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Sample records for alkaline earth oxides

  1. 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.

  2. 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.

  3. 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

  4. 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)

  5. 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 ...

  6. 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

  7. 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

  8. 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.)

  9. 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

  10. 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).

  11. 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)

  12. 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, ...

  13. 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.

  14. 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

  15. 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

  16. Ion bombardment effects on surface states in selected oxide systems: rutile and alkaline earth titanates

    International Nuclear Information System (INIS)

    Gruen, D.M.

    1978-01-01

    In this paper, the nature of the surface states of n-type TiO 2 and SrTiO 3 is discussed and the role of ion bombardment in modifying the properties of these states is elucidated. Insofar as possible, the interrelationships between oxide nonstoichiometry, surface states, ion bombardment effects and photoelectrolysis are explored

  17. Development of a critically evaluated thermodynamic database for the systems containing alkaline-earth oxides

    Science.gov (United States)

    Shukla, Adarsh

    In a thermodynamic system which contains several elements, the phase relationships among the components are usually very complex. Especially, systems containing oxides are generally very difficult to investigate owing to the very high experimental temperatures and corrosive action of slags. Due to such difficulties, large inconsistencies are often observed among the available experimental data. In order to investigate and understand the complex phase relationships effectively, it is very useful to develop thermodynamic databases containing optimized model parameters giving the thermodynamic properties of all phases as functions of temperature and composition. In a thermodynamic optimization, adjustable model parameters are calculated using, simultaneously, all available thermodynamic and phase-equilibrium data in order to obtain one set of model equations as functions of temperature and composition. Thermodynamic data, such as activities, can aid in the evaluation of the phase diagrams, and information on phase equilibria can be used to deduce thermodynamic properties. Thus, it is frequently possible to resolve discrepancies in the available data. From the model equations, all the thermodynamic properties and phase diagrams can be back-calculated, and interpolations and extrapolations can be made in a thermodynamically correct manner. The data are thereby rendered self-consistent and consistent with thermodynamic principles, and the available data are distilled into a small set of model parameters, ideal for computer storage. As part of a broader research project at the Centre de Recherche en Calcul Thermochimique (CRCT), Ecole Polytechnique to develop a thermodynamic database for multicomponent oxide systems, this thesis deals with the addition of components SrO and BaO to the existing multicomponent database of the SiO2-B2O3-Al2O 3-CaO-MgO system. Over the years, in collaboration with many industrial companies, a thermodynamic database for the SiO2-B2O 3-Al2O3-Ca

  18. 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.

  19. 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.

  20. 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.

  1. 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.

  2. 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.

  3. 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.

  4. Fundamental mechanisms of oxidation of alkaline earth-bearing metal precursors: yttrium-barium-copper-silver-palladium and silver bariate

    Science.gov (United States)

    Sitaraman, Vilayannur R.

    Noble-metal-bearing metallic precursors can be selectively oxidized to yield oxide/noble metal composites. This processing method is investigated for producing 123/Ag-Pd laminates from a solid metallic Y-Ba-Cu-Ag-Pd precursor. A unique feature heretofore unnoticed is the external oxidation mechanism of Ba. The extent of external oxidation at 840C in a 3%H2-Ar atmosphere (PO2 ˜ 10-19 atm.) as measured by a segregation factor, is higher for Ba than for Y. Combined with the fact that Ba does not have significant solid solubility in Ag, Cu or Pd, this means that a short circuit transport path is possible for transport of Ba through such metals as described in chapter 1. Since diffusion through grain boundaries, is fast, the effective permeability of Ba can be relatively high even though its solubility is low. This proposed mechanism is proven using a model system, the Ag5Ba intermetallic compound. Both internal and external oxidation has been demonstrated in this material. Grain boundary diffusion is demonstrated using Ag clad Ag 5Ba. Due to a change in the mechanism from external to internal oxidation of Y in Y-Ba-Cu-Ag-Pd alloys, the imbalance in the surface stoichiometry caused by Ba segregation is not easily removed. A mechanism proposed by Meijering for copper oxide dissolution, Cu migration and Cu reoxidation at the outer surface is also consistent with the microstructural observations in oxidized Y-Ba-Cu-Ag-Pd specimens.

  5. 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...

  6. 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)

  7. 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)

  8. 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)

  9. catalysed oxidation of atenolol by alkaline permanganate

    Indian Academy of Sciences (India)

    Unknown

    Abstract. Kinetics of ruthenium (III) catalyzed oxidation of atenolol by permanganate in alkaline medium at constant ionic strength of 0⋅30 mol dm3 has been studied spectrophotometrically using a rapid kinetic accessory. Reaction between permanganate and atenolol in alkaline medium exhibits 1 : 8 stoichiometry.

  10. 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

  11. 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

  12. 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

  13. 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.

  14. 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)

  15. Catalytic oxidation of soot over alkaline niobates

    International Nuclear Information System (INIS)

    Pecchi, G.; Cabrera, B.; Buljan, A.; Delgado, E.J.; Gordon, A.L.; Jimenez, R.

    2013-01-01

    Highlights: ► No previous reported studies about alkaline niobates as catalysts for soot oxidation. ► NaNbO 3 and KNbO 3 perovskite-type oxides show lower activation energy than other lanthanoid perovskite-type oxides. ► The alkaline niobate does not show deactivation by metal loss. - Abstract: The lack of studies in the current literature about the assessment of alkaline niobates as catalysts for soot oxidation has motivated this research. In this study, the synthesis, characterization and assessment of alkaline metal niobates as catalysts for soot combustion are reported. The solids MNbO 3 (M = Li, Na, K, Rb) are synthesized by a citrate method, calcined at 450 °C, 550 °C, 650 °C, 750 °C, and characterized by AAS, N 2 adsorption, XRD, O 2 -TPD, FTIR and SEM. All the alkaline niobates show catalytic activity for soot combustion, and the activity depends basically on the nature of the alkaline metal and the calcination temperature. The highest catalytic activity, expressed as the temperature at which combustion of carbon black occurs at the maximum rate, is shown by KNbO 3 calcined at 650 °C. At this calcination temperature, the catalytic activity follows an order dependent on the atomic number, namely: KNbO 3 > NaNbO 3 > LiNbO 3 . The RbNbO 3 solid do not follow this trend presumably due to the perovskite structure was not reached. The highest catalytic activity shown by of KNbO 3 , despite the lower apparent activation energy of NaNbO 3 , stress the importance of the metal nature and suggests the hypothesis that K + ions are the active sites for soot combustion. It must be pointed out that alkaline niobate subjected to consecutive soot combustion cycles does not show deactivation by metal loss, due to the stabilization of the alkaline metal inside the perovskite structure.

  16. 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)

  17. 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 ...

  18. 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.

  19. 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.

  20. 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.

  1. 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.

  2. 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.

  3. 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 ...

  4. 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 ...

  5. 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 ...

  6. 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

  7. 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 ...

  8. 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.

  9. 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.

  10. 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...

  11. 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.

  12. 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).

  13. 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.

  14. 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

  15. 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....

  16. 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...

  17. Thermal stability and oxidizing properties of mixed alkaline earth-alkali molten carbonates: A focus on the lithium-sodium carbonate eutectic system with magnesium additions

    International Nuclear Information System (INIS)

    Frangini, Stefano; Scaccia, Silvera

    2013-01-01

    Highlights: • TG/DSC analysis was conducted on magnesium-containing eutectic Li/Na eutectic carbonates. • Magnesium influence on the oxygen solubility properties of carbonate was also experimentally determined at 600 °C and 650 °C. • A reproducible partial decarbonation process in premelting region caused formation of magnesium oxycarbonate-like phases. • The acidobase buffering action of magnesium oxycarbonate species could explain the high basic/oxidizing properties of such carbonate melts. • A general correlation between thermal instability in premelting region and basic/oxidizing melt properties was established. - Abstract: A comparative study on thermal behavior and oxygen solubility properties of eutectic 52/48 lithium/sodium carbonate salt containing minor additions of magnesium up to 10 mol% has been made in order to determine whether a general correlation between these two properties can be found or not. Consecutive TG/DSC heating/cooling thermal cycles carried out under alternating CO 2 and N 2 gas flows allowed to assign thermal events observed in the premelting region to a partial decarbonation process of the magnesium-alkali mixed carbonates. The observed decarbonation process at 460 °C is believed to come from initial stage of thermal decomposition of magnesium carbonate resulting in the metastable formation of magnesium oxycarbonate-like phases MgO·2MgCO 3 , in a similar manner as previously reported for lanthanum. Reversible formation and decomposition of the magnesium carbonate phase has been observed under a CO 2 gas atmosphere. The intensity of the decomposition process shows a maximum for a 3 mol% MgO addition that gives also the highest oxygen solubility, suggesting therefore that instability thermal analysis in the premelting region can be considered as providing an effective measure of the basicity/oxidizing properties of alkali carbonate melts with magnesium or, in more general terms, with cations that are strong modifiers of

  18. 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.

  19. 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)

  20. Electrochemical oxidation and detection of sodium urate in alkaline ...

    African Journals Online (AJOL)

    Electrochemical behaviour of copper oxides electrode in the presence of sodium urate was investigated. The correlation between the anodic oxidation and the amperometric detection of sodium urate in the alkaline medium on copper oxides electrode was analysed by cyclic voltammetry (CV) and electrochemical ...

  1. 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

  2. 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

  3. 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.

  4. 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)

  5. 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

  6. Rare Earth Oxide Thin Films

    CERN Document Server

    Fanciulli, Marco

    2007-01-01

    Thin rare earth (RE) oxide films are emerging materials for microelectronic, nanoelectronic, and spintronic applications. The state-of-the-art of thin film deposition techniques as well as the structural, physical, chemical, and electrical properties of thin RE oxide films and of their interface with semiconducting substrates are discussed. The aim is to identify proper methodologies for the development of RE oxides thin films and to evaluate their effectiveness as innovative materials in different applications.

  7. 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.

  8. 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.

  9. 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

  10. Development of nano indium tin oxide (ITO) grains by alkaline ...

    Indian Academy of Sciences (India)

    Unknown

    Bull. Mater. Sci., Vol. 25, No. 6, November 2002, pp. 505–507. © Indian Academy of Sciences. 505. Development of nano indium tin oxide (ITO) grains by alkaline hydrolysis of In(III) and Sn(IV) salts. NIMAI CHAND ... et al 1996; Yanagisawa and Udawatte 2000; Denoy and. Pradeep 1997) with low Sn content (In : Sn ≥ 90 ...

  11. 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.

  12. 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

  13. 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

  14. 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

  15. 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

  16. Metallothermic reduction of rare earth oxides

    International Nuclear Information System (INIS)

    Sharma, R.A.

    1986-01-01

    Rare earth oxides can be reduced to rare earth metals by a novel, high yield, metallothermic process. The oxides are dispersed in a suitable, molten, calcium chloride bath along with sodium metal. The sodium reacts with the calcium chloride to produce calcium metal which reduces the rare earth oxides to rare earth metals. The metals are collected in a discrete layer in the reaction vessel

  17. 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.

  18. 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.)

  19. 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...

  20. 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

  1. 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.

  2. Electro-oxidation of methanol on copper in alkaline solution

    International Nuclear Information System (INIS)

    Heli, H.; Jafarian, M.; Mahjani, M.G.; Gobal, F.

    2004-01-01

    The electro-oxidation of methanol on copper in alkaline solutions has been studied by the methods of cyclic voltammetry, quasi-steady state polarization and chronoamperometry. It has been found that in the course of an anodic potential sweep the electro-oxidation of methanol follows the formation of Cu III and is catalysed by this species through a mediated electron transfer mechanism. The reaction also continues in the early stages of the reversed cycle until it is stopped by the prohibitively negative potentials. The process is diffusion controlled and the current-time responses follow Cottrellian behavior. The rate constants, turnover frequency, anodic transfer coefficient and the apparent activation energy of the electro-oxidation reaction are reported

  3. Kinetics studies of oxidation of niacinamide by alkaline potassium permanganate

    Directory of Open Access Journals (Sweden)

    Sandipsingh Gour

    2012-04-01

    Full Text Available The oxidation of niacinamide in alkaline media is carried out using potassium permanganate as a oxiding agent. The reaction was monitored using UV-Visible spectrophotometer at 525 nm. It was found to be zero order with respect to oxidant,, fractional order with respect to hydrogen ion concentration and first order with respect to substrate. The thermodynamic parameters(were determinied . The average (?G# was found to be 87.60 KJ/mol. The values ?S# was found to be -0.2132 KJ/mole and energy of activation was found to be 23.95 KJ/mole. A suitable mechanism is proposed based on the experimental conditions.

  4. Obtainment of zirconium oxide and partially stabilized zirconium oxide with yttrium and rare earth oxides, from Brazilian zirconite, for ceramic aim

    International Nuclear Information System (INIS)

    Ribeiro, S.

    1991-05-01

    This work presents experimental results for processing of brazilian zirconite in order to obtain zirconium oxide with Yttrium and Rare Earth oxide by mutual coprecipitation for ceramics purposes. Due to analysis of experimental results was possible to obtain the optimum conditions for each one of technological route stage, such as: alkaline fusion; acid leaching; sulfactation and coprecipitation. (author)

  5. Combined wet oxidation and alkaline hydrolysis of polyvinylchloride

    DEFF Research Database (Denmark)

    Sørensen, E.; Bjerre, A.B.

    1992-01-01

    In view of the widespread aversion to burning polyvinylchloride (PVC) together with municipal waste, we have attempted an alternative approach to its decomposition. This paper describes a combined wet oxidation/alkaline hydrolysis yielding water soluble, biodegradable products. Experiments were...... carried out at temperatures from 180-260 degree C and reaction times of 8-24 min. The chloride liberated provides information on the rate constants. Considering the measured Cl- and Chemical Oxygen Demand (COD) values, we find hydrolysis and oxidation processes to be interdependent. The main products...... are Cl- and CO-2, the rest comprising a range of water-soluble compounds, a small, Cl-free residue, and a recognizable amount of H-2....

  6. Precipitation of uranium oxide by reduction in alkaline solution

    International Nuclear Information System (INIS)

    Pottier, P.; Claus, J.

    1964-01-01

    In the first part of the report the authors study the reaction mechanism for this reduction which makes it possible to precipitate a hydrated uranium oxide from alkaline uranyl carbonate solutions. The research into the effects of different variables on numerous cycles are then summarized. Optical, X-ray and thermogravimetric examinations then make it possible to predict the properties of this oxide. In the second part the authors carry out calculations for the continuous operation of single cells and cells in series. These calculations give the data required for the construction of 2 cells having capacities of 0.3 and 10 litres. Results obtained from the continuous operation of this latter cell lead to certain conclusions concerning the applicability of this method to the hydrometallurgy of uranium. (authors) [fr

  7. Effective alkaline metal-catalyzed oxidative delignification of hybrid poplar.

    Science.gov (United States)

    Bhalla, Aditya; Bansal, Namita; Stoklosa, Ryan J; Fountain, Mackenzie; Ralph, John; Hodge, David B; Hegg, Eric L

    2016-01-01

    Strategies to improve copper-catalyzed alkaline hydrogen peroxide (Cu-AHP) pretreatment of hybrid poplar were investigated. These improvements included a combination of increasing hydrolysis yields, while simultaneously decreasing process inputs through (i) more efficient utilization of H2O2 and (ii) the addition of an alkaline extraction step prior to the metal-catalyzed AHP pretreatment. We hypothesized that utilizing this improved process could substantially lower the chemical inputs needed during pretreatment. Hybrid poplar was pretreated utilizing a modified process in which an alkaline extraction step was incorporated prior to the Cu-AHP treatment step and H2O2 was added batch-wise over the course of 10 h. Our results revealed that the alkaline pre-extraction step improved both lignin and xylan solubilization, which ultimately led to improved glucose (86 %) and xylose (95 %) yields following enzymatic hydrolysis. An increase in the lignin solubilization was also observed with fed-batch H2O2 addition relative to batch-only addition, which again resulted in increased glucose and xylose yields (77 and 93 % versus 63 and 74 %, respectively). Importantly, combining these strategies led to significantly improved sugar yields (96 % glucose and 94 % xylose) following enzymatic hydrolysis. In addition, we found that we could substantially lower the chemical inputs (enzyme, H2O2, and catalyst), while still maintaining high product yields utilizing the improved Cu-AHP process. This pretreatment also provided a relatively pure lignin stream consisting of ≥90 % Klason lignin and only 3 % xylan and 2 % ash following precipitation. Two-dimensional heteronuclear single-quantum coherence (2D HSQC) NMR and size-exclusion chromatography demonstrated that the solubilized lignin was high molecular weight (Mw ≈ 22,000 Da) and only slightly oxidized relative to lignin from untreated poplar. This study demonstrated that the fed-batch, two-stage Cu-AHP pretreatment

  8. 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

  9. 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.

  10. 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

  11. 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

  12. 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

  13. 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 ...

  14. 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

  15. 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,…

  16. 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 ...

  17. 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

  18. 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

  19. 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 ...

  20. 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...

  1. 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.

  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. 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

  4. 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.

  5. 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.)

  6. 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.

  7. 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.

  8. 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

  9. 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)

  10. 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,* ...

  11. 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

  12. 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

  13. Kinetics and mechanism of oxidation of L-leucine by alkaline ...

    Indian Academy of Sciences (India)

    The kinetics of oxidation of L-leucine by diperiodatocuprate (III) (DPC) in aqueous alkaline medium at a constant ionic strength of 0.10mol dm-3 was studied spectrophotometrically. The reaction between L-leucine and DPC in alkaline medium exhibits 1:4 stoichiometry (L-leucine: DPC). The reaction is of first order in [DPC] ...

  14. 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

  15. 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

  16. Deuterium Labelling of L-Tyrosine with Raney Alloys in Alkaline Deuterium Oxide Solutions

    OpenAIRE

    Tsuzuki, Hirohisa; Mukumoto, Mamoru; Udagawa, Jun; Mataka, Shuntaro; Tashiro, Masashi

    1997-01-01

    The synthesis of deuteriated L-tyrosines with Raney alloys in alkaline deuterium oxide solutions, involving reductive debromination of brominated L-tyrosines and hydrogen-deuterium (H-D) exchange of L-tyrosines, without causing racemization, is presented.

  17. Sodic alkaline stress mitigation by exogenous melatonin in tomato needs nitric oxide as a downstream signal.

    Science.gov (United States)

    Liu, Na; Gong, Biao; Jin, Zhiyong; Wang, Xiufeng; Wei, Min; Yang, Fengjuan; Li, Yan; Shi, Qinghua

    2015-08-15

    The present study was designed to determine the interactive effect of exogenous melatonin and nitric oxide (NO) on sodic alkaline stress mitigation in tomato seedlings. It was observed that exogenous melatonin treatment elevated NO levels in alkaline-stressed tomato roots. However, exogenous NO had little effects on melatonin levels. Importantly, melatonin-induced NO generation was accompanied by increased tolerance to alkaline stress. Chemical scavenging of NO reduced melatonin-induced alkaline stress tolerance and defense genes' expression. However, inhibition of melatonin biosynthesis had a little effect on NO-induced alkaline stress tolerance. These results strongly suggest that NO, acting as a downstream signal, is involved in the melatonin-induced tomato tolerance to alkaline stress. This process creates a new signaling pathway for improving stress tolerance in plant. Copyright © 2015 Elsevier GmbH. All rights reserved.

  18. 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.

  19. 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

  20. 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.

  1. Alkaline electrochemical advanced oxidation process for chromium oxidation at graphitized multi-walled carbon nanotubes.

    Science.gov (United States)

    Xue, Yudong; Zheng, Shili; Sun, Zhi; Zhang, Yi; Jin, Wei

    2017-09-01

    Alkaline electrochemical advanced oxidation processes for chromium oxidation and Cr-contaminated waste disposal were reported in this study. The highly graphitized multi-walled carbon nanotubes g-MWCNTs modified electrode was prepared for the in-situ electrochemical generation of HO 2 - . RRDE test results illustrated that g-MWCNTs exhibited much higher two-electron oxygen reduction activity than other nanocarbon materials with peak current density of 1.24 mA cm -2 , %HO 2 - of 77.0% and onset potential of -0.15 V (vs. Hg/HgO). It was originated from the highly graphitized structure and good electrical conductivity as illustrated from the Raman, XRD and EIS characterizations, respectively. Large amount of reactive oxygen species (HO 2 - and ·OH) were in-situ electro-generated from the two-electron oxygen reduction and chromium-induced alkaline electro-Fenton-like reaction. The oxidation of Cr(III) was efficiently achieved within 90 min and the conversion ratio maintained more than 95% of the original value after stability test, offering an efficient and green approach for the utilization of Cr-containing wastes. Copyright © 2017 Elsevier Ltd. All rights reserved.

  2. IrPdRu/C as H2Oxidation Catalysts for Alkaline Fuel Cells.

    Science.gov (United States)

    Wang, Hongsen; Abruña, Héctor D

    2017-05-24

    H 2 oxidation kinetics on Pt in alkaline media are very sluggish, being over 100 times slower than in acidic media, and thus, new and more active H 2 oxidation electrocatalysts must be developed in order to enable alkaline exchange membrane fuel cells (AEMFCs). In this Communication, we present a new type of catalysts-carbon-supported IrPdRu nanoparticles-as H 2 oxidation catalysts in alkaline media. These catalysts exhibit higher activity than Pt/C and Ir/C catalysts and are also quite stable. In particular, Ir 3 Ru 7 /C and Ir 3 Pd 1 Ru 6 /C catalysts are significantly more active and less expensive than Pt/C and Ir/C, and are thus promising new anode catalysts for alkaline fuel cell applications.

  3. 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%.

  4. 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

  5. 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.

  6. 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.

  7. 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

  8. 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.

  9. 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 ...

  10. 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

  11. 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.)

  12. Hydrogen transfer reaction on rare earth oxides

    International Nuclear Information System (INIS)

    Minachev, Kh.M.; Atal'yan, O.K.; Markov, M.A.

    1978-01-01

    The ketone reduction by alcohols is studied on a large group of rare earth oxides. The reactions of octanol-2 with cyclohexan one, n. butanol with dipropyl ketone and acetone have been chosen for a model. It has been shown that La,Nd,Sm,Gd,Dy,Er and Y oxides are active in the reactions of hydrogen transfer from n. butanol to dipropyl ketone and acetone and from octanol-2 to cyclohexanone the last reaction being the most selective. The comparative reactivity of ketones-acceptors of hydrogen at their interaction with n. butanol is in conformity with the values of their normal oxidative potentials. By addition of ketone to n. butanol the general degree of catalytic transformation of the latter increases and the selectivity in ketonization ratio decreases. It has been established that catalyst activity increases with the temperature rise

  13. An oxidant, detergent and salt stable alkaline protease from Bacillus ...

    African Journals Online (AJOL)

    A novel soil bacterium, Bacillus cereus SIU1 was earlier isolated from non-saline, slightly alkaline soil of Eastern Uttar Pradesh, India. The isolate B. cereus SIU1 was grown in modified glucose yeast extract (modified GYE) medium at pH 9.0 and 45°C. It produced maximum protease at 20 h incubation. The enzyme was ...

  14. Study of the oxides nature effect of rare and rare earth elements on the aluminium-chromium catalyst properties

    International Nuclear Information System (INIS)

    Dadashev, B.A.; Abbasov, S.G.; Sarydzhanov, A.A.; AN Azerbajdzhanskoj SSR, Baku. Inst. Neftekhimicheskikh Protsessov)

    1975-01-01

    Adsorption studies have shown that oxides of rare and rare earth elements REE appreciably influence the structure of aluminium-chrome catalyst. Alkaline promotors, unlike REE, contribute to the formation of developed contact surface. Electrophysical investigations show that oxides of rare elements introduced into the catalyst increase its conductivity and activation energy. As for REE oxides, they decrease the conductivity and increase the activation energy. Catalysts with developed surface and high conductivity are also more active in the reaction of isopentane dehydration

  15. Kinetic study of the alkaline metals oxidation by dry oxygen

    International Nuclear Information System (INIS)

    Touzain, Ph.

    1967-06-01

    The oxidation of lithium, sodium, potassium, rubidium, cesium and sodium-potassium alloys by dry oxygen is studied at several temperatures and in the oxygen pressure range 40 to 400 mmHg. One distinguishes three different oxidation behaviours (inflammation, ignition and slow combustion) whose zones are precised in function of the temperature. The slow oxidation kinetic laws, the composition of oxides and the motive of oxides colorations are determined. At least, the experimental data are construed theoretically. (author) [fr

  16. 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.

  17. 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.)

  18. 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.

  19. 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

  20. 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...

  1. 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.

  2. 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.

  3. 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.

  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. Corrosion of uncoated and oxide-coated basalt fibre in different alkaline media

    International Nuclear Information System (INIS)

    Rybin, V.A.; Utkin, A.V.; Baklanova, N.I.

    2016-01-01

    Highlights: • Alkaline corrosion of uncoated and coated basalt fibre in alkali media was studied. • Degradation of the fibre involves the dissolution of alumosilicate network in alkali media. • Insoluble shell from iron and calcium hydroxides and carbonates is formed. • Zirconia and titania coatings slow down the corrosion of basalt fibre significantly. - Abstract: The corrosion behaviour of the zirconium dioxide and titanium dioxide coated basalt fibre in sodium and calcium hydroxide solutions was studied. The morphology, elemental, phase composition of fibre before and after exposure to alkaline media was examined by different analytical techniques. It was shown that the oxide coatings slow down corrosion, and zirconium dioxide slows down corrosion of basalt fibre to a higher extent than titanium dioxide. The morphology and composition of solid corrosion products depend on a type of alkaline medium. The schemes of corrosion for the uncoated and coated basalt fibres in alkaline media were proposed.

  6. 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.

  7. 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

  8. 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)

  9. 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

  10. Sulfide oxidation at halo-alkaline conditions in a fed-batch bioreactor

    NARCIS (Netherlands)

    Bosch, van den P.L.F.; Beusekom, van O.C.; Buisman, C.J.N.; Janssen, A.J.H.

    2007-01-01

    A biotechnological process is described to remove hydrogen sulfide (H2S) from high-pressure natural gas and sour gases produced in the petrochemical industry. The process operates at halo-alkaline conditions and combines an aerobic sulfide-oxidizing reactor with an anaerobic sulfate (SO) and

  11. Kinetics and mechanism of oxidation of L-leucine by alkaline ...

    Indian Academy of Sciences (India)

    J. Chem. Sci. Vol. 124, No. 4, July 2012, pp. 809–819. c Indian Academy of Sciences. Kinetics and mechanism of oxidation of L-leucine by alkaline ... Post Graduate Department of Studies in Chemistry, Karnatak University, Dharwad 580003, India e-mail: ... anism of this drug by DPC, there was a need for under- standing the ...

  12. Oxidant and solvent stable alkaline protease from Aspergillus flavus ...

    African Journals Online (AJOL)

    The enzyme retained 80% of its original activity in the presence of non ionic and ionic surfactants and 100% with 10% H2O2 after 1 h of incubation at 30°C. In addition, the enzyme showed excellent compatibility with some commercial powder detergents. The compatibility of our protease with several detergents, oxidants ...

  13. Development of nano indium tin oxide (ITO) grains by alkaline ...

    Indian Academy of Sciences (India)

    Unknown

    As the indium tin oxide (ITO) is an advanced ceramic material with many electronic and optical applications due to its high electrical conductivity and transparency .... Caulton K G and Hubert-Pfalzgraf L G 1990 Chem. Rev. 90. 969. Denoy M D and Pradeep B 1997 Bull. Mater. Sci. 20 1029. Gehman B L, Jonson S, Rudolf T, ...

  14. Comparative electrocatalytic oxidation of ethanol, ethylene glycol and glycerol in alkaline medium at Pd-decorated FeCo@Fe/C core-shell nanocatalysts

    CSIR Research Space (South Africa)

    Fashedemi, OO

    2014-05-01

    Full Text Available Electrocatalytic oxidation of alcohols in alkaline solutions is critical for the development of direct alkaline alcohol fuel cells (DAAFCs). This work investigated alcohol oxidation reaction (AOR) at a novel palladium-based core-shell nano catalyst...

  15. Production of rare earth oxide and product obtained

    International Nuclear Information System (INIS)

    David, C.; Seon, F.

    1988-01-01

    Rare earth oxides of high specific surface area by reaction of at least a rare earth salt and a strong base in presence of carboxylate ions or by reaction of a rare earth carboxylate and a strong base. The precipitate is washed and calcined [fr

  16. 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.

  17. Theoretical study of support effect of Au catalyst for glucose oxidation of alkaline fuel cell anode

    Energy Technology Data Exchange (ETDEWEB)

    Ishimoto, Takayoshi, E-mail: ishimoto@ifrc.kyushu-u.ac.jp [Frontier Energy Research Division, INAMORI Frontier Research Center, Kyushu University, 744 Motooka, Nishi-ku, Fukuoka 819-0395 (Japan); Hamatake, Yumi [Frontier Energy Research Division, INAMORI Frontier Research Center, Kyushu University, 744 Motooka, Nishi-ku, Fukuoka 819-0395 (Japan); Kazuno, Hiroki; Kishida, Takayuki [OLYMPUS Corporation, 2-3 Kuboyama-cho, Hachioji-shi, Tokyo 192-8512 (Japan); Koyama, Michihisa, E-mail: koyama@ifrc.kyushu-u.ac.jp [Frontier Energy Research Division, INAMORI Frontier Research Center, Kyushu University, 744 Motooka, Nishi-ku, Fukuoka 819-0395 (Japan); International Institute for Carbon-Neutral Energy Research, Kyushu University, 744 Motooka, Nishi-ku, Fukuoka 819-0395 (Japan)

    2015-01-01

    Highlights: • The catalytic activity of Au in alkaline solution is studied theoretically. • Carbon and oxide materials are used to estimate support effect for glucose oxidation. • The glucose oxidation on SnO{sub 2}(1 1 0) supported Au catalyst shows high activity. • The charge transfer from Au catalyst to support materials is dominant. - Abstract: We theoretically analyzed the glucose oxidation reaction mechanism and reaction activity of Au catalyst supported by carbon (graphite(0 0 0 1), (101{sup ¯}0), and (112{sup ¯}0)) and oxide (ZrO{sub 2}(1 1 1) and SnO{sub 2}(1 1 0)) in alkaline solution environment by using density functional theory method. We observed large stabilization of Au catalyst on support materials due to the electron transfer in the case of graphite(112{sup ¯}0) and SnO{sub 2}(1 1 0) systems. The catalytic activity for glucose oxidation reaction over Au supported by graphite(101{sup ¯}0) and (112{sup ¯}0) is calculated to be low in comparison with those of unsupported system. We found that SnO{sub 2}(1 1 0) supported Au catalyst shows high activity toward the glucose oxidation. One of the main factors for the observed high catalytic activity is charge transfer from Au catalyst to support materials. When the atomic charge of Au catalyst becomes positive by the support effect, the activity of glucose oxidation reaction on Au catalyst is improved.

  18. Electrochemical Extraction of Rare Earth Metals in Molten Fluorides : Conversion of Rare Earth Oxides into Rare Earth Fluorides Using Fluoride Additives

    NARCIS (Netherlands)

    Abbasalizadeh, A.; Malfliet, Annelies; Seetharaman, Seshadri; Sietsma, J.; Yang, Y.

    2017-01-01

    In the present research on rare earth extraction from rare earth oxides (REOs), conversion of rare earth oxides into rare earth fluorides with fluoride fluxes is investigated in order to overcome the problem of low solubility of the rare earth oxides in molten fluoride salts as well as the formation

  19. 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.

  20. 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.

  1. 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.

  2. 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.

  3. 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.

  4. Production of ceramic layers on aluminum alloys by plasma electrolytic oxidation in alkaline silicate electrolytes

    Science.gov (United States)

    Lugovskoy, Alex; Zinigrad, Michael; Kossenko, Aleksey; Kazanski, Barbara

    2013-01-01

    Plasma electrolytic oxidation (PEO) of aluminum alloy 5052 in alkaline-silicate electrolytes having different SiO2/Na2O ratios (silicate indexes) was studied. For all the electrolytes 20-90 μm thick technological layer was obtained; composition, structure and properties of the oxidized layer were studied. For each sample, the oxidized layer consists of a denser internal and looser external sublayer. While for “n = 1 electrolytes” the oxidized layer is mainly formed by several kinds of alumina, the principal constituent of the oxidized layer for “n = 3 electrolytes” is mullite. Measurements of microhardness evidenced that it is apparently not influenced by the kind of silicate (n = 1 or n = 3) and by its concentration in the electrolyte. Electrolytes with silicate index n = 3 ensure better corrosion protection than those with n = 1. Corrosion protection parameters are significantly better for all PEO oxidized samples than for the untreated Al5052 alloy.

  5. 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

  6. Actinides in Hanford Tank Waste Simulants: Chemistry of Selected Species in Oxidizing Alkaline Solutions

    International Nuclear Information System (INIS)

    Nash, Kenneth L.; Laszak, Ivan; Borkowski, Marian; Hancock, Melissa; Rao, Linfeng; Reed, Wendy

    2004-01-01

    To enhance removal of selected troublesome nonradioactive matrix elements (P, Cr, Al, S) from the sludges in radioactive waste tanks at the Hanford site, various chemical washing procedures have been evaluated. It is intended that leaching should leave the actinides in the residual sludge phase for direct vitrification. Oxidative treatment with strongly alkaline solutions has emerged as the best approach to accomplishing this feat. However, because the most important actinide ions in the sludge can exist in multiple oxidation states, it is conceivable that changes in actinide oxidation state speciation could interfere with hopes and plans for actinide insolubility. In this presentation, we discuss both the impact of oxidative alkaline leachants on actinide oxidation state speciation and the chemistry of oxidized actinide species in the solution phase. Actinide oxidation does occur during leaching, but the solubility behavior is complex. Mixed ligand complexes may dominate solution phase speciation of actinides under some circumstances. This work was supported by the U.S. Department of Energy, Offices of Science and Waste Management, Environmental Management Science Program under Contract DEAC03- 76SF0098 at Lawrence Berkeley National Laboratory and Contract W-31-109- ENG-38 at Argonne National Laboratory

  7. Ammonium carbonate and/or bicarbonate plus alkaline chlorate oxidant for recovery of uranium values

    International Nuclear Information System (INIS)

    Stapp, P.R.

    1983-01-01

    In accordance with the present invention, uranium values are extracted from materials containing uranium in valence states lower than its hexavalent state by contacting the materials containing uranium with an aqueous alkaline leach solution containing an alkaline chlorate in an amount sufficient to oxidize at least a portion of the uranium in valence states lower than its hexavalent state to its hexavalent state. In a further embodiment of the present invention, the alkaline leach solution is an aqueous solution of a carbonate selected from the group consisting of ammonium carbonate, ammonium bicarbonate and mixtures thereof. In yet another embodiment of the present invention, at least one catalytic compound of a metal selected from the group consisting of copper, cobalt, iron, nickel, chromium and mixtures thereof adapted to assure the presence of the ionic species Cu ++ , Co ++ , Fe +++ , Ni ++ , Cr +++ and mixtures thereof, respectively, during the contacting of the material containing uranium with the alkaline leach solution and in an amount sufficient to catalyze the oxidation of at least a portion of the uranium in its lower valence states to its hexavalent state, is present

  8. 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

  9. 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

  10. 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.

  11. 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.

  12. 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.

  13. 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

  14. 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 ...

  15. Electrochemical determination of activation energies for methanol oxidation on polycrystalline platinum in acidic and alkaline electrolytes.

    Science.gov (United States)

    Cohen, Jamie L; Volpe, David J; Abruña, Héctor D

    2007-01-07

    The oxidation pathways of methanol (MeOH) have been the subject of intense research due to its possible application as a liquid fuel in polyelectrolyte membrane (PEM) fuel cells. The design of improved catalysts for MeOH oxidation requires a deep understanding of these complex oxidation pathways. This paper will provide a discussion of the literature concerning the extensive research carried out in acidic and alkaline electrolytes. It will highlight techniques that have proven useful in the determination of product ratios, analysis of surface poisoning, anion adsorption, and oxide formation processes, in addition to the effects of temperature on the MeOH oxidation pathways at bulk polycrystalline platinum (Pt(poly)) electrodes. This discussion will provide a framework with which to begin the analysis of activation energy (E(a)) values. This kinetic parameter may prove useful in characterizing the rate-limiting step of the MeOH oxidation at an electrode surface. This paper will present a procedure for the determination of E(a) values for MeOH oxidation at a Pt(poly) electrode in acidic and alkaline media. Values from 24-76 kJ mol(-1) in acidic media and from 36-86 kJ mol(-1) in alkaline media were calculated and found to be a function of applied potential and direction of the potential sweep in a voltammetric experiment. Factors that influence the magnitude of the calculated E(a) include surface poisoning from MeOH oxidation intermediates, anion adsorption from the electrolyte, pH effects, and oxide formation processes. These factors are all potential, and temperature, dependent and must clearly be addressed when citing E(a) values in the literature. Comparison of E(a) values must be between systems of comparable electrochemical environment and at the same potential. E(a) values obtained on bulk Pt(poly), compared with other catalysts, may give insight into the superiority of other Pt-based catalysts for MeOH oxidation and lead to the development of new catalysts

  16. Effect of organics and alkalinity on the sulfur oxidizing bacteria (SOB) biosensor.

    Science.gov (United States)

    Hassan, Sedky H A; Van Ginkel, Steven W; Oh, Sang-Eun

    2013-01-01

    The environmental risk assessment of toxic chemicals in stream water requires the use of a low cost standardized toxicity bioassay. Here, a biosensor for detection of toxic chemicals in stream water was studied using sulfur oxidizing bacteria (SOB) in continuous mode. The biosensor depends on the ability of SOB to oxidize sulfur particles under aerobic conditions to produce sulfuric acid. The reaction results in an increase in electrical conductivity (EC) and a decrease in pH. The biosensor is based on the inhibition of SOB in the presence of toxic chemicals by measuring changes in EC and pH. We found that the SOB biosensor can detect Cr(6+)at a low concentration (50 ppb) which is lower than many whole-cell biosensors. The effect of organic material in real stream water on SOB activity was studied. Due to the presence of mixotrophic SOB, we found that the presence of organic matter increases SOB activity which decreases the biosensor start up period. Low alkalinity (22 mg L(-1) CaCO(3)) increased effluent EC and decreased effluent pH which is optimal for biosensor operation. While at high alkalinity (820 mg L(-1) CaCO(3), the activity of SOB little decreased. We found that system can detect 50 ppb of Cr(6+) at low alkalinity (22 mg L(-1) CaCO(3)) in few hours while, complete inhibition was observed after 35 h of operation at high alkalinity (820 mg L(-1) CaCO(3)). Copyright © 2012 Elsevier Ltd. All rights reserved.

  17. Ag supported on carbon fiber cloth as the catalyst for hydrazine oxidation in alkaline medium

    International Nuclear Information System (INIS)

    Liu, Ran; Ye, Ke; Gao, Yinyi; Zhang, Wenping; Wang, Guiling; Cao, Dianxue

    2015-01-01

    Highlights: • CFC supported microspherical Ag is obtained by square-wave potential method. • Ag/CFC electrode has high catalytic activity toward hydrazine oxidation. • Hydrazine oxidation on the electrode proceeds by a near 4-electron pathway. - Abstract: Silver particles with microspheric structure are directly electrodeposited on carbon fiber cloth (CFC) substrate by square-wave potential electrodeposition method. The electrocatalytic behaviors of the Ag/CFC electrode toward hydrazine oxidation in alkaline solution are examined by cyclic voltammetry and chronoamperometry. An onset oxidation potential of -0.5 V and a peak current density of 30 mA cm −2 are achieved in the solution containing 1.0 mol L −1 KOH and 20.0 mmol L −1 hydrazine. The microspheric structure of the Ag/CFC electrode provides large electroactive surface area, hence, abundant active sites are vacant for hydrazine oxidation. The calculated apparent activation energies at different potentials show that hydrazine electro-oxidation at higher potential has faster kinetics than that at lower potential. In addition, the transfer electron number of hydrazine oxidation reaction on the Ag/CFC electrode is close to four, suggesting hydrazine is almost completely electrooxidized on the electrode and the full use of hydrazine fuel is basically achieved.

  18. 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)

  19. Bifunctional Perovskite Oxide Catalysts for Oxygen Reduction and Evolution in Alkaline Media.

    Science.gov (United States)

    Gupta, Shiva; Kellogg, William; Xu, Hui; Liu, Xien; Cho, Jaephil; Wu, Gang

    2016-01-01

    Oxygen electrocatalysis, namely of the oxygen reduction reaction (ORR) and the oxygen evolution reaction (OER), governs the performance of numerous electrochemical energy systems such as reversible fuel cells, metal-air batteries, and water electrolyzers. However, the sluggish kinetics of these two reactions and their dependency on expensive noble metal catalysts (e.g, Pt or Ir) prohibit the sustainable commercialization of these highly innovative and in-demand technologies. Bifunctional perovskite oxides have emerged as a new class of highly efficient non-precious metal catalysts (NPMC) for oxygen electrocatalysis in alkaline media. In this review, we discuss the state-of-the-art understanding of bifunctional properties of perovskites with regards to their OER/ORR activity in alkaline media and review the associated reaction mechanisms on the oxides surface and the related activity descriptors developed in the recent literature. We also summarize the present strategies to modify their electronic structure and to further improve their performance for the ORR/OER through highlighting the new concepts relating to the role of surface redox chemistry and oxygen deficiency of perovskite oxides for the ORR/OER activity. In addition, we provide a brief account of recently developed advanced perovskite-nanocarbon hybrid bifunctional catalysts with much improved performances. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  20. Mechanistic study of nickel based catalysts for oxygen evolution and methanol oxidation in alkaline medium

    Science.gov (United States)

    Chen, Dayi; Minteer, Shelley D.

