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Sample records for metallic rare earth

  1. Rare Earth Metals: Resourcefulness and Recovery

    NASA Astrophysics Data System (ADS)

    Wang, Shijie

    2013-10-01

    When we appreciate the digital revolution carried over from the twentieth century with mobile communication and the Internet, and when we enjoy our high-tech lifestyle filled with iDevices, hybrid cars, wind turbines, and solar cells in this new century, we should also appreciate that all of these advanced products depend on rare earth metals to function. Although there are only 136,000 tons of annual worldwide demand, (Cho, Rare Earth Metals, Will We Have Enough?)1 rare earth metals are becoming such hot commodities on international markets, due to not only to their increasing uses, including in most critical military hardware, but also to Chinese growth, which accounts for 95% of global rare earth metal production. Hence, the 2013 technical calendar topic, planned by the TMS/Hydrometallurgy and Electrometallurgy Committee, is particularly relevant, with four articles (including this commentary) contributed to the JOM October Issue discussing rare earth metals' resourcefulness and recovery.

  2. Recycling of rare earth metals from rare earth-transition metal alloy scrap by liquid metal extraction

    DOEpatents

    Ellis, T.W.; Schmidt, F.A.

    1995-08-01

    A method is described for treating rare earth metal-bearing scrap, waste or other material (e.g. Nd--Fe--B or Dy--Tb--Fe scrap) to recover the rare earth metal comprising melting the rare earth metal-bearing material, melting a Group IIA metal extractant, such as Mg, Ca, or Ba, in which the rare earth is soluble in the molten state, and contacting the melted material and melted extractant at a temperature and for a time effective to extract the rare earth from the melted material into the melted extractant. The rare earth metal is separated from the extractant metal by vacuum sublimation or distillation. 2 figs.

  3. Recycling of rare earth metals from rare earth-transition metal alloy scrap by liquid metal extraction

    DOEpatents

    Ellis, Timothy W.; Schmidt, Frederick A.

    1995-08-01

    Method of treating rare earth metal-bearing scrap, waste or other material (e.g. Nd--Fe--B or Dy--Tb--Fe scrap) to recover the rare earth metal comprising melting the rare earth metal-bearing material, melting a Group IIA metal extractant, such as Mg, Ca, or Ba, in which the rare earth is soluble in the molten state, and contacting the melted material and melted extractant at a temperature and for a time effective to extract the rare earth from the melted material into the melted extractant. The rare earth metal is separated from the extractant metal by vacuum sublimation or distillation.

  4. Gyroscopic g factor of rare earth metals

    NASA Astrophysics Data System (ADS)

    Ogata, Y.; Chudo, H.; Ono, M.; Harii, K.; Matsuo, M.; Maekawa, S.; Saitoh, E.

    2017-02-01

    We develop the in situ magnetization measurement apparatus for observing the Barnett effect consisting of a fluxgate sensor, a high speed rotor with frequencies of up to 1.5 kHz, and a magnetic shield at room temperature. The effective magnetic field (Barnett field) in a sample arising from rotation magnetizes the sample and is proportional to the rotational frequency. The gyroscopic g factor, g ' , of rare earth metals, in particular, Gd, Tb, and Dy, was estimated to be 2.00 ± 0.08, 1.53 ± 0.17, and 1.15 ± 0.32, respectively, from the slopes of the rotation dependence of the Barnett field. This study provides a technique to determine the g ' factor even in samples where the spectroscopic method may not be available.

  5. METHOD OF MAKING ALLOYS OF SECOND RARE EARTH SERIES METALS

    DOEpatents

    Baker, R.D.; Hayward, B.R.

    1963-01-01

    >This invention relates to a process for alloying the second rare earth series metals with Mo, Nb, or Zr. A halide of the rare earth metal is mixed with about 1 to 20 at.% of an oxide of Mo, Nb, or Zr. Iodine and an alkali or alkaline earth metal are added, and the resulting mixture is heated in an inert atmosphere to 350 deg C. (AEC)

  6. 40 CFR 421.270 - Applicability: Description of the primary rare earth metals subcategory.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... primary rare earth metals subcategory. 421.270 Section 421.270 Protection of Environment ENVIRONMENTAL... CATEGORY Primary Rare Earth Metals Subcategory § 421.270 Applicability: Description of the primary rare... production of rare earth metals and mischmetal by primary rare earth metals facilities......

  7. Method for treating rare earth-transition metal scrap

    DOEpatents

    Schmidt, Frederick A.; Peterson, David T.; Wheelock, John T.; Jones, Lawrence L.

    1992-12-29

    Rare earth-transition metal (e.g., iron) scrap (e.g., Nd-Fe-B scrap) is flux (slag) remelted to reduce tramp non-metallic impurities, such as oxygen and nitrogen, and metallic impurities, such as Li, Na, Al, etc., picked up by the scrap from previous fabrication operations. The tramp impurities are reduced to concentrations acceptable for reuse of the treated alloy in the manufacture of end-use articles, such as permanent magnets. The scrap is electroslag or inductoslag melted using a prefused, rare earth fluoride-bearing flux of CaF.sub.2, CaCl.sub.2 or mixtures thereof or the slag resulting from practice of the thermite reduction process to make a rare earth-iron alloy.

  8. Method for treating rare earth-transition metal scrap

    DOEpatents

    Schmidt, F.A.; Peterson, D.T.; Wheelock, J.T.; Jones, L.L.

    1992-12-29

    Rare earth-transition metal (e.g., iron) scrap (e.g., Nd-Fe-B scrap) is flux (slag) remelted to reduce tramp non-metallic impurities, such as oxygen and nitrogen, and metallic impurities, such as Li, Na, Al, etc., picked up by the scrap from previous fabrication operations. The tramp impurities are reduced to concentrations acceptable for reuse of the treated alloy in the manufacture of end-use articles, such as permanent magnets. The scrap is electroslag or inductoslag melted using a rare earth fluoride-bearing flux of CaF[sub 2], CaCl[sub 2] or mixtures thereof or the slag resulting from practice of the thermite reduction process to make a rare earth-iron alloy. 3 figs.

  9. Rare earth metal trifluoromethanesulfonates catalyzed benzyl-etherification.

    PubMed

    Kawada, Atsushi; Yasuda, Kayo; Abe, Hitoshi; Harayama, Takashi

    2002-03-01

    Rare earth metal trifluoromethanesulfonates [rare earth metal triflate, RE(OTf)3] were found to be efficient catalyst for benzyl-etherification. In the presence of a catalytic amount of RE(OTf)3, condensation of benzyl alcohols and aliphatic alcohols proceeded smoothly to afford the benzyl ethers. The condensation between benzyl alcohols and thiols also proceeded, and thio ethers were obtained in good yield. In these reactions, RE(OTf)3 could be recovered easily after the reactions were completed and could be reused without loss of activity.

  10. Trace metal and rare earth content of black precipitation events

    SciTech Connect

    Landsberger, S. . Dept. of Nuclear Engineering); Davies, T.D. . School of Environmental Sciences); Tranter, M. )

    1990-01-01

    The authors have used the techniques of non-destructive neutron activation analysis to determine trace metal and rare earth content of black precipitation events occurring in the Cairngorm Mountains in remote areas of Scotland. Thirty-one elements were determined in the particulate matter of snowpack cores that were sliced into sections. An additional analysis was performed for a black acidic snow event. Based on these results and on wind trajectories, increased loadings of many of the heavy metals and rare earth elements appeared to have originated from central Europe. Enrichment factor calculations show anthropogenic emissions for indium, arsenic, zinc, and selenium.

  11. Charge-separated and molecular heterobimetallic rare earth-rare earth and alkaline earth-rare earth aryloxo complexes featuring intramolecular metal-pi-arene interactions.

    PubMed

    Deacon, Glen B; Junk, Peter C; Moxey, Graeme J; Ruhlandt-Senge, Karin; St Prix, Courtney; Zuniga, Maria F

    2009-01-01

    Treatment of a rare earth metal (Ln) and a potential divalent rare earth metal (Ln') or an alkaline earth metal (Ae) with 2,6-diphenylphenol (HOdpp) at elevated temperatures (200-250 degrees C) afforded heterobimetallic aryloxo complexes, which were structurally characterised. A charge-separated species [(Ln'/Ae)(2)(Odpp)(3)][Ln(Odpp)(4)] was obtained for a range of metals, demonstrating the similarities between the chemistry of the divalent rare earth metals and the alkaline earth metals. The [(Ln'/Ae)(2)(Odpp)(3)](+) cation in the heterobimetallic structures is unusual in that it consists solely of bridging aryloxide ligands. A molecular heterobimetallic species [AeEu(Odpp)(4)] (Ae = Ca, Sr, Ba) was obtained by treating an alkaline earth metal and Eu metal with HOdpp at elevated temperatures. Similarly, [BaSr(Odpp)(4)] was prepared by treating Ba metal and Sr metal with HOdpp. Treatment of [Ba(2)(Odpp)(4)] with [Mg(Odpp)(2)(thf)(2)] in toluene afforded [Ba(2)(Odpp)(3)][Mg(Odpp)(3)(thf)]. Analogous solution-based syntheses were not possible for [(Ln'/Ae)(2)(Odpp)(3)][Ln(Odpp)(4)] complexes, for which the free-metal route was essential. As a result of the absence of additional donor ligands, the crystal structures of the heterobimetallic complexes feature extensive pi-Ph-metal interactions involving the pendant phenyl groups of the Odpp ligands, thus enabling the large electropositive metal atoms to attain coordination saturation. The charge-separated heterobimetallic species were purified by extraction with toluene/thf mixtures at ambient temperature (Ba-containing compounds) or by extraction with toluene under pressure above the boiling point of the solvent (other products). In donor solvents, heterobimetallic complexes other than those containing barium were found to fragment into homometallic species.

  12. Distributions of rare earths and heavy metals in field-grown maize after application of rare earth-containing fertilizer.

    PubMed

    Xu, Xingkai; Zhu, Wangzhao; Wang, Zijian; Witkamp, Geert-Jan

    2002-07-03

    Rare earths are widely applied in Chinese agriculture to improve crop nutrition through the use of fertilizers, yet little is known of their accumulation in field-grown crops. We have studied the distribution of 16 rare earths (Sc, Y and 14 lanthanide elements) in field-grown maize and the concentration of heavy metals in the grains after application of rare earth-containing fertilizer. When maize entered the vigorous vegetation growth stage (e.g. early stem-elongation stage), rare earth-containing fertilizer was applied to the soil with irrigation water. At 10 days after application of the rare earths, significantly dose-dependent accumulative effects of individual rare earth concentrations in the roots and the plant tops of maize were observed, with the exception of Sc and Lu. At the level of 2 kg rare earths ha(-1), accumulative concentrations of most light rare earths (e.g. La, Ce, Pr and Nd) and Gd in the plant tops were much larger than those in the control. Concentrations of individual rare earths in a field-grown maize after application of rare earths decreased in the order of root>leaf>stem>grain. During the maize growth period, selective accumulation of individual rare earths (e.g. La, Ce) in the roots seemed to be in dynamic equilibrium, and the distribution of these elements in the plant tops was variable. At a dosage of less than 10 kg rare earths ha(-1), no apparent accumulative concentrations of individual rare earths appeared in the maize grains. Under the experimental conditions, application of rare earth-containing fertilizer did not induce an increase in the concentrations of heavy metals in the grains. We conclude that the present dosage of rare earths (<0.23 kg ha(-1) year(-1)) currently applied in China can hardly affect the safety of maize grains in arable soil, even over a long period.

  13. Thin Films of the Rare-Earth Metals,

    DTIC Science & Technology

    A vacuum thermal method of producing thin films (1-10 mu m) of rare earth metals (Sm, Dy, Tn, and Yb) is described and its efficiency is compared with...existing methods (which are briefly reviewed). A very effective method of obtaining the thin films in question is by reducing the corresponding

  14. Rare earth-transition metal scrap treatment method

    DOEpatents

    Schmidt, F.A.; Peterson, D.T.; Wheelock, J.T.; Jones, L.L.; Lincoln, L.P.

    1992-02-11

    Rare earth-transition metal (e.g. iron) scrap (e.g. Nd-Fe-B scrap) is melted to reduce the levels of tramp oxygen and nitrogen impurities therein. The tramp impurities are reduced in the melt by virtue of the reaction of the tramp impurities and the rare earth to form dross on the melt. The purified melt is separated from the dross for reuse. The oxygen and nitrogen of the melt are reduced to levels acceptable for reuse of the treated alloy in the manufacture of end-use articles, such as permanent magnets. 3 figs.

  15. Rare earth-transition metal scrap treatment method

    DOEpatents

    Schmidt, Frederick A.; Peterson, David T.; Wheelock, John T.; Jones, Lawrence L.; Lincoln, Lanny P.

    1992-02-11

    Rare earth-transition metal (e.g. iron) scrap (e.g. Nd-Fe-B scrap) is melted to reduce the levels of tramp oxygen and nitrogen impurities therein. The tramp impurities are reduced in the melt by virtue of the reaction of the tramp impurities and the rare earth to form dross on the melt. The purified melt is separated from the dross for reuse. The oxygen and nitrogen of the melt are reduced to levels acceptable for reuse of the treated alloy in the manufacture of end-use articles, such as permanent magnets.

  16. Correlations in rare-earth transition-metal permanent magnets

    SciTech Connect

    Skomski, R. Manchanda, P.; Kashyap, A.

    2015-05-07

    It is investigated how electron-electron correlations affect the intrinsic properties of rare-earth transition-metal magnets. Focusing on orbital moment and anisotropy, we perform model calculations for 3d-4f alloys and density-functional theory (DFT) calculations for NdCo{sub 5}. On an independent-electron level, the use of a single Slater determinant with broken spin symmetry introduces Hund's rule correlations, which govern the behavior of rare-earth ions and of alloys described by the local spin density approximation (LSDA) and LSDA + U approximations to DFT. By contrast, rare-earth ions in intermetallics involve configuration interactions between two or more Slater determinants and lead to phenomena such as spin-charge distribution. Analyzing DFT as a Legendre transformation and using Bethe's crystal-field theory, we show that the corresponding density functionals are very different from familiar LSDA-type expressions and outline the effect of spin-charge separation on the magnetocrystalline anisotropy.

  17. Synthesis and luminescence of some rare earth metal complexes

    NASA Astrophysics Data System (ADS)

    Bochkarev, Mikhail N.; Pushkarev, Anatoly P.

    2016-12-01

    In the present paper the synthesis, photoand electroluminescent properties of new rare earth metal complexes prepared and studied at the Razuvaev Institute of Organometallic Chemistry during the last decade are reviewed. The obtained compounds give luminescence in UV, visible and NIR regions. The substituted phenolates, naphtholates, mercaptobenzothiazolate, 8-oxyquinolinolate, polyfluorinated alcoholates and chalcogenophosphinates were used as ligands. The synthesis and structure of unusual three-nuclear sulfidenitride clusters of Nd and Dy are described. The new excitation mechanism of ytterbium phenolates and naphtholates, which includes the stage of reversible reduction of Yb to divalent state and oxidation of the ligands in the excitation process, is discussed.

  18. Metal sulfide and rare-earth phosphate nanostructures and methods of making same

    SciTech Connect

    Wong, Stanislaus; Zhang, Fen

    2016-06-28

    The present invention provides a method of producing a crystalline rare earth phosphate nanostructure. The method comprising: providing a rare earth metal precursor solution and providing a phosphate precursor solution; placing a porous membrane between the metal precursor solution and the phosphate precursor solution, wherein metal cations of the metal precursor solution and phosphate ions of the phosphate precursor solution react, thereby producing a crystalline rare earth metal phosphate nanostructure.

  19. [Rare-earth metals as a factor in mutagenicity].

    PubMed

    Solovykh, G N; Golinskaia, L V; Kanunikova, E A

    2012-01-01

    Both the regions of the Orenburg Region area and individual examined streams and reservoirs were shown to be characterized by a varying load index for rare earth elements. The total level of rare earth elements was directly correlated with different types of mutations.

  20. Rare-Earth Metal Postmetallocene Catalysts with Chelating Amido Ligands

    NASA Astrophysics Data System (ADS)

    Li, Tianshu; Jenter, Jelena; Roesky, Peter W.

    This review deals with the synthesis and the catalytic application of noncyclopentadienyl complexes of the rare-earth elements. The main topics of the review are amido metal complexes with chelating bidentate ligands, which show the most similarities to cyclopentadienyl ligands. Benzamidinates and guanidinates will be reviewed in a separate contribution within this book. Beside the synthesis of the complexes, the broad potential of these compounds in homogeneous catalysis is demonstrated. Most of the reviewed catalytic transformations are either C-C multiple bond transformation such as the hydroamination and hydrosilylation or polymerization reaction of polar and nonpolar monomers. In this area, butadiene and isoprene, ethylene, as well as lactides and lactones were mostly used as monomers.

  1. Sonochemical synthesis of mesoporous transition metal and rare earth oxides.

    PubMed

    Wang, Yanqin; Yin, Lunxiang; Gedanken, Arahon

    2002-11-01

    Straight-extended layered mesostructures based on transItion metal (Fe, Cr) and rare earth (Y, Ce, La, Sm, Er) oxides are synthesized by sonication for 3 h. After a longer period of sonication (6 h), hexagonal mesostructures based on Y- and Er-oxides are obtained. The surface areas of the Y-based hexagonal mesophases before and after extraction are 46.5, 256 m2/g, respectively. For Er-based hexagonal mesophases, the surface areas before and after extraction are 157 and 225 m2/g. The pore sizes after extraction are 5.0 and 2.2 nm for Y- and Er-based mesophases, respectively. Hexagonal mesostructures are also obtained for Zr-based material after sonication for 3 h and the hexagonal structure is still maintained after calcinations at 400 degrees C for 4 h, although the surface area is only 35 m2/g.

  2. Minerals yearbook, 1988. Rare-earth minerals and metals

    SciTech Connect

    Hedrick, J.B.; Templeton, D.A.

    1988-01-01

    Domestic production of rare-earth concentrates decreased in 1988. Foreign sources of processed rare earths obtained a slightly larger share of the U.S. market, while domestic exports saw a marked increase compared to 1987 levels. Rare earths were used in high-technology applications such as laser crystals, high-strength permanent magnets, optical fibers, magnetic resonance imaging (MRI) scanners, and high-temperature superconductors. Topics discussed in the report include domestic data coverage, legislation and government programs, environmental issues, domestic production, consumption and uses, stocks, prices, foreign trade, world capacity, world review--Australia, Brazil, Canada, China, Egypt, Greenland, Japan, Madagascar, Malaysia, Mozambique, Sri Lanka, Thailand--and technology.

  3. Molecular rare-earth-metal hydrides in non-cyclopentadienyl environments.

    PubMed

    Fegler, Waldemar; Venugopal, Ajay; Kramer, Mathias; Okuda, Jun

    2015-02-02

    Molecular hydrides of the rare-earth metals play an important role as homogeneous catalysts and as counterparts of solid-state interstitial hydrides. Structurally well-characterized non-metallocene-type hydride complexes allow the study of elementary reactions that occur at rare-earth-metal centers and of catalytic reactions involving bonds between rare-earth metals and hydrides. In addition to neutral hydrides, cationic derivatives have now become available.

  4. Molten metal containment vessel with rare earth oxysulfide protective coating thereon and method of making same

    DOEpatents

    Krikorian, Oscar H.; Curtis, Paul G.

    1992-01-01

    An improved molten metal containment vessel is disclosed in which wetting of the vessel's inner wall surfaces by molten metal is inhibited by coating at least the inner surfaces of the containment vessel with one or more rare earth oxysulfide or rare earth sulfide compounds to inhibit wetting and or adherence by the molten metal to the surfaces of the containment vessel.

  5. 40 CFR 421.270 - Applicability: Description of the primary rare earth metals subcategory.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... primary rare earth metals subcategory. 421.270 Section 421.270 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) EFFLUENT GUIDELINES AND STANDARDS NONFERROUS METALS MANUFACTURING POINT SOURCE CATEGORY Primary Rare Earth Metals Subcategory § 421.270 Applicability: Description of the primary...

  6. 40 CFR 421.270 - Applicability: Description of the primary rare earth metals subcategory.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... primary rare earth metals subcategory. 421.270 Section 421.270 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) EFFLUENT GUIDELINES AND STANDARDS NONFERROUS METALS MANUFACTURING POINT SOURCE CATEGORY Primary Rare Earth Metals Subcategory § 421.270 Applicability: Description of the primary...

  7. 40 CFR 421.270 - Applicability: Description of the primary rare earth metals subcategory.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... primary rare earth metals subcategory. 421.270 Section 421.270 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) EFFLUENT GUIDELINES AND STANDARDS NONFERROUS METALS MANUFACTURING POINT SOURCE CATEGORY Primary Rare Earth Metals Subcategory § 421.270 Applicability: Description of the primary...

  8. 40 CFR 421.270 - Applicability: Description of the primary rare earth metals subcategory.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... primary rare earth metals subcategory. 421.270 Section 421.270 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) EFFLUENT GUIDELINES AND STANDARDS NONFERROUS METALS MANUFACTURING POINT SOURCE CATEGORY Primary Rare Earth Metals Subcategory § 421.270 Applicability: Description of the primary...

  9. The DNA-binding and bioactivity of rare earth metal complexes.

    PubMed

    Yang, Li; Wang, Bochu; Tan, Jun; Zhu, Liancai

    2013-08-01

    Recently more and more attention is paid to the rare earth metal complexes, because the properties of the rare earth metals are similar to those of the transition metals such as the similar atomic and the ionic radius. A large number of rare metal complexes were synthesized, and their bioactivities were also studied. This review highlights recent researches on the interaction of some rare earth metal complexes with DNA, analyzes how the configuration of the complexes influences the binding affinity, and focuses on the pharmacological activities of the complexes, such as anticancer, antibacterial, antioxidant, anti-inflammatory and anti-virus.

  10. Solvent extraction of rare-earth metals by carboxylic acids

    SciTech Connect

    Preez, A.C. du; Preston, J.S.

    1992-04-01

    The solvent extraction of the trivalent lanthanides and yttrium from nitrate media by solutions of carboxylic acids in xylene has been studied. Commercially available carboxylic acids such as Versatic 10 and naphthenic acids were used, as well as model compounds of known structure, such as 2-ethylhexanoic and 3-cyclohexylpropanoic acids. In a few cases, extraction of the metals from sulphate and chloride solutions was also investigated. The dependence of the extraction properties of the carboxylic acids on the atomic number of the lanthanide shows a definite relationship to the steric bulk of the carboxylic acid molecule quantified by means of the steric parameter, E{sub s}{prime} of the substituent alkyl group. The stoichiometries of the extracted complexes for representative light (La), middle (Gd) and heavy (Lu) rare-earth metals were investigated by the slope-analysis technique for a sterically hindered acid (Versatic 10 acid; -E{prime}{sub s} = 3.83) and an acid with low steric hindrance (3-cyclohexylpropanoic acid; -E{prime}{sub s} = 0.28). 14 refs., 13 figs., 3 tabs.

