a question of immediate applicability to separations technology. This brief overview of actinide coordination chemistry in the Raymond group at UC Berkeley/LBNL examines the validity of using lanthanide analogs as structural models for the actinides, with particular attention paid to single crystal X-ray diffraction structures. Although lanthanides are commonly accepted as reasonable analogs for the actinides, these comparisons suggest the careful study of actinide materials independent of their lanthanide analogs to be of utmost importance to present and future efforts in nuclear industries. (authors)

  10. Luminescent Lanthanide Reporters for High-Sensitivity Novel Bioassays

    Energy Technology Data Exchange (ETDEWEB)

    Anstey, Mitchell R. [Sandia National Lab. (SNL-CA), Livermore, CA (United States); Fruetel, Julia A. [Sandia National Lab. (SNL-CA), Livermore, CA (United States); Foster, Michael E. [Sandia National Lab. (SNL-CA), Livermore, CA (United States); Hayden, Carl C. [Sandia National Lab. (SNL-CA), Livermore, CA (United States); Buckley, Heather L. [Sandia National Lab. (SNL-CA), Livermore, CA (United States); Arnold, John [Sandia National Lab. (SNL-CA), Livermore, CA (United States)

    2013-09-01

    Biological imaging and assay technologies rely on fluorescent organic dyes as reporters for a number of interesting targets and processes. However, limitations of organic dyes such as small Stokes shifts, spectral overlap of emission signals with native biological fluorescence background, and photobleaching have all inhibited the development of highly sensitive assays. To overcome the limitations of organic dyes for bioassays, we propose to develop lanthanide-based luminescent dyes and demonstrate them for molecular reporting applications. This relatively new family of dyes was selected for their attractive spectral and chemical properties. Luminescence is imparted by the lanthanide atom and allows for relatively simple chemical structures that can be tailored to the application. The photophysical properties offer unique features such as narrow and non-overlapping emission bands, long luminescent lifetimes, and long wavelength emission, which enable significant sensitivity improvements over organic dyes through spectral and temporal gating of the luminescent signal.Growth in this field has been hindered due to the necessary advanced synthetic chemistry techniques and access to experts in biological assay development. Our strategy for the development of a new lanthanide-based fluorescent reporter system is based on chelation of the lanthanide metal center using absorbing chromophores. Our first strategy involves "Click" chemistry to develop 3-fold symmetric chelators and the other involves use of a new class of tetrapyrrole ligands called corroles. This two-pronged approach is geared towards the optimization of chromophores to enhance light output.

  11. Addition compounds of yttrium and lanthanide perrhenates with tetramethylene sulphoxide

    International Nuclear Information System (INIS)

    Umeda, K.

    1977-01-01

    Adducts of lanthanide perrhenates with tetramethylene sulfoxide are prepared and characterized. The compounds having as general formula Ln(Re04) 3 .7.5 TMSO(ln=La-Lu and Y) are characterized by elemental analysis, infrared spectra, molar conductance measurements, x-ray powder patterns, differential scanning calorimetry curves, melting temperature range measurements and thermogravimetric analysis [pt

  12. Shining light on the antenna chromophore in lanthanide based dyes.

    Science.gov (United States)

    Junker, Anne Kathrine R; Hill, Leila R; Thompson, Amber L; Faulkner, Stephen; Sørensen, Thomas Just

    2018-03-21

    Lanthanide based dyes and assays exploit the antenna effect, where a sensitiser-chromophore is used as a light harvesting antenna and subsequent excited state energy transfer populates the emitting lanthanide centred excited state. A rudimentary understanding of the design criteria for designing efficient dyes and assays based on the antenna effect is in place. By preparing kinetically inert lanthanide complexes based on the DO3A scaffold, we are able to study the excited state energy transfer from a 7-methoxy-coumarin antenna chromophore to europium(iii) and terbium(iii) centred excited states. By contrasting the photophysical properties of complexes of metal centres with and without accessible excited states, we are able to separate the contributions from the heavy atom effect, photoinduced electron transfer quenching, excited state energy transfer and molecular conformations. Furthermore, by studying the photophysical properties of the antenna chromophore, we can directly monitor the solution structure and are able to conclude that excited state energy transfer from the chromophore singlet state to the lanthanide centre does occur.

  13. A facile building-block synthesis of multifunctional lanthanide MOFs

    NARCIS (Netherlands)

    Tanase, S.; Mittelmeijer-Hazeleger, M.C.; Rothenberg, G.; Mathonière, C.; Jubera, V.; Smits, J.M.M.; de Gelder, R.

    2011-01-01

    We report a building blocks approach providing a direct route to multifunctional MOFs, that display photoluminescent properties, robustness, porosity and in some cases unique magnetic properties. The self-assembly of [Mo(CN)8]4− with several in situ prepared lanthanide building blocks gives 3D

  14. Studies of lanthanide complexes by a combination of spectroscopic methods

    Czech Academy of Sciences Publication Activity Database

    Krupová, Monika; Bouř, Petr; Andrushchenko, Valery

    2015-01-01

    Roč. 22, č. 1 (2015), s. 44 ISSN 1211-5894. [Discussions in Structural Molecular Biology. Annual Meeting of the Czech Society for Structural Biology /13./. 19.03.2015-21.03.2015, Nové Hrady] Institutional support: RVO:61388963 Keywords : lanthanide complexes * chirality sensing * chirality amplification * spectroscopy Subject RIV: CF - Physical ; Theoretical Chemistry

  15. Lanthanide co-ordination frameworks: Opportunities and diversity

    International Nuclear Information System (INIS)

    Hill, Robert J.; Long, De-Liang; Hubberstey, Peter; Schroeder, Martin; Champness, Neil R.

    2005-01-01

    Significant successes have been made over recent years in preparing co-ordination framework polymers that show macroscopic material properties, but in the vast majority of cases this has been achieved with d-block metal-based systems. Lanthanide co-ordination frameworks also offer attractive properties in terms of their potential applications as luminescent, non-linear optical and porous materials. However, lanthanide-based systems have been far less studied to date than their d-block counterparts. One possible reason for this is that the co-ordination spheres of lanthanide cations are more difficult to control and, in the absence of design strategies for lanthanide co-ordination frameworks, it is significantly more difficult to target materials with specific properties. However, this article highlights some of the exciting possibilities that have emerged from the earliest investigations in this field with new topological families of compounds being discovered from relatively simple framework components, including unusual eight, seven and five-connected framework systems. Our own research, as well as others, is leading to a much greater appreciation of the factors that control framework formation and the resultant observed topologies of these polymers. As this understanding develops targeting particular framework types will become more straightforward and the development of designed polyfunctional materials more accessible. Thus, it can be seen that lanthanide co-ordination frameworks have the potential to open up previously unexplored directions for materials chemistry. This article focuses on the underlying concepts for the construction of these enticing and potentially highly important materials

  16. Method of cleaning alkaline metal

    International Nuclear Information System (INIS)

    Kawakami, Yukio; Naito, Kesahiro; Iizawa, Katsuyuki; Nakasuji, Takashi

    1981-01-01

    Purpose: To prevent scattering of used sodium and aqueous alkaline solution when cleaning used sodium and metallic sodium adhering to equipment with an aqueous alkaline solution. Method: A sodium treating container is filled with an aqueous alkaline solution, and stainless steel gauze is sunk in the container. Equipment to be cleaned such as equipment with sodium adhering to it are retained under the gauze and are thus cleaned. On the other hand, the surface of the aqueous alkaline solution is covered with a fluid paraffin liquid covering material. Thus, the hydrogen produced by the reaction of the sodium and the aqueous alkaline solution will float up, pass through the liquid covering material and be discharged. The sodium will pass through the gauze and float upwardly while reacting with the aqueous alkaline solution in a partic ulate state to the boundary between the aqueous alkaline solution and up to the covering material, and thus the theratment reaction will continue. Thus, the cover material prevents the sodium and the aqueous alkaline solution from scattering. (Kamimura, M.)

  17. Selective liquid chromatographic separation of yttrium from heavier rare earth elements using acetic acid as a novel eluent.

    Science.gov (United States)

    Kifle, Dejene; Wibetoe, Grethe

    2013-09-13

    One of the major difficulties in the rare earth elements separation is purification of yttrium from heavy rare earth elements. Thus, an HPLC method using acetic acid as novel eluent was explored for selective separation of yttrium form the heavy rare earth elements. When acetic acid is used as a mobile phase yttrium eluted with the lighter lanthanides. This is contrary to its relative position amongst heavier lanthanides when eluents commonly used for separation of rare earth elements were employed. The shift in elution position of yttrium with acetic acid as eluent may reflect a relatively lower stability constant of the yttrium-AcOH complex (in the same order as for the lighter lanthanides) compared to the corresponding AcOH complexes with heavy lanthanides, enabling selective separation of yttrium from the latter. The method was successfully used for selective separation of yttrium in mixed rare earth sample containing about 80% of yttrium and about 20% of heavy rare earth oxides. Thus, the use of AcOH as eluent is an effective approach for separating and determining the trace amounts of heavy rare earth elements in large amounts of yttrium matrix. Separation was performed on C18 column by running appropriate elution programs. The effluent from the column was monitored with diode array detector at absorbance wavelength of 658nm after post column derivatization with Arsenazo III. Copyright © 2013 Elsevier B.V. All rights reserved.

  18. Alkaline direct alcohol fuel cells

    Science.gov (United States)

    Antolini, E.; Gonzalez, E. R.

    The faster kinetics of the alcohol oxidation and oxygen reduction reactions in alkaline direct alcohol fuel cells (ADAFCs), opening up the possibility of using less expensive metal catalysts, as silver, nickel and palladium, makes the alkaline direct alcohol fuel cell a potentially low cost technology compared to acid direct alcohol fuel cell technology, which employs platinum catalysts. A boost in the research regarding alkaline fuel cells, fuelled with hydrogen or alcohols, was due to the development of alkaline anion-exchange membranes, which allows the overcoming of the problem of the progressive carbonation of the alkaline electrolyte. This paper presents an overview of catalysts and membranes for ADAFCs, and of testing of ADAFCs, fuelled with methanol, ethanol and ethylene glycol, formed by these materials.

  19. Three-dimensional architectures based on lanthanide-substituted double-Keggin-type polyoxometalates and lanthanide cations or lanthanide-organic complexes.

    Science.gov (United States)

    An, Haiyan; Han, Zhengbo; Xu, Tieqi

    2010-12-20

    A family of three-dimensional (3D) architectures based on lanthanide-substituted polyoxometaloborate building blocks, [LnK(H(2)O)(12)][Ln(H(2)O)(6)](2)[(H(2)O)(4)LnBW(11)O(39)H](2)·20H(2)O (Ln = Ce 1, Nd 2), H(2)K(2)(H(2)O)(n)[(C(6)NO(2)H(5))Ln(H(2)O)(5)](2)[(H(2)O)(4)LnBW(11)O(39)H](2)·18H(2)O (Ln = Ce n = 8 3, Nd n = 9 4, C(6)NO(2)H(5) = pyridine-4-carboxylic acid), have been synthesized and characterized by elemental analysis, IR spectroscopy, thermogravimetric (TG) analysis, powder X-ray diffraction and single crystal X-ray diffraction. Compounds 1 and 2 are isostructural, and are built up of lanthanide-substituted double-Keggin-type polyoxoanions [{(H(2)O)(4)Ln(BW(11)O(39)H)}(2)](10-) linked by Ln(3+) cations to form a 3D open framework with one-dimensional (1D) channels. The polyoxoanion [{(H(2)O)(4)Ln(BW(11)O(39)H)}(2)](10-) consists of two α(1)-type mono-Ln-substituted Keggin anions, constituted by two [BW(11)O(39)H](8-) polyoxoanions and two lanthanide cations. When pyridine-4-carboxylic acid ligand was added to the reaction system of 1, 2, compounds 3, 4 were obtained. Isostructural compounds 3 and 4 are constructed from the lanthanide-substituted double-Keggin-type polyoxoanions [{(H(2)O)(4)Ln(BW(11)O(39)H)}(2)](10-) linked by the [Ln(C(6)NO(2)H(5))](3+) bridges to form a 3D channel framework. From the topological point of view, the 3D nets of compounds 1-4 are binodal with three- and six-connected nodes and exhibit a rutile topology. Compounds 1-4 represent the examples of 3D architectures based on lanthanide-substituted polyoxometalates. The magnetic properties of compounds 1-4 have been studied by measuring their magnetic susceptibility in the temperature range 2-300 K.

  20. Alkaline galvanic cells

    Energy Technology Data Exchange (ETDEWEB)

    Eisenberg, M.

    1993-06-01

    A battery is described having an anode, a cathode and an electrolyte with the anode having zinc or a zinc alloy as an active anodic material, the cathode having a metal oxide or hydroxide as an active cathodic material, and the electrolyte comprising a solution of a first salt formed by the reaction of one or more acids selected from the group consisting of boric acid, phosphoric acid and arsenic acid with an alkali or earth alkali hydroxide present in an amount to produce a stoichiometric, excess of said hydroxide to said acid in the range of 2.5 to 11.0 equivalents per liter, and a solution of a second salt which is a soluble alkali or earth alkali fluoride in an amount corresponding to a concentration range of 0.01 to 1.0 equivalents per liter of total solution.