    2015-06-01

    Nickel based catalysts have been studied as catalysts for either organic compound (especially methanol) oxidation or oxygen evolution reactions in alkaline medium for decades, but methanol oxidation and oxygen evolution reactions occur at a similar potential range and pH with nickel based catalysts. In contrast to previous studies, we studied these two reactions simultaneously under various pH and methanol concentrations with electrodes containing a series of NiOOH surface concentrations. We found that nickel based catalysts are more suitable to be used as oxygen evolution catalysts than methanol oxidation catalysts based on the observation that: The rate-determining step of methanol oxidation involves NiOOH, OH- and methanol while high methanol to OH- ratio could poison the NiOOH sites. Since NiOOH is involved in the rate-determining step, methanol oxidation suffers from high overpotential and oxygen evolution is favored over methanol oxidation in the presence of an equivalent amount (0.1 M) of alkali and methanol.

  1. 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

  2. Microwave-assisted pechini synthesis of Pd-Ni nanocatalyst for ethanol electro-oxidation in alkaline medium

    CSIR Research Space (South Africa)

    Rohwer, M

    2012-11-01

    Full Text Available counterparts. For these reasons, electrocatalysts for the oxidation of ethanol in alkaline medium deserve special attention. Pd and its alloys, e.g. Pd-Ni, have been investigated widely as catalysts for ethanol electro-oxidation, and form the subject...

  3. Preparation of nanosized non-oxide powders using diatomaceous earth

    Directory of Open Access Journals (Sweden)

    Šaponjić A.

    2009-01-01

    Full Text Available In this paper the nanosized non-oxide powders were prepared by carbothermal reduction and subsequent nitridation of diatomaceous earth which is a waste product from coal exploitation. Our scope was to investigate the potential use of diatomaceous earth as a main precursor for low-cost nanosized non-oxide powder preparation as well as to solve an environmental problem. The influence of carbon materials (carbonized sucrose, carbon cryogel and carbon black as a reducing agent on synthesis and properties of low-cost nanosized nonoxide powders was also studied. The powders were characterized by specific surface area, X-ray and SEM investigations. It was found that by using diatomaceous earth it is was possible to produce either a mixture of non-oxide powders (Si3N4/SiC or pure SiC powders depending on temperature.

  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

    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.)

  5. Evolution of the Oxidation State of the Earth's Mantle

    Science.gov (United States)

    Danielson, L. R.; Righter, K.; Keller, L.; Christoffersen, E.; Rahman, Z.

    2015-01-01

    The oxidation state of the Earth's mantle during formation remains an unresolved question, whether it was constant throughout planetary accretion, transitioned from reduced to oxidized, or from oxidized to reduced. We investigate the stability of Fe3(+) at depth, in order to constrain processes (water, late accretion, dissociation of FeO) which may reduce or oxidize the Earth's mantle. In our previous experiments on shergottite compositions, variable fO2, T, and P less than 4 GPa, Fe3(+)/sigma Fe decreased slightly with increasing P, similar to terrestrial basalt. For oxidizing experiments less than 7GPa, Fe3(+)/sigma Fe decreased as well, but it's unclear from previous modelling whether the deeper mantle could retain significant Fe3(+). Our current experiments expand our pressure range deeper into the Earth's mantle and focus on compositions and conditions relevant to the early Earth. Preliminary multi-anvil experiments with Knippa basalt as the starting composition were conducted at 5-7 GPa and 1800 C, using a molybdenum capsule to set the fO2 near IW, by buffering with Mo-MoO3. TEM and EELS analyses revealed the run products quenched to polycrystalline phases, with the major phase pyroxene containing approximately equal to Fe3(+)/2(+). Experiments are underway to produce glassy samples that can be measured by EELS and XANES, and are conducted at higher pressures.

  6. Comparison of the chemical properties of wheat straw and beech fibers following alkaline wet oxidation and laccase treatments

    DEFF Research Database (Denmark)

    Schmidt, A. S.; Mallon, S.; Thomsen, Anne Belinda

    2002-01-01

    reacted differently in the two processes. The chemical composition changed little following enzyme treatment. After alkaline wet oxidation, fibers enriched in cellulose were obtained. With both materials, almost all hemicellulose (80%) together with a large portion of the lignin were solubilised......Wheat straw (Triticum aestivum) and beech (Fagus sylvatica), were used to evaluate the effects of two pre-treatment processes (alkaline wet oxidation and enzyme treatment with laccase) on lignocellulosic materials for applications in particleboards and fiberboards. Wheat straw and beech fibers...... by alkaline wet oxidation, but essentially all cellulose remained in the solid fraction. Following enzyme treatment most material remained as a solid. For wheat straw, reaction with acetic anhydride indicated that both treatments resulted in more hydroxyl groups being accessible for reaction. The enzyme...

  7. 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

  8. Steady-state analysis of the nickel oxide in neutral and weakly alkaline solutions

    International Nuclear Information System (INIS)

    Albu, C.; Deconinck, D.; Hotoiu, L.; Deconinck, J.; Topa, V.

    2013-01-01

    Thin passive nickel oxides are investigated in neutral and weakly alkaline pH solutions under steady-state conditions. The chemical species considered in the oxide film are nickel interstitials and vacancies, as well as oxygen vacancies. The set of differential equations used in this study is solved using the finite element method (FEM) and is able to reproduce the experimental data present in the literature. Steady-state oxide thickness variation with the applied electrode potential presents a linear behavior with an average slope of 2 nm/V. The role of dominant species in these thin films is investigated in terms of current density produced by the reactions at the interfaces, the reactions involving production and consumption of Ni 2+ vacancies playing a major role in the steady-state properties of the oxide. We show that the mass transport of species in the oxide is influenced more by the migration component of the flux than the diffusion component. Our results also show that the flux of Ni 2+ vacancies is approximately two orders of magnitude higher than the flux of oxygen vacancies and Ni 2+ interstitials, making them the dominant defects in the oxide (thus the p-type electronic character is present). Also, the Ni 2+ vacancies were found to have density levels of 10 20 –10 21 cm −3 close to the metal–film interface. Variations of the steady-state thickness and logarithm of the current density with the electrolyte pH, show a linear increase and decrease respectively. Some of these results are compared with data from experiments and simulations done on the iron oxide, showing that Ni forms steady-state passive films that are thinner than the ones formed on Fe under the same environment conditions (pH, temperature, and applied potential)

  9. 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)

  10. Polyoxometalate electrocatalysts based on earth-abundant metals for efficient water oxidation in acidic media

    Science.gov (United States)

    Blasco-Ahicart, Marta; Soriano-López, Joaquín; Carbó, Jorge J.; Poblet, Josep M.; Galan-Mascaros, J. R.

    2018-01-01

    Water splitting is a promising approach to the efficient and cost-effective production of renewable fuels, but water oxidation remains a bottleneck in its technological development because it largely relies on noble-metal catalysts. Although inexpensive transition-metal oxides are competitive water oxidation catalysts in alkaline media, they cannot compete with noble metals in acidic media, in which hydrogen production is easier and faster. Here, we report a water oxidation catalyst based on earth-abundant metals that performs well in acidic conditions. Specifically, we report the enhanced catalytic activity of insoluble salts of polyoxometalates with caesium or barium counter-cations for oxygen evolution. In particular, the barium salt of a cobalt-phosphotungstate polyanion outperforms the state-of-the-art IrO2 catalyst even at pH < 1, with an overpotential of 189 mV at 1 mA cm-2. In addition, we find that a carbon-paste conducting support with a hydrocarbon binder can improve the stability of metal-oxide catalysts in acidic media by providing a hydrophobic environment.

  11. Spectroscopic and mechanistic investigations into oxidation of aspartame by diperiodatocuprate(III in aqueous alkaline medium

    Directory of Open Access Journals (Sweden)

    Jayant I. Gowda

    2015-12-01

    Full Text Available The oxidation of aspartame (ASP by diperiodatocuprate(III (DPC in aqueous alkaline medium at 298 K and a constant ionic strength of 0.30 mol dm−3 was studied spectrophotometrically. The reaction between aspartame and diperiodatocuprate(III in alkaline medium exhibits 1:6 stoichiometry in the reaction. The order of the reaction with respect to [diperiodatocuprate(III] was unity, while the apparent order with respect to [aspartame] was less than unity over the concentration range studied. The rate of the reaction increased with increase in [OH−] whereas the rate decreased with increase in [$ {\\text{IO}}^-_4 $]. Increasing the ionic strength of the medium increased the rate. The main products were identified by FT-IR, NMR, and LC-MS spectral studies. The probable mechanism was proposed. The activation parameters with respect to slow step of the mechanism were computed and discussed. Thermodynamic quantities were also calculated. Kinetic studies suggest that [Cu(H2IO6(H2O2] is the reactive species of Cu(III.

  12. 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

  13. 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.

  14. 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.)

  15. Wild soybean roots depend on specific transcription factors and oxidation reduction related genesin response to alkaline stress.

    Science.gov (United States)

    DuanMu, Huizi; Wang, Yang; Bai, Xi; Cheng, Shufei; Deyholos, Michael K; Wong, Gane Ka-Shu; Li, Dan; Zhu, Dan; Li, Ran; Yu, Yang; Cao, Lei; Chen, Chao; Zhu, Yanming

    2015-11-01

    Soil alkalinity is an important environmental problem limiting agricultural productivity. Wild soybean (Glycine soja) shows strong alkaline stress tolerance, so it is an ideal plant candidate for studying the molecular mechanisms of alkaline tolerance and identifying alkaline stress-responsive genes. However, limited information is available about G. soja responses to alkaline stress on a genomic scale. Therefore, in the present study, we used RNA sequencing to compare transcript profiles of G. soja root responses to sodium bicarbonate (NaHCO3) at six time points, and a total of 68,138,478 pairs of clean reads were obtained using the Illumina GAIIX. Expression patterns of 46,404 G. soja genes were profiled in all six samples based on RNA-seq data using Cufflinks software. Then, t12 transcription factors from MYB, WRKY, NAC, bZIP, C2H2, HB, and TIFY families and 12 oxidation reduction related genes were chosen and verified to be induced in response to alkaline stress by using quantitative real-time polymerase chain reaction (qRT-PCR). The GO functional annotation analysis showed that besides "transcriptional regulation" and "oxidation reduction," these genes were involved in a variety of processes, such as "binding" and "response to stress." This is the first comprehensive transcriptome profiling analysis of wild soybean root under alkaline stress by RNA sequencing. Our results highlight changes in the gene expression patterns and identify a set of genes induced by NaHCO3 stress. These findings provide a base for the global analyses of G. soja alkaline stress tolerance mechanisms.

  16. Relation of oxidative stress, zinc and alkaline phosphatase in protein energy malnutrition.

    Science.gov (United States)

    Jain, Anuradha; Jadhav, Ashish Anantrao; Varma, Meena

    2013-02-01

    To determine serum zinc (Zn), total anti-oxidant capacity (TAC), malondialdehyde (MDA), alkaline phosphatase (ALP) and albumin in protein energy malnutrition (PEM) and to analyse the appropriateness of using low weight-for-age for detecting childhood under-nutrition. This study comprised 455 children (355 malnourished and 100 normal). They were classified according to the Nutrition Subcommittee of Indian Academy of Pediatrics, Z-Score Classification and Composite Index of Anthropometric Failure. Serum Zn, TAC, MDA, ALP and albumin levels were determined. The serum Zn, TAC, ALP and albumin levels were found to be significantly decreased and MDA levels were significantly increased in malnourished children as compared with control (P nutrition (low weight-for-age) may be missing out a considerable proportion of undernourished children present in the population.

  17. Variable dimensionality and new uranium oxide topologies in the alkaline-earth metal uranyl selenites AE[UO2)(SeO3)2] (AE=Ca, Ba) and Sr[UO2)(SeO3)2] · 2H2O

    International Nuclear Information System (INIS)

    Almond, Philip M.; Peper, Shane M.; Bakker, Eric; Albrecht-Schmitt, Thomas E.

    2002-01-01

    Three new alkaline-earth metal uranyl selenites, Ca[UO 2 )(SeO 3 ) 2 ] (1), Sr[UO 2 )(SeO 3 ) 2 ] · 2H 2 O (2), and Ba[UO 2 )(SeO 3 ) 2 ] (3), have been prepared from the reactions of CaCO 3 and Ca(OH) 2 , SrCl 2 and Sr(OH) 2 , or BaCl 2 and Ba(OH) 2 with UO 3 and SeO 2 under mild hydrothermal conditions. Single-crystal X-ray diffraction experiments reveal that the structures of 1-3 differ in both connectivity and dimensionality even though all contain the same fundamental building unit, namely [UO 2 (SeO 3 ) 4 ]. This polyhedron consists of a linear uranyl unit that is bound by one chelating and three bridging selenite anions creating a pentagonal bipyramidal environment around the U(VI) center. The crystal structure of 1 contains one-dimensional ribbons where the edges are terminated by monodentate selenite anions. The interior of the ribbons are constructed from edge-sharing pentagonal bipyramidal UO 7 units. The structure of 2 is also one-dimensional; however, here there are chains of edge-sharing pentagonal bipyramidal UO 7 dimers that are connected by bridging selenite anions. Ba[(UO 2 )(SeO 3 ) 2 ] (3) is two-dimensional, and the highly ruffled anionic sheets present in this structure are formed from both bridging and chelating/bridging selenite anions bound to uranyl moieties. The anionic substructures in 1-3 are separated by Ca 2+ , Sr 2+ , or Ba 2+ cations. Crystallographic data (193 K, MoKα, λ=0.71073): 1, triclinic, space group P1-bar, a=5.5502(6) A, b=6.6415(7) A, c=11.013(1) A, α=104.055(2) deg., β=93.342(2) deg., γ=110.589(2) deg. , Z=2, R(F)=4.56% for 100 parameters with 1530 reflections with I>2σ(I); 2, triclinic, space group P1-bar, a=7.0545(5) A, b=7.4656(5) A, c=10.0484(6) A, α=106.995(1) deg., β=108.028(1) deg., γ=98.875(1) deg., Z=2, R(F)= 2.43% for 128 parameters with 2187 reflections with I>2σ(I); 3, monoclinic, space group P2 1 /c, a=7.3067(6) A, b=8.1239(7) A, c=13.651(1) A, β=100.375(2) deg., Z=4, R(F)=4.31% for 105 parameters

  18. Kinetics and Mechanistic Study of Permanganate Oxidation of Fluorenone Hydrazone in Alkaline Medium

    Directory of Open Access Journals (Sweden)

    Ahmed Fawzy

    2016-01-01

    Full Text Available The oxidation kinetics of fluorenone hydrazone (FH using potassium permanganate in alkaline medium were measured at a constant ionic strength of 0.1 mol dm−3 and at 25°C using UV/VIS spectrophotometer. A first-order kinetics has been monitored in the reaction of FH with respect to [permanganate]. Less-than-unit order dependence of the reaction on [FH] and [OH−] was revealed. No pronounced effect on the reaction rate by increasing ionic strength was recorded. Intervention of free radicals was observed in the reaction. The reaction mechanism describing the kinetic results was illustrated which involves formation of 1 : 1 intermediate complex between fluorenone hydrazones and the active species of permanganate. 9H-Fluorenone as the corresponding ketone was found to be the final oxidation product of fluorenone hydrazone as confirmed by GC/MS analysis and FT-IR spectroscopy. The expression rate law for the oxidation reaction was deduced. The reaction constants and mechanism have been evaluated. The activation parameters associated with the rate-limiting step of the reaction, along with the thermodynamic quantities of the equilibrium constants, have been calculated and discussed.

  19. 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.

  20. 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.

  1. 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.

  2. 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.

  3. 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)

  4. 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

  5. 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)

  6. Chemical and structural changes associated with Cu-catalyzed alkaline-oxidative delignification of hybrid poplar.

    Science.gov (United States)

    Li, Zhenglun; Bansal, Namita; Azarpira, Ali; Bhalla, Aditya; Chen, Charles H; Ralph, John; Hegg, Eric L; Hodge, David B

    2015-01-01

    Alkaline hydrogen peroxide pretreatment catalyzed by Cu(II) 2,2'-bipyridine complexes has previously been determined to substantially improve the enzymatic hydrolysis of woody plants including hybrid poplar as a consequence of moderate delignification. In the present work, cell wall morphological and lignin structural changes were characterized for this pretreatment approach to gain insights into pretreatment outcomes and, specifically, to identify the extent and nature of lignin modification. Through TEM imaging, this catalytic oxidation process was shown to disrupt cell wall layers in hybrid poplar. Cu-containing nanoparticles, primarily in the Cu(I) oxidation state, co-localized with the disrupted regions, providing indirect evidence of catalytic activity whereby soluble Cu(II) complexes are reduced and precipitated during pretreatment. The concentration of alkali-soluble polymeric and oligomeric lignin was substantially higher for the Cu-catalyzed oxidative pretreatment. This alkali-soluble lignin content increased with time during the catalytic oxidation process, although the molecular weight distributions were unaltered. Yields of aromatic monomers (including phenolic acids and aldehydes) were found to be less than 0.2 % (wt/wt) on lignin. Oxidation of the benzylic alcohol in the lignin side-chain was evident in NMR spectra of the solubilized lignin, whereas minimal changes were observed for the pretreatment-insoluble lignin. These results provide indirect evidence for catalytic activity within the cell wall. The low yields of lignin-derived aromatic monomers, together with the detailed characterization of the pretreatment-soluble and pretreatment-insoluble lignins, indicate that the majority of both lignin pools remained relatively unmodified. As such, the lignins resulting from this process retain features closely resembling native lignins and may, therefore, be amenable to subsequent valorization.

  7. 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

  8. 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

  9. 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

  10. 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.

  11. 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

  12. Carbon supported Pd-Sn and Pd-Ru-Sn nanocatalysts for ethanol electro-oxidation in alkaline medium

    CSIR Research Space (South Africa)

    Modibedi, RM

    2011-04-01

    Full Text Available Carbon supported Pd-Sn and Pd-Ru-Sn nanocatalysts were prepared by the chemical reduction method, using sodium borohydride and ethylene glycol mixture as the reducing agent. The catalytic activity towards ethanol electro-oxidation in alkaline medium...

  13. Establishing the potential dependent equilibrium oxide coverage on platinum in alkaline solution and its influence on the oxygen reduction

    DEFF Research Database (Denmark)

    Wiberg, Gustav; Arenz, Matthias

    2012-01-01

    Publication year: 2012 Source:Journal of Power Sources, Volume 217 Gustav K.H. Wiberg, Matthias Arenz The oxidation process of polycrystalline platinum subjected to alkaline solution is re-examined using a combination of cyclic voltammetry and potential hold techniques in Ar, H2 and O2 purged 0.1...

  14. 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.

  15. The cathodic reduction of dioxygen on uranium oxide in dilute alkaline aqueous solution

    International Nuclear Information System (INIS)

    Hocking, W.H.; Betteridge, J.S.; Shoesmith, D.W.

    1991-09-01

    The cathodic reduction of dioxygen on uranium oxide in dilute alkaline aqueous solutions has been investigated within the context of a program to develop a comprehensive model to predict the behaviour of used CANDU (Canada Deuterium Uranium) nuclear fuel under disposal-vault conditions. Two different kinds of ceramic UO 2 were studied: reactor-grade CANDU fuel with normal p-type electrical conductivity and low-resistance material that exhibits n-type photoelectrochemical behaviour. The transport of electroactive species in solution was controlled by varying the rotation rate of rotating disc electrodes (RDE) and rotating ring-disc electrodes (RRDE). Steady-state polarization measurements were made using the current-interrupt method to compensate for the potential drop caused by ohmic resistance. Any release of peroxide to solution from the UO 2 (disc) surface could be monitored by oxidizing it at the Au ring of an RRDE. The existing theory for the cathodic 0 2 -reduction process as applied to RDE and RRDE experiments has been reviewed as a starting point for the interpretation of the results obtained in our work. (37 figs., 2 tabs., 170 refs.)

  16. High purity samarium oxide from mixed rare earth carbonates

    International Nuclear Information System (INIS)

    Queiroz, Carlos A. da S.; Seneda, Jose A.; Vasconcellos, Mari E. de; Pedreira Filho, Walter dos R.

    2013-01-01

    A simple and economical chemical process for the production of highly pure samarium oxides is discussed. The raw material, which was used in the form of rare earth carbonates was produced industrially from the chemical treatment of Brazilian monazite. Ion exchange chromatography was performed using a strong cationic resin that is typically employed in water treatment processes to fractionate rare earth elements (REE) without the use of retention ions. Under these conditions, 99.9% pure Sm 2 O 3 was eluted using the ammonium salt of ethylenediaminetetraacetic acid (EDTA) at a controlled pH. The EDTA-samarium complex was separated from EDTA and then precipitated as oxalate and fired to samarium oxide. Molecular absorption spectrophotometry was used to monitor the samarium content during the proposed process, and sector field inductively coupled plasma mass spectrometry was used to certify the purity of the samarium oxide. Typical samarium oxide obtained from the proposed procedure contained the following contaminants in micrograms per gram: Sc (20.90); Y (11.80); La (8.4); Ce (4.3); Pr (2.5); Nd (5.1); Eu (94); Gd (114); Tb (3.6); Dy (2.5), Ho (2.3); Er (3.0); Tm (2.3); Yb (38,2); Lu (25.6). The high-purity samarium oxides produced in the present study can be used as an alternative to imported products in research and development applications. (author)

  17. 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.

  18. 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.

  19. Preparation and characterization of electrocatalysts based on palladium for electro-oxidation of alcohols in alkaline medium

    International Nuclear Information System (INIS)

    Brandalise, Michele

    2012-01-01

    In this study Pd/C, Au/C, PdAu/C, PdAuPt/C, PdAuBi/C and PdAuIr/C electrocatalysts were prepared by the sodium borohydride reduction method for the electrochemical oxidation of methanol, ethanol and ethylene glycol. This methodology consists in mix an alkaline solution of sodium borohydride to a mixture containing water/isopropyl alcohol, metallic precursors and the Vulcan XC 72 carbon support. The electrocatalysts were characterized by energy dispersive X-ray (EDX), X-ray diffraction (XRD), transmission electron microscopy (TEM) and cyclic voltammetry. The electrochemical oxidation of the alcohols was studied by chronoamperometry using a thin porous coating technique. The mechanism of ethanol electro-oxidation was studied by Fourier Transformed Infrared (FTIR) in situ. The most effective electrocatalysts were tested in alkaline single cells directly fed with methanol, ethanol or ethylene glycol. Preliminary studies showed that the most suitable atomic composition for preparing the ternary catalysts is 50:45:05. Electrochemical data in alkaline medium show that the electrocatalysts PdAuPt/C (50:45:05) showed the better activity for methanol electro oxidation, while PdAuIr/C was the most active for ethanol oxidation and PdAuBi/C (50:45:05) was the most effective for ethylene glycol oxidation in alkaline medium. These results show that the addition of gold in the composition of electrocatalysts increases their catalytic activities. The spectroelectrochemical FTIR in situ data permitted to conclude that C-C bond is not broken and the acetate is formed. (author)

  20. Enrichment of Thermophilic Ammonia-Oxidizing Archaea from an Alkaline Hot Spring in the Great Basin, USA

    Science.gov (United States)

    Zhang, C.; Huang, Z.; Jiang, H.; Wiegel, J.; Li, W.; Dong, H.

    2010-12-01

    One of the major advances in the nitrogen cycle is the recent discovery of ammonia oxidation by archaea. While culture-independent studies have revealed occurrence of ammonia-oxidizing archaea (AOA) in nearly every surface niche on earth, most of these microorganisms have resisted isolation and so far only a few species have been identified. The Great Basin contains numerous hot springs, which are characterized by moderately high temperature (40-65 degree C) and circumneutral or alkaline pH. Unique thermophilic archaea have been identified based on molecular DNA and lipid biomarkers; some of which may be ammonia oxidizers. This study aims to isolate some of these archaea from a California hot spring that has pH around 9.0 and temperature around 42 degree C. Mat material was collected from the spring and transported on ice to the laboratory. A synthetic medium (SCM-5) was inoculated with the mat material and the culture was incubated under varying temperature (35-65 degree C) and pH (7.0-10.0) conditions using antibiotics to suppress bacterial growth. Growth of the culture was monitored by microscopy, decrease in ammonium and increase in nitrite, and increases in Crenarchaeota and AOA abundances over time. Clone libraries were constructed to compare archaeal community structures before and after the enrichment experiment. Temperature and pH profiles indicated that the culture grew optimally at pH 9.0 and temperature 45 degree C, which are consistent with the geochemical conditions of the natural environment. Phylogenetic analysis showed that the final OTU was distantly related to all known hyperthermophilic archaea. Analysis of the amoA genes showed two OTUs in the final culture; one of them was closely related to Candidatus Nitrososphaera gargensis. However, the enrichment culture always contained bacteria and attempts to separate them from archaea have failed. This highlights the difficulty in bringing AOA into pure culture and suggests that some of the AOA may

  1. High electrocatalytic performance of nitrogen-doped carbon nanofiber-supported nickel oxide nanocomposite for methanol oxidation in alkaline medium

    Energy Technology Data Exchange (ETDEWEB)

    Al-Enizi, Abdullah M. [Department of Chemistry, King Saud University, PO Box: 2455, Riyadh 11451 (Saudi Arabia); Elzatahry, Ahmed A., E-mail: aelzatahry@ksu.edu.sa [Materials Science and Technology Program, College of Arts and Science, Qatar University, Doha 2713 (Qatar); Advanced Technology and New Materials Research Institute, City of Scientific Research and Technology Applications, New Borg El-Arab City, Alexandria 21934 (Egypt); Abdullah, Aboubakr M., E-mail: bakr@qu.edu.qa [Center for Advanced Materials, Qatar University, Doha 2713 (Qatar); Vinu, Ajayan [Future Industries Institute, University of South Australia, Building X-X2-09, Mawson Lakes Campus, Mawson Lakes 5095 SA (Australia); Iwai, Hideo [Materials Analysis Station, National Institute for Materials Science, 1-2-1 Sengen, Tsukuba, Ibaraki, 305-0047 (Japan); Al-Deyab, Salem S. [Petrochemical Research Chair, Department of Chemistry, King Saud University, PO Box: 2455, Riyadh 11451 (Saudi Arabia)

    2017-04-15

    Highlights: • A mixture of Polyvinylpyrrolidone (PVP), graphene and emeraldine base polyaniline (PANi) was electrospun and used as starting materials to prepare a nitrogen-doped carbon nanofiber (N-CNF). • Nickel oxide was loaded on the N-CNF to form a nanocomposite which was calcined later at different temperatures. • The effect of calcination temperature on the electrocatalytic behavior of the nanocomposite was studied which shows that the nanocomposite calcined at 500 °C was proved to be very high compared to the other calcination temperatures. • The stability of catalyst was excellent and its resistance to the adsorption of the intermediates generated from the methanol oxidation was very high. - Abstract: Nitrogen-Doped Carbon Nanofiber (N-CNF)–supported NiO composite was prepared by electrospinning a sol-gel mixture of graphene and polyaniline (PANi) with aqueous solutions of Polyvinylpyrrolidone (PVP) followed by a high-temperature annealing process. The electrospun was stabilized for 2 h at 280 °C, carbonized for 5 h at 1200 °C then loaded by 10% NiO. The electrocatalytic activities of the produced nanocomposite have been studied using cyclic voltammetry, and chronoamperometry. Also, N-CNF was characterized by X-ray diffraction (XRD), thermogravimetric analysis (TGA), surface area (BET), X-ray photoelectron spectroscopy (XPS), transmission electron microscope (TEM), and scanning-electron microscopy (SEM). The obtained N-doped carbon nanofiber was found to have a nitrogen content of 2.6 atomic% with a diameter range of (140–160) nm, and a surface area (393.3 m{sup 2} g{sup −1}). In addition, it showed a high electrocatalytic behavior towards methanol oxidation reaction in alkaline medium and high stability and resistivity to the adsorption of intermediates.

  2. Colorimetric study of oxidation kinetics of thiolactic acid (2 - mercaptopropionic acid) by hexacyanoferrate (III) in acid and alkaline media

    International Nuclear Information System (INIS)

    Kachhwaha, O.P.; Potter, P.C.; Kapoor, R.C.

    1985-01-01

    The oxidation kinetics of thiolactic acid by hexacyanoferrate (III) in acid and alkaline media employing the calorimetric method have been described. The two compounds react in equimolar ratio in both media, but the kinetic results are different in both media. In acid medium the total order is three, two with respect to thiol and one in oxidant. The rate of the reaction shows an inverse proportionality to (H + ) and also varies inversely with decreasing dielectric constant of the medium. In alkaline medium, the total order of the reaction is two, being unity in each reactant. The rate increases with increased pH value. Additions of ferrocyanide and dithio dilactic acid have no effect on the rate in both media. Additions of a neutral electrolyte does not affect the rate in the acid medium, while a positive salt effect was observed in an alkaline medium. Activation parameters have been evaluated in both media and in a medium of low dialectric. Different reaction schemes have been proposed for acid and alkaline media and have satisfactory explained the experimental data, except for the pH rate. (author)

  3. Vanadium carbide and graphite promoted Pd electrocatalyst for ethanol oxidation in alkaline media

    Science.gov (United States)

    Yan, Zaoxue; Zhang, Mingmei; Xie, Jimin; Shen, Pei Kang

    2013-12-01

    The vanadium carbide particles with the diameter of 1-3 nm on graphitized resin (GC-V8C7) are synthesized through ionic exchange process. The materials are characterized by XRD, Raman, TEM, SEM and EDS measurements. The results prove that the ion-exchange resin as both carbon source and dispersion media favors the formation of very uniform and small (1-3 nm) V8C7 particles, and protect the V8C7 from conglomeration even at the temperature of 1500 °C. Meanwhile, the vanadium compound is found efficient catalytic effect on graphitization of ion-exchange resin, leading to high graphitization degree of GC-V8C7. Pd particles are loaded on the GC-V8C7 materials as electrocatalyst (Pd/GC-V8C7) for ethanol oxidation in alkaline media. The cyclic voltammograms measurements show that both V8C7 and GC (graphitized ion-exchange resin) give Pd electrocatalyst improved catalytic performance in activity, stability and overpotential, compared with that of Pd supporting on Vulcan XC-72 carbon (Pd/C). The present synthesizing method of GC-V8C7 is simple and effective, which can be readily scaled up for mass production of other nanomaterials.

  4. Pd-Au/C catalysts with different alloying degrees for ethanol oxidation in alkaline media

    International Nuclear Information System (INIS)

    Qin, Yuan-Hang; Li, Yunfeng; Lv, Ren-Liang; Wang, Tie-Lin; Wang, Wei-Guo; Wang, Cun-Wen

    2014-01-01

    High alloyed Pd-Au/C catalyst is prepared through a rate-limiting strategy in water/ethylene glycol solution. Pd/C and low alloyed Pd-Au/C catalysts are prepared with trisodium citrate and sodium borohydride as stabilizing and reducing agents, respectively. Transmission electron microscopy (TEM) shows that the synthesized Pd(Au) particles are well dispersed on the catalysts. X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) show that the high alloyed Pd-Au/C catalyst presents a relatively homogenous structure while the low alloyed Pd-Au/C catalyst presents a Pd-rich shell/Au-rich core structure. Electrochemical characterization shows that the low alloyed Pd-Au/C catalyst exhibits the best catalytic activity for ethanol oxidation reaction (EOR) in alkaline media, which could be attributed to its relatively large exposed Pd surface area as compared with the high alloyed Pd-Au/C catalyst due to its Pd-rich shell structure and its enhanced adsorption of OH ads as compared with Pd/C catalyst due to its core-shell structure

  5. 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

  6. International strategic minerals inventory summary report; rare-earth oxides

    Science.gov (United States)

    Jackson, W.D.; Christiansen, Grey

    1993-01-01

    Bastnaesite, monazite, and xenotime are currently the most important rare-earth minerals. Bastnaesite occurs as a primary mineral in carbonatites. Monazite and xenotime also can be found in primary deposits but are recovered principally from heavy-mineral placers that are mined for titanium or tin. Each of these minerals has a different composition of the 15 rare-earth elements. World resources of economically exploitable rare-earth oxides (REO) are estimated at 93.4 million metric tons in place, composed of 93 percent in primary deposits and 7 percent in placers. The average mineral composition is 83 percent bastnaesite, 13 percent monazite, and 4 percent of 10 other minerals. Annual global production is about 67,000 metric tons of which 41 percent is from placers and 59 percent is from primary deposits; mining methods consist of open pits (94 percent) and dredging (6 percent). This output could be doubled if the operations that do not currently recover rare earths would do so. Resources are more than sufficient to meet the demand for the predictable future. About 52 percent of the world's REO resources are located in China. Ranking of other countries is as follows: Namibia (22 percent), the United States (15 percent), Australia (6 percent), and India (3 percent); the remainder is in several other countries. Conversely, 38 percent of the production is in China, 33 percent in the United States, 12 percent in Australia, and 5 percent each in Malaysia and India. Several other countries, including Brazil, Canada, South Africa, Sri Lanka, and Thailand, make up the remainder. Markets for rare earths are mainly in the metallurgical, magnet, ceramic, electronic, chemical, and optical industries. Rare earths improve the physical and rolling properties of iron and steel and add corrosion resistance and strength to structural members at high temperatures. Samarium and neodymium are used in lightweight, powerful magnets for electric motors. Cerium and yttrium increase the

  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. 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.

  10. 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.

  11. 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.

  12. 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.

  13. 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.

  14. 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)

  15. 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.

  16. Recovery of manganese oxides from spent alkaline and zinc-carbon batteries. An application as catalysts for VOCs elimination.

    Science.gov (United States)

    Gallegos, María V; Falco, Lorena R; Peluso, Miguel A; Sambeth, Jorge E; Thomas, Horacio J

    2013-06-01

    Manganese, in the form of oxide, was recovered from spent alkaline and zinc-carbon batteries employing a biohydrometallurgy process, using a pilot plant consisting in: an air-lift bioreactor (containing an acid-reducing medium produced by an Acidithiobacillus thiooxidans bacteria immobilized on elemental sulfur); a leaching reactor (were battery powder is mixed with the acid-reducing medium) and a recovery reactor. Two different manganese oxides were recovered from the leachate liquor: one of them by electrolysis (EMO) and the other by a chemical precipitation with KMnO4 solution (CMO). The non-leached solid residue was also studied (RMO). The solids were compared with a MnOx synthesized in our laboratory. The characterization by XRD, FTIR and XPS reveal the presence of Mn2O3 in the EMO and the CMO samples, together with some Mn(4+) cations. In the solid not extracted by acidic leaching (RMO) the main phase detected was Mn3O4. The catalytic performance of the oxides was studied in the complete oxidation of ethanol and heptane. Complete conversion of ethanol occurs at 200°C, while heptane requires more than 400°C. The CMO has the highest oxide selectivity to CO2. The results show that manganese oxides obtained using spent alkaline and zinc-carbon batteries as raw materials, have an interesting performance as catalysts for elimination of VOCs. Copyright © 2013 Elsevier Ltd. All rights reserved.

  17. 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.

  18. Synthesis, characterization and solubility of alkaline earth uranyl carbonates M2[UO2(CO3)3].xH20; M: Mg, Ca, Sr, Ba

    International Nuclear Information System (INIS)

    Amayri, S.

    2002-11-01

    The release and dispersion of uranium from closed uranium mining sites and the resulting uranium contamination of the natural environment of such sites is a major problem examined in this dissertation. Knowledge of the pollution pathways and processes is indispensable for an assessment of the radiological implications for the human population, to be taken into account in the planning of site rehabilitation work. The formation of secondary uranium minerals may contribute to an immobilization of the uranium, but it is possible as well that such secondary uranium minerals will release uranium. A major task of this dissertation therefore was to examine the conditions of formation of alkaline earth uranyl carbonates in the context of their natural occurrence as observed at some sites, and to answer the question of whether hitherto unknown alkaline earth uranyl carbonates may form in the natural environment, and ought to be taken into account as new source terms. (orig./CB) [de

  19. 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.

  20. 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

  1. Electrochemical behaviour of metal hexacyanoferrate converted to metal hydroxide films immobilized on indium tin oxide electrodes-Catalytic ability towards alcohol oxidation in alkaline medium

    International Nuclear Information System (INIS)

    Ganesh, V.; Latha Maheswari, D.; Berchmans, Sheela

    2011-01-01

    Graphical abstract: - Abstract: In this work, we demonstrate a simple method to modify indium tin oxide (ITO) electrodes in order to perform electro-catalytic oxidation of alcohols in alkaline medium. Metal hexacyanoferrate (MHCF) films such as nickel hexacyanoferrate (NiHCF) and copper hexacyanoferrate (CuHCF) were successfully immobilized on ITO electrodes using an electrochemical method. Scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS) were employed to characterize the structural and morphological aspects of MHCF films. Cyclic voltammetry (CV) was used to study the redox properties and to determine the surface coverage of these films on ITO electrodes. Electrochemical potential cycling was carried out in alkaline medium in order to alter the chemical structure of these films and convert to their corresponding metal hydroxide films. SEM and XPS were performed to analyze the structure and morphology of metal hydroxide modified electrodes. Electro-catalytic oxidation ability of these films towards methanol and ethanol in alkaline medium was investigated using CV. From these studies we found that metal hydroxide modified electrodes show a better catalytic performance and good stability for methanol oxidation along with the alleviation of CO poisoning effect. We have obtained an anodic oxidation current density of ∼82 mA cm -2 for methanol oxidation, which is at least 10 fold higher than that of any metal hydroxide modified electrodes reported till date. The onset potential for methanol oxidation is lowered by ∼200 mV compared to other chemically modified electrodes reported. A plausible mechanism was proposed for the alcohol oxidation based on the redox properties of these modified electrodes. The methodology adapted in this work does not contain costlier noble metals like platinum and ruthenium and is economically viable.

  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. EFFECTS OF ALKALINE SANDY LOAM ON SULFURIC SOIL ACIDITY AND SULFIDIC SOIL OXIDATION

    Directory of Open Access Journals (Sweden)

    Patrick S. Michael

    2015-08-01

    Full Text Available  In poor soils, addition of alkaline sandy loam containing an adequate proportion of sand, silt and clay would add value by improving the texture, structure and organic matter (OM for general use of the soils. In acid sulfate soils (ASS, addition of alkaline sandy would improve the texture and leach out salts as well as add a sufficient proportion of OM for vegetation establishment. In this study, addition of alkaline sandy loam into sulfuric soil effectively increased the pH, lowered the redox and reduced the sulfate content, the magnitude of the effects dependent on moisture content. Addition of alkaline sandy loam in combination with OM was highly effective than the effects of the lone alkaline sandy loam. When alkaline sandy was added alone or in combination with OM into sulfidic soil, the effects on pH and the redox were similar as in the sulfuric soil but the effect on sulfate content was variable. The effects under aerobic conditions were higher than under anaerobic conditions. The findings of this study have important implications for the general management of ASS where lime availability is a concern and its application is limited.International Journal of Environment Volume-4, Issue-3, June-August 2015Page: 42-54

  7. Numerical Simulation on the Device of Rare Earth Oxide Preparation by Rare Earth Chloride Spray Pyrolysis

    Directory of Open Access Journals (Sweden)

    Yan Liu

    2015-01-01

    Full Text Available Based on the industrial applications of jet pyrolysis technology and it being used for the production of rare earth oxides, the paper hopes to find out an efficient, economic, and environmental friendly new technology which is suitable for production of rare earth oxides. In this paper, a chloride pyrolysis water model is designed, and standard κ-ε turbulence model and VOF model were coupled to simulate the three-dimensional steady gas-liquid flow in jet reactor. The valuable parameter we got provides strong basis for the experimental equipment manufacturing in thermal state and determining test program. Conclusions show that when the drainage tube diameter is 3 mm, it can guarantee that two-phase distribution of the gas-liquid is more uniform and easy for gas-liquid mixing in the tail region of the Venturi tube. If the fluid near the middle of the duct in front of the Venturi starts to reach equilibrium as constant speed flowing, it proves that elongated pipe is conducive to obtain a stable flow of air required by experiments. In the adjustable pipeline location of the Venturi tube, fluid can form a closed loop and generate reflux in the export where atomization and gas-liquid mixing have good effects.

  8. Kinetic and Mechanistic Studies of Oxidation of an Antiallergic Drug with Bromamine-T in Acid and Alkaline Media

    International Nuclear Information System (INIS)

    Puttaswamy; Anu Sukhdev

    2012-01-01

    Cetrizine dihydrochloride (CTZH) is widely used as an anti-allergic drug. Sodium N-bromo-p-toluenesulfonamide or bromamine-T (BAT) is the bromine analogue of chloramine-T (CAT) and is found to be a better oxidizing agent than CAT. In the present research, the kinetics of oxidation of CTZH with BAT in acid and alkaline media was studied at 313 K. The experimental rate laws obtained are: -d[BAT]/dt = k[BAT] [CTZH] 0.80 [H + ] -0.48 in acid medium and -d[BAT]/dt = k[BAT][CTZH] 0.48 [OH - ] 0.52 [PTS] -0.40 in alkaline medium where PTS is p-toluenesulfonamide. Activation parameters and reaction constants were evaluated. The solvent isotope effect was studied using D 2 O. The dielectric effect is positive. The stoichiometry of the reaction was found to be 1:1 and the oxidation products were identified as 4-chlorobenzophenone and (2-piperazin-1-yl-ethoxy)-acetic acid in both media. The rate of oxidation of CTZH is faster in acid medium. Suitable mechanisms and related rate laws have been worked out

  9. Fate of Zinc Oxide Nanoparticles Coated onto Macronutrient Fertilizers in an Alkaline Calcareous Soil.

    Directory of Open Access Journals (Sweden)

    Narges Milani

    Full Text Available Zinc oxide (ZnO nanoparticles may provide a more soluble and plant available source of Zn in Zn fertilizers due to their greater reactivity compared to equivalent micron- or millimetre-sized (bulk particles. However, the effect of soil on solubility, spatial distribution and speciation of ZnO nanoparticles has not yet been investigated. In this study, we examined the diffusion and solid phase speciation of Zn in an alkaline calcareous soil following application of nanoparticulate and bulk ZnO coated fertilizer products (monoammonium phosphate (MAP and urea using laboratory-based x-ray techniques and synchrotron-based μ-x-ray fluorescence (μ-XRF mapping and absorption fine structure spectroscopy (μ-XAFS. Mapping of the soil-fertilizer reaction zones revealed that most of the applied Zn for all treatments remained on the coated fertilizer granule or close to the point of application after five weeks of incubation in soil. Zinc precipitated mainly as scholzite (CaZn2(PO42.2H2O and zinc ammonium phosphate (Zn(NH4PO4 species at the surface of MAP granules. These reactions reduced dissolution and diffusion of Zn from the MAP granules. Although Zn remained as zincite (ZnO at the surface of urea granules, limited diffusion of Zn from ZnO-coated urea granules was also observed for both bulk and nanoparticulate ZnO treatments. This might be due to either the high pH of urea granules, which reduced solubility of Zn, or aggregation (due to high ionic strength of released ZnO nanoparticles around the granule/point of application. The relative proportion of Zn(OH2 and ZnCO3 species increased for all Zn treatments with increasing distance from coated MAP and urea granules in the calcareous soil. When coated on macronutrient fertilizers, Zn from ZnO nanoparticles (without surface modifiers was not more mobile or diffusible compared to bulk forms of ZnO. The results also suggest that risk associated with the presence of ZnO NPs in calcareous soils would be

  10. Proton damage measurements of rare earth oxide scintillators

    International Nuclear Information System (INIS)

    Hollerman, W.A.; Fisher, J.H.; Shelby, G.A.; Holland, L.R.; Jenkins, G.M.