  11. Synthesis, structure and reactivity of rare-earth metal complexes containing anionic phosphorus ligands.

    PubMed

    Li, Tianshu; Kaercher, Sabrina; Roesky, Peter W

    2014-01-07

    A comprehensive review of structurally characterized rare-earth metal complexes containing anionic phosphorus ligands is presented. Since rare-earth elements form hard ions and phosphorus is considered as a soft ligand, the rare-earth metal phosphorus coordination is regarded as a less favorite combination. Three classes of phosphorus ligands, (1) the monoanionic organophosphide ligands (PR2(-)) bearing one negative charge on the phosphorus atom; (2) the dianionic phosphinidene (PR(2-)) and P(3-) ligands; and (3) the pure inorganic polyphosphide ligands (Pn(x-)), are included here. Particular attention has been paid to the synthesis, structure, and reactivity of the rare-earth metal phosphides.

  12. Yttrium and rare earth stabilized fast reactor metal fuel

    DOEpatents

    Guon, Jerold; Grantham, LeRoy F.; Specht, Eugene R.

    1992-01-01

    To increase the operating temperature of a reactor, the melting point and mechanical properties of the fuel must be increased. For an actinide-rich fuel, yttrium, lanthanum and/or rare earth elements can be added, as stabilizers, to uranium and plutonium and/or a mixture of other actinides to raise the melting point of the fuel and improve its mechanical properties. Since only about 1% of the actinide fuel may be yttrium, lanthanum, or a rare earth element, the neutron penalty is low, the reactor core size can be reduced, the fuel can be burned efficiently, reprocessing requirements are reduced, and the nuclear waste disposal volumes reduced. A further advantage occurs when yttrium, lanthanum, and/or other rare earth elements are exposed to radiation in a reactor, they produce only short half life radioisotopes, which reduce nuclear waste disposal problems through much shorter assured-isolation requirements.

  13. Rare-earth metal prices in the USA ca. 1960 to 1994

    USGS Publications Warehouse

    Hedrick, J.B.

    1997-01-01

    Rare-earth metal prices were compiled from the late 1950s and early 1960s through 1994. Although commercial demand for rare-earth metals began in 1908, as the alloy mischmetal, commercial quantities of a wide range of individual rare-earth metals were not available until the late 1950s. The discovery of a large, high-grade rare-earth deposit at Mountain Pass, CA, USA, in 1949, was significant because it led to the production of commercial quantities of rare-earth elements that reduced prices and encouraged wider application of the materials. The availability of ore from Mountain Pass, and other large rare-earth deposits, especially those in Australia and China, has provided the world with abundant resources for rare-earth metal production. This availability, coupled with improved technology from Government and private-sector metallurgical research, has resulted in substantial decreases in rare-earth metal prices since the late 1950s and early 1960s. Price series for the individual rare-earth metals (except promethium) are quoted on a kilogram basis from the late 1950s and early 1960s through 1994. Prices are given in US dollars on an actual and constant dollar basis. Industrial and economic factors affecting prices during this time period are examined.

  14. Rare-earth metal prices in the USA ca. 1960 to 1994

    USGS Publications Warehouse

    Hedrick, James B.

    1997-01-01

    Rare-earth metal prices were compiled from the late 1950s and early 1960s through 1994. Although commercial demand for rare-earth metals began in 1908, as the alloy mischmetal, commercial quantities of a wide range of individual rare-earth metals were not available until the late 1950s. The discovery of a large, high-grade rare-earth deposit at Mountain Pass. CA, USA, in 1949, was significant because it led to the production of commercial quantities or rare-earth elements that reduced prices and encouraged wider application of the materials. The availability of ore from Mountain Pass, and other large rare-earth deposits, especially those in Australia and China, has provided the world with abundant resources for rare-earth metal production. This availability, coupled with improved technology from Government and private-sector metallurgical research, has resulted in substantial decreases in rare-earth metal prices since the late 1950s and early 1960s. Price series for the individual rare-earth metals (except promethium) are quoted on a kilogram basis from the late 1950s and early 1960s through 1994. Prices are given in US dollars on an actual and constant dollar basis. Industrial and economic factors affecting prices during this time period are examined.

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

    PubMed

    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.

  16. Rare earths

    USGS Publications Warehouse

    Gambogi, J.

    2013-01-01

    Global mine production of rare earths was estimated to have declined slightly in 2012 relative to 2011 (Fig. 1). Production in China was estimated to have decreased to 95 from 105 kt (104,700 from 115,700 st) in 2011, while new mine production in the United States and Australia increased.

  17. Novel polymerization catalysts and hydride clusters from rare-earth metal dialkyls.

    PubMed

    Nishiura, Masayoshi; Hou, Zhaomin

    2010-04-01

    This Review gives an overview on recent progress in the synthesis and chemistry of rare-earth metal dialkyl complexes bearing monoanionic ancillary ligands, with an emphasis on novel polymerization catalysts. These structurally well-defined and highly reactive compounds are prepared either by alkane elimination reactions between trialkyl rare-earth complexes and acidic neutral ligands, or by the metathetical reactions of rare-earth trihalides with the alkali metal salts of the corresponding ligands. On treatment with an appropriate borate compound, the dialkyl complexes are converted into the corresponding cationic monoalkyl species, which serve as excellent catalysts for the polymerization and copolymerization of a variety of olefins to yield a series of new polymer materials that exhibit novel properties. Alternatively, hydrogenation of the dialkyl rare-earth complexes with H(2) affords a new class of rare-earth polyhydride complexes with unique features in terms of both their structure and reactivity.

  18. Environmental Defects And Economic Impact On Global Market Of Rare Earth Metals

    NASA Astrophysics Data System (ADS)

    Charalampides, G.; Vatalis, K.; Karayannis, V.; Baklavaridis, A.

    2016-11-01

    Rare earth elements include the 14 lanthanides as well as lanthanium and often yttrium. Actually, most of them are not very rare and occur widely dispersed in a variety of rocks. Rare earth metals are vital to some of the world's faster growing industries: catalysts, Nd-magnets, ceramics, glass, metallurgy, battery alloys, electronics and phosphors. Worldwide, the main countries for distribution of rare earths deposits include China, USA, Russia, Brasil, India, Australia, Greenland and Malaysia. The mining and processing of rare earth metals usually result in significant environmental defects. Many deposits are associated with high concentrations of radioactive elements such as uranium and thorium, which requires separate treatment and disposal. The accumulation of rare earth elements in soils has occurred due to pollution caused by the exploitation of rare earth resources and the wide use of rare earths as fertilizers in agriculture. This accumulation has a toxic effect on the soil microfauna community. However, there are large differences in market prices due to the degree of purity determined by the specifications in the applications. The main focus of this article is to overview Rare Earth Metals’ overall impact on global economy and their environmental defects on soils during processing techniques and as they are used as fertilizers.

  19. Direct experimental evidence for the Ruderman-Kittel-Kasuya-Yosida interaction in rare-earth metals.

    PubMed

    Hindmarch, A T; Hickey, B J

    2003-09-12

    We show that the ferromagnetic heavy rare-earth (RE) metals show a transport spin polarization at the Fermi level in the majority spin, whereas in ferromagnetic light rare earths it is in the minority spin. The sign of the polarization is in agreement with what is expected due to the Ruderman-Kittel-Kasuya-Yosida (RKKY) coupling formalism. We show that magnetotransport measurements on magnetic multilayer samples containing magnetic REs provide a unique opportunity to verify the RKKY coupling scheme in pure rare-earth metals, allowing us to probe both the sign and temperature dependence of the spin-density oscillation.

  20. Selective transformations of cyclopentadienyl ligands of transition-metal and rare-earth metal complexes.

    PubMed

    Liu, Ruiting; Zhou, Xigeng

    2013-04-21

    Cyclopentadienyl and substituted cyclopentadienyl ligands are observed in a wide range of organometallic complexes. In addition to serving as ancillary ligands, these ligands have come into their own as intermediates in organometallic reactions, and shown many unique reaction modes involving ring C-H, C-C and C=C bond cleavages. This feature article summarizes the progressive development of cyclopentadienyl-based reactions of metallocene complexes of transition metals and rare-earth metals, with the aim of further developing the fundamental modes of reactivity of such systems together with their synthetic applications.

  1. Oligomeric rare-earth metal cluster complexes with endohedral transition metal atoms

    SciTech Connect

    Steinberg, Simon; Zimmermann, Sina; Brühmann, Matthias; Meyer, Eva; Rustige, Christian; Wolberg, Marike; Daub, Kathrin; Bell, Thomas; Meyer, Gerd

    2014-11-15

    Comproportionation reactions of rare-earth metal trihalides (RX{sub 3}) with the respective rare-earth metals (R) and transition metals (T) led to the formation of 22 oligomeric R cluster halides encapsulating T, in 19 cases for the first time. The structures of these compounds were determined by single-crystal X-ray diffraction and are composed of trimers ((T{sub 3}R{sub 11})X{sub 15}-type, P6{sub 3}/m), tetramers ((T{sub 4}R{sub 16})X{sub 28}(R{sub 4}) (P-43m), (T{sub 4}R{sub 16})X{sub 20} (P4{sub 2}/nnm), (T{sub 4}R{sub 16})X{sub 24}(RX{sub 3}){sub 4} (I4{sub 1}/a) and (T{sub 4}R{sub 16})X{sub 23} (C2/m) types of structure) and pentamers ((Ru{sub 5}La{sub 14}){sub 2}Br{sub 39}, Cc) of (TR{sub r}){sub n} (n=2–5) clusters. These oligomers are further enveloped by inner (X{sup i}) as well as outer (X{sup a}) halido ligands, which possess diverse functionalities and interconnect like oligomers through i–i, i–a and/or a–i bridges. The general features of the crystal structures for these new compounds are discussed and compared to literature entries as well as different structure types with oligomeric T centered R clusters. Dimers and tetramers originating from the aggregation of (TR{sub 6}) octahedra via common edges are more frequent than trimers and pentamers, in which the (TR{sub r}) clusters share common faces. - Graphical abstract: Rare earth-metal cluster complexes with endohedral transition metal atoms (TR{sub 6}) may connect via common edges or faces to form dimers, trimers, tetramers and pentamers of which the tetramers are the most prolific. Packing effects and electron counts play an important role. - Highlights: • Rare-earth metal cluster complexes encapsulate transition metal atoms. • Oligomers are built via connection of octahedral clusters via common edges or faces. • Dimers through pentamers with closed structures are known. • Tetramers including a tetrahedron of endohedral atoms are the most prolific.

  2. Oligomeric rare-earth metal cluster complexes with endohedral transition metal atoms

    NASA Astrophysics Data System (ADS)

    Steinberg, Simon; Zimmermann, Sina; Brühmann, Matthias; Meyer, Eva; Rustige, Christian; Wolberg, Marike; Daub, Kathrin; Bell, Thomas; Meyer, Gerd

    2014-11-01

    Comproportionation reactions of rare-earth metal trihalides (RX3) with the respective rare-earth metals (R) and transition metals (T) led to the formation of 22 oligomeric R cluster halides encapsulating T, in 19 cases for the first time. The structures of these compounds were determined by single-crystal X-ray diffraction and are composed of trimers ({T3R11}X15-type, P63/m), tetramers ({T4R16}X28{R4} (P-43m), {T4R16}X20 (P42/nnm), {T4R16}X24(RX3)4 (I41/a) and {T4R16}X23 (C2/m) types of structure) and pentamers ({Ru5La14}2Br39, Cc) of {TRr}n (n=2-5) clusters. These oligomers are further enveloped by inner (Xi) as well as outer (Xa) halido ligands, which possess diverse functionalities and interconnect like oligomers through i-i, i-a and/or a-i bridges. The general features of the crystal structures for these new compounds are discussed and compared to literature entries as well as different structure types with oligomeric T centered R clusters. Dimers and tetramers originating from the aggregation of {TR6} octahedra via common edges are more frequent than trimers and pentamers, in which the {TRr} clusters share common faces.

  3. Asymmetric Catalysis with bis(hydroxyphenyl)diamides/rare-earth metal complexes.

    PubMed

    Kumagai, Naoya; Shibasaki, Masakatsu

    2013-01-02

    A series of asymmetric catalysts composed of conformationally flexible amide-based chiral ligands and rare-earth metals was developed for proton-transfer catalysis. These ligands derived from amino acids provide an intriguing chiral platform for the formation of asymmetric catalysts upon complexation with rare-earth metals. The scope of this arsenal of catalysts was further broadened by the development of heterobimetallic catalytic systems. The cooperative function of hydrogen bonding and metal coordination resulted in intriguing substrate specificity and stereocontrol, and the dynamic nature of the catalysts led to a switch of their function. Herein, we summarize our recent exploration of this class of catalysts.

  4. High-temperature desulfurization of gasifier effluents with rare earth and rare earth/transition metal oxides

    SciTech Connect

    Dooley, Kerry M.; Kalakota, Vikram; Adusumilli, Sumana

    2011-02-11

    We have improved the application of mixed rare-earth oxides (REOs) as hot gas desulfurization adsorbents by impregnating them on stable high surface area supports and by the inclusion of certain transition metal oxides. We report comparative desulfurization experiments at high temperature (900 K) using a synthetic biomass gasifier effluent containing 0.1 vol % H2S, along with H2, CO2, and water. More complex REO sorbents outperform the simpler CeO2/La2O3 mixtures, in some cases significantly. Supporting REOs on Al2O3 (~20 wt % REO) or ZrO2 actually increased the sulfur capacities found after several cycles on a total weight basis. Another major increase in sulfur capacity took place when MnOx or FeOx is incorporated. Apparently most of the Mn or Fe is dispersed on or near the surface of the mixed REOs because the capacities with REOs greatly exceeded those of Al2O3-supported MnOx or FeOx alone at these conditions. In contrast, incorporating Cu has little effect on sulfur adsorption capacities. Both the REO and transition metal/REO adsorbents could be regenerated completely using air for at least five repetitive cycles.

  5. Rare-Earth Metals and Their Applications in Aviation

    DTIC Science & Technology

    1984-08-01

    promethium , samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, scandium and yttrium. Based on the...yttrium. Aside from these, promethium is an artifical element, it has radioactivity and is almost non-existent in the earth’s crust. The term "rate-earth

  6. Metal enhanced fluorescence in rare earth doped plasmonic core-shell nanoparticles.

    PubMed

    Derom, S; Berthelot, A; Pillonnet, A; Benamara, O; Jurdyc, A M; Girard, C; Colas des Francs, G

    2013-12-13

    We theoretically and numerically investigate metal enhanced fluorescence of plasmonic core-shell nanoparticles doped with rare earth (RE) ions. Particle shape and size are engineered to maximize the average enhancement factor (AEF) of the overall doped shell. We show that the highest enhancement (11 in the visible and 7 in the near-infrared) is achieved by tuning either the dipolar or the quadrupolar particle resonance to the rare earth ion's excitation wavelength. Additionally, the calculated AEFs are compared to experimental data reported in the literature, obtained in similar conditions (plasmon mediated enhancement) or when a metal-RE energy transfer mechanism is involved.

  7. Direct evidence of the anisotropy of magnetization in rare-earth metals and rare-earth/Fe2 alloys

    NASA Astrophysics Data System (ADS)

    Benito, L.; Dumesnil, K.; Ward, R. C. C.

    2014-08-01

    We report on the genuine origin of the anisotropy of the magnetization M in rare-earth (RE) metals and RE-based alloys. Taking Ho-based layered nanostructures as testing ground, we prove that the anisotropy of M is substantial despite that the sixfold magnetic anisotropy constant K66 vanishes, which contradicts the established wisdom [E. R. Callen and H. B. Callen, J. Phys. Chem. Solids 16, 310 (1960), 10.1016/0022-3697(60)90161-X]. Furthermore, we show that the symmetric anisotropic contributions to M and K66 vary with temperature distinctively from one another, which indicates that both anisotropic effects are unrelated and stem from dissimilar microscopic sources. Our findings are discussed according to the theory [R. J. Elliott and M. F. Thorpe, J. Appl. Phys. 39, 802 (1968), 10.1063/1.2163622] that predicts the emergence of symmetric anisotropic indirect-exchange terms under the presence of orbital moments. We show evidence that the anisotropy of M is caused by the indirect-exchange coupling among localized 4f magnetic moments mediated by spin-orbit coupled conduction electrons, which ultimately generates a spatially nonuniform spin polarization that replicates the lattice symmetry.

  8. Shifted homologous relationships between the transplutonium and early rare-earth metals

    SciTech Connect

    Ward, J.W.

    1984-01-01

    The physico-chemical properties of the late actinide metals americium through einsteinium are compared with their rare-earth counterparts. Localization of the 5f electrons beginning at americium signals the appearance of true rare-earth-like properties, but the homologous relationship is shifted to place americium below praseodymium, einsteinium then below europium. The comparison of crystal structure, phase transitions, vapor pressures and heats of vaporization reveals remarkable similarities, especially for Sm-Cf and Eu-Es, where the stability of the divalent metal becomes established and divalent chemistry then follows. There is of course a major perturbation at the half-filled shell at curium, and it may be argued that americium is the anomaly in the so-called second rare-earth series. However, the response of americium, berkelium and californium under pressure reveals the true perturbation to be a thermodynamic one, occurring at curium.

  9. Rare earth element recycling from waste nickel-metal hydride batteries.

    PubMed

    Yang, Xiuli; Zhang, Junwei; Fang, Xihui

    2014-08-30

    With an increase in number of waste nickel-metal hydride batteries, and because of the importance of rare earth elements, the recycling of rare earth elements is becoming increasingly important. In this paper, we investigate the effects of temperature, hydrochloric acid concentration, and leaching time to optimize leaching conditions and determine leach kinetics. The results indicate that an increase in temperature, hydrochloric acid concentration, and leaching time enhance the leaching rate of rare earth elements. A maximum rare earth elements recovery of 95.16% was achieved at optimal leaching conditions of 70°C, solid/liquid ratio of 1:10, 20% hydrochloric acid concentration, -74μm particle size, and 100min leaching time. The experimental data were best fitted by a chemical reaction-controlled model. The activation energy was 43.98kJ/mol and the reaction order for hydrochloric acid concentration was 0.64. The kinetic equation for the leaching process was found to be: 1-(1-x)(1/3)=A/ρr0[HCl](0.64)exp-439,8008.314Tt. After leaching and filtration, by adding saturated oxalic solution to the filtrate, rare earth element oxalates were obtained. After removing impurities by adding ammonia, filtering, washing with dilute hydrochloric acid, and calcining at 810°C, a final product of 99% pure rare earth oxides was obtained.

  10. Rare earth metal oxazoline complexes in asymmetric catalysis.

    PubMed

    Ward, Benjamin D; Gade, Lutz H

    2012-11-07

    Polydentate oxazolines have been employed as highly effective stereodirecting ligands for asymmetric catalysis with metals from across most of the periodic table. Despite their highly versatile coordination chemistry, the use of these ligands tends to be polarised towards late transition metals; their use with early transition metals and the f-elements is significantly less developed. This current article aims to review the coordination chemistry and catalytic applications of Group 3 and lanthanide complexes supported by ligands possessing oxazoline moieties. Oxazoline-containing ligands were first employed in molecular lanthanide catalysis as early as 1997, yet there is still a significant void in the chemical literature in this respect. The ligands generally employed include bis(oxazolinyl)methane ("BOX"), 2,6-bis(oxazolinyl)pyridine ("pybox"), 1,1,1-tris(oxazolinyl)ethane ("trisox"), and others. The complexes are employed in a wide-range of catalytic applications, especially in Lewis acid catalysis, but also in the stereospecific polymerisation of olefins.

  11. Rare-earth-doped bifunctional alkaline-earth metal fluoride nanocrystals via a facile microwave-assisted process.

    PubMed

    Pang, Min; Liu, Dapeng; Lei, Yongqian; Song, Shuyan; Feng, Jing; Fan, Weiqiang; Zhang, Hongjie

    2011-06-20

    Rare-earth-doped magnetic-optic bifunctional alkaline-earth metal fluoride nanocrystals have been successfully synthesized via a facile microwave-assisted process. The as-prepared nanocrystals were monodisperse and could form stable colloidal solutions in polar solvents, such as water and ethanol. They show bright-green fluorescence emisson. Furthermore, Gd(3+)-doped ones exhibit paramagnetic behavior at room temperature and superparamagnetic behavior at 2 K.

  12. Yttrium and rare earth stabilized fast reactor metal fuel

    SciTech Connect

    Guon, J.; Grantham, L.F.; Specht, E.R.

    1992-05-12

    This patent describes an improved metal alloy reactor fuel consisting essentially of uranium, plutonium, and at least one element from the group consisting of yttrium, lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium and lutetium.

  13. Catalysis of Ugi four component coupling reactions by rare earth metal triflates.

    PubMed

    Okandeji, Babajide O; Gordon, Jonathan R; Sello, Jason K

    2008-07-18

    Substoichiometric quantities of scandium and ytterbium triflate increase the yield of Ugi four component coupling reactions of aromatic aldehydes 2- to 7-fold. These rare earth metal triflates enhance the reaction yields primarily via activation of the imine intermediate of this multicomponent reaction.

  14. Adsorption Behavior of Rare Earth Metal Cations in the Interlayer Space of γ-ZrP.

    PubMed

    Takei, Takahiro; Iidzuka, Kiyoaki; Miura, Akira; Yanagida, Sayaka; Kumada, Nobuhiro; Magome, Eisuke; Moriyoshi, Chikako; Kuroiwa, Yoshihiro

    2016-10-04

    Adsorption competencies of rare earth metal cations in γ-zirconium phosphate were examined by ICP, synchrotron X-ray diffraction (SXRD), and ab initio simulation. The adsorption amounts are around 0.06-0.10 per zirconium phosphate. From the SXRD patterns of the adsorbed samples, the basal spacing estimated by c sin β increased linearly with an increasing ionic radius of rare earth metal cation, though a and b lattice constants show no change. These SXRD patterns can be classified into four groups that have different super lattices. The four superlattices have multiplicities of x131, x241, and x221 for the xabc axis, and the location of the rare earth metal cation in the original unit cell changes depending on the superlattice cell. In the x131 superlattice, Yb and Er occupied the site near the zirconium phosphate layer, though La and Ce in the x221 superlattice remained in the center position between the phosphate sheet. For the ab initio simulation of γ-ZrP with the typical rare earth metal cations (Tb, Eu, Dy, and La), the results of simulation show a similar tendency of the position estimated by SXRD refinements.

  15. New technology of extracting the amount of rare earth metals from the red mud

    NASA Astrophysics Data System (ADS)

    Martoyan, G. A.; Karamyan, G. G.; Vardan, G. A.

    2016-01-01

    The paper outlined the environmental and economic problems associated with red mud - the waste generated in processing of bauxite ore for aluminum production. The chemical analysis of red mud has identified a number of useful elements including rare earth metals. The electromembrane technology of red mud processing with extraction of valuable elements is described. A possible scheme of separation of these metals through electrolysis is also given.

  16. Rare earth zirconium oxide buffer layers on metal substrates

    DOEpatents

    Williams, Robert K.; Paranthaman, Mariappan; Chirayil, Thomas G.; Lee, Dominic F.; Goyal, Amit; Feenstra, Roeland

    2001-01-01

    A laminate article comprises a substrate and a biaxially textured (RE.sub.x A.sub.(1-x)).sub.2 O.sub.2-(x/2) buffer layer over the substrate, wherein 0metal-organic decomposition. The laminate article can include a layer of YBCO over the (RE.sub.x A.sub.(1-x)).sub.2 O.sub.2-(x/2) buffer layer. A layer of CeO.sub.2 between the YBCO layer and the (RE.sub.x A.sub.(1-x)).sub.2 O.sub.2-(x/2) buffer layer can also be include. Further included can be a layer of YSZ between the CeO.sub.2 layer and the (RE.sub.x A.sub.(1-x)).sub.2 O.sub.2-(x/2) buffer layer. The substrate can be a biaxially textured metal, such as nickel. A method of forming the laminate article is also disclosed.