  1. Adsorption behaviors of trivalent actinides and lanthanides on pyridine resin in lithium chloride aqueous solution

    International Nuclear Information System (INIS)

    Tatsuya Suzuki

    2013-01-01

    The adsorption behaviors of trivalent actinides and lanthanides on pyridine resin in lithium chloride aqueous solution were investigated. The adsorbed amounts of lanthanides and the degree of mutual separation of lanthanides increased with an increase in the concentration of lithium chloride in aqueous solution. The group separation of the trivalent actinides and lanthanides was observed. This separation phenomenon is similar in a hydrochloric acid solution. However, the adsorption behavior of lanthanides in lithium chloride is different from their behavior in a hydrochloric acid solution. This fact shows that the adsorption mechanisms of lanthanides in a lithium chloride aqueous solution and in a hydrochloric acid solution are different; the adsorption mechanisms are attributed to the ion exchange in a hydrochloric acid solution, and to the complex formation with pyridine group in a lithium chloride solution. (author)

  2. Lanthanide-doped CaS and SrS luminescent nanocrystals : A single-source precursor approach for doping

    NARCIS (Netherlands)

    Zhao, Yiming|info:eu-repo/dai/nl/355358352; Rabouw, Freddy T.|info:eu-repo/dai/nl/413318036; Puffelen, Tim Van; van Walree, Kees|info:eu-repo/dai/nl/147609089; Gamelin, Daniel R.; De Mello Donegá, Celso|info:eu-repo/dai/nl/125593899; Meijerink, A|info:eu-repo/dai/nl/075044986

    2014-01-01

    The incorporation of dopants with optical or magnetic functionalities into colloidal nanocrystals (NCs) has been a longstanding challenge for nanomaterial research. A deeper understanding of the doping kinetics will aid a better control of the doping process. In particular, alkaline-earth sulfides

  3. Architectures moléculaire et supramoléculaires à base de Lanthanides Luminescents

    OpenAIRE

    Bozoklu, Gulay

    2011-01-01

    The construction of preprogrammed, sophisticated and nanoscopic polymetallic lanthanide complexes for the development of luminescent materials that possess new or improved photophysical properties (dual emission, intermetallic energy transfer, etc.) is one of the hot topics in the lanthanide supramolecular chemistry. Understanding, controlling and programming self assembly of lanthanide complexes is a key challenge due to the difficulty in controlling the coordination environment of these ion...

  4. Spectrally resolved confocal microscopy using lanthanide centred near-IR emission

    DEFF Research Database (Denmark)

    Liao, Zhiyu; Tropiano, Manuel; Mantulnikovs, Konstantins

    2015-01-01

    The narrow, near infrared (NIR) emission from lanthanide ions has attracted great interest, particularly with regard to developing tools for bioimaging, where the long lifetimes of lanthanide excited states can be exploited to address problems arising from autofluorescence and sample transparency....... Despite the promise of lanthanide-based probes for near-IR imaging, few reports on their use are present in the literature. Here, we demonstrate that images can be recorded by monitoring NIR emission from lanthanide complexes using detectors, optical elements and a microscope that were primarily designed...... for the visible part of the spectrum....

  5. Lanthanide Selective Sorbents: Self-Assembled Monolayers on Mesoporous Supports (SAMMS)

    Energy Technology Data Exchange (ETDEWEB)

    Fryxell, Glen E.; Wu, Hong; Lin, Yuehe; Shaw, Wendy J.; Birnbaum, Jerome C.; Linehan, John C.; Nie, Zimin; Kemner, Kenneth M.; Kelly, Shelley

    2004-11-01

    Through the marriage of mesoporous ceramics with self-assembled monolayer chemistry, the genesis of a powerful new class of environmental sorbent materials has been realized. By coating the mesoporous ceramic backbone with a monolayer terminated with a lanthanide-specific ligand, it is possible to couple high lanthanide binding affinity with the high loading capacity (resulting from the extremely high surface area of the support). This lanthanide-specific ligand field is created by pairing a “hard” anionic Lewis base with a suitable synergistic ligand, in a favorable chelating geometry. Details of the synthesis, characterization, lanthanide binding studies, binding kinetics, competition experiments and sorbent regeneration studies are summarized.

  6. Highly Luminescent, Water-Soluble Lanthanide Fluorobenzoates: Syntheses, Structures and Photophysics, Part I: Lanthanide Pentafluorobenzoates.

    Science.gov (United States)

    Kalyakina, Alena S; Utochnikova, Valentina V; Bushmarinov, Ivan S; Ananyev, Ivan V; Eremenko, Igor L; Volz, Daniel; Rönicke, Franziska; Schepers, Ute; Van Deun, Rik; Trigub, Alexander L; Zubavichus, Yan V; Kuzmina, Natalia P; Bräse, Stefan

    2015-12-01

    Highly luminescent, photostable, and soluble lanthanide pentafluorobenzoates have been synthesized and thoroughly characterized, with a focus on Eu(III) and Tb(III) complexes as visible emitters and Nd(III) , Er(III) , and Yb(III) complexes as infrared emitters. Investigation of the crystal structures of the complexes in powder form and as single crystals by using X-ray diffraction revealed five different structural types, including monomeric, dimeric, and polymeric. The local structure in different solutions was studied by using X-ray absorption spectroscopy. The photoluminescence quantum yields (PLQYs) of terbium and europium complexes were 39 and 15 %, respectively; the latter value was increased almost twice by using the heterometallic complex [Tb0.5 Eu0.5 (pfb)3 (H2 O)] (Hpfb=pentafluorobenzoic acid). Due to the effectively utilized sensitization strategy (pfb)(-) →Tb→Eu, a pure europium luminescence with a PLQY of 29 % was achieved. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. Maximum Permissible Concentrations and Negligible Concentrations for Rare Earth Elements (REEs)

    NARCIS (Netherlands)

    Sneller FEC; Kalf DF; Weltje L; Wezel AP van; CSR

    2000-01-01

    In this report maximum permissible concentrations (MPCs) and negligible concentrations (NCs) are derived for Rare Earth Elements (REEs), which are also known as lanthanides. The REEs selected for derivation of environmental risk limits in this report are Yttrium (Y), Lanthanum (La), Cerium (Ce),

  8. Organometallic complex chemistry of plutonium and selected lanthanides

    International Nuclear Information System (INIS)

    Seemann, U.

    1987-01-01

    This study deals with the metallo-organic chemistry of plutonium and also with that of some lanthanides. For plutonium, the conversion of Cs 2 PuCl 6 with four equivalents KCp is investigated. In the series Sm, Gd, Dy and Er, compounds of the type Cp 2 LnX and the base adducts with acetonitrile are analysed. The ligand X passes the series Cl, N 3 , NCS and NCO. Both, the thermal and the vibrational spectroscopic behaviour is investigated. In addition, the effect of a changed ligand sphere on the optical spectrum is discussed. The adduct-free compounds are described by a ternary reaction not yet known from literature. For the first time, force constant calculations are carried out on metallo-organic compounds of lanthanides. With the exception of Cp 2 LnCl compounds, all compouds are presented for the first time in the framework of this study. (orig.) [de

  9. Advancing the scientific basis of trivalent actinide-lanthanide separations

    Energy Technology Data Exchange (ETDEWEB)

    Nash, K.L. [Washington State University, Department of Chemistry, PO Box 644630, Pullman, WA 99164-4630 (United States)

    2013-07-01

    For advanced fuel cycles designed to support transmutation of transplutonium actinides, several options have been demonstrated for process-scale aqueous separations for U, Np, Pu management and for partitioning of trivalent actinides and fission product lanthanides away from other fission products. The more difficult mutual separation of Am/Cm from La-Tb remains the subject of considerable fundamental and applied research. The chemical separations literature teaches that the most productive alternatives to pursue are those based on ligand donor atoms less electronegative than O, specifically N- and S-containing complexants and chloride ion (Cl{sup -}). These 'soft-donor' atoms have exhibited usable selectivity in their bonding interactions with trivalent actinides relative to lanthanides. In this report, selected features of soft donor reagent design, characterization and application development will be discussed. The roles of thiocyanate, aminopoly-carboxylic acids and lactate in separation processes are detailed. (authors)

  10. Optical Properties of Lanthanides in Condensed Phase, Theory and Applications

    Directory of Open Access Journals (Sweden)

    Renata Reisfeld

    2015-04-01

    Full Text Available The basic theories of electronic levels and transition probabilities of lanthanides are summarized. Their interpretation allows practical preparation of new materials having application in lighting, solar energy utilization, optoelectronics, biological sensors, active waveguides and highly sensitive bioassays for in vitro detection in medical applications. The ways by which the weak fluorescence arising from electronic transition within the four f-configurations can be intensified will be discussed. This includes the intermixing of the four f-states with ligands of the host matrix, excitation to higher d-electronic states. Additional intensification of luminescence by plasmonic interaction with gold, silver and copper nanoparticles will be discussed. A short history of the time development of the research and the names of the scientists who made the major contribution of our understanding of lanthanides spectroscopy are presented.

  11. Chemical purification of lanthanides for low-background experiments

    Science.gov (United States)

    Boiko, R. S.

    2017-10-01

    There are many potentially active isotopes among the lanthanide elements which are possible to use for low-background experiments to search for double β decay, dark matter, to investigate rare α and β decays. These kind of experiments require very low level of radioactive contamination, but commercially available compounds of lanthanides are always contamined by uranium, thorium, radium, potassium, etc. A simple chemical method based on liquid-liquid extraction has been applied for the purification of CeO2, Nd2O3 and Gd˙2O˙3 from radioactive traces. Detailed schemes of purification procedure are described. Measurements by using HPGe spectrometry demonstrate high efficiency in K, Ra, Th, U contaminations reduction on at least one order of magnitude.

  12. Advancing the scientific basis of trivalent actinide-lanthanide separations

    International Nuclear Information System (INIS)

    Nash, K.L.

    2013-01-01

    For advanced fuel cycles designed to support transmutation of transplutonium actinides, several options have been demonstrated for process-scale aqueous separations for U, Np, Pu management and for partitioning of trivalent actinides and fission product lanthanides away from other fission products. The more difficult mutual separation of Am/Cm from La-Tb remains the subject of considerable fundamental and applied research. The chemical separations literature teaches that the most productive alternatives to pursue are those based on ligand donor atoms less electronegative than O, specifically N- and S-containing complexants and chloride ion (Cl - ). These 'soft-donor' atoms have exhibited usable selectivity in their bonding interactions with trivalent actinides relative to lanthanides. In this report, selected features of soft donor reagent design, characterization and application development will be discussed. The roles of thiocyanate, aminopoly-carboxylic acids and lactate in separation processes are detailed. (authors)

  13. Superabsorbing gel for actinide, lanthanide, and fission product decontamination

    Science.gov (United States)

    Kaminski, Michael D.; Mertz, Carol J.

    2016-06-07

    The present invention provides an aqueous gel composition for removing actinide ions, lanthanide ions, fission product ions, or a combination thereof from a porous surface contaminated therewith. The composition comprises a polymer mixture comprising a gel forming cross-linked polymer and a linear polymer. The linear polymer is present at a concentration that is less than the concentration of the cross-linked polymer. The polymer mixture is at least about 95% hydrated with an aqueous solution comprising about 0.1 to about 3 percent by weight (wt %) of a multi-dentate organic acid chelating agent, and about 0.02 to about 0.6 molar (M) carbonate salt, to form a gel. When applied to a porous surface contaminated with actinide ions, lanthanide ions, and/or other fission product ions, the aqueous gel absorbs contaminating ions from the surface.

  14. Ecotoxicité et comportement environnemental des lanthanides

    OpenAIRE

    Vignati, Davide,

    2017-01-01

    International audience; Le nom lanthanides indique une série de quinze éléments du tableau périodique allant du lanthane (La) au lutétium (Lu). Les lantha-nides font partie des éléments qualifiés de stratégiques à cause de leur importance dans plusieurs secteurs économiques tels que les énergies vertes, l'électronique et les applications médicales (1). L'utilisation croissante de ces éléments est en train d'en augmenter les concentrations environnementales et d'en altérer les cycles géochimiq...

  15. Ammonothermal synthesis of alkali-alkaline earth metal and alkali-rare earth metal carbodiimides. K{sub 5-x}M{sub x}(CN{sub 2}){sub 2+x}(HCN{sub 2}){sub 1-x} (M = Sr, Eu) and Na{sub 4.32}Sr{sub 0.68}(CN{sub 2}){sub 2.68}(HCN{sub 2}){sub 0.32}

    Energy Technology Data Exchange (ETDEWEB)

    Mallmann, Mathias; Haeusler, Jonas; Cordes, Niklas; Schnick, Wolfgang [Department of Chemistry, University of Munich (LMU) (Germany)

    2017-12-13

    Alkali-alkaline earth metal and alkali-rare earth metal carbodiimides, namely K{sub 5-x}M{sub x}(CN{sub 2}){sub 2+x}(HCN{sub 2}){sub 1-x} (x = 0 - 1) (M = Sr, Eu) and Na{sub 4.32}Sr{sub 0.68}(CN{sub 2}){sub 2.68}(HCN{sub 2}){sub 0.32}, were synthesized under ammonothermal conditions in high-pressure autoclaves. The structures of the three compounds can be derived from homeotypic K{sub 5}H(CN{sub 2}){sub 3} and Na{sub 5}H(CN{sub 2}){sub 3} by partial substitution of K{sup +} or Na{sup +}by Sr{sup 2+} or Eu{sup 2+}. The reactions were carried out in two step syntheses (T{sub 1} = 673 K, T{sub 2} = 823 K) starting from sodium or potassium azide, dicyandiamide and strontium or Eu(NH{sub 2}){sub 2}, respectively. The crystal structures were solved and refined from single-crystal X-ray diffraction data [K{sub 4.16}Sr{sub 0.84}(CN{sub 2}){sub 2.84}(HCN{sub 2}){sub 0.16}: space group Im3m (no. 229), a = 7.8304(5) Aa, Z = 2, R{sub 1} = 0.024, wR{sub 2} = 0.052; K{sub 4.40}Eu{sub 0.60}(CN{sub 2}){sub 2.60}(HCN{sub 2}){sub 0.40}: space group Im anti 3m (no. 229), a = 7.8502(6) Aa, Z = 2, R{sub 1} = 0.022, wR{sub 2} = 0.049]. In contrast to the potassium carbodiimides, the sodium-strontium carbodiimide was only synthesized as microcrystalline powder. The crystal structure was determined by powder X-ray diffraction and refined by the Rietveld method [Na{sub 4.32}Sr{sub 0.68}(CN{sub 2}){sub 2.68}(HCN{sub 2}){sub 0.32}: space group Im3m (no. 229), a = 7.2412(1) Aa, Z = 2, R{sub wp} = 0.050]. The presence of hydrogencyanamide units ([HNCN]{sup -}) next to carbodiimide units ([CN{sub 2}]{sup 2-}) in all compounds was confirmed by FT-IR spectroscopy. (copyright 2017 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  16. Magnetic dipole moments of odd-odd lanthanides

    International Nuclear Information System (INIS)

    Sharma, S.D.; Gandhi, R.