    1990-01-01

    This paper reports on the development of a measurement technique to determine the degradation in light output under exposure to 3 MeV protons. The rare earth oxide scintillators included Gd 2 O 2 S doped with Pr, Tb, and Eu; Y 2 O 2 S doped with Tb and Eu; Y 3 Al 5 O 12 (YAG) doped with Ce; and ZnS doped with Ag. Four scintillator samples were painted on a rotable water cooled turret used to measure the proton beam current with thermocouples for temperature monitoring. The data acquisition and storage system consists of an ACRO module interfaced to a Macintosh SE/30 computer running LabVIEW software. Results indicate that the YAG doped with Ce scintillator coating withstood a proton dose an order of magnitude larger than that tolerated by the other phosphor compounds. This fact has significant implications for the use of this material for experimental scintillator applications

  11. 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-...

  12. Influence of rare earth additions on the oxidation resistance of chromia forming alloys

    International Nuclear Information System (INIS)

    Pillis, Marina Fuser

    1995-01-01

    The addition of rare earths to alloys, either in elemental form or as surface coatings reduces the oxidation rate of chromia forming alloys. The rare earths either act as nucleation sites for surface oxides or get incorporates into the surface oxide and diffuse to oxide grain boundaries. If the latter occurs, a change in the defect structure close to the grain boundaries, probably takes place. In this manner, the rare earths inhibits the movement of chromium ions to the oxide/gas interface. The influence of rare earth additions to AISI 316, AISI 316L and Ni-20 Cr on their oxidation behavior has been studied., AISI 316+Ce, AISI 316+Y, Ni-20 Cr and Ni-20 Cr-2 Al-1 Ce were prepared by melting and AISI 316L, AISI 316L+Ce O 2 and AISI 316L+Y 2 O 3 by powder compaction. The effect of superficial deposits of rare earth oxides was also studied. The alloys were coated with rare earth oxides by high temperature conversion of the respective rare earth nitrates. Isothermal oxidation tests were carried out at 900-1100 deg C and the cyclic oxidation tests consisted of 6 cycles of 2 hours each at 900 deg C, followed by cooling to room temperature. All the tests were carried out in air. Oxidation behavior was evaluated gravimetrically. Scanning electron microscopy was used to study surface morphology. Energy dispersive analysis and X-ray diffraction techniques were used to identify oxide constituents. Overall, it has been observed that with the addition of rare earths, oxidation resistance increases by decreasing oxidation rates and increasing oxide adhesion. Addition of rare earths to AISI 316 prepared by melting resulted in rapid formation of a chromium rich oxide layered near the metal/oxide interface which reduced overall oxidation rate. The addition of Ce O 2 to AISI 316L was found to improve oxidation behavior after 10 hours at 1100 deg C and also inhibit the formation of volatile Cr O 3 . The isothermal oxidation behavior of rare earth oxide covered Ni-20 Cr at 900 deg C

  13. 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

  14. Arsanilic acid modified superparamagnetic iron oxide nanoparticles for Purification of alkaline phosphatase from hen's egg yolk.

    Science.gov (United States)

    Farzi-Khajeh, Hamed; Safa, Kazem D; Dastmalchi, Siavoush

    2017-09-01

    Recent studies of magnetic carrier technology have focused on its applications in separation and purification technologies, due to easy separation of the target from the reaction medium by applying an external magnetic field. In the present study, Fe 3 O 4 superparamagnetic nanoparticles were prepared to utilize a chemical co-precipitation method, then the surfaces of the nanoparticles were modified with arsanilic acid derivatives which were used as the specific nanocarriers for the affinity purification of alkaline phosphatase from the hen's egg yolk. The six different types of magnetic nanocarriers with varied lengths of the linkers were obtained. All samples were characterized step by step and validated using FTIR, SEM, EDX, VSM and XRD analysis methods As the results were shown, the use of inflexible tags with long linkers on the surface of the nanocarrier could lead to better results for separation of alkaline phosphatase from the hen's egg yolk with 76.2% recovery and 1361.7-fold purification. The molecular weight of the purified alkaline phosphatase was estimated to be 68kDa by SDS-PAGE. The results of this study showed that the novel magnetic nanocarriers were capable of purifying alkaline phosphatase in a practically time and cost effective way. Copyright © 2017 Elsevier B.V. All rights reserved.

  15. ALT1, a Snf2 Family Chromatin Remodeling ATPase, Negatively Regulates Alkaline Tolerance through Enhanced Defense against Oxidative Stress in Rice

    Science.gov (United States)

    Guo, Mingxin; Wang, Ruci; Wang, Juan; Hua, Kai; Wang, Yueming; Liu, Xiaoqiang; Yao, Shanguo

    2014-01-01

    Alkaline salt stress adversely affects rice growth, productivity and grain quality. However, the mechanism underlying this process remains elusive. We characterized here an alkaline tolerant mutant, alt1 in rice. Map-based cloning revealed that alt1 harbors a mutation in a chromatin remodeling ATPase gene. ALT1-RNAi transgenic plants under different genetic background mimicked the alt1 phenotype, exhibiting tolerance to alkaline stress in a transcript dosage-dependent manner. The predicted ALT1 protein belonged to the Ris1 subgroup of the Snf2 family and was localized in the nucleus, and transcription of ALT1 was transiently suppressed after alkaline treatment. Although the absorption of several metal ions maintained well in the mutant under alkaline stress, expression level of the genes involved in metal ions homeostasis was not altered in the alt1 mutant. Classification of differentially expressed abiotic stress related genes, as revealed by microarray analysis, found that the majority (50/78) were involved in ROS production, ROS scavenging, and DNA repair. This finding was further confirmed by that alt1 exhibited lower levels of H2O2 under alkaline stress and tolerance to methyl viologen treatment. Taken together, these results suggest that ALT1 negatively functions in alkaline tolerance mainly through the defense against oxidative damage, and provide a potential two-step strategy for improving the tolerance of rice plants to alkaline stress. PMID:25473841

  16. Two dimensional visible-light-active Pt-BiOI photoelectrocatalyst for efficient ethanol oxidation reaction in alkaline media

    Science.gov (United States)

    Zhai, Chunyang; Hu, Jiayue; Sun, Mingjuan; Zhu, Mingshan

    2018-02-01

    Two dimensional (2D) BiOI nanoplates were synthesized and used as support for the deposition of Pt nanoparticles. Owing to broad visible light absorption (up to 660 nm), the as-obtained Pt-BiOI electrode was used as effective photoelectrocatalyst in the application of catalytic ethanol oxidation in alkaline media under visible light irradiation. Compared to dark condition, the Pt-BiOI modified electrode displayed 3 times improved catalytic activity towards ethanol oxidation under visible light irradiation. The synergistic effect of electrocatalytic and photocatalytic, and the unique of 2D structures contribute to the improvement of catalytic activity. The mechanism of enhanced photoelectrocatalytic process is proposed. The present results suggest that 2D visible-light-activated BiOI can be served as promising support for the decoration of Pt and applied in the fields of photoelectrochemical and photo-assisted fuel cell applications

  17. Magnetic properties of rare earth oxides with perovskite structure

    International Nuclear Information System (INIS)

    Hinatsu, Yukio

    2008-01-01

    A perovskite composite oxide is represented by the general formula of ABO 3 . Cations at the B site characterize magnetic properties of the oxide. Many studies have been accumulated for transition metal elements at the B sites. In this report the studies of rare earth elements at the B sites are reviewed. In rare elements, tetravalent ions such as Ce 4+ , Pr 4+ and Tb 4+ can occupy the B sites with Ba and Sr ions at the A sites. Both the SrTbO 3 and BaTbO 3 have an orthorhombic structure and show the antiferromagnetic transition at about 33 K, which is originated from terbium ions coupled antiferromagnetically with the six neighboring terbium ions. A tetravalent praseodymium perovskite SrPrO 3 shows no existence of the magnetic ordering down to 2.0 K. This is in contrast to the result of isomorphous BaPrO 3 , which shows an antiferromagnetic transition at 11.5 K. A double perovskite structure is represented by the formula A 2 LnMO 6 (A=Ba, Sr, Ca; M=Ru, Ir). In a double perovskite compound Ba 2 PrRuO 6 , the Pr 3+ and Ru 5+ ions are arranged with regularity over the six-coordinate B sites. This compound transforms to an antiferromagnetic state below 117 K. Antiferromagnetic transition temperatures T N for isomorphous Sr and Ca show a clear tendency, T N (A=Ba)>T N (Sr)>T N (Ca), in the compounds with the same rare earth elements (Ln). The 6H-perovskite structure Ba 3 LnRu 2 O 9 consists of linkages between LnO 6 octahedra and Ru 2 O 9 dimers made from face-shared RuO 6 octahedra. The 6H-perovskite structure Ba 3 MRu 2 O 9 (M=Sc, Y, La, Nd-Gd, Dy-Lu) have the valence state of Ba 3 M 3+ Ru 2 4.5+ O 9 . The magnetic susceptibilities show a broad maximum at 135-370 K. This magnetic behavior is ascribed to the antiferromagnetic coupling between two Ru ions in a Ru 2 O 9 dimer and to the magnetic interaction between the Ru 2 O 9 dimers. (author)

  18. 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.)

  19. Microwave activation of palladium nanoparticles for enhanced ethanol electrocatalytic oxidation reaction in alkaline medium

    CSIR Research Space (South Africa)

    Rohwer, MB

    2015-02-01

    Full Text Available gave higher electrochemical active surface area (EASA= 67 m(SUP2)g(SUP-1), aggregation/uniformity of dispersion, showed higher amount of the palladium oxides, and showed remarkable electrocatalytic behaviour towards ethanol oxidation reaction...

  20. 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.

  1. 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

  2. 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

  3. Microwave-Assisted Synthesis of Co3(PO42 Nanospheres for Electrocatalytic Oxidation of Methanol in Alkaline Media

    Directory of Open Access Journals (Sweden)

    Prabhakarn Arunachalam

    2017-04-01

    Full Text Available Low-cost and high-performance advanced electrocatalysts for direct methanol fuel cells are of key significance for the improvement of environmentally-pleasant energy technologies. Herein, we report the facile synthesis of cobalt phosphate (Co3(PO42 nanospheres by a microwave-assisted process and utilized as an electrocatalyst for methanol oxidation. The phase formation, morphological surface structure, elemental composition, and textural properties of the synthesized (Co3(PO42 nanospheres have been examined by powder X-ray diffraction (XRD, Fourier transform-infrared spectroscopy (FT-IR, field emission-scanning electron microscopy (FE-SEM, high-resolution transmission electron microscopy (HRTEM, X-ray photoelectron spectroscopy (XPS, and nitrogen adsorption-desorption isotherm investigations. The performance of an electrocatalytic oxidation of methanol over a Co3(PO42 nanosphere-modified electrode was evaluated in an alkaline solution using cyclic voltammetry (CV and chronopotentiometry (CP techniques. Detailed studies were made for the methanol oxidation by varying the experimental parameters, such as catalyst loading, methanol concentration, and long-term stability for the electro-oxidation of methanol. The good electrocatalytic performances of Co3(PO42 should be related to its good surface morphological structure and high number of active surface sites. The present investigation illustrates the promising application of Co3(PO42 nanospheres as a low-cost and more abundant electrocatalyst for direct methanol fuel cells.

  4. Microwave assisted synthesis and characterization of Ni/NiO nanoparticles as electrocatalyst for methanol oxidation in alkaline solution

    Science.gov (United States)

    Arunachalam, Prabhakarn; Ghanem, Mohamed A.; Al-Mayouf, Abdullah M.; Al-shalwi, Matar; Hamed Abd-Elkader, Omar

    2017-02-01

    Nickel/Nickel oxide (Ni/NiO) nanoparticles catalyst is prepared by microwave-assisted liquid-phase deposition using ethylene glycol (EG) and water mixture under atmospheric conditions. The physicochemical characterizations of the catalyst carried out by surface area analyzer, x-ray diffraction (XRD), x-ray photoelectron spectroscopy (XPS), electron microscopes measurements suggest the formation of crystalline nanoparticles structure of NiO. The surface area of Ni/NiO prepared using EG/water mixture reaches 70 m2 g-1 which is 2-fold enhsancement in surface area in comparison with NiO prepared in pure EG and an order of magnitude higher than that of bulk nickel prepared in pure water. The methanol electro-oxidation activity of the Ni/NiO nanoparticles obtained in EG/water mixture displayed more than 4-fold increase in oxidation current at 1.7 V versus RHE in comparison with NiO nanoparticles obtained in EG and 20-fold increase compared to bulk nickel catalyst concord with the enhancement of electro-active surface area. The results show the Ni/NiO nanoparticles produced by microwave assisted synthesis has superior activity for methanol oxidation in alkaline solution over the other nickel based catalysts and has potential for mass production.

  5. 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.

  6. 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.

  7. 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.

  8. 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)

  9. 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.

  10. 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.

  11. 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.

  12. 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.

  13. Oxidative dehydrogenation of ethane on rare-earth oxide-based catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Buyevskaya, O.; Baerns, M. [Institut fuer Angewandte Chemie Berlin-Adlershof e.V., Berlin (Germany)

    1998-12-31

    Results on the oxidative dehydrogenation of ethane on rare-earth oxide (REO) based catalysts (Na-P-Sm-O, Sm-Sr(Ca)-O, La-Sr-O and Nd-Sr-O) are described. Oxygen adsorption was found to be a key factor which determines the activity of this type of catalysts. Continuous flow experiments in the presence of catalysts which reveal strong oxygen adsorption showed that the reaction mixture is ignited resulting in an enhanced heat generation at the reactor inlet. The heat produced by the oxidative reactions was sufficient under the conditions chosen for the endothermic thermal pyrolysis which takes place preferentially in the gas phase. Ignition of the reaction mixture is an important catalyst function. Contrary to non-catalytic oxidative dehydrogenation, reaction temperatures above 700 C could be achieved without significant external heat input. Ethylene yields of up to 34-45% (S=66-73%) were obtained on REO-based catalysts under non-isothermal conditions (T{sub max}=810-865 C) at contact times in the order of 30 to 40 ms. (orig.)

  14. 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

  15. Speciation and Oxidative Stability of Alkaline Soluble, Non-Pertechnetate Technetium

    Energy Technology Data Exchange (ETDEWEB)

    Levitskaia, Tatiana G. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Rapko, Brian M. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Anderson, Amity [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Peterson, James M. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Chatterjee, Sayandev [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Walter, Eric D. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Cho, Herman M. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Washton, Nancy M. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States)

    2014-09-30

    The long half-life, complex chemical behavior in tank waste, limited incorporation in mid- to high-temperature immobilization processes, and high mobility in subsurface environments make technetium (Tc) one of the most difficult contaminants to dispose of and/or remediate. Technetium exists predominantly in the liquid tank waste phase as the relatively mobile form of pertechnetate, TcO4-. However, based on experimentation to date a significant fraction of the soluble Tc cannot be effectively separated from the wastes and may be present as a non- pertechnetate species. The presence of a non-pertechnetate species significantly complicates disposition of low-activity waste (LAW), and the development of methods to either convert them to pertechnetate or to separate directly is needed. The challenge is the uncertainty regarding the chemical form of the alkaline-soluble low-valent non-pertechnetate species in the liquid tank waste. This report summarizes work done in fiscal year (FY) 2014 exploring the chemistry of a low-valence technetium(I) species, [(CO)3Tc(H2O)3]+, a compound of interest due to its implication in the speciation of alkaline-soluble technetium in several Hanford tank waste supernatants.

  16. Order of Activity of Nitrogen, Iron Oxide, and FeNx Complexes towards Oxygen Reduction in Alkaline Medium.

    Science.gov (United States)

    Zhu, Yansong; Zhang, Bingsen; Wang, Da-Wei; Su, Dang Sheng

    2015-12-07

    In alkaline medium, it seems that both metal-free and iron-containing carbon-based catalysts, such as nitrogen-doped nanocarbon materials, FeOx -doped carbon, and Fe/N/C catalysts, are active for the oxygen reduction reaction (ORR). However, the order of activity of these different active compositions has not been clearly determined. Herein, we synthesized nitrogen-doped carbon black (NCB), Fe3 O4 /CB, Fe3 O4 /NCB, and FeN4 /CB. Through the systematic study of the ORR catalytic activity of these four catalysts in alkaline solution, we confirmed the difference in the catalytic activity and catalytic mechanism for nitrogen, iron oxides, and Fe-N complexes, respectively. In metal-free NCB, nitrogen can improve the ORR catalytic activity with a four-electron pathway. Fe3 O4 /CB catalyst did not exhibit improved activity over that of NCB owing to the poor conductivity and spinel structure of Fe3 O4 . However, FeN4 coordination compounds as the active sites showed excellent ORR catalytic activity. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. Kinetics and Mechanism of Oxidation of Triethylene Glycol and Tetraethylene Glycol by Ditelluratoargentate (III in Alkaline Medium

    Directory of Open Access Journals (Sweden)

    Jinhuan Shan

    2013-01-01

    Full Text Available The kinetics of oxidation of triethylene glycol and tetraethylene glycol by ditelluratoargentate (III (DTA in alkaline liquids has been studied spectrophotometrically in the temperature range of 293.2 K–313.2 K. The reaction rate showed first-order dependence in DTA and fractional order with respect to triethylene glycol or tetraethylene glycol. It was found that the pseudo-first-order rate constant (kobs increased with an increase in concentration of OH− and a decrease in concentration of H4TeO6 2−. There was a negative salt effect and no free radicals were detected. A plausible mechanism involving a two-electron transfer was proposed, and the rate equations derived from the mechanism explained all the experimental results and observations. The activation parameters along with the rate constants of the rate-determining step were calculated.

  18. Nanocarbon/oxide composite catalysts for bifunctional oxygen reduction and evolution in reversible alkaline fuel cells: A mini review

    Science.gov (United States)

    Chen, Mengjie; Wang, Lei; Yang, Haipeng; Zhao, Shuai; Xu, Hui; Wu, Gang

    2018-01-01

    A reversible fuel cell (RFC), which integrates a fuel cell with an electrolyzer, is similar to a rechargeable battery. This technology lies on high-performance bifunctional catalysts for the oxygen reduction reaction (ORR) in the fuel cell mode and the oxygen evolution reaction (OER) in the electrolyzer mode. Current catalysts are platinum group metals (PGM) such as Pt and Ir, which are expensive and scarce. Therefore, it is highly desirable to develop PGM-free catalysts for large-scale application of RFCs. In this mini review, we discussed the most promising nanocarbon/oxide composite catalysts for ORR/OER bifunctional catalysis in alkaline media, which is mainly based on our recent progress. Starting with the effectiveness of selected oxides and nanocarbons in terms of their activity and stability, we outlined synthetic methods and the resulting structures and morphologies of catalysts to provide a correlation between synthesis, structure, and property. A special emphasis is put on understanding of the possible synergistic effect between oxide and nanocarbon for enhanced performance. Finally, a few nanocomposite catalysts are discussed as typical examples to elucidate the rules of designing highly active and durable bifunctional catalysts for RFC applications.

  19. 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

  20. Fast microwave-assisted solvothermal synthesis of metal nanoparticles (Pd, Ni, Sn) supported on sulfonated MWCNTs: Pd-based bimetallic catalysts for ethanol oxidation in alkaline medium

    CSIR Research Space (South Africa)

    Ramulifho, T

    2012-01-01

    Full Text Available -MWCNT-Pd and its "mixed" bimetallic electrocatalysts (i.e., SF-MWCNT-PdSn mix and SF-MWCNT-PdNi) towards ethanol oxidation in alkaline medium was investigated. The result shows that the mixed Pd-based catalysts (obtained by simple ultrasonic...

  1. Process for the preparation of rare earth oxide precursors and products obtained

    International Nuclear Information System (INIS)

    Magnier, C.; Gourlaouen, C.; Le Loarer, J.; Latourrette, B.

    1987-01-01

    Rare earth oxides are generally obtained by hydroxides calcination. Filtration of hydroxides is very difficult, the invention claims the use of basic salts obtained by reaction of a basic compound on a trivalent rare earth salt aqueous solution in a ratio OH - /RE 3+ ≤ 5, the precipitate obtained is easily separated [fr

  2. Physico-chemical characteristics of sulfated mixed oxides of Sn with some rare earth elements

    International Nuclear Information System (INIS)

    Jyothi, T.M.; Mirakar, S.P.; Sreekumar, K.; Sugunan, S.; Talawar, M.B.

    2000-01-01

    A series of binary mixed oxides of tin with three rare earth elements viz. La, Ce and Sm were prepared by coprecipitation method and sulfate treatment was performed by treating the mixed hydroxides with sulfuric acid or ammonium sulfate. The physico-chemical characterization has been done by XRD, BET-SA, SEM, EDX, TG-DTA and IR spectroscopy. Adsorption of n-butylamine was used to probe the acidic properties of the catalysts. The strength and distribution of acid sites depend on the mixed metal oxide composition, as well as on the preparation method. The rare earth modified sulfated tin oxide catalysis are more active in the oxidative dehydrogenation of cyclohexanol and cyclohexane, compared to the corresponding mixed oxide systems and sulfated tin oxide. Among the different sulfated oxide systems investigated, cerium promoted catalysts displayed a better selectivity towards dehydrogenation products. (author)

  3. Research and development of tungsten electrodes added with rare earth oxides

    International Nuclear Information System (INIS)

    Zuoren Nie; Ying Chen; Meiling Zhou; Tieyong Zuo

    2001-01-01

    The recent research and development of tungsten electrodes used in TIG and Plasma technologies are introduced, and the tungsten materials as well as the effects of rare earth oxides are specially discussed. in W-La 2 O 3 , W-CeO 2 , W-Y 2 O 3 and W-ThO 2 electrode materials, the W-2.2mass%La 2 O 3 electrode exhibited the best properties when the current is of little or middle volume, and when the electrodes are used in large current, the W-Y 2 O 3 electrode is the best. By a comparative study between the tungsten electrodes activated with single metal oxides, as above-mentioned, and those containing two or three rare earth oxides, namely La 2 O 3 , CeO 2 and Y 2 O 3 , it was indicated that the welding arc properties of the tungsten electrodes activated with combined rare earth oxides additions is superior than that of the electrodes containing single oxides as above mentioned. It was also shown that the operating properties of tungsten electrodes depend intensively on the rare earth oxides contained in the electrodes, and the actions of rare earth oxides during arcing are the most important factors to the electrodes' operating properties, temperature, work function as well as the arc stability. (author)

  4. Solid-phase electrochemical reduction of graphene oxide films in alkaline solution.

    Science.gov (United States)

    Basirun, Wan J; Sookhakian, Mehran; Baradaran, Saeid; Mahmoudian, Mohammad R; Ebadi, Mehdi

    2013-09-24

    Graphene oxide (GO) film was evaporated onto graphite and used as an electrode to produce electrochemically reduced graphene oxide (ERGO) films by electrochemical reduction in 6 M KOH solution through voltammetric cycling. Fourier transformed infrared and Raman spectroscopy confirmed the presence of ERGO. Electrochemical impedance spectroscopy characterization of ERGO and GO films in ferrocyanide/ferricyanide redox couple with 0.1 M KCl supporting electrolyte gave results that are in accordance with previous reports. Based on the EIS results, ERGO shows higher capacitance and lower charge transfer resistance compared to GO.

  5. Purification and characterization of thiol dependent, oxidation-stable serine alkaline protease from thermophilic Bacillus sp.

    Directory of Open Access Journals (Sweden)

    Aysha Kamran

    2015-06-01

    Full Text Available Alkaline serine protease was purified to homogeneity from culture supernatant of a thermophilic, alkaliphilic Bacillus sp. by 80% ammonium sulphate precipitation followed by CM-cellulose and DEAE-cellulose ion exchange column chromatography. The enzyme was purified up to 16.5-fold with 6900 U/mg activity. The protease exhibited maximum activity towards casein at pH 8.0 and at 80 °C. The enzyme was stable at pH 8.0 and 80 °C temperature up to 2 h. The Ca2+ and Mn2+ enhanced the proteolytic activity up to 44% and 36% as compared to control, respectively. However, Zn2+, K+, Ba2+, Co2+, Hg2+ and Cu2+ significantly reduced the enzyme activity. PMSF (phenyl methyl sulphonyl fluoride completely inhibited the protease activity, whereas the activity of protease was stimulated up to two folds in the presence of 5 mM 2-mercaptoethanol. The enzyme was also stable in surfactant (Tween-80 and other commercial detergents (SDS, Triton X-100.

  6. Preparation of zirconium oxide by alkaline fusion from zirconium silicate and its characterization

    International Nuclear Information System (INIS)

    Zaghete, M.A.; Varela, J.A.; Castro e Castro, J.H.

    1985-01-01

    Zirconia was prepared from zirconite by alkaline fusion. The purity of zirconia (with hafnium) was determined by atomic absorption spectroscopy and was found to be 90.94%. An unglomerated hidrous zirconia powder was obtained by washing with acetone and alcohol, and by controlling the drying rate, atmosphere and temperature of the oven. The physical characteristics of the hidrous zirconia powder were determined after calcining in several conditions. The crystalline structure after calcining at 800 0 C results only in monoclinic structure. The mean partide size of zirconia powder, determined by sedimentation varied from 2,4μm to 3,5μ depending on the calcining conditions. The surface areas determined by BET method varied from 33,8 m 2 /g when calcined at 700 0 C during 5 hours to 3,5 m 2 /g when calcined at 1000 0 C, during 3 hours. The zirconia powder were pressed at 200 MPa and the pore size distribution determined by mercury porosimetry showed a midpore diameter of 0,06μm indicating that the aglomeretes were broken during compaction. (Author) [pt

  7. 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

  8. 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

  9. EQCM behavior of copper anodes in alkaline medium and characterization of the electrocatalysis of ethanol oxidation by Cu(III

    Directory of Open Access Journals (Sweden)

    Paixão Thiago R. L. C.

    2006-01-01

    Full Text Available The anodic oxidation of copper electrodes in alkaline solutions was investigated by using voltammetry, chronoamperometry, impedance measurements and the electrochemical quartz crystal microbalance (EQCM. Experiments were carried out in NaOH solutions in the 0.1 to 3.0 mol L-1 concentration range. The formation of soluble and insoluble species such as Cu(OH4(2- and Cu2O during the electrodic dissolution of copper anodes was characterized by analyzing potentiodynamic mass responses and the relationship between mass changes and charge. On the other hand, EQCM data were not effective to confirm the nature of other copper species proposed in literature named as CuO and Cu(OH2 because of viscoelastic changes in the film layer electrodeposited onto the quartz crystal. The participation of a Cu(III soluble species in the electrocatalytic oxidation of ethanol was proved by EQCM measurements, data providing valuable information on the mechanism of the electrode process and formation of a Cu(II insoluble species from the reaction of Cu(III with ethanol.

  10. Kinetics and mechanism of oxidation of L-leucine by alkaline ...

    Indian Academy of Sciences (India)

    forms active sites of enzymes and helps in maintain- ing their proper conformation by keeping them in proper ionic states. So, oxidation of L-leucine may help in understanding some aspects of enzyme kinet- ics. Recent research has discovered that L-leucine acts in a unique way: it can help burn fat without burning muscle.

  11. 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.

  12. 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

  13. 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.)

  14. Powder of a copper oxide superconductor precursor, fabrication process and use for the preparation of superconducting oxide

    International Nuclear Information System (INIS)

    Dehaudt, P.

    1990-01-01

    The precursor powder comprises at least a copper compound (hydroxide, oxide and hydroxynitrates), at least a rare earth and/or yttrium compound (nitrates, hydroxides and hydroxynitrates) or bismuth oxide and at least an alkaline earth nitrate. It can be prepared by atomization drying of a suspension a copper precipitate or coprecipitate and other elements of the superconducting oxide in solution [fr

  15. Some major aspects of the chemical behavior of rare earth oxides: An overview

    International Nuclear Information System (INIS)

    Bernal, S.; Blanco, G.; Calvino, J.J.; Omil, J.A. Perez; Pintado, J.M.

    2006-01-01

    The chemical behavior of sesquioxides and higher rare earth oxides is briefly reviewed. In the first case processes implying no change in the lanthanoid oxidation state are considered, whereas in the second one the analysis is focused on their redox behavior

  16. Some major aspects of the chemical behavior of rare earth oxides: An overview

    Energy Technology Data Exchange (ETDEWEB)

    Bernal, S. [Departamento de Ciencia de los Materiales, Ingenieria Metalurgica y Quimica Inorganica, Facultad de Ciencias, Universidad de Cadiz, Apartado 40, E-11510 Puerto Real, Cadiz (Spain)]. E-mail: serafin.bernal@uca.es; Blanco, G. [Departamento de Ciencia de los Materiales, Ingenieria Metalurgica y Quimica Inorganica, Facultad de Ciencias, Universidad de Cadiz, Apartado 40, E-11510 Puerto Real, Cadiz (Spain); Calvino, J.J. [Departamento de Ciencia de los Materiales, Ingenieria Metalurgica y Quimica Inorganica, Facultad de Ciencias, Universidad de Cadiz, Apartado 40, E-11510 Puerto Real, Cadiz (Spain); Omil, J.A. Perez [Departamento de Ciencia de los Materiales, Ingenieria Metalurgica y Quimica Inorganica, Facultad de Ciencias, Universidad de Cadiz, Apartado 40, E-11510 Puerto Real, Cadiz (Spain); Pintado, J.M. [Departamento de Ciencia de los Materiales, Ingenieria Metalurgica y Quimica Inorganica, Facultad de Ciencias, Universidad de Cadiz, Apartado 40, E-11510 Puerto Real, Cadiz (Spain)

    2006-02-09

    The chemical behavior of sesquioxides and higher rare earth oxides is briefly reviewed. In the first case processes implying no change in the lanthanoid oxidation state are considered, whereas in the second one the analysis is focused on their redox behavior.

  17. Characterization of Pt-Pd/C Electrocatalyst for Methanol Oxidation in Alkaline Medium

    Directory of Open Access Journals (Sweden)

    S. S. Mahapatra

    2011-01-01

    Full Text Available The Pt-Pd/C electrocatalyst was synthesized on graphite substrate by the electrochemical codeposition technique. The physicochemical characterization of the catalyst was done by SEM, XRD, and EDX. The electrochemical characterization of the Pt-Pd/C catalyst for methanol electro-oxidation was studied over a range of NaOH and methanol concentrations using cyclic voltammetry, quasisteady-state polarization, chronoamperometry, and electrochemical impedance spectroscopy. The activity of methanol oxidation increased with pH due to better OH species coverage on the electrode surface. At methanol concentration (>1.0 M, there is no change in the oxidation peak current density because of excess methanol at the electrode surface and/or depletion of OH− at the electrode surface. The Pt-Pd/C catalyst shows good stability and the low value of Tafel slope and charge transfer resistance. The enhanced electrocatalytic activity of the electrodes is ascribed to the synergistic effect of higher electrochemical surface area, preferred OH− adsorption, and ad-atom contribution on the alloyed surface.

  18. Investigation of the Alkaline Electrochemical Interface and Development of Composite Metal/Metal-Oxides for Hydrogen and Oxygen Electrodes

    Science.gov (United States)

    Bates, Michael

    Understanding the fundamentals of electrochemical interfaces will undoubtedly reveal a path forward towards a society based on clean and renewable energy. In particular, it has been proposed that hydrogen can play a major role as an energy carrier of the future. To fully utilize the clean energy potential of a hydrogen economy, it is vital to produce hydrogen via water electrolysis, thus avoiding co-production of CO2 inherent to reformate hydrogen. While significant research efforts elsewhere are focused on photo-chemical hydrogen production from water, the inherent low efficiency of this method would require a massive land-use footprint to achieve sufficient hydrogen production rates to integrate hydrogen into energy markets. Thus, this research has primarily focused on the water splitting reactions on base-metal catalysts in the alkaline environment. Development of high-performance base-metal catalysts will help move alkaline water electrolysis to the forefront of hydrogen production methods, and when paired with solar and wind energy production, represents a clean and renewable energy economy. In addition to the water electrolysis reactions, research was conducted to understand the de-activation of reversible hydrogen electrodes in the corrosive environment of the hydrogen-bromine redox flow battery. Redox flow batteries represent a promising energy storage option to overcome the intermittency challenge of wind and solar energy production methods. Optimization of modular and scalable energy storage technology will allow higher penetration of renewable wind and solar energy into the grid. In Chapter 1, an overview of renewable energy production methods and energy storage options is presented. In addition, the fundamentals of electrochemical analysis and physical characterization of the catalysts are discussed. Chapter 2 reports the development of a Ni-Cr/C electrocatalyst with unprecedented mass-activity for the hydrogen evolution reaction (HER) in alkaline

  19. Oxidation of arsenite by molecular oxygen in strong alkaline solution under γ-radiation

    International Nuclear Information System (INIS)

    Burkitbaev, M.M.

    1996-01-01

    The kinetics and mechanism of radiation-stimulated process in 1 mole/1 l of potassium hydroxide have been studied. Radiation chemical yield of (G(As)(Y)) oxygenation grows directly proportionally to oxygen concentration and inversely proportionally to dose rate in proportion 1/2. Mechanism of oxidation, including two chain cycles (long chain cycle - with participation of O - ; O 2 - ; O 3 - radicals and short chain one -with participation of arsenic contenting radicals: As(IV), As(IV)O, As(IV)O 2 ) is proposed. (author)

  20. Development of Alkaline Oxidative Dissolution Methods for Chromium (III) Compounds Present in Hanford Site Tank Sludges

    International Nuclear Information System (INIS)

    Krot, N.N.; Shilov, V.P.; Fedoseev, A.M.; Budantseva, N.A.; Nikonov, M.V.; Yusov, A.B.; Garnov, A.Yu.; Charushnikova, I.A.; Perminov, V.P.; Astafurova, L.N.; Lapitskaya, T.S.; Makarenkov, V.I.

    1999-01-01

    The high-level radioactive waste sludge in the underground storage tanks at the Hanford Site contains various chromium(III)solid phases. Dissolution and removal of chromium from tank waste sludges is desirable prior to high-level waste vitrification because increased volume is required to incorporate the residual chromium. Unfortunately, dissolution of chromium from the sludge to form Cr(OH) 4 - through treatment with heated NaOH solution (also used to dissolve aluminum phases and metathesize phosphates to sodium salts) generally has been unsuccessful in tests with both simulated and genuine Hanford waste sludges. Oxidative dissolution of the Cr(III) compounds to form soluble chromate has been proposed as an alternative chromium solid phase dissolution method and results of limited prior testing have been reported

  1. Ni/Pd-Decorated Carbon NFs as an Efficient Electrocatalyst for Methanol Oxidation in Alkaline Medium

    Science.gov (United States)

    Mohamed, Ibrahim M. A.; Khalil, Khalil Abdelrazek; Mousa, Hamouda M.; Barakat, Nasser A. M.

    2017-01-01

    In this study, Ni/Pd-decorated carbon nanofibers (NFs) were fabricated as an electrocatalyst for methanol oxidation. These NFs were synthesized based on carbonization of poly(vinyl alcohol), which has high carbon content compared to many polymers used to prepare carbon NFs. Typically, calcination of an electrospun mat composed of nickel acetate, palladium acetate, and poly(vinyl alcohol) can produce Ni/Pd-doped carbon NFs. The introduced NFs were characterized by scanning electron microscopy, transmission electron microscopy (TEM), high-resolution transmission electron microscopy, line TEM energy dispersive x-ray spectrometry, field emission scanning electron microscopy, and x-ray powder diffraction. These physicochemical characterizations are acceptable tools to investigate the crystallinity and chemistry of the fabricated Ni/Pd-carbon NFs. Accordingly, the prepared NFs were tested to enhance the economic and catalytic behavior of methanol electrooxidation. Experimentally, the obtained onset potential was small compared to many reported materials; 0.32 V (versus Ag/AgCl as a reference electrode). At the same time, the current density changed from 5.08 mA/cm2 in free methanol at 0.6 V to 12.68 mA/cm2 in 0.1 mol/L methanol, which can be attributed to the MeOH oxidation. Compared to nanoparticles, the NFs have a distinct effect on the electrocatalytic performance of material due to the effect of the one-dimensional structure, which facilitates the electron transfer. Overall, the presented work opens a new way for non-precious one-dimensional nanostructured catalysts for direct methanol fuel cell technology.

  2. Facile and scalable fabrication engineering of fullerenol nanoparticles by improved alkaline-oxidation approach and its antioxidant potential in maize

    International Nuclear Information System (INIS)

    Liu, Fu-yang; Xiong, Feng-xia; Fan, Yi-kang; Li, Juan; Wang, He-zhong; Xing, Geng-mei; Yan, Feng-ming; Tai, Fu-ju; He, Rui

    2016-01-01

    A feasible in operation, labor-saving and low-cost one-step technology to fabricate fullerenol nanoparticles (FNPs) up to 10 g in laboratory was developed by improved alkaline-oxidation approach using moderately concentrated sodium hydroxide solution as the hydroxylation agent and o-dichlorobenzene as the solvent. This strategy paves the avenue for industrial-scale bulk production of FNPs. The resulted product, [C 60 (OH) 22 ·8H 2 O] n , were characterized by various measurements including matrix-assisted laser desorption ionization time-of-flight mass spectrometry, high-resolution 1 H nuclear magnetic resonance spectrometry, Fourier transform infrared spectroscopy, UV-Visible spectrophotometer, thermogravimetric analysis, differential scanning calorimetry, dynamic light scattering analysis, scanning electron microscopy, and electron spin resonance spectrometer. Radical scavenging assay in vitro confirmed the high efficiency of water-soluble [C 60 (OH) 22 ·8H 2 O] n as a novel radical scavenger. Furthermore, [C 60 (OH) 22 ·8H 2 O] n as an excellent candidate has the potential to serve as the plant defense stimulation agent in maize.

  3. Facile and scalable fabrication engineering of fullerenol nanoparticles by improved alkaline-oxidation approach and its antioxidant potential in maize

    Science.gov (United States)

    Liu, Fu-yang; Xiong, Feng-xia; Fan, Yi-kang; Li, Juan; Wang, He-zhong; Xing, Geng-mei; Yan, Feng-ming; Tai, Fu-ju; He, Rui

    2016-11-01

    A feasible in operation, labor-saving and low-cost one-step technology to fabricate fullerenol nanoparticles (FNPs) up to 10 g in laboratory was developed by improved alkaline-oxidation approach using moderately concentrated sodium hydroxide solution as the hydroxylation agent and o-dichlorobenzene as the solvent. This strategy paves the avenue for industrial-scale bulk production of FNPs. The resulted product, [C60(OH)22·8H2O]n, were characterized by various measurements including matrix-assisted laser desorption ionization time-of-flight mass spectrometry, high-resolution 1H nuclear magnetic resonance spectrometry, Fourier transform infrared spectroscopy, UV-Visible spectrophotometer, thermogravimetric analysis, differential scanning calorimetry, dynamic light scattering analysis, scanning electron microscopy, and electron spin resonance spectrometer. Radical scavenging assay in vitro confirmed the high efficiency of water-soluble [C60(OH)22·8H2O]n as a novel radical scavenger. Furthermore, [C60(OH)22·8H2O]n as an excellent candidate has the potential to serve as the plant defense stimulation agent in maize.

  4. Facile and scalable fabrication engineering of fullerenol nanoparticles by improved alkaline-oxidation approach and its antioxidant potential in maize

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Fu-yang [Henan Agricultural University, Collaborative Innovation Center of Henan Grain Crops, State Key Laboratory of Wheat and Maize Crop Science, College of Life Science (China); Xiong, Feng-xia; Fan, Yi-kang [Henan Agricultural University, NanoAgro Center, College of Plant Protection (China); Li, Juan [Chinese Academy of Sciences, Lab. for Bio-Environmental Health Sciences of Nanoscale Materials, Institute of High Energy Physics (China); Wang, He-zhong [Henan Agricultural University, NanoAgro Center, College of Plant Protection (China); Xing, Geng-mei [Chinese Academy of Sciences, Lab. for Bio-Environmental Health Sciences of Nanoscale Materials, Institute of High Energy Physics (China); Yan, Feng-ming [Henan Agricultural University, NanoAgro Center, College of Plant Protection (China); Tai, Fu-ju, E-mail: taifj2008@163.com [Henan Agricultural University, Collaborative Innovation Center of Henan Grain Crops, State Key Laboratory of Wheat and Maize Crop Science, College of Life Science (China); He, Rui, E-mail: herui@henau.edu.cn [Henan Agricultural University, NanoAgro Center, College of Plant Protection (China)

    2016-11-15

    A feasible in operation, labor-saving and low-cost one-step technology to fabricate fullerenol nanoparticles (FNPs) up to 10 g in laboratory was developed by improved alkaline-oxidation approach using moderately concentrated sodium hydroxide solution as the hydroxylation agent and o-dichlorobenzene as the solvent. This strategy paves the avenue for industrial-scale bulk production of FNPs. The resulted product, [C{sub 60}(OH){sub 22}·8H{sub 2}O]{sub n}, were characterized by various measurements including matrix-assisted laser desorption ionization time-of-flight mass spectrometry, high-resolution {sup 1}H nuclear magnetic resonance spectrometry, Fourier transform infrared spectroscopy, UV-Visible spectrophotometer, thermogravimetric analysis, differential scanning calorimetry, dynamic light scattering analysis, scanning electron microscopy, and electron spin resonance spectrometer. Radical scavenging assay in vitro confirmed the high efficiency of water-soluble [C{sub 60}(OH){sub 22}·8H{sub 2}O]{sub n} as a novel radical scavenger. Furthermore, [C{sub 60}(OH){sub 22}·8H{sub 2}O]{sub n} as an excellent candidate has the potential to serve as the plant defense stimulation agent in maize.