  17. Process optimization and kinetics for leaching of rare earth metals from the spent Ni-metal hydride batteries.

    PubMed

    Meshram, Pratima; Pandey, B D; Mankhand, T R

    2016-05-01

    Nickel-metal hydride batteries (Ni-MH) contain not only the base metals, but valuable rare earth metals (REMs) viz. La, Sm, Nd, Pr and Ce as well. In view of the importance of resource recycling and assured supply of the contained metals in such wastes, the present study has focussed on the leaching of the rare earth metals from the spent Ni-MH batteries. The conditions for the leaching of REMs from the spent batteries were optimized as: 2M H2SO4, 348K temperature and 120min of time at a pulp density (PD) of 100g/L. Under this condition, the leaching of 98.1% Nd, 98.4% Sm, 95.5% Pr and 89.4% Ce was achieved. Besides the rare earth metals, more than 90% of base metals (Ni, Co, Mn and Zn) were also leached out in this condition. Kinetic data for the dissolution of all the rare earth metals showed the best fit to the chemical control shrinking core model. The leaching of metals followed the mechanism involving the chemical reaction proceeding on the surface of particles by the lixiviant, which was corroborated by the XRD phase analysis and SEM-EDS studies. The activation energy of 7.6, 6.3, 11.3 and 13.5kJ/mol was acquired for the leaching of neodymium, samarium, praseodymium and cerium, respectively in the temperature range 305-348K. From the leach liquor, the mixed rare earth metals were precipitated at pH∼1.8 and the precipitated REMs was analyzed by XRD and SEM studies to determine the phases and the morphological features.

  18. Efficient separation of transition metals from rare earths by an undiluted phosphonium thiocyanate ionic liquid.

    PubMed

    Rout, Alok; Binnemans, Koen

    2016-06-21

    The ionic liquid trihexyl(tetradecyl)phosphonium thiocyanate has been used for the extraction of the transition metal ions Co(ii), Ni(ii), Zn(ii), and the rare-earth ions La(iii), Sm(iii) and Eu(iii) from aqueous solutions containing nitrate or chloride salts. The transition metal ions showed a high affinity for the ionic liquid phase and were efficiently extracted, while the extraction efficiency of the rare-earth ions was low. This difference in extraction behavior enabled separation of the pairs Co(ii)/Sm(iii), Ni(ii)/La(iii) and Zn(ii)/Eu(iii). These separations are relevant for the recycling of rare earths and transition metals from samarium cobalt permanent magnets, nickel metal hydride batteries and lamp phosphors, respectively. The extraction of metal ions from a chloride or nitrate solution with a thiocyanate ionic liquid is an example of "split-anion extraction", where different anions are present in the aqueous and ionic liquid phase. Close to 100% loading was possible for Co(ii) and Zn(ii) up to a concentration of 40 g L(-1) of the transition metal salt in the initial aqueous feed solution, whereas the extraction efficiency for Ni(ii) gradually decreased with increase in the initial feed concentration. Stripping of Co(ii), Zn(ii) and Ni(ii) from the loaded ionic liquid phase was possible by a 15 wt% NH3 solution. The ionic liquid could reused after extraction and stripping.

  19. High-temperature corrosion of metals in the salt and metallic melts containing rare earths

    NASA Astrophysics Data System (ADS)

    Karpov, V. V.; Abramov, A. V.; Zhilyakov, A. Yu.; Belikov, S. V.; Volkovich, V. A.; Polovov, I. B.; Rebrin, O. I.

    2016-09-01

    A complex of independent methods was employed to study the corrosion resistance of molybdenum, zirconium, tantalum and tungsten in chloride, chloride-fluoride and fluoride-oxide melts based on LiCl, CaCl2, NaCl- KCl, LiF, and containing rare earths. Tests were conducted for 30 h at 750-1050 °C. The metals showed excellent corrosion resistance in fused chlorides (the corrosion rates were below 0.0005 g/(m2 h). Despite the presence of chemically active fluoride ions in the chloride-fluoride melts, the metals studied also showed very low corrosion rates, except molybdenum, for which the rate of corrosion was 0,8 g/(m2 h). The corrosion resistance of tantalum was considerably reduced in the fluoride-oxide melts; the corrosion rate was over 1 g/(m2 h) corresponding to the 8-th grade of stability and placing tantalum to the group of "low stability" materials.

  20. Effect of rare earth metal on the spin-orbit torque in magnetic heterostructures

    NASA Astrophysics Data System (ADS)

    Ueda, Kohei; Pai, Chi-Feng; Tan, Aik Jun; Mann, Maxwell; Beach, Geoffrey S. D.

    2016-06-01

    We report the effect of the rare earth metal Gd on current-induced spin-orbit torques (SOTs) in perpendicularly magnetized Pt/Co/Gd heterostructures, characterized using harmonic measurements and spin-torque ferromagnetic resonance (ST-FMR). By varying the Gd metal layer thickness from 0 nm to 8 nm, harmonic measurements reveal a significant enhancement of the effective fields generated from the Slonczewski-like and field-like torques. ST-FMR measurements confirm an enhanced effective spin Hall angle and show a corresponding increase in the magnetic damping constant with increasing Gd thickness. These results suggest that Gd plays an active role in generating SOTs in these heterostructures. Our finding may lead to spin-orbitronics device application such as non-volatile magnetic random access memory, based on rare earth metals.

  1. Ground-state properties of rare-earth metals: an evaluation of density-functional theory.

    PubMed

    Söderlind, Per; Turchi, P E A; Landa, A; Lordi, V

    2014-10-15

    The rare-earth metals have important technological applications due to their magnetic properties, but are scarce and expensive. Development of high-performance magnetic materials with less rare-earth content is desired, but theoretical modeling is hampered by complexities of the rare earths electronic structure. The existence of correlated (atomic-like) 4f electrons in the vicinity of the valence band makes any first-principles theory challenging. Here, we apply and evaluate the efficacy of density-functional theory for the series of lanthanides (rare earths), investigating the influence of the electron exchange and correlation functional, spin-orbit interaction, and orbital polarization. As a reference, the results are compared with those of the so-called 'standard model' of the lanthanides in which electrons are constrained to occupy 4f core states with no hybridization with the valence electrons. Some comparisons are also made with models designed for strong electron correlations. Our results suggest that spin-orbit coupling and orbital polarization are important, particularly for the magnitude of the magnetic moments, and that calculated equilibrium volumes, bulk moduli, and magnetic moments show correct trends overall. However, the precision of the calculated properties is not at the level of that found for simpler metals in the Periodic Table of Elements, and the electronic structures do not accurately reproduce x-ray photoemission spectra.

  2. Selective extraction and recovery of rare earth metals from phosphor powders in waste fluorescent lamps using an ionic liquid system.

    PubMed

    Yang, Fan; Kubota, Fukiko; Baba, Yuzo; Kamiya, Noriho; Goto, Masahiro

    2013-06-15

    The recycling of rare earth metals from phosphor powders in waste fluorescent lamps by solvent extraction using ionic liquids was studied. Acid leaching of rare earth metals from the waste phosphor powder was examined first. Yttrium (Y) and europium (Eu) dissolved readily in the acid solution; however, the leaching of other rare earth metals required substantial energy input. Ionization of target rare earth metals from the waste phosphor powders into the leach solution was critical for their successful recovery. As a high temperature was required for the complete leaching of all rare earth metals, ionic liquids, for which vapor pressure is negligible, were used as an alternative extracting phase to the conventional organic diluent. An extractant, N, N-dioctyldiglycol amic acid (DODGAA), which was recently developed, showed a high affinity for rare earth metal ions in liquid-liquid extraction although a conventional commercial phosphonic extractant did not. An effective recovery of the rare earth metals, Y, Eu, La and Ce, from the metal impurities, Fe, Al and Zn, was achieved from the acidic leach solution of phosphor powders using an ionic liquid containing DODGAA as novel extractant system.

  3. Optimization of film synthesized rare earth transition metal permanent magnet systems

    SciTech Connect

    Cadieu, F.J.

    1992-01-01

    Progress is reported in three areas: high coercivity Sm-Fe-Ti-V, Sm-Fe-Zr, and two element Sm-Fe Sm{sub 5}(Fe,T){sub 17} type crystalline phases; ThMn{sub 12} type pseudobinary SmFe{sub 12-x}T{sub x}(0{le}{times}{le}1.5); and sputter process control for the synthesis of precisely textured rare earth-transition metal magnetic films. (DLC)

  4. Optimization of film synthesized rare earth transition metal permanent magnet systems

    SciTech Connect

    Cadieu, F.J.

    1990-01-01

    This report reviews work on the optimization of film synthesized rare earth transition metal permanent magnet systems. Topics include: high coercivity in Sm-Fe-Ti-V, Sm-Fe-V, and two element systems; ThMn{sub 12} type pseudobinary SmFe{sub 12 {minus} X}T{sub X}; and sputter process control for the synthesis of precisely textured RE-TM magnetic films. (JL)

  5. Neutral binuclear rare-earth metal complexes with four μ₂-bridging hydrides.

    PubMed

    Rong, Weifeng; He, Dongliang; Wang, Meiyan; Mou, Zehuai; Cheng, Jianhua; Yao, Changguang; Li, Shihui; Trifonov, Alexander A; Lyubov, Dmitrii M; Cui, Dongmei

    2015-03-25

    The first neutral rare-earth metal dinuclear dihydrido complexes [(NPNPN)LnH2]2 (2-Ln; Ln = Y, Lu; NPNPN: N[Ph2PNC6H3((i)Pr)2]2) bearing μ2-bridging hydride ligands have been synthesized. In the presence of THF, 2-Y undergoes intramolecular activation of the sp(2) C-H bond to form dinuclear aryl-hydride complex 3-Y containing three μ2-bridging hydride ligands.

  6. A rule for counting neighbours in rare-earth transition metal compounds

    NASA Astrophysics Data System (ADS)

    Brommer, P. E.

    1991-09-01

    In (R, T) compounds (R: rare earth; T: 3d transition metal) such as R 2T 17, R 2T 14B, and so on, the exchange interaction between a rare-earth spin (operator) SR and the neighbouring 3d spins can be written as -2 JRTzRTSR·< ST>, where < ST> is a site average of the expectation value of the transition metal spins in the molecular field approximation. zRT is the number of nearest T neighbours of an R-atom. A more precise definition is given in the main text. Analogously, zTR, the average number of nearest R neighbours of a T atom can be defined. We stress that a consistent definition must lead to the relation zRTNR = zTRNT for a stoichiometric compound containing NR rare-earth atoms and NT transition metal atoms per formula unit. Appropriate definitions are discussed for more intricate cases, in particular for off-stoichiometric compounds.

  7. Rare Earth Metal-Mediated Precision Polymerization of Vinylphosphonates and Conjugated Nitrogen-Containing Vinyl Monomers.

    PubMed

    Soller, Benedikt S; Salzinger, Stephan; Rieger, Bernhard

    2016-02-24

    This review focuses on introducing and explaining the rare earth metal-mediated group transfer polymerization (REM-GTP) of polar monomers and is composed of three main sections: poly(vinylphosphonate)s, surface-initiated group transfer polymerization (SI-GTP), and extension to N-coordinating Michael-type monomers (2-vinylpridine (2VP), 2-isopropenyl-2-oxazoline (IPOx)). The poly(vinylphosphonate)s section is divided into two parts: radical, anionic, and silyl ketene acetal group transfer polymerization (SKA-GTP) of vinylphosphonates in comparison to REM-GTP, and properties of poly(vinylphosphonate)s. The mechanism of vinylphosphonate REM-GTP is discussed in detail for initiation and propagation including activation enthalpies ΔH(‡) and entropies ΔS(‡) according to the Eyring equation. SI-GTP is presented as a method for surface functionalization, and recent trends for 2VP and IPOx polymerization are summarized. This review will serve as a good resource or guideline for researchers who are currently working in the field of rare earth metal mediated polymerization catalysis as well as for those who are interested in beginning to employ rare earth metal complexes for the synthesis of new materials from polar monomers.

  8. Rare earth thermoelectrics

    SciTech Connect

    Mahan, G.D.

    1997-09-01

    The author reviews the thermoelectric properties of metallic compounds which contain rare-earth atoms. They are the group of metals with the largest value ever reported of the Seebeck coefficient. An increase by 50% of the Seebeck would make these compounds useful for thermoelectric devices. The largest Seebeck coefficient is found for compounds of cerium (e.g., CePd{sub 3}) and ytterbium (e.g., YbAl{sub 3}). Theoretical predictions are in agreement with the maximum observed Seebeck. The author discusses the theoretical model which has been used to calculate the Seebeck coefficient. He is solving this model for other configurations (4f){sup n} of rare-earth ground states.

  9. The t-matrix resistivity of liquid rare earth metals using pseudopotential

    SciTech Connect

    Bhatia, Kamaldeep G.; Bhatt, N. K.; Vyas, P. R.; Gohel, V. B.

    2015-06-24

    Present theoretical study of liquid metal resistivity of some trivalent (La,Ce,Gd) and divalent (Eu,Yb) rare earth metals using pseudopotential has been carried out employing Ziman’s weak scattering and transition matrix (t-matrix) approaches. Our computed results of liquid metal resistivity using t-matrix approach are better than resistivity computed using Ziman’s approach and are also in excellent agreement with experimental results and other theoretical findings. The present study confirms that for f-shell metals pseudopotential must be determined uniquely and t-matrix approach is more physical in comparison with Ziman’s nearly free electron approach. The present pseudopotential accounts s-p-d hybridization properly. Such success encourages us to study remaining liquid state properties of these metals.

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

    PubMed

    Huang, Wenliang; Diaconescu, Paula L

    2015-09-21

    Rare-earth metal complexes of reduced π ligands are reviewed with an emphasis on their electronic structure and bonding interactions. This perspective discusses reduced carbocyclic and acyclic π ligands; in certain categories, when no example of a rare-earth metal complex is available, a closely related actinide analogue is discussed. In general, rare-earth metals have a lower tendency to form covalent interactions with π ligands compared to actinides, mainly uranium. Despite predominant ionic interactions in rare-earth chemistry, covalent bonds can be formed with reduced carbocyclic ligands, especially multiply reduced arenes.

  11. Synthesis and styrene polymerisation catalysis of eta5- and eta1-pyrrolyl-ligated cationic rare earth metal aminobenzyl complexes.

    PubMed

    Nishiura, Masayoshi; Mashiko, Tomohiro; Hou, Zhaomin

    2008-05-07

    The cationic rare earth metal aminobenzyl complexes bearing mono(pyrrolyl) ligands are synthesised and structurally characterised, and the coordination mode of the pyrrolyl ligands is found to show significant influence on the polymerisation of styrene.

  12. Speciation of rare-earth metal complexes in ionic liquids: a multiple-technique approach.

    PubMed

    Nockemann, Peter; Thijs, Ben; Lunstroot, Kyra; Parac-Vogt, Tatjana N; Görller-Walrand, Christiane; Binnemans, Koen; Van Hecke, Kristof; Van Meervelt, Luc; Nikitenko, Sergey; Daniels, John; Hennig, Christoph; Van Deun, Rik

    2009-01-01

    The dissolution process of metal complexes in ionic liquids was investigated by a multiple-technique approach to reveal the solvate species of the metal in solution. The task-specific ionic liquid betainium bis(trifluoromethylsulfonyl)imide ([Hbet][Tf(2)N]) is able to dissolve stoichiometric amounts of the oxides of the rare-earth elements. The crystal structures of the compounds [Eu(2)(bet)(8)(H(2)O)(4)][Tf(2)N](6), [Eu(2)(bet)(8)(H(2)O)(2)][Tf(2)N](6) x 2 H(2)O, and [Y(2)(bet)(6)(H(2)O)(4)][Tf(2)N](6) were found to consist of dimers. These rare-earth complexes are well soluble in the ionic liquids [Hbet][Tf(2)N] and [C(4)mim][Tf(2)N] (C(4)mim = 1-butyl-3-methylimidazolium). The speciation of the metal complexes after dissolution in these ionic liquids was investigated by luminescence spectroscopy, (1)H, (13)C, and (89)Y NMR spectroscopy, and by the synchrotron techniques EXAFS (extended X-ray absorption fine structure) and HEXS (high-energy X-ray scattering). The combination of these complementary analytical techniques reveals that the cationic dimers decompose into monomers after dissolution of the complexes in the ionic liquids. Deeper insight into the solution processes of metal compounds is desirable for applications of ionic liquids in the field of electrochemistry, catalysis, and materials chemistry.

  13. Cooperative thermodynamic control of selectivity in the self-assembly of rare earth metal-ligand helices.

    PubMed

    Johnson, Amber M; Young, Michael C; Zhang, Xing; Julian, Ryan R; Hooley, Richard J

    2013-11-27

    Metal-selective self-assembly with rare-earth cations is possible with suitable rigid, symmetrical bis-tridentate ligands. Kinetically controlled formation is initially observed, with smaller cations preferentially incorporated. Over time, the more thermodynamically favorable complexes with larger metals are formed. This thermodynamic control is a cooperative supramolecular phenomenon and only occurs upon multiple-metal-based self-assembly: single-metal ML3 analogues do not show reversible selectivity. The selectivity is dependent on small variations in lanthanide ionic radius and occurs despite identical coordination-ligand coordination geometries and minor size differences in the rare-earth metals.

  14. Synthesis, characterization and reactivity of heteroleptic rare earth metal bis(phenolate) complexes.

    PubMed

    Qi, Ruipeng; Liu, Bao; Xu, Xiaoping; Yang, Zijian; Yao, Yingming; Zhang, Yong; Shen, Qi

    2008-10-07

    The synthesis, characterization and reactivity of heteroleptic rare earth metal complexes supported by the carbon-bridged bis(phenolate) ligand 2,2'-methylene-bis(6-tert-butyl-4-methyl-phenoxo) (MBMP2-) are described. Reaction of (C5H5)3Ln(THF) with MBMPH2 in a 1:1.5 molar ratio in THF at 50 degrees C produced the heteroleptic rare earth metal bis(phenolate) complexes (C5H5)Ln(MBMP)(THF)n (Ln=La, n=3 (); Ln=Yb (), Y (), n=2) in nearly quantitative yields. The residual C5H5- groups in complexes to can be substituted by the bridged bis(phenolate) ligands at elevated temperature to give the neutral rare earth metal bis(phenolate) complexes, and the ionic radii have a profound effect on the structures of the final products. Complex reacted with MBMPH2 in a 1:0.5 molar ratio in toluene at 80 degrees C to produce a dinuclear complex (MBMP)La(THF)(micro-MBMP)2La(THF)2 () in good isolated yield; whereas complexes and reacted with MBMPH2 under the same conditions to give (MBMP)Ln(MBMPH)(THF)2 (Ln=Yb (), Y ()) as the final products, in which one hydroxyl group of the phenol is coordinated to the rare earth metal in a neutral fashion. The reactivity of complexes and with some metal alkyls was explored. Reaction of complex with 1 equiv. of AlEt3 in toluene at room temperature afforded unexpected ligand redistributed products, and a discrete ion pair ytterbium complex [(MBMP)Yb(THF)2(DME)][(MBMP)2Yb(THF)2] () was isolated in moderate yield. Furthermore, reaction of complex with 1 equiv. of ZnEt2 in toluene gave a ligand redistributed complex [(micro-MBMP)Zn(THF)]2 () in reasonable isolated yield. Similar reaction of complex with ZnEt2 also afforded complex ; whereas the reaction of complex with 1 equiv. of n-BuLi in THF afforded the heterodimetallic complex [(THF)Yb(MBMP)2Li(THF)2] (). All of these complexes were well characterized by elemental analyses, IR spectra, and single-crystal structure determination, in the cases of complexes , and -.

  15. Rare-earth transition-metal intermetallics: Structure-bonding-property relationships

    SciTech Connect

    Han, M. K.

    2006-01-01

    The explorations of rare-earth, transition metal intermetallics have resulted in the synthesis and characterization, and electronic structure investigation, as well as understanding the structure-bonding property relationships. The work has presented the following results: (1) Understanding the relationship between compositions and properties in LaFe13-xSix system: A detailed structural and theoretical investigation provided the understanding of the role of a third element on stabilizing the structure and controlling the transformation of cubic NaZn{sub 13}-type structures to the tetragonal derivative, as well as the relationship between the structures and properties. (2) Synthesis of new ternary rare-earth iron silicides Re2-xFe4Si14-y and proposed superstructure: This compound offers complex structural challenges such as fractional occupancies and their ordering in superstructure. (3) Electronic structure calculation of FeSi2: This shows that the metal-semiconductor phase transition depends on the structure. The mechanism of band gap opening is described in terms of bonding and structural distortion. This result shows that the electronic structure calculations are an essential tool for understanding the relationship between structure and chemical bonding in these compounds. (4) Synthesis of new ternary rare-earth Zinc aluminides Tb3Zn3.6Al7.4: Partially ordered structure of Tb3Zn3.6Al7.4 compound provides new insights into the formation, composition and structure of rare-earth transition-metal intermetallics. Electronic structure calculations attribute the observed composition to optimizing metal-metal bonding in the electronegative (Zn, Al) framework, while the specific ordering is strongly influenced by specific orbital interactions. (5) Synthesis of new structure type of Zn39(CrxAl1-x)81

  16. Rare-Earth Transition-Metal Intermetallics: Structure-bonding-Property Relationships

    SciTech Connect

    Han, Mi-Kyung

    2006-01-01

    Our explorations of rare-earth, transition metal intermetallics have resulted in the synthesis and characterization, and electronic structure investigation, as well as understanding the structure-bonding-property relationships. Our work has presented the following results: (1) Understanding the relationship between compositions and properties in LaFe13-xSix system: A detailed structural and theoretical investigation provided the understanding of the role of a third element on stabilizing the structure and controlling the transformation of cubic NaZn13-type structures to the tetragonal derivative, as well as the relationship between the structures and properties. (2) Synthesis of new ternary rare-earth iron silicides RE2-xFe4Si14-y and proposed superstructure: This compound offers complex structural challenges such as fractional occupancies and their ordering in superstructure. (3) Electronic structure calculation of FeSi2: This shows that the metal-semiconductor phase transition depends on the structure. The mechanism of band gap opening is described in terms of bonding and structural distortion. This result shows that the electronic structure calculations are an essential tool for understanding the relationship between structure and chemical bonding in these compounds. (4) Synthesis of new ternary rare-earth Zinc aluminides Tb3Zn3.6Al7.4: Partially ordered structure of Tb3.6Zn13-xAl7.4 compound provides new insights into the formation, composition and structure of rare-earth transition-metal intermetallics. Electronic structure calculations attribute the observed composition to optimizing metal-metal bonding in the electronegative (Zn, Al) framework, while the specific ordering is strongly influenced by specific orbital interactions. (5) Synthesis of new structure type of Zn39(CrxAl1-x

  17. Moderate pressure synthesis of rare earth nickelate with metal-insulator transition using polymeric precursors

    SciTech Connect

    Napierala, C.; Lepoittevin, C.; Edely, M.; Sauques, L.; Giovanelli, F.; Laffez, P.; VanTedeloo, G.