    1988-01-01

    Magnetic dipole moments of odd-odd lanthanides. Collective model of odd-odd nuclei is applied to predict the magnetic dipole moments, (μ) of odd-odd lanthanides. A simplified version of expression for μ based on diagonalisation of Hamiltonian (subsequent use of eigenvectors to compute μ) is developed for cases of ground state as well as excited states using no configuration mixing and is applied to the cases of odd-odd lanthanides. The formulae applied to the eleven (11) cases of ground states show significant improvement over the results obtained using shell model. Configuration mixing and coriolis coupling is expected to cause further improvement in the results. On comparing the earlier work in this direction the present analysis has clarified that in the expression μ the projection factors have different signs for the case I=Ωp - Ωn and I=Ωn - Ωp, and sign of μ is negative in general in the second case while it is positive in all others of spin projection alignments. Although the general expression holds for excited states as well but in lanthanide region, the experimental reports of magnetic dipole moments of excite states (band heads of higher rational sequences) are not available except in case of five (5) neutron resonance states which cannot be handled on the basis of the present approach with no configuration mixing. Although in the present discussion, the model could not be applied to excited states but the systematics of change in its magnitude with increasing spin at higher rational states is very well understood. The particle part supressed under faster rotation of the nuclear core and thus finally at higher spin I, the value μ is given by μ=g c I (same as in case of even-even nuclei). These systematics are to be verified whenever enough data for higher excited states are available. (author). 11 refs

  17. Using lanthanide chelates and uranyl compounds for diagnostic by fluoroimmunoassays

    International Nuclear Information System (INIS)

    Santos, Elen G.; Tomiyama, Claudia S.; Kodaira, Claudia A.; Felinto, Maria C.F.C.; Lourenco, Ana V. S.; Brito, Hermi F.

    2009-01-01

    The importance of the luminescence of lanthanide ions and UO 2 2+ is related to its peculiar characteristics, e.g. long lifetime and line-like emission bands in the visible, which make these ions unique among the species that are known to luminescence. Recent developments in the field of supramolecular chemistry have allowed the design of ligands capable of encapsulating lanthanide ions, thus forming kinetically inert complexes. By introduction of chromophoric groups in these ligands, an intense luminescence of the ion can be obtained via the 'antenna effect', defined as a light conversion process involving distinct absorbing (ligand) and emitting (metal ion) components. In such a process, the quantities that contribute to the luminescence intensity are the efficiency of the absorption, the efficiency of the ligand-metal energy transfer, and the efficiency of the metal luminescence. Encapsulation of lanthanide ions with suitable ligands may therefore give rise to 'molecular devices' capable to emit strong, long-lived luminescence. Besides the intrinsic interest in their excited state properties, compounds of lanthanide ions, in particular of the Eu 3+ and Tb 3+ ions, and now UO 2 2+ are important for their potential use as luminescent labels for biological species in fluoroimmunoassays (FIAs). This is most interesting because fluorimetric labeling represents an alternative method to the use of radioactive labels, which has long been the most common way of quantifying immunoreactions. In this article we report information about luminescent materials, which gave a good signal to quantify biological molecules by TR-FIA, DELFIA , DSLFIA, RIA and FRET. (author)

  18. Thermodecomposition of lanthanides (III) and ytrium (III) glucoheptonates

    International Nuclear Information System (INIS)

    Giolito, J.

    1987-01-01

    The lanthanides (III) and yttrium (III) glucoheptonates as well the D-glucoheptono 1-4 lactone were studied using common analytical methods, elemental microanalysis of carbon and hydrogen, thermogravimetry and differential scanning calorimetry. These compounds were prepared from the reaction between the lanthanides (III) and yttrium (III) hydroxides and glucoheptonic acid aqueous solution obtained by means of the delta lactone hydrolysis of this acid. After stoichiometric reaction the compounds were precipitated by the addition of absolute ethanol, washed with the same solvent and dried in desiccator. Thermogravimetric the (TG) curves of the lanthanides glucoheptonates of the ceric group present thermal profiles with enough differences permitting an easy caracterization of each compound and the yttrium (III) glucoheptonate TG curve showed a great similarity with the erbium (III) compound TG curve. The differential scanning calometry (DSC) curves showed endothermic and exothermic peaks by their shape, height and position (temperature) permit an easy and rapid identification of each compound specially if DSC and TG curves were examined simultaneously. (author) [pt

  19. Magnetic circular dichroism of porphyrin lanthanide M3+ complexes.

    Science.gov (United States)

    Andrushchenko, Valery; Padula, Daniele; Zhivotova, Elena; Yamamoto, Shigeki; Bouř, Petr

    2014-10-01

    Lanthanide complexes exhibit interesting spectroscopic properties yielding many applications as imaging probes, natural chirality amplifiers, and therapeutic agents. However, many properties are not fully understood yet. Therefore, we applied magnetic circular dichroism (MCD) spectroscopy, which provides enhanced information about the underlying electronic structure to a series of lanthanide compounds. The metals in the M(3+) state included Y, La, Eu, Tb, Dy, Ho, Er, Tm, Yb, and Lu; the spectra were collected for selected tetraphenylporphin (TPP) and octaethylporphin (OEP) complexes in chloroform. While the MCD and UV-VIS absorption spectra were dominated by the porphyrin signal, metal binding significantly modulated them. MCD spectroscopy was found to be better suited to discriminate between various species than absorption spectroscopy alone. The main features and trends in the lanthanide series observed in MCD and absorption spectra of the complexes could be interpreted at the Density Functional Theory (DFT) level, with effective core potentials on metal nuclei. The sum over state (SOS) method was used for simulation of the MCD intensities. The combination of the spectroscopy and quantum-chemical computations is important for understanding the interactions of the metals with the organic compounds. © 2014 Wiley Periodicals, Inc.

  20. Lanthanide phosphonates: Synthesis, thermal stability and magnetic characterization

    Energy Technology Data Exchange (ETDEWEB)

    Amghouz, Z., E-mail: amghouz.uo@uniovi.es [Departamentos de Quimica Fisica y Analitica y Quimica Organica e Inorganica, Universidad de Oviedo - CINN, 33006 Oviedo (Spain); Garcia, J.R.; Garcia-Granda, S. [Departamentos de Quimica Fisica y Analitica y Quimica Organica e Inorganica, Universidad de Oviedo - CINN, 33006 Oviedo (Spain); Clearfield, A. [Department of Chemistry, Texas A and M University, College Station, TX 77842-3012 (United States); Rodriguez Fernandez, J.; Pedro, I. de [CITIMAC, Facultad de Ciencias, Universidad de Cantabria, 39005 Santander (Spain); Blanco, J.A. [Departamento de Fisica, Universidad de Oviedo, 33007 Oviedo (Spain)

    2012-09-25

    Highlights: Black-Right-Pointing-Pointer Report of the complete series of lanthanide 1,4-phenylbis(phosphonate). Black-Right-Pointing-Pointer Synthesis under conventional hydrothermal synthesis or microwave-assisted hydrothermal synthesis. Black-Right-Pointing-Pointer Cation size is the key factor for the structural and particles size variations. Black-Right-Pointing-Pointer Thermal behaviour is characterized by unusual very high thermal stability. - Abstract: Series of novel organic-inorganic hybrids materials based on trivalent lanthanides (Ln = Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu) and 1,4-phenylbis(phosphonate) obtained under hydrothermal conditions either by oven heat or microwave irradiation. The anhydrous compounds containing La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, and Ho, are isostructural. However, the compounds based on Y, Er, Tm, Yb, and Lu are hydrated and their structures have not yet been solved. The series of compounds are characterized by PXRD, TEM, SEM-EDX and thermal analyses (TG-MS and DSC). TEM study show a variable particles size with a minimum mean-particle size of ca. 30 nm. These compounds exhibit unusual very high thermal stability. The size of particles and the thermal stability are depending on lanthanide(III) cation features. All the investigated materials show paramagnetic behaviour. The magnetic susceptibility data follow a Curie-Weiss laws with paramagnetic effective moments in good agreement with those expected for Ln{sup 3+} free ions.

  1. Humic and hymatomelanic acids interaction with lanthanide ions

    Science.gov (United States)

    Jerzykiewicz, Maria

    2012-10-01

    The interactions of lanthanide ions, REE(III), with semiquinone radicals naturally occurring in humic (HA) and hymatomelanic (HY) acids of different origin were studied mainly by EPR spectroscopy. Quantitative EPR analysis proved that only the semiquinone free radical concentration in both, HA and HY, was affected by interaction with some of the lanthanide ions, whereas the EPR g parameters of the formed radical-REE(III) complexes remained unchanged. The radical concentration was practically unaffected by the REE(III) ions with 4f1-4f6 electron configurations and in some degree increased by REE(III) ions with 4f8-4f14 configuration. The lanthanide playing an exceptional role was Gd(III) (4f7), which diminished strongly the free radicals concentration. The quenching ability of Gd(III) was stronger towards the radicals provided by HA than by HY, what was assigned to higher content in HA of both, oxygen-containing functional groups and conjugated aromatic rings, leading to more efficient Gd(III)-radical interaction. The semiquinone free radicals of HA and HY originated from the compost were more reactive than those from peat, as the humic acids from mature compost with less bulk density have more accessible functional groups.

  2. Novel open-framework architectures in lanthanide phosphonates

    Science.gov (United States)

    Groves, John A.; Stephens, Nicholas F.; Wright, Paul A.; Lightfoot, Philip

    2006-03-01

    Two novel three-dimensional lanthanide coordination polymers have been prepared hydrothermally with the phosphonic acid N,N-piperazine bis(methylenephosphonic acid), H 2O 3PCH 2N(C 2H 4) 2NCH 2PO 3H 2 ( LH 4). The structures of Gd 2( LH 2) 3ṡ3H 2O (I) and Nd 2( LH 2) 3ṡ9H 2O (II) have been characterised by single crystal X-ray techniques. One-dimensional 'lanthanide-phosphate' chains are a key feature in both structures, although there are major structural differences between the chains, with (I) displaying octahedral GdO 6 coordination and (II) showing eight-coordinate NdO 8 polyhedra. In each case, three-dimensional connectivity is completed by coordination of the phosphonate group resulting in open framework structures encapsulating loosely bound water molecules. Isostructural Y 3+ and Yb 3+ analogues of (I) have been prepared, suggesting that cation size is a key factor in controlling the differing reaction products. In the case of Y 2( LH 2) 3ṡ5H 2O, isostructural to (I), it is shown that the extra-framework water molecules may be removed reversibly without framework collapse. Structural relationships to other known lanthanide phosphonates are discussed.

  3. PIXE methodology of rare earth element analysis and its applications

    International Nuclear Information System (INIS)

    Ma Xinpei

    1992-01-01

    The Proton Induced X-ray Emission (PIXE) methodology of rare earth element (REEs) analysis is discussed, including the significance of REE analysis, the principle of PIXE applied to REE, selection of characteristic X-ray for Lanthanide series elements, deconvolution of highly over lapped PIXE spectrum and minimum detection limit (MDL) of REEs. Some practical applications are presented. And the specialities of PIXE analysis to the high pure REE chemicals are discussed. (author)

  4. Electron paramagnetic resonance and neutron activation study of lanthanide ions behaviour in fluorite. Application to the geochemical study of Montroc and Burc veins (Tarn)

    International Nuclear Information System (INIS)

    Meary, Alain

    1983-01-01

    In order to obtain a better understanding of fluorite deposits, rare earth impurities have been analyzed for a large number of samples taken from cross-sections of several low temperature hydrothermal veins; two types of measurements have been used: Electron Paramagnetic Resonance (EPR) and Neutron Activation Analysis (NAA). This enabled us to measure a 'deficit of spins' relative to the total lanthanide concentration, this deficit reveals that the paramagnetic center observed by EPR is not the only mode of incorporation. For Gd no marked deficit is observed; that is the ratio of spin concentrations to total concentration [Gd 3+ ]/[Gd total ] is close to 1 in all the samples; on the other hand, the ratios [Eu 2+ ]/[Eu total ], [Ce 3- F i - ]/[Ce total ], and [Yb 3+ ]/ [Yb total ] exhibit large variations. The first result suggests that the major part of the lanthanides in the samples is incorporated in the crystal lattice and that clustering of lanthanides ions is not important. Deficit of spins observed for Ce and Nd are probably due to the dissociation of paramagnetic complexes Ce 3+ -F i - and Nd 3+ -F i - ; for Eu, it may be attributed to the oxidized state Eu 3+ . Moreover, the sign and the amplitude of the anomaly exhibited by Eu in the normalized lanthanides spectra may be correlated with the majority valence state of Eu in the crystal: a marked positive anomaly belongs to a deficit of paramagnetic divalent Eu and, inversely, if divalent Eu is the majority valence state, the Eu anomaly appears to be negative. The results obtained for the Montroc vein are consistent with a model involving discontinuous injections of hydrothermal solutions. They may be connected to variations of oxygen fugacity arising from cooling of these solutions and from precipitation of sulfides during fluorite precipitation. (author) [fr

  5. Lanthanide Chemistry: From Coordination in Chemical Complexes Shaping Our Technology to Coordination in Enzymes Shaping Bacterial Metabolism.