  5. White-rot fungi pretreatment combined with alkaline/oxidative pretreatment to improve enzymatic saccharification of industrial hemp.

    Science.gov (United States)

    Xie, Chunliang; Gong, Wenbing; Yang, Qi; Zhu, Zuohua; Yan, Li; Hu, Zhenxiu; Peng, Yuande

    2017-11-01

    White-rot fungi combined with alkaline/oxidative (A/O) pretreatments of industrial hemp woody core were proposed to improve enzymatic saccharification. In this study, hemp woody core were treated with only white rot fungi, only A/O and combined with the two methods. The results showed that Pleurotus eryngii (P. eryngii) was the most effective fungus for pretreatment. Reducing sugars yield was 329mg/g with 30 Filter Paper Unit (FPU)/g cellulase loading when treated 21day. In the A/O groups, the results showed that when treated with 3% NaOH and 3% H 2 O 2 , the yield of reducing sugars was 288mg/g with 30FPU/g cellulase loading. After combination pretreatment with P. eryngii and A/O pretreatment, the reducing sugar yield from enzymatic hydrolysis of combined sample increased 1.10-1.29-fold than that of bio-treated or A/O pretreatment sample at the same conditions, suggesting that P. eryngii combined with A/O pretreatment was an effective method to improve enzyme hydrolysis. Copyright © 2017 Elsevier Ltd. All rights reserved.

  6. Rare earth elements and oxides in liquid phase epitaxy

    Czech Academy of Sciences Publication Activity Database

    Procházková, Olga; Grym, Jan; Zavadil, Jiří; Kopecká, M.

    2006-01-01

    Roč. 100, č. 8 (2006), s. 640-- ISSN 0009-2770. [Sjezd chemických společností /58./. Ústí nad Labem, 04.09.2006-08.09.2006] R&D Projects: GA ČR(CZ) GA102/06/0153 Institutional research plan: CEZ:AV0Z20670512 Keywords : semiconductor technology * rare earth metals Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 0.431, year: 2006

  7. Arsenic mobilization in an oxidizing alkaline groundwater: Experimental studies, comparison and optimization of geochemical modeling parameters

    International Nuclear Information System (INIS)

    Hafeznezami, Saeedreza; Lam, Jacquelyn R.; Xiang, Yang; Reynolds, Matthew D.; Davis, James A.; Lin, Tiffany; Jay, Jennifer A.

    2016-01-01

    Arsenic (As) mobilization and contamination of groundwater affects millions of people worldwide. Progress in developing effective in-situ remediation schemes requires the incorporation of data from laboratory experiments and field samples into calibrated geochemical models. In an oxidizing aquifer where leaching of high pH industrial waste from unlined surface impoundments led to mobilization of naturally occurring As up to 2 mg L −1 , sequential extractions of solid phase As as well as, batch sediment microcosm experiments were conducted to understand As partitioning and solid-phase sorptive and buffering capacity. These data were combined with field data to create a series of geochemical models of the system with modeling programs PHREEQC and FITEQL. Different surface complexation modeling approaches, including component additivity (CA), generalized composite (GC), and a hybrid method were developed, compared and fitted to data from batch acidification experiments to simulate potential remediation scenarios. Several parameters strongly influence the concentration of dissolved As including pH, presence of competing ions (particularly phosphate) and the number of available sorption sites on the aquifer solids. Lowering the pH of groundwater to 7 was found to have a variable, but limited impact (<63%) on decreasing the concentration of dissolved As. The models indicate that in addition to lowering pH, decreasing the concentration of dissolved phosphate and/or increasing the number of available sorption sites could significantly decrease the As solubility to levels below 10 μg L −1 . The hybrid and GC modeling results fit the experimental data well (NRMSE<10%) with reasonable effort and can be implemented in further studies for validation. - Highlights: • Samples were collected from an oxidizing aquifer where high pH waste has led to mobilization of naturally occurring As. • Three surface complexation modeling approaches were used in modeling adsorption

  8. 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

  9. Recycling of the rare earth oxides from spent rechargeable batteries using waste metallurgical slags

    Directory of Open Access Journals (Sweden)

    Tang K.

    2013-01-01

    Full Text Available A high temperature process for recycling spent nickel-metal hydride rechargeable batteries has been recently developed at SINTEF/NTNU. The spent battery modules were first frozen with liquid nitrogen for the de-activation and brittle fracture treatment. The broken steel scraps and plastics were then separated by the mechanical classification and magnetic separation. The remaining positive and negative electrodes, together with the polymer separator, were heated to 600-800oC in order to remove the organic components and further separate the Ni-based negative electrode. XRF analyses indicate that the heat-treated materials consist mainly of nickel, rare earth and cobalt oxides. The valuable rare earth oxides were further recovered by the high-temperature slagging treatment. The waste metallurgical slags, consist mainly of SiO2 and CaO, were used as the rare earth oxide absorbent. After the high temperature slagging treatment, over 98% of nickel and cobalt oxides were reduced to the metal phase; meanwhile almost all rare earth oxides remain in the molten slags. Furthermore, EPMA and XRF analyses of the slag samples indicate that the rare earth oxides selectively precipitate in the forms of solid xSiO2•yCaO•zRe2O3. The matrix of slag phase is Re2O3 deficient, typically being less than 5 wt%. This provides a sound basis to further develop the high-temperature process of concentrating the Re2O3 oxides in slags.

  10. Water oxidation using earth-abundant transition metal catalysts: opportunities and challenges.

    Science.gov (United States)

    Kärkäs, Markus D; Åkermark, Björn

    2016-10-07

    Catalysts for the oxidation of H2O are an integral component of solar energy to fuel conversion technologies. Although catalysts based on scarce and precious metals have been recognized as efficient catalysts for H2O oxidation, catalysts composed of inexpensive and earth-abundant element(s) are essential for realizing economically viable energy conversion technologies. This Perspective summarizes recent advances in the field of designing homogeneous water oxidation catalysts (WOCs) based on Mn, Fe, Co and Cu. It reviews the state of the art catalysts, provides insight into their catalytic mechanisms and discusses future challenges in designing bioinspired catalysts based on earth-abundant metals for the oxidation of H2O.

  11. Shape-controlled syntheses of metal oxide nanoparticles by the introduction of rare-earth metals.

    Science.gov (United States)

    Song, Hyo-Won; Kim, Na-Young; Park, Ji-Eun; Ko, Jae-Hyeon; Hickey, Robert J; Kim, Yong-Hyun; Park, So-Jung

    2017-02-23

    Here, we report the size- and shape-controlled synthesis of metal oxide nanoparticles through the introduction of rare-earth metals. The addition of gadolinium oleate in the synthesis of iron oxide nanoparticles induced sphere-to-cube shape changes of nanoparticles and generated iron oxide nanocubes coated with gadolinium. Based on experimental investigations and density functional theory (DFT) calculations, we attribute the shape change to the facet-selective binding of undecomposed gadolinium oleates. While many previous studies on the shape-controlled syntheses of nanoparticles rely on the stabilization of specific crystal facets by anionic surfactants or their decomposition products, this study shows that the interaction between growing transition metal oxide nanoparticles and rare-earth metal complexes can be used as a robust new mechanism for shape-controlled syntheses. Indeed, we demonstrated that this approach was applicable to other transition metal oxide nanoparticles (i.e., manganese oxide and manganese ferrite) and rare earth metals (i.e., gadolinium, europium, and cerium). This study also demonstrates that the nature of metal-ligand bonding can play an important role in the shape control of nanoparticles.

  12. An oxidant and organic solvent tolerant alkaline lipase by P. aeruginosa mutant: downstream processing and biochemical characterization

    Directory of Open Access Journals (Sweden)

    Deepali Bisht

    2013-12-01

    Full Text Available An extracellular alkaline lipase from Pseudomonas aeruginosa mutant has been purified to homogeneity using acetone precipitation followed by anion exchange and gel filtration chromatography and resulted in 27-fold purification with 19.6% final recovery. SDS-PAGE study suggested that the purified lipase has an apparent molecular mass of 67 kDa. The optimum temperature and pH for the purified lipase were 45°C and 8.0, respectively. The enzyme showed considerable stability in pH range of 7.0-11.0 and temperature range 35-55 °C. The metal ions Ca2+, Mg2+ and Na+ tend to increase the enzyme activity, whereas, Fe2+ and Mn2+ ions resulted in discreet decrease in the activity. Divalent cations Ca+2 and Mg+2 seemed to protect the enzyme against thermal denaturation at high temperatures and in presence of Ca+2 (5 mM the optimum temperature shifted from 45°C to 55°C. The purified lipase displayed significant stability in the presence of several hydrophilic and hydrophobic organic solvents (25%, v/v up to 168 h. The pure enzyme preparation exhibited significant stability and compatibility with oxidizing agents and commercial detergents as it retained 40-70% of its original activities. The values of Km and Vmax for p-nitrophenyl palmitate (p-NPP under optimal conditions were determined to be 2.0 mg.mL-1 and 5000 μg.mL-1.min-1, respectively.

  13. 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)

  14. 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.

  15. 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.

  16. 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.

  17. 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.

  18. 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.

  19. [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.

  20. Study of poly(vinyl alcohol)/titanium oxide composite polymer membranes and their application on alkaline direct alcohol fuel cell

    Science.gov (United States)

    Yang, Chun-Chen; Chiu, Shwu-Jer; Lee, Kuo-Tong; Chien, Wen-Chen; Lin, Che-Tseng; Huang, Ching-An

    The novel poly(vinyl alcohol)/titanium oxide (PVA/TiO 2) composite polymer membrane was prepared using a solution casting method. The characteristic properties of the PVA/TiO 2 composite polymer membrane were investigated by thermal gravimetric analysis (TGA), a scanning electron microscopy (SEM), a micro-Raman spectroscopy, a methanol permeability measurement and the AC impedance method. An alkaline direct alcohol (methanol, ethanol and isopropanol) fuel cell (DAFC), consisting of an air cathode based on MnO 2/C inks, an anode based on PtRu (1:1) black and a PVA/TiO 2 composite polymer membrane, was assembled and examined for the first time. The results indicate that the alkaline DAFC comprised of a cheap, non-perfluorinated PVA/TiO 2 composite polymer membrane shows an improved electrochemical performances. The maximum power densities of alkaline DAFCs with 4 M KOH + 2 M CH 3OH, 2 M C 2H 5OH and 2 M isopropanol (IPA) solutions at room temperature and ambient air are 9.25, 8.00, and 5.45 mW cm -2, respectively. As a result, methanol shows the highest maximum power density among three alcohols. The PVA/TiO 2 composite polymer membrane with the permeability values in the order of 10 -7 to 10 -8 cm 2 s -1 is a potential candidate for use on alkaline DAFCs.

  1. A study on the separation method of total rare earth oxides in Xenotime

    International Nuclear Information System (INIS)

    Shim, Sang Kwon; Park, Hea Kyung; Kim, Kyung Lim

    1990-01-01

    This study is concerned with the separation method of total rare earth oxides in Xenotime by acid digest method. Thioacetamide was used as a carrier, tartaric acid was used as a masking agent and oxalic acid was used as a precipitant. So the effects of three acid digest methods, pH of the solution, digesting time,tartaric acid, oxalic acid and aging time were oberved. The results showed that the best acid digest method was sulfuric acid leaching and mixed acid digest method, and that pH of the solution was 2, digesting time was 4 hours, tartaric acid was 100 ml of 2% solution, oxalic acid was 8 gr. and aging time was 1 hour. Through this experiment, it was confirmed by X-ray diffractometer that the separated total rare earth oxides consisted of the Yttrium and the other rare earth elements : Gadolinium, Dysprosium, Erbium, Ytterbium and trace rare earth elements. The pure rare earth oxides being separated by this method were dried and ignited at 900 deg C (Author)

  2. Preparation of ammonium sulfate, calcium oxide and rare earth concentrate from phospho-gypsum

    International Nuclear Information System (INIS)

    Andrianov, A.M.; Rusin, N.F.; Dejneka, G.F.; Zinchenko, T.A.; Burova, T.I.

    1978-01-01

    A technological scheme is proposed which gives ammonium sulfate, purified (from admixtures of silicon, iron, titanium, aluminium) calcium oxide with direct yield of calcium 91% and rare-earth concentrate, containing 5.6% of Ln 2 O 3 with direct yield of 99.5%

  3. Ferromagnetism in rare earth doped cerium oxide bulk samples

    Energy Technology Data Exchange (ETDEWEB)

    Dimri, M. Chandra; Kooskora, H.; Subbi, J.; Heinmaa, I.; Stern, R. [National Institute of Chemical Physics and Biophysics, Tallinn (Estonia); Khanduri, H. [National Institute of Chemical Physics and Biophysics, Tallinn (Estonia); Tallinn University of Technology, Tallinn (Estonia); Mere, A.; Krustok, J. [Tallinn University of Technology, Tallinn (Estonia)

    2012-02-15

    Magnetic properties of rare earth (RE) doped ceria (RE = Nd, Sm, Gd, Tb, Er and Dy) samples have been investigated and reported in this paper. Room temperature ferromagnetism (FM) was observed in calcined powders as well as in sintered samples of Nd and Sm doped CeO{sub 2}, whereas other RE dopants (Gd, Tb, Er and Dy) in CeO{sub 2} exhibit paramagnetic behaviour. The origin of magnetism in these samples can be related to oxygen vacancies and formation of fluorite crystal structure. Though the magnetization was found to be lower as compared to transition metal (TM) doped ceria, the segregation of metallic and secondary phases can be avoided in RE doped CeO{sub 2}. CeO{sub 2} doped with Sm ions in different concentration (1, 5 and 15%) were also studied to see the dopant effects on magnetic properties. The origin of magnetism in these samples may be related to the oxygen vacancies created due to RE dopants, which was confirmed from the peak around 555 cm{sup -1} in Raman spectra. (Copyright copyright 2012 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  4. Method of forming an oxide superconducting thin film having an R1A2C3 crystalline phase over an R2A1C1 crystalline phase

    International Nuclear Information System (INIS)

    Lelental, M.; Romanofsky, H.J.

    1992-01-01

    This patent describes a process which comprises forming a mixed rare earth alkaline earth copper oxide layer on a substrate and converting the mixed rare earth alkaline earth copper oxide layer to an electrically conductive layer. It comprises crystalline R 1 A 2 C 3 oxide phase by heating in the presence of oxygen, wherein rare earth and R is in each instance chosen from among yttrium, lanthanum, samarium, europium, gadolinium, dysprosium, holmium, erbium, thulium, ytterbium, and lutetium and alkaline earth and A is in each instance chosen from among calcium, strontium and barium, characterized in that a crystalline R 2 A 1 C 1 oxide phase is first formed as a layer on the substrate and the crystalline R 1 A 2 C 3 oxide phase is formed over the crystalline R 2 A 1 C 1 oxide phase by coating a mixed rare earth alkaline earth copper oxide on the crystalline R 2 A 1 C 1 oxide phase and heating the mixed rare earth alkaline earth copper oxide to a temperature of at least 1000 degrees C

  5. Research on manufacturing aluminum - rare earth alloy with a high content of rare earth (> 20% RE) from total rare earth oxides by thermit reduction

    International Nuclear Information System (INIS)

    Ngo Trong Hiep; Dam Van Tien; Tran Duy Hai; Ngo Xuan Hung and Ly Thanh Vu

    2004-01-01

    In this report, several theoretical principles of thermit reduction method used for metal oxides to obtain metals, ferroalloys and ligatua with technical purity are presented. Manufacture of aluminum-rare earth alloys by thermit reduction is also described in the report. Data that are generalized based on thermo-kinetic calculation of the thermit reduction and selection of technological flow-sheet based on thermal effect will partly clarify research results in investigating typical features of the process and identify measures to reduce metal loss in discharged slags. (author)

  6. Process for obtaining sintered conglomerates with a high density of rare earth oxides and actinides

    International Nuclear Information System (INIS)

    Pasto, A.E.

    1974-01-01

    The invention concerns a method to produce agglomerates of actinide and rare earth oxides possessing a cubic-monoclinic transformation in order to obtain high densities close to the theoretical density, and the articles produced by the method. The process is based on the use of a rare earth or actinide oxide, in particular Eu 2 O 3 , with a cubic-monoclinic phase transformation, the oxide being sintered by hot compression at a temperature 50 deg C to 100 deg C above the transformation temperature. The sintered agglomerates obtained can have a purity of at least 99.9% and a density of practically 100%. These agglomerates are suitable in particular for the formation of nuclear reactor control rods [fr

  7. 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.

  8. 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

  9. Oxides for sustainable photovoltaics with earth-abundant materials

    Science.gov (United States)

    Wagner, Alexander; Stahl, Mathieu; Ehrhardt, Nikolai; Fahl, Andreas; Ledig, Johannes; Waag, Andreas; Bakin, Andrey

    2014-03-01

    Energy conversion technologies are aiming to extremely high power capacities per year. Nontoxicity and abundance of the materials are the key requirements to a sustainable photovoltaic technology. Oxides are among the key materials to reach these goals. We investigate the influence of thin buffer layers on the performance of an ZnO:Al/buffer/Cu2O solar cells. Introduction of a thin ZnO or Al2O3 buffer layer, grown by thermal ALD, between ZnO:Al and Cu2O resulted in 45% increase of the solar cell efficiency. VPE growth of Cu2O employing elemental copper and pure oxygen as precursor materials is presented. The growth is performed on MgO substrates with the (001) orientation. On- and off- oriented substrates have been employed and the growth results are compared. XRD investigations show the growth of the (110) oriented Cu2O for all temperatures, whereas at a high substrate temperature additional (001) Cu2O growth occurs. An increase of the oxygen partial pressure leads to a more pronounced 2D growth mode, whereby pores between the islands still remain. The implementation of off-axis substrates with 3.5° and 5° does not lead to an improvement of the layer quality. The (110) orientation remains predominant, the grain size decreases and the FWHM of the (220) peak increases. From the AFM images it is concluded, that the (110) surface grows with a tilt angle to the substrate surface.

  10. Stress Survival Islet 2, Predominantly Present in Listeria monocytogenes Strains of Sequence Type 121, Is Involved in the Alkaline and Oxidative Stress Responses.

    Science.gov (United States)

    Harter, Eva; Wagner, Eva Maria; Zaiser, Andreas; Halecker, Sabrina; Wagner, Martin; Rychli, Kathrin

    2017-08-15

    The foodborne pathogen Listeria monocytogenes is able to survive a variety of stress conditions leading to the colonization of different niches like the food processing environment. This study focuses on the hypervariable genetic hot spot lmo0443 to lmo0449 haboring three inserts: the stress survival islet 1 (SSI-1), the single-gene insert LMOf2365_0481 , and two homologous genes of the nonpathogenic species Listeria innocua : lin0464 , coding for a putative transcriptional regulator, and lin0465 , encoding an intracellular PfpI protease. Our prevalence study revealed a different distribution of the inserts between human and food-associated isolates. The lin0464-lin0465 insert was predominantly found in food-associated strains of sequence type 121 (ST121). Functional characterization of this insert showed that the putative PfpI protease Lin0465 is involved in alkaline and oxidative stress responses but not in acidic, gastric, heat, cold, osmotic, and antibiotic stresses. In parallel, deletion of lin0464 decreased survival under alkaline and oxidative stresses. The expression of both genes increased significantly under oxidative stress conditions independently of the alternative sigma factor σ B Furthermore, we showed that the expression of the protease gene lin0465 is regulated by the transcription factor lin0464 under stress conditions, suggesting that lin0464 and lin0465 form a functional unit. In conclusion, we identified a novel stress survival islet 2 (SSI-2), predominantly present in L. monocytogenes ST121 strains, beneficial for survival under alkaline and oxidative stresses, potentially supporting adaptation and persistence of L. monocytogenes in food processing environments. IMPORTANCE Listeria monocytogenes strains of ST121 are known to persist for months and even years in food processing environments, thereby increasing the risk of food contamination and listeriosis. However, the molecular mechanism underlying this remarkable niche-specific adaptation

  11. Stress Survival Islet 2, Predominantly Present in Listeria monocytogenes Strains of Sequence Type 121, Is Involved in the Alkaline and Oxidative Stress Responses

    Science.gov (United States)

    Harter, Eva; Wagner, Eva Maria; Zaiser, Andreas; Halecker, Sabrina; Wagner, Martin

    2017-01-01

    ABSTRACT The foodborne pathogen Listeria monocytogenes is able to survive a variety of stress conditions leading to the colonization of different niches like the food processing environment. This study focuses on the hypervariable genetic hot spot lmo0443 to lmo0449 haboring three inserts: the stress survival islet 1 (SSI-1), the single-gene insert LMOf2365_0481, and two homologous genes of the nonpathogenic species Listeria innocua: lin0464, coding for a putative transcriptional regulator, and lin0465, encoding an intracellular PfpI protease. Our prevalence study revealed a different distribution of the inserts between human and food-associated isolates. The lin0464-lin0465 insert was predominantly found in food-associated strains of sequence type 121 (ST121). Functional characterization of this insert showed that the putative PfpI protease Lin0465 is involved in alkaline and oxidative stress responses but not in acidic, gastric, heat, cold, osmotic, and antibiotic stresses. In parallel, deletion of lin0464 decreased survival under alkaline and oxidative stresses. The expression of both genes increased significantly under oxidative stress conditions independently of the alternative sigma factor σB. Furthermore, we showed that the expression of the protease gene lin0465 is regulated by the transcription factor lin0464 under stress conditions, suggesting that lin0464 and lin0465 form a functional unit. In conclusion, we identified a novel stress survival islet 2 (SSI-2), predominantly present in L. monocytogenes ST121 strains, beneficial for survival under alkaline and oxidative stresses, potentially supporting adaptation and persistence of L. monocytogenes in food processing environments. IMPORTANCE Listeria monocytogenes strains of ST121 are known to persist for months and even years in food processing environments, thereby increasing the risk of food contamination and listeriosis. However, the molecular mechanism underlying this remarkable niche

  12. Electrochemical determination of the oxidation potentials and the thermodynamic stability of the valence states of the transuranium elements in aqueous alkaline media

    International Nuclear Information System (INIS)

    Peretrukhin, V.F.; Spitsyn, V.I.

    1982-01-01

    The oxidation potentials of neptunium, plutonium, and americium in the valance states from (III) to (VII) have been determined experimentally in 0.1-15 M NaOH. Heptavalent plutonium and americium are thermodynamically able to oxidize water with the evolution of oxygen in 0.1-15 M NaOH, neptunium(VII) in 0.1-7 M NaOH. All valance states of plutonium resist disproportionation in alkaline solutions; in the case of neptunium and americium only one disproportionation reaction is possible; of the hexavalent state in to penta- and heptavalent states. The degree of completion of the reaction can be calculated accurately from the oxidation potentials determined

  13. 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.

  14. Evolution of the Oxidation State of the Earth's Mantle: Challenges of High Pressure Quenching

    Science.gov (United States)

    Danielson, L. R.; Righter, K.; Keller, L.; Christoffersen, R.; Rahman, Z.

    2015-01-01

    The oxidation state of the Earth's mantle during formation remains an unresolved question, whether it was constant throughout planetary accretion, transitioned from reduced to oxidized, or from oxidized to reduced. We investigate the stability of Fe3+ at depth, in order to constrain processes (water, late accretion, dissociation of FeO) which may reduce or oxidize the Earth's mantle. Experiments of more mafic compositions and at higher pressures commonly form a polyphase quench intergrowth composed primarily of pyroxenes, with interstitial glass which hosts nearly all of the more volatile minor elements. In our previous experiments on shergottite compositions, variable fO2, T, and P is less than 4 GPa, Fe3+/TotFe decreased slightly with increasing P, similar to terrestrial basalt. For oxidizing experiments less than 7GPa, Fe3+/TotFe decreased as well, but it's unclear from previous modelling whether the deeper mantle could retain significant Fe3+. Our current experiments expand our pressure range deeper into the Earth's mantle and focus on compositions and conditions relevant to the early Earth. Experiments with Knippa basalt as the starting composition were conducted at 1-8 GPa and 1800 C, using a molybdenum capsule to set the fO2 near IW, by buffering with Mo-MoO3. TEM and EELS analyses revealed the run products from 7-8 GPa quenched to polycrystalline phases, with the major phase pyroxene containing approximately equal Fe3+/2+. A number of different approaches have been employed to produce glassy samples that can be measured by EELS and XANES. A more intermediate andesite was used in one experiment, and decompression during quenching was attempted after, but both resulted in a finer grained polyphase texture. Experiments are currently underway to test different capsule materials may affect quench texture. A preliminary experiment using liquid nitrogen to greatly enhance the rate of cooling of the assembly has also been attempted and this technique will be

  15. X-ray fluorescence analysis of high purity rare earth oxides for common trace rare earth impurities

    International Nuclear Information System (INIS)

    Chandola, L.C.; Dixit, R.M.; Khanna, P.P.; Deshpande, S.S.; Machado, I.J.; Kapoor, S.K.

    1990-01-01

    Methods for the determination of individual trace common rare earth (RE) elements have been developed for fifteen RE oxide matrices viz. La 2 O 3 to Lu 2 O 3 and Y 2 O 3 . In general, for each matrix, two or three neighbouring elements on both sides of the matrix element are determined. The minimum determination limit (MDL) achieved is 0.002% for most of the elements. Special efforts were made to use a small amount of sample (as low as 400 mg) for the analysis by the use of double layer pellet technique and critical thickness studies. Practical experiences with 15 RE matrices, most of which are investigated for the first time, are discussed. Details of selection of instrumental parameters and analysis lines, precision and accuracy and preparation of samples and synthetic standards are given. Theoretical minimum detection limit (TMDL) for each analyte element is calculated in all the 15 matrices. (author). 50 tabs., 2 figs

  16. Synthesis of honeycomb-like mesoporous nitrogen-doped carbon nanospheres as Pt catalyst supports for methanol oxidation in alkaline media

    Science.gov (United States)

    Zhang, Yunmao; Liu, Yong; Liu, Weihua; Li, Xiying; Mao, Liqun

    2017-06-01

    This paper reports the convenient synthesis of honeycomb-like mesoporous nitrogen-doped carbon spheres (MNCS) using a self-assembly strategy that employs dopamine (DA) as a carbon and nitrogen precursor and a polystyrene-b-poly(ethylene oxide) (PS173-b-PEO170) diblock copolymer as a soft template. The MNCS have large BET surface areas of up to 554 m2 g-1 and high nitrogen contents of up to 6.9 wt%. The obtained MNCS are used as a support for Pt catalysts, which promote methanol oxidation in alkaline media. The MNCS-supported Pt (Pt/MNCS) catalyst has a larger electrochemically active surface area (ESA) (89.2 m2 g-1) than does a commercially available Vulcan XC-72R supported Pt/C catalyst. Compared to the Pt/C catalyst, Pt/MNCS displays a higher peak current density (1007 mA mg-1) and is more stable during methanol oxidation. These improvements are attributed to the honeycomb-like porous structure of the MNCS and the introduction of nitrogen to the carbon support. The MNCS effectively stabilize Pt nanoparticles and assuage the agglomeration of the nanoparticles, suggesting that MNCS are potential and promising application as electrocatalyst supports in alkaline direct methanol fuel cells.

  17. Ethanol electro-oxidation in alkaline medium using Pd/MWCNT and PdAuSn/MWCNT electrocatalysts prepared by electron beam irradiation

    International Nuclear Information System (INIS)

    Geraldes, Adriana Napoleao; Silva, Dionisio Furtunato da; Andrade e Silva, Leonardo Gondin de; Spinace, Estevam Vitorio; Oliveira Neto, Almir; Santos, Mauro Coelho dos

    2015-01-01

    Environmental problems and the world growing demand for energy has mobilized the scientific community in finding of clean and renewable energy sources. In this context, fuel cells appear as appropriate technology for generating electricity through alcohols electro-oxidation. Multi Wall Carbon Nanotubes (MWCNT)-supported Pd and trimetallic PdAuSn (Pd:Au:Sn 50:10:40 atomic ratio) electrocatalysts were prepared using electron beam irradiation. The obtained materials were characterized by VC, Chronoamperometry, EDX, TEM and XRD. The catalytic activities of electrocatalysts toward ethanol electro-oxidation were evaluated in alkaline medium in a single alkaline direct ethanol fuel cell (ADEFC) in a range temperature 60 to 90 deg C. The best performances were obtained at 85 deg C: 33 mW.cm -2 and 31 mW.cm -2 for Pd/ MWCNT and PdAuSn/MWCNT electrocatalysts, respectively. X-ray diffractograms of electrocatalysts showed the presence of Pd-rich (fcc) and Au-rich (fcc) phases. Cyclic voltammetry and chronoamperometry experiments showed that PdAuSn/MWCNT electrocatalyst demonstrated similar activity toward ethanol electro-oxidation at room temperature, compared to electrocatalyst Pd/MWCNT. (author)

  18. Electrocatalysis of the Ethylene glycol oxidation reaction and in situ Fourier-transform infared study on PtMo/C electrocatalysts in alkaline and acid media

    Science.gov (United States)

    Pech-Rodríguez, W. J.; Calles-Arriaga, C.; González-Quijano, D.; Vargas-Gutiérrez, G.; Morais, C.; Napporn, T. W.; Rodríguez-Varela, F. J.

    2018-01-01

    PtMo/C (Pt:Mo atomic ratios of 1:1, 2:1 and 3:1) and Pt/C electrocatalysts synthesized by the formic acid method are investigated for the ethylene glycol oxidation reaction (EGOR) in alkaline and acid media. From XRD measurements, the crystallite sizes are between 2.5 and 4.3 nm. Electrochemical characterization of the EGOR on the electrocatalysts shows that the PtMo/C series exhibit higher electrocatalytic activity. When comparing the two electrolytes, the mass current densities obtained in alkaline media are significantly higher than in the acid counterpart. Among the bimetallic anodes, Pt1Mo1/C delivered a high performance in both media. In situ FTIR spectroscopy analysis has been performed to study the pathway of the EGOR. In alkaline media, the PtMo/C electrocatalysts have a higher selectivity for the C2 pathway resulting in the formation of species such as glycolate, glyoxal and glyoxylate. On the other hand, in acid electrolyte, the PtMo/C anodes show a preferential C1 pathway at high potentials and the main intermediate is identified as glycolic acid. The results indicate that the higher catalytic activity of PtMo/C electrocatalysts towards the EGOR may be attributed to the bifunctional mechanism and also to an electronic effect because of the incorporation of Mo atoms into the catalysts structure.

  19. The role of rare earth oxide nanoparticles in suppressing the photobleaching of fluorescent organic dyes

    Science.gov (United States)

    Guha, Anubhav; Basu, Anindita

    2013-03-01

    Organic dyes are widely used for both industrial as well as in scientific applications such as the fluorescent tagging of materials. However the process of photobleaching can rapidly degrade dye fluorescence rendering the material non-functional. Thus exploring novel methods for preventing photobleaching can have widespread benefits. In this work we show that the addition of minute quantities of rare earth (RE) oxide nanoparticles can significantly suppress the photobleaching of dyes. The fluorescence of Rhodamine and AlexaFluor dyes was measured as a function of time with and without the addition of CeO2 and La2O3 nanoparticle additives (two RE oxides that contain an oxygen vacancy based defect structure), as well as with FeO nanoparticles (which has an oxygen excess stoichiometry). We find that the rare earth oxides significantly prolonged the lifetimes of the dyes. The results allow us to develop a model based upon the presence of oxygen vacancies defects that allow the RE oxides to act as oxygen scavengers. This enables the RE oxide particles to effectively remove reactive oxygen free radicals generated in the dye solutions during the photoabsorption process. Current affiliation: Harvard University

  20. Recent developments in the MOCVD and ALD of rare earth oxides and silicates

    International Nuclear Information System (INIS)

    Jones, Anthony C.; Aspinall, Helen C.; Chalker, Paul R.; Potter, Richard J.; Kukli, Kaupo; Rahtu, Antti; Ritala, Mikko; Leskelae, Markku

    2005-01-01

    Lanthanide, or rare-earth oxides are currently being investigated as alternatives to SiO 2 as the dielectric insulating layer in sub-0.1 μm CMOS technology. Metalorganic chemical vapour deposition (MOCVD) and atomic layer deposition (ALD) are promising techniques for the deposition of these high-κ dielectric oxides and in this paper some of our recent research into the MOCVD and ALD of PrO x , La 2 O 3 , Gd 2 O 3 , Nd 2 O 3 and their related silicates are reviewed

  1. Study of NiO cathode modified by rare earth oxide additive for MCFC by electrochemical impedance spectroscopy

    International Nuclear Information System (INIS)

    Huang Bo; Chen Gang; Li Fei; Yu Qingchun; Hu Keao

    2004-01-01

    The preparation and subsequent oxidation of nickel cathodes modified by impregnation with rare earth oxide were evaluated by surface and bulk analysis. The electrochemical behaviors of rare earth oxide impregnated nickel oxide cathodes were also evaluated in a molten 62 mol% Li 2 CO 3 +38 mol% K 2 CO 3 eutectic at 650 deg. C by electrochemical impedance spectroscopy (EIS) as a function of rare earth oxide content and immersion time. The rare earth oxide-impregnated nickel cathodes show almost the similar porosity, pore size, and morphology to the reference nickel cathode. The stability tests of rare earth oxide-impregnated nickel oxide cathodes show that the rare earth oxide additive can dramatically reduce the solubility of nickel oxide in a eutectic carbonate mixture under the standard cathode gas condition. The impedance response of all cathode materials at different immersion time is characterized by the presence of depressed semicircles in the high frequency range changing over into the lines with the angles of which observed with the real axis differing 45 deg. or 90 deg. in the low frequency range. The experimental Nyquist plots can be well analyzed theoretically with a modified model based on the well-known Randles-Ershler equivalent circuit model. In the new model, the double layer capacity (C d ) is replaced by the parallel combination of C d and b/ω; therefore, this circuit is modified to be the parallel combination of (C d ), b/ω, and the charge transfer resistance (R ct ) based on the Randles-Ershler equivalent circuit, to take into consideration both the non-uniformity of electric field at the electrode/electrolyte interface owing to the roughness of electrode surface, and the variety of relaxation times with adsorbed species on the electrode surface. The impedance spectra for all cathode materials show important variations during the 200 h of immersion. The incorporation of lithium in its structure and the low dissolution of nickel oxide and rare

  2. Influence of Rare Earth Doping on the Structural and Catalytic Properties of Nanostructured Tin Oxide

    Directory of Open Access Journals (Sweden)

    Maciel Adeilton

    2008-01-01

    Full Text Available AbstractNanoparticles of tin oxide, doped with Ce and Y, were prepared using the polymeric precursor method. The structural variations of the tin oxide nanoparticles were characterized by means of nitrogen physisorption, carbon dioxide chemisorption, X-ray diffraction, and X-ray photoelectron spectroscopy. The synthesized samples, undoped and doped with the rare earths, were used to promote the ethanol steam reforming reaction. The SnO2-based nanoparticles were shown to be active catalysts for the ethanol steam reforming. The surface properties, such as surface area, basicity/base strength distribution, and catalytic activity/selectivity, were influenced by the rare earth doping of SnO2and also by the annealing temperatures. Doping led to chemical and micro-structural variations at the surface of the SnO2particles. Changes in the catalytic properties of the samples, such as selectivity toward ethylene, may be ascribed to different dopings and annealing temperatures.

  3. Solid state chemistry of rare earth oxides. Final report, September 1, 1950--July 31, 1977

    International Nuclear Information System (INIS)

    Eyring, L.

    1977-07-01

    Work under Contract E(11-1)-1109 and its antecedents has been primarily for the purpose of obtaining detailed thermodynamic, kinetic and structural information on the complex rare earth oxides of praseodymium and terbium. These systems exhibit homologous series of ordered phases, order-disorder transformations, wide-range nonstoichiometric phases, chemical hysteresis in two-phase regions and many other solid state reaction phenomena. Fluorite-related materials of importance to ERDA occur as nuclear fuels, radiation power sources, insulators and solid electrolytes. The rare earth oxides serve directly as model systems for such similar materials and, in a more general sense, they serve as models of solids in general since they exhibit nearly the full range of solid state properties

  4. The electrochemical reduction of PdCl42- and PdCl62- in polyaniline: Influence of Pd deposit morphology on methanol oxidation in alkaline solution

    International Nuclear Information System (INIS)

    Hatchett, David W.; Millick, Nicole M.; Kinyanjui, John M.; Pookpanratana, Sujitra; Baer, Marcus; Hofmann, Timo; Luinetti, Alessio; Heske, Clemens

    2011-01-01

    Graphical abstract: Display Omitted Highlights: → The synthesis of PANI/Pd composites using PdCl 4 2- and PdCl 6 2- is achieved. → Conductivity of PANI/Pd composites is observed in alkaline solution (pH ∼ 14). → Oxidation of methanol at PANI/Pd is influenced to be the Pd surface morphology. → Surface poisoning is minimized for PANI/Pd produced using PdCl 4 2- . → The Pd metal acts as a solid state dopant in PANI. - Abstract: The controlled uptake and electrochemical reduction of metal precursors PdCl 4 2- and PdCl 6 2- in polyaniline (PANI) is demonstrated. The formation of PANI/Pd composites is achieved with a reduction in proton doping and an increase in the oxidation of the polymer with Pd deposits physically blocking the nitrogen groups. High surface area filaments (PdCl 4 2- ) or a rough encapsulation (PdCl 6 2- ) of Pd metal on PANI are obtained. The structural differences highlight the influence of the metal precursor oxidation state on the morphology of the Pd deposits in PANI. Thermal gravimetric analysis provides an estimate of the Pd content for each composite of ∼40%. X-ray Photoelectron Spectroscopy and X-ray-excited Auger Electron Spectroscopy analyses confirm the deposition of Pd metal. The catalytic oxidation of methanol was demonstrated for both PANI/Pd composites in alkaline solutions that prohibit proton doping of the polymer. The data indicates that Pd metal acts as a solid-state dopant that may delocalize the charge on the polymer backbone to maintain conductivity. Methanol oxidation at PANI/Pd composites produced using PdCl 4 2- was enhanced relative to the composite produced using PdCl 6 2- and a planar Pd electrode. Comparison of PANI/Pd composite produced using PdCl 4 2- with other Pd catalysts from the literature indicates surface poisoning is reduced when Pd is coupled with the polymer. The composite is robust and stable in alkaline solution with the charge density decreasing by 5% on the positive scan and 13% on the

  5. Investigation of catalytic oxidation of diamond by water vapor and carbon dioxide in the presence of alkali melts of some rare earth oxides

    International Nuclear Information System (INIS)

    Kulakova, I.I.; Rudenko, A.P.; Sulejmenova, A.S.; Tolstopyatova, A.A.

    1978-01-01

    The results of an investigation of the catalytic oxydation of diamond by carbon dioxide and water vapors at 906 deg C in the presence of melts of some rare earth oxides in potassium hydroxide are given. The ion La 3+ was shown to possess the most catalytic activity. The earlier proposed mechanisms of the diamond oxidation by CO 2 and H 2 O were corroborated. The ions of rare earth elements were found to accelerate the different stages of the process

  6. 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.

  7. 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

  8. Biotemplated Synthesis and Characterization of Mesoporous Nitric Oxide-Releasing Diatomaceous Earth Silica Particles.

    Science.gov (United States)

    Grommersch, Bryan M; Pant, Jitendra; Hopkins, Sean P; Goudie, Marcus J; Handa, Hitesh

    2018-01-24

    Diatomaceous earth (DE), a nanoporous silica material composed of fossilized unicellular marine algae, possesses unique mechanical, molecular transport, optical, and photonic properties exploited across an array of biomedical applications. The utility of DE in these applications stands to be enhanced through the incorporation of nitric oxide (NO) technology shown to modulate essential physiological processes. In this work, the preparation and characterization of a biotemplated diatomaceous earth-based nitric oxide delivery scaffold are described for the first time. Three aminosilanes [(3-aminopropyl)triethoxysilane (APTES), N-(6-aminohexyl)aminomethyltriethoxysilane (AHAMTES), and 3-aminopropyldimethylethoxysilane (APDMES)] were evaluated for their ability to maximize NO loading via the covalent attachment of N-acetyl-d-penicillamine (NAP) to diatomaceous earth. The use of APTES cross-linker resulted in maximal NAP tethering to the DE surface, and NAP-DE was converted to NO-releasing S-nitroso-N-acetyl-penicillamine (SNAP)-DE by nitrosation. The total NO loading of SNAP-DE was determined by chemiluminescence to be 0.0372 ± 0.00791 μmol/mg. Retention of diatomaceous earth's unique mesoporous morphology throughout the derivatization was confirmed by scanning electron microscopy. SNAP-DE exhibited 92.95% killing efficiency against Gram-positive bacteria Staphylococcus aureus as compared to the control. The WST-8-based cytotoxicity testing showed no negative impact on mouse fibroblast cells, demonstrating the biocompatible potential of SNAP-DE. The development of NO releasing diatomaceous earth presents a unique means of delivering tunable levels of NO to materials across the fields of polymer chemistry, tissue engineering, drug delivery, and wound healing.

  9. The Silver Oxide-Zinc Alkaline Primary Cell. Part 2. Effects of Various Types of Negative Electrodes on Cell Characteristics

    National Research Council Canada - National Science Library

    Shepherd, C. M

    1951-01-01

    ... (generally a potassium hydroxide solution). During discharge, the silver peroxide in the positive electrode is reduced to metallic silver and the metallic zinc in the negative electrode is oxidized either to zinc oxide or to a complex zincate ion...