    2010-07-15

    Rare earth nickelates exhibit a reversible metal-semiconductor phase transition that is, in the infrared range, responsible for a thermo-optical contrast. The state of the art synthesis of these compounds usually requires high oxygen pressure to stabilize Ni in the oxidation state 3{sup +}. In this work, using polymeric precursor associated with moderate pressure annealing, we show that it is possible to obtain fully oxidized rare earth nickelate with metal-insulator transition. Using thermogravimetric analysis, X-ray diffraction and transmission electronic microscopy we compare different samples synthesized at different oxygen pressures and demonstrate their structural similarity. Thermo-optical properties were measured, in the infrared range, using reflectance measurements and confirmed the metal-insulator transition at 60 {sup o}C in both samples.TEM observations lead to the conclusion that the structure commonly obtained at 175 bar is perfectly observed in the 20 bar sample without major structural defects. The two samples exhibit a thermochromic behavior and thermo-optical properties of the two samples are equivalent. - Graphical Abstract: Thermochromic behavior of Nd{sub 0.3}Sm{sub 0.7}NiO{sub 3} samples annealed under 20 and 175 bar at 278 and 373 K.

  18. Molecular heterometallic hydride clusters composed of rare-earth and d-transition metals.

    PubMed

    Shima, Takanori; Luo, Yi; Stewart, Timothy; Bau, Robert; McIntyre, Garry J; Mason, Sax A; Hou, Zhaomin

    2011-09-18

    Heteromultimetallic hydride clusters containing both rare-earth and d-transition metals are of interest in terms of both their structure and reactivity. However, such heterometallic complexes have not yet been investigated to a great extent because of difficulties in their synthesis and structural characterization. Here, we report the synthesis, X-ray and neutron diffraction studies, and hydrogen addition and release properties of a family of rare-earth/d-transition-metal heteromultimetallic polyhydride complexes of the core structure type 'Ln(4)MH(n)' (Ln = Y, Dy, Ho; M = Mo, W; n = 9, 11, 13). Monitoring of hydrogen addition to a hydride cluster such as [{(C(5)Me(4)SiMe(3))Y}(4)(μ-H)(9)Mo(C(5)Me(5))] in a single-crystal to single-crystal process by X-ray diffraction has been achieved for the first time. Density functional theory studies reveal that the hydrogen addition process is cooperatively assisted by the Y/Mo heteromultimetallic sites, thus offering unprecedented insight into the hydrogen addition and release process of a metal hydride cluster.

  19. Catalytic enantioselective construction of tetrasubstituted carbons by self-assembled poly rare earth metal complexes.

    PubMed

    Shibasaki, Masakatsu; Kanai, Motomu

    2007-07-07

    Rare earth metal-based enantioselective catalysts that can promote practical cyanation reactions of ketones and ketoimines were developed. These catalytic enantioselective tetrasubstituted carbon-forming reactions are useful platforms for the synthesis of biologically active compounds. ESI-MS and crystallographic studies of the asymmetric catalysts revealed that the active catalysts are polymetallic complexes produced through the assembly of modules. The higher-order structure of the polymetallic complexes has strong effects on catalyst activity and enantioselectivity. Controlling the higher-order structure of artificial polymetallic asymmetric catalysts is a new strategy for optimizing asymmetric catalysts. Recent progress in this approach is also described.

  20. Narcissistic self-sorting in self-assembled cages of rare Earth metals and rigid ligands.

    PubMed

    Johnson, Amber M; Wiley, Calvin A; Young, Michael C; Zhang, Xing; Lyon, Yana; Julian, Ryan R; Hooley, Richard J

    2015-05-04

    Highly selective, narcissistic self-sorting can be achieved in the formation of self-assembled cages of rare earth metals with multianionic salicylhydrazone ligands. The assembly process is highly sensitive to the length of the ligand and the coordination geometry. Most surprisingly, high-fidelity sorting is possible between ligands of identical coordination angle and geometry, differing only in a single functional group on the ligand core, which is not involved in the coordination. Supramolecular effects allow discrimination between pendant functions as similar as carbonyl or methylene groups in a complex assembly process.

  1. Synthesis of Chiral Aminocyclopropanes by Rare-Earth-Metal-Catalyzed Cyclopropene Hydroamination.

    PubMed

    Teng, Huai-Long; Luo, Yong; Wang, Baoli; Zhang, Liang; Nishiura, Masayoshi; Hou, Zhaomin

    2016-12-05

    The search for efficient and selective routes for the synthesis of chiral aminocyclopropane derivatives is of great interest and importance as these structures are important components of biologically active natural products and pharmaceuticals. We herein report the enantioselective intermolecular hydroamination of substituted cyclopropenes with various amines catalyzed by chiral half-sandwich rare-earth-metal complexes. This method constitutes a 100 % atom-efficient route for the synthesis of a variety of chiral α-aminocyclopropane derivatives in high yields (up to 96 %) and excellent stereoselectivity (up to >20:1 d.r. and 99 % ee) under mild reaction conditions (25 °C).

  2. Processing of Phosphorus Slag with Recovery of Rare Earth Metals and Obtaining Silicon Containing Cake

    NASA Astrophysics Data System (ADS)

    Karshigina, Zaure; Abisheva, Zinesh; Bochevskaya, Yelena; Akcil, Ata; Sharipova, Aynash; Sargelova, Elmira

    2016-10-01

    The present research is devoted to the processing of slag generating during the yellow phosphorus production. In this paper are presented studies on leaching of phosphorus production slag by nitric acid with recovery of rare earth metals (REMs) into solution. REMs recovery into the solution achieved 98 % during the leaching process with using 7.5 mol/L of HNO3, liquid-to-solid ratio is 2.6:1, temperature is 60°C, process duration is 1 hour and stirrer speed is 500 rpm. Behaviour during the leaching of associated components such as calcium, aluminium, and iron was studied. After the leaching cake contains ∼⃒75-85 % of SiO2 and it might be useful for obtaining of precipitated silicon dioxide. With the purpose of separation from the impurities, recovery and concentrating of REMs, the obtained solution after leaching was subjected to extraction processing methods. The influence of ratio of organic and aqueous phases (O: A) on the extraction of rare earth metals by tributyl phosphate (TBP) with concentrations from 20 up to 100 % was studied. The REMs extraction with increasing TBP concentration under changes O:A ratio from 1:20 down to 1:1 into the organic phase from the solutions after nitric acid leaching increased from 22.2 up to 99.3%. The duration effect of REMs extraction process was studied by tributyl phosphate. It is revealed that with increasing of duration of the extraction process from 10 to 30 minutes REMs recovery into the organic phase almost did not changed. The behaviour of iron in the extraction process by TBP was studied. It was found that such accompanying components as calcium and aluminium by tributyl phosphate didn't extracted. To construct isotherm of REMs extraction of by tributyl phosphate was used variable volume method. It was calculated three-step extraction is needed for REMs recovery from the solutions after nitric acid leaching of phosphorus production slag. The process of the three-steps counter current extraction of rare earth

  3. Rare earth elements and critical metal content of extracted landfilled material and potential recovery opportunities

    SciTech Connect

    Gutiérrez-Gutiérrez, Silvia C.; Coulon, Frédéric; Jiang, Ying; Wagland, Stuart

    2015-08-15

    Highlights: • Samples from multiple core drills were obtained from 4× landfill sites in the UK. • Each sample analysed for rare earth elements, critical metals and valuable metals. • Two stage microwave digestion method ensuring high yield. • High quantities of copper and aluminium were observed in the soil layers of landfill. • Across 4× landfills aluminium and copper present has a value of around $400 million. - Abstract: Rare earth elements (REEs), Platinum group metals (PGMs) and other critical metals currently attract significant interest due to the high risks of supply shortage and substantial impact on the economy. Their uses in many applications have made them present in municipal solid waste (MSW) and in commercial and industrial waste (C&I), since several industrial processes produce by-products with high content of these metals. With over 4000 landfills in the UK alone, the aim of this study was to assess the existence of these critical metals within landfills. Samples collected from four closed landfills in UK were subjected to a two-step acid digestion to extract 27 metals of interest. Concentrations across the four landfill sites were 58 ± 6 mg kg{sup −1} for REEs comprising 44 ± 8 mg kg{sup −1} for light REEs, 11 ± 2 mg kg{sup −1} for heavy REEs and 3 ± 1 mg kg{sup −1} for Scandium (Sc) and 3 ± 1.0 mg kg{sup −1} of PGMs. Compared to the typical concentration in ores, these concentrations are too low to achieve a commercially viable extraction. However, content of other highly valuable metals (Al and Cu) was found in concentrations equating to a combined value across the four landfills of around $400 million, which increases the economic viability of landfill mining. Presence of critical metals will mainly depend on the type of waste that was buried but the recovery of these metals through landfill mining is possible and is economically feasible only if additional materials (plastics, paper, metallic items and other) are

  4. Application of Freeze-Dried Powders of Genetically Engineered Microbial Strains as Adsorbents for Rare Earth Metal Ions.

    PubMed

    Moriwaki, Hiroshi; Masuda, Reiko; Yamazaki, Yuki; Horiuchi, Kaoru; Miyashita, Mari; Kasahara, Jun; Tanaka, Tatsuhito; Yamamoto, Hiroki

    2016-10-12

    The adsorption behaviors of the rare earth metal ions onto freeze-dried powders of genetically engineered microbial strains were compared. Cell powders obtained from four kinds of strains, Bacillus subtilis 168 wild type (WT), lipoteichoic acid-defective (ΔLTA), wall teichoic acid-defective (ΔWTA), and cell wall hydrolases-defective (EFKYOJLp) strains, were used as an adsorbent of the rare earth metal ions at pH 3. The adsorption ability of the rare earth metal ions was in the order of EFKYOJLp > WT > ΔLTA > ΔWTA. The order was the same as the order of the phosphorus quantity of the strains. This result indicates that the main adsorption sites for the ions are the phosphate groups and the teichoic acids, LTA and WTA, that contribute to the adsorption of the rare earth metal ions onto the cell walls. The contribution of WTA was clearly greater than that of LTA. Each microbial powder was added to a solution containing 16 kinds of rare earth metal ions, and the removals (%) of each rare earth metal ion were obtained. The scandium ion showed the highest removal (%), while that of the lanthanum ion was the lowest for all the microbial powders. Differences in the distribution coefficients between the kinds of lanthanide ions by the EFKYOJLp and ΔWTA powders were greater than those of the other strains. Therefore, the EFKYOJLp and ΔWTA powders could be applicable for the selective extraction of the lanthanide ions. The ΔLTA powder coagulated by mixing with a rare earth metal ion, although no sedimentation of the WT or ΔWTA powder with a rare earth metal ion was observed under the same conditions. The EFKYOJLp powder was also coagulated, but its flocculating activity was lower than that of ΔLTA. The ΔLTA and EFKYOJLp powders have a long shape compared to those of the WT or ΔWTA strain. The shapes of the cells will play an important role in the sedimentation of the microbial powders with rare earth metal ions. As the results, three kinds of the genetically

  5. Dehydration of fructose to 5-hydroxymethylfurfural by rare earth metal trifluoromethanesulfonates in organic solvents.

    PubMed

    Wang, Fenfen; Shi, Ai-Wu; Qin, Xiao-Xia; Liu, Chun-Ling; Dong, Wen-Sheng

    2011-05-15

    The catalytic dehydration of fructose to 5-hydroxymethylfurfural (HMF) was investigated by using various rare earth metal trifluoromethanesulfonates, that is, Yb(OTf)(3), Sc(OTf)(3), Ho(OTf)(3), Sm(OTf)(3), Nd(OTf)(3) as catalysts in DMSO. It is found that the catalytic activity increases with decreasing ionic radius of rare earth metal cations. Among the examined catalysts, Sc(OTf)(3) exhibits the highest catalytic activity. Fructose conversion of 100% and a HMF yield of 83.3% are obtained at 120°C after 2h by using Sc(OTf)(3) as the catalyst. Moreover, the catalytic dehydration of fructose was also carried out in different solvents, for example, DMA, 1,4-dioxane, and a mixture of PEG-400 and water. The results show that among the solvents DMSO is the most efficient in promoting the dehydration of fructose to HMF, and no rehydration byproducts such as levulinic acid and formic acid are detected.

  6. Structure and magnetism of epitaxial rare-earth-transition-metal films

    SciTech Connect

    Fullerton, E.E.; Sowers, C.H.; Pearson, J.P.; Bader, S.D.

    1996-10-01

    Growth of epitaxial transition-metal superlattices; has proven essential in elucidating the role of crystal orientation and structure on magnetic properties such as giant magnetoresistance, interlayer coupling, and magnetic surface anisotropies. Extending these studies to the growth of epitaxial rare earth-transition metal (RE-TM) films and superlattices promises to play an equally important role in exploring and optimizing the properties of hard magnets. For instance, Skomski and Coey predict that a giant energy product (120 MG Oe) is possible in multilayer structures consisting of aligned hard-magnet layers exchanged coupled with soft-phase layers with high magnetization. Epitaxy provides one route to synthesizing such exchange-hardened magnets on controlled length scales. Epitaxial growth also allows the magnetic properties to be tailored by controlling the crystal orientation and the anisotropies of the magnetic layers and holds the possibility of stabilizing metastable phases. This paper describes the epitaxy and magnetic properties for several alloys.

  7. Rare Earth Metal Complexes of Bidentate Nitroxide Ligands: Synthesis and Electrochemistry.

    PubMed

    Kim, Jee Eon; Bogart, Justin A; Carroll, Patrick J; Schelter, Eric J

    2016-01-19

    We report rare earth metal complexes with tri- and bidentate ligands including strongly electron-donating nitroxide groups. The tridentate ligand 1,3,5-tris(2'-tert-butylhydroxylaminoaryl)benzene (H3arene-triNOx) was complexed to cerium(IV) in a 2:1 ligand-to-metal stoichiometry as Ce(Harene-triNOx)2 (1). Cyclic voltammetry of this compound showed stabilization of the tetravalent cerium cation with a Ce(IV/III) couple at E1/2 = -1.82 V versus Fc/Fc(+). On the basis of the uninvolvement of the third nitroxide group in the coordination chemistry with the cerium(IV) cation, the ligand system was redesigned toward a simpler bidentate mode, and a series of rare earth metal-arene-diNOx complexes were prepared with La(III), Ce(IV), Pr(III), Tb(III), and Y(III), [RE(arene-diNOx)2](-) ([2-RE](-), RE = La, Pr, Y, Tb) and Ce(IV)(arene-diNOx)2, where H2arene-diNOx = 1,3-bis(2'-tert-butylhydroxylaminoaryl)benzene. The core structures were isostructural throughout the series, with three nitroxide groups in η(2) binding modes and one κ(1) nitroxide group coordinated to the metal center in the solid state. In all cases except Ce(IV)(arene-diNOx)2, electrochemical analysis described two subsequent, ligand-based, quasi-reversible redox waves, indicating that a stable [N-O•] group was generated on the electrochemical time scale. Chemical oxidation of the terbium complex was performed, and isolation of the resulting complex, Tb(arene-diNOx)2·CH2Cl2 (3·CH2Cl2), confirmed the assignment of the cyclic voltammograms. Magnetic data showed no evidence of mixing between the Tb(III) states and the states of the open-shell ligand.

  8. Rare earth elements and critical metal content of extracted landfilled material and potential recovery opportunities.

    PubMed

    Gutiérrez-Gutiérrez, Silvia C; Coulon, Frédéric; Jiang, Ying; Wagland, Stuart

    2015-08-01

    Rare earth elements (REEs), Platinum group metals (PGMs) and other critical metals currently attract significant interest due to the high risks of supply shortage and substantial impact on the economy. Their uses in many applications have made them present in municipal solid waste (MSW) and in commercial and industrial waste (C&I), since several industrial processes produce by-products with high content of these metals. With over 4000 landfills in the UK alone, the aim of this study was to assess the existence of these critical metals within landfills. Samples collected from four closed landfills in UK were subjected to a two-step acid digestion to extract 27 metals of interest. Concentrations across the four landfill sites were 58±6mgkg(-1) for REEs comprising 44±8mgkg(-1) for light REEs, 11±2mgkg(-1) for heavy REEs and 3±1mgkg(-1) for Scandium (Sc) and 3±1.0mgkg(-1) of PGMs. Compared to the typical concentration in ores, these concentrations are too low to achieve a commercially viable extraction. However, content of other highly valuable metals (Al and Cu) was found in concentrations equating to a combined value across the four landfills of around $400 million, which increases the economic viability of landfill mining. Presence of critical metals will mainly depend on the type of waste that was buried but the recovery of these metals through landfill mining is possible and is economically feasible only if additional materials (plastics, paper, metallic items and other) are also recovered for reprocessing.

  9. Recovery of Rare Earths, Precious Metals and Other Critical Materials from Geothermal Waters with Advanced Sorbent Structures

    DOE Data Explorer

    Pamela M. Kinsey

    2015-09-30

    The work evaluates, develops and demonstrates flexible, scalable mineral extraction technology for geothermal brines based upon solid phase sorbent materials with a specific focus upon rare earth elements (REEs). The selected organic and inorganic sorbent materials demonstrated high performance for collection of trace REEs, precious and valuable metals. The nanostructured materials typically performed better than commercially available sorbents. Data contains organic and inorganic sorbent removal efficiency, Sharkey Hot Springs (Idaho) water chemsitry analysis, and rare earth removal efficiency from select sorbents.

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

    PubMed

    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.

  11. Production method for making rare earth compounds

    DOEpatents

    McCallum, R.W.; Ellis, T.W.; Dennis, K.W.; Hofer, R.J.; Branagan, D.J.

    1997-11-25

    A method of making a rare earth compound, such as a earth-transition metal permanent magnet compound, without the need for producing rare earth metal as a process step, comprises carbothermically reacting a rare earth oxide to form a rare earth carbide and heating the rare earth carbide, a compound-forming reactant (e.g., a transition metal and optional boron), and a carbide-forming element (e.g., a refractory metal) that forms a carbide that is more thermodynamically favorable than the rare earth carbide whereby the rare earth compound (e.g., Nd{sub 2}Fe{sub 14}B or LaNi{sub 5}) and a carbide of the carbide-forming element are formed.

  12. Production method for making rare earth compounds

    DOEpatents

    McCallum, R. William; Ellis, Timothy W.; Dennis, Kevin W.; Hofer, Robert J.; Branagan, Daniel J.

    1997-11-25

    A method of making a rare earth compound, such as a earth-transition metal permanent magnet compound, without the need for producing rare earth metal as a process step, comprises carbothermically reacting a rare earth oxide to form a rare earth carbide and heating the rare earth carbide, a compound-forming reactant (e.g. a transition metal and optional boron), and a carbide-forming element (e.g. a refractory metal) that forms a carbide that is more thermodynamically favorable than the rare earth carbide whereby the rare earth compound (e.g. Nd.sub.2 Fe.sub.14 B or LaNi.sub.5) and a carbide of the carbide-forming element are formed.

  13. Role of surface oxygen-to-metal ratio on the wettability of rare-earth oxides

    NASA Astrophysics Data System (ADS)

    Khan, Sami; Azimi, Gisele; Yildiz, Bilge; Varanasi, Kripa K.

    2015-02-01

    Hydrophobic surfaces that are robust can have widespread applications in drop-wise condensation, anti-corrosion, and anti-icing. Recently, it was shown that the class of ceramics comprising the lanthanide series rare-earth oxides (REOs) is intrinsically hydrophobic. The unique electronic structure of the rare-earth metal atom inhibits hydrogen bonding with interfacial water molecules resulting in a hydrophobic hydration structure where the surface oxygen atoms are the only hydrogen bonding sites. Hence, the presence of excess surface oxygen can lead to increased hydrogen bonding and thereby reduce hydrophobicity of REOs. Herein, we demonstrate how surface stoichiometry and surface relaxations can impact wetting properties of REOs. Using X-ray Photoelectron Spectroscopy and wetting measurements, we show that freshly sputtered ceria is hydrophilic due to excess surface oxygen (shown to have an O/Ce ratio of ˜3 and a water contact angle of ˜15°), which when relaxed in a clean, ultra-high vacuum environment isolated from airborne contaminants reaches close to stoichiometric O/Ce ratio (˜2.2) and becomes hydrophobic (contact angle of ˜104°). Further, we show that airborne hydrocarbon contaminants do not exclusively impact the wetting properties of REOs, and that relaxed REOs are intrinsically hydrophobic. This study provides insight into the role of surface relaxation on the wettability of REOs.

  14. Role of surface oxygen-to-metal ratio on the wettability of rare-earth oxides

    SciTech Connect

    Khan, Sami; Varanasi, Kripa K.; Azimi, Gisele; Yildiz, Bilge

    2015-02-09

    Hydrophobic surfaces that are robust can have widespread applications in drop-wise condensation, anti-corrosion, and anti-icing. Recently, it was shown that the class of ceramics comprising the lanthanide series rare-earth oxides (REOs) is intrinsically hydrophobic. The unique electronic structure of the rare-earth metal atom inhibits hydrogen bonding with interfacial water molecules resulting in a hydrophobic hydration structure where the surface oxygen atoms are the only hydrogen bonding sites. Hence, the presence of excess surface oxygen can lead to increased hydrogen bonding and thereby reduce hydrophobicity of REOs. Herein, we demonstrate how surface stoichiometry and surface relaxations can impact wetting properties of REOs. Using X-ray Photoelectron Spectroscopy and wetting measurements, we show that freshly sputtered ceria is hydrophilic due to excess surface oxygen (shown to have an O/Ce ratio of ∼3 and a water contact angle of ∼15°), which when relaxed in a clean, ultra-high vacuum environment isolated from airborne contaminants reaches close to stoichiometric O/Ce ratio (∼2.2) and becomes hydrophobic (contact angle of ∼104°). Further, we show that airborne hydrocarbon contaminants do not exclusively impact the wetting properties of REOs, and that relaxed REOs are intrinsically hydrophobic. This study provides insight into the role of surface relaxation on the wettability of REOs.

  15. Effects of rare earth elements on the distribution of mineral elements and heavy metals in horseradish.

    PubMed

    Wang, Lihong; Huang, Xiaohua; Zhou, Qing

    2008-09-01

    In order to investigate the effects of rare earth elements (REEs) on horseradish, the distribution of the mineral elements and heavy metals in different organs of horseradish have been studied by using inductively coupled plasma-atomic emission spectrometry (ICP-AES). Meanwhile, three variable major parameters, namely the concentration of REEs, the type of REEs, and the growth stage of plant were chosen. The results indicated that the test REEs, Ce(III) and Tb(III), could be accumulated in leaves, stems and roots of horseradish. In addition, we found that the content of mineral elements was increased in horseradish treated with 20mgl(-1) of Ce(III), but not those with the 20mgl(-1) of Tb(III). Moreover, the content of mineral elements in horseradish was decreased with the increasing concentration of REEs (100, 300mgl(-1)). Furthermore, we found that there were the opposite effects on the content of the heavy metals in horseradish treated with REEs. Finally, we found that the effect of REEs on the accumulation of REEs, and the content of mineral elements or heavy metals of horseradish during vigorous growth stage, no matter positive or negative, was more obvious than that of the other growth stages. These results demonstrated that the distribution behaviors of mineral elements and heavy metals in horseradish can be affected by the type and concentration of REEs, and the growth period of plant.

  16. Binary rare earth element-Ni/Co metallic glasses with distinct β-relaxation behaviors

    SciTech Connect

    Zhu, Z. G.; Wang, Z.; Wang, W. H.