    Science.gov (United States)

    Martinez-Gomez, Norma Cecilia; Vu, Huong N; Skovran, Elizabeth

    2016-10-17

    Lanthanide chemistry has only been extensively studied for the last 2 decades, when it was recognized that these elements have unusual chemical characteristics including fluorescent and potent magnetic properties because of their unique 4f electrons.1,2 Chemists are rapidly and efficiently integrating lanthanides into numerous compounds and materials for sophisticated applications. In fact, lanthanides are often referred to as "the seeds of technology" because they are essential for many technological devices including smartphones, computers, solar cells, batteries, wind turbines, lasers, and optical glasses.3-6 However, the effect of lanthanides on biological systems has been understudied. Although displacement of Ca 2+ by lanthanides in tissues and enzymes has long been observed,7 only a few recent studies suggest a biological role for lanthanides based on their stimulatory properties toward some plants and bacteria.8,9 Also, it was not until 2011 that the first biochemical evidence for lanthanides as inherent metals in bacterial enzymes was published.10 This forum provides an overview of the classical and current aspects of lanthanide coordination chemistry employed in the development of technology along with the biological role of lanthanides in alcohol oxidation. The construction of lanthanide-organic frameworks will be described. Examples of how the luminescence field is rapidly evolving as more information about lanthanide-metal emissions is obtained will be highlighted, including biological imaging and telecommunications.11 Recent breakthroughs and observations from different exciting areas linked to the coordination chemistry of lanthanides that will be mentioned in this forum include the synthesis of (i) macrocyclic ligands, (ii) antenna molecules, (iii) coordination polymers, particularly nanoparticles, (iv) hybrid materials, and (v) lanthanide fuel cells. Further, the role of lanthanides in bacterial metabolism will be discussed, highlighting the

  6. Metabolism and toxicity of rare earths

    International Nuclear Information System (INIS)

    Masse, R.

    1982-01-01

    From a radioprotection point of view, cerium is the most important element of rare earths. Isotopes 141, 143, 144 are present in fallout from weapon test. After some data concerning ecological concentration of cerium, the following points were emphasized: metabolism of cerium and lanthanides; route of intake into the human body (pulmonary pathway, digestive pathway, transcutaneous pathway); distribution of cerium after diffusion in blood (protein-bound cerium, organ distribution). Pathological effects due to contamination by 144 Ce were also studied and metabolic data (ICRP 30) were given with application for establishing limits of personnel exposure. (40 references) [fr

  7. Coordination symmetry determination of some lanthanide complexes by x-ray diffraction

    International Nuclear Information System (INIS)

    Oliveira Paiva Santos, C. de.

    1983-01-01

    The x-ray determination of the crystal and molecular structures of three lanthanide complexes is described. The work is a contribution to the study of the coordination chemistry of lanthanide ions with organic ligands and in particular, it aims to compare the observed point symmetry of the ion environment with spectroscopic predictions. (author)

  8. Process for recovering yttrium and lanthanides from wet-process phosphoric acid

    Energy Technology Data Exchange (ETDEWEB)

    Janssen, J.A.; Weterings, C.A.

    1983-06-28

    Process for recovering yttrium and lanthanides from wet-process phosphoric acid by adding a flocculant to the phosphoric acid, separating out the resultant precipitate and then recovering yttrium and lanthanides from the precipitate. Uranium is recovered from the remaining phosphoric acid.

  9. Adducts compounds of lanthanides (III) trifluoreacetates and yttrium and the N,N - dimenthylformamide

    International Nuclear Information System (INIS)

    Silva, M. das G. da.

    1983-01-01

    Some studies on lanthanides, f transition elements, and yttrium are presented. Adducts of lanthanides trifluoroacetates and N,N -dimethylformamide are described. The characterization of complexes from elementar analysis, conductance measurements, X-ray patterns, vibrational, electronics and fluorescence spectra are analysed. (M.J.C.) [pt

  10. Preparation, characterization and thermal behaviour study of double selenates of lanthanides, yttrium and beryllium

    International Nuclear Information System (INIS)

    Ribeiro, C.A.

    1988-01-01

    The lanthanides (III) and yttrium (III) double selenates were studied using common analytical methods, atomic absorption, X-ray diffraction infra-red absorption, thermogravimetry and differential thermal analysis. These compounds were prepared from the mixture of lanthanides (III) and yttrium (III) selenates aqueous solution and basic beryllium selenates aqueous solution, obeying equimolar relation (1:1) to the cation

  11. Rare earths: harvesting basic research for technology

    International Nuclear Information System (INIS)

    Jagatap, B.N.

    2014-01-01

    In recent years, rare earths are increasingly becoming a versatile platform for basic research that presents enormous technological potentials. A variety of nano-sized inorganic matrices varying from oxides, phosphates, gallates and aluminates, tungstates, stannates, vanadates to fluorides doped with different lanthanide ions have been synthesized and their optical properties have been investigated in the Chemistry Group, BARC. Another interesting application is laser cooling of solids using rare earth doped glasses with potential applications in remote cooling of electronic devices. Combining the luminescence properties of rare earths with photonic crystals is yet another potent area with wide ranging applications. In this presentation we provide an overview of these developments with examples from the R and D programs of the Chemistry Group, BARC

  12. Diverse lanthanide coordination polymers tuned by the flexibility of ligands and the lanthanide contraction effect: syntheses, structures and luminescence.

    Science.gov (United States)

    Zhou, Xiaoyan; Guo, Yanling; Shi, Zhaohua; Song, Xueqin; Tang, Xiaoliang; Hu, Xiong; Zhu, Zhentong; Li, Pengxuan; Liu, Weisheng

    2012-02-14

    Two new flexible exo-bidentate ligands were designed and synthesized, incorporating different backbone chain lengths bearing two salicylamide arms, namely 2,2'-(2,2'-oxybis(ethane-2,1-diyl)bis(oxy))bis(N-benzylbenzamide) (L(I)) and 2,2'-(2,2'-(ethane-1,2-diylbis(oxy))bis(ethane-2,1-diyl))bis(oxy)bis(N-benzylbenzamide) (L(II)). These two structurally related ligands are used as building blocks for constructing diverse lanthanide polymers with luminescent properties. Among two series of lanthanide nitrate complexes which have been characterized by elemental analysis, TGA analysis, X-ray powder diffraction, and IR spectroscopy, ten new coordination polymers have been determined using X-ray diffraction analysis. All the coordination polymers exhibit the same metal-to-ligand molar ratio of 2 : 3. L(I), as a bridging ligand, reacts with lanthanide nitrates forming two different types of 2D coordination complexes: herringbone framework {[Ln(2)(NO(3))(6)(L(I))(3)·mC(4)H(8)O(2)](∞) (Ln = La (1), and Pr (2), m = 1, 2)} as type I,; and honeycomb framework {[Ln(2)(NO(3))(6)(L(I))(3)·nCH(3)OH](∞) (Ln = Nd (3), Eu (4), Tb (5), and Er (6), n = 0 or 3)} as type II, which change according to the decrease in radius of the lanthanide. For L(II), two distinct structure types of 1D ladder-like coordination complexes were formed with decreasing lanthanide radii: [Ln(2)(NO(3))(6)(L(II))(3)·2C(4)H(8)O(2)](∞) (Ln = La (7), Pr (8), Nd (9)) as type III, [Ln(2)(NO(3))(6)(L(I))(3)·mC(4)H(8)O(2)·nCH(3)OH](∞) (Ln = Eu (10), Tb (11), and Er (12), m, n = 2 or 0) as type IV. The progressive structural variation from the 2D supramolecular framework to 1D ladder-like frameworks is attributed to the varying chain length of the backbone group in the flexible ligands. The photophysical properties of trivalent Sm, Eu, Tb, and Dy complexes at room temperature were also investigated in detail.

  13. Effect of certain alkaline metals on Pr doped glasses to investigate spectroscopic studies

    Science.gov (United States)

    Lenkennavar Susheela, K.; Madhu, A.; Eraiah, B.; Kokila, M. K.

    2018-02-01

    Incorporation of different Alkaline earth metal like Barium, Calcium and strontium in sodium lead borate glass doped with Pr3+ is studied. Physical parameters such as density, molar volume, molar refractivity etc have been evaluated. Effect of different atomic size of alkaline metal using optical and physical parameters is analysed. XRD and FTIR were carried out to know the structural behaviour of the glasses. Absorption and Emission spectra are recorded at room temperature and the results were discussed.

  14. Uranium prospecting in alkaline mountain chimneys of Serra Negra and Salitre - Minas Gerais, Brasil

    International Nuclear Information System (INIS)

    Souza Filho, J.G.C.

    1974-01-01

    The occurence of radioactive minerals such as apatite and pyrochlore, in the alkaline chimneys of Serra Negra and Salitre (Minas Gerais, Brazil), is discussed. Also mentioned are other minerals of interest associated with the alkaline magma such as columbite, fluorite, monazite, zircon, baddeleyite, etc, which in favourable conditions may occur in deposits of great economical value, and which may present high contents of rare earths, thorium and uranium

  15. Effect of indium addition in U-Zr metallic fuel on lanthanide migration

    Science.gov (United States)

    Kim, Yeon Soo; Wiencek, T.; O'Hare, E.; Fortner, J.; Wright, A.; Cheon, J. S.; Lee, B. O.

    2017-02-01

    Advanced fast reactor concepts to achieve ultra-high burnup (∼50%) require prevention of fuel-cladding chemical interaction (FCCI). Fission product lanthanide accumulation at high burnup is substantial and significantly contributes to FCCI upon migration to the cladding interface. Diffusion barriers are typically used to prevent interaction of the lanthanides with the cladding. A more active method has been proposed which immobilizes the lanthanides through formation of stable compounds with an additive. Theoretical analysis showed that indium, thallium, and antimony are good candidates. Indium was the strongest candidate because of its low reactivity with iron-based cladding alloys. Characterization of the as-fabricated alloys was performed to determine the effectiveness of the indium addition in forming compounds with lanthanides, represented by cerium. Tests to examine how effectively the dopant prevents lanthanide migration under a thermal gradient were also performed. The results showed that indium effectively prevented cerium migration.

  16. Effect of indium addition in U-Zr metallic fuel on lanthanide migration

    Energy Technology Data Exchange (ETDEWEB)

    Kim, Yeon Soo; Wiencek, T.; O' Hare, E.; Fortner, J.; Wright, A.; Cheon, J. S.; Lee, B. O.

    2017-02-01

    Advanced fast reactor concepts to achieve ultra-high burnup (~50%) require prevention of fuel-cladding chemical interaction (FCCI). Fission product lanthanide accumulation at high burnup is substantial and significantly contributes to FCCI upon migration to the cladding interface. Diffusion barriers are typically used to prevent interaction of the lanthanides with the cladding. A more active method has been proposed which immobilizes the lanthanides through formation of stable compounds with an additive. Theoretical analysis showed that indium, thallium, and antimony are good candidates. Indium was the strongest candidate because of its low reactivity with iron-based cladding alloys. Characterization of the as-fabricated alloys was performed to determine the effectiveness of the indium addition in forming compounds with lanthanides, represented by cerium. Tests to examine how effectively the dopant prevents lanthanide migration under a thermal gradient were also performed. The results showed that indium effectively prevented cerium migration.

  17. Crystal structure study of new lanthanide silicates with silico-carnotite structure

    International Nuclear Information System (INIS)

    Piccinelli, F.; Lausi, A.; Speghini, A.; Bettinelli, M.

    2012-01-01

    The crystal structures of new rare earth-based silicate compounds (Ca 3 Eu 2 Si 3 O 12 , Ca 3 Gd 2 Si 3 O 12 , Ca 3 Dy 2 Si 3 O 12 , Ca 3 Er 2 Si 3 O 12 and Ca 3 Lu 2 Si 3 O 12 ) have been determined using powder X-ray diffraction. From Rietveld refinement calculations on the collected powder patterns we observe a different distribution of the rare earth ions on the three available crystal sites characterized by different coordination numbers, depending on the ionic radius of the rare earth ion. The reasons of the instability of the silico-carnotite structure for lanthanide ions larger than Eu 3+ have been deduced. In addition, in order to detect crystal phase transitions, the powder patterns of Ca 3 Eu 2 Si 3 O 12 and Ca 3 Sm 2 Si 3 O 12 samples have been collected as a function of the temperature (RT-1000 °C range), but no phase transitions have been observed. - Graphical abstract: Synchrotron X-ray diffraction allows us the accurate determination of the RE 3+ ions distribution on the three available crystal sites of the silico-carnotite structure. Highlights: ► The structure of the Ca 3 M 2 Si 3 O 12 (M=Eu, Gd, Dy, Er and Lu) was determined. ► Different distribution of RE 3+ ions on the three available crystal sites was observed. ► The instability of the silico-carnotite structure for RE=La→Sm was discussed.

  18. Synthesis and Characterization of Alkaline-Earth Indium Sulfides

    Science.gov (United States)

    1990-06-01

    CaS and In2S3 in an evacuated silica ampule, has the normal spinel structure (a = 10.77 ).1 This report is surprising, since the large Ca 2 + ion would...Ca3.1In6.6S13, 4 has been synthesized as yellow whiskers by iodine transport of a mixture of CaS and In2S3 . An X-ray single-crystal structure determination 5...mixture of CaS (Cerac 99.99%) and In2S3 (prepared from In(NO3)3 and H2S at 750’C) was pre-reacted in a graphite crucible in an evacuated silica

  19. Spectroscopic characterization of manganese-doped alkaline earth ...

    Indian Academy of Sciences (India)

    1. Introduction. Recent technological applications have generated more importance in the studies of different types of glasses owing to their structural properties.1,2 One of them is phosphate glass, which owing to their hygroscopic nature and volatil- ity was not considered to have industrial and technological applications.

  20. Topological nodal loop semimetals and insulators in alkaline earth triarsenides

    Science.gov (United States)

    Pickett, Warren E.; Quan, Yundi; Dong, Lianyang; Siegrist, Theo; Trinh, Jennifer; Ramirez, Arthur J.; Li, Haoxiang; Zhou, Xiaoqing; Dessau, Daniel S.