  10. Aeration to degas CO2, increase pH, and increase iron oxidation rates for efficient treatment of net alkaline mine drainage

    International Nuclear Information System (INIS)

    Kirby, C.S.; Dennis, A.; Kahler, A.

    2009-01-01

    Passive treatment systems for mine drainage use no energy other than gravity, but they require greater area than active treatment systems. Researchers are considering 'hybrid' systems that have passive and active components for increased efficiency, especially where space limitations render passive-only technology ineffective. Flow-through reactor field experiments were conducted at two large net-alkaline anthracite mine discharges in central Pennsylvania. Assuming an Fe removal rate of 20 g m -2 day -1 and Fe loading from field data, 3.6 x 10 3 and 3.0 x 10 4 m 2 oxidation ponds would be required for the passive treatment of Site 21 and Packer 5 discharges, respectively. However, only a small area is available at each site. This paper demonstrates aeration to drive off CO 2 , increase pH, and increase Fe(II) oxidation rates, enabling treatment within a small area compared to passive treatment methods, and introduces a geochemical model to accurately predict these rates as well as semi-passive treatment system sizing parameters. Both net-alkaline discharges were suboxic with a pH of ∼5.7, Fe(II) concentration of ∼16 mg L -1 , and low Mn and Al concentrations. Flow rates were ∼4000 L min -1 at Site 21 and 15,000 L min -1 at Packer 5. Three-h aeration experiments with flow rates scaled to a 14-L reactor resulted in pH increases from 5.7 to greater than 7, temperature increases from 12 to 22 deg. C, dissolved O 2 increases to saturation with respect to the atmosphere, and Fe(II) concentration decreases from 16 to -1 . A 17,000-L pilot-scale reactor at Site 21 produced similar results although aeration was not as complete as in the smaller reactor. Two non-aerated experiments at Site 21 with 13 and 25-h run times resulted in pH changes of ≤0.2 and Fe(II) concentration decreases of less than 3 mg L -1 . An Fe(II) oxidation model written in a differential equation solver matched the field experiments very well using field-measured pH, temperature, dissolved O 2

  11. Effects of rare earth doping on multi-core iron oxide nanoparticles properties

    Science.gov (United States)

    Petran, Anca; Radu, Teodora; Borodi, Gheorghe; Nan, Alexandrina; Suciu, Maria; Turcu, Rodica

    2018-01-01

    New multi-core iron oxide magnetic nanoparticles doped with rare earth metals (Gd, Eu) were obtained by a one step synthesis procedure using a solvothermal method for potential biomedical applications. The obtained clusters were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), energy-dispersive X-ray microanalysis (EDX), X-ray photoelectron spectroscopy (XPS) and magnetization measurements. They possess high colloidal stability, a saturation magnetization of up to 52 emu/g, and nearly spherical shape. The presence of rare earth ions in the obtained samples was confirmed by EDX and XPS. XRD analysis proved the homogeneous distribution of the trivalent rare earth ions in the inverse-spinel structure of magnetite and the increase of crystal strain upon doping the samples. XPS study reveals the valence state and the cation distribution on the octahedral and tetrahedral sites of the analysed samples. The observed shift of the XPS valence band spectra maximum in the direction of higher binding energies after rare earth doping, as well as theoretical valence band calculations prove the presence of Gd and Eu ions in octahedral sites. The blood protein adsorption ability of the obtained samples surface, the most important factor of the interaction between biomaterials and body fluids, was assessed by interaction with bovine serum albumin (BSA). The rare earth doped clusters surface show higher afinity for binding BSA. In vitro cytotoxicity test results for the studied samples showed no cytotoxicity in low and medium doses, establishing a potential perspective for rare earth doped MNC to facilitate multiple therapies in a single formulation for cancer theranostics.

  12. Rare-earth metal oxide doped transparent mesoporous silica plates under non-aqueous condition as a potential UV sensor.

    Science.gov (United States)

    Lee, Sang-Joon; Park, Sung Soo; Lee, Sang Hyun; Hong, Sang-Hyun; Ha, Chang-Sik

    2013-11-01

    Transparent mesoporous silica plates doped with rare-earth metal oxide were prepared using solvent-evaporation method based on the self-organization between structure-directing agent and silicate in a non-aqueous solvent. A triblock copolymer, Pluronic (F127 or P123), was used as the structure-directing agent, while tetraethyl orthosilicate (TEOS) was used as a silica source. The pore diameter and the surface area of the mesoporous silica plate prepared with the optimized conditions were ca 40 A and 600 m2 g(-1), respectively, for both structure-directing agent. Rare-earth metal oxides (Eu, Tb, Tm oxide) in mesochannel were formed via one-step synthetic route based on the preparation method of a silica plate. Optical properties of rare-earth metal oxide-doped mesoporous silica plates were investigated by UV irradiation and photoluminescence (PL) spectroscopy. Under the exitation wavelength of 254 nm, the doped mesoporous silica plates emitted red, green and blue for Eu, Tb and Tm oxides, respectively. Rare-earth metal oxide-doped mesoporous silica plates showed enhanced PL intensity compared to that of the bulk rare-earth metal oxide.

  13. {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.

  14. Surface chemistry of rare-earth oxide surfaces at ambient conditions: reactions with water and hydrocarbons.

    Science.gov (United States)

    Külah, Elçin; Marot, Laurent; Steiner, Roland; Romanyuk, Andriy; Jung, Thomas A; Wäckerlin, Aneliia; Meyer, Ernst

    2017-03-22

    Rare-earth (RE) oxide surfaces are of significant importance for catalysis and were recently reported to possess intrinsic hydrophobicity. The surface chemistry of these oxides in the low temperature regime, however, remains to a large extent unexplored. The reactions occurring at RE surfaces at room temperature (RT) in real air environment, in particular, in presence of polycyclic aromatic hydrocarbons (PAHs), were not addressed until now. Discovering these reactions would shed light onto intermediate steps occurring in automotive exhaust catalysts before reaching the final high operational temperature and full conversion of organics. Here we first address physical properties of the RE oxide, nitride and fluoride surfaces modified by exposure to ambient air and then we report a room temperature reaction between PAH and RE oxide surfaces, exemplified by tetracene (C 18 H 12 ) on a Gd 2 O 3 . Our study evidences a novel effect - oxidation of higher hydrocarbons at significantly lower temperatures (~300 K) than previously reported (>500 K). The evolution of the surface chemical composition of RE compounds in ambient air is investigated and correlated with the surface wetting. Our surprising results reveal the complex behavior of RE surfaces and motivate follow-up studies of reactions between PAH and catalytic surfaces at the single molecule level.

  15. Separation of pure Cerium oxides from rare earth compounds. Homogeneous precipitation using Urea-Hydrogen Peroxide

    International Nuclear Information System (INIS)

    Umeda, K.; Abrao, E.

    1975-01-01

    The obtainment of ceric oxide (CeO 2 ) of purity higher than 97% by application of homogeneous precipitation technique is described. The selective separation of cerium was reached by hydrolysis of urea in the presence of hydrogen peroxide, using a rare earths concentrate named rare earths chloride, a natural mixture of all lanthanides provenient from the industrialization of monazite. The best conditions for the preparation of CeO 2 of 94% purity are: 35-70g R 2 O 3 /1 and pH2,0 hydrolysis temperature: 88-90 0 C, urea/R 2 O 3 ratio: 4, H 2 O 2 /Ce 2 O 3 ratio: 1,5-5,0 and hydrolysis duration: 4 hours. A leaching procedure of the precipitate with 0,25-0,75M NHO 3 leads to a product of 97-99,5% CeO 2

  16. 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.

  17. Intracellular alkalinization by phosphate uptake via type III sodium-phosphate cotransporter participates in high-phosphate-induced mitochondrial oxidative stress and defective insulin secretion.

    Science.gov (United States)

    Nguyen, Tuyet Thi; Quan, Xianglan; Xu, Shanhua; Das, Ranjan; Cha, Seung-Kuy; Kong, In Deok; Shong, Minho; Wollheim, Claes B; Park, Kyu-Sang

    2016-12-01

    Elevated plasma levels of inorganic phosphate (P i ) are harmful, causing, among other complications, vascular calcification and defective insulin secretion. The underlying molecular mechanisms of these complications remain poorly understood. We demonstrated the role of P i transport across the plasmalemma on P i toxicity in INS-1E rat clonal β cells and rat pancreatic islet cells. Type III sodium-phosphate cotransporters (NaP i s) are the predominant P i transporters expressed in insulin-secreting cells. Transcript and protein levels of sodium-dependent phosphate transporter 1 and 2 (PiT-1 and -2), isotypes of type III NaP i , were up-regulated by high-P i incubation. In patch-clamp experiments, extracellular P i elicited a Na + -dependent, inwardly rectifying current, which was markedly reduced under acidic extracellular conditions. Cellular uptake of P i elicited cytosolic alkalinization; intriguingly, this pH change facilitated P i transport into the mitochondrial matrix. Increased mitochondrial P i uptake accelerated superoxide generation, mitochondrial permeability transition (mPT), and endoplasmic reticulum stress-mediated translational attenuation, leading to reduced insulin content and impaired glucose-stimulated insulin secretion. Silencing of PiT-1/2 prevented P i -induced superoxide generation and mPT, and restored insulin secretion. We propose that P i transport across the plasma membrane and consequent cytosolic alkalinization could be a therapeutic target for protection from P i toxicity in insulin-secreting cells, as well as in other cell types.-Nguyen, T. T., Quan, X., Xu, S., Das, R., Cha, S.-K., Kong, I. D., Shong, M., Wollheim, C. B., Park, K.-S. Intracellular alkalinization by phosphate uptake via type III sodium-phosphate cotransporter participates in high-phosphate-induced mitochondrial oxidative stress and defective insulin secretion. © FASEB.

  18. The oxidation state of Hadean magmas and implications for early Earth's atmosphere.

    Science.gov (United States)

    Trail, Dustin; Watson, E Bruce; Tailby, Nicholas D

    2011-11-30

    Magmatic outgassing of volatiles from Earth's interior probably played a critical part in determining the composition of the earliest atmosphere, more than 4,000 million years (Myr) ago. Given an elemental inventory of hydrogen, carbon, nitrogen, oxygen and sulphur, the identity of molecular species in gaseous volcanic emanations depends critically on the pressure (fugacity) of oxygen. Reduced melts having oxygen fugacities close to that defined by the iron-wüstite buffer would yield volatile species such as CH(4), H(2), H(2)S, NH(3) and CO, whereas melts close to the fayalite-magnetite-quartz buffer would be similar to present-day conditions and would be dominated by H(2)O, CO(2), SO(2) and N(2) (refs 1-4). Direct constraints on the oxidation state of terrestrial magmas before 3,850 Myr before present (that is, the Hadean eon) are tenuous because the rock record is sparse or absent. Samples from this earliest period of Earth's history are limited to igneous detrital zircons that pre-date the known rock record, with ages approaching ∼4,400 Myr (refs 5-8). Here we report a redox-sensitive calibration to determine the oxidation state of Hadean magmatic melts that is based on the incorporation of cerium into zircon crystals. We find that the melts have average oxygen fugacities that are consistent with an oxidation state defined by the fayalite-magnetite-quartz buffer, similar to present-day conditions. Moreover, selected Hadean zircons (having chemical characteristics consistent with crystallization specifically from mantle-derived melts) suggest oxygen fugacities similar to those of Archaean and present-day mantle-derived lavas as early as ∼4,350 Myr before present. These results suggest that outgassing of Earth's interior later than ∼200 Myr into the history of Solar System formation would not have resulted in a reducing atmosphere.

  19. Carbon Supported Oxide-Rich Pd-Cu Bimetallic Electrocatalysts for Ethanol Electrooxidation in Alkaline Media Enhanced by Cu/CuOx

    Directory of Open Access Journals (Sweden)

    Zengfeng Guo

    2016-04-01

    Full Text Available Different proportions of oxide-rich PdCu/C nanoparticle catalysts were prepared by the NaBH4 reduction method, and their compositions were tuned by the molar ratios of the metal precursors. Among them, oxide-rich Pd0.9Cu0.1/C (Pd:Cu = 9:1, metal atomic ratio exhibits the highest electrocatalytic activity for ethanol oxidation reaction (EOR in alkaline media. X-ray photoelectron spectroscopy (XPS and high resolution transmission electron microscopy (HRTEM confirmed the existence of both Cu and CuOx in the as-prepared Pd0.9Cu0.1/C. About 74% of the Cu atoms are in their oxide form (CuO or Cu2O. Besides the synergistic effect of Cu, CuOx existed in the Pd-Cu bimetallic nanoparticles works as a promoter for the EOR. The decreased Pd 3d electron density disclosed by XPS is ascribed to the formation of CuOx and the spill-over of oxygen-containing species from CuOx to Pd. The low Pd 3d electron density will decrease the adsorption of CH3COads intermediates. As a result, the electrocatalytic activity is enhanced. The onset potential of oxide-rich Pd0.9Cu0.1/C is negative shifted 150 mV compared to Pd/C. The oxide-rich Pd0.9Cu0.1/C also exhibited high stability, which indicated that it is a candidate for the anode of direct ethanol fuel cells (DEFCs.

  20. Enhanced activity of rare earth doped PtRu/C catalysts for methanol electro-oxidation

    International Nuclear Information System (INIS)

    An Xiaosha; Fan Youjun; Chen Dejun; Wang Qiang; Zhou Zhiyou; Sun Shigang

    2011-01-01

    Highlights: → The electrocatalytic activity of PtRuRE/C catalysts is higher than that of the JM PtRu/C for methanol oxidation (except for PtRuGd/C), generating a decreasing order of PtRuEu/C > PtRuEr/C > PtRuY/C > PtRuSm/C > PtRuLa/C > JM PtRu/C > PtRuGd/C. → The CO-tolerance performance of PtRuRE/C catalysts is better than JM PtRu/C. → The electronic effect of rare earth plays an important role in the catalytic performance of PtRuRE/C for methanol electrooxidation. - Abstract: PtRuRE/C catalysts were prepared through doping the commercial JM PtRu/C catalyst with rare earth (RE = La, Eu, Gd, Y, Sm and Er). The doping was conducted by chemical reduction and sintering treatment methods. The catalysts were characterized by transmission electron microscopy (TEM), energy dispersive X-ray (EDX) spectroscopy, X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). The results demonstrated that the rare earth doping did not significantly change the average size of the JM PtRu/C particles, and modified the PtRu surface with two element states of the metal and oxide. Studies of cyclic voltammetry and chronoamperometry indicated that the electrocatalytic activity of PtRuRE/C catalysts was higher than that of the JM PtRu/C for methanol oxidation (except for PtRuGd/C), generating a decreasing order of PtRuEu/C > PtRuEr/C > PtRuY/C > PtRuSm/C > PtRuLa/C > JM PtRu/C > PtRuGd/C. It has revealed that among the PtRuRE/C catalysts the PtRuEu/C exhibited the best performance. In addition, the reaction process of methanol electrocatalytic oxidation on several catalysts was investigated by in situ FTIR spectroscopy at molecule level. The results demonstrated that the adsorbates derived from methanol dissociative adsorption on the catalysts were the linear-bonded CO (CO L ), and the CO-tolerance performance of PtRuRE/C catalysts was better than JM PtRu/C. It has revealed also that the electronic effect of rare earth plays an important role in the catalytic performance

  1. Optical emission spectrographic analysis of thulium oxide for rare earth impurities

    International Nuclear Information System (INIS)

    Chandola, L.C.; Khanna, P.P.; Dixit, V.C.

    1988-01-01

    An optical emission spectrographic method has been developed for the analysis of high purity thulium oxide to determine rare earth elements Er, Yb, Lu and Y. A 1200 groove/mm grating blazed at 3300 A is used to record the spectrum on Kodak SA-1 photographic plates after the excitation of the graphite-sample (1:1) mixture in DC arc. The determination range is 0.008 per cent to 0.1 per cent and the relative standard deviation is 17.6 per cent. (author). 15 refs., 5 tables, 5 figs

  2. Scintillation property of rare earth-free SnO-doped oxide glass

    OpenAIRE

    Masai, Hirokazu; Yanagida, Takayuki; Fujimoto, Yutaka; Koshimizu, Masanori; Yoko, Toshinobu

    2012-01-01

    The authors have demonstrated scintillation of rare earth (RE)-free Sn-doped oxide glass by excitation of ionizing radiation. It is notable that light emission is attained for RE-free transparent glass due to s[2]-sp transition of Sn[2+] centre and the emission correlates with the excitation band at 20 eV. We have also demonstrated that excitation band of emission centre can be tuned by the chemical composition of the host glass. The present result is valuable not only for design of RE-free i...

  3. High performance nano-Ni/Graphite electrode for electro-oxidation in direct alkaline ethanol fuel cells

    Science.gov (United States)

    Soliman, Ahmed B.; Abdel-Samad, Hesham S.; Abdel Rehim, Sayed S.; Ahmed, Mohamed A.; Hassan, Hamdy H.

    2016-09-01

    Ni/Graphite electrocatalysts (Ni/G) are successfully prepared through electrodeposition of Ni from acidic (pH = 0.8) and feebly acidic (pH = 5.5) aqueous Ni (II) baths. The efficiencies of such electrodes are investigated as anodes for direct alkaline ethanol fuel cells through their ethanol electrooxidation cyclic voltammetric (CV) response in alkaline medium. A direct proportionality between the amount of the electrodeposited Ni and its CV response is found. The amounts of the deposited Ni from the two baths are recorded using the Electrochemical Quartz Crystal Microbalance (eQCM). The Ni/G electrodes prepared from the feebly acidic bath show a higher electrocatalytic response than those prepared from the acidic bath. Surface morphology of the Ni particles electrodeposited from feebly acidic bath appears in a nano-scale dimension. Various electrochemical experiments are conducted to confirm that the Ni/G ethanol electrooxidation CV response greatly depends on the pH rather than nickel ion concentration of the deposition bath. The eQCM technique is used to detect the crystalline phases of nickel as α-Ni(OH)2/γ-NiOOH and β-Ni(OH)2/β-NiOOH and their in-situ inter-transformations during the potentiodynamic polarization.

  4. Controlling the Molecular Weight of Lignosulfonates by an Alkaline Oxidative Treatment at Moderate Temperatures and Atmospheric Pressure: A Size-Exclusion and Reverse-Phase Chromatography Study

    Directory of Open Access Journals (Sweden)

    Chamseddine Guizani

    2017-11-01

    Full Text Available The molecular weights of lignosulfonates (LSs are modified by a rather simple process involving an alkaline oxidative treatment at moderate temperatures (70–90 °C and atmospheric pressure. Starting from LSs with an average molecular weight of 90,000 Da, and using such a treatment, one can prepare controlled molecular weight LSs in the range of 30,000 to 3500 Da based on the average mass molecular weight. The LS depolymerisation was monitored via reverse-phase and size-exclusion chromatography. It has been shown that the combination of O2, H2O2 and Cu as a catalyst in alkaline conditions at 80 °C induces a high LS depolymerisation. The depolymerisation was systemically accompanied by a vanillin production, the yields of which reached 1.4 wt % (weight percentage on LS raw basis in such conditions. Also, the average molecular weight and vanillin concentration were correlated and depended linearly on the temperature and reaction duration.

  5. 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

  6. Electrostatic tuning of Kondo effect in a rare-earth-doped wide-band-gap oxide

    KAUST Repository

    Li, Yongfeng

    2013-04-29

    As a long-lived theme in solid-state physics, the Kondo effect reflects the many-body physics involving the short-range Coulomb interactions between itinerant electrons and localized spins in metallic materials. Here we show that the Kondo effect is present in ZnO, a prototypical wide-band-gap oxide, doped with a rare-earth element (Gd). The localized 4f electrons of Gd ions do not produce remanent magnetism, but interact strongly with the host electrons, giving rise to a saturating resistance upturn and negative magnetoresistance at low temperatures. Furthermore, the Kondo temperature and resistance can be electrostatically modulated using electric-double-layer gating with liquid ionic electrolyte. Our experiments provide the experimental evidence of tunable Kondo effect in ZnO, underscoring the magnetic interactions between localized and itinerant electrons and the emergent transport behaviors in such doped wide-band-gap oxides.

  7. Monitoring, field experiments, and geochemical modeling of Fe(II) oxidation kinetics in a stream dominated by net-alkaline coal-mine drainage, Pennsylvania, USA

    Science.gov (United States)

    Cravotta,, Charles A.

    2015-01-01

    Watershed-scale monitoring, field aeration experiments, and geochemical equilibrium and kinetic modeling were conducted to evaluate interdependent changes in pH, dissolved CO2, O2, and Fe(II) concentrations that typically take place downstream of net-alkaline, circumneutral coal-mine drainage (CMD) outfalls and during aerobic treatment of such CMD. The kinetic modeling approach, using PHREEQC, accurately simulates observed variations in pH, Fe(II) oxidation, alkalinity consumption, and associated dissolved gas concentrations during transport downstream of the CMD outfalls (natural attenuation) and during 6-h batch aeration tests on the CMD using bubble diffusers (enhanced attenuation). The batch aeration experiments demonstrated that aeration promoted CO2 outgassing, thereby increasing pH and the rate of Fe(II) oxidation. The rate of Fe(II) oxidation was accurately estimated by the abiotic homogeneous oxidation rate law −d[Fe(II)]/dt = k1·[O2]·[H+]−2·[Fe(II)] that indicates an increase in pH by 1 unit at pH 5–8 and at constant dissolved O2 (DO) concentration results in a 100-fold increase in the rate of Fe(II) oxidation. Adjusting for sample temperature, a narrow range of values for the apparent homogeneous Fe(II) oxidation rate constant (k1′) of 0.5–1.7 times the reference value of k1 = 3 × 10−12 mol/L/min (for pH 5–8 and 20 °C), reported by Stumm and Morgan (1996), was indicated by the calibrated models for the 5-km stream reach below the CMD outfalls and the aerated CMD. The rates of CO2 outgassing and O2ingassing in the model were estimated with first-order asymptotic functions, whereby the driving force is the gradient of the dissolved gas concentration relative to equilibrium with the ambient atmosphere. Although the progressive increase in DO concentration to saturation could be accurately modeled as a kinetic function for the conditions evaluated, the simulation of DO as an instantaneous equilibrium process did not affect the

  8. Transesterification of rapeseed oil for biodiesel production in trickle-bed reactors packed with heterogeneous Ca/Al composite oxide-based alkaline catalyst.

    Science.gov (United States)

    Meng, Yong-Lu; Tian, Song-Jiang; Li, Shu-Fen; Wang, Bo-Yang; Zhang, Min-Hua

    2013-05-01

    A conventional trickle bed reactor and its modified type both packed with Ca/Al composite oxide-based alkaline catalysts were studied for biodiesel production by transesterification of rapeseed oil and methanol. The effects of the methanol usage and oil flow rate on the FAME yield were investigated under the normal pressure and methanol boiling state. The oil flow rate had a significant effect on the FAME yield for the both reactors. The modified trickle bed reactor kept over 94.5% FAME yield under 0.6 mL/min oil flow rate and 91 mL catalyst bed volume, showing a much higher conversion and operational stability than the conventional type. With the modified trickle bed reactor, both transesterification and methanol separation could be performed simultaneously, and glycerin and methyl esters were separated additionally by gravity separation. Copyright © 2013 Elsevier Ltd. All rights reserved.

  9. Green synthesis of core-shell gold-palladium@palladium nanocrystals dispersed on graphene with enhanced catalytic activity toward oxygen reduction and methanol oxidation in alkaline media

    Science.gov (United States)

    Zheng, Jie-Ning; Li, Shan-Shan; Ma, Xiaohong; Chen, Fang-Yi; Wang, Ai-Jun; Chen, Jian-Rong; Feng, Jiu-Ju

    2014-09-01

    Well-defined core-shell gold-palladium@palladium nanocrystals (AuPd@Pd) are facilely prepared by a simple and green wet-chemical method at 25 °C. A Good's buffer, 2-[4-(2-hydroxyethyl)-1-piperazinyl] ethanesulfonic acid (HEPES), is used as a reducing agent and a shape-directing agent, while there is no template, seed, organic solvent, or surfactant involved. The AuPd@Pd nanocrystals are uniformly dispersed on graphene nanosheets by ultrasonication, resulting in the formation of graphene supported AuPd@Pd (G-AuPd@Pd). The as-prepared nanocomposites exhibit the improved catalytic activity, good tolerance, and better stability for oxygen reduction reaction (ORR) and methanol oxidation reaction (MOR) in alkaline media, compared with the G-Pd and commercial Pd black catalysts. The as-developed method may provide a promising pathway for large-scale fabrication of AuPd-based catalysts.

  10. 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.

  11. Metal oxide nanoparticles embedded in rare-earth matrix for low temperature thermal imaging applications

    Science.gov (United States)

    Rauwel, E.; Galeckas, A.; Rauwel, P.; Hansen, P.-A.; Wragg, D.; Nilsen, O.; Fjellvåg, H.

    2016-05-01

    We report on the synthesis and characterization of nanocomposites comprising of oxide nanoparticles (NPs) (ZnO, CaHfO3 and SrHfO3) embedded in rare-earth oxide (Eu2O3, Nd2O3) matrices by using atomic layer deposition. The different oxide surroundings allowed highlighting the role of interface defects in the recombination processes of charge carriers in the NPs. We provide a comparative analysis of optical absorption and emission properties of the constituents: thin films, free-standing and embedded NPs, and discuss the intrinsic and extrinsic nature of the luminescent sites in different nanocomposites. The photoluminescence properties of ZnO nanocomposites are clearly distinguishable from those of free-standing NPs in terms of overall quantum efficiency as well as intensity ratios of the characteristic blue and green emission bands associated with radiative transitions involving excitons and intrinsic defects, respectively. In contrast to PL enhancement due to surface-passivating effect of the surrounding media in the case of ZnO nanocomposites, the embedment of hafnia perovskites into oxide matrices generally leads to suppressed luminescence in the visible range, thus confirming its extrinsic, surface-defect related nature.

  12. Facile fabrication of graphene-based aerogel with rare earth metal oxide for water purification

    Science.gov (United States)

    Pan, Liupeng; Liu, Shunli; Oderinde, Olayinka; Li, Kewen; Yao, Fang; Fu, Guodong

    2018-01-01

    We report a one-step facile fabrication of macroscopic multifunctional graphene-based aerogel with three-dimensional interconnected networks under the synergistic effects of the reduction of graphene oxide sheets by L-ascorbic acid and in situ simultaneous deposition of nanoparticles on graphene sheets. The functional components, Nd2O3 nanoparticles, can be easily incorporated with graphene sheets to assemble bulk macroscopic graphene materials under mild conditions. The reduced graphene oxide/neodymium oxide (rGO/Nd2O3) aerogel showed remarkable adsorption capacity towards different types of dyes, especially for anionic dyes, with the adsorption capacity for indigo disulphonate (ID) being more than 220 mg g-1 within one hour while the adsorption capacity at equilibrium is as high as 397 mg g-1. The method proposed is proven to be universal to induce macroscopic assembly of reduced graphene sheets with rare earth metal oxides and thus facilitates to accessing various graphene-based multifunctional nanocomposites in the form of macroscopic aerogels.

  13. Well-dispersed NiO nanoparticles supported on nitrogen-doped carbon nanotube for methanol electrocatalytic oxidation in alkaline media

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Pengcheng; Zhou, Yingke, E-mail: zhouyk888@hotmail.com; Hu, Min; Chen, Jian

    2017-01-15

    Highlights: • Nitrogen-doped carbon nanotube supporting ultrafine NiO nanoparticles with high dispersity are facile synthesized. • The nitrogen doping, calcination temperature and NiO loading present great effects on the catalyst morphology, structure and electrochemical performance. • NiO-NCNT-3x-400 demonstrates remarkable catalytic activity and stability for the methanol electrolytic oxidation reaction. - Abstract: Nitrogen-doped carbon nanotube supporting NiO nanoparticles were synthesized by a chemical precipitation process coupled with subsequent calcination. The morphology and structure of the composites were characterized by transmission electron microscopy (TEM), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS), and the electrochemical performance was evaluated using cyclic voltammetry and chronoamperometric technique. The effects of nitrogen doping, calcination temperature and content of NiO nanoparticles on the electrocatalytic activity toward methanol oxidation were systematically studied. The results show that the uniformly dispersed ultrafine NiO nanoparticles supported on nitrogen-doped carbon nanotube are obtained after calcination at 400 °C. The optimized composite catalysts present high electrocatalytic activity, fast charge-transfer process, excellent accessibility and stability for methanol oxidation reaction, which are promising for application in the alkaline direct methanol fuel cells.

  14. Rare-earth hafnium oxide materials for magnetohydrodynamic (MHD) generator application

    Energy Technology Data Exchange (ETDEWEB)

    Marchant, D. D; Bates, J. L.

    1979-01-01

    Several ceramic materials based on rare-earth hafnium oxides have been identified as potential high-temperature electrodes and low-temperature current leadouts for open cycle coal-fired MHD generator channels. The electrode-current leadouts combination must operate at temperatures between 400 and 2000K with an electrical conductivity greater than 10/sup -2/ ohm/sup -1/ cm/sup -1/. The electrodes will be exposed to flowing (linear flow rates up to 100 m/s) potassium seeded coal combustion gases (plasma core temperatures between 2400 to 3200/sup 0/K) and coal slag. During operation the electrodes must conduct direct electric current at densities near 1.5 amp/cm/sup 2/. Consequently, the electrodes must be resistant to electrochemical decompositions and interactions with both the coal slag and potassium salts (e.g., K/sub 2/SO/sub 4/, K/sub 2/CO/sub 3/). The current leadout materials are placed between the hot electrodes and the water-cooled copper structural members and must have electrical conductivities greater than 10/sup -2/ ohm/sup -1/ cm/sup -1/ between 1400 and 400/sup 0/K. The current leadouts must be thermally and electrochemically compatible with the electrode, copper, and potassium salts. Ideally, the electrodes and current leadouts should exhibit minimal ionic conductivity. The fabrication, electrical conductivity, and electrochemical corrosion of rare-earth hafnium oxide materials are discussed. (WHK)

  15. Characterization of Rare Earth Oxide/Gold Composites Synthesized by Control of Surface Composition

    Science.gov (United States)

    Yasmin, Zannatul; Dennis, Robert; Sardar, Dhiraj; Zhang, Maogen; Gorski, Waldemar; Nash, Kelly

    2010-10-01

    The need for novel nanosized biosensors has resulted in increase interest in nanocomposites. The challenge in development of materials is that they should offer robust and tunable characteristics (fluorescence, magnetic, thermal behaviors, etc.) while remaining biocompatible. In this study, we use small molecules to attach transition metal nanostructures (gold spheres) to select rare earth oxide (Er^3+:Y2O3) particles synthesized by a urea precipitation method. The goal is to enhance the fluorescence of the rare earth materials through surface plasmons resonance generated by the gold structure while achieving dispersibility of the particles. The attachment of gold nanoparticles (Au NPs, ˜20 nm) to the surface of rare earth nanoparticles (RENPs, ˜100 nm) is achieved by the surface modification with (3-Mercaptopropyl) trimethoxy-silane (MPTS); the average numbers of Au NPs per RENP is controlled by the composition of MPTS and Propyltrimethoxysilane (PTMS, without functional groups). Characterization of the physical properties is performed by Fourier transform infrared spectroscopy and scanning electron microscopy. Fluorescence spectroscopy is used to compare the radiative decay rates of nanocomposites to unmodified particles. The resulting structures will be used in studies of bulk and particle polymer composites for potential biosensing and drug delivery applications.

  16. Nanotubes of rare earth cobalt oxides for cathodes of intermediate-temperature solid oxide fuel cells

    Energy Technology Data Exchange (ETDEWEB)

    Sacanell, Joaquin [Departamento de Fisica, Centro Atomico Constituyentes, CNEA, Av. Gral. Paz 1499, 1650 San Martin, Buenos Aires (Argentina); CINSO (Centro de Investigaciones en Solidos), CITEFA-CONICET, J.B. de La Salle 4397, 1603 Villa Martelli, Buenos Aires (Argentina); Leyva, A. Gabriela [Departamento de Fisica, Centro Atomico Constituyentes, CNEA, Av. Gral. Paz 1499, 1650 San Martin, Buenos Aires (Argentina); Escuela de Ciencia y Tecnologia, UNSAM. Av. Gral. Paz 1499, 1650 San Martin, Buenos Aires (Argentina); Bellino, Martin G.; Lamas, Diego G. [CINSO (Centro de Investigaciones en Solidos), CITEFA-CONICET, J.B. de La Salle 4397, 1603 Villa Martelli, Buenos Aires (Argentina)

    2010-04-02

    In this work we studied the electrochemical properties of cathodes for intermediate-temperature solid oxide fuel cells (IT-SOFCs) prepared with nanotubes of La{sub 0.6}Sr{sub 0.4}CoO{sub 3} (LSCO). Their nanostructures consist of agglomerated nanoparticles in tubular structures of sub-micrometric diameter. The resulting cathodes are highly porous both at the micro- and the nanoscale. This fact increases significantly the access to active sites for the oxygen reduction. We investigated the influence of the diameter of the precursor nanotubes on the polarization resistance of the LSCO cathodes on CeO{sub 2}-10 mol.% Sm{sub 2}O{sub 3} (SDC) electrolytes under air atmosphere, evaluated in symmetrical [LSCO/SDC/LSCO] cells. Our results indicate an optimized performance when the diameter of precursor nanotubes is sufficiently small to become dense nanorods after cathode sintering. We present a phenomenological model that successfully explains the behavior observed and considers that a small starting diameter acts as a barrier that prevents grains growth. This is directly related with the lack of contact points between nanotubes in the precursor, which are the only path for the growth of ceramic grains. We also observed that a conventional sintering process (of 1 h at 1000 C with heating and cooling rates of 10 C min{sup -1}) has to be preferred against a fast firing one (1 or 2 min at 1100 C with heating and cooling rates of 100 C min{sup -1}) in order to reach a higher performance. However, a good adhesion of the cathode can be achieved with both methods. Our results suggest that oxygen vacancy diffusion is enhanced while decreasing LSCO particle size. This indicates that the high performance of our nanostructured cathodes is not only related with the increase of the number of active sites for oxygen reduction but also to the fact that the nanotubes are formed by nanoparticles. (author)

  17. INVESTIGATION OF DNA REPAIR BY SISTER CHROMATID EXCHANGE (SCE) ANALYSIS AND THE ALKALINE SINGLE CELL GEL ASSAY (SCG) IN MAMMALIAN GO-LYMPHOCYTES AFTER IN VITRO EXPOSURE TO ETHYLENE OXIDE (EO)

    Science.gov (United States)

    Investigation ofDNA Repair by Sister Chromatid Exchange (SCE) Analysis and the Alkaline Single Cell Gel Assay (SCG) in Mammalian Go-Lymphocytes after In Vitro Exposure to Ethylene Oxide (EO). EO is a large volume chemical used primarily as an intermediate in manufacturing...

  18. Electrocatalytic oxidation of meso-erythritol in anion-exchange membrane alkaline fuel cell on PdAg/CNT catalyst

    Science.gov (United States)

    Benipal, Neeva; Qi, Ji; McSweeney, Ryan F.; Liang, Changhai; Li, Wenzhen

    2018-01-01

    C-C bond cleavage during electrocatalytic oxidation of glycerol and C3+ polyols often occurs and can significantly affect the Faradaic efficiency, fuel utilization, and output power density of a direct polyol fuel cell, although this has not been deeply investigated. With the goal of acquiring new knowledge of C-C bond breaking of polyols, this study examines the electrocatalytic oxidation of a C4 polyol meso-erythritol on carbon nanotube supported Pd-based catalysts (Pd/CNT, PdAg/CNT, and PdAg3/CNT) in an anion-exchange membrane fuel cell (AEMFC). Our results show that PdAg/CNT improves the fuel efficiency of meso-erythritol oxidation by contributing to the C-C bond cleavage of meso-erythritol in C3 and C2 chemicals. Based on the analysis of electro-oxidation products and half-cell cyclic voltammetry (CV) of intermediates, a meso-erythritol electro-oxidation pathway has been proposed to demonstrate that Ag is likely to assist Pd to promote the cleavage of C-C bonds of meso-erythritol.

  19. Syntheses of rare-earth metal oxide nanotubes by the sol-gel method assisted with porous anodic aluminum oxide templates

    International Nuclear Information System (INIS)

    Kuang Qin; Lin Zhiwei; Lian Wei; Jiang Zhiyuan; Xie Zhaoxiong; Huang Rongbin; Zheng Lansun

    2007-01-01

    In this paper, we report a versatile synthetic method of ordered rare-earth metal (RE) oxide nanotubes. RE (RE=Y, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Yb) oxide nanotubes were successfully prepared from corresponding RE nitrate solution via the sol-gel method assisted with porous anodic aluminum oxide (AAO) templates. Scanning electron microscopy (SEM), transmission electron microscopy (TEM), high-resolution TEM, and X-ray diffraction (XRD) have been employed to characterize the morphology and composition of the as-prepared nanotubes. It is found that as-prepared RE oxides evolve into bamboo-like nanotubes and entirely hollow nanotubes. A new possible formation mechanism of RE oxide nanotubes in the AAO channels is proposed. These high-quantity RE oxide nanotubes are expected to have promising applications in many areas such as luminescent materials, catalysts, magnets, etc. - Graphical abstract: A versatile synthetic method for the preparation of ordered rare-earth (RE) oxide nanotubes is reported, by which RE (RE=Y, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Yb) oxide nanotubes were successfully prepared from corresponding RE nitrate solution via the sol-gel method assisted with porous anodic aluminum oxide (AAO) templates

  20. Structure-property relationship of bifunctional MnO2 nanostructures: highly efficient, ultra-stable electrochemical water oxidation and oxygen reduction reaction catalysts identified in alkaline media.

    Science.gov (United States)

    Meng, Yongtao; Song, Wenqiao; Huang, Hui; Ren, Zheng; Chen, Sheng-Yu; Suib, Steven L

    2014-08-13

    Manganese oxides of various structures (α-, β-, and δ-MnO2 and amorphous) were synthesized by facile methods. The electrocatalytic properties of these materials were systematically investigated for catalyzing both oxygen evolution reaction (OER) and oxygen reduction reaction (ORR) in alkaline media. Extensive characterization was correlated with the activity study by investigating the crystal structures (XRD, HRTEM), morphologies (SEM), porosities (BET), surfaces (XPS, O2-TPD/MS), and electrochemical properties (Tafel analysis, Koutechy-Levich plots, and constant-current electrolysis). These combined results show that the electrocatalytic activities are strongly dependent on the crystallographic structures, and follow an order of α-MnO2 > AMO > β-MnO2 > δ-MnO2. Both OER studies and ORR studies reveal similar structure-determined activity trends in alkaline media. In the OER studies, α-MnO2 displays an overpotential of 490 mV compared to 380 mV shown by an Ir/C catalyst in reaching 10 mA cm(-2). Meanwhile, α-MnO2 also exhibits stability for 3 h when supplying a constant current density of 5 mA cm(-2). This was further improved by adding Ni(2+) dopants (ca. 8 h). The superior OER activity was attributed to several factors, including abundant di-μ-oxo bridges existing in α-MnO2 as the protonation sites, analogous to the OEC in PS-II of the natural water oxidation system; the mixed valencies (AOS = 3.7); and the lowest charge transfer resistances (91.8 Ω, η = 430 mV) as revealed from in situ electrochemical impedance spectroscopy (EIS). In the ORR studies, when reaching 3 mA cm(-2), α-MnO2 shows 760 mV close to 860 mV for the best ORR catalyst (20% Pt/C). The outstanding ORR activity was due to the strongest O2 adsorption capability of α-MnO2 suggested by temperature-programmed desorption. As a result, this discovery of the structure-related electrocatalytic activities could provide guidance in the further development of easily prepared, scalable, and low

  1. Electrochemical oxidation of ethanol using PtRh/C electrocatalysts in alkaline medium and synthesized by sodium borohydride and alcohol reduction

    International Nuclear Information System (INIS)

    Fontes, Eric Hossein

    2017-01-01

    PtRh/C were prepared by the following atomic proportions: (100,0), (0,100), (90,10), (70,30) and (50,50). The methods employed in the synthesis of these materials were reduction by sodium borohydride and reduction by alcohol. The metal salts used were H 2 PtCl 6 3•6H 2 0 and (RhNO 3 ) 3 , the support used was Carbon black XC72 and the bulk metal composition was 20% and 80% of support. The electrocatalysts were characterized by Energy Dispersive X-ray spectroscopy, X-ray diffraction and Transmission electron microscopy. The ethanol electrochemical oxidation mechanism was investigated by in situ Fourier Transform Infrared Spectroscopy couple to an Attenuated Total Reflection technique. The electrocatalytic activity were evaluated by Cyclic Voltammetry, Linear Sweep Voltammetry and Chronoamperometry techniques. The Fuel Cells tests were made in a single direct alcohol fuel cell with alkaline membrane. The working electrodes were prepared by a thin porous coating technique. X-ray diffraction allowed to verify metallic alloys, segregate phases and to calculate the percentage of metallic alloys. It was else possible to identify crystallographic phases. Infrared Spectroscopy allowed to verify that the electrochemical oxidation of ethanol was carried out by an incomplete mechanism. PtRh(70:30)/C prepared by sodium borohydride produced large amounts of carbon dioxide and acetaldehyde. Rh/C showed electrocatalytic activity when compared with other materials studied.

  2. Sulfate-dependent acetate oxidation under extremely natron-alkaline conditions by syntrophic associations from hypersaline soda lakes

    NARCIS (Netherlands)

    Sorokin, D.Y.; Abbas, B.; Tourova, T.P.; Bumazhkin, B.K.; Kolganova, T.V.; Muyzer, G.