    2015-10-21

    We report the formation of a series of rare earth element (RE)-Ni/Co binary metallic glasses (MGs) with unusual distinct β-relaxation peak compared with that of most of the reported MGs which usually exhibit as an excess wing or a shoulder. The β-relaxation behavior of RE-Ni/Co MGs is sensitive to the composition and the atomic radii of the RE and can be tuned through changing the fraction of RE-Ni (or Co) atomic pairs. The novel RE-Ni/Co MGs with distinct β-relaxation can serve as model system to investigate the nature of the β-relaxation as well as its relations with other physical and mechanical properties of MGs.

  17. Rare earth-transition metal-magnesium compounds-An overview

    SciTech Connect

    Rodewald, Ute Ch.; Chevalier, Bernard Poettgen, Rainer

    2007-05-15

    Intermetallic rare earth-transition metal-magnesium compounds play an important role as precipitations in modern light weight alloys and as host materials for hydrogen storage applications. Recent results on the crystal chemistry, the chemical bonding peculiarities, physical properties, and hydrogenation behavior of these materials are reviewed. - Graphical abstract: View of the Sm{sub 4}RhMg crystal structure approximately along the direction. Samarium, rhodium, and magnesium atoms are drawn as medium gray, filled (hidden in the trigonal prisms), and open circles, respectively. The three-dimensional network of corner-sharing RhSm{sub 6} trigonal prisms and the Mg{sub 4} tetrahedra are emphasized. The Sm1 atoms do not participate in the network of condensed trigonal prisms.

  18. Remarkable rare-earth metal silicide oxides with planar Si6 rings.

    PubMed

    Wang, Limin; Tang, Zhongjia; Lorenz, Bernd; Guloy, Arnold M

    2008-08-27

    New rare-earth silicide oxides, La10Si8O3 (1) and Ce10Si8O3 (2), were synthesized through high-temperature reactions of the pure elements under controlled oxygen atmosphere conditions. The remarkable silicides crystallize in a unique crystal structure (space group P6/mmm; a = 10.975(3) A (La) and 10.844(1) A (Ce); c = 4.680(1) A (La) and 4.561(1) A (Ce)) that features a 3-D framework of corner-shared O-centered (La/Ce)6 octahedra, reminiscent of hexagonal tungsten bronzes, with planar Si6 rings enclosed within its hexagonal channels. Band structure calculations indicate the compounds are metallic, with optimized La-Si bonds, and a benzene-like [Si6]6- anion. Compound 1 exhibits temperature independent paramagnetism. Compound 2 exhibits Curie-Weiss paramagnetism, and an antiferromagnetic ordering below 7 K.

  19. Coercivity of domain wall motion in thin films of amorphous rare earth-transition metal alloys

    NASA Technical Reports Server (NTRS)

    Mansuripur, M.; Giles, R. C.; Patterson, G.

    1991-01-01

    Computer simulations of a two dimensional lattice of magnetic dipoles are performed on the Connection Machine. The lattice is a discrete model for thin films of amorphous rare-earth transition metal alloys, which have application as the storage media in erasable optical data storage systems. In these simulations, the dipoles follow the dynamic Landau-Lifshitz-Gilbert equation under the influence of an effective field arising from local anisotropy, near-neighbor exchange, classical dipole-dipole interactions, and an externally applied field. Various sources of coercivity, such as defects and/or inhomogeneities in the lattice, are introduced and the subsequent motion of domain walls in response to external fields is investigated.

  20. Coordination Polymerization of Renewable 3-Methylenecyclopentene with Rare-Earth-Metal Precursors.

    PubMed

    Liu, Bo; Li, Shihui; Wang, Meiyan; Cui, Dongmei

    2017-04-10

    Coordination polymerization of renewable 3-methylenecyclopentene has been investigated for the first time using rare-earth metal-based precursors bearing various bulky ligands. All the prepared complexes catalyze controllable polymerization of 3-methylenecyclopentene into high molecular weight polymers, of which the NPN- and NSN-tridentate non-Cp ligated lutetium-based catalytic systems exhibited extremely high activities up to 11 520 kg/(molLu ⋅h) in a dilute toluene solution (3.2 g/100 mL) at room temperature. The resultant polymers have pure 1,4-regioregularity (>99 %) and tailorable number average molecular weights (1-20×10(4) ) with narrow molecular weight distributions (polydispersity index (PDI)=1.45-1.79). DFT simulations were employed to study the polymerization mechanism and stereoregularity control.

  1. Coherent spectroscopy of rare-earth-metal-ion-doped whispering-gallery-mode resonators

    SciTech Connect

    McAuslan, D. L.; Korystov, D.; Longdell, J. J.

    2011-06-15

    We perform an investigation into the properties of Pr{sup 3+}:Y{sub 2}SiO{sub 5} whispering-gallery-mode resonators as a first step toward achieving the strong coupling regime of cavity QED with rare-earth-metal-ion-doped crystals. Direct measurement of cavity QED parameters are made using photon echoes, giving good agreement with theoretical predictions. By comparing the ions at the surface of the resonator to those in the center, it is determined that the physical process of making the resonator does not negatively affect the properties of the ions. Coupling between the ions and resonator is analyzed through the observation of optical bistability and normal-mode splitting.

  2. Basic character of rare earth metal alkoxides. Utilization in catalytic C-C bond-forming reactions and catalytic asymmetric nitroaldol reactions

    SciTech Connect

    Sasai, H.; Suzuki, T.; Arai, S.

    1992-05-20

    In a recent paper, the authors reported that Zr(O-t-Bu){sub 4} was an efficient and convenient basic reagent in organic synthesis. However, all reactions examined were performed with stoichiometric quantities of the reagent. The authors envisioned that rare earth metal alkoxides would be stronger bases than group 4 metal alkoxides due to the lower ionization potential (ca. 5.4-6.4 eV) and the lower electronegativity (1.1-1.3) of rare earth elements; thus, the catalytic use of rare earth metal alkoxides in organic synthesis was expected. Although a variety of rare earth metal alkoxides have been prepared for the last three decades, to the authors knowledge, there have been few reports concerning the basicity of rare earth metal alkoxides. Herein, the authors report several carbon-carbon bond-forming reactions catalyzed by rare earth metal alkoxides and their application to a catalytic asymmetric nitroaldol reaction.

  3. Rare earth gas laser

    DOEpatents

    Krupke, W.F.

    1975-10-31

    A high energy gas laser with light output in the infrared or visible region of the spectrum is described. Laser action is obtained by generating vapors of rare earth halides, particularly neodymium iodide or, to a lesser extent, neodymium bromide, and disposing the rare earth vapor medium in a resonant cavity at elevated temperatures; e.g., approximately 1200/sup 0/ to 1400/sup 0/K. A particularly preferred gaseous medium is one involving a complex of aluminum chloride and neodymium chloride, which exhibits tremendously enhanced vapor pressure compared to the rare earth halides per se, and provides comparable increases in stored energy densities.

  4. Reactivity of functionalized indoles with rare-earth metal amides. Synthesis, characterization and catalytic activity of rare-earth metal complexes incorporating indolyl ligands.

    PubMed

    Feng, Zhijun; Wei, Yun; Zhou, Shuangliu; Zhang, Guangchao; Zhu, Xiancui; Guo, Liping; Wang, Shaowu; Mu, Xiaolong

    2015-12-21

    The reactivity of several functionalized indoles 2-(RNHCH2)C8H5NH (R = C6H5 (1), (t)Bu (2), 2,6-(i)Pr2C6H3 (3)) with rare-earth metal amides is described. Reactions of 1 or 2 with [(Me3Si)2N]3RE(μ-Cl)Li(THF)3 (RE = Eu, Yb) respectively produced the europium complexes [2-(C6H5N[double bond, length as m-dash]CH)C8H5N]2Eu[N(SiMe3)2] (4) and [2-((t)BuN[double bond, length as m-dash]CH)C8H5N]Eu[N(SiMe3)2]2 (5), and the ytterbium complex [2-((t)BuN[double bond, length as m-dash]CH)C8H5N]2Yb[N(SiMe3)2] (6), containing bidentate anionic indolyl ligands via dehydrogenation of the amine to the imine. In contrast, reactions of the more sterically bulky indole 3 with [(Me3Si)2N]3RE(μ-Cl)Li(THF)3 afforded complexes [2-(2,6-(i)Pr2C6H3NCH2)C8H5N]RE[N(SiMe3)2](THF)2 (RE = Yb (7), Y (8), Er (9), Dy (10)) with the deprotonated indolyl ligand. While reactions of 3 with yttrium and ytterbium amides in refluxing toluene respectively gave the complexes [2-(2,6-(i)Pr2C6H3N[double bond, length as m-dash]CH)C8H5N]3Y (11) and [2-(2,6-(i)Pr2C6H3N[double bond, length as m-dash]CH)C8H5N]2Yb(II)(THF)2 (12), along with transformation of the amino group to the imino group, and also with a reduction of Yb(3+) to Yb(2+) in the formation of 12. Reactions of 3 with samarium and neodymium amides provided novel dinuclear complexes {[μ-η(5):η(1):η(1)-2-(2,6-(i)Pr2C6H3NCH2)C8H5N]RE[N(SiMe3)2]}2 (RE = Sm (13), Nd (14)) having indolyl ligands in μ-η(5):η(1):η(1) hapticities. The pathway for the transformation of the amino group to the imino group is proposed on the basis of the experimental results. The new complexes displayed excellent activity in the intramolecular hydroamination of aminoalkenes.

  5. Strategic design and refinement of Lewis acid-base catalysis by rare-earth-metal-containing polyoxometalates.

    PubMed

    Suzuki, Kosuke; Sugawa, Midori; Kikukawa, Yuji; Kamata, Keigo; Yamaguchi, Kazuya; Mizuno, Noritaka

    2012-06-18

    Efficient polyoxometalate (POM)-based Lewis acid-base catalysts of the rare-earth-metal-containing POMs (TBA(6)RE-POM, RE = Y(3+), Nd(3+), Eu(3+), Gd(3+), Tb(3+), or Dy(3+)) were designed and synthesized by reactions of TBA(4)H(4)[γ-SiW(10)O(36)] (TBA = tetra-n-butylammonium) with RE(acac)(3) (acac = acetylacetonato). TBA(6)RE-POM consisted of two silicotungstate units pillared by two rare-earth-metal cations. Nucleophilic oxygen-enriched surfaces of negatively charged POMs and the incorporated rare-earth-metal cations could work as Lewis bases and Lewis acids, respectively. Consequently, cyanosilylation of carbonyl compounds with trimethylsilyl cyanide ((TMS)CN) was efficiently promoted in the presence of the rare-earth-metal-containing POMs via the simultaneous activation of coupling partners on the same POM molecules. POMs with larger metal cations showed higher catalytic activities for cyanosilylation because of the higher activation ability of C═O bonds (higher Lewis acidities) and sterically less hindered Lewis acid sites. Among the POM catalysts examined, the neodymium-containing POM showed remarkable catalytic performance for cyanosilylation of various kinds of structurally diverse ketones and aldehydes, giving the corresponding cyanohydrin trimethylsilyl ethers in high yields (13 substrates, 94-99%). In particular, the turnover frequency (714,000 h(-1)) and the turnover number (23,800) for the cyanosilylation of n-hexanal were of the highest level among those of previously reported catalysts.

  6. Fenton-Like Reaction Catalyzed by the Rare Earth Inner Transition Metal Cerium

    PubMed Central

    HECKERT, ERIC G.; SEAL, SUDIPTA; SELF, WILLIAM T.

    2011-01-01

    Cerium (Ce) is a rare earth metal that is not known to have any biological role. Cerium oxide materials of several sizes and shapes have been developed in recent years as a scaffold for catalysts. Indeed even cerium oxide nanoparticles themselves have displayed catalytic activities and antioxidant properties in tissue culture and animal models. Because of ceria's ability to cycle between the +3 and +4 states at oxygen vacancy sites, we investigated whether cerium metal would catalyze a Fenton-like reaction with hydrogen peroxide. Indeed, cerium chloride did exhibit radical production in the presence of hydrogen peroxide, as assessed by relaxation of supercoiled plasmid DNA. Radical production in this reaction was also followed by production of radical cation of 2,2′-azinobis-(3-ethylbenzthiazoline-6-sulfonic acid) (ABTS). Radical scavengers and spin traps were capable of competing with ABTS for radicals produced in this cerium dependent Fenton-like reaction. Electron paramagnetic resonance experiments reveal both hydroxyl radical and superoxide anion in a reaction containing cerium and hydrogen peroxide. Based on these results we propose that cerium is capable of redox-cycling with peroxide to generate damaging oxygen radicals. PMID:18678042

  7. Fenton-like reaction catalyzed by the rare earth inner transition metal cerium.

    PubMed

    Heckert, Eric G; Seal, Sudipta; Self, William T

    2008-07-01

    Cerium (Ce) is a rare earth metal that is not known to have any biological role. Cerium oxide materials of several sizes and shapes have been developed in recent years as a scaffold for catalysts. Indeed even cerium oxide nanoparticles themselves have displayed catalytic activities and antioxidant properties in tissue culture and animal models. Because of ceria's ability to cycle between the +3 and +4 states at oxygen vacancy sites, we investigated whether cerium metal would catalyze a Fenton-like reaction with hydrogen peroxide. Indeed, cerium chloride did exhibit radical production in the presence of hydrogen peroxide, as assessed by relaxation of supercoiled plasmid DNA. Radical production in this reaction was also followed by production of radical cation of 2,2'-azinobis-(3-ethylbenzthiazoline-6-sulfonic acid) (ABTS). Radical scavengers and spin traps were capable of competing with ABTS for radicals produced in this cerium dependent Fenton-like reaction. Electron paramagnetic resonance experiments reveal both hydroxyl radical and superoxide anion in a reaction containing cerium and hydrogen peroxide. Based on these results we propose that cerium is capable of redox-cycling with peroxide to generate damaging oxygen radicals.

  8. Bis(imidazolin-2-iminato) rare earth metal complexes: synthesis, structural characterization, and catalytic application.

    PubMed

    Trambitas, Alexandra G; Melcher, Daniel; Hartenstein, Larissa; Roesky, Peter W; Daniliuc, Constantin; Jones, Peter G; Tamm, Matthias

    2012-06-18

    Reaction of anhydrous rare earth metal halides MCl(3) with 2 equiv of 1,3-bis(2,6-diisopropylphenyl)imidazolin-2-imine (Im(Dipp)NH) and 2 equiv of trimethylsilylmethyl lithium (Me(3)SiCH(2)Li) in THF furnished the complexes [(Im(Dipp)N)(2)MCl(THF)(n)] (M = Sc, Y, Lu). The molecular structures of all three compounds were established by single-crystal X-ray diffraction analyses. The coordination spheres around the pentacoordinate metal atoms are best described as trigonal bipyramids. Reaction of YbI(2) with 2 equiv of LiCH(2)SiMe(3) and 2 equiv of the imino ligand Im(Dipp)NH in tetrahydrofuran did not result in a divalent complex, but instead the Yb(III) complex [(Im(Dipp)N)(2)YbI(THF)(2)] was obtained and structurally characterized. Treatment of [(Im(Dipp)N)(2)MCl(THF)(n)] with 1 equiv of LiCH(2)SiMe(3) resulted in the formation of [(Im(Dipp)N)(2)M(CH(2)SiMe(3))(THF)(n)]. The coordination arrangement of these compounds in the solid state at the metal atoms is similar to that found for the starting materials, although the introduction of the neosilyl ligand induces a significantly greater distortion from the ideal trigonal-bipyramidal geometry. [(Im(Dipp)N)(2)Y(CH(2)SiMe(3))(THF)(2)] was used as precatalyst in the intramolecular hydroamination/cyclization reaction of various terminal aminoalkenes and of one aminoalkyne. The complex showed high catalytic activity and selectivity. A comparison with the previously reported dialkyl yttrium complex [(Im(Dipp)N)Y(CH(2)SiMe(3))(2)(THF)(3)] showed no clear tendency in terms of activity.

  9. Highly efficient hydrophosphonylation of aldehydes and unactivated ketones catalyzed by methylene-linked pyrrolyl rare earth metal amido complexes.

    PubMed

    Zhou, Shuangliu; Wu, Zhangshuan; Rong, Jiewei; Wang, Shaowu; Yang, Gaosheng; Zhu, Xiancui; Zhang, Lijun

    2012-02-27

    A series of rare earth metal amido complexes bearing methylene-linked pyrrolyl-amido ligands were prepared through silylamine elimination reactions and displayed high catalytic activities in hydrophosphonylations of aldehydes and unactivated ketones under solvent-free conditions for liquid substrates. Treatment of [(Me(3)Si)(2)N](3)Ln(μ-Cl)Li(THF)(3) with 2-(2,6-Me(2)C(6)H(3)NHCH(2))C(4)H(3)NH (1, 1 equiv) in toluene afforded the corresponding trivalent rare earth metal amides of formula {(μ-η(5):η(1)):η(1)-2-[(2,6-Me(2)C(6)H(3))NCH(2)](C(4)H(3)N)LnN(SiMe(3))(2)}(2) [Ln=Y (2), Nd (3), Sm (4), Dy (5), Yb (6)] in moderate to good yields. All compounds were fully characterized by spectroscopic methods and elemental analyses. The yttrium complex was also characterized by (1)H NMR spectroscopic analyses. The structures of complexes 2, 3, 4, and 6 were determined by single-crystal X-ray analyses. Study of the catalytic activities of the complexes showed that these rare earth metal amido complexes were excellent catalysts for hydrophosphonylations of aldehydes and unactivated ketones. The catalyzed reactions between diethyl phosphite and aldehydes in the presence of the rare earth metal amido complexes (0.1 mol%) afforded the products in high yields (up to 99%) at room temperature in short times of 5 to 10 min. Furthermore, the catalytic addition of diethyl phosphite to unactivated ketones also afforded the products in high yields of up to 99% with employment of low loadings (0.1 to 0.5 mol%) of the rare earth metal amido complexes at room temperature in short times of 20 min. The system works well for a wide range of unactivated aliphatic, aromatic or heteroaromatic ketones, especially for substituted benzophenones, giving the corresponding α-hydroxy diaryl phosphonates in moderate to high yields.

  10. Synthesis and structural characterization of amido scorpionate rare earth metals complexes.

    PubMed

    Márquez-Segovia, Isabel; Lara-Sánchez, Agustín; Otero, Antonio; Fernández-Baeza, Juan; Castro-Osma, José Antonio; Sánchez-Barba, Luis F; Rodríguez, Ana M

    2014-07-07

    The reactivity of hybrid scorpionate/cyclopentadienyl ligands in the form of the protio derivatives as a mixture of two regioisomers, namely bpzcpH [1-{2,2-bis(3,5-dimethylpyrazol-1-yl)-1,1-diphenylethyl}-1,3-cyclopentadiene and 2-{2,2-bis(3,5-dimethylpyrazol-1-yl)-1,1-diphenylethyl}-1,3-cyclopentadiene] and bpztcpH [1-{2,2-bis(3,5-dimethylpyrazol-1-yl)-1-tert-butylethyl}-1,3-cyclopentadiene and 2-{2,2-bis(3,5-dimethylpyrazol-1-yl)-1-tert-butylethyl}-1,3-cyclopentadiene], with the tris(silylamide) precursors [M{N(SiHMe2)2}3(thf)x] of rare earth metals (including the group 3 metals scandium and yttrium) is related to the atomic radii of the metal centres. The reaction with the precursor containing the smallest ion, [Sc{N(SiHMe2)2}3(thf)], did not proceed even heating at reflux temperature in toluene. The reaction with the precursors that contain a medium-sized metal ion, i.e., [M{N(SiHMe2)2}3(thf)2] (M = Y, Lu), proceeded only at high temperature and gave good yields of the silylenediamide-containing derivatives [M{κ(2)-NN-Me2Si(NSiHMe2)2}(bpzcp)] (M = Y , Lu ) and [M{κ(2)-NN-Me2Si(NSiHMe2)2}(bpztcp)] (M = Y , Lu ) by an double activation of Si-H and Si-N bonds. However, the reaction with the precursors that contained the largest metal ions, i.e., [M{N(SiHMe2)2}3(thf)2] (M = Nd, Sm), proceeded rapidly at room temperature to afford the bis(silylamide) complexes [M{N(SiHMe2)2}2(bpzcp)] (M = Nd , Sm ) and [M{N(SiHMe2)2}2(bpztcp)] (M = Nd , Sm ). Additionally, the alkyl heteroscorpionate yttrium and lutetium complexes [M(CH2SiMe3)2(NNCp)] (M = Y, Lu) reacted with an excess of HN(SiHMe2)2 to give the mixed alkyl/amide derivatives [M{N(SiHMe2)2}(CH2SiMe3)(bpzcp)] (M = Y , Lu ) and [M{N(SiHMe2)2}(CH2SiMe3)(bpztcp)] (M = Y , Lu ). The structures of the complexes were determined by spectroscopic methods and the X-ray crystal structures of , and were also established.

  11. Magnetic ordering temperatures in rare earth metal dysprosium under ultrahigh pressures

    SciTech Connect

    Samudrala, Gopi K.; Tsoi, Georgiy M.; Weir, Samuel T.; Vohra, Yogesh K.

    2014-04-03

    Magnetic ordering temperatures in heavy rare earth metal Dysprosium (Dy) have been studied using an ultrasensitive electrical transport measurement technique in a designer diamond anvil cell to extreme conditions of pressure to 69 GPa and temperature to 10 K. Previous studies using magnetic susceptibility measurements at high pressures were only able to track magnetic ordering temperature till 7 GPa in the hexagonal close packed (hcp) phase of Dy. Our studies indicate that the magnetic ordering temperature shows an abrupt drop of 80 K at the hcp-Sm phase transition followed by a gradual decrease that continues till 17 GPa. This is followed by a rapid increase in the magnetic ordering temperatures in the double hexagonal close packed phase and finally leveling off in the distorted face centered cubic phase of Dy. Lastly, our studies reaffirm that 4f-shell remain localized in Dy and there is no loss of magnetic moment or 4f-shell delocalization for pressures up to 69 GPa.

  12. TOPICAL REVIEW: Ferromagnetic nitride-based semiconductors doped with transition metals and rare earths

    NASA Astrophysics Data System (ADS)

    Bonanni, A.

    2007-09-01

    This review summarizes the state-of-the-art in the search for room temperature ferromagnetic semiconductors based on transition-metal- and rare-earth-doped nitrides. The major methods of synthesis are reported, together with an overview of the magnetic, structural, electrical and optical characterization of the materials systems, where available. The controversial experimental results concerning the actual value of the apparent Curie temperature in magnetically doped nitrides are highlighted, the inadequacy of standard characterization methods alone and the necessity of a possibly exhaustive structural investigation of the systems are proven and underlined. Furthermore, the dependence on the fabrication parameters of the magnetic ions incorporation into the semiconductor matrix is discussed, with special attention to the fundamental concepts of solubility limit and spinodal decomposition. It is argued that high-temperature ferromagnetic features in magnetically doped nitrides result from the presence of nanoscale regions containing a high concentration of the magnetic constituents. Various functionalities of these multicomponent systems are listed. Moreover, we give an extensive overview on the properties of single magnetic-impurity states in the nitride host. The understanding of this limit is crucial when considering the most recent suggestions for the control of the magnetic ion distribution—and consequently of the magnetic response—through the Fermi level engineering as well as to indicate roads for achieving high-temperature ferromagnetism in the systems containing a uniform distribution of magnetic ions.