    The XAs3 class of semimetals has remained unexplored since their discovery in the 1980s by Bauhofer and von Schnering. We have discovered that this class, with X=Ca, Sr, Ba, Eu, are nodal loop semimetals (NLS), having a single loop of accidental degeneracies crossing the Fermi energy and a gap elsewhere in the zone: the nodal loop region dominates the transport Large single crystals of monoclinic SrAs3 have been synthesized, allowing studies of its magnetotransport properties andits ARPES spectrum. Density functional calculations reveal that monoclinic CaAs3, the sole insulating member of this class, would be a NLS in the absence of spin-orbit coupling (SOC). The position and characters of the nodal Fermi surfaces and associated boundard states will be discussed. The stark low symmetry of monoclinic CaAs3 (with only inversion symmetry) makes it the ``hydrogen atom'' of NLSs; unlike all other classes, space group symmetry does not provide any ``protection'' of its loop of accidental degeneracies. Supported by the NSF DMREF program.

  1. Syntheses and Structural Characterization of the Alkaline Earth and ...

    Indian Academy of Sciences (India)

    dell

    checkCIF/PLATON report. You have not supplied any structure factors. As a result the full set of tests cannot be run. THIS REPORT IS FOR GUIDANCE ONLY. IF USED AS PART OF A REVIEW PROCEDURE. FOR PUBLICATION, IT SHOULD NOT REPLACE THE EXPERTISE OF AN EXPERIENCED. CRYSTALLOGRAPHIC ...

  2. Synthesis and infrared spectra of alkaline earth metal carbonates ...

    Indian Academy of Sciences (India)

    The metal carbonate, MCO3 (M = Ca, Sr and Ba), was synthesized by a novel method of reacting aqueous solution of each of Ca2+, Sr2+ and Ba2+ salts with urea at high temperature, ∼ 80°C. The reaction products were characterized through elemental analysis and infrared spectra. The infrared spectra of the products are ...

  3. Mixed alkaline earth effect in sodium aluminosilicate glasses

    DEFF Research Database (Denmark)

    Kjeldsen, Jonas; Smedskjær, Morten Mattrup; Mauro, John C.

    2013-01-01

    modifiers. We suggest that, since the elastic properties of the investi-gated system are compositionally independent, the minimum in Vickers microhardness is closely correlated to the minimum in isokom temperatures. Both of these properties are related to plasticflow and the translational motion......, glass transition temperature, Vickers microhardness, and isokomtemperatures (viz., the temperatures atη=10^13.5 and 10^12.2 Pa s). The observed min-ima in fragility, glass transition temperature, and isokom temperature are ascribed to bond weakening in the local structural environment around the network...

  4. Synthesis of monomeric and polymeric alkali and alkaline earth ...

    Indian Academy of Sciences (India)

    trimethylsilyl)amide with phosphinoselenoic amide ligand (1) at ambient temperature. The calcium complex 4 was prepared by two synthetic routes: in the first method, commonly known as salt metathesis reaction, the potassium complex 2 was ...

  5. Structural variations in layered alkaline earth metal cyclohexyl ...

    Indian Academy of Sciences (India)

    Administrator

    sensors and nonlinear optical materials (Wan et al 1994). Zirconium phosphonates were the first examples of this class of compounds which has structures ... various diseases of bones and calcium metabolism made the chemistry of calcium phosphonates particularly appealing. This led to the synthesis and structural ...

  6. Synthesis and infrared spectra of alkaline earth metal carbonates ...

    Indian Academy of Sciences (India)

    Unknown

    ... Sr2+ and Ba2+ salts with urea at high temperature, ~ 80°C. The reaction products were characterized through elemental analysis and infrared spectra. The infrared spectra of the products are the same as those of the corresponding commercially obtained carbonates. A general reaction describing the formation of MCO3 ...

  7. Structural variations in layered alkaline earth metal cyclohexyl ...

    Indian Academy of Sciences (India)

    2O) (M = Ca, Sr and Ba) (1–3) and M(C6H11PO3)(H2O) (M = Mg, Ca, Sr, and Ba) (4–7) have been synthesized under mild reaction conditions. All new compounds have been characterized using elemental analysis, IR, TGA and powder X-ray ...

  8. Aluminum/alkaline earth metal composites and method for producing

    Science.gov (United States)

    Russell, Alan M; Anderson, Iver E; Kim, Hyong J; Freichs, Andrew E

    2014-02-11

    A composite is provided having an electrically conducting Al matrix and elongated filaments comprising Ca and/or Sr and/or Ba disposed in the matrix and extending along a longitudinal axis of the composite. The filaments initially comprise Ca and/or Sr and/or Ba metal or allow and then may be reacted with the Al matrix to form a strengthening intermetallic compound comprising Al and Ca and/or Sr and/or Ba. The composite is useful as a long-distance, high voltage power transmission conductor.

  9. Spectroscopic characterization of manganese-doped alkaline earth ...

    Indian Academy of Sciences (India)

    technological applications, such as medical use and sealing materials.5. The interest in glasses containing transition metal ions has grown6 because these ... mation on some of structural and dynamic phenomenon of a material; and to identify the site symmetry around the transi- tion metal ions in glasses.8 The aim of ...

  10. Comparative investigation on the effect of alkaline earth oxides on ...

    Indian Academy of Sciences (India)

    Unknown

    bands due to electronic transition from 2Eg → 2T2g energy level in an octahedral coordination of Cu2+ ion. ... due to its d–d spin allowed ligand field transition whereas. Cr6+ (3d0) produces lemon yellow colour due to ... analytical reagent grade sodium carbonate, calcium car- bonate, strontium carbonate and barium ...

  11. Dissolution of alkaline earth sulfates in the presence of montmorillonite

    Science.gov (United States)

    Eberl, D.D.; Landa, E.R.

    1985-01-01

    In a study of the effect of montmorillonite on the dissolution of BaSO4 (barite), SrSO4 (celestite), and 226Ra from U mill tailings, it was found that: (1) More of these substances dissolve in an aqueous system that contains montmorillonite than dissolve in a similar system without clay, due to the ion exchange properties of the clay; (2) Na-montmorillonite is more effective in aiding dissolution than is Ca-montmorillonite; (3) the amount of Ra that moves from mill tailings to an exchanger increases as solution sulfate activity decreases. Leaching experiments suggest that 226Ra from H2SO4-circuit U mill tailings from Edgemont, South Dakota, is not present as pure Ra sulfate or as an impurity in anhydrite or gypsum; it is less soluble, and probably occurs as a trace constituent in barite.

  12. Improvement of the ICRP20 alkaline earth model

    International Nuclear Information System (INIS)

    Schlenker, R.A.; Keane, A.T.

    1982-01-01

    The ICRP20 model has been adjusted to fit data on the retention of 226 Ra in soft tissue and data on the short-term retention of 226 Ra in bone. New values of five parameters are given for use in the Ra retention functions. Effective retention integrals have been recalculated using the new parameters. In addition, new estimates have been made of the percentages of the body's natural Ca, Sr, Ba and Ra which reside in soft tissue. A reanalysis of autoradiographic data has also been performed

  13. Destructive Adsorption of Carbon Tetrachloride on Alkaline Earth Metal Oxides

    NARCIS (Netherlands)

    Weckhuysen, B.M.; Mestl, Gerhard; Rosynek, Michael P.; Krawietz, Thomas R.; Haw, James F.; Lunsford, Jack H.

    1998-01-01

    The destructive adsorption of CCl4 on MgO, CaO, SrO, and BaO has been studied as a function of the reaction temperature and the amount of CCl4 injected. The reaction was followed using in situ Raman spectroscopy, X-ray photoelectron spectroscopy, Fourier transform infrared spectroscopy, and 13 C

  14. Positronium hydride defects in thermochemically reduced alkaline-Earth oxides

    International Nuclear Information System (INIS)

    Monge, M.A.; Pareja, R.; Gonzalez, R.; Chen, Y.

    1997-01-01

    Thermochemical reduction of both hydrogen-doped MgO and CaO single crystals results in large concentrations of hydride (H - ) ions. In MgO crystals, positron lifetime and Doppler broadening experiments show that positrons are trapped at H - centers forming positronium hydride molecules [e + - H - ]. A value of 640 ps is obtained for the lifetime of the PsH states located in an anion vacancy In MgO positrons are also trapped at H 2- sites at low temperatures. The H 2- ions were induced in the crystals by blue light illumination. The formation of PsH states in CaO could not be conclusively established. (orig.)

  15. Syntheses and structural characterization of the alkaline earth and ...

    Indian Academy of Sciences (India)

    13 The structures were solved by Direct Methods (SHELXS-97)14 and refined by full- matrix least-square methods against F2 (SHELXL-97). All non-hydrogen atoms were refined with anisotropic displacement parameters. The hydrogen atoms ...

  16. RESISTIVITIES AND BAND STRUCTURES OF ALKALINE-EARTH-PNICTIDE SYSTEMS

    NARCIS (Netherlands)

    XU, R; DEGROOT, RA; VANDERLUGT, W

    1993-01-01

    The electrical resistivities p of the liquid Sr-Bi and Sr-Sb alloys have been determined for compositions covering the whole concentration range. Plotted as a function of composition the results resemble those obtained previously for Mg-Bi by other authors. There is a very sharp resistivity maximum

  17. Moessbauer effect of the alkaline and alkaline earth metal nitroprusside powders

    CERN Document Server

    Yang, T H; Kim, H S; Hong, C Y; Kim, H B; Cho, H Y; Kim, D Y; Moon, Y S

    2000-01-01

    We observe Moessbauer spectra of Fe atoms centered in nitroprusside anions of sodium nitroprusside (Na sub 2 [Fe(CN) sub 5 NO] 2H sub 2 O). potassium-nitroprusside (K sub 2 [Fe(CN)] sub 5 NO centre dot 2.5H sub 2 O), rubidium nitroprusside (Rb sub 2 [Fe(CN) sub 5 NO centre dot H sub 2 O), magnesium nitroprusside (Mg[Fe(CN) sub 5 NO], calcium nitroprusside (Ca[Fe(CN) sub 5 NO]centre dot 4H sub 2 O), and barium nitroprusside (Ba[Fe(CN) sub 5 NO]centre dot 3H sub 2 O) samples which have photochromic properties. We compare the Moessbauer parameters, the values of the isomer shifts and the quadrupole splittings of the samples with those of a sodium nitroprusside single crystal which is a standard material. The values of the isomer shifts and the quadrupole splittings of the various compounds are close to each other. The values of the line broadening of all samples are between 2.1 GAMMA sub N and 2.5 GAMMA sub N. The Moessbauer Lamb factors (f) are between 0.252(1) and 0.340(2). These values are obtained from the s...

  18. Production by metallothermics of pure alloys of rare earths and transition metals

    International Nuclear Information System (INIS)

    Jourdan, A.

    1988-01-01

    Industrial process of production of high purity master alloys ingots by the thermite process from a rare earth compound which is reduced by a reducing agent like alkaline or alkaline earth metals. The process is characterized by introduction of the transition metal into the initial reaction mixture, at least in part, as a compound than can be reduced by the reducing agent [fr

  19. Geology and petrology of Lages Alkaline District, Santa Catarina State

    International Nuclear Information System (INIS)

    Scheibe, L.F.

    1986-01-01

    A 1:100.000 geological map shows the main outcrops, covering about 50 Km 2 , of the leucocratic alkaline rocks, ultra basic alkaline rocks, carbonatites and volcanic breccias which intruded the Gondwanic sedimentary rocks within a short time interval and characterize the Alkaline District of Lages. Chemical analyses of 33 whole-rock samples confirm the petrographic classification, but the agpaitic indexes, mostly below 1.0, do not reflect the mineralogical variations of the leucocratic alkaline rocks adequately. Partial REE analyses indicate that the light as well as the heavy rare earth contents decrease from the basic to the more evolved rocks, the La/Y ratio remaining approximately constant. Eleven new K/Ar ages from porphyritic nepheline syenites porphyritic phonolites, ultra basic alkaline rocks and pipe-breccias, together with six already available ages, show a major concentration in the range 65 to 75 Ma, with a mode at ca. 70 Ma. But one Rb/Sr whole-rock reference isochron diagram gives an age of 82+-6 Ma for the agpaitic phonolites of the Serra Chapada, which are considered younger than the miaskitic porphyriric nepheline syenites. The 87 Sr/ 86 Sr ratios of 0.705-0.706 are compatible with a sub continental mantelic origin, devoid of crustal contamination. A petrogenetic model based on subtraction diagrams and taking into consideration the geologic, petrographic, mineralogic and petrochemical characteristics of the alkaline rocks of Lages consists of limited partial melting with CO 2 , contribution of the previously metasomatized upper mantle, in a region submitted to decompression. (author)

  20. Catalytic Diversity in Alkaline Hydrothermal Vent Systems on Ocean Worlds

    Science.gov (United States)

    Cameron, Ryan D.; Barge, Laura; Chin, Keith B.; Doloboff, Ivria J.; Flores, Erika; Hammer, Arden C.; Sobron, Pablo; Russell, Michael J.; Kanik, Isik

    2016-10-01

    Hydrothermal systems formed by serpentinization can create moderate-temperature, alkaline systems and it is possible that this type of vent could exist on icy worlds such as Europa which have water-rock interfaces. It has been proposed that some prebiotic chemistry responsible for the emergence of life on Earth and possibly other wet and icy worlds could occur as a result ofredox potential and pH gradients in submarine alkaline hydrothermal vents (Russell et al., 2014). Hydrothermal chimneys formed in laboratory simulations of alkaline vents under early Earth conditions have precipitate membranes that contain minerals such as iron sulfides, which are hypothesized to catalyze reduction of CO2 (Yamaguchi et al. 2014, Roldan et al. 2014) leading to further organic synthesis. This CO2 reduction process may be affected by other trace components in the chimney, e.g. nickel or organic molecules. We have conducted experiments to investigate catalytic properties of iron and iron-nickel sulfides containing organic dopants in slightly acidic ocean simulants relevant to early Earth or possibly ocean worlds. We find that the electrochemical properties of the chimney as well as the morphology/chemistry of the precipitate are affected by the concentration and type of organics present. These results imply that synthesis of organics in water-rock systems on ocean worlds may lead to hydrothermal precipitates which can incorporate these organic into the mineral matrix and may affect the role of gradients in alkaline vent systems.Therefore, further understanding on the electroactive roles of various organic species within hydrothermal chimneys will have important implications for habitability as well as prebiotic chemistry. This work is funded by NASA Astrobiology Institute JPL Icy Worlds Team and a NAI Director's Discretionary Fund award.Yamaguchi A. et al. (2014) Electrochimica Acta, 141, 311-318.Russell, M. J. et al. (2014), Astrobiology, 14, 308-43.Roldan, A. (2014) Chem. Comm. 51

  1. A series of three-dimensional architectures constructed from lanthanide-substituted polyoxometalosilicates and lanthanide cations or lanthanide-organic complexes as linkers.