    2014-01-01

    So far, anaerobic sulfate-dependent acetate oxidation at high pH has only been demonstrated for a low-salt-tolerant syntrophic association of a clostridium ‘Candidatus Contubernalis alkalaceticum’ and its hydrogenotrophic sulfate-reducing partner Desulfonatronum cooperativum. Anaerobic enrichments

  3. Estimation of rare earth elements in gadolinium oxide by inductively coupled plasma mass spectrometry

    International Nuclear Information System (INIS)

    Kumar, Sanjukta A.; Venkataramani, B.; Kotekar, M.K.

    2007-01-01

    A method was developed for the direct determination of trace quantities of rare earth elements (REEs) in gadolinium oxide dissolved in nitric acid by inductively coupled plasma mass spectrometry. The matrix suppression effect of Gd on the ion peak signals of REEs impurities was effectively compensated with spiking In as an internal standard. The recoveries of spiked sample for REEs were found to be in the range of 91-109% by using the proposed method. The relative standard deviation varied between 1.5 to 6%. The methodology had been found to be suitable for the direct determination of trace REEs in Gd 2 O 3 and the results obtained from this method keep in good agreement with that acquired from inductively coupled plasma emission spectrometry. (author)

  4. Anomalous positive flatband voltage shifts in metal gate stacks containing rare-earth oxide capping layers

    KAUST Repository

    Caraveo-Frescas, J. A.

    2012-03-09

    It is shown that the well-known negative flatband voltage (VFB) shift, induced by rare-earth oxide capping in metal gate stacks, can be completely reversed in the absence of the silicon overlayer. Using TaN metal gates and Gd2O3-doped dielectric, we measure a ∼350 mV negative shift with the Si overlayer present and a ∼110 mV positive shift with the Si overlayer removed. This effect is correlated to a positive change in the average electrostatic potential at the TaN/dielectric interface which originates from an interfacial dipole. The dipole is created by the replacement of interfacial oxygen atoms in the HfO2 lattice with nitrogen atoms from TaN.

  5. 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

  6. 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.

  7. Durability of carbon-supported manganese oxide nanoparticles for the oxygen reduction reaction (ORR) in alkaline medium

    Czech Academy of Sciences Publication Activity Database

    Roche, I.; Chainet, E.; Chatenet, M.; Vondrák, Jiří

    2008-01-01

    Roč. 38, č. 9 (2008), s. 1195-1201 ISSN 0021-891X R&D Projects: GA AV ČR KJB4813302; GA ČR GA104/02/0731 Grant - others:CNRS(FR) 18105 Institutional research plan: CEZ:AV0Z40320502 Keywords : oxygen reduction reaction * rotating ring-disc electrode * carbon-supported manganese oxide Subject RIV: CA - Inorganic Chemistry Impact factor: 1.540, year: 2008

  8. Use of rare earth oxides as tracers to identify sediment source areas for agricultural hillslopes

    Science.gov (United States)

    Deasy, C.; Quinton, J. N.

    2010-11-01

    Understanding sediment sources is essential to enable more effective targeting of in-field mitigation approaches to reduce diffuse pollution from agricultural land. In this paper we report on the application of rare earth element oxides to arable soils at hillslope scale in order to determine sediment source areas and their relative importance, using a non-intrusive method of surface spraying. Runoff, sediments and rare earth elements lost from four arable hillslope lengths at a site in the UK with clay soils were monitored from three rainfall events after tracer application. Measured erosion rates were low, reflecting the typical event conditions occurring at the site, and less than 1% of the applied REO tracers were recovered, which is consistent with the results of comparable studies. Tracer recovery at the base of the hillslope was able to indicate the relative importance of different hillslope sediment source areas, which were found to be consistent between events. The principal source of eroded sediments was the upslope area, implying that the wheel tracks were principally conduits for sediment transport, and not highly active sites of erosion. Mitigation treatments for sediment losses from arable hillslopes should therefore focus on methodologies for trapping mobile sediments within wheel track areas through increasing surface roughness or reducing the connectivity of sediment transport processes.

  9. Copper(II catalysis for oxidation of l-tryptophan by hexacyanoferrate(III in alkaline medium: A kinetic and mechanistic approach

    Directory of Open Access Journals (Sweden)

    Basim H. Asghar

    2017-12-01

    Full Text Available The catalytic effect of copper(II catalyst on the oxidation of l-tryptophan (Trp by hexacyanoferrate(III (HCF, has been investigated spectrophotometrically in an aqueous alkaline medium at a constant ionic strength of 0.5 mol dm−3 and at 25 °C. The stoichiometry for both the uncatalyzed and catalyzed reactions was 1:2 (Trp:HCF. The reactions exhibited first order kinetics with respect to [HCF] and less than unit orders with respect to [Trp] and [OH−]. The catalyzed reaction exhibited fractional-first order kinetics with respect to [CuII]. The reaction rates were found to increase as the ionic strength and dielectric constant of the reaction medium increase. The effect of temperature on the rates of reactions has also been studied, and the activation parameters associated with the rate-determining steps of the reactions have been evaluated and discussed. Addition of the reaction product HCF(II to the reaction mixture did not affect the rates. Plausible mechanistic schemes for uncatalyzed and catalyzed reactions explaining all of the observed kinetic results have been proposed. In both cases, the final oxidation products are identified as indole-3-acetaldehyde, ammonia, and carbon dioxide. The rate laws associated with the reactions’ mechanisms are derived. The rate constants of the slow steps of the reactions along with the equilibrium constants are also calculated. Keywords: Oxidation, Kinetics, l-Tryptophan, Hexacyanoferrate(III, Copper(II, Catalysis

  10. Preparation and characterization of electrocatalysts based on palladium for electro-oxidation of alcohols in alkaline medium; Preparacao e caracterizacao de eletrocatalisadores a base de paladio para oxidacao eletroquimica de alcoois em meio alcalino

    Energy Technology Data Exchange (ETDEWEB)

    Brandalise, Michele

    2012-07-01

    In this study Pd/C, Au/C, PdAu/C, PdAuPt/C, PdAuBi/C and PdAuIr/C electrocatalysts were prepared by the sodium borohydride reduction method for the electrochemical oxidation of methanol, ethanol and ethylene glycol. This methodology consists in mix an alkaline solution of sodium borohydride to a mixture containing water/isopropyl alcohol, metallic precursors and the Vulcan XC 72 carbon support. The electrocatalysts were characterized by energy dispersive X-ray (EDX), X-ray diffraction (XRD), transmission electron microscopy (TEM) and cyclic voltammetry. The electrochemical oxidation of the alcohols was studied by chronoamperometry using a thin porous coating technique. The mechanism of ethanol electro-oxidation was studied by Fourier Transformed Infrared (FTIR) in situ. The most effective electrocatalysts were tested in alkaline single cells directly fed with methanol, ethanol or ethylene glycol. Preliminary studies showed that the most suitable atomic composition for preparing the ternary catalysts is 50:45:05. Electrochemical data in alkaline medium show that the electrocatalysts PdAuPt/C (50:45:05) showed the better activity for methanol electro oxidation, while PdAuIr/C was the most active for ethanol oxidation and PdAuBi/C (50:45:05) was the most effective for ethylene glycol oxidation in alkaline medium. These results show that the addition of gold in the composition of electrocatalysts increases their catalytic activities. The spectroelectrochemical FTIR in situ data permitted to conclude that C-C bond is not broken and the acetate is formed. (author)

  11. Bi-modified Pd/C catalyst via irreversible adsorption and its catalytic activity for ethanol oxidation in alkaline medium

    International Nuclear Information System (INIS)

    Cai, Jindi; Huang, Yiyin; Guo, Yonglang

    2013-01-01

    Highlights: • Pd-Bi/C catalysts were easily prepared by irreversible adsorption of Bi on Pd/C surface. • The adsorption of Bi increases the oxygen-containing species obviously on Pd-Bi/C surface. • Only a little amount of Bi on Pd-Bi/C can play a significant role in ethanol oxidation reaction (EOR). • Current density of EOR on Pd-Bi/C (20:1) is 2.4 times higher than that on Pd/C. • Anti-poisoning ability and durability of Pd-Bi/C (20:1) is greatly enhanced. -- Abstract: A facile approach to promote ethanol electro-oxidation on Pd-based catalysts is presented by the modification of Bi on Pd/C catalyst via irreversible adsorption. X-ray diffraction (XRD), transmission electron microscope (TEM) and X-ray photoelectron spectroscopy (XPS) measurements show that the modification of Bi has no significant effect on the Pd morphology and particle size distribution. Bi(III) and Pd(0) are the dominant forms in Pd-Bi/C catalyst. Electrochemical tests show that the modification of the appropriate amount of Bi on Pd/C catalyst can remarkably enhance activity toward ethanol oxidation reaction (EOR) up to about 2.4 times higher compared to Pd/C catalyst. The Pd-Bi/C (20:1) catalyst exhibits excellent stability and enhances CO tolerance. The enhanced electrochemical performance of Pd-Bi/C catalyst is attributed to the electronic effect and the bifunctional mechanism. The high exchange current density and the low apparent activation energy on Pd-Bi/C (20:1) catalyst reveal its faster kinetics and higher intrinsic activity compared to Pd/C catalyst

  12. Band edge electronic structure of transition metal/rare earth oxide dielectrics

    Science.gov (United States)

    Lucovsky, Gerald

    2006-10-01

    This article addresses band edge electronic structure of transition metal/rare earth (TM/RE) non-crystalline and nano-crystalline elemental and complex oxide high- k dielectrics for advanced semiconductor devices. Experimental approaches include X-ray absorption spectroscopy (XAS) from TM, RE and oxygen core states, photoconductivity (PC), and visible/vacuum ultra-violet (UV) spectroscopic ellipsometry (SE) combined with ab initio theory is applied to small clusters. These measurements are complemented by Fourier transform infra-red absorption (FTIR), X-ray photoelectron spectroscopy (XPS), high-resolution transmission electron microscopy (HRTEM) and X-ray diffraction (XRD). Two issues are highlighted: Jahn-Teller term splittings that remove d-state degeneracies of states at the bottom of the conduction band, and chemical phase separation and crystallinity in Zr and Hf silicates and ternary (Zr(Hf)O 2) x(Si 3N 4) y(SiO 2) 1- x- y alloys. Engineering solutions for optimization of both classes of high- k dielectric films, including limits imposed on the continued and ultimate scaling of the equivalent oxide thickness (EOT) are addressed.

  13. 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)

  14. Giant Cellular Vacuoles Induced by Rare Earth Oxide Nanoparticles are Abnormally Enlarged Endo/Lysosomes and Promote mTOR-Dependent TFEB Nucleus Translocation.

    Science.gov (United States)

    Lin, Jun; Shi, Shan-Shan; Zhang, Ji-Qian; Zhang, Yun-Jiao; Zhang, Li; Liu, Yun; Jin, Pei-Pei; Wei, Peng-Fei; Shi, Rong-Hua; Zhou, Wei; Wen, Long-Ping

    2016-11-01

    Many nanomaterials are reported to disrupt lysosomal function and homeostasis, but how cells sense and then respond to nanomaterial-elicited lysosome stress is poorly understood. Nucleus translocation of transcription factor EB (TFEB) plays critical roles in lysosome biogenesis following lysosome stress induced by starvation. The authors previously reported massive cellular vacuolization, along with autophagy induction, in cells treated with rare earth oxide (REO) nanoparticles. Here, the authors identify these giant cellular vacuoles as abnormally enlarged and alkalinized endo/lysosomes whose formation is dependent on macropinocytosis. This vacuolization causes deactivation of mammalian target of rapamycin (mTOR), a TFEB-interacting kinase that resides on the lysosome membrane. Subsequently, TFEB is dephosphorylated at serine 142 and translocated into cell nucleus. This nucleus translocation of TFEB is observed only in vacuolated cells and it is critical for maintaining lysosome homeostasis after REO nanoparticle treatment, as knock-down of TFEB gene significantly compromises lysosome function and enhances cell death in nanoparticle-treated cells. Our results reveal that cellular vacuolization, which is commonly observed in cells treated with REOs and other nanomaterials, represents a condition of profound lysosome stress, and cells sense and respond to this stress by facilitating mTOR-dependent TFEB nucleus translocation in an effort to restore lysosome homeostasis. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. Structural characterization of alkaline and oxidative stressed degradation products of lurasidone using LC/ESI/QTOF/MS/MS.

    Science.gov (United States)

    Talluri, M V N Kumar; Dharavath, Shireesha; Kalariya, Pradipbhai D; Prasanth, B; Srinivas, R

    2015-02-01

    A selective, accurate, precise and robust stability indicating liquid chromatography assay method was developed for the monitoring of a novel antipsychotic drug, lurasidone, in the presence of its degradation products (DPs). Also, we investigated degradation behavior of the drug under various stressed conditions such as hydrolytic (acidic, basic and neutral), oxidation, photolytic and thermal. The drug was found to be degraded under base hydrolytic and oxidative conditions, while it was stable in acid and neutral hydrolytic, photolytic and thermal conditions. The method showed adequate separation of lurasidone and its DPs on Xterra C18 (150 mm × 4.6 mm i.d., 3.5 μm) column using 20 mM ammonium formate (pH 3.0): acetonitrile as a mobile phase in gradient elution mode at a flow rate of 0.6 mL/min. This method was extended to liquid chromatography electrospray ionization quadrupole time-of-flight mass spectrometry (LC/ESI/QTOF/MS/MS) for structural characterization of DPs. A total of five DPs were characterized by LC/ESI/QTOF/MS/MS studies. Most probable mechanisms for the formation of DPs were proposed. The developed method was validated in terms of specificity, linearity, accuracy, precision, and robustness as per International Conference on Harmonization Guideline Q2 (R1). Copyright © 2014 Elsevier B.V. All rights reserved.

  16. Conditions for the formation of pure birnessite during the oxidation of Mn(II) cations in aqueous alkaline medium

    Energy Technology Data Exchange (ETDEWEB)

    Boumaiza, Hella [Laboratoire de Chimie des Matériaux et Catalyse, Faculté des Sciences de Tunis, Université El Manar (Tunisia); Laboratoire de Chimie Physique et Microbiologie pour l' Environnement (LCPME)-UMR 7564, CNRS-Université de Lorraine, 405, rue de Vandoeuvre, 54600 Villers-lès-Nancy (France); Département de Génie Biologique et Chimique, Institut National des Sciences Appliquées et de Technologies (INSAT), Université de Carthage, Tunis (Tunisia); Coustel, Romain [Laboratoire de Chimie Physique et Microbiologie pour l' Environnement (LCPME)-UMR 7564, CNRS-Université de Lorraine, 405, rue de Vandoeuvre, 54600 Villers-lès-Nancy (France); Medjahdi, Ghouti [Institut Jean Lamour, Centre de Compétences Rayons X et Spectroscopie (X-Gamma), UMR 7198 CNRS-Université de Lorraine (France); Ruby, Christian, E-mail: Christian.ruby@univ-lorraine.fr [Laboratoire de Chimie Physique et Microbiologie pour l' Environnement (LCPME)-UMR 7564, CNRS-Université de Lorraine, 405, rue de Vandoeuvre, 54600 Villers-lès-Nancy (France); and others

    2017-04-15

    Birnessite was synthetized through redox reaction by mixing MnO{sub 4}{sup -}, Mn{sup 2+} and OH{sup -} solutions. The Mn(VII): Mn(II) ratio of 0.33 was chosen and three methods were used consisting in a quick mixing under vigorous stirring of two of the three reagents and then on the dropwise addition of the third one. The obtained solids were characterized by XRD, FTIR and XPS spectroscopies. Their average oxidation states were determined from ICP and CEC measurements while their surface properties were investigated by XPS. This study provides an increased understanding of the importance of dissolved oxygen in the formation of birnessite and hausmannite and shows the ways to obtain pure birnessite. The role of counter-ion ie. Na{sup +} or K{sup +} was also examined. - Graphical abstract: Pathways of birnessite formation. - Highlights: • Pure birnessite is prepared through a redox reaction. • Hausmannite formation is prevented by controlling dissolved O2. • The employed counterion influences the purity of birnessite. • Initial Mn(OH){sub 2} is oxidized by both MnO{sub 4}{sup -} and dissolved O{sub 2}.

  17. Use of rare earth oxides and iron oxides as soil erosion tracers in water erosion experiments at hillslope scale

    Science.gov (United States)

    Guzmán, G.; Cañasveras, J. C.; Barrón, V.; Boulal, H.; Gómez, H.; Conde, E.; Fernández, M.; Gómez, J. A.

    2010-05-01

    The characteristics of the ideal soil erosion have been defined by several authors, for example by Zhang et al. (2001). Despite intensive research on erosion tracers in the last decades there is not a single tracer fulfilling all these characteristics. That is why research on different soil erosion tracers remains as an active field. Two desirable characteristics in erosion tracers are that they should be relatively inexpensive (to purchase and analyze) and that they should be determined with high accuracy in soil or sediment. The availability of multiple tracers is another of the key requirements. In this communication we present our preliminary results on the use of two different sets of erosion tracers. One set are iron oxides with different magnetic and optical properties (Fe3O4, α-Fe2O3 and FeOOH) analyzed by NIRS and magnetic susceptibility measurements. The other set consists of five rare earth oxides (La2O3, Pr6O11, Nd2O3, Sm2O3 and Gd2O3) analyzed using inductively coupled plasma mass spectrometry (ICP-MS). These two groups were studied under controlled and natural conditions, through several water erosion experiments, in field plots with different soil management, crops and scale. In one experiment these tracers were used to determine the source of sediment within sprinkle irrigated fields planted with cotton on shoulders. For this purpose, rainfall simulations were performed under controlled conditions at two scales, one with a portable rainfall simulator at small scale (0.81m2) and with the sprinkler irrigation system in the whole cotton field (2450 m2). Furrows were tagged with both groups of tracers, keeping shoulders untagged (where cotton was planted). Soil samples before and after the rainfall simulations were collected as well as sediment samples. In another experiment four olive orchard plots (330 m2) with different soil managements (cover crop and conventional tillage) were also tagged with the two groups of tracers. Soil samples were taken at

  18. 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.

  19. Micro-arc oxidization of a novel Mg–1Ca alloy in three alkaline KF electrolytes: Corrosion resistance and cytotoxicity

    Energy Technology Data Exchange (ETDEWEB)

    Jia, Z.J.; Li, M.; Liu, Q.; Xu, X.C. [Center for Biomedical Materials and Tissue Engineering, Academy for Advanced Interdisciplinary Studies, Peking University, Beijing 100871 (China); Cheng, Y., E-mail: chengyan@pku.edu.cn [Center for Biomedical Materials and Tissue Engineering, Academy for Advanced Interdisciplinary Studies, Peking University, Beijing 100871 (China); Zheng, Y.F. [Center for Biomedical Materials and Tissue Engineering, Academy for Advanced Interdisciplinary Studies, Peking University, Beijing 100871 (China); Department of Advanced Materials and Nanotechnology, College of Engineering, Peking University, Beijing 100871 (China); Xi, T.F. [Center for Biomedical Materials and Tissue Engineering, Academy for Advanced Interdisciplinary Studies, Peking University, Beijing 100871 (China); Wei, S.C. [Center for Biomedical Materials and Tissue Engineering, Academy for Advanced Interdisciplinary Studies, Peking University, Beijing 100871 (China); Department of Oral and Maxillofacial Surgery, School and Hospital of Stomatology, Peking University, Beijing 100871 (China)

    2014-02-15

    A newly-developed Mg–1Ca (wt%) alloy was treated by micro-arc oxidization (MAO) in KF-silicate- (Si coating), KF-phosphate- (P coating) and KF-silicate-phosphate (SiP coating) electrolytes. The microstructure, composition and corrosion resistance of the resultant MAO coatings were investigated using scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), and X-ray diffractometry (XRD). Electrochemical analysis and immersion test in Hanks’ solution and MTT assay for in-vitro toxicity against MG63 cells were subsequently carried out. Results showed that all the three MAO coatings contributed to the improvement of corrosion resistance and cytocompatibility of substrate; however, P coating outperformed the two others due to its specific microstructure and composition.

  20. Role of Ru(IlI) as an inhibitor in oxidation of lactose by (Cu(bipy)2)2+ in alkaline medium: spectrophotometric and kinetic studies

    International Nuclear Information System (INIS)

    Singh, Ashok Kumar; Singh, Manjula; Srivastava, Jaya; Rahmani, Shahla

    2013-01-01

    Kinetics of oxidation of lactose by (Cu(bipy) 2 ) 2+ in alkaline medium using Ru(III) as an inhibitor has been studied spectrophotometrically at 40 °C. The studies show that the rate of the reaction is zero order with respect to (Cu(bipy) 2 ) 2+ and first order with respect to (lactose). The order of reaction is found to be two at low concentrations of OH - (from 1.48×10 5 to 3.47×10 5 M) and less than two at its high concentrations (from 4.27×10 5 to 6.31×10 5 M). There is a substantial decrease in the pseudo-zero order rate constant with increase in the concentration of Ru(III) chloride, indicating the role of Ru(III) chloride as an inhibitor. Decrease in the rate with increase in dielectric constant of the medium is observed, while ionic strength of the medium and bipyridyl concentration has no influence on the rate. Based on kinetic data and spectrophotometric evidences, a suitable mechanism is proposed for the studied reaction. (author)

  1. Carbon quantum dots directly generated from electrochemical oxidation of graphite electrodes in alkaline alcohols and the applications for specific ferric ion detection and cell imaging.

    Science.gov (United States)

    Liu, Mengli; Xu, Yuanhong; Niu, Fushuang; Gooding, J Justin; Liu, Jingquan

    2016-04-25

    Carbon quantum dots (CQDs) are attracting tremendous interest owing to their low toxicity, water dispersibility, biocompatibility, optical properties and wide applicability. Herein, CQDs with an average diameter of (4.0 ± 0.2) nm and high crystallinity were produced simply from the electrochemical oxidation of a graphite electrode in alkaline alcohols. The as-formed CQDs dispersion was colourless but the dispersion gradually changed to bright yellow when stored in ambient conditions. Based on UV-Vis absorption, fluorescence spectroscopy, X-ray photoelectron spectroscopy (XPS), Fourier transform infrared spectroscopy (FTIR) and high-resolution transmission electron microscopy (HRTEM), this colour change appeared to be due to oxygenation of surface species over time. Furthermore, the CQDs were used in specific and sensitive detection of ferric ion (Fe(3+)) with broad linear ranges of 10-200 μM with a low limit of detection of 1.8 μM (S/N = 3). The application of the CQDs for Fe(3+) detection in tap water was demonstrated and the possible mechanism was also discussed. Finally, based on their good characteristics of low cytotoxicity and excellent biocompatibility, the CQDs were successfully applied to cell imaging.

  2. Two 3D structured Co-Ni bimetallic oxides as cathode catalysts for high-performance alkaline direct methanol fuel cells

    Science.gov (United States)

    Liu, Yan; Shu, Chengyong; Fang, Yuan; Chen, Yuanzhen; Liu, Yongning

    2017-09-01

    Two NiCo2O4 bimetallic oxides were synthesized via a facile hydrothermal method. SEM and TEM observations show that these materials have three-dimensional (3D) dandelion-like (DL) and flower-like (FL) morphologies. Their large specific surface areas (90.68 and 19.8 m2·g-1) and porous structures provide many active sites and effective transport pathways for the oxygen reduction reaction (ORR). Electrochemical measurements with a rotating ring-disc electrode (RRDE) indicate that the electron transfer numbers of the NiCo2O4-DL and NiCo2O4-FL catalysts for ORR in an alkaline solution are 3.97 and 3.91, respectively. Fuel cells were assembled with the bimetallic oxides, PtRu/C and a polymer fiber membrane (PFM) as cathode catalysts, anode catalyst and electrolyte film, respectively. For NiCo2O4-DL, the peak power density reaches up to 73.5 mW·cm-2 at 26 °C, which is the highest room-temperature value reported to date. The high catalytic activity of NiCo2O4 is mainly attributed to the presence of many Co3+ cations that directly donate electrons to O2 to reduce it via a more efficient and effective route. Furthermore, the catalytic performance of NiCo2O4-DL is superior to that of NiCo2O4-FL because it has a higher specific surface area and is less crystalline.

  3. Electro-oxidation of methanol in alkaline conditions using Pd–Ni nanoparticles prepared from organometallic precursors and supported on carbon vulcan

    Energy Technology Data Exchange (ETDEWEB)

    Manzo-Robledo, A., E-mail: amanzor@ipn.mx [UPALM, Laboratorio de Electroquímica y Corrosión, Escuela Superior de Ingeniería Química e Industrias Extractivas-IPN (Mexico); Costa, Natália J. S. [Universidade de São Paulo, Instituto de Química (Brazil); Philippot, K. [CNRS, LCC, Laboratoire de Chimie de Coordination (France); Rossi, Liane M. [Universidade de São Paulo, Instituto de Química (Brazil); Ramírez-Meneses, E. [Universidad Iberoamericana, Departamento de Ingeniería y Ciencias Químicas (Mexico); Guerrero-Ortega, L. P. A. [UPALM, Laboratorio de Electroquímica y Corrosión, Escuela Superior de Ingeniería Química e Industrias Extractivas-IPN (Mexico); Ezquerra-Quiroga, S. [Universidad Iberoamericana, Departamento de Ingeniería y Ciencias Químicas (Mexico)

    2015-12-15

    Oxidation of low-molecular weight alcohols as energy sources using metal nanoparticles has attracted considerable interest for use as a power source in portable electronic devices. In this work, a series of mono- and bimetallic nanoparticles based on palladium and nickel (Pd, Pd{sub 90}Ni{sub 10}, Pd{sub 50}Ni{sub 50}, Pd{sub 10}Ni{sub 90}, and Ni) have been synthesized from organometallic precursors, namely tris(dibenzylideneacetone) dipalladium(0), Pd{sub 2}(dba){sub 3}, and bis(1,5-cyclooctadiene)nickel(0), Ni(cod){sub 2}. Well-defined metal particles in the nanometric scale from 4.2 to 6.3 nm were observed by transmission electron microscopy. The as-prepared nanoparticles were mixed with a carbon Vulcan matrix (10 % wt. of the catalyst in turn) for investigation as electrocatalysts in methanol oxidation reaction (MOR) in alkaline conditions. The i–E profiles from cyclic voltammetry for the monometallic systems indicated a redox process attributed only to palladium or nickel, as expected. With the bimetallic nanomaterials, the redox process and the i–E characteristics are functions of the amount of nickel associated to palladium. From a fundamental point of view, it has been established that the OH ions’ interfacial interaction and the MOR kinetics are affected by the presence of nickel (decreasing the faradic current) as supported by the current versus potential profiles obtained as a function of methanol concentration and with temperature variation.

  4. Characterization of potassic materials of Pocos de Caldas alkaline massif, Southeastern Brazil

    International Nuclear Information System (INIS)

    Goncalves, P.; Navarro, F.C.; Roveri, C.D.; Bergerman, M.G.

    2016-01-01

    Potassium, which has featured in Brazil's agricultural sector and in the world's in the application of fertilizers, is present in magmatic rocks, such as nepheline syenite and phonolite, found in the Alkaline Massif of Pocos de Caldas (AMPC). The rare earth elements (REE), in turn, also occur in this region and have important uses in various industrial fields. The aim of this study was to investigate the potential of potassic rocks of AMPC in the fertilizer and rare earths industry. Five samples were collected and characterized. It was observed that there was no preferential concentration by granulometric range of potassium oxide, alumina, silica and iron oxide. Feldspathic mass, potash feldspar, and muscovite were found in all samples. The samples show REE with amounts greater than those found in the earth's crust, except for lutetium and scandium and possessed average content of potassium oxide from 8.70 to 14.40%. (author)

  5. Aerosol synthesis and electrochemical analysis of niobium mixed-metal oxides for the ethanol oxidation reaction in acid and alkaline electrolyte

    Science.gov (United States)

    Konopka, Daniel A.

    Direct ethanol fuel cells are especially important among emerging electrochemical power systems with the potential to offset a great deal of the energy demand currently met through the use of fossil fuels. Ethanol can be refined from petroleum sources or attained from renewable biomass, and is more easily and safely stored and transported than hydrogen, methanol or gasoline. The full energy potential of ethanol in fuel cells can only be realized if the reaction follows a total oxidation pathway to produce CO2. This must be achieved by the development of advanced catalysts that are electrically conductive, stable in corrosive environments, contain a high surface area on which the reaction can occur, and exhibit a bi-functional effect for the ethanol oxidation reaction (EOR). The latter criterion is achievable in mixed-metal systems. Platinum is an effective metal for catalyzing surface reactions of many adsorbates and is usually implemented in the form of Pt nanoparticles supported on inexpensive carbon. This carbon is believed to be neutral in the catalysis of Pt. Instead, carbon can be replaced with carefully designed metals and metal oxides as co-catalysis or support structures that favorably alter the electronic structure of Pt slightly through a strong metal support interaction, while also acting as an oxygen source near adsorbates to facilitate the total oxidation pathway. Niobium mixed-metal-oxides were explored in this study as bi-functional catalyst supports to Pt nanoparticles. We developed a thermal aerosol synthesis process by which mesoporous powders of mixed-metal-oxides decorated with Pt nanoparticles could be obtained from liquid precursors within ˜5 seconds or less, followed by carefully refined chemical and thermal post-treatments. Exceptionally high surface areas of 170--180m2/g were achieved via a surfactant-templated 3D wormhole-type porosity, comparable on a per volume basis to commercial carbon blacks and high surface area silica supports

  6. 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

  7. Preparation and characterization of Pt Sn / C-rare earth and PtRu / C-rare earth using an alcohol reduction process for ethanol electron-oxidation

    International Nuclear Information System (INIS)

    Rodrigues, Rita Maria de Sousa

    2011-01-01

    The electro catalyst PtRu / C-rare earth and PtSn/C-rare earth (20 wt%) were prepared by alcohol reduction method using H 2 PtCl 6 .6H 2 O Ru Cl xH 2 O, SnCl 2 .2H 2 O as a source of metals 85 % Vulcan - 15 % rare earth as a support and, finally, ethylene glycol as reducing agent. The electrocatalysts were characterized physically by X-ray diffraction (XRD), energy dispersive X-ray (EDX), and transmission electron microscopy (TEM). Analyses by EDX showed that the atomic ratios of different electrocatalysts, prepared by alcohol reduction method are similar to the nominal starting compositions indicating that this methodology is promising for the preparation of electrocatalysts. In all the XRD patterns for the prepared electrocatalysts there is a broad peak at about 2θ = 25 o , which is associated with the carbon support and four additional diffraction peaks at approximately 2θ = 40 o , 47 o , 67 o e 82 o , which in turn are associated with the plans (111), (200), (220) e (311), respectively, of face-centered cubic structure (FCC) platinum. The results of X-ray diffraction also showed average crystallite sizes between 2.0 and 4.0 nm for PtSn e 2,0 a 3,0 para PtRu. The studies for the electrochemical oxidation of ethanol in acid medium were carried out using the technique of chronoamperometry in a solution 0,5 mol.L-1 H 2 SO 4 , + 1,0 mol.L-1 de C 2 H 5 OH. The polarization curves obtained in the fuel cell unit, powered directly by ethanol, are in agreement with the results of voltammetry and chronoamperometry noting the beneficial effect of rare earths in the preparation of electrocatalysts and attesting that the electrocatalysts PtSn/C are more effective than PtRu/C for the oxidation of ethanol.

  8. Biodiesel production using alkali earth metal oxides catalysts synthesized by sol-gel method

    Directory of Open Access Journals (Sweden)

    Majid Mohadesi

    2014-03-01

    Full Text Available Biodiesel fuel is considered as an alternative to diesel fuel. This fuel is produced through transesterification reactions of vegetable oils or animal fat by alcohols in the presence of different catalysts. Recent studies on this process have shown that, basic heterogeneous catalysts have a higher performance than other catalysts. In this study different alkali earth metal oxides (CaO, MgO and BaO doped SiO2 were used as catalyst for the biodiesel production process. These catalysts were synthesis by using the sol-gel method. A transesterification reaction was studied after 8h by mixing corn oil, methanol (methanol to oil molar ratio of 16:1, and 6 wt. % catalyst (based on oil at 60oC and 600rpm. Catalyst loading was studied for different catalysts ranging in amounts from 40, 60 to 80%. The purity and yield of the produced biodiesel for 60% CaO/SiO2 was higher than other catalysts and at 97.3% and 82.1%, respectively.

  9. Nanocomposites of graphene oxide and upconversion rare-earth nanocrystals with superior optical limiting performance

    KAUST Repository

    Wei, Wei

    2012-04-20

    Upconversion rare-earth nanomaterials (URENs) possess highly efficient near-infrared (NIR), e.g., 980 nm, laser absorption and unique energy upconversion capabilities. On the other hand, graphene and its derivatives, such as graphene oxide (GO), show excellent performance in optical limiting (OL); however, the wavelengths of currently used lasers for OL studies mainly focus on either 532 or 1064 nm. To design new-generation OL materials working at other optical regions, such as the NIR, a novel nanocomposites, GO-URENs, which combines the advantages of both its components, is synthesized by a one-step chemical reaction. Transmission electron microscopy, X-ray diffraction, infrared spectroscopy, and fluorescence studies prove that the α-phase URENs uniformly attach on the GO surface via covalent chemical bonding, which assures highly efficient energy transfer between URENs and GO, and also accounts for the significantly improved OL performance compared to either GO or URENs. The superior OL effect is also observed in the proof-of-concept thin-film product, suggesting immediate applications in making high-performance laser-protecting products and optoelectronic devices. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. Effects of rare earth oxide additive on surface and tribological properties of polyimide composites

    Science.gov (United States)

    Pan, Zihe; Wang, Tianchang; Chen, Li; Idziak, Stefan; Huang, Zhaohui; Zhao, Boxin

    2017-09-01

    Rare earth oxide La2O3 microparticles-reinforced polyimide (PI) composites (La-PI-Cs) were fabricated, aiming to improve the tribological property of PI. Surface roughness, surface composition, bulk structure, friction force (Ff) and coefficient of friction (COF) at macro/micro preload, and anti-wear performances of La-PI-Cs were studied and compared with neat PI. With La2O3 microparticles, La-PI-Cs showed larger surface roughness, lower surface energy, and higher hydrophobicity than neat PI, and displayed beneficial layered structure different from the compact structure of PI. Owing to these advantages, La-PI-Cs were found to show a 70% reduction in Ff and COF, and a 30% reduction in wear rate, indicating significantly lowered friction and enhanced anti-wear properties after adding La2O3 microparticles. Our research findings demonstrated an easy and low cost method to fabricate polymer composites with low friction and high wear resistance, and help meet the demanding of polymer composites with high tribological performances in broaden applications.

  11. Rare earth doped optical fiber fabrication by standard and sol-gel derived granulated oxides

    Science.gov (United States)

    Etissa, D.; Neff, M.; Pilz, S.; Ryser, M.; Romano, V.

    2012-04-01

    We present our progress in the production of ytterbium (Yb) doped optical fibers fabricated by two variants of the granulated aluminophosphosilicate method. We show advantages and disadvantages of mixing rare earth and aluminophosphosilicate granulated oxides directly (variant 1) or by using the sol-gel method to produce doped granulate material (variant 2). For both methods we studied the effects of varying the dopant concentrations and of introducing iterative melting and milling procedures. In particular, the sol-gel based method eases the inclusion of P2O5 and thus, in combination with Al2O3, higher dopant concentration of Yb and Er are possible. Sintering the sol-gel material at high temperature eliminated bubbles in the core. We fabricated optical fibers that, piecewise, between individual strong scatterers, exhibited attenuation losses as low as 0.35dB/m. For our comparative study we determined volume percentage and distribution of chemical elements in the fabricated fiber glasses by the analytical technique of Energy-Dispersive X-ray, Electro Probe Microanalysis and the degree of crystallization by X-Ray Diffraction analysis. Furthermore we measured fluctuations of the refractive index profile and scattering losses of the fiber core.

  12. Characteristics of the behavior of rare-earth oxides and composites on their base by charged particles and neutrons irradiated

    International Nuclear Information System (INIS)

    Tuseev, T.; Aksenova, T.I.; Berdauletov, A.K.

    2000-01-01

    In this work the results of comparative investigation of adsorption curves versus REM order number (La, Ce, Nd, Pr, Gd) and dose neutron irradiation are presented. It is discovered that the original REM oxides have high adsorption capacity both for donor gases and for acceptor ones. The adsorption capacity for oxygen and hydrogen becomes lower when the REM order number is higher, but it is contrary for water molecules. The obtained results showed that adsorption properties of REM oxides were changing on identical laws. But oxides of metals, having anomalous properties (variable valency, high cross-section capture) revealed especial adsorption properties under irradiation. In the time of consideration of possible mechanism of radiation - stimulated gas adsorption on oxide surface it is necessary to take in attention both the formation of radiation defects in crystal lattice and the characteristics of electron structure and presence of 4 f - cover in rare-earth metals

  13. Degradation of amaranth dye in alkaline medium by ultrasonic cavitation coupled with electrochemical oxidation using a boron-doped diamond anode

    International Nuclear Information System (INIS)

    Barros, Willyam R.P.; Steter, Juliana R.; Lanza, Marcos R.V.; Motheo, Artur J.

    2014-01-01

    Amaranth dye is used widely in the processing of paper, textiles, foods, cosmetics, beverages and medicines, and effluents contaminated with this compound are discharged daily into the environment. Recent studies have shown that azo dyes, especially those such as amaranth dye that have been classified as endocrine disruptors, may cause adverse effects to animal and human health. This paper describes the application of electrochemical oxidation (with a boron-doped diamond BDD thin-film anode) coupled with ultrasound sonolysis (20 kHz and 523 W cm −2 ) to the removal of amaranth dye from dilute alkaline solution. The electrochemical and sonoelectrochemical processes (ECh and SECh, respectively) were carried out at constant current density (10 to 50 mA cm −2 ) in a single compartment cylindrical cell. Sonolysis was virtually less useful for the decolorization and degradation of amaranth dye, whilst ECh and SECh were more effective in degrading the dye with almost complete removal (90 - 95%) attained after 90 min of experiment at an applied current density of 50 mA cm −2 . Degradation of the dye followed pseudo first-order kinetics in both processes, but the rate of reaction was faster with the SECh treatment confirming a synergistic effect between the cavitation process and the electrochemical system. Additionally, at low applied current densities (10 and 25 mA cm −2 ), SECh was considerably more effective than ECh for the amaranth dye mineralization. Although at 35 and 50 mA cm −2 , the two processes showed the respective removal of total organic carbon values: (i) 85% for the ECh and 90% for the SECh at 35 mA cm −2 ; (ii) 96% for the ECh and 98% for the SECh at 50 mA cm −2 . It is concluded that SECh presented the most favorable results for the decontamination of wastewaters containing azo dye compounds

  14. Composite catalyst for carbon monoxide and hydrocarbon oxidation

    Science.gov (United States)

    Liu, Wei; Flytzani-Stephanopoulos, Maria

    1996-01-01

    A method and composition for the complete oxidation of carbon monoxide and/or hydrocarbon compounds. The method involves reacting the carbon monoxide and/or hydrocarbons with an oxidizing agent in the presence of a metal oxide composite catalyst. The catalyst is prepared by combining fluorite-type oxygen ion conductors with active transition metals. The fluorite oxide, selected from the group consisting of cerium oxide, zirconium oxide, thorium oxide, hafnium oxide, and uranium oxide, and may be doped by alkaline earth and rare earth oxides. The transition metals, selected from the group consisting of molybdnum, copper, cobalt, maganese, nickel, and silver, are used as additives. The atomic ratio of transition metal to fluorite oxide is less than one.

  15. Chlorination of UO2, PuO2, and rare-earth oxides using ZrCl4

    International Nuclear Information System (INIS)

    Sakamura, Yoshiharu; Inoue, Tadashi; Iwai, Takashi; Moriyama, Hirotake

    2001-01-01

    A new chlorination method using ZrCl 4 , which has a high reactivity with oxygen, has been investigated for more efficient oxide treatment. After actinide oxides are chlorinated and dissolved in a molten salt bath, actinide metals can be selectively collected using the electrorefining process. This process is well suited for pyrochemical reprocessing of metallic fuels. In LiCl-KCI eutectic melts, rare-earth oxides (Y 2 O 3 , La 2 O 3 , CeO 2 , and Nd 2 O 3 ) and actinide oxides (UO 2 and PuO 2 ) were chlorinated by adding ZrCl 4 . As a result, rare-earth and actinide elements were dissolved into the salt as trivalent ions and ZrO 2 was precipitated. When an excess of ZrCI 4 was added, oxides in powder form were completely chlorinated in five hours. It was demonstrated that the ZrCI 4 chlorination method, free from corrosive gas such as chlorine, was very simple and useful. (author)

  16. Design of Higher-k and More Stable Rare Earth Oxides as Gate Dielectrics for Advanced CMOS Devices

    Directory of Open Access Journals (Sweden)

    Yi Zhao

    2012-08-01

    Full Text Available High permittivity (k gate dielectric films are widely studied to substitute SiO2 as gate oxides to suppress the unacceptable gate leakage current when the traditional SiO2 gate oxide becomes ultrathin. For high-k gate oxides, several material properties are dominantly important. The first one, undoubtedly, is permittivity. It has been well studied by many groups in terms of how to obtain a higher permittivity for popular high-k oxides, like HfO2 and La2O3. The second one is crystallization behavior. Although it’s still under the debate whether an amorphous film is definitely better than ploy-crystallized oxide film as a gate oxide upon considering the crystal boundaries induced leakage current, the crystallization behavior should be well understood for a high-k gate oxide because it could also, to some degree, determine the permittivity of the high-k oxide. Finally, some high-k gate oxides, especially rare earth oxides (like La2O3, are not stable in air and very hygroscopic, forming hydroxide. This topic has been well investigated in over the years and significant progresses have been achieved. In this paper, I will intensively review the most recent progresses of the experimental and theoretical studies for preparing higher-k and more stable, in terms of hygroscopic tolerance and crystallization behavior, Hf- and La-based ternary high-k gate oxides.

  17. Fe-oxide mineralogy of the Jiujiang red earth sediments and implications for Quaternary climate change, southern China.