  13. Rare-earth vs. heavy metal pigments and their colors from first principles.

    PubMed

    Tomczak, Jan M; Pourovskii, Leonid V; Vaugier, Loig; Georges, Antoine; Biermann, Silke

    2013-01-15

    Many inorganic pigments contain heavy metals hazardous to health and environment. Much attention has been devoted to the quest for nontoxic alternatives based on rare-earth elements. However, the computation of colors from first principles is a challenge to electronic structure methods, especially for materials with localized f-orbitals. Here, starting from atomic positions only, we compute the colors of the red pigment cerium fluorosulfide as well as mercury sulfide (classic vermilion). Our methodology uses many-body theories to compute the optical absorption combined with an intermediate length-scale modelization to assess how coloration depends on film thickness, pigment concentration, and granularity. We introduce a quantitative criterion for the performance of a pigment. While for mercury sulfide, this criterion is satisfied because of large transition matrix elements between wide bands, cerium fluorosulfide presents an alternative paradigm: the bright red color is shown to stem from the combined effect of the quasi-2D and the localized nature of states. Our work shows the power of modern computational methods, with implications for the theoretical design of materials with specific optical properties.

  14. In Vivo Uptake of Rare Earth Metals by Triple-Negative Breast Cancer Cells.

    PubMed

    Roncati, Luca; Gatti, Antonietta Morena; Barbolini, Giuseppe; Piscioli, Francesco; Pusiol, Teresa; Maiorana, Antonio

    2017-02-09

    Rare earth metals (REM) are a group of 17 chemical elements in the periodic table, namely scandium (Sc), yttrium (Y) and the lanthanides. In relation to atomic volume and geological behavior, the lanthanides are further subdivided into light, medium and heavy REM. They find many applications in the technological field; however, their impact on the human health is still conflicting and, for many aspects, unknown. During a research program carried on 113 cases of female breast cancer, immunohistochemically categorized in Her2-positive (29 cases), Her2-negative (57 cases) and triple negative (27 cases), aimed to evaluate the role of environmental particulate in carcinogenesis by elemental microanalysis, for the first time in literature we have detected a REM uptake, in detail europium (Eu), dysprosium (Dy) and praseodymium (Pr), inside the neoplastic cells belonging to a single triple negative breast cancer. Curiously, the woman affected by this form of malignancy had worked in the ceramic industry, a well-known source of REM, during her life, and she was the one and only patient of our series to be dedicated to this activity. The medical repercussions of our findings are here discussed: in fact, a REM detection in only 1 of 113 examined cases seems to exclude active roles in breast carcinogenesis and discloses new possibilities for therapeutic developments in triple negative breast cancer.

  15. Effect of patch borders on coercivity in amorphous rare earth-transition metal thin films

    NASA Technical Reports Server (NTRS)

    Patterson, G.; Fu, H.; Giles, R. C.; Mansuripur, M.

    1991-01-01

    The coercivity at the micron scale is a very important property of magneto-optical media. It is a key factor that determines the magnetic domain wall movement and domain reversal. How the coercivity is influenced by a special type of patch borders is discussed. Patch formation is a general phenomenon in growth processes of amorphous rare earth transition metal thin films. Different patches may stem from different seeds and the patch borders are formed when they merge. Though little is known about the exact properties of the borders, we may expect that the exchange interaction at the patch border is weaker than that within a patch, since there is usually a spatial gap between two patches. Computer simulations were performed on a 2-D hexagonal lattice consisting of 37 complete patches with random shape and size. From the series of simulations we may conclude that the domain in the patch with borders of 30 percent exchange strength can expand most easily to the whole lattice, because the exchange strength can expand most easily to the whole lattice, because the exchange strength of the border is not too high to prevent the domain from growing within the patch and it is not too low to prevent the domain from expanding beyond the patch.

  16. Sol-gel-derived hybrid materials multi-doped with rare-earth metal ions

    NASA Astrophysics Data System (ADS)

    Zelazowska, E.; Rysiakiewicz-Pasek, E.; Borczuch-Laczka, M.; Cholewa-Kowalska, K.

    2012-06-01

    Four different hybrid organic-inorganic materials based on TiO2-SiO2 matrices with organic additives and doped with rare-earth metal ions (III) from the group of europium, cerium, terbium, neodymium, dysprosium and samarium, were synthesized by sol-gel method. Tetraethyl orthosilicate, titanium (IV) isopropoxide and organic compounds, such as butyl acrylate, butyl methacrylate, ethyl acetoacetate, ethylene glycol dimethacrylate, ethyl acetate, propylene carbonate, organic solvents and certain inorganic salts were used in the synthesis. The inorganic part of the sols, which were used in the synthesis of all the hybrid materials, was prepared separately and then the organic parts were added. The materials obtained were aged for three weeks at room temperature and then heated in an electric oven for three hours at temperatures of 80 °C-150 °C. Scanning electron microscopy equipped with energy dispersive X-ray spectroscopy (SEM/EDX); X-ray diffraction (XRD); Fourier transform infrared spectroscopy (KBr technique); 29Si magic-angle spinning nuclear magnetic resonance; and fluorescence spectroscopy were used for the examination of morphology, microstructure and luminescence properties, respectively. Photoluminescence properties with relatively intense narrow emission lines of Tb, Eu, Dy, Nd, Sm respectively to the RE-ions doping, were observed for all the hybrid materials.

  17. Magnetic ordering temperatures in rare earth metal dysprosium under ultrahigh pressures

    DOE PAGES

    Samudrala, Gopi K.; Tsoi, Georgiy M.; Weir, Samuel T.; ...

    2014-04-03

    Magnetic ordering temperatures in heavy rare earth metal Dysprosium (Dy) have been studied using an ultrasensitive electrical transport measurement technique in a designer diamond anvil cell to extreme conditions of pressure to 69 GPa and temperature to 10 K. Previous studies using magnetic susceptibility measurements at high pressures were only able to track magnetic ordering temperature till 7 GPa in the hexagonal close packed (hcp) phase of Dy. Our studies indicate that the magnetic ordering temperature shows an abrupt drop of 80 K at the hcp-Sm phase transition followed by a gradual decrease that continues till 17 GPa. This ismore » followed by a rapid increase in the magnetic ordering temperatures in the double hexagonal close packed phase and finally leveling off in the distorted face centered cubic phase of Dy. Lastly, our studies reaffirm that 4f-shell remain localized in Dy and there is no loss of magnetic moment or 4f-shell delocalization for pressures up to 69 GPa.« less

  18. Methylene-bridged, intramolecular donor-acceptor systems based on rare-earth metals and phosphinomethanides.

    PubMed

    Pieper, Martin; Lamm, Jan-Hendrik; Neumann, Beate; Stammler, Hans-Georg; Mitzel, Norbert W

    2017-04-06

    New geminally bonded intramolecular donor-acceptor systems, Cp2LnCH2PR2 (Ln = Y, Ho, Er, R = CHMe2, CMe3), were prepared by salt elimination reactions between the dicyclopentadienyl-element chlorides (Cp2LnCl, Ln = Y, Ho, Er) and diorganylphosphinomethanides (R2PCH2Li; R = CHMe2, CMe3). These compounds, 1-6, were characterized by elemental analyses, mass spectrometry and X-ray diffraction experiments and the yttrium species additionally by NMR spectroscopy. In the solid state the molecular structures differ from each other, depending on the steric demand of the phosphorus substituents. For all iso-Pr-substituted compounds, dimers [Cp2LnCH2P(CHMe2)2]2 with six-membered Ln-C-P-Ln-C-P rings in a chair-like conformation were observed. The sterically more demanding tert-butyl groups prevent dimerization but instead lead to species that undergo complexation of LiCl units by two monomers: [Cp2LnCH2P(CMe3)2·LiCl]. The solution NMR data for the yttrium compounds are consistent with the solid-state structures. Conversion with phenylacetylene afforded heteroleptic cyclobutane-like alkynyl-rare-earth metal complexes [Cp2Ln(μ-C[triple bond, length as m-dash]CPh)]2 [Ln = Y (7), Ho (8), Er (9)]. Treatment of compounds 1-6 with 1,8-diethynylanthracene led to single metalation and dimerization and products with similar structural motifs as observed for complexes 7-9. Reactions with dihydrogen and carbon dioxide resulted in Y-C bond breaking, yielding Cp2YH/R2PCH3 and CO2 insertion products, respectively.

  19. Synthesis and catalytic activity of heterogeneous rare-earth metal catalysts coordinated with multitopic Schiff-base ligands.

    PubMed

    Sun, Yilin; Wu, Guangming; Cen, Dinghai; Chen, Yaofeng; Wang, Limin

    2012-08-28

    Four multitopic Schiff-base ligand precursors were synthesized via condensation of 4,4'-diol-3,3'-diformyl-1,1'-diphenyl or 1,3,5-tris(4-hydroxy-5-formylphenyl)benzene with 2,6-diisopropylaniline or 2,6-dimethylaniline. Amine elimination reactions of Ln[N(SiMe(3))(2)](3) (Ln = La, Nd, Sm or Y) with these multitopic ligand precursors gave ten heterogeneous rare-earth metal catalysts. These heterogeneous rare-earth metal catalysts are active for intramolecular hydroalkoxylation of alkynols, and the catalytic activities are influenced by the ligand and metal ion. The recycling experiment on the most active heterogeneous catalyst showed the catalyst has a good reusability.

  20. Metal loading effect on rare earth element binding to humic acid: Experimental and modelling evidence

    NASA Astrophysics Data System (ADS)

    Marsac, Rémi; Davranche, Mélanie; Gruau, Gérard; Dia, Aline

    2010-03-01

    The effect of metal loading on the binding of rare earth elements (REE) to humic acid (HA) was studied by combining ultrafiltration and Inductively Coupled Plasma Mass Spectrometry techniques. REE-HA complexation experiments were performed at pH 3 for REE/C molar ratios ranging from ca 4 × 10 -4 to 2.7 × 10 -2. Results show that the relative amount of REE bound to HA strongly increases with decreasing REE/C. A middle-REE (MREE) downward concavity is shown by patterns at high metal loading, whereas patterns at low metal loading display a regular increase from La to Lu. Humic Ion Model VI modelling are close to the experimental data variations, provided that (i) the ΔLK 2 parameter (i.e. the Model VI parameter taken into account the presence of strong but low density binding sites) is allowed to increase regularly from La to Lu (from 1.1 to 2.1) and (ii) the published log KMA values (i.e. the REE-HA binding constants specific to Model VI) are slightly modified, in particular with respect to heavy REE. Modelling approach provided evidence that logKdREE patterns with varying REE/C likely arises because REE binding to HA occurs through two types of binding sites in different density: (i) a few strong sites that preferentially complex the heavy REE and thus control the logKdREE atterns at low REE/C; (ii) a larger amount of weaker binding sites that preferentially complex the middle-REE and thus control the logKdREE pattern at high REE/C. Hence, metal loading exerts a major effect on HA-mediated REE binding, which could explain the diversity of published conditional constants for REE binding with HA. A literature survey suggests that the few strong sites activated at low REE/C could be multidentate carboxylic sites, or perhaps N-, or P-functional groups. Finally, an examination of the literature field data proposed that the described loading effect could account for much of the variation in REE patterns observed in natural organic-rich waters (DOC > 5 mg L -1 and 4

  1. Subcell Structure and Two Different Superstructures of the Rare Earth Metal Silicide Carbides Y

    SciTech Connect

    Jeitschko, Wolfgang; Gerdes, Martin H.; Witte, Anne M.; Rodewald, Ute Ch.

    2001-01-01

    be represented by the formula (R{sup +3}){sub 3}(Si{sup {minus}3}){sub 2}(C{sub 2}){sup {minus}3}. A more detailed analysis of the interatomic distances showed that the shortest R-R distances are comparable with the R-R distances in the structures of the rare earth elements, thus indicating some R-R bonding. Therefore, the oxidation numbers of the rare earth atoms are slightly lower than +3, in agreement with the metallic conductivity of these compounds. As a consequence, considering the relatively short Si-Si bonds, the absolute value of the oxidation number of the silicon atoms may be lower than 3, resulting in a Si-Si bond order somewhat higher than 0.5.

  2. Mineral resource of the month: rare earth elements

    USGS Publications Warehouse

    ,

    2011-01-01

    The article provides information on rare earth elements, which are group of 17 natural metallic elements. The rare earth elements are scandium, yttrium and lanthanides and classified into light rare earth elements (LREE) and heavy rate earth elements (HREE). The principal ores of the rare earth elements are identified. An overview of China's production of 97 percent of the rare earths in the world is provided. Commercial applications of rare earths are described.

  3. Homoleptic rare-earth metal(III) tetramethylaluminates: structural chemistry, reactivity, and performance in isoprene polymerization.

    PubMed

    Zimmermann, Melanie; Frøystein, Nils Age; Fischbach, Andreas; Sirsch, Peter; Dietrich, H Martin; Törnroos, Karl W; Herdtweck, Eberhardt; Anwander, Reiner

    2007-01-01

    The complexes [Ln(AlMe4)3] (Ln=Y, La, Ce, Pr, Nd, Sm, Ho, Lu) have been synthesized by an amide elimination route and the structures of [Lu{(micro-Me)2AlMe2}3], [Sm{(micro-Me)2AlMe2}3], [Pr{(micro-Me)2AlMe2}3], and [La{(micro-Me)2AlMe2}2{(micro-Me)3AlMe}] determined by X-ray crystallography. These structures reveal a distinct Ln3+ cation size-dependency. A comprehensive insight into the intrinsic properties and solution coordination phenomena of [Ln(AlMe4)3] complexes has been gained from extended dynamic 1H and 13C NMR spectroscopic studies, as well as 1D 89Y, 2D 1H/89Y, and 27Al NMR spectroscopic investigations. [Ce(AlMe4)3] and [Pr(AlMe4)3] have been used as alkyl precursors for the synthesis of heterobimetallic alkylated rare-earth metal complexes. Both carboxylate and siloxide ligands can be introduced by methane elimination reactions that give the heterobimetallic complexes [Ln{(O2CAriPr)2(micro-AlMe2)}2(AlMe4)(C6H14)n] and [Ln{OSi(OtBu)3}(AlMe3)(AlMe4)2], respectively. [Pr{OSi(OtBu)3}(AlMe3)(AlMe4)2] has been characterized by X-ray structure analysis. All of the cerium and praseodymium complexes are used as precatalysts in the stereospecific polymerization of isoprene (1-3 equivalents of Et2AlCl as co-catalyst) and compared to the corresponding neodymium-based initiators reported previously. The superior catalytic performance of the homoleptic complexes leads to quantitative yields of high-cis-1,4-polyisoprene (>98%) in almost all of the polymerization experiments. In the case of the binary catalyst mixtures derived from carboxylate or siloxide precatalysts quantitative formation of polyisoprene is only observed for nLn:nCl=1:2. The influence of the metal size is illustrated for the heterobimetallic lanthanum, cerium, praseodymium, neodymium, and gadolinium carboxylate complexes, and the highest activities are observed for praseodymium as a metal center in the presence of one equivalent of Et2AlCl.

  4. Alaska's rare earth deposits and resource potential

    USGS Publications Warehouse

    Barker, James C.; Van Gosen, Bradley S.

    2012-01-01

    Alaska’s known mineral endowment includes some of the largest and highest grade deposits of various metals, including gold, copper and zinc. Recently, Alaska has also been active in the worldwide search for sources of rare earth elements (REE) to replace exports now being limitedby China. Driven by limited supply of the rare earths, combined with their increasing use in new ‘green’ energy, lighting, transportation, and many other technological applications, the rare earth metals neodymium, europium and, in particular, the heavy rare earth elements terbium, dysprosium and yttrium are forecast to soon be in critical short supply (U.S. Department of Energy, 2010).

  5. Improved method for preparing rare earth sesquichalcogenides

    DOEpatents

    Takeshita, T.; Beaudry, B.J.; Gschneidner, K.A. Jr.

    1982-04-14

    An improved method for the preparation of high purity rare earth sesquichalcogenides is described. The rare earth, as one or more pieces of the metal, is sealed under a vacuum with a stoichiometric amount of sulfur or selenium and a small amount of iodine into a quartz reaction vessel. The sealed vessel is then heated to above the vaporization temperature of the chalcogen and below the melting temperature of the rare earth metal and maintained until the product has been formed. The iodine is then vaporized off leaving a pure product. The rare earth sulfides and selenides thus formed are useful as semiconductors and as thermoelectric generators. 3 tables.

  6. Observation of vapor pressure enhancement of rare-earth metal-halide salts in the temperature range relevant to metal-halide lamps

    SciTech Connect

    Curry, J. J.; Henins, A.; Hardis, J. E.; Estupinan, E. G.; Lapatovich, W. P.; Shastri, S. D.

    2012-02-20

    Total vapor-phase densities of Dy in equilibrium with a DyI{sub 3}/InI condensate and Tm in equilibrium with a TmI{sub 3}/TlI condensate have been measured for temperatures between 900 K and 1400 K. The measurements show strong enhancements in rare-earth vapor densities compared to vapors in equilibrium with the pure rare-earth metal-halides. The measurements were made with x-ray induced fluorescence on the sector 1-ID beam line at the Advanced Photon Source. The temperature range and salt mixtures are relevant to the operation of metal-halide high-intensity discharge lamps.

  7. Ln₃FeGaQ₇: A new series of transition-metal rare-earth chalcogenides

    SciTech Connect

    Yin, Wenlong; Wang, Wendong; Kang, Lei; Lin, Zheshuai; Feng, Kai; Shi, Youguo; and others

    2013-06-01

    A new series of transition-metal rare-earth chalcogenides, Ln₃FeGaQ₇ (Ln=Nd, Sm, Gd, Dy, Q=S; Ln=Nd, Gd, Dy, Q=Se), have been synthesized by solid state reactions. They are isostructural and crystallize in the space group P6₃. They adopt a three-dimensional framework composed of LnQ₇ monocapped trigonal prisms with the interesting 1[FeS₃]⁴⁻ chains and isolated GaQ₄ tetrahedra lying in two sets of channels in the framework. Magnetic susceptibility measurements on Ln₃FeGaQ₇ (Ln=Gd, Dy; Q=S, Se) indicate that they are paramagnetic and obey the Curie–Weiss law. Based on the diffuse reflectance spectra, Ln₃FeGaQ₇ (Ln=Gd, Dy; Q=S, Se) should have band gaps smaller than 0.5 eV. Electronic conductivity measurement on Dy₃FeGaSe₇ demonstrates semiconducting behavior with σ₃₀₀=0.124 S/cm. The first-principles calculations were also performed to study the electronic structures of these compounds. - Graphical abstract: Ln₃FeGaQ₇ adopt a three-dimensional framework composed of LnQ₇ monocapped trigonal prisms with interesting 1[FeS₃]⁴⁻ chains and isolated GaQ₄ tetrahedra lying in two sets of channels in the framework. Highlights: • New compounds, Ln₃FeGaQ₇ (Ln=Nd, Sm, Gd, Dy, Q=S, Se), were synthesized. • They are isostructural and crystallize in the noncentrosymmetric space group P6₃. • They adopt a three-dimensional framework built by LnQ₇ monocapped trigonal prisms. • Ln₃FeGaQ₇ (Ln=Gd, Dy; Q=S, Se) are paramagnetic and obey the Curie–Weiss law. • Electronic conductivity of Dy₃FeGaSe₇ shows semiconducting behavior.

  8. Materials flow analysis of neodymium, status of rare earth metal in the Republic of Korea.

    PubMed

    Swain, Basudev; Kang, Leeseung; Mishra, Chinmayee; Ahn, JoongWoo; Hong, Hyun Seon

    2015-11-01

    Materials flow analysis of neodymium, status of rare earth elements (REEs) in the Republic of Korea has been investigated. Information from various resources like the Korean Ministry of Environment, Korea international trade association, United Nations Commodity Trade Statistics Database and from individual industry were collected and analyzed for materials flow analysis of neodymium. Demand of neodymium in the Republic of Korea for the year 2010 was 409.5 tons out of which the majority of neodymium, i.e., 68.41% was consumed by domestic electronics industry followed by medical appliances manufacturing (13.36%). The Republic Korea is one of the biggest consumer and leading exporter of these industrial products, absolutely depends on import of neodymium, as the country is lacking natural resources. The Republic of Korea has imported 325.9 tons of neodymium permanent magnet and 79.5 tons of neodymium containing equipment parts mainly for electronics, medical appliances, and heavy/light vehicles manufacturing industry. Out of which 95.4 tons of neodymium permanent magnet get exported as an intermediate product and 140.6 tons of neodymium in the form of consumable products get exported. Worldwide the neodymium is at the high end of supply chain critical metal because of increasing demand, scarcity and irreplaceable for technological application. To bring back the neodymium to supply stream the recycling of end of life neodymium-bearing waste can be a feasible option. Out of total domestic consumption, only 21.9 tons of neodymium have been collected and subsequently recycled. From material flow analysis, the requirement for an efficient recycling system and element-wise material flow management for these REEs in the Republic of Korea were realized and recommended.

  9. Polymerization of 1,3-Conjugated Dienes with Rare-Earth Metal Precursors

    NASA Astrophysics Data System (ADS)

    Zhang, Zhichao; Cui, Dongmei; Wang, Baoli; Liu, Bo; Yang, Yi

    This chapter surveys the publications except patents related to cis-1,4-, trans-1,4-, 3,4-regio-, and stereoselective polymerizations of 1,3-conjugated dienes with rare-earth metal-based catalytic systems during the past decade from 1999 to 2009. The concerned catalyst systems are classified into the conventional Ziegler-Natta catalysts, the modified Ziegler-Natta catalysts, and the single-site cationic systems composed of lanthanocene and noncyclopentadienyl precursors, respectively. For the conventional Ziegler-Natta catalysts of the most promising industry applicable recipe, the multicomponents based on lanthanide carboxylate or phosphate or alkoxide precursors, research works concern mainly about optimizing the catalyst preparation and polymerization techniques. Special emphases are put on the factors that influence the catalyst homogeneority, catalytic activity and efficiency, as well as cis-1,4-selectivity. Meanwhile, tailor-made lanthanide aryloxide and amide complexes are designed and fully characterized to mimic the conventional Ziegler-Natta catalysts, anticipated to elucidate the key processes, alkylation and cationization, for generating the active species. Regarding to the single-site catalytic systems generally comprising well-defined complexes containing lanthanide-carbon bonds, investigations cover their versatile catalytic activity and efficiency, and the distinguished regio- and stereoselectivity for both polymerization of dienes and copolymerization of dienes with alkenes. The correlation between the sterics and electronics of ligands and the molecular structures of the complexes and their catalytic performances are highlighted. The isolation of the probable active species in these polymerization processes from the stoichiometric reactions of the precursors with activators will be presented.

  10. Mineral resource of the month: rare earths

    USGS Publications Warehouse

    Hedrick, James B.

    2004-01-01

    As if classified as a top-secret project, the rare earths have been shrouded in secrecy. The principal ore mineral of the group, bastnäsite, rarely appears in the leading mineralogy texts. The long names of the rare-earth elements and some unusual arrangements of letters, many Scandinavian in origin, may have intimidated even those skilled in phonics. Somewhat obscurely labeled, the rare earths are neither rare nor earths (the historical term for oxides). They are a relatively abundant group of metallic elements that occur in nature as nonmetallic compounds and have hundreds of commercial applications.

  11. Optimization of film synthesized rare earth transition metal permanent magnet systems. Progress report, August 1, 1989--July 1990

    SciTech Connect

    Cadieu, F.J.