    Science.gov (United States)

    An, Haiyan; Zhang, Hua; Chen, Zhaofei; Li, Yangguang; Liu, Xuan; Chen, Hao

    2012-07-21

    Six 3D architectures based on lanthanide-substituted polyoxometalosilicates, KLn[(H(2)O)(6)Ln](2)[(H(2)O)(4)LnSiW(11)O(39)](2)·nH(2)O (Ln = La 1, n = 42; Ce 2, n = 40), H[(H(2)O)(6)Nd](2)[(H(2)O)(7)Nd][(H(2)O)(4)NdSiW(11)O(39)][(H(2)O)(3)NdSiW(11)O(39)]·13H(2)O (3), H(2)K(2)[(Hpic)(H(2)O)(5)Ln](2)[(H(2)O)(4)LnSiW(11)O(39)](2)·nH(2)O (Ln = La 4, n = 18.5; Ce 5, n = 35; Nd 6, n = 36; Hpic = 4-picolinic acid), have been synthesized and characterized by elemental analysis, IR and UV-vis spectroscopy, TG analysis, powder X-ray diffraction and single crystal X-ray diffraction. Compounds 1 and 2 are isostructural, built up of lanthanide-substituted polyoxoanions [{(H(2)O)(4)Ln(SiW(11)O(39))}(2)](10-) linked by Ln(3+) cations to form a 3D open framework with 1D channels. The polyoxoanion [{(H(2)O)(4)Ln(SiW(11)O(39))}(2)](10-) consists of two α(1)-type mono-Ln-substituted Keggin anions. When Nd(3+) ion was used instead of La(3+) or Ce(3+) ions, compound 3 with a different structure was obtained, containing two kinds of polyoxoanions [{(H(2)O)(4)Nd(SiW(11)O(39))}(2)](10-) and [{(H(2)O)(3)Nd(SiW(11)O(39))}(2)](10-) which are connected together by Nd(3+) ions to yield a 3D framework. When 4-picolinic acid was added to the reaction system of 1-3, isostructural compounds 4-6 were obtained, constructed from the polyoxoanions [{(H(2)O)(4)Ln(SiW(11)O(39))}(2)](10-) linked by picolinate-chelated lanthanide centers to form a 3D channel framework. From a topological viewpoint, the 3D nets of 1, 2, 4, 5 and 6 exhibit a (3,6)-connected rutile topology, whereas the 3D structure of 3 possesses a rare (3,3,6,10)-connected topology. The magnetic properties of 2, 3, 5 and 6 have been studied by measuring their magnetic susceptibilities in the temperature range 2-300 K.

  2. Radiation-induced disorder in compressed lanthanide zirconates.

    Science.gov (United States)

    Park, Sulgiye; Tracy, Cameron L; Zhang, Fuxiang; Park, Changyong; Trautmann, Christina; Tkachev, Sergey N; Lang, Maik; Mao, Wendy L; Ewing, Rodney C

    2018-02-28

    The effects of swift heavy ion irradiation-induced disordering on the behavior of lanthanide zirconate compounds (Ln 2 Zr 2 O 7 where Ln = Sm, Er, or Nd) at high pressures are investigated. After irradiation with 2.2 GeV 197 Au ions, the initial ordered pyrochlore structure (Fd3[combining macron]m) transformed to a defect-fluorite structure (Fm3[combining macron]m) in Sm 2 Zr 2 O 7 and Nd 2 Zr 2 O 7 . For irradiated Er 2 Zr 2 O 7 , which has a defect-fluorite structure, ion irradiation induces local disordering by introducing Frenkel defects despite retention of the initial structure. When subjected to high pressures (>29 GPa) in the absence of irradiation, all of these compounds transform to a cotunnite-like (Pnma) phase, followed by sluggish amorphization with further compression. However, if these compounds are irradiated prior to compression, the high pressure cotunnite-like phase is not formed. Rather, they transform directly from their post-irradiation defect-fluorite structure to an amorphous structure upon compression (>25 GPa). Defects and disordering induced by swift heavy ion irradiation alter the transformation pathways by raising the energetic barriers for the transformation to the high pressure cotunnite-like phase, rendering it inaccessible. As a result, the high pressure stability field of the amorphous phase is expanded to lower pressures when irradiation is coupled with compression. The responses of materials in the lanthanide zirconate system to irradiation and compression, both individually and in tandem, are strongly influenced by the specific lanthanide composition, which governs the defect energetics at extreme conditions.

  3. Structural and electronic relationships between the lanthanide and actinide elements

    International Nuclear Information System (INIS)

    Johansson, Boerje

    2000-01-01

    The similarity and difference between the solid state properties of the 4f and 5f transition metals are pointed out. The heavier 5f elements show properties which have direct correspondence to the early 4f transition metals, suggesting a localized behaviour of the 5f electrons for those metals. On the other hand, the fact that Pu metal has a 30% lower volume than its neighbour heavier element, Am, suggests a tremendous difference in the properties of the 5f electrons for this element relative to the heavier actinides. This change in behaviour between Pu and Am can be viewed as a Mott transition within the 5f shell as a function of the atomic number Z. On the metallic 5f side of the Mott transition (i.e., early actinides), the elements show most unusual crystal structures, the common feature being their low symmetry. An analogous behaviour for the lanthanides is found in cerium metal under compression, where structures typical for the light actinides have been observed experimentally. A generalized phase diagram for the actinides is shown to contain features comparable to the individual phase diagram of Ce metal. The crystal structure behaviour of the lanthanides and heavier actinides is determined by the number of 5d (or 6d) electrons in the metallic state, since for these elements the f electrons are localized and nonbonding. For the earlier actinide metals electronic structure calculations - where the 5f orbitals are treated as part of the valence bands - account very well for the observed ground state crystal structures. The distorted structures can be understood as Peierls distortions away from the symmetric bcc structure and originate from strongly bonding 5f electrons occupying relatively narrow 5f states. High pressure is an extremely useful experimental tool to demonstrate the interrelationship between the lanthanides and the actinides

  4. Increasing lanthanide luminescence by use of the RETEL effect.

    Science.gov (United States)

    Leif, Robert C; Vallarino, Lidia M; Becker, Margie C; Yang, Sean

    2006-08-01

    Luminescent lanthanide complexes produce emissions with the narrowest-known width at half maximum; however, their significant use in cytometry required an increase in luminescence intensity. The companion review, Leif et al., Cytometry 2006;69A:767-778, described a new technique for the enhancement of lanthanide luminescence, the Resonance Energy Transfer Enhanced Luminescence (RETEL) effect, which increases luminescence and is compatible with standard slide microscopy. The luminescence of the europium ion macrocyclic complex, EuMac, was increased by employing the RETEL effect. After adding the nonluminescent gadolinium ion complex of the thenoyltrifluoroacetonate (TTFA) ligand or the sodium salt of TTFA in ethanol solution, the EuMac-labeled sample was allowed to dry. Both a conventional arc lamp and a time-gated UV LED served as light sources for microscopic imaging. The emission intensity was measured with a CCD camera. Multiple time-gated images were summed with special software to permit analysis and effective presentation of the final image. With the RETEL effect, the luminescence of the EuMac-streptavidin conjugate increased at least six-fold upon drying. Nuclei of apoptotic cells were stained with DAPI and tailed with 5BrdUrd to which a EuMac-anti-5BrdU conjugate was subsequently attached. Time-gated images showed the long-lived EuMac luminescence but did not show the short-lived DAPI fluorescence. Imaging of DNA-synthesizing cells with an arc lamp showed that both S phase and apoptotic cells were labeled, and that their labeling patterns were different. The images of the luminescent EuMac and fluorescent DAPI were combined to produce a color image on a white background. This combination of simple chemistry, instrumentation, and presentation should make possible the inexpensive use of the lanthanide macrocycles, Quantum Dyes, as molecular diagnostics for cytological and histopathological microscopic imaging. (c) 2006 International Society for Analytical

  5. Magnetic Circular Dichroism of Porphyrin Lanthanide M3+ Complexes

    Czech Academy of Sciences Publication Activity Database

    Andrushchenko, Valery; Padula, Daniele; Zhivotova, E.; Yamamoto, S.; Bouř, Petr

    2014-01-01

    Roč. 26, č. 10 (2014), s. 655-662 ISSN 0899-0042 R&D Projects: GA ČR GA13-03978S; GA ČR GAP208/11/0105; GA MŠk(CZ) LH11033 Grant - others:GA AV ČR(CZ) M200550902 Institutional support: RVO:61388963 Keywords : magnetic circular dichroism * lanthanides * porphyrin complexes * density functional theory * sum over state computations Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 1.886, year: 2014

  6. Lanthanide crown ether complexes of p-sulfonatocalix[5]arene.

    Science.gov (United States)

    Dalgarno, Scott J; Hardie, Michaele J; Warren, John E; Raston, Colin L

    2004-08-21

    Two types of arrays are formed in water involving aza-crown ethers, p-sulfonatocalix[5]arene and europium(III) ions. One is a co-ordination polymer connecting calixarenes, sodium ions and lanthanide ions based on "ferris wheel" moieties incorporating aza-18-crown-6 and sodium ions. The second structure is a host-guest arrangement with di-protonated diaza-18-crown-6 in the cavity of the calixarenes as part of secondary coordination spheres of aquated europium(iii) ions.

  7. Status of the lanthanides and actinides in the periodic table

    International Nuclear Information System (INIS)

    Holden, N.E.

    1985-01-01

    In extended discussions and correspondence with Ekkehard Fluck, the author was made aware of a problem with the Periodic Table, i.e., which element should be shown in the main table as the representative of the lanthanide series and the actinide series. In earlier discussion, he came to the conclusion that lanthanum and actinium are not the elements which should appear, but rather lutetium and lawrencium are more appropriate for inclusion in their place. This paper will attempt to justify the reasons for the above conclusions. 4 refs

  8. Luminescent Lanthanide MOFs: A Unique Platform for Chemical Sensing.

    Science.gov (United States)

    Zhao, Shu-Na; Wang, Guangbo; Poelman, Dirk; Voort, Pascal Van Der

    2018-04-07

    In recent years, lanthanide metal-organic frameworks (LnMOFs) have developed to be an interesting subclass of MOFs. The combination of the characteristic luminescent properties of Ln ions with the intriguing topological structures of MOFs opens up promising possibilities for the design of LnMOF-based chemical sensors. In this review, we present the most recent developments of LnMOFs as chemical sensors by briefly introducing the general luminescence features of LnMOFs, followed by a comprehensive investigation of the applications of LnMOF sensors for cations, anions, small molecules, nitroaromatic explosives, gases, vapors, pH, and temperature, as well as biomolecules.

  9. Recent progress in actinide and lanthanide solvent extraction

    International Nuclear Information System (INIS)

    Musikas, C.; Hubert, H.; Benjelloun, N.; Vitorge, P.; Bonnin, M.; Forchioni, A.; Chachaty, C.

    1983-04-01

    Work in progress on actinide solvent extraction is briefly reviewed in this paper. 1 H and 31 P NMR are used to elucidate several fundamental unsolved problems concerning organophosphorous extractants often used in actinides extraction: determination of site of dialkylthiophosphate protonation and addition of basic phosphine oxide to dibutylthiophosphoric acid dimer. Extraction of Am III and Eu from high radioactivity level wastes by tetrasubsituted methylene diamides is investigated. Trivalent actinide-lanthanide group are separated by solvent extraction using soft donor ligand complexes which are more stable. The synergism of dinonylnaphtalene sulfonic acid (HDNNS) associated with several neutral donors like TBP, TOPO, amides are examined in the trivalent and tetravalent actinide extraction

  10. Introduction to molecular magnetism from transition metals to lanthanides

    CERN Document Server

    Benelli, Cristiano

    2015-01-01

    This first introduction to the rapidly growing field of molecular magnetism is written with Masters and PhD students in mind, while postdocs and other newcomers will also find it an extremely useful guide. Adopting a clear didactic approach, the authors cover the fundamental concepts, providing many examples and give an overview of the most important techniques and key applications. Although the focus is one lanthanide ions, thus reflecting the current research in the field, the principles and the methods equally apply to other systems. The result is an excellent textbook from both a scientif

  11. Lanthanide-Organic Gels as a Multifunctional Supramolecular Smart Platform.

    Science.gov (United States)

    Silva, José Yago Rodrigues; da Luz, Leonis Lourenço; Mauricio, Filipe Gabriel Martinez; Vasconcelos Alves, Iane Bezerra; Ferro, Jamylle Nunes de Souza; Barreto, Emiliano; Weber, Ingrid Távora; de Azevedo, Walter Mendes; Júnior, Severino Alves

    2017-05-17

    A multifunctional smart supramolecular platform based on a lanthanide-organic hydrogel is presented. This platform, which provides unique biocompatibility and tunable optical properties, is synthesized by a simple, fast, and reproducible eco-friendly microwave-assisted route. Photoluminescent properties enable the production of coated light-emitting diodes (LED), unique luminescent barcodes dependent on the excitation wavelength and thin-films for use in tamper seals. Moreover, piroxicam entrapped in hydrogel acts as a transdermal drug release device efficient in inhibiting edemas as compared to a commercial reference.

  12. Laser Cooling of Lanthanides: from Optical Clocks to Quantum Simulators

    Directory of Open Access Journals (Sweden)

    Golovizin A.