    Science.gov (United States)

    Yin, Ke; Hong, Hanlie; Algeo, Thomas J; Churchman, Gordon Jock; Li, Zhaohui; Zhu, Zongmin; Fang, Qian; Zhao, Lulu; Wang, Chaowen; Ji, Kaipeng; Lei, Weidong; Duan, Zhenggang

    2018-02-26

    Diffuse reflectance spectrophotometry (DRS) is a new, fast, and reliable method to characterize Fe-oxides in soils. The Fe-oxide mineralogy of the Jiujiang red earth sediments was investigated using DRS to investigate the climate evolution of southern China since the mid-Pleistocene. The DRS results show that hematite/(hematite + goethite) ratios [Hm/(Hm + Gt)] exhibit an upward decreasing trend within the Jiujiang section, suggesting a gradual climate change from warm and humid in the middle Pleistocene to cooler and drier in the late Pleistocene. Upsection trends toward higher (orthoclase + plagioclase)/quartz ratios [(Or + Pl)/Q] and magnetic susceptibility values (χ lf ) support this inference, which accords with global climate trends at that time. However, higher-frequency climatic subcycles observed in loess sections of northern China are not evident in the Jiujiang records, indicating a relatively lower climate sensitivity of the red earth sediments in southern China.

  18. Surface interactions with compartmentalized cellular phosphates explain rare earth oxide nanoparticle hazard and provide opportunities for safer design.

    Science.gov (United States)

    Li, Ruibin; Ji, Zhaoxia; Chang, Chong Hyun; Dunphy, Darren R; Cai, Xiaoming; Meng, Huan; Zhang, Haiyuan; Sun, Bingbing; Wang, Xiang; Dong, Juyao; Lin, Sijie; Wang, Meiying; Liao, Yu-Pei; Brinker, C Jeffrey; Nel, Andre; Xia, Tian

    2014-02-25

    Growing international exploitation of rare earth oxides (REOs) for commercial and biological use has increased the possibility of human exposure and adverse health effects. Occupational exposure to rare earth materials in miners and polishers leads to a severe form of pneumoconiosis, while gadolinium-containing MRI contrast agents cause nephrogenic systemic fibrosis in patients with renal impairment. The mechanisms for inducing these adverse pro-fibrogenic effects are of considerable importance for the safety assessment of REO particles as well as presenting opportunities for safer design. In this study, using a well-prepared REO library, we obtained a mechanistic understanding of how REOs induce cellular and pulmonary damage by a compartmentalized intracellular biotransformation process in lysosomes that results in pro-fibrogenic growth factor production and lung fibrosis. We demonstrate that rare earth oxide ion shedding in acidifying macrophage lysosomes leads to biotic phosphate complexation that results in organelle damage due to stripping of phosphates from the surrounding lipid bilayer. This results in nanoparticle biotransformation into urchin shaped structures and setting in motion a series of events that trigger NLRP3 inflammasome activation, IL-1β release, TGF-β1 and PDGF-AA production. However, pretreatment of REO nanoparticles with phosphate in a neutral pH environment prevents biological transformation and pro-fibrogenic effects. This can be used as a safer design principle for producing rare earth nanoparticles for biological use.

  19. Low-Temperature Oxidation Reactions and Cool Flames at Earth and Reduced Gravity

    Science.gov (United States)

    Pearlman, Howard

    1999-01-01

    Non-isothermal studies of cool flames and low temperature oxidation reactions in unstirred closed vessels are complicated by the perturbing effects of natural convection at earth gravity. Buoyant convection due to self-heating during the course of slow reaction produces spatio-temporal variations in the thermal and thus specie concentration fields due to the Arrhenius temperature dependence of the reaction rates. Such complexities have never been quantitatively modeled and were the primary impetus for the development of CSTR's (continuously stirred tank reactors) 30 years ago. While CSTR's have been widely adopted since they offer the advantage of spatial uniformity in temperature and concentration, all gradients are necessarily destroyed along with any structure that may otherwise develop. Microgravity offers a unique environment where buoyant convection can be effectively minimized and the need for stirring eliminated. Moreover, eliminating buoyancy and the need for stirring eliminates complications associated with the induced hydrodynamic field whose influence on heat transport and hot spot formation, hence explosion limits, is not fully realized. The objective of this research is to quantitatively determine and understand the fundamental mechanisms that control the onset and evolution of low temperature reactions and cool flames in both static and flow reactors. Microgravity experiments will be conducted to obtain benchmark data on the structure (spatio-temporal temperature, concentration, flow fields), the dynamics of the chemical fronts, and the ignition diagrams (pressure vs. temperature). Ground-based experiments will be conducted to ascertain the role of buoyancy. Numerical simulations including detailed kinetics will be conducted and compared to experiment.

  20. Solution-Processed Rare-Earth Oxide Thin Films for Alternative Gate Dielectric Application.

    Science.gov (United States)

    Zhuang, Jiaqing; Sun, Qi-Jun; Zhou, Ye; Han, Su-Ting; Zhou, Li; Yan, Yan; Peng, Haiyan; Venkatesh, Shishir; Wu, Wei; Li, Robert K Y; Roy, V A L

    2016-11-16

    Previous investigations on rare-earth oxides (REOs) reveal their high possibility as dielectric films in electronic devices, while complicated physical methods impede their developments and applications. Herein, we report a facile route to fabricate 16 REOs thin insulating films through a general solution process and their applications in low-voltage thin-film transistors as dielectrics. The formation and properties of REOs thin films are analyzed by atomic force microscopy (AFM), X-ray diffraction (XRD), spectroscopic ellipsometry, water contact angle measurement, X-ray photoemission spectroscopy (XPS), and electrical characterizations, respectively. Ultrasmooth, amorphous, and hydrophilic REO films with thickness around 10 nm have been obtained through a combined spin-coating and postannealing method. The compositional analysis results reveal the formation of RE hydrocarbonates on the surface and silicates at the interface of REOs films annealed on Si substrate. The dielectric properties of REO films are investigated by characterizing capacitors with a Si/Ln 2 O 3 /Au (Ln = La, Gd, and Er) structure. The observed low leakage current densities and large areal capacitances indicate these REO films can be employed as alternative gate dielectrics in transistors. Thus, we have successfully fabricated a series of low-voltage organic thin-film transistors based on such sol-gel derived REO films to demonstrate their application in electronics. The optimization of REOs dielectrics in transistors through further surface modification has also been studied. The current study provides a simple solution process approach to fabricate varieties of REOs insulating films, and the results reveal their promising applications as alternative gate dielectrics in thin-film transistors.

  1. 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

  2. Oxidation state of the Earth's upper mantle during the last 3800 million years: Implications for the origin of life

    Science.gov (United States)

    Delano, J. W.

    1993-01-01

    A popular, as well as scientifically rigorous, scenario for the origin of life on Earth involves the production of organic molecules by interaction of lightning (or other forms of energy) with a chemically reducing atmosphere in the early history of Earth. Experiments since the 1950's have convincingly demonstrated that the yield of organic molecules is high when the atmosphere contains molecular hydrogen, methane, ammonia, and water vapor. Additional work has also shown that such a highly reducing atmosphere might not, however, have been sufficiently long-lived in the presence of intense solar ultraviolet radiation for life to have formed from it. One way of maintaining such an atmosphere would be to have a continual replenishment of the reduced gases by prolonged volcanic outgassing from a reducing of Earth's interior. The length of time that this replenishment might need to continue is in part constrained by the flux of asteroids onto the Earth's surface containing sufficient energy to destroy most, if not all, life that had developed up to that point in time. If a reducing atmosphere is a key ingredient for the origin of life on Earth, the time of the last environmental sterilization due to large impacts would be an important constraint. In a deep marine setting (e.g., hydrothermal vent), the last global sterilization might have occurred at 4200-4000 Ma. On the Earth's surface, the last global sterilization event might have occurred at 4000-3700 Ma. If these are meaningful constraints, how likely is it that a reducing atmosphere could have survived on the Earth until about 3800 Ma ago? Due to the importance of replenishing this atmosphere with reducing components by volcanic outgassing from the mantle, geochemical information on the history of the mantle's oxidation state would be useful for addressing this question. Geochemical and experimental data discussed in this abstract suggest that extrusive mafic volcanics derived from the upper mantle have had

  3. 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.

  4. 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.

  5. 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.

  6. 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.

  7. 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).

  8. 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.

  9. 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.)

  10. Synthesis of CoO/Reduced Graphene Oxide Composite as an Alternative Additive for the Nickel Electrode in Alkaline Secondary Batteries

    International Nuclear Information System (INIS)

    Fu, Gaoliang; Chang, Kun; Shangguan, Enbo; Tang, Hongwei; Li, Bao; Chang, Zhaorong; Yuan, Xiao-Zi; Wang, Haijiang

    2015-01-01

    Highlights: • CoO/RGO nanosheets with sandwiched structures were synthesized by hydrothermal method. • CoO/RGO composite can be as a good additive for Ni-MH battery. • Using CoO/RGO as the additive can greatly reduce the utilization of CoO in the commercial battery. • Particularly, the high rate capability of the electrode was enhanced significantly. - Abstract: A series of CoO/reduced graphene oxide (CoO/RGO) composites with different proportions are successfully synthesized via a hydrothermal method. As an additive for the nickel-based alkaline secondary battery cathode, the electrochemical performances of the proposed CoO/RGO composite are systematically investigated on its cyclic stability, rate capability, capacity recovery performance, cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS), in comparison with commercial CoO. Scanning Electron Microscopy (SEM) and Transmission Electron Microscopy (TEM) images show that the CoO nanoparticles are in-situ anchored on the surface of soft and flexible graphene sheets. Electrochemical results indicate that the CoO/RGO composites exhibite the highest performance when the weight ratio of CoO and RGO is 5:5. The optimized CoO/RGO composites as an additive for the nickel electrode not only can substantially reduce the CoO additive but also possess good electrochemical performances, especially for the high-rate capability. The discharge capacity of the nickel electrode with 5 wt% of CoO/RGO (5:5) addition deliver a high discharge capacity of 284.3, 264.6,235.4 and 208.6 mAh g −1 at 0.2, 1.0, 5.0 and 10.0 C, respectively. The capacity recovery rate at 0.2 C can reach 98.4%. CV and EIS test indicate that the incorporation of RGO can significantly enhance the reversible property, current density of cathodic peak, proton diffusion and conductivity of the nickel electrode.

  11. Synthesis and characterization of rare-earth oxide transition-metal arsenides and selenides

    Energy Technology Data Exchange (ETDEWEB)

    Peschke, Simon Friedrich

    2017-04-06

    The present thesis includes two different quaternary systems that have been studied extensively. On the one hand, several samples of the REFeAsO{sub 1-x}F{sub x} family of iron-based superconductors were prepared using a novel solid state metathesis reaction, which also provided a possibility to prepare late rare-earth compounds of this family at ambient pressure. Comparison of structural and physical properties of those samples with samples from conventional solid state and high pressure syntheses revealed both, commonalities as well as striking differences. The observations gave reason to the conclusion that superconducting properties strongly depend, beside electronic infl uence, on the structural parameters. On the other hand, the quaternary system RE-T-Se-O with T = Ti-Mn was investigated using a NaI/KI flux mediated synthesis route. It has been shown that oC -La{sub 2}O{sub 2}MnSe{sub 2} is exclusively accessible in su fficient purity by the use of a fl ux material. Therefore, further syntheses in this quaternary system were performed by a flux mediated synthesis route leading to a large amount of new materials. Among them, a new polymorph mC-La{sub 2}O{sub 2}MnSe{sub 2} which forms, together with La{sub 4}MnSe{sub 3}O{sub 4} and La{sub 6}MnSe{sub 4}O{sub 6}, the series La{sub 2n+2}MnSe{sub n+2}O{sub 2n+2}. In addition, the alternative preparation method also enabled a large scale synthesis of the first examples of rare-earth chromium oxyselenides with chromium in the oxidation state +II, namely RE{sub 2}CrSe{sub 2}O{sub 2} (RE = La-Nd), which opened the door to study their magnetism in detail by powder neutron diffraction and muon spin rotation techniques. Research into the La-V-Se-O system revealed the first fi ve quaternary compounds of this family with interesting magnetic properties including ferromagnetism, antiferromagnetism, metamagnetism and more complex behaviour. In addition, the crystal structure of two new quaternary titanium containing

  12. Pyro-Electrochemical Reduction of a Mixture of Rare Earth Oxides and NiO in LiCl molten Salt

    Energy Technology Data Exchange (ETDEWEB)

    Lee, Min Woo; Jeong, Sang Mun [Department of Chemical Engineering, Chungbuk National University, Cheongju (Korea, Republic of)

    2017-06-15

    An electrochemical reduction of a mixture of NiO and rare earth oxides has been conducted to increase the reduction degree of rare earth oxides. Cyclic voltammetry (CV) measurement was carried out to determine the electrochemical reduction behavior of the mixed oxide in molten LiCl medium. Constant voltage electrolysis was performed with various supplied charges to understand the mechanism of electrochemical reduction of the mixed oxide as a working electrode. After completion of the electrochemical reduction, crystal structure of the reaction intermediates was characterized by using an X-ray diffraction method. The results clearly demonstrate that the rare earth oxide was converted to RE-Ni intermetallics via co-reduction with NiO.

  13. Novel precursors for the deposition of rare earth oxides; Neuartige Precursor zur Abscheidung von Selten-Erd-Oxiden

    Energy Technology Data Exchange (ETDEWEB)

    Ahlers, Mareike

    2010-02-22

    During this work rare earth solvates with nitrate and perchlorate anions have been investigated. All compounds have been structurally characterized and analyzed using thermal gravimetric analysis. The decomposition residues were analyzed using powder diffraction methods. Almost all compounds showed a characteristically intense exothermic decomposition step during the thermal decomposition, most likely caused by an intramolecular redox reaction between the nitrate or perchlorate anion respectively and the organic solvent molecules. The nitrates RE(NO{sub 3}){sub 3}(CH(OCH{sub 3}){sub 3}){sub 2} (RE = Sm, Eu) were isolated and characterized for the first time as the intermediate of the dehydration reaction with trimethyl orthoformate. The known compound group of dimethoxyethane solvates was then expanded with RE(NO{sub 3}){sub 3}(O{sub 2}C{sub 4}H{sub 10}) (RE = La, Sm, Eu). Considering the possible use as precursor material the already described neodymium compound is also discussed. The thermal decomposition of these compounds yields the respective cubic rare earth oxide and shows the typical intense exothermic decomposition reaction. A variety of different precursor system based on nitrate solvates for the deposition of rare earth oxide layers on a silicon surface was developed and investigated in collaboration with the group of Prof. Dr. Al-Shamery (Univ. Oldenburg). Ultra thin films on a H-Si(111) surface were obtained via the deposition of the precursor, which was dissolved in organic solvents. An oxide layer was detected after the heating of the sample. The film thickness was measured as < 10 nm, whereas the thickness of the film was controlled by the concentration of the precursor solution. Sm(ClO{sub 4}){sub 3}(CH(OCH{sub 3}){sub 3}){sub 3} was isolated and characterized for the first time as the intermediate of the dehydration reaction with trimethyl orthoformate. Eu(ClO{sub 4}){sub 3}(CH(OCH{sub 3}){sub 3}){sub 2}(MeOH){sub 2} was obtained without

  14. Rare Earth Oxide Fluoride Nanoparticles And Hydrothermal Method For Forming Nanoparticles

    Science.gov (United States)

    Fulton, John L.; Hoffmann, Markus M.

    2003-12-23

    A hydrothermal method for forming nanoparticles of a rare earth element, oxygen and fluorine has been discovered. Nanoparticles comprising a rare earth element, oxygen and fluorine are also described. These nanoparticles can exhibit excellent refractory properties as well as remarkable stability in hydrothermal conditions. The nanoparticles can exhibit excellent properties for numerous applications including fiber reinforcement of ceramic composites, catalyst supports, and corrosion resistant coatings for high-temperature aqueous solutions.

  15. Synthesis of the missing oxide of xenon, XeO2, and its implications for Earth's missing xenon.

    Science.gov (United States)

    Brock, David S; Schrobilgen, Gary J

    2011-04-27

    The missing Xe(IV) oxide, XeO(2), has been synthesized at 0 °C by hydrolysis of XeF(4) in water and 2.00 M H(2)SO(4(aq)). Raman spectroscopy and (16/18)O isotopic enrichment studies indicate that XeO(2) possesses an extended structure in which Xe(IV) is oxygen bridged to four neighboring oxygen atoms to give a local square-planar XeO(4) geometry based on an AX(4)E(2) valence shell electron pair repulsion (VSEPR) arrangement. The vibrational spectra of Xe(16)O(2) and Xe(18)O(2) amend prior vibrational assignments of xenon doped SiO(2) and are in accordance with prior speculation that xenon depletion from the Earth's atmosphere may occur by xenon insertion at high temperatures and high pressures into SiO(2) in the Earth's crust.

  16. Emission Properties, Solubility, Thermodynamic Analysis and NMR Studies of Rare-Earth Complexes with Two Different Phosphine Oxides

    Directory of Open Access Journals (Sweden)

    Hiroki Iwanaga

    2010-07-01

    Full Text Available The paper proposes novel molecular designs for rare-earth complexes involving the introduction of two different phosphine oxide structures into one rare-earth ion. These designs are effective for improving solubility and emission intensity. Additionally, the complexes are indispensable for realizing high performances in LEDs and security media. The thermodynamic properties of Eu(III complexes are correlated with the solubility. Correlations between coordination structures and emission intensity were explained by NMR analysis. The luminous flux of red LED devices with Eu(III complexes is very high (20 mA, 870 m lumen. A new white LED has its largest spectra intensity in the red region and a human look much more vividly under this light.

  17. Determination of rare earth elements, hafnium and cadmium in sintered pellets of mixed thorium and uranium oxides by neutron activation

    International Nuclear Information System (INIS)

    Cardoso, S.N.M.

    1987-01-01

    This work shows the development of a method for determination of the rare-earth elements (Eu, Sm, Dy and Gd), Hf and Cd contents in sinterized U and Th mixed oxides by neutron activation analysis. The sample is dissolved in nitric/fluoridric (0,1% HF) medium, to dryness and redissolved in 6N HCl solution. The Hf is extracted into organic phase (0,5 M TTA/benzene), irradiated and analysed through 181 Hf isotope energy peak. The aqueous phase is treated with NH 4 OH for the precipitation of hidroxides. Then, these are dissolved in 6N HNO 3 solution. The extraction of U and Th is made in two steps, one with TBP/CCl 4 and another with 0,5 M TTA/C 6 H 6 . Then the rare-earth elements and Cd are irradiated and determined by gamma spectrometry. (author) [pt

  18. Application of neutron actication analysis to the determination of impurities in rare earth oxides produced at IPEN-CNEN/SP

    International Nuclear Information System (INIS)

    Saiki, M.; Oliveira Lellis, L. de.

    1988-07-01

    This paper describes a method for trace analysis in high purity rare earth oxides. This method is an application of instrumental neutron activation analysis. The results of analysis obtained in La 2 O 3 , CeO 2 , Pr 6 O 11 Nd 2 O 3 , Sm 2 O 3 and Gd 2 O 3 produced at IPEN-CNEN/SP are presented. A detailed study of the possible interference found in the neutron activation of these materials is also made. The sensitivity of the method is determined for impurities not detected in each sample. (author) [pt

  19. XAS study of V2O5/Al2O3 catalysts doped with rare earth oxides

    International Nuclear Information System (INIS)

    Centeno, M.A.; Malet, P.; Capitan, M.J.; Benitez, J.J.; Carrizosa, I.; Odriozola, J.A.

    1995-01-01

    This paper reports on XAS studies of well dispersed V 2 O 5 /Al 2 O 3 and V 2 O 5 /Sm 2 O 3 /Al 2 O 3 samples. XAS spectra at V-K and Sm-L III edges show that the rare earth oxide favours the formation of regular tetrahedral units, [VO 4 ], over the surface of the support. Positions of the preedge peak at the V-K edge, and intensities of the white line at the Sm-L III edge also suggest modifications in the electronic density around V and Sm atoms when they are simultaneously supported over Al 2 O 3 . ((orig.))

  20. Investigations on fabricating strategies and utilization of rare earth based multicomponent oxide powders in radiation detection

    International Nuclear Information System (INIS)

    Shinde, Seema; Pitale, S.S.; Banthia, S.; Ghosh, M.; Tyagi, M.; Sen, S.; Gadkari, S.C.

    2014-01-01

    Materials containing rare earths demonstrate a broad field of applications as high energy radiation detectors, mainly due to their fascinating optical properties. Currently, Ce 3+ -doped rare earth silicates and garnets dominate the scintillator market because they show a high light yield, fast decay time, and high chemical stability. Moreover, the emission wavelength of silicates (410-440 nm) matches the wavelength sensitivity of conventional PMTs while, Si-photo-detector readouts are possible with garnets (emission near 550 nm). The composition, structure and phase of rare earth silicates are rather complex. For example, there are many phases like oxyorthosilicate R 2 SiO 5 , disilicate R 2 Si 2 O 7 , hexagonal R x (SiO 4 ) 6 O 2 oxyapatite etc (where R= Rare earth element). The controlled synthesis of single phase rare earth silicates and garnets nanomaterials is not easy and can only be reached with precisely controlled experimental conditions. In this work, we provide a broad overview of our recent scientific developments linked to a few aspects of synthesizing cerium activated rare earth based silicates and garnet materials, namely Gd 2 SiO 5 :Ce 3+ , Gd 4.67 (SiO 4 ) 3 O, Gd 2 Si 2 O 7 :Ce 3+ and Gd 3 Al x Ga 1-x O 12 :Ce 3+ (where 0≤x≤5) exploiting the advantages of solution combustion, chemical co-precipitation and hydrothermal techniques. A brief summary of results based on synthesis strategy adopted, composition, size shape and corresponding luminescence features of Gd based compounds are tabulated. The room temperature photoluminescence (PL) features of compounds listed. Efforts towards finding new properties and new materials will be continued and several applications, in particular energy-conversion and scintillator detectors, will benefit from these rare earth materials

  1. Influence of rare-earth based orthovanadate nanoparticles and cerium oxide on bioenergetic processes in mitochondria of hepatocytes

    Directory of Open Access Journals (Sweden)

    Е. А. Аверченко

    2015-10-01

    Full Text Available The features of influence of newly synthesized nanoparticles (NPs based on the rare earth elements, namely orthovanadates and cerium oxide, with the different geometrical parameters on the mitochondrial potential (ΔΨm and respiration and oxidative phosphorylation of the liver were investigated. Reduction of ΔΨm, as well as the ATP level in isolated mitochondria under influence of orthovanadates and CeO2 (1-2 nm NPs suggests that energy processes in the mitochondria are the target of the action of NPs. The highest inhibitory effect was shown by ekstrasmall spherical (orthovanadate and CeO2 of 1-2 nm particles and only CeO2 with sizes of 8-10 nm have no a negative influence on all investigated parameters.

  2. Net alkalinity and net acidity 2: Practical considerations

    Science.gov (United States)

    Kirby, C.S.; Cravotta, C.A.

    2005-01-01

    The pH, alkalinity, and acidity of mine drainage and associated waters can be misinterpreted because of the chemical instability of samples and possible misunderstandings of standard analytical method results. Synthetic and field samples of mine drainage having various initial pH values and concentrations of dissolved metals and alkalinity were titrated by several methods, and the results were compared to alkalinity and acidity calculated based on dissolved solutes. The pH, alkalinity, and acidity were compared between fresh, unoxidized and aged, oxidized samples. Data for Pennsylvania coal mine drainage indicates that the pH of fresh samples was predominantly acidic (pH 2.5-4) or near neutral (pH 6-7); ??? 25% of the samples had pH values between 5 and 6. Following oxidation, no samples had pH values between 5 and 6. The Standard Method Alkalinity titration is constrained to yield values >0. Most calculated and measured alkalinities for samples with positive alkalinities were in close agreement. However, for low-pH samples, the calculated alkalinity can be negative due to negative contributions by dissolved metals that may oxidize and hydrolyze. The Standard Method hot peroxide treatment titration for acidity determination (Hot Acidity) accurately indicates the potential for pH to decrease to acidic values after complete degassing of CO2 and oxidation of Fe and Mn, and it indicates either the excess alkalinity or that required for neutralization of the sample. The Hot Acidity directly measures net acidity (= -net alkalinity). Samples that had near-neutral pH after oxidation had negative Hot Acidity; samples that had pH mine drainage treatment can lead to systems with insufficient Alkalinity to neutralize metal and H+ acidity and is not recommended. The use of net alkalinity = -Hot Acidity titration is recommended for the planning of mine drainage treatment. The use of net alkalinity = (Alkalinitymeasured - Aciditycalculated) is recommended with some cautions

  3. 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

  4. 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.

  5. 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.

  6. 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

  7. Development of novel rare earth doped fluoride and oxide scintillators for two-dimensional imaging

    Czech Academy of Sciences Publication Activity Database

    Yoshikawa, A.; Yanagida, T.; Yokota, Y.; Kamada, K.; Kawaguchi, N.; Fukuda, K.; Yamazaki, A.; Watanabe, K.; Uritani, A.; Iguchi, T.; Boulon, G.; Nikl, Martin

    2011-01-01

    Roč. 29, č. 12 (2011), s. 1178-1182 ISSN 1002-0721 Grant - others:AV ČR(CZ) M100100910 Institutional research plan: CEZ:AV0Z10100521 Keywords : scintillator * gamma-ray detection * neutron detection * fluoride * Ce * Eu * rare earth Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 0.901, year: 2011

  8. Enhanced methanol oxidation and oxygen reduction reactions on palladium-decorated FeCo@Fe/C core–shell nanocatalysts in alkaline medium

    CSIR Research Space (South Africa)

    Fashedemi, OO

    2013-12-01

    Full Text Available Pt catalysts, (iii) reaction dynamics are best facilitated in alkaline media compared to the acidic media, (iv) alcohol cross-over from the anode to the cathode may be minimised since cell conductance is affected by the electro-osmotic drag..., importantly, tolerates the presence of alcohol in the cathode side should alcohol cross-over occur during cell operation. Pd-based core shell nanocatalysts are known to enhance ORR activities. Core–shell nanostructures represent efficient electro- catalysts...

  9. 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

  10. Thermochemistry of rare earth doped uranium oxides LnxU1-xO2-0.5x+y (Ln = La, Y, Nd)

    Science.gov (United States)

    Zhang, Lei; Navrotsky, Alexandra

    2015-10-01

    Lanthanum, yttrium, and neodymium doped uranium dioxide samples in the fluorite structure have been synthesized, characterized in terms of metal ratio and oxygen content, and their enthalpies of formation measured by high temperature oxide melt solution calorimetry. For oxides doped with 10-50 mol % rare earth (Ln) cations, the formation enthalpies from constituent oxides (LnO1.5, UO2 and UO3 in a reaction not involving oxidation or reduction) become increasingly exothermic with increasing rare earth content, while showing no significant dependence on the varying uranium oxidation state. The oxidation enthalpy of LnxU1-xO2-0.5x+y is similar to that of UO2 to UO3 for all three rare earth doped systems. Though this may suggest that the oxidized uranium in these systems is energetically similar to that in the hexavalent state, thermochemical data alone can not constrain whether the uranium is present as U5+, U6+, or a mixture of oxidation states. The formation enthalpies from elements calculated from the calorimetric data are generally consistent with those from free energy measurements.

  11. The origin of life in alkaline hydrothermal vents

    Science.gov (United States)

    Sojo, V.; Herschy, B.; Whicher, A.; Camprubí, E.; Lane, N.

    2016-12-01

    The origin of life remains one of Science's greatest unresolved questions. The answer will no doubt involve almost all the basic disciplines, including Physics, Chemistry, Astronomy, Geology, and Biology. Chiefly, it is the link between the latter two that must be elucidated: how geochemistry gave rise to biochemistry. Serpentinizing systems such as alkaline hydrothermal vents offer the most robust combination of conditions to have hosted the origin of life on the early Earth, while bearing many parallels to modern living cells. Stark gradients of concentration, pH, oxidation/reduction, and temperature provided the ability to synthesise and concentrate organic products, drive polymerisation reactions, and develop an autotrophic lifestyle independent of foreign sources of organics. In the oxygen-depleted waters of the Hadean, alkaline vents would have acted as electrochemical flow reactors, in which alkaline fluids saturated in H2 mixed with the relatively acidic CO2-rich waters of the ocean, through interconnected micropores made of thin inorganic walls containing catalytic Fe(Ni)S minerals. Perhaps not coincidentally, the unit cells of these Fe(Ni)S minerals closely resemble the active sites of crucial ancestral bioenergetic enzymes. Meanwhile, differences in pH across the thin barriers produced natural proton gradients similar to those used for carbon fixation in modern archaea and bacteria. At the earliest stages, the problem of the origin of life is the problem of the origin of carbon fixation. I will discuss work over the last decade that suggests several possible hypotheses for how simple one-carbon molecules could have given rise to more complex organics, particularly within a serpentinizing alkaline hydrothermal vent. I will discuss the perplexing differences in carbon and energy metabolism in methanogenic archaea and acetogenic bacteria, thought to be the earliest representatives of each domain, to propose a possible ancestral mechanism of CO2 reduction in

  12. Production of nitrogen oxides by lightning and coronae discharges in simulated early Earth, Venus and Mars environments.

    Science.gov (United States)

    Nna Mvondo, D; Navarro-Gonzalez, R; McKay, C P; Coll, P; Raulin, F

    2001-01-01

    We present measurements for the production of nitrogen oxides (NO and N2O) in CO2-N2 mixtures that simulate different stages of the evolution of the atmospheres of the Earth, Venus and Mars. The nitrogen fixation rates by two different types of electrical discharges, namely lightning and coronae, were studied over a wide range in CO2 and N2 mixing ratios. Nitric oxide (NO) is formed with a maximum energy yield estimated to be ~1.3 x 10(16) molecule J-1 at 80% CO2 and ~1.3 x 10(14) molecule J-1 at 50% CO2 for lightning and coronae discharges, respectively. Nitrous oxide (N2O) is only formed by coronae discharge with a maximum energy yield estimated to be ~1.2 x 10(13) molecule J-1 at 50% CO2. The pronounced difference in NO production in lightning and coronae discharges and the lack of formation of N2O in lightning indicate that the physics and chemistry involved in nitrogen fixation differs substantially in these two forms of electric energy. c2001 COSPAR. Published by Elsevier Science Ltd. All rights reserved.

  13. Rare earths

    International Nuclear Information System (INIS)

    Cranstone, D.A.

    1980-01-01

    There has been no Canadian production of the rare earth oxides since 1977. World production in 1978, the last year for which figures are available, is estimated to have been about 41000 tonnes, mostly from Australia and the United States. The United States Bureau of Mines estimates that world reserves contain about 7 million tonnes of rare earth oxides and 35 million tonnes of yttrium. The largest yttrium reserves are in India, while China is believed to have the world's largest reserves of rare earth oxides. World consumption of rare aarths increased slightly in 1980, but is still only a small fraction of known reserves. Rare earths are used mainly in high-strength magnets, automobile exhaust systems, fluorescent tube and television screen phosphors, metallurgical applications, petroleum cracking catalysts, and glass polishing

  14. Metal-oxygen hybridization and core-level spectra in actinide and rare-earth oxides

    Czech Academy of Sciences Publication Activity Database

    Kolorenč, Jindřich

    2016-01-01

    Roč. 1, č. 44 (2016), s. 3007-3012 ISSN 2059-8521 R&D Projects: GA ČR GC15-05872J Institutional support: RVO:68378271 Keywords : actinide * lanthanide * oxide * electronic structure * photoemission Subject RIV: BM - Solid Matter Physics ; Magnetism

  15. Net alkalinity and net acidity 2: Practical considerations

    Science.gov (United States)

    Kirby, C.S.; Cravotta, C.A.

    2005-01-01

    The pH, alkalinity, and acidity of mine drainage and associated waters can be misinterpreted because of the chemical instability of samples and possible misunderstandings of standard analytical method results. Synthetic and field samples of mine drainage having various initial pH values and concentrations of dissolved metals and alkalinity were titrated by several methods, and the results were compared to alkalinity and acidity calculated based on dissolved solutes. The pH, alkalinity, and acidity were compared between fresh, unoxidized and aged, oxidized samples. Data for Pennsylvania coal mine drainage indicates that the pH of fresh samples was predominantly acidic (pH 2.5-4) or near neutral (pH 6-7); ??? 25% of the samples had pH values between 5 and 6. Following oxidation, no samples had pH values between 5 and 6. The Standard Method Alkalinity titration is constrained to yield values >0. Most calculated and measured alkalinities for samples with positive alkalinities were in close agreement. However, for low-pH samples, the calculated alkalinity can be negative due to negative contributions by dissolved metals that may oxidize and hydrolyze. The Standard Method hot peroxide treatment titration for acidity determination (Hot Acidity) accurately indicates the potential for pH to decrease to acidic values after complete degassing of CO2 and oxidation of Fe and Mn, and it indicates either the excess alkalinity or that required for neutralization of the sample. The Hot Acidity directly measures net acidity (= -net alkalinity). Samples that had near-neutral pH after oxidation had negative Hot Acidity; samples that had pH calculated based on initial pH and dissolved concentrations of Fe, Mn, and Al minus the initial alkalinity. Acidity calculated from the pH and dissolved metals concentrations, assuming equivalents of 2 per mole of Fe and Mn and 3 per mole of Al, was equivalent to that calculated based on complete aqueous speciation of FeII/FeIII. Despite changes in

  16. 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.

  17. Plasma electrolytic oxidation of A1050 aluminium alloy in homogeneous silicate-alkaline electrolytes with edta{sup 4−} complexes of Fe, Co, Ni, Cu, La and Ba under alternating polarization conditions

    Energy Technology Data Exchange (ETDEWEB)

    Rogov, A.B., E-mail: alex-lab@bk.ru [Nikolaev Institute of Inorganic Chemistry, 3, Acad. Lavrentiev Ave., Novosibirsk, 630090 (Russian Federation); Scientific and Technical Centre “Pokrytie-A” (OOO), 15, Dzerzhinskogo Ave., Novosibirsk, 630015 (Russian Federation)

    2015-11-01

    This work is devoted to the synthesis of coatings containing a number of transition elements by plasma electrolytic oxidation (PEO) on aluminium A1050 alloy. The paper discusses PEO coatings obtained in silicate-alkaline electrolytes containing complexes of Fe, Co, Ni, Cu, La and Ba with ethylenediaminetetraacetic anion edta{sup 4−}. It is also focused on the chemical basis of the electrolyte components choice and their role in the process of PEO. Possible mechanism of coating formation process is also discussed. Alternating current mode (symmetrical sinusoidal current pulses, initial average current density - 100 mA cm{sup −2}) was used to produce the coatings. The PEO process was characterized by behaviours of the anodic and cathodic peak voltage curves. Coating surfaces and cross sections are studied by optical dark field microscopy and scanning electron microscopy, X-ray and energy dispersive analysis. - Highlights: • Alkaline homogeneous electrolyte with transition metal-edta{sup 4-} complexes. • Coatings contain Fe, Co, Ni, Cu, La, Ba elements in alumina-silica matrix. • Alternating symmetric sinusoidal current of 100 mA cm{sup −2} was applied. • Borax buffer solution and silicate passivating agent were used.

  18. EFFECTIVE ALKALINE PEROXIDE OXIDATION PRETREATMENT OF SHEA TREE SAWDUST FOR THE PRODUCTION OF BIOFUELS: KINETICS OF DELIGNIFICATION AND ENZYMATIC CONVERSION TO SUGAR AND SUBSEQUENT PRODUCTION OF ETHANOL BY FERMENTATION USING Saccharomyces cerevisiae

    Directory of Open Access Journals (Sweden)

    A. O. Ayeni

    Full Text Available Abstract Shea tree sawdust delignification kinetic data during alkaline peroxide pretreatment were investigated at temperatures of 120 °C, 135 °C, and 150 °C. The activation energy during delignification was 76.4 kJ/mol and the Arrhenius constant was calculated as 8.4 x 106 per min. The reducing sugar yield for the treated to the untreated biomass was about 22-fold. Enzymatic hydrolysis conditions studied were; time (72 h and 96 h, substrate concentration (20, 30, 40, and 50 g/L, and enzyme loadings (10, 25, 40, 50 FPU/g dry biomass, which showed the optimum conditions of 96 h, 40 g/L, and 25 FPU/g dry biomass at 45 °C hydrolysis temperature. At the optimized enzymatic hydrolysis conditions, the reducing sugar yield was 416.32 mg equivalent glucose/g treated dry biomass. After 96 h fermentation of treated biomass, the ethanol obtained at 2% effective cellulose loading was 12.73 g/L. Alkaline peroxide oxidation pretreatment and subsequent enzymatic hydrolysis improved the ethanol yield of the biomass.

  19. Oxidation by hydrogen in the chemistry and physics of the rare-earth metals.

    Science.gov (United States)

    Simon, Arndt

    2012-04-27

    Rare-earth metals (RE) easily react with hydrogen. For decades the bonding of hydrogen has been discussed controversially in terms of either the "proton model" or the "anion model". Detailed investigations of metal-rich compounds of the rare-earth metals provide clear evidence for the incorporation of hydrogen as a hydride anion. Several categories of compounds can be distinguished regarding their behavior towards hydrogen. Low-valence compounds with metal-metal bonding frequently provide their excess electrons to form hydride ions as found with the halide hydrides REXH(n). However, there are exceptions, such as, LaI which does not react with hydrogen as a result of special electronic and electrostatic conditions. The opposite is true with La(2)C(3) although this compound does not provide excess metal valence electrons. An amorphous phase La(2)C(3)H(1.5) forms at very low temperature, around 450 K. The presence of hydrogen strongly influences the electrical and magnetic properties, for example, spin-glass formation and colossal magneto resistance arising in the presence of 4f(n) cores with the lanthanoid elements. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  20. THE GREAT OXIDATION OF EARTH'S ATMOSPHERE: CONTESTING THE YOYO MODEL VIA TRANSITION STABILITY ANALYSIS

    International Nuclear Information System (INIS)

    Cuntz, M.; Roy, D.; Musielak, Z. E.

    2009-01-01

    A significant controversy regarding the climate history of the Earth and its relationship to the development of complex life forms concerns the rise of oxygen in the early Earth's atmosphere. Geological records show that this rise occurred about 2.4 Gyr ago, when the atmospheric oxygen increased from less than 10 -5 present atmospheric level (PAL) to more than 0.01 PAL and possibly above 0.1 PAL. However, there is a debate whether this rise happened relatively smoothly or with well-pronounced ups and downs (the Yoyo model). In our study, we explore a simplified atmospheric chemical system consisting of oxygen, methane, and carbon that is driven by the sudden decline of the net input of reductants to the surface as previously considered by Goldblatt et al. Based on the transition stability analysis for the system equations, constituting a set of non-autonomous and non-linear differential equations, as well as the inspection of the Lyapunov exponents, it is found that the equations do not exhibit chaotic behavior. In addition, the rise of oxygen occurs relative smoothly, possibly with minor bumps (within a factor of 1.2), but without major jumps. This result clearly argues against the Yoyo model in agreement with recent geological findings.

  1. Yttrium aluminum garnet (YAG) obtained by rare-earth mixed oxide (RE{sub 2}O{sub 3})

    Energy Technology Data Exchange (ETDEWEB)

    Castro, D.F.; Daguano, J.K.M.F.; Rodrigues Junior, D., E-mail: claudinei@demar.eel.usp.b [Universidade de Sao Paulo (EEL/USP), Lorena, SP (Brazil). Escola de Engenharia; Santos, C. [Centro Universitario de Volta Redonda (MEMAT/UNIFOA), RJ (Brazil); Suzuki, P.A. [Laboratorio Nacional de Luz Sincrotron (LNLS), Campinas, SP (Brazil); Silva, O.M.M. [Centro Tecnico Aeroespacial (CTA-IAE), Sao Jose dos Campos, SP (Brazil). Inst. de Atividades Espaciais. Div. de Materiais

    2010-07-01

    In this work, the substitution of commercial Y{sub 2}O{sub 3} by a rare earth mixed oxide, RE{sub 2}O{sub 3}, to form Yttrium aluminum Garnet-Y{sub 3}Al{sub 5}O{sub 12}, was investigated. Al{sub 2}O{sub 3}:Y{sub 2}O{sub 3} and Al{sub 2}O{sub 3}:RE{sub 2}O{sub 3} powder-mixtures, in a molar ratio of 60:40, were milled and subsequently cold uniaxially-pressed. Compacts were sintered at 1000, 1400 or 1600 deg C, for 120 minutes. RE{sub 2}O{sub 3} oxide was characterized by high-resolution synchrotron X-ray diffraction (HRXRD) and compared to Y{sub 2}O{sub 3}. X-ray diffraction pattern of the RE{sub 2}O{sub 3} indicates a true solid solution formation. Rietveld refinement of the sintered YAG and (RE)AG reveled a similar crystal structure to the YAGs obtained by the use of Al{sub 2}O{sub 3}-Y{sub 2}O{sub 3} or Al{sub 2}O{sub 3}-RE{sub 2}O{sub 3} respectively. Microstructural analysis of both, YAG or (RE)AG, revealed similar grain sizes of about 2.5 {mu}m besides mechanical properties, with hardness of 400HV and fracture toughness of 3.8MPa.m1/2. It could be, thus, demonstrated that pure Y{sub 2}O{sub 3} can be substituted by the rare-earth solid solution, RE{sub 2}O{sub 3}, in the formation YAGs, presenting similar microstructural and mechanical properties. (author)

  2. Nuclear analysis of a rare earth containing protective oxide on aluminium

    Energy Technology Data Exchange (ETDEWEB)

    Gorman, J.D.; Paterson, P.J.K. [Royal Melbourne Inst. of Tech., VIC (Australia); Hughes, A.E. [Commonwealth Scientific and Industrial Research Organisation (CSIRO), Melbourne, VIC (Australia). Div. of Materials Science

    1996-12-31

    The aim is study was to examine the thickness of the conversion coating as well as the elemental depth distribution of cerium and molybdenum using Rutherford Backscattering Spectroscopy (RBS), Scanning Electron Microscopy (SEM), Scanning Auger Electron Spectroscopy and Forward Recoil Spectroscopy (FRS). In addition, RBS has been used to examine how changes in processing conditions, particularly the treatment temperatures, influences the coating thickness and Ce distribution at each process step. SEM established that a crazed oxide structure was developed over the matrix of the alloy using the above process steps. RBS was chosen to provide elemental concentration versus depth information on these samples since it is largely insensitive to surface topography when the detector is set to high scattering angles. A other advantage of using RBS for this particular system is that the heavy elements incorporated into the coating such as Ce and Mo because of their high atomic number compared to the aluminium oxide, are well separated from aluminium and oxygen at their higher recoil energies. Forward Recoil Spectroscopy is capable of detecting hydrogen and it has been used to confirm that the coating is hydrated and to establish the hydrogen distribution within the final oxide coating on each alloy. 7 refs., 1 tab., 4 figs.