    1990-12-31

    This report reviews work on the optimization of film synthesized rare earth transition metal permanent magnet systems. Topics include: high coercivity in Sm-Fe-Ti-V, Sm-Fe-V, and two element systems; ThMn{sub 12} type pseudobinary SmFe{sub 12 {minus} X}T{sub X}; and sputter process control for the synthesis of precisely textured RE-TM magnetic films. (JL)

  12. Optimization of film synthesized rare earth transition metal permanent magnet systems. Progress report, August 1, 1991--July 31, 1992

    SciTech Connect

    Cadieu, F.J.

    1992-08-01

    Progress is reported in three areas: high coercivity Sm-Fe-Ti-V, Sm-Fe-Zr, and two element Sm-Fe Sm{sub 5}(Fe,T){sub 17} type crystalline phases; ThMn{sub 12} type pseudobinary SmFe{sub 12-x}T{sub x}(0{le}{times}{le}1.5); and sputter process control for the synthesis of precisely textured rare earth-transition metal magnetic films. (DLC)

  13. Heavy metals and rare earth elements source-sink in some Egyptian cigarettes as determined by neutron activation analysis.

    PubMed

    Nada, A; Abdel-Wahab, M; Sroor, A; Abdel-Haleem, A S; Abdel-Sabour, M F

    1999-07-01

    Heavy metals and rare earth elements in two types of cigarettes were studied. The contents of trace elements were determined by using delayed neutron activation analysis. In the present study 11 elements have been detected in popular and fine brand cigarettes marketed in Egypt. Evaluation of these elements with their potential hazards for smokers is briefly discussed. The material balance (source and sink) for each element was determined. Also the ratio of element recovery to the total amount was assessed.

  14. ansa-Rare-earth-metal catalysts for rapid and stereoselective polymerization of renewable methylene methylbutyrolactones.

    PubMed

    Hu, Yangjian; Miyake, Garret M; Wang, Baoli; Cui, Dongmei; Chen, Eugene Y-X

    2012-03-12

    Two ansa-half-sandwich rare-earth-metal (REM) dialkyl complexes supported by an ethylene-bridged fluorenyl (Flu)-N-heterocyclic carbene (NHC) ligand, [M{C(2)H(4)(η(5)-Flu-κ(1)-NHC)}(CH(2)SiMe(3))(2)] (M=Y, 1; Lu, 2), and a chiral ansa-sandwich samarocene incorporating a C(2) ligand, [Sm(η(5)-C(12)H(8))(2)(thf)(2)] (3), have been investigated for the coordination-addition polymerization of renewable methylene butyrolactones, α-methylene-γ-butyrolactone (MBL) and γ-methyl-α-methylene-γ-butyrolactone ((γ)MMBL). Both ansa-half-sandwich complexes 1 and 2 exhibit exceptional activity for the polymerization of (γ)MMBL at room temperature in dimethylformamide (DMF); with a 0.25 mol% catalyst loading, quantitative monomer conversion can be achieved under 1 min, giving a high turn-over frequency (TOF) of 24,000 h(-1). This TOF value represents a rate enhancement, by a factor of 8, 22, or 2400, over the polymerizations by unbridged samarocene [Sm(Cp*)(2)(thf)(2)] (Cp*=η(5) -pentamethylcyclopentadienyl), by bridged ansa-samarocene 3 with C(2) ligation, or by the corresponding REM trialkyls without the ansa-Flu-NHC ligation, respectively. Complexes 1 and 2 are also highly active for the polymerization of β-methyl-α-methylene-γ-butyrolactone ((β)MMBL), realizing the first example of the metal-mediated coordination polymerization of this monomer and its copolymerization with (γ)MMBL. More remarkably, the resulting P(β)MMBL homopolymer is highly stereoregular (91% mm) and exhibits a high T(g) of 290 °C. In sharp contrast, catalysts 1 and 2 have poor activity and efficiency in the polymerization of the parent MBL or the acyclic analog methyl methacrylate. Polymerization and kinetic studies using the most active catalyst (1) of the series have uncovered characteristics of its (γ)MMBL polymerization and yielded a unimolecular propagation mechanism. A surprising chain-initiation pathway for the polymerization in DMF by 1 has been revealed, and catalytic

  15. A mini-review on rare earth metal-doped TiO2 for photocatalytic remediation of wastewater.

    PubMed

    Saqib, Najm Us; Adnan, Rohana; Shah, Irfan

    2016-08-01

    Titanium dioxide (TiO2) has been considered a useful material for the treatment of wastewater due to its non-toxic character, chemical stability and excellent electrical and optical properties which contribute in its wide range of applications, particularly in environmental remediation technology. However, the wide band gap of TiO2 photocatalyst (anatase phase, 3.20 eV) limits its photocatalytic activity to the ultraviolet region of light. Besides that, the electron-hole pair recombination has been found to reduce the efficiency of the photocatalyst. To overcome these problems, tailoring of TiO2 surface with rare earth metals to improve its surface, optical and photocatalytic properties has been investigated by many researchers. The surface modifications with rare earth metals proved to enhance the efficiency of TiO2 photocatalyts by way of reducing the band gap by shifting the working wavelength to the visible region and inhibiting the anatase-to-rutile phase transformations. This review paper summarises the attempts on modification of TiO2 using rare earth metals describing their effect on the photocatalytic activities of the modified TiO2 photocatalyst.

  16. Rare earths, the lanthanides, yttrium and scandium

    USGS Publications Warehouse

    Bedinger, G.; Bleiwas, D.

    2012-01-01

    In 2011, rare earths were recovered from bastnasite concentrates at the Mountain Pass Mine in California. Consumption of refined rare-earth products decreased in 2011 from 2010. U.S. rare-earth imports originated primarily from China, with lesser amounts from Austria, Estonia, France and Japan. The United States imported all of its demand for yttrium metal and yttrium compounds, with most of it originating from China. Scandium was imported in various forms and processed domestically.

  17. Electronic Stopping of Slow Protons in Transition and Rare Earth Metals: Breakdown of the Free Electron Gas Concept

    NASA Astrophysics Data System (ADS)

    Roth, D.; Bruckner, B.; Moro, M. V.; Gruber, S.; Goebl, D.; Juaristi, J. I.; Alducin, M.; Steinberger, R.; Duchoslav, J.; Primetzhofer, D.; Bauer, P.

    2017-03-01

    The electronic stopping cross sections (SCS) of Ta and Gd for slow protons have been investigated experimentally. The data are compared to the results for Pt and Au to learn how electronic stopping in transition and rare earth metals correlates with features of the electronic band structures. The extraordinarily high SCS observed for protons in Ta and Gd cannot be understood in terms of a free electron gas model, but are related to the high densities of both occupied and unoccupied electronic states in these metals.

  18. Uphill transport of rare-earth metals through a highly stable supported liquid membrane based on an ionic liquid.

    PubMed

    Kubota, Fukiko; Shimobori, Yousuke; Koyanagi, Yusuke; Shimojo, Kojiro; Kamiya, Noriho; Goto, Masahiro

    2010-01-01

    We have developed a highly stable supported liquid membrane based on ionic liquids (ILs) for the separation of rare-earth metals, employing N,N-dioctyldiglycol amic acid as a mobile carrier. The quantitative transport of Y and Eu through the membrane was successfully attained, and separation from metal impurities, Zn, was efficiently accomplished. A membrane stable enough for long-term operation was constructible from imidazolium-based ILs having a longer alkyl chain, such as octyl or dodecyl groups in an imidazolium cation.

  19. Electronic Stopping of Slow Protons in Transition and Rare Earth Metals: Breakdown of the Free Electron Gas Concept.

    PubMed

    Roth, D; Bruckner, B; Moro, M V; Gruber, S; Goebl, D; Juaristi, J I; Alducin, M; Steinberger, R; Duchoslav, J; Primetzhofer, D; Bauer, P

    2017-03-10

    The electronic stopping cross sections (SCS) of Ta and Gd for slow protons have been investigated experimentally. The data are compared to the results for Pt and Au to learn how electronic stopping in transition and rare earth metals correlates with features of the electronic band structures. The extraordinarily high SCS observed for protons in Ta and Gd cannot be understood in terms of a free electron gas model, but are related to the high densities of both occupied and unoccupied electronic states in these metals.

  20. Phase Characteristics of a U-20Pu-3Am-2Np-15Zr Metallic Alloy Containing Rare Earths

    SciTech Connect

    Douglas E. Burkes; J. Rory Kennedy; Thomas Hartmann; Cynthia A. Papesch

    2009-12-01

    Metallic fuel alloys consisting of uranium, plutonium, and zirconium with minor additions of americium and neptunium are under evaluation for potential use to transmute long-lived transuranic actinide isotopes in fast reactors. The current irradiation test series design, designated AFC2, includes minor additions of rare earth elements to simulate expected fission product carry-over from the electrochemical molten salt reprocessing technique. The metal fuel alloys have been fabricated by an arc casting technique. The as-cast fuel alloys have been investigated for phase and thermal properties, specifically, enthalpies of transition, transition temperatures, and room temperature phase characteristics. Results and observations related to these characteristics for the “fresh” fuel alloys are provided. The alloy compositions are based on a U-20Pu-3Am-2Np-15Zr alloy, along with additions of 1 and 1.5 wt% RE (at the expense of U) where RE denotes rare earth alloy of cerium, lanthanum, praseodymium and neodymium). Phase behavior and associated transitions have been compared to available U-Pu-Zr ternary diagrams with acceptable agreement. Enthalpies of transition were deconvoluted from heating and cooling thermal traces for relatively reliable values. The rare earth additions to the base alloy have a minimal influence on the room temperature phases present, but the room temperature phases present slightly impacted the enthalpies of transition and transition temperatures.

  1. Imidazolin-2-iminato complexes of rare earth metals with very short metal-nitrogen bonds: experimental and theoretical studies.

    PubMed

    Panda, Tarun K; Trambitas, Alexandra G; Bannenberg, Thomas; Hrib, Cristian G; Randoll, Sören; Jones, Peter G; Tamm, Matthias

    2009-06-15

    The reactions of 1,3-bis(2,6-diisopropylphenyl)imidazolin-2-imine (Im(Dipp)NH, 1-H) with trimethylsilylmethyl lithium (LiCH(2)SiMe(3)) and anhydrous rare earth metal trichlorides MCl(3) afforded the imidazolin-2-iminato complexes [(1)MCl(2)(THF)(3)] (2a, M = Sc; 2b, M = Y; 2c, M = Lu) and [(1)GdCl(2)(THF)(2)] x [LiCl(THF)(2)] (2d). Treatment of complexes 2 with dipotassium cyclooctatetradienide, K(2)(C(8)H(8)) resulted in the formation of two- or three-legged piano-stool complexes of the type [(eta(8)-C(8)H(8))M(1)(THF)(n)] (3a, M = Sc, n = 1; 3b, M = Y, n = 2; 3c, M = Lu, n = 2; 3d, M = Gd, n = 2). X-ray diffraction analyses of all eight complexes 2 and 3 revealed the presence of very short metal-nitrogen bonds, which are among the shortest ever observed for these elements. [(eta(8)-C(8)H(8))Sc(1)(THF)] (3a) reacted with 2,6-dimethylphenyl isothiocyanate (Xy-NCS) to form the [2 + 2]-cycloaddition product 4, which contains a thioureato-N,N' moiety. The related COT-titanium complex [(eta(8)-C(8)H(8))TiCl(1)] (6) could be obtained from [(1)TiCl(3)] (5) by reaction with K(2)(C(8)H(8)) and was structurally characterized. As a theoretical analysis of the nature of the metal-nitrogen bond, density functional theory (DFT) calculations have been carried out for complexes 3a and 6 and also for the model complexes [(eta(8)-C(8)H(8))Sc(NIm(Me))] (7), [(eta(8)-C(8)H(8))Ti(NIm(Me))](+) (8), and [(eta(8)-C(8)H(8))Ti(NXy)] (9), revealing a marked similarity of the bonding in imidazolin-2-iminato and conventional imido metal complexes.

  2. Antimony film sensor for sensitive rare earth metal analysis in environmental samples.

    PubMed

    Makombe, Martin; van der Horst, Charlton; Silwana, Bongiwe; Iwuoha, Emmanuel; Somerset, Vernon

    2016-07-02

    A sensor for the adsorptive stripping voltammetric determination of rare earth elements has been developed. The electrochemical procedure is based on the oxidation of the rare earth elements complexed with alizarin complexone at a glassy carbon electrode that was in situ modified with an antimony film, during an anodic scan from -0.2 V to 1.1 V (vs. Ag/AgCl) and deposition potential of -0.1 V (vs. Ag/AgCl). The factors influencing the adsorptive stripping capability were optimised, including the complexing agent concentration, plating concentration of antimony and deposition time. The detection of rare earth elements (La, Ce and Pr) were realised in 0.08 M sodium acetate (pH = 5.8) solution as supporting electrolyte, with 2 × 10(-6) M alizarin complexone and 1.0 mg L(-1) antimony solution. Under the optimised conditions, a deposition time of 360 s was obtained and a linear response was observed between 1 and 25 µg L(-1). The reproducibility of the voltammetric measurements was found to be within 5.0% RSD for 12 replicate measurements of cerium(III) concentration of 5 µg L(-1) using the same electrode surface. The detection limits obtained using stripping analysis was 0.06, 0.42 and 0.71 μg L(-1) for Ce(III), La(III) and Pr(III), respectively. The developed sensor has been successfully applied for the determination of cerium, lanthanum and praseodymium in municipal tap water samples.

  3. Model calculation of the static magnetic susceptibility in light rare earth metallic systems

    NASA Astrophysics Data System (ADS)

    Hammoud, Y.; Parlebas, J. C.

    1991-05-01

    Using the impurity Anderson model in the large N_f approximation, where N_f is the orbital and spin degeneracy of the f level, we calculate the zero temperature static paramagnetic susceptibility of light rare earth metallic systems. The calculation is performed for large values of the Coulomb U_ff electron-electron interactions with respect of the V hybridization of f1 and f2 configurations with the conduction states (i.e. f0 configuration) : we only keep the leading terms in a development in successive powers of 1/U_ff and V. Our numerical results on the magnetic susceptibility start from a simple analytic expression and are discussed in terms of the f level position, the hybridization V, the shape and filling of the conduction band and also the finite U_ff effects. Finally we present calculated curves for the susceptibility versus V in connection with the αγ transition of cerium and utilizing the same parameters as those used previously to obtain core level LIII absorption spectra : also in the case of the susceptibility, the hybridization appears to be an important parameter to describe the phase change from γ to α cerium. Nous utilisons le modèle d'Anderson à une impureté dans l'approximation des grands N_f où N_f est la dégénérescence d'orbitale et de spin du niveau f et nous calculons alors la susceptibilité paramagnétique statique (à température nulle) dans les systèmes métalliques de terres rares légères. Nous effectuons notre calcul pour des valeurs de l'interaction de Coulomb U_ff grandes par rapport à l'hybridation V des configurations f1 et f2 avec les états de conduction (c.-à-d. la configuration f0): nous ne retenons que les termes les plus imporatnts dans un développement en puissances successives de 1/U_ff et V. Ensuite nous discutons nos résultats numériques à partir d'une forme analytique simple obtenue pour la susceptibilité magnétique en fonction de la position du niveau f, de l'hybridation V, de la forme et du

  4. Ames Lab 101: Rare Earths

    ScienceCinema

    Gschneidner, Karl

    2016-07-12

    "Mr. Rare Earth," Ames Laboratory scientist Karl Gschneidner Jr., explains the importance of rare-earth materials in many of the technologies we use today -- ranging from computers to hybrid cars to wind turbines. Gschneidner is a world renowned rare-earths expert at the U.S. Department of Energy's Ames Laboratory.

  5. Ames Lab 101: Rare Earths

    SciTech Connect

    Gschneidner, Karl

    2010-01-01

    "Mr. Rare Earth," Ames Laboratory scientist Karl Gschneidner Jr., explains the importance of rare-earth materials in many of the technologies we use today -- ranging from computers to hybrid cars to wind turbines. Gschneidner is a world renowned rare-earths expert at the U.S. Department of Energy's Ames Laboratory.

  6. Living catalyzed-chain-growth polymerization and block copolymerization of isoprene by rare-earth metal allyl precursors bearing a constrained-geometry-conformation ligand.

    PubMed

    Jian, Zhongbao; Cui, Dongmei; Hou, Zhaomin; Li, Xiaofang

    2010-05-07

    Aminophenyl functionalized cyclopentadienyl ligated rare-earth metal allyl mediated cationic systems display high cis-1,4 selectivity for the polymerization of isoprene, and living reversible and rapid chain transfer to aluminium additives.

  7. Structure of a piperidine-modified calix[4]arene derivative and spectral resolution of its interaction with rare earth metals with chemometric methods.

    PubMed

    Wang, Li; Wang, Xiaoya; Wang, Yanmei

    2013-03-15

    A piperidine-modified calix[4]arene derivative was synthesized and its structure was confirmed with X-ray diffraction data. UV-visible spectroscopy was used to study its molecular recognition of rare earth ions. The results revealed the calix[4]arene derivative could separate tight metal picrate ion pairs by complexation with the rare earth metal ions in tetrahydrofuran. Resolution of the UV-visible spectra with chemometric methods revealed that the derivative and the rare earth ions Eu(3+), Dy(3+), and Tb(3+) formed ML(2) complexes with stability constants of 10(8.26), 10(8.29), and 10(7.41) respectively.

  8. 3,3'-Bis(trisarylsilyl)-substituted binaphtholate rare earth metal catalysts for asymmetric hydroamination.

    PubMed

    Gribkov, Denis V; Hultzsch, Kai C; Hampel, Frank

    2006-03-22

    Chiral 3,3'-bis(trisarylsilyl)-substituted binaphtholate rare earth metal complexes (R)-[Ln{Binol-SiAr3}(o-C6H4CH2NMe2)(Me2NCH2Ph)] (Ln = Sc, Lu, Y; Binol-SiAr3 = 3,3'-bis(trisarylsilyl)-2,2'-dihydroxy-1,1'-binaphthyl; Ar = Ph (2-Ln), 3,5-xylyl (3-Ln)) and (R)-[La{Binol-Si(3,5-xylyl)3}{E(SiMe3)2}(THF)2] (E = CH (4a), N (4b)) are accessible via facile arene, alkane, and amine elimination. They are efficient catalysts for the asymmetric hydroamination/cyclization of aminoalkenes, giving TOF of up to 840 h(-1) at 25 degrees C for 2,2-diphenyl-pent-4-enylamine (5c) using (R)-2-Y. Enantioselectivities of up to 95% ee were achieved in the cyclization of 5c with (R)-2-Sc. The reactions show apparently zero-order rate dependence on substrate concentration and first-order rate dependence on catalyst concentration, but rates depend on total amine concentrations. Activation parameters for the cyclization of pent-4-enylamine using (R)-2-Y (deltaH(S)(double dagger) = 57.4(0.8) kJ mol(-1) and deltaS(S)(double dagger) = -102(3) J K(-1) mol(-1); deltaH(R)(double dagger) = 61.5(0.7) kJ mol(-1) and deltaS(R)(double dagger) = -103(3) J K(-1) mol(-1)) indicate a highly organized transition state. The binaphtholate catalysts were also applied to the kinetic resolution of chiral alpha-substituted aminoalkenes with resolution factors f of up to 19. The 2,5-disubstituted aminopentenes were formed in 7:1 to > or = 50:1 trans diastereoselectivity, depending on the size of the alpha-substituent of the aminoalkene. Rate studies with (S)-1-phenyl-pent-4-enylamine ((S)-15e) gave the activation parameters for the matching (deltaH(double dagger) = 52.2(2.8) kJ mol(-1), deltaS(double dagger) = -127(8) J K(-1) mol(-1) using (S)-2-Y) and mismatching (deltaH(double dagger) = 57.7(1.3) kJ mol(-1), deltaS(double dagger) = -126(4) J K(-1) mol(-1) using (R)-2-Y) substrate/catalyst combination. The absolute configuration of the Mosher amide of (2S)-2-methyl-4,4-diphenyl-pyrrolidine and (2R)-methyl-(5S

  9. Magnetocaloric effect in heavy rare-earth elements doped Fe-based bulk metallic glasses with tunable Curie temperature

    NASA Astrophysics Data System (ADS)

    Li, Jiawei; Huo, Juntao; Law, Jiayan; Chang, Chuntao; Du, Juan; Man, Qikui; Wang, Xinmin; Li, Run-Wei

    2014-08-01

    The effects of heavy rare earth (RE) additions on the Curie temperature (TC) and magnetocaloric effect of the Fe-RE-B-Nb (RE = Gd, Dy and Ho) bulk metallic glasses were studied. The type of dopping RE element and its concentration can easily tune TC in a large temperature range of 120 K without significantly decreasing the magnetic entropy change (ΔSM) and refrigerant capacity (RC) of the alloys. The observed values of ΔSM and RC of these alloys compare favorably with those of recently reported Fe-based metallic glasses with enhanced RC compared to Gd5Ge1.9Si2Fe0.1. The tunable TC and large glass-forming ability of these RE doped Fe-based bulk metallic glasses can be used in a wide temperature range with the final required shapes.

  10. Synchrotron Diffraction Studies of Spontaneous Magnetostriction in Rare Earth Transition Metal Compounds

    SciTech Connect

    Yang, Ning

    2004-12-19

    Thermal expansion anomalies of R2Fe14B and R2Fe17Cx (x = 0,2) (R = Y, Nd, Gd, Tb, Er) stoichiometric compounds are studied with high-energy synchrotron X-ray powder diffraction using Debye-Schemer geometry in temperature range 10K to 1000K. Large spontaneous magnetostriction up to their Curie temperatures (Tc) is observed. The a-axes show relatively larger invar effects than c-axes in the R2Fe14B compounds whereas the R2Fe17Cx show the contrary anisotropies. The iron sub-lattice is shown to dominate the spontaneous magnetostriction of the compounds. The contribution of the rare earth sublattice is roughly proportional to the spin magnetic moment of the rare earth in the R2Fe14B compounds but in R2Fe17Cx, the rare earth sub-lattice contribution appears more likely to be dominated by the local bonding. The calculation of spontaneous magnetostrain of bonds shows that the bonds associated with Fe(j2) sites in R2Fe14B and the dumbbell sites in R2Fe17Cx have larger values, which is strongly related to their largest magnetic moment and Wigner-Seitz atomic cell volume. The roles of the carbon atoms in increasing the Curie temperatures of the R2Fe17 compounds are attributed to the increased separation of Fe hexagons. The R2Fe17 and R2Fe14B phases with magnetic rare earth ions also show anisotropies of thermal expansion above c. For R2Fe17 and R2Fe14B the a a/a c > 1 whereas the anisotropy is reversed with the interstitial carbon in R2Fe17. The average bond magnetostrain is shown to be a possible predictor of the magnetic moment of Fe sites in the compounds. Both of the theoretical and

  11. Supramolecular structures and stereochemical versatility of azoquinoline containing novel rare earth metal complexes.