    2015-01-01

    Full Text Available We discuss current progress in laser cooling of lanthanides (Er, Yb, Dy, Tm etc. focusing on applications. We describe some important peculiarities taking Thulium atom as an example: Two stage laser cooling, trapping in an optical lattice, anisotropic interactions and spectroscopy of narrow transitions. Specific level structure and presence of magic wavelengths make ultracold Thulium a favorable candidate for optical clock applications. On the other hand, abundance of Feshbach resonances allow to tune interactions in ultracold gases and thus reach quantum degeneracy. It opens intriguing perspectives for novel quantum simulators employing dipole-dipole interactions in an optical lattice.

  13. Lanthanide luminescence for functional materials and bio-sciences.

    Science.gov (United States)

    Eliseeva, Svetlana V; Bünzli, Jean-Claude G

    2010-01-01

    Recent startling interest for lanthanide luminescence is stimulated by the continuously expanding need for luminescent materials meeting the stringent requirements of telecommunication, lighting, electroluminescent devices, (bio-)analytical sensors and bio-imaging set-ups. This critical review describes the latest developments in (i) the sensitization of near-infrared luminescence, (ii) "soft" luminescent materials (liquid crystals, ionic liquids, ionogels), (iii) electroluminescent materials for organic light emitting diodes, with emphasis on white light generation, and (iv) applications in luminescent bio-sensing and bio-imaging based on time-resolved detection and multiphoton excitation (500 references).

  14. Lanthanides and actinides extraction by calixarenes containing CMPO groups

    International Nuclear Information System (INIS)

    Garcia Carrera, A.

    2001-01-01

    In the framework of the French program SPIN concerning the radioactive waste management, researches are performed to develop processes allowing the separation of long-lived radioisotopes in order to their transmutation or their specific conditioning. These studies deal with the extraction and the separation of trivalent lanthanides and actinides in acid solution. Many systems ''calixarene-diluent-aqueous phase'' are examined by extraction liquid-liquid and membrane transport. The extraction efficiency and the selectivity of the synthesized calixarene-CMPO and of the CMPO are compared with these cations, as the nitric acid extraction by these molecules. (A.L.B.)

  15. Contribution for the studies of rare earth dithionates

    International Nuclear Information System (INIS)

    Schmitz, L.C.

    1988-01-01

    The main objective of this work is the synthesis and investigation of some properties of rare earth dithionates. The rare earth dithionates were prepared from the respective sulphates, by the reaction of the latter with BaS sub(2) O sub(6) in aqueous solutions. The lanthanide ion content was estimated by complexometric titration with EDTA; analysis for H were carried out by microanalysis and the water content was determinated by Karl Fischer titration. This experimental results in addition to thermogravimetric (TG) data gave the stoichiometry of the compounds. (author)

  16. 2nd Generation Alkaline Electrolysis

    DEFF Research Database (Denmark)

    Yde, Lars; Kjartansdóttir, Cecilia Kristin; Allebrod, Frank

    This report provides the results of the 2nd Generation Alkaline Electrolysis project which was initiated in 2008. The project has been conducted from 2009-2012 by a consortium comprising Århus University Business and Social Science – Centre for Energy Technologies (CET (former HIRC)), Technical...

  17. Zinc electrode in alkaline electrolyte

    Energy Technology Data Exchange (ETDEWEB)

    McBreen, J.

    1995-12-31

    The zinc electrode in alkaline electrolyte is unusual in that supersaturated zincate solutions can form during discharge and spongy or mossy zinc deposits can form on charge at low overvoltages. The effect of additives on regular pasted ZnO electrodes and calcium zincate electrodes is discussed. The paper also reports on in situ x-ray absorption (XAS) results on mossy zinc deposits.

  18. Efficient Separation of Lanthanides Using Poly (Styrene-Divinyl Benzene) Aminated Anion Exchanger

    International Nuclear Information System (INIS)

    Borai, E.H.; Hassan, R.S.; El- Dessouky, M.I.; Ghonem, A.

    2008-01-01

    New chromatographic method was developed for the determination and separation of lanthanides using AS4A anionic column. The behavior of the column towards lanthanides was studied through many parameters, From the data obtained it is found that, affinity of the column toward investigated ions increase by increasing eluent concentration and it decrease retention factors. With the two investigated eluent (oxalic and citric acids), elution order for lanthanide elements was obtained in their atomic number from La to Lu. Retention times and retention orders obtained at these conditions clearly show that, lanthanides in AS4A are displaced according to anion exchange mechanism. More over separation of lanthanides using AS4A was studied using isocratic and gradient elution programs. Light and the first intermediate lanthanide elements were separated successfully by applying a gradient program containing 70% oxalic acid (100 mM) and 30% water. The problem of separation for heavy and the last intermediate lanthanide elements was solved using 100 mM alpha hydroxy isobutyric acid (α-HIBA)

  19. Electrochemical behaviour of alkaline copper complexes

    Indian Academy of Sciences (India)

    cyanide- plating bath for copper has been developed using alkaline trisodium citrate and triethanolamine solutions5. The present investigation presents cyclic voltammetric studies on the electrochemical behaviour of alkaline copper complexes, ...

  20. Pyridinophane platform for stable lanthanide(III) complexation.

    Science.gov (United States)

    Castro, Goretti; Bastida, Rufina; Macías, Alejandro; Pérez-Lourido, Paulo; Platas-Iglesias, Carlos; Valencia, Laura

    2013-05-20

    A detailed investigation of the solid state and solution structures of lanthanide(III) complexes with the macrocyclic ligand 2,11,20-triaza[3.3.3](2,6)pyridinophane (TPP) is reported. The solid state structures of 14 different Ln(3+) complexes have been determined using X-ray crystallography. The ligand is coordinating to the Ln(3+) ion by using its six nitrogen atoms, while nitrate or triflate anions and water molecules complete the metal coordination environments. The structure of the complexes in solution has been investigated by (1)H and (13)C NMR spectroscopy, as well as by DFT calculations (TPSSh model) performed in aqueous solution. The structures obtained from these calculations for the complexes with the lightest Ln(3+) ions (La-Sm) are in very good agreement with those determined by the analysis of the Ln(3+)-induced paramagnetic shifts. A structural change occurs across the lanthanide series at Sm(3+); the complexes of the large Ln(3+) ions (La-Nd) are chiral due to the nonplanar conformation of the macrocycle, and present effective C3v symmetries in solution as a consequence of a fast interconversion of two enantiomeric forms with C3 symmetry. The activation free energy for this enantiomerization process, as estimated by using DFT calculations, amounts to 33.0 kJ·mol(-1). The TPP ligand in the complexes of the heaviest Ln(3+) ions (Eu-Lu) presents a half-chair conformation, which results in C(s) symmetries in solution.

  1. Lanthanide sorbent based on magnetite nanoparticles functionalized with organophosphorus extractants.

    Science.gov (United States)

    Basualto, Carlos; Gaete, José; Molina, Lorena; Valenzuela, Fernando; Yañez, Claudia; Marco, Jose F

    2015-06-01

    In this work, an adsorbent was prepared based on the attachment of organophosphorus acid extractants, namely, D2EHPA, CYANEX 272, and CYANEX 301, to the surface of superparamagnetic magnetite (Fe 3 O 4 ) nanoparticles. The synthesized nanoparticles were coated with oleic acid, first by a chemisorption mechanism and later by the respective extractant via physical adsorption. The obtained core-shell functionalized magnetite nanoparticle composites were characterized by dynamic light scattering, scanning electron microscopy, transmission electron microscopy, thermogravimetry, infrared absorption and vibrating sample magnetometry. All the prepared nanoparticles exhibited a high saturation magnetization capacity that varied between 72 and 46 emu g -1 and decreased as the magnetite nanoparticle was coated with oleic acid and functionalized. The scope of this study also included adsorption tests for lanthanum, cerium, praseodymium, and neodymium and the corresponding analysis of their results. Sorption tests indicated that the functionalized nanoparticles were able to extract the four studied lanthanide metal ions, although the best extraction performance was observed when the sorbent was functionalized with CYANEX 272, which resulted in a loading capacity of approximately 12-14 mg La /g MNP . The magnetization of the synthesized nanoparticles was verified during the separation of the lanthanide-loaded sorbent from the raffinate by using a conventional magnet.

  2. Energetic lanthanide complexes: coordination chemistry and explosives applications

    International Nuclear Information System (INIS)

    Manner, V W; Barker, B J; Sanders, V E; Laintz, K E; Scott, B L; Preston, D N; Sandstrom, M; Reardon, B L

    2014-01-01

    Metals are generally added to organic molecular explosives in a heterogeneous composite to improve overall heat and energy release. In order to avoid creating a mixture that can vary in homogeneity, energetic organic molecules can be directly bonded to high molecular weight metals, forming a single metal complex with Angstrom-scale separation between the metal and the explosive. To probe the relationship between the structural properties of metal complexes and explosive performance, a new series of energetic lanthanide complexes has been prepared using energetic ligands such as NTO (5-nitro-2,4-dihydro-1,2,4-triazole-3-one). These are the first examples of lanthanide NTO complexes where no water is coordinated to the metal, demonstrating novel control of the coordination environment. The complexes have been characterized by X-ray crystallography, NMR and IR spectroscopies, photoluminescence, and sensitivity testing. The structural and energetic properties are discussed in the context of enhanced blast effects and detection. Cheetah calculations have been performed to fine-tune physical properties, creating a systematic method for producing explosives with 'tailor made' characteristics. These new complexes will be benchmarks for further study in the field of metalized high explosives.

  3. Lanthanide-IMAC enrichment of carbohydrates and polyols.

    Science.gov (United States)

    Schemeth, Dieter; Rainer, Matthias; Messner, Christoph B; Rode, Bernd M; Bonn, Günther K

    2014-03-01

    In this study a new type of immobilized metal ion affinity chromatography resin for the enrichment of carbohydrates and polyols was synthesized by radical polymerization reaction of vinyl phosphonic acid and 1,4-butandiole dimethacrylate using azo-bis-isobutyronitrile as radical initiator. Interaction between the chelated trivalent lanthanide ions and negatively charged hydroxyl groups of carbohydrates and polyols was observed by applying high pH values. The new method was evaluated by single standard solutions, mixtures of standards, honey and a more complex extract of Cynara scolymus. The washing step was accomplished by acetonitrile in excess volumes. Elution of enriched carbohydrates was successfully performed with deionized water. The subsequent analysis was carried out with matrix-free laser desorption/ionization-time of flight mass spectrometry involving a TiO2 -coated steel target, especially suitable for the measurement of low-molecular-weight substances. Quantitative analysis of the sugar alcohol xylitol as well as the determination of the maximal loading capacity was performed by gas chromatography in conjunction with mass spectrometric detection after chemical derivatization. In a parallel approach quantum mechanical geometry optimizations were performed in order to compare the coordination behavior of various trivalent lanthanide ions. Copyright © 2013 John Wiley & Sons, Ltd.

  4. Quantum chemistry of unusual oxidation degrees of lanthanides and actinides

    International Nuclear Information System (INIS)

    Spitsyn, V.I.; Ionova, G.V.

    1984-01-01

    The electronic structure and properties of actinides in unusual valence forms were considered in the framework of quantum-mechanical concepts. Hartree-Fock atomic calculations of the actinide series as well as molecular orbital calculations of octahedral oxydions of uranium, neptuniun, plutonium and americium in hight and higher valence forms, octahedral tri-and tetravalent chloride complexes from protactinium through einsteinium were conducted. A possible existence of some new valence forms of actinides was considered, based on such calculations. The cation-cation interaction mechanism was suggested. Peculiarities of the trans-effect manifestation in actinide chemistry were considered. New possibilities were shown of using the Moessbauer isomer shifts on actinide nuclei to interpret the chemical properties. The influence of relativi;tic effects on the actinide chemical properties was analyzed. A high value of the spin-orbital splitting Was snown to determine a gradual stabilization and stability of bivalent state at the and of the actinide series, substantial difference in stability of the tetravalent state of lanthanides and actinides, conceptual possibility of preparing lanthanyl groups at the end of the lanthanide series

  5. Lanthanide sorbent based on magnetite nanoparticles functionalized with organophosphorus extractants

    Science.gov (United States)

    Basualto, Carlos; Gaete, José; Molina, Lorena; Valenzuela, Fernando; Yañez, Claudia; Marco, Jose F.

    2015-06-01

    In this work, an adsorbent was prepared based on the attachment of organophosphorus acid extractants, namely, D2EHPA, CYANEX 272, and CYANEX 301, to the surface of superparamagnetic magnetite (Fe3O4) nanoparticles. The synthesized nanoparticles were coated with oleic acid, first by a chemisorption mechanism and later by the respective extractant via physical adsorption. The obtained core-shell functionalized magnetite nanoparticle composites were characterized by dynamic light scattering, scanning electron microscopy, transmission electron microscopy, thermogravimetry, infrared absorption and vibrating sample magnetometry. All the prepared nanoparticles exhibited a high saturation magnetization capacity that varied between 72 and 46 emu g-1 and decreased as the magnetite nanoparticle was coated with oleic acid and functionalized. The scope of this study also included adsorption tests for lanthanum, cerium, praseodymium, and neodymium and the corresponding analysis of their results. Sorption tests indicated that the functionalized nanoparticles were able to extract the four studied lanthanide metal ions, although the best extraction performance was observed when the sorbent was functionalized with CYANEX 272, which resulted in a loading capacity of approximately 12-14 mgLa/gMNP. The magnetization of the synthesized nanoparticles was verified during the separation of the lanthanide-loaded sorbent from the raffinate by using a conventional magnet.

  6. Photodegradation of a polypropylene filled with lanthanide complexes

    Directory of Open Access Journals (Sweden)

    Valérie Massardier

    2015-01-01

    Full Text Available Abstract This research aims at studying the photodegradation of a polypropylene formulation filled with lanthanide complexes. These complexes can be used as tracers for the identification of polymer materials in order to facilitate an high speed automatic sorting of plastic wastes for an economically efficient recycling. By paying attention to the evolution of carbonyl absorption bands in FTIR spectra, it is observed that the addition of lanthanide complexes into our formulation improves UV stability of polypropylene by reducing the extent of photo-degradation. Furthermore, TG analyses show that the traced blends can maintain better thermal properties, after irradiation. A significant increase of the crystallinity degree and a decrease of the melting temperature are more pronounced for the unfilled UV–irradiated PP. This might result from chemi-crystallization that can occur when chain entanglements are broken as a result of chain scissions. From SEM analyses, it is observed that the severity of surface cracks induced by photo degradation is reduced for filled PP. The mechanical tests are in agreement with this result and show a fundamental change in the behavior of the as-exposed blends from a ductile to a brittle material.