  3. Biological consilience of hydrogen sulfide and nitric oxide in plants: Gases of primordial earth linking plant, microbial and animal physiologies.

    Science.gov (United States)

    Yamasaki, Hideo; Cohen, Michael F

    2016-05-01

    Hydrogen sulfide (H2S) is produced in the mammalian body through the enzymatic activities of cystathionine β-synthase (CBS), cystathionine γ-lyase (CSE) and 3-mercaptopyruvate sulfurtransferase (3MST). A growing number of studies have revealed that biogenic H2S produced in tissues is involved in a variety of physiological responses in mammals including vasorelaxation and neurotransmission. It is now evident that mammals utilize H2S to regulate multiple signaling systems, echoing the research history of the gaseous signaling molecules nitric oxide (NO) and carbon monoxide (CO) that had previously only been recognized for their cytotoxicity. In the human diet, meats (mammals, birds and fishes) and vegetables (plants) containing cysteine and other sulfur compounds are the major dietary sources for endogenous production of H2S. Plants are primary producers in ecosystems on the earth and they synthesize organic sulfur compounds through the activity of sulfur assimilation. Although plant H2S-producing activities have been known for a long time, our knowledge of H2S biology in plant systems has not been updated to the extent of mammalian studies. Here we review recent progress on H2S studies, highlighting plants and bacteria. Scoping the future integration of H2S, NO and O2 biology, we discuss a possible linkage between physiology, ecology and evolutional biology of gas metabolisms that may reflect the historical changes of the Earth's atmospheric composition. Copyright © 2016 Elsevier Inc. All rights reserved.

  4. Earth Abundant Fe/Mn-Based Layered Oxide Interconnected Nanowires for Advanced K-Ion Full Batteries.

    Science.gov (United States)

    Wang, Xuanpeng; Xu, Xiaoming; Niu, Chaojiang; Meng, Jiashen; Huang, Meng; Liu, Xiong; Liu, Ziang; Mai, Liqiang

    2017-01-11

    K-ion battery (KIB) is a new-type energy storage device that possesses potential advantages of low-cost and abundant resource of K precursor materials. However, the main challenge lies on the lack of stable materials to accommodate the intercalation of large-size K-ions. Here we designed and constructed a novel earth abundant Fe/Mn-based layered oxide interconnected nanowires as a cathode in KIBs for the first time, which exhibits both high capacity and good cycling stability. On the basis of advanced in situ X-ray diffraction analysis and electrochemical characterization, we confirm that interconnected K 0.7 Fe 0.5 Mn 0.5 O 2 nanowires can provide stable framework structure, fast K-ion diffusion channels, and three-dimensional electron transport network during the depotassiation/potassiation processes. As a result, a considerable initial discharge capacity of 178 mAh g -1 is achieved when measured for KIBs. Besides, K-ion full batteries based on interconnected K 0.7 Fe 0.5 Mn 0.5 O 2 nanowires/soft carbon are assembled, manifesting over 250 cycles with a capacity retention of ∼76%. This work may open up the investigation of high-performance K-ion intercalated earth abundant layered cathodes and will push the development of energy storage systems.

  5. Zirconium oxide obtainment from brazilian zircon concentrate

    International Nuclear Information System (INIS)

    Ribeiro, S.; Martins, A.H.

    1991-01-01

    This work presents the experimental results of studies about alkaline melting, acid leaching and sulfation steps for obtention of zirconium oxide and partially stabilized zirconia by yttrium and rare-earth coprecipitation in chlorine medium, starting from the brazilian zircon concentrate. Using statistical methods of factorial design and the Packett-Burman approach, the results are discussed and the optimal conditions of the production steps were determined. (author)

  6. 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.

  7. 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…

  8. Influence of rare earth additions on the oxidation resistance of chromia forming alloys; Influencia da adicao de terras raras sobre a resistencia a oxidacao de ligas formadoras de cromia

    Energy Technology Data Exchange (ETDEWEB)

    Pillis, Marina Fuser

    1995-12-31

    The addition of rare earths to alloys, either in elemental form or as surface coatings reduces the oxidation rate of chromia forming alloys. The rare earths either act as nucleation sites for surface oxides or get incorporates into the surface oxide and diffuse to oxide grain boundaries. If the latter occurs, a change in the defect structure close to the grain boundaries, probably takes place. In this manner, the rare earths inhibits the movement of chromium ions to the oxide/gas interface. The influence of rare earth additions to AISI 316, AISI 316L and Ni-20 Cr on their oxidation behavior has been studied., AISI 316+Ce, AISI 316+Y, Ni-20 Cr and Ni-20 Cr-2 Al-1 Ce were prepared by melting and AISI 316L, AISI 316L+Ce O{sub 2} and AISI 316L+Y{sub 2} O{sub 3} by powder compaction. The effect of superficial deposits of rare earth oxides was also studied. The alloys were coated with rare earth oxides by high temperature conversion of the respective rare earth nitrates. Isothermal oxidation tests were carried out at 900-1100 deg C and the cyclic oxidation tests consisted of 6 cycles of 2 hours each at 900 deg C, followed by cooling to room temperature. All the tests were carried out in air. Oxidation behavior was evaluated gravimetrically. Scanning electron microscopy was used to study surface morphology. Energy dispersive analysis and X-ray diffraction techniques were used to identify oxide constituents. Overall, it has been observed that with the addition of rare earths, oxidation resistance increases by decreasing oxidation rates and increasing oxide adhesion. Addition of rare earths to AISI 316 prepared by melting resulted in rapid formation of a chromium rich oxide layered near the metal/oxide interface which reduced overall oxidation rate. The addition of Ce O{sub 2} to AISI 316L was found to improve oxidation behavior after 10 hours at 1100 deg C and also inhibit the formation of volatile Cr O{sub 3}. The isothermal oxidation behavior of rare earth oxide covered

  9. Calc-Alkaline Liquid Lines of Descent Produced Under Oxidizing Conditions: An Experimental and Petrologic Study of Basaltic Tephras from the Western Aleutians, AK

    Science.gov (United States)

    Waters, L. E.; Cottrell, E.; Kelley, K. A.; Coombs, M. L.

    2017-12-01

    Buldir, a volcano in the western Aleutian Arc, features eruptive products that form one of the most strongly calc-alkaline compositional trends observed in modern island arcs. Previous studies of Buldir and nearby submarine dredge samples suggest that Buldir's mineral phases and isotopic signatures may be introduced through mixing of two distinct magmas and/or melts, as no experimental study has been able to create a liquid line of descent (LLD) as calc-alkaline as Buldir's whole rock trend. To further test this hypothesis, we present new experimental results and petrographic analysis of tephras from the 2015 field season of the GeoPRISMS shared platform. Tephras (51.4-54.8 wt% SiO2) have a phenocryst assemblage of olivine + plagioclase + cpx + spinel ± hornblende (hbl). In natural samples, plagioclase comprises most of the crystal volume, followed by either olivine or hornblende. In samples that contain abundant hbl (Hbl Mg#=65-80), olivine and plagioclase span a range of compositions from Fo72-86 and An60-93, respectively. In samples without hbl, olivines are more forsteritic (Fo79-90), and plagioclase is less calcic (An65-83). Spinel is ubiquitous; with Cr- rich spinel inclusions in olivine and hbl, and magnetite in the groundmass. Our petrologic observations do not require magma mixing. To determine whether these observations could be consistent with the LLD of a single parental liquid, we conducted a series of phase equilibrium experiments at 100 MPa in a rapid-quench cold-seal (MHC) apparatus on the most primitive natural lava from Buldir (9.34 wt% MgO). Experiments were equilibrated in noble metal capsules pre-saturated with Fe, and buffered at Re-ReO2 under water-saturated conditions. Spinel [(Mg80, Fe2+20)(Fe3+52, Cr83, Al66)O4] is the liquidus phase, followed by olivine, then plagioclase, then cpx, and lastly, hbl. Once cpx and hbl saturate, spinel composition shifts to magnetite. Experimental run products demonstrate that all mineral phases observed in

  10. Catalytic oxidation of dye waste water by biomass charcoal loaded multiple rare earth composite material

    Science.gov (United States)

    Suriga; CHEN, Liping

    2017-01-01

    The main purpose of this study is to investigate the individual effect as well as the interactions of different influencing factors like catalyst dosage, aeration rate, temperature and pH on the removal of methylene blue (MB) using biomass charcoal loaded multiple rare earth composite material. Design-Expert 7.0 was used to design testing program and establish response surface model. The result showed that among the factors, catalyst dosage played the most important role, then pH value, aeration rate and temperature in turn. By the optimization of process parameters, the optimum experimental conditions were catalyst dosage of 2.50 g, aeration rate of 2.5 L·min-1, temperature of 21 °C and pH value of 12, under these optimum conditions, maximum predicted and observed decolorization rate were 100.00% and 99.61%, the observed value was well match with the predicted value.

  11. Ethyl Acetate Abatement on Copper Catalysts Supported on Ceria Doped with Rare Earth Oxides

    Directory of Open Access Journals (Sweden)

    Sónia Alexandra Correia Carabineiro

    2016-05-01

    Full Text Available Different lanthanide (Ln-doped cerium oxides (Ce0.5Ln0.5O1.75, where Ln: Gd, La, Pr, Nd, Sm were loaded with Cu (20 wt. % and used as catalysts for the oxidation of ethyl acetate (EtOAc, a common volatile organic compound (VOC. For comparison, both Cu-free (Ce-Ln and supported Cu (Cu/Ce-Ln samples were characterized by N2 adsorption at −196 °C, scanning/transmission electron microscopy, energy-dispersive X-ray spectroscopy, X-ray diffraction, X-ray photoelectron spectroscopy and temperature programmed reduction in H2. The following activity sequence, in terms of EtOAc conversion, was found for bare supports: CeO2 ≈ Ce0.5Pr0.5O1.75 > Ce0.5Sm0.5O1.75 > Ce0.5Gd0.5O1.75 > Ce0.5Nd0.5O1.75 > Ce0.5La0.5O1.75. Cu addition improved the catalytic performance, without affecting the activity order. The best catalytic performance was obtained for Cu/CeO2 and Cu/Ce0.5Pr0.5O1.75 samples, both achieving complete EtOAc conversion below ca. 290 °C. A strong correlation was revealed between the catalytic performance and the redox properties of the samples, in terms of reducibility and lattice oxygen availability. Νo particular correlation between the VOC oxidation performance and textural characteristics was found. The obtained results can be explained in terms of a Mars-van Krevelen type redox mechanism involving the participation of weakly bound (easily reduced lattice oxygen and its consequent replenishment by gas phase oxygen.

  12. Ethyl Acetate Abatement on Copper Catalysts Supported on Ceria Doped with Rare Earth Oxides.

    Science.gov (United States)

    Carabineiro, Sónia Alexandra Correia; Konsolakis, Michalis; Marnellos, George Emmanouil-Nontas; Asad, Muhammad Faizan; Soares, Olívia Salomé Gonçalves Pinto; Tavares, Pedro Bandeira; Pereira, Manuel Fernando Ribeiro; Órfão, José Joaquim de Melo; Figueiredo, José Luís

    2016-05-17

    Different lanthanide (Ln)-doped cerium oxides (Ce0.5Ln0.5O1.75, where Ln: Gd, La, Pr, Nd, Sm) were loaded with Cu (20 wt. %) and used as catalysts for the oxidation of ethyl acetate (EtOAc), a common volatile organic compound (VOC). For comparison, both Cu-free (Ce-Ln) and supported Cu (Cu/Ce-Ln) samples were characterized by N₂ adsorption at -196 °C, scanning/transmission electron microscopy, energy-dispersive X-ray spectroscopy, X-ray diffraction, X-ray photoelectron spectroscopy and temperature programmed reduction in H₂. The following activity sequence, in terms of EtOAc conversion, was found for bare supports: CeO₂ ≈ Ce0.5Pr0.5O1.75 > Ce0.5Sm0.5O1.75 > Ce0.5Gd0.5O1.75 > Ce0.5Nd0.5O1.75 > Ce0.5La0.5O1.75. Cu addition improved the catalytic performance, without affecting the activity order. The best catalytic performance was obtained for Cu/CeO₂ and Cu/Ce0.5Pr0.5O1.75 samples, both achieving complete EtOAc conversion below ca. 290 °C. A strong correlation was revealed between the catalytic performance and the redox properties of the samples, in terms of reducibility and lattice oxygen availability. Νo particular correlation between the VOC oxidation performance and textural characteristics was found. The obtained results can be explained in terms of a Mars-van Krevelen type redox mechanism involving the participation of weakly bound (easily reduced) lattice oxygen and its consequent replenishment by gas phase oxygen.

  13. Commercial alkaline earth boroaluminosilicate glasses for sealing solid oxide cell stacks Part II: Characterization of devitrification and glass-ceramic phase assemblages

    DEFF Research Database (Denmark)

    Agersted, Karsten; Balic-Zunic, T.

    2017-01-01

    nucleation, and that the growth mechanism gradually changed from three-dimensional growth at the onset of devitrification towards one-dimensional growth in later stages, when heterogeneous nucleation was absent or less dominating. Most glasses developed entangled and fibrous microstructures with little...... diopside, substituting for Al and Si, but the so established substitution partly disappeared with time during the heat treatment....

  14. Calcium-borosilicate glass-ceramics wasteforms to immobilize rare-earth oxide wastes from pyro-processing

    Energy Technology Data Exchange (ETDEWEB)

    Kim, Miae [Department of Materials Science and Engineering and Division of Advanced Nuclear Engineering, Pohang University of Science and Technology (POSTECH), Pohang, Gyeongbuk, 790-784 (Korea, Republic of); Heo, Jong, E-mail: jheo@postech.ac.kr [Department of Materials Science and Engineering and Division of Advanced Nuclear Engineering, Pohang University of Science and Technology (POSTECH), Pohang, Gyeongbuk, 790-784 (Korea, Republic of); Department of Materials Engineering, Adama Science and Technology University (ASTU), PO Box 1888, Adama (Ethiopia)

    2015-12-15

    Glass-ceramics containing calcium neodymium(cerium) oxide silicate [Ca{sub 2}Nd{sub 8-x}Ce{sub x}(SiO{sub 4}){sub 6}O{sub 2}] crystals were fabricated for the immobilization of radioactive wastes that contain large portions of rare-earth ions. Controlled crystallization of alkali borosilicate glasses by heating at T ≥ 750 °C for 3 h formed hexagonal Ca–silicate crystals. Maximum lanthanide oxide waste loading was >26.8 wt.%. Ce and Nd ions were highly partitioned inside Ca–silicate crystals compared to the glass matrix; the rare-earth wastes are efficiently immobilized inside the crystalline phases. The concentrations of Ce and Nd ions released in a material characterization center-type 1 test were below the detection limit (0.1 ppb) of inductively coupled plasma mass spectroscopy. Normalized release values performed by a product consistency test were 2.64·10{sup −6} g m{sup −2} for Ce ion and 2.19·10{sup −6} g m{sup −2} for Nd ion. Results suggest that glass-ceramics containing calcium neodymium(cerium) silicate crystals are good candidate wasteforms for immobilization of lanthanide wastes generated by pyro-processing. - Highlights: • Glass-ceramic wasteforms containing Ca{sub 2}Nd{sub 8-x}Ce{sub x}(SiO{sub 4}){sub 6}O{sub 2} crystals were synthesized to immobilize lanthanide wastes. • Maximum lanthanide oxide waste loading was >26.8 wt.%. • Ce and Nd ions were highly partitioned inside Ca–Nd–silicate crystals compared to glass matrix. • Amounts of Ce and Nd ions released in the material characterization center-type 1 were below the detection limit (0.1 ppb). • Normalized release values performed by a PCT were 2.64• 10{sup −6} g m{sup −2} for Ce ions and 2.19• 10{sup −6} g m{sup −2} for Nd ions.

  15. A Comparative Study of Mn/Co Binary Metal Catalysts Supported on Two Commercial Diatomaceous Earths for Oxidation of Benzene

    Directory of Open Access Journals (Sweden)

    Marco Tomatis

    2018-03-01

    Full Text Available Two commercial diatomaceous earths were used as supports for the preparation of Mn/Co binary metal catalysts at different metal loads (5 to 10 wt % Mn and 5 to 15 wt % Co by incipient wetness deposition. The activity of the prepared catalysts towards the complete oxidation of benzene to CO2 and water was investigated between 100 and 400 °C. Raw supports and synthesized catalysts were characterized by XRD, N2 physisorption, SEM-EDS, H2-TPR, and TPD. The purification treatment of food-grade diatomite significantly affected the crystallinity of this support while reducing its specific surface area (SSA. A loss of SSA, associated with the increase in the metal load, was observed on samples prepared on natural diatomite, while the opposite trend occurred with food-grade diatomite-supported catalysts. Metal nanoparticles of around 50 nm diameter were observed on the catalysts’ surface by SEM analysis. EDS analysis confirmed the uniform deposition of the active phases on the support’s surface. A larger H2 consumption was found by TPR analysis of natural diatomite-based samples in comparison to those prepared at the same metal load on food-grade diatomite. During the catalytic oxidation experiment, over 90% conversion of benzene were achieved at a reaction temperature of 225 °C by all of the prepared samples. In addition, the formation of coke during the oxidation tests was demonstrated by TGA analysis and the soluble fraction of the produced coke was characterized by GC-MS.

  16. Fabrication and sealing performance of rare-earth containing glass–ceramic seals for intermediate temperature solid oxide fuel cell applications

    DEFF Research Database (Denmark)

    Abdoli, H.; Alizadeh, P.; Agersted, Karsten

    2014-01-01

    The opportunity of using two rare-earth metal oxides in an aluminosilicate glass for seal applications was investigated in this work. Substitution of La2O3 with Y2O3 in the system changed thermal and physical properties such as transition temperature, flowing behavior, and thermal expansion...

  17. Investigation on the reduction of the oxides of Pd and graphite in alkaline medium and the simultaneous evolution of oxygen reduction reaction and peroxide generation features

    International Nuclear Information System (INIS)

    Kar, Tathagata; Devivaraprasad, Ruttala; Bera, Bapi; Ramesh, Rahul; Neergat, Manoj

    2016-01-01

    Highlights: • Reduction of GO, PdO and parallel evolution of ORR is investigated in 0.1 M KOH. • The results are compared with those of carbon, graphite, c-RGO and Pd. • Peroxide generation and ORR activity increase with reduction of GO to e-RGO. • Peroxide generation decreases and ORR activity increases with reduction of PdO. • Carbon-based materials show peroxide yield of 40–75% as compared to ∼5% with Pd/C. - Abstract: Palladium oxide (PdO) and graphene oxide (GO) are subjected to electrochemical cycling in oxygen-saturated 0.1 M KOH electrolyte in the potential range (−1.2–0.2 V vs. Ag/AgCl (saturated KCl)) relevant to oxygen reduction reaction (ORR). Parallel to ORR, GO and PdO get gradually reduced to graphene and Pd, respectively. With cycling, the half-wave potential of ORR shifts positively with both the oxides. The simultaneous evolution of the peroxide oxidation current on the Pt ring electrode is investigated. On PdO that reduces to Pd, ORR proceeds by the four-electron reduction to OH − and the peroxide oxidation current on the ring electrode decreases with cycling. On the other hand, on GO that reduces to graphene, the ORR proceeds primarily by the two-electron reduction of oxygen and the peroxide oxidation current on the ring electrode increases with cycling. The voltammetric features stabilize with the reduction of the oxides. The ORR and the peroxide oxidation current on the ring electrode with electrochemically reduced GO (e-RGO), chemically reduced GO (c-RGO), carbon-black, and graphite are comparable and they are different from those of the Pd-based precious metal catalyst. The evolution of ORR polarization curves and the peroxide oxidation current on the ring electrode are explained on the basis of the removal of adsorbed-oxygenated species, oxides and by the hydrogen under potential deposition (H upd ) at lower potentials. The results are supported with Koutecky-Levich plots and the voltammograms.

  18. Review- Magnetic orientation and magnetic anisotropy in paramagnetic layered oxides containing rare-earth ions

    Directory of Open Access Journals (Sweden)

    Shigeru Horii, Atsushi Ishihara, Takayuki Fukushima, Tetsuo Uchikoshi, Hiraku Ogino, Tohru S Suzuki, Yoshio Sakka, Jun-ichi Shimoyama and Kohji Kishio

    2009-01-01

    Full Text Available The magnetic anisotropies and easy axes of magnetization at room temperature were determined, and the effects of rare-earth (RE ions were clarified for RE-based cuprates, RE-doped bismuth-based cuprates and RE-doped Bi-based cobaltite regarding the grain orientation by magnetic field. The easy axis, determined from the powder orientation in a static field of 10 T, depended qualitatively on the type of RE ion for all three systems. On the other hand, the magnetization measurement of the c-axis oriented powders, aligned in static or rotating fields, revealed that the type of RE ion strongly affected not only the directions of the easy axis but also the absolute value of magnetic anisotropy, and an appropriate choice of RE ion is required to minimize the magnetic field used for grain orientation. We also studied the possibility of triaxial grain orientation in high-critical-temperature superconductors by a modulated oval magnetic field. In particular, triaxial orientation was attempted in a high-oxygen-pressure phase of orthorhombic RE-based cuprates Y2Ba4Cu7Oy. Although the experiment was performed in epoxy resin, which is not practical, in-plane alignment within 3° was achieved.

  19. 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.

  20. Defect Clustering and Nano-Phase Structure Characterization of Multi-Component Rare Earth Oxide Doped Zirconia-Yttria Thermal Barrier Coatings

    Science.gov (United States)

    Zhu, Dongming; Chen, Yuan L.; Miller, Robert A.

    2003-01-01

    Advanced oxide thermal barrier coatings have been developed by incorporating multi-component rare earth oxide dopants into zirconia-yttria to effectively promote the creation of the thermodynamically stable, immobile oxide defect clusters and/or nano-scale phases within the coating systems. The presence of these nano-sized defect clusters has found to significantly reduce the coating intrinsic thermal conductivity, improve sintering resistance, and maintain long-term high temperature stability. In this paper, the defect clusters and nano-structured phases, which were created by the addition of multi-component rare earth dopants to the plasma-sprayed and electron-beam physical vapor deposited thermal barrier coatings, were characterized by high-resolution transmission electron microscopy (TEM). The defect cluster size, distribution, crystallographic and compositional information were investigated using high-resolution TEM lattice imaging, selected area diffraction (SAD), electron energy-loss spectroscopy (EELS) and energy dispersive spectroscopy (EDS) analysis techniques. The results showed that substantial defect clusters were formed in the advanced multi-component rare earth oxide doped zirconia- yttria systems. The size of the oxide defect clusters and the cluster dopant segregation was typically ranging from 5 to 50 nm. These multi-component dopant induced defect clusters are an important factor for the coating long-term high temperature stability and excellent performance.

  1. Kinetic study of the alkaline metals oxidation by dry oxygen; Etude cinetique de l'oxydation des metaux alcalins par l'oxygene sec

    Energy Technology Data Exchange (ETDEWEB)

    Touzain, Ph. [Commissariat a l' Energie Atomique, Grenoble (France). Centre d' Etudes Nucleaires

    1967-06-15

    The oxidation of lithium, sodium, potassium, rubidium, cesium and sodium-potassium alloys by dry oxygen is studied at several temperatures and in the oxygen pressure range 40 to 400 mmHg. One distinguishes three different oxidation behaviours (inflammation, ignition and slow combustion) whose zones are precised in function of the temperature. The slow oxidation kinetic laws, the composition of oxides and the motive of oxides colorations are determined. At least, the experimental data are construed theoretically. (author) [French] L'oxydation du lithium, du sodium, du potassium, du rubidium, du cesium et des alliages sodium-potassium par l'oxygene sec est etudiee a diverses temperatures et a des pressions comprises entre 40 et 400 mmHg d'oxygene. On distingue trois processus d'oxydation differents (l'inflammation, l'ignition et la combustion lente) dont les domaines en fonction de la temperature sont precises. Les lois cinetiques d'oxydation lente, la nature des oxydes formes ainsi que les causes des colorations de ces oxydes sont determinees. Enfin les resultats obtenus sont interpretes theoriquement. (auteur)

  2. Secondary alkaline batteries

    Science.gov (United States)

    McBreen, J.

    1984-03-01

    The overall reactions (charge/discharge characteristics); electrode structures and materials; and cell construction are studied for nickel oxide-cadmium, nickel oxide-iron, nickel oxide-hydrogen, nickel oxide-zinc, silver oxide-zinc, and silver oxide-cadmium, silver oxide-iron, and manganese dioxide-zinc batteries.

  3. 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

  4. The electro-oxidation of the mixture of formaldehyde and 2-propanol on gold (100 and (111 single crystal planes in alkaline medium

    Directory of Open Access Journals (Sweden)

    BRANISLAV Z. NIKOLIC

    2000-12-01

    Full Text Available The effect of formaldehyde on the oxidation of 2-propanol and vice versa on gold single crystal planes (100 and 111 was studied. An activating effect in the reaction of the simultaneous oxidation of 2-propanol and formaldehyde was obtained on a gold (100 plane. In the case of a gold (111 electrode, the activation effect was not obtained. It was concluded that the adsorption of formaldehyde on the electrode surface prevents the adsorption of poisoning species formed during the electro-oxidation of 2-propanol on the Au(100 plane, while this is not the case on the Au(111 plane. The different behaviour is caused by the difference in the symmetry of the surface atoms of these two Au single-crystal planes.

  5. 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

  6. 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.

  7. Two promising alkaline β-glucosidases isolated by functional metagenomics from agricultural soil, including one showing high tolerance towards harsh detergents, oxidants and glucose.

    Science.gov (United States)

    Biver, Sophie; Stroobants, Aurore; Portetelle, Daniel; Vandenbol, Micheline

    2014-03-01

    New β-glucosidase activities were identified by screening metagenomic libraries constructed with DNA isolated from the topsoil of a winter wheat field. Two of the corresponding proteins, displaying an unusual preference for alkaline conditions, were selected for purification by Ni-NTA chromatography. AS-Esc6, a 762-amino-acid enzyme belonging to glycoside hydrolase family 3, proved to be a mesophilic aryl-β-glucosidase with maximal activity around pH 8 and 40 °C. A similar pH optimum was found for AS-Esc10, a 475-amino-acid GH1-family enzyme, but this enzyme remained significantly active across a wider pH range and was also markedly more stable than AS-Esc6 at pH greater than 10. AS-Esc10 was found to degrade cellobiose and diverse aryl glycosides, with an optimal temperature of 60 °C and good stability up to 50 °C. Unlike AS-Esc6, which showed a classically low inhibitory constant for glucose (14 mM), AS-Esc10 showed enhanced activity in the presence of molar concentrations of glucose. AS-Esc10 was highly tolerant to hydrogen peroxide and also to sodium dodecyl sulfate, this being indicative of kinetic stability. This unique combination of properties makes AS-Esc10 a particularly promising candidate whose potential in biotechnological applications is worth exploring further.

  8. Anionic catalyst binders based on trimethylamine-quaternized poly(2,6-dimethyl-1,4-phenylene oxide) for alkaline electrolyzers

    Czech Academy of Sciences Publication Activity Database

    Schauer, Jan; Hnát, J.; Brožová, Libuše; Žitka, Jan; Bouzek, K.

    2015-01-01

    Roč. 473, 1 January (2015), s. 267-273 ISSN 0376-7388 Institutional support: RVO:61389013 Keywords : poly(2,6-dimethyl-1,4-phenylene oxide) * bromination * trimethylamine Subject RIV: CD - Macromolecular Chemistry Impact factor: 5.557, year: 2015

  9. Unravelling the sulphur isotope systematics of an alkaline magmatic province: implications for REE mineralization and exploration

    Science.gov (United States)

    Hutchison, W.; Finch, A.; Boyce, A.; Friis, H.; Borst, A. M.; Horsburgh, N. J.

    2017-12-01

    Some of the world's best alkaline rare earth element (REE) deposits are formed in magmatic systems that are sealed (i.e., those that are autometasomatised and maintain reducing conditions). Conversely, in open systems where oxidizing fluids infiltrate, it is commonly assumed that REE are redistributed over a wider (less concentrated) zone. Sulphur isotope fractionation is sensitive to variations in temperature and redox, and, although sulphide minerals are relatively abundant in alkaline systems, there have been few attempts to test these hypotheses and develop a sulphur isotope proxy for alkaline metasomatism and formation of associated REE deposits. The Gardar Rift Province in southern Greenland was volcanically active in two periods between 1300 and 1100 Ma and is an ideal natural laboratory to explore sulphur isotope systematics because a near-complete alkaline magmatic lineage is exposed. We present new δ34S from across the province with a particular focus on three alkaline systems (Ilímaussaq, Motzfeldt and Ivigtût) that also host major REE deposits. Primitive mafic rocks from regional Gardar dykes and lavas have a restricted range of δ34S between 0 and 3 ‰ and fractional crystallization imparts no observable change in δ34S. In a few cases high-δ34S rocks (>15 ‰) occur when intrusive units have assimilated local sedimentary crust (δ34S = 25 ‰). Most δ34S variation takes place in the roof zones of alkaline intrusions during late-magmatic and hydrothermal stages, and we identify clear differences between the complexes. At Ilímaussaq, where the magmatic series is exceptionally reduced (below QFM buffer), roof zone δ34S remains narrow (0-3 ‰). At Motzfeldt, a more open oxidizing roof zone (MH buffer), δ34S ranges from -12 ‰ in late-stage fluorite veins to +12 ‰ where local crust has been assimilated. Ivigtût is intermediate between these end-members varying between -5 to +5 ‰. The δ34S variations primarily relate to temperature and

  10. 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)

  11. Efficient visible-light photocatalytic oxidation of gaseous NO with graphitic carbon nitride (g–C{sub 3}N{sub 4}) activated by the alkaline hydrothermal treatment and mechanism analysis

    Energy Technology Data Exchange (ETDEWEB)

    Nie, Haoyu; Ou, Man [School of Chemical Engineering, Nanjing University of Science and Technology, Nanjing, Jiangsu 210094 (China); Nanjing AIREP Environmental Protection Technology Co., Ltd., Nanjing, Jiangsu 210091 (China); Zhong, Qin, E-mail: zq304@mail.njust.edu.cn [School of Chemical Engineering, Nanjing University of Science and Technology, Nanjing, Jiangsu 210094 (China); Nanjing AIREP Environmental Protection Technology Co., Ltd., Nanjing, Jiangsu 210091 (China); Zhang, Shule; Yu, Lemeng [School of Chemical Engineering, Nanjing University of Science and Technology, Nanjing, Jiangsu 210094 (China); Nanjing AIREP Environmental Protection Technology Co., Ltd., Nanjing, Jiangsu 210091 (China)

    2015-12-30

    Highlights: • Various porous g–C{sub 3}N{sub 4} samples were obtained by the alkaline hydrothermal treatment. • 0.12CN possesses the largest BET specific surface area and pore volume. • The NO conversion in the presence of 0.12CN reaches 40.4%. • Reasons for the enhanced PCO performance with treated g–C{sub 3}N{sub 4} was analyzed. • Further mechanism of the PCO of NO relevant with active species was investigated. - Abstract: In this paper, an enhanced visible-light photocatalytic oxidation (PCO) of NO (∼400 ppm) in the presence of the graphitic carbon nitride (g–C{sub 3}N{sub 4}) treated by the alkaline hydrothermal treatment is evaluated. Various g–C{sub 3}N{sub 4} samples were treated in different concentrations of NaOH solutions and the sample treated in 0.12 mol L{sup −1} of NaOH solution possesses the largest BET specific surface area as well as the optimal ability of the PCO of NO. UV–vis diffuse reflection spectra (DRS) and photoluminescence (PL) spectra were also conducted, and the highly improved photocatalytic performance is ascribed to the large specific surface area and high pore volume, which provides more adsorption and active sites, the wide visible-light adsorption edge and the narrow band gap, which is favorable for visible-light activation, as well as the decreased recombination rate of photo-generated electrons and holes, which could contribute to the production of active species. Fluorescence spectra and a trapping experiment were conducted to further the mechanism analysis of the PCO of NO, illustrating that superoxide radicals (·O{sub 2}{sup −}) play the dominant role among active species in the PCO of NO.

  12. Carbon supported Pd-Ni and Pd-Ru-Ni nanocatalysts for the alkaline direct ethanol fuel cell (DEFC)

    CSIR Research Space (South Africa)

    Modibedi, M

    2011-09-01

    Full Text Available alkaline anion exchange membranes (AAEMs) as the electrolyte which protects the electrodes from carbonate formation. Pd has proved to be a good electrocatalyst for ethanol oxidation in alkaline medium, showing higher activity and better steady...

  13. Assessment for the role of rare earth oxide in the R2O3 - RuO2 - Pt composite electrode

    International Nuclear Information System (INIS)

    Do Ngoc Lien; Nguyen Van Sinh

    2004-01-01

    Our work has showed several results related to assessment for the role of rare earth oxide in the R 2 O 3 - RuO 2 - Pt composite electrode. The precursor method was used for preparing composite electrode in the following forms: a- RuO 2 - Pt electrode b- La 2 O 3 (55%) - RuO 2 (45%) - Pt electrode c- CeO 2 (60%) - RuO 2 (40%) - Pt electrode By measurements of anodic polarization and cyclic potential for the types of a, b, c electrodes we can see that the La 2 O 3 (55%) - 45% RuO 2 - Pt electrode will be the best anodic electrode. It means that the partial replacement of ruthenium oxide by lanthanum oxide in composite oxide electrode will be an effective one. (author)

  14. 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.

  15. Regional framework and geology of iron oxide-apatite-rare earth element and iron oxide-copper-gold deposits of the Mesoproterozoic St. Francois Mountains Terrane, southeast Missouri

    Science.gov (United States)

    Day, Warren C.; Slack, John F.; Ayuso, Robert A.; Seeger, Cheryl M.

    2016-01-01

    This paper provides an overview on the genesis of Mesoproterozoic igneous rocks and associated iron oxide ± apatite (IOA) ± rare earth element, iron oxide-copper-gold (IOCG), and iron-rich sedimentary deposits in the St. Francois Mountains terrane of southeast Missouri, USA. The St. Francois Mountains terrane lies along the southeastern margin of Laurentia as part of the eastern granite-rhyolite province. The province formed during two major pulses of igneous activity: (1) an older early Mesoproterozoic (ca. 1.50–1.44 Ga) episode of volcanism and granite plutonism, and (2) a younger middle Mesoproterozoic (ca. 1.33–1.30 Ga) episode of bimodal gabbro and granite plutonism. The volcanic rocks are predominantly high-silica rhyolite pyroclastic flows, volcanogenic breccias, and associated volcanogenic sediments with lesser amounts of basaltic to andesitic volcanic and associated subvolcanic intrusive rocks. The iron oxide deposits are all hosted in the early Mesoproterozoic volcanic and volcaniclastic sequences. Previous studies have characterized the St. Francois Mountains terrane as a classic, A-type within-plate granitic terrane. However, our new whole-rock geochemical data indicate that the felsic volcanic rocks are effusive derivatives from multicomponent source types, having compositional similarities to A-type within-plate granites as well as to S- and I-type granites generated in an arc setting. In addition, the volcanic-hosted IOA and IOCG deposits occur within bimodal volcanic sequences, some of which have volcanic arc geochemical affinities, suggesting an extensional tectonic setting during volcanism prior to emplacement of the ore-forming systems.The Missouri iron orebodies are magmatic-related hydrothermal deposits that, when considered in aggregate, display a vertical zonation from high-temperature, magmatic ± hydrothermal IOA deposits emplaced at moderate depths (~1–2 km), to magnetite-dominant IOA veins and IOCG deposits emplaced at shallow

  16. 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.

  17. The effect of rare earth ions on structural, morphological and thermoelectric properties of nanostructured tin oxide based perovskite materials

    Science.gov (United States)

    Rajasekaran, P.; Alagar Nedunchezhian, A. S.; Yalini Devi, N.; Sidharth, D.; Arivanandhan, M.; Jayavel, R.

    2017-11-01

    Metal oxide based materials are promising for thermoelectric applications especially at elevated temperature due to their high thermal stability. Recently, perovskite based oxide materials have been focused as a novel thermoelectric material due to their tunable electrical conductivity. Thermoelectric properties of BaSnO3 has been extensively investigated. However, the effect of various rare earth doping on the thermoelectric properties of BaSnO3 is not studied in detail. In the present work, Ba1‑x RE x SnO3 (RE  =  La and Sr) materials with x  =  0.05 were prepared by polymerization complex (PC) method in order to study the effect of RE incorporation on the structural, morphological and thermoelectric characteristics of BaSnO3. The structural and morphological properties of the synthesized materials were studied by XRD and TEM analysis. XRD analysis confirmed the mixed phases of the synthesized samples. The TEM images of Ba1‑x Sr x SnO3 shows hexagonal and cubic morphology while, Ba1‑x La x SnO3 exhibit rod like morphology. Various functional groups of the perovskite material were identified using FTIR analysis. Formation of the perovskite material was further confirmed by XPS analysis. The Seebeck coefficient of Ba0.95La0.05SnO3 was relatively higher than that of Ba0.95Sr0.05SnO3, especially at high temperature. The rod like morphology of Ba0.95La0.05SnO3 may facilitate fast electron transport which results high thermal power compared to Ba0.95Sr0.05SnO3 despite of its poor crystalline nature. The substitution of La3+ on the Ba2+ site could vary the carrier density which results high Seebeck coefficient of Ba0.95La0.05SnO3 compared to Ba0.95Sr0.05SnO3. From the experimental results, it is obvious that Ba0.95La0.05SnO3 could be a promising thermoelectric material for high temperature application.

  18. Effect of ozone on ruthenium species in alkaline medium. Pt. II. Oxidation of pentahydroxo nitrosyl ruthenate(II) ion RuNO(OH)52-

    International Nuclear Information System (INIS)

    Floquet, S.; Eysseric, C.

    2006-01-01

    Oxidation of the nitrosyl ruthenium complex RuNO(OH) 5 2- has been carried out in sodium hydroxide solutions in contact with a gas flow containing ozone. The RuNO(OH) 5 2- complex is converted successively into ruthenate and perruthenate ions. An empirical kinetic rate law for the first step has been determined and was shown to depend on concentrations of (i) the ruthenium complex, (ii) the hydroxide ions and (iii) ozone concentration in the gas flow. The second step of the reaction, corresponding to the perruthenate ion formation, shows a complex mechanism and four competing reactions have been proposed to represent it. The influences on the second step kinetics of several parameters such as ozone or hydroxide concentrations or the conditions of the gas-liquid exchange area are also qualitatively discussed. (orig.)

  19. Effect of ozone on ruthenium species in alkaline medium. Pt. II. Oxidation of pentahydroxo nitrosyl ruthenate(II) ion RuNO(OH){sub 5}{sup 2-}

    Energy Technology Data Exchange (ETDEWEB)

    Floquet, S. [Commissariat a l' Energie Atomique (CEA/Valrho), Bagnols-sur-Ceze (France); Inst. Lavoisier, IREM UMR 8637, Univ. de Versailles Saint-Quentin, Versailles (France); Eysseric, C. [Commissariat a l' Energie Atomique (CEA/Valrho), Bagnols-sur-Ceze (France)

    2006-07-01

    Oxidation of the nitrosyl ruthenium complex RuNO(OH){sub 5}{sup 2-} has been carried out in sodium hydroxide solutions in contact with a gas flow containing ozone. The RuNO(OH){sub 5}{sup 2-} complex is converted successively into ruthenate and perruthenate ions. An empirical kinetic rate law for the first step has been determined and was shown to depend on concentrations of (i) the ruthenium complex, (ii) the hydroxide ions and (iii) ozone concentration in the gas flow. The second step of the reaction, corresponding to the perruthenate ion formation, shows a complex mechanism and four competing reactions have been proposed to represent it. The influences on the second step kinetics of several parameters such as ozone or hydroxide concentrations or the conditions of the gas-liquid exchange area are also qualitatively discussed. (orig.)

  20. Low-temperature SCR of NO with NH{sub 3} over activated semi-coke composite-supported rare earth oxides

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Jinping; Yan, Zheng; Liu, Lili; Zhang, Yingyi; Zhang, Zuotai; Wang, Xidong, E-mail: xidong@pku.edu.cn

    2014-08-01

    The catalysts with different rare earth oxides (La, Ce, Pr and Nd) loaded onto activated semi-coke (ASC) via hydrothermal method are prepared for the selective catalytic reduction (SCR) of NO with NH{sub 3} at low temperature (150–300 °C). It is evidenced that CeO{sub 2} loaded catalysts present the best performance, and the optimum loading amount of CeO{sub 2} is about 10 wt%. Composite catalysts by doping La, Pr and Nd into CeO{sub 2} are prepared to obtain further improved catalytic properties. The SCR mechanism is investigated through various characterizations, including XRD, Raman, XPS and FT-IR, the results of which indicate that the oxygen defect plays an important role in SCR process and the doped rare earth elements effectively serve as promoters to increase the concentration of oxygen vacancies. It is also found that the oxygen vacancies in high concentration are favored for the adsorption of O{sub 2} and further oxidation of NO, which facilitates a rapid progressing of the following reduction reactions. The SCR process of NO with NH{sub 3} at low temperature over the catalysts of ASC composite-supported rare earth oxides mainly follows the Langmuir–Hinshlwood mechanism.