  7. Basic understanding of the lanthanide related upconversion emissions

    Science.gov (United States)

    Dong, Hao; Sun, Ling-Dong; Yan, Chun-Hua

    2013-06-01

    With abundant energy levels of 4f electron configurations, trivalent lanthanide ions (Ln3+) are endowed with unique and fascinating luminescent properties. Inheriting the native transition behaviour of the lanthanide ions, Ln3+ based nanomaterials have aroused great interest for a wide range of applications, including lighting and displays, optical fibers and amplifiers, responsive luminescent stains for biomedical analysis, in vivo and in vitro imaging, and enhancement for silicon solar cell devices. It should be noted that the application depends completely on the corresponding luminescent behaviour. To deepen the understanding of the luminescent mechanism is important for the developing of the field and the design of new Ln3+ based luminescent materials toward applications. In this review, we focused mainly on the recent developments on upconversion (UC) emission studies. Firstly, the emphasis was put on the introduction of basic luminescent properties of Ln3+ with f-f transitions, and then the corresponding mechanisms and properties of UC emission were discussed in detail, the potential researches with respect to UC mechanisms and properties were finally outlined.

  8. Luminescent multifunctional lanthanides-based metal-organic frameworks.

    Science.gov (United States)

    Rocha, João; Carlos, Luís D; Paz, Filipe A Almeida; Ananias, Duarte

    2011-02-01

    Metal-organic frameworks based on trivalent lanthanides (LnMOFs) are a very promising class of materials for addressing the challenges in engineering of luminescent centres. Lanthanide-bearing phosphors find numerous applications in lighting, optical communications, photonics and biomedical devices. In this critical review we discuss the potential of LnMOFs as multifunctional systems, which combine light emission with properties such as microporosity, magnetism, chirality, molecule and ion sensing, catalysis and activity as multimodal imaging contrast agents. We argue that these materials present a unique chance of observing synergy between several of these properties, such as the coupling between photoluminescence and magnetism. Moreover, an integrated approach towards the design of efficient, stable, cheap, environmentally-friendly and multifunctional luminescent LnMOFs is still missing. Although research into LnMOFs is at its early stage and much basic knowledge is still needed, the field is ripe for new ideas, which will enable sensor devices and photonic prototypes to become a commercial reality (81 references).

  9. Lanthanide-based fluorescent tracers in complex media

    International Nuclear Information System (INIS)

    Brichart, Thomas

    2014-01-01

    Tracers are objects allowing the determination of the position or the distribution of a product; tracers are currently used in a great variety of domains. Despite the fact that each field has it's own specifications, it is possible to find tracers in medicine (contrast agents), anti-counterfeiting or geological exploration. We have developed lanthanide complex tracers for oil field injection waters. Those tracers, derived from the DOTA, have been detected at concentration lower than 1 ppb, thanks to a simple and compact apparatus. This detection has been made possible by the use of time-resolved fluorescence spectroscopy, this technique allows us to get rid of the background noise created by the intrinsic fluorescence of oil residues that are present in production waters. We also demonstrated how we can, through a reverse microemulsion synthesis, encapsulate several different dyes inside a single nanoparticle composed of a gold core and a silica shell. We showed as well, how those particles can be used as smart tracers to gather data, such as temperature, pH, solvents, etc. inside the well. Finally the use of lanthanides and scale inhibitors properties allowed us to create a simple and fast dosing protocol of such scale inhibitors in injection waters. This dosage will then allow the quick adjustment of their concentration inside each well. (author) [fr

  10. Alkali-metal/alkaline-earth-metal fluorine beryllium borate NaSr{sub 3}Be{sub 3}B{sub 3}O{sub 9}F{sub 4} with large nonlinear optical properties in the deep-ultraviolet region

    Energy Technology Data Exchange (ETDEWEB)

    Reshak, A. H., E-mail: maalidph@yahoo.com [New Technologies—Research Centre, University of West Bohemia, Univerzitni 8, 306 14 Pilsen (Czech Republic); Center of Excellence Geopolymer and Green Technology, School of Material Engineering, University Malaysia Perlis, 01007 Kangar, Perlis (Malaysia); Huang, Hongwei [School of Materials Science and Technology, China University of Geosciences, Beijing 100083 (China); Kamarudin, H. [Center of Excellence Geopolymer and Green Technology, School of Material Engineering, University Malaysia Perlis, 01007 Kangar, Perlis (Malaysia); Auluck, S. [Council of Scientific and Industrial Research—National Physical Laboratory, Dr. K S Krishnan Marg, New Delhi 110012, India and Physics Department, Indian Institute of Technology - Delhi, Hauz Khas, New Delhi 110016 (India)

    2015-02-28

    The linear optical response and second harmonic generation (SHG) in alkali-metal/alkaline-earth-metal fluorine beryllium borate NaSr{sub 3}Be{sub 3}B{sub 3}O{sub 9}F{sub 4} are investigated by means of density functional theory. Calculations are performed using four types of exchange correlations: Ceperley-Alder local density approximation, Perdew Burke and Ernzerhof general gradient approximation, Engel-Vosko generalized gradient approximation, and the recently modified Becke-Johnson potential (mBJ). The mBJ approach brings the calculated band gap (7.20 eV) in excellent agreement with the experimental one (7.28 eV). The calculated values of the uniaxial anisotropy δε=−0.076 and the birefringence Δn(0)=0.052 indicate considerable anisotropy in the linear optical properties, which makes it favorable for the second harmonic generation. The dominant component of the second harmonic generation is χ{sub 111}{sup (2)}(ω). The value of |χ{sub 111}{sup (2)}(ω)| is about 1.2 pm/V at λ = 1064 nm in agreement with previous calculations. To analyze the origin of the high SHG of NaSr{sub 3}Be{sub 3}B{sub 3}O{sub 9}F{sub 4} single crystals, we have correlated the features of |χ{sub 111}{sup (2)}(ω)| spectra with the features of ε{sub 2}(ω) spectra as a function of ω/2 and ω. From the calculated dominant component |χ{sub 111}{sup (2)}(ω)|, we find that the microscopic first hyperpolarizability, β{sub 111}, the vector components along the dipole moment direction is 0.5 × 10{sup −30} esu at static limit and 0.6 × 10{sup −30} esu at λ = 1064 nm.

  11. 2,2',-bipyridine and 1,10-phenanthroline complexes of lanthanide(III) trifluoroacetates

    International Nuclear Information System (INIS)

    Misra, S.N.; Singh, M.

    1983-01-01

    The syntheses and characterization of lanthanide(III) triflloroacetate complexes with 2,2'-bipyridine and 1,10-phenanthroline are reported. Lanthanide(III) trifluoroacetates yield compounds of the type Ln(CF 3 COO) 3 .bipy or phen with 2,2'-bipyridine and 1,10-phenanthroline. Their properties and structures have been studied using chemical analyses. electronic and infrared spectra. Thermal analysis of a few complexes have also been done. The infrared data show that the trifluoroacetate group acts as a bidentate ligand making the coordination number of lanthanide eight. (author)

  12. Lanthanide complexes that respond to changes in cyanide concentration in water

    Energy Technology Data Exchange (ETDEWEB)

    Routledge, Jack D.; Zhang, Xuejian; Connolly, Michael; Tropiano, Manuel; Blackburn, Octavia A.; Beer, Paul D.; Aldridge, Simon; Faulkner, Stephen [Inorganic Chemistry Laboratory, Department of Chemistry, University of Oxford (United Kingdom); Kenwright, Alan M. [Department of Chemistry, Durham University (United Kingdom)

    2017-06-26

    Cyanide ions are shown to interact with lanthanide complexes of phenacylDO3A derivatives in aqueous solution, giving rise to changes in the luminescence and NMR spectra. These changes are the consequence of cyanohydrin formation, which is favored by the coordination of the phenacyl carbonyl group to the lanthanide center. These complexes display minimal affinity for fluoride and can detect cyanide at concentrations less than 1 μm. By contrast, lanthanide complexes with DOTAM derivatives display no affinity for cyanide in water, but respond to changes in fluoride concentration. (copyright 2017 Wiley-VCH Verlag GmbH and Co. KGaA, Weinheim)

  13. Features of the reaction of heterocyclic analogs of chalcone with lanthanide shift reagents

    Energy Technology Data Exchange (ETDEWEB)

    Turov, A.V.; Khilya, V.P. [Taras Shevchenko Kiev Univ. (Russian Federation)

    1994-10-01

    The PMR spectra of heterocyclic analogs of 2-hydroxychalcone containing thiazole, benzofuran, triazole, imidazole, benzodioxane, or pyridine rings in the presence of lanthanide shift reagents are studied. It is found that the most effective reagent for modifying the spectra of these compounds is Yb(fod)3. The broadening of the spectra of 2-hydroxy chalcones in the presence of lanthanide shift reagents is explained by the dynamic effects of complex formation. An example is given of the determination of the conformation of molecules of 2-hydroxychalcone by the simultaneous use of lanthanide shift reagents and the homonuclear Overhauser effect. 9 refs., 1 fig., 1 tab.

  14. Development of alkaline fuel cells.

    Energy Technology Data Exchange (ETDEWEB)

    Hibbs, Michael R.; Jenkins, Janelle E.; Alam, Todd Michael; Janarthanan, Rajeswari; Horan, James L.; Caire, Benjamin R.; Ziegler, Zachary C.; Herring, Andrew M.; Yang, Yuan; Zuo, Xiaobing; Robson, Michael H.; Artyushkova, Kateryna; Patterson, Wendy; Atanassov, Plamen Borissov

    2013-09-01

    This project focuses on the development and demonstration of anion exchange membrane (AEM) fuel cells for portable power applications. Novel polymeric anion exchange membranes and ionomers with high chemical stabilities were prepared characterized by researchers at Sandia National Laboratories. Durable, non-precious metal catalysts were prepared by Dr. Plamen Atanassovs research group at the University of New Mexico by utilizing an aerosol-based process to prepare templated nano-structures. Dr. Andy Herrings group at the Colorado School of Mines combined all of these materials to fabricate and test membrane electrode assemblies for single cell testing in a methanol-fueled alkaline system. The highest power density achieved in this study was 54 mW/cm2 which was 90% of the project target and the highest reported power density for a direct methanol alkaline fuel cell.

  15. Notes on Contributions to the Science of Rare Earth Element Enrichment in Coal and Coal Combustion Byproducts

    OpenAIRE

    James C. Hower; Evan J. Granite; David B. Mayfield; Ari S. Lewis; Robert B. Finkelman

    2016-01-01

    Coal and coal combustion byproducts can have significant concentrations of lanthanides (rare earth elements). Rare earths are vital in the production of modern electronics and optics, among other uses. Enrichment in coals may have been a function of a number of processes, with contributions from volcanic ash falls being among the most significant mechanisms. In this paper, we discuss some of the important coal-based deposits in China and the US and critique classification systems used to eval...

  16. Rb-Sr age of the Sivamalai alkaline complex, Tamil Nadu

    International Nuclear Information System (INIS)

    Subba Rao, T.V.; Narayana, B.L.; Gopalan, K.

    1994-01-01

    The Sivamalai alkaline complex comprises ferro-, pyroxene- hornblende-and nepheline-syenites. Field relations show that the nepheline syenites followed the emplacement of non-feldspathoidal syenites. Mineralogical data on the syenite suite have been reviewed. The Sivamalai alkaline rocks are not strongly enriched in rare-earth elements like most miaskites. Rb-Sr isotopic analyses of a suite of six samples from the various members of the complex define an isochron corresponding to an age of 623 ± 21 Ma (2σ) and initial Sr ratio of 0.70376 ± 14 (2σ). This is consistent with a model of fractional crystallization of a parent magma derived from an upper mantle source with apparently no isotopic evidence for more than one magma source for the complex. The Sivamalai alkaline complex represents a Pan-African alkaline magmatic event in the southern granulite terrane of peninsular India. (author). 26 refs., 4 figs., 4 tabs

  17. Flexible Photonics: Polymer LEDs Made from Monochromatic Red Emitting Lanthanide/Polymer Blends. Phase 1

    National Research Council Canada - National Science Library

    O'Regan, Marie

    1999-01-01

    .... Spectrally pure, red emitting flexible LEDs have been fabricated. Close to a four-fold increase in device efficiency is obtained when a suitable lanthanide complex is blended with the semi-conducting host polymer...

  18. Double-double effect and its contribution to the lanthanide chemistry

    International Nuclear Information System (INIS)

    Fidelis, I.

    1973-01-01

    Different aspects of the double-double effect and its theoretical explanation have been discussed. Some new conclusions pertaining to the thermodynamics of complexation of lanthanides based on own experimental results and existing literature data have been presented. (author)

  19. FY17 Progress in Modeling of Lanthanide Transport in Metallic Fuels

    Energy Technology Data Exchange (ETDEWEB)

    Unal, Cetin [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Matthews, Christopher [Los Alamos National Lab. (LANL), Los Alamos, NM (United States)

    2017-09-19

    A critical review of fuel-clad-chemical interactions along with modelling requirements is published. The mechanism of lanthanide transport is studied experimentally (NEUP collaboration) and using simulations and initial results are published in Refs.

  20. Direct conversion of glucose to 5-(hydroxymethyl)furfural in ionic liquids with lanthanide catalysts

    DEFF Research Database (Denmark)

    Ståhlberg, Tim; Sørensen, Mathilde Grau; Riisager, Anders

    2010-01-01

    with alkylimidazolium chlorides. Notably, a higher reactivity was observed when the hydrophobicity of the imidazolium cation was increased, in contrast to analogous chromium catalyst systems. This indicates a different reaction mechanism for the lanthanides than for the chromium catalyst systems....