    PubMed

    El-Sonbati, A Z; Issa, R M; El-Gawad, A M Abd

    2007-09-01

    Rare earth complexes of 5-(phenylazo)-8-hydroxyquinoline (HL) of composition [M(L)(2)X.H(2)O] [where M=La, Ce, Pr, Nd and X=NO(3)(-) or NCS(-)] have been prepared and characterized on the basis of their chemical analyses, (1)H NMR, magnetic measurements, conductance, and visible and IR spectral data. Composition, conductance and IR spectral data of the complexes show that the HL acts as a bidentate monobasic ligand. The visible spectra of Pr(3+) and Nd(3+) show characteristic f-f transitions, and the nephelauxetic effect (1-beta) of these transitions has been evaluated. These data indicate the weak involvement of the 4f orbitals in complex formation.

  12. Catalytic asymmetric ring-opening of meso-aziridines with malonates under heterodinuclear rare earth metal Schiff base catalysis.

    PubMed

    Xu, Yingjie; Lin, Luqing; Kanai, Motomu; Matsunaga, Shigeki; Shibasaki, Masakatsu

    2011-04-20

    Catalytic asymmetric ring-opening of meso-aziridines with malonates is described. The combined use of two rare earth metal sources with different properties promoted the desired ring-opening reaction. A 1:1:1 mixture of a heterobimetallic La(O-iPr)(3)/Yb(OTf)(3)/Schiff base 1a (0.25-10 mol %) efficiently promoted the reaction of five-, six-, and seven-membered ring cyclic meso-aziridines as well as acyclic meso-aziridines with dimethyl, diethyl, and dibenzyl malonates, giving chiral cyclic and acyclic γ-amino esters in 99-63% yield and >99.5-97% ee.

  13. Synthesis and reactivity of rare earth metal alkyl complexes stabilized by anilido phosphinimine and amino phosphine ligands.

    PubMed

    Liu, Bo; Cui, Dongmei; Ma, Jia; Chen, Xuesi; Jing, Xiabin

    2007-01-01

    Anilido phosphinimino ancillary ligand H(2)L(1) reacted with one equivalent of rare earth metal trialkyl [Ln{CH(2)Si(CH(3))(3)}(3)(thf)(2)] (Ln=Y, Lu) to afford rare earth metal monoalkyl complexes [L(1)LnCH(2)Si(CH(3))(3)(THF)] (1 a: Ln=Y; 1 b: Ln=Lu). In this process, deprotonation of H(2)L(1) by one metal alkyl species was followed by intramolecular C--H activation of the phenyl group of the phosphine moiety to generate dianionic species L(1) with release of two equivalnts of tetramethylsilane. Ligand L(1) coordinates to Ln(3+) ions in a rare C,N,N tridentate mode. Complex l a reacted readily with two equivalents of 2,6-diisopropylaniline to give the corresponding bis-amido complex [(HL(1))LnY(NHC(6)H(3)iPr(2)-2,6)(2)] (2) selectively, that is, the C--H activation of the phenyl group is reversible. When 1 a was exposed to moisture, the hydrolyzed dimeric complex [{(HL(1))Y(OH)}(2)](OH)(2) (3) was isolated. Treatment of [Ln{CH(2)Si(CH(3))(3)}(3)(thf)(2)] with amino phosphine ligands HL(2-R) gave stable rare earth metal bis-alkyl complexes [(L(2-R))Ln{CH(2)Si(CH(3))(3)}(2)(thf)] (4 a: Ln=Y, R=Me; 4 b: Ln=Lu, R=Me; 4 c: Ln=Y, R=iPr; 4 d: Ln=Y, R=iPr) in high yields. No proton abstraction from the ligand was observed. Amination of 4 a and 4 c with 2,6-diisopropylaniline afforded the bis-amido counterparts [(L(2-R))Y(NHC(6)H(3)iPr(2)-2,6)(2)(thf)] (5 a: R=Me; 5 b: R=iPr). Complexes 1 a,b and 4 a-d initiated the ring-opening polymerization of d,l-lactide with high activity to give atactic polylactides.

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

    NASA Astrophysics Data System (ADS)

    Ling-Wei, Li

    2016-03-01

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

  15. Regio- and Stereochemical Control in Ocimene Polymerization by Half-Sandwich Rare-Earth Metal Dialkyl Complexes.

    PubMed

    Peng, Deqian; Du, Gaixia; Zhang, Pengfei; Yao, Bo; Li, Xiaofang; Zhang, Shaowen

    2016-06-01

    The polymerization of ocimene has been first achieved by half-sandwich rare-earth metal dialkyl complexes in combination with activator and Al(i) Bu3 . The regio- and stereoselectivity in the ocimene polymerization can be controlled by tuning the cyclopentadienyl ligand and the central metal of the complex. The chiral cyclopentadienyl-ligated Sc complex 1 prepares syndiotactic cis-1,4-polyocimene (cis-1,4-selectivity up to 100%, rrrr = 100%), while the corresponding Lu, Y, and Dy complexes 2-4 and the achiral pentamethylcyclopentadienyl Sc, Lu, and Y complexes 5-7 afford isotactic trans-1,2-polyocimenes (trans-1,2-selectivity up to 100%, mm = 100%).

  16. Separation of rare earths from transition metals by liquid-liquid extraction from a molten salt hydrate to an ionic liquid phase.

    PubMed

    Rout, Alok; Binnemans, Koen

    2014-02-28

    The solvent extraction of trivalent rare-earth ions and their separation from divalent transition metal ions using molten salt hydrates as the feed phase and an undiluted fluorine-free ionic liquid as the extracting phase were investigated in detail. The extractant was tricaprylmethylammonium nitrate, [A336][NO3], and the hydrated melt was calcium nitrate tetrahydrate, Ca(NO3)2·4H2O. The extraction behavior of rare-earth ions was studied for solutions of individual elements, as well as for mixtures of rare earths in the hydrated melt. The influence of different extraction parameters was investigated: the initial metal loading in the feed phase, percentage of water in the feed solution, equilibration time, and the type of hydrated melt. The extraction of rare earths from Ca(NO3)2·4H2O was compared with extraction from CaCl2·4H2O by [A336][Cl] (Aliquat 336). The nitrate system was found to be the better one. The extraction and separation of rare earths from the transition metals nickel, cobalt and zinc were also investigated. Remarkably high separation factors of rare-earth ions over transition metal ions were observed for extraction from Ca(NO3)2·4H2O by the [A336][NO3] extracting phase. Furthermore, rare-earth ions could be separated efficiently from transition metal ions, even in melts with very high concentrations of transition metal ions. Rare-earth oxides could be directly dissolved in the Ca(NO3)2·4H2O phase in the presence of small amounts of Al(NO3)3·9H2O or concentrated nitric acid. The efficiency of extraction after dissolving the rare-earth oxides in the hydrated nitrate melt was identical to extraction from solutions with rare-earth nitrates dissolved in the molten phase. The stripping of the rare-earth ions from the loaded ionic liquid phase and the reuse of the recycled ionic liquid were also investigated in detail.

  17. Synthesis and structure of some nano-sized rare-earth metal ions doped potassium hexacyanoferrates

    NASA Astrophysics Data System (ADS)

    Narayan, Himanshu; Alemu, Hailemichael; Nketsa, Pusetso F.; Manatha, Toka J.; Madhavi Thakurdesai, And

    2015-05-01

    Rare-earth ions doped potassium hexacyanoferrates (KR-HCF); with the general formula KRFe(CN)6 · 3H2 O [with, R≡Y, Gd and Yb] nanoparticles were synthesized through precipitation. Characterization was done through particle-size analyzer, scanning electron microscopy (SEM), Fourier Transform infra-red (FTIR) and Raman spectroscopy, and powder X-ray diffraction (XRD). The XRD data was analyzed on FullProf Software Suite program and the unit-cell structure and lattice parameters of KR-HCF samples were determined from scratch and refined further. All the three KR-HCF nanoparticles seem to crystallize in the orthorhombic primitive PMMM space-group. Reasonably good agreement was found with the previously reported lattice constants of KGd-HCF and KYb-HCF orthorhombic single-crystals, except that they assume different space-groups. The observed dissimilarity of space-groups may be attributed to the different time scales involved in the synthesis process. Moreover, the crystal structure of KYFe(CN)6 · 3H2 O nanoparticles is being reported for the very first time.

  18. Rare earth metals are essential for methanotrophic life in volcanic mudpots.

    PubMed

    Pol, Arjan; Barends, Thomas R M; Dietl, Andreas; Khadem, Ahmad F; Eygensteyn, Jelle; Jetten, Mike S M; Op den Camp, Huub J M

    2014-01-01

    Growth of Methylacidiphilum fumariolicum SolV, an extremely acidophilic methanotrophic microbe isolated from an Italian volcanic mudpot, is shown to be strictly dependent on the presence of lanthanides, a group of rare earth elements (REEs) such as lanthanum (Ln), cerium (Ce), praseodymium (Pr) and neodymium (Nd). After fractionation of the bacterial cells and crystallization of the methanol dehydrogenase (MDH), it was shown that lanthanides were essential as cofactor in a homodimeric MDH comparable with one of the MDHs of Methylobacterium extorquens AM1. We hypothesize that the lanthanides provide superior catalytic properties to pyrroloquinoline quinone (PQQ)-dependent MDH, which is a key enzyme for both methanotrophs and methylotrophs. Thus far, all isolated MxaF-type MDHs contain calcium as a catalytic cofactor. The gene encoding the MDH of strain SolV was identified to be a xoxF-ortholog, phylogenetically closely related to mxaF. Analysis of the protein structure and alignment of amino acids showed potential REE-binding motifs in XoxF enzymes of many methylotrophs, suggesting that these may also be lanthanide-dependent MDHs. Our findings will have major environmental implications as metagenome studies showed (lanthanide-containing) XoxF-type MDH is much more prominent in nature than MxaF-type enzymes.

  19. A geological reconnaissance of electrical and electronic waste as a source for rare earth metals.

    PubMed

    Mueller, Sandra R; Wäger, Patrick A; Widmer, Rolf; Williams, Ian D

    2015-11-01

    The mining of material resources requires knowledge about geogenic and anthropogenic deposits, in particular on the location of the deposits with the comparatively highest concentration of raw materials. In this study, we develop a framework that allows the establishment of analogies between geological and anthropogenic processes. These analogies were applied to three selected products containing rare earth elements (REE) in order to identify the most concentrated deposits in the anthropogenic cycle. The three identified anthropogenic deposits were characterised according to criteria such as "host rock", "REE mineralisation" and "age of mineralisation", i.e. regarding their "geological" setting. The results of this characterisation demonstrated that anthropogenic deposits have both a higher concentration of REE and a longer mine life than the evaluated geogenic deposit (Mount Weld, Australia). The results were further evaluated by comparison with the geological knowledge category of the United Nations Framework Classification for Fossil Energy and Mineral Reserves and Resources 2009 (UNFC-2009) to determine the confidence level in the deposit quantities. The application of our approach to the three selected cases shows a potential for recovery of REE in anthropogenic deposits; however, further exploration of both potential and limitations is required.

  20. Metal sulfide and rare-earth phosphate nanostructures and methods of making same

    SciTech Connect

    Wong, Stanislaus; Zhang, Fen

    2014-05-13

    The present invention provides a method of producing a crystalline metal sulfide nanostructure. The metal is a transitional metal or a Group IV metal. In the method, a porous membrane is placed between a metal precursor solution and a sulfur precursor solution. The metal cations of the metal precursor solution and sulfur ions of the sulfur precursor solution react, thereby producing a crystalline metal sulfide nanostructure.

  1. China's rare-earth industry

    USGS Publications Warehouse

    Tse, Pui-Kwan

    2011-01-01

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

  2. Toxicity evaluation of high-fluorescent rare-earth metal nanoparticles for bioimaging applications.

    PubMed

    Hernandez-Adame, Luis; Cortez-Espinosa, Nancy; Portales-Pérez, Diana P; Castillo, Claudia; Zhao, Wayne; Juarez, Zaida N; Hernandez, Luis R; Bach, Horacio; Palestino, Gabriela

    2017-04-01

    Research on nanometer-sized luminescent semiconductors and their biological applications in detectors and contrasting agents is an emergent field in nanotechnology. When new nanosize technologies are developed for human health applications, their interaction with biological systems should be studied in depth. Rare-earth elements are used in medical and industrial applications, but their toxic effects are not known. In this work, the biological interaction between terbium-doped gadolinium oxysulfide nanoparticles (GOSNPs) with human peripheral blood mononuclear cells (PBMC), human-derived macrophages (THP-1), and human cervical carcinoma cell (HeLa) were evaluated. The GOSNPs were synthetized using a hydrothermal method to obtain monodisperse nanoparticles with an average size of 91 ± 9 nm. Characterization techniques showed the hexagonal phase of the Gd2 O2 S:Tb(3+) free of impurities, and a strong green emission at λemi  = 544 nm produced by Tb(3+) was observed. Toxic effects of GOSNPs were evaluated using cell viability, apoptosis, cell-cycle progression, and immunological response techniques. In addition, an Artemia model was used to assess the toxicity in vivo. Results indicated cell apoptosis in both types of cells with less sensitivity for PBMC cells compared to HeLa cells. In addition, no toxic effects were observed in the in vivo model of Artemia. Moreover, GOSNPs significantly reduced the activation and cell-cycle progression of PBMC and HeLa cells, respectively. Interestingly, an increase in proinflammatory cytokines was not observed. Our data suggest that fluorescence applications of GOSNPs for biolabeling are not toxic in primary immune cells and they may have an immunomodulatory effect. © 2015 Wiley Periodicals, Inc. J Biomed Mater Res Part B: Appl Biomater, 105B: 605-615, 2017.

  3. Phase stable rare earth garnets

    DOEpatents

    Kuntz, Joshua D.; Cherepy, Nerine J.; Roberts, Jeffery J.; Payne, Stephen A.

    2013-06-11

    A transparent ceramic according to one embodiment includes a rare earth garnet comprising A.sub.hB.sub.iC.sub.jO.sub.12, where h is 3.+-.10%, i is 2.+-.10%, and j is 3.+-.10%. A includes a rare earth element or a mixture of rare earth elements, B includes at least one of aluminum, gallium and scandium, and C includes at least one of aluminum, gallium and scandium, where A is at a dodecahedral site of the garnet, B is at an octahedral site of the garnet, and C is at a tetrahedral site of the garnet. In one embodiment, the rare earth garment has scintillation properties. A radiation detector in one embodiment includes a transparent ceramic as described above and a photo detector optically coupled to the rare earth garnet.

  4. The Not-So-Rare Earths.

    ERIC Educational Resources Information Center

    Muecke, Gunter K.; Moller, Peter

    1988-01-01

    Describes the characteristics of rare earth elements. Details the physical chemistry of rare earths. Reviews the history of rare earth chemistry and mineralogy. Discusses the mineralogy and crystallography of the formation of rare earth laden minerals found in the earth's crust. Characterizes the geologic history of rare earth elements. (CW)

  5. Precious metals and rare earth elements in municipal solid waste--sources and fate in a Swiss incineration plant.

    PubMed

    Morf, Leo S; Gloor, Rolf; Haag, Olaf; Haupt, Melanie; Skutan, Stefan; Di Lorenzo, Fabian; Böni, Daniel

    2013-03-01

    In Switzerland many kinds of waste, e.g. paper, metals, electrical and electronic equipment are separately collected and recycled to a large extent. The residual amount of municipal solid waste (MSW) has to be thermally treated before final disposal. Efforts to recover valuable metals from incineration residues have recently increased. However, the resource potential of critical elements in the waste input (sources) and their partitioning into recyclable fractions and residues (fate) is unknown. Therefore, a substance flow analysis (SFA) for 31 elements including precious metals (Au, Ag), platinum metal group elements (Pt, Rh) and rare earth elements (La, Ce, etc.) has been conducted in a solid waste incinerator (SWI) with a state-of-the-art bottom ash treatment according to the Thermo-Re® concept. The SFA allowed the determination of the element partitioning in the SWI, as well as the elemental composition of the MSW by indirect analysis. The results show that the waste-input contains substantial quantities of precious metals, such as 0.4 ± 0.2mg/kg Au and 5.3 ± 0.7 mg/kg Ag. Many of the valuable substances, such as Au and Ag are enriched in specific outputs (e.g. non-ferrous metal fractions) and are therefore recoverable. As the precious metal content in MSW is expected to rise due to its increasing application in complex consumer products, the results of this study are essential for the improvement of resource recovery in the Thermo-Re® process.

  6. Prediction of the lowest-energy structures of rare-earth metallic clusters with a Moebius inversion pair potential

    SciTech Connect

    Luo, You-Hua; Wang, Yuzhu

    2001-07-01

    The Moebius inversion pair potential has been employed, in combination with genetic algorithms, to predict the lowest-energy structures of the rare-earth metallic clusters La{sub N}, Ce{sub N}, and Pr{sub N} (N=3--20). Results are given for the symmetries, binding energies, nearest-neighbor distances of these clusters, and lowest-energy configurations of Ce{sub N} clusters. Also, the calculated second finite difference of the total energy shows that for three species elements, the 13-atom clusters with I{sub d} symmetry are particularly stable. Some minor peaks are also found at size N=4, 6, 11, and 15, which indicates that the corresponding clusters are relatively stable in structure. Present work points out a route to studying clusters.

  7. Production of copper-based rare earth composite metal materials by coprecipitation and applications for gaseous ammonia removal.

    PubMed

    Hung, Chang-Mao

    2011-04-01

    This study addresses the oxidation of ammonia (NH3) at temperatures between 423 and 673 K by selective catalytic oxidation (SCO) over a copper-based, rare earth composite metal material that was prepared by coprecipitating copper nitrate, lanthanum nitrate, and cerium nitrate at various molar ratios. The catalysts were characterized using Brunner, Emmett, and Teller spectroscopy, Fourier-transform infrared spectroscopy, Xray diffraction, ultraviolet-visible spectroscopy, cyclic voltammetric spectroscopy, and scanning electron microscopy. At a temperature of 673 K and an oxygen content of 4%, approximately 99.5% of the NH3 was reduced by catalytic oxidation over the 6:1:3 copper-lanthanum-cerium (molar ratio) catalyst. Nitrogen (N2) was the main product of this NH3-SCO process. Results from the activity and selectivity tests revealed that the optimal catalyst for catalytic performance had the highest possible cerium content and specific surface area (43 m2/g).

  8. Rare earth metals used in biodegradable magnesium-based stents do not interfere with proliferation of smooth muscle cells but do induce the upregulation of inflammatory genes.

    PubMed

    Drynda, Andreas; Deinet, Nicole; Braun, Nicole; Peuster, Matthias

    2009-11-01

    Rare earth metals are added to corrodible magnesium-based alloys in low amounts (up to 10%) to improve their mechanical properties and to decrease the degradation rate. Cerium (Ce), neodymium (Nd), yttrium (Y), and ytterbium (Yb) are already used for degradable cardiovascular stents. Little is known about the biocompatibility of rare earth metals released during the degradation process of the implant. Therefore the biocompatibility of rare earth metals was assessed with regard to metabolic activity of human vascular smooth muscle cells (SMCs). After coincubation with the trivalent chlorides (0.5-100 microg/mL) of rare earth metals for 24, 72, 144, and 240 h metabolic activity was determined at each time point using the colometric WST-1 test. The tested rare earth metals did not lead to significant changes in metabolic activity over a wide concentration range. However, at high concentrations a decrease was observed. Apoptotic or necrotic effects were not observed. Furthermore, we analyzed the effects of Ce, Nd, Y, and Yb on the expression of genes involved in inflammatory processes. The expression of IL-6, IL-8, and ICAM-1 in SMCs after exposure to Ce, Nd, Y, and Yb (5 and 50 microg/mL) was measured using quantitative real-time PCR. Significant up-regulation of IL-6, IL-8, and ICAM-1 genes were only found after 24 h, mainly for a concentration of 50 microg/mL. Our cell culture data indicate that rare earth metals influence cellular processes of vascular cells. Whether adverse effects occur also in in vivo is the topic of further investigations.

  9. Magnetocaloric effect in heavy rare-earth elements doped Fe-based bulk metallic glasses with tunable Curie temperature

    SciTech Connect

    Li, Jiawei; Huo, Juntao; Chang, Chuntao E-mail: dujun@nimte.ac.cn; Du, Juan E-mail: dujun@nimte.ac.cn; Man, Qikui; Wang, Xinmin; Li, Run-Wei; Law, Jiayan

    2014-08-14

    The effects of heavy rare earth (RE) additions on the Curie temperature (T{sub C}) and magnetocaloric effect of the Fe-RE-B-Nb (RE = Gd, Dy and Ho) bulk metallic glasses were studied. The type of dopping RE element and its concentration can easily tune T{sub C} in a large temperature range of 120 K without significantly decreasing the magnetic entropy change (ΔS{sub M}) and refrigerant capacity (RC) of the alloys. The observed values of ΔS{sub M} and RC of these alloys compare favorably with those of recently reported Fe-based metallic glasses with enhanced RC compared to Gd{sub 5}Ge{sub 1.9}Si{sub 2}Fe{sub 0.1}. The tunable T{sub C} and large glass-forming ability of these RE doped Fe-based bulk metallic glasses can be used in a wide temperature range with the final required shapes.

  10. Behavior and distribution of heavy metals including rare Earth elements, thorium, and uranium in sludge from industry water treatment plant and recovery method of metals by biosurfactants application.

    PubMed

    Gao, Lidi; Kano, Naoki; Sato, Yuichi; Li, Chong; Zhang, Shuang; Imaizumi, Hiroshi

    2012-01-01

    In order to investigate the behavior, distribution, and characteristics of heavy metals including rare earth elements (REEs), thorium (Th), and uranium (U) in sludge, the total and fractional concentrations of these elements in sludge collected from an industry water treatment plant were determined and compared with those in natural soil. In addition, the removal/recovery process of heavy metals (Pb, Cr, and Ni) from the polluted sludge was studied with biosurfactant (saponin and sophorolipid) elution by batch and column experiments to evaluate the efficiency of biosurfactant for the removal of heavy metals. Consequently, the following matters have been largely clarified. (1) Heavy metallic elements in sludge have generally larger concentrations and exist as more unstable fraction than those in natural soil. (2) Nonionic saponin including carboxyl group is more efficient than sophorolipid for the removal of heavy metals in polluted sludge. Saponin has selectivity for the mobilization of heavy metals and mainly reacts with heavy metals in F3 (the fraction bound to carbonates) and F5 (the fraction bound to Fe-Mn oxides). (3) The recovery efficiency of heavy metals (Pb, Ni, and Cr) reached about 90-100% using a precipitation method with alkaline solution.

  11. Rare-earth neutral metal injection into an electron beam ion trap plasma

    SciTech Connect

    Magee, E. W. Beiersdorfer, P.; Brown, G. V.; Hell, N.

    2014-11-15

    We have designed and implemented a neutral metal vapor injector on the SuperEBIT high-energy electron beam ion trap at the Lawrence Livermore National Laboratory. A horizontally directed vapor of a europium metal is created using a thermal evaporation technique. The metal vapor is then spatially collimated prior to injection into the trap. The source's form and quantity constraints are significantly reduced making plasmas out of metal with vapor pressures ≤10{sup −7} Torr at ≥1000 °C more obtainable. A long pulsed or constant feed metal vapor injection method adds new flexibility by varying the timing of injection and rate of material being introduced into the trap.

  12. Rare Earth Optical Temperature Sensor

    NASA Technical Reports Server (NTRS)

    Chubb, Donald L. (Inventor); Jenkins, Phillip (Inventor)

    2004-01-01

    A rare earth optical temperature sensor is disclosed for measuring high temperatures. Optical temperature sensors exist that channel emissions from a sensor to a detector using a light pipe. The invention uses a rare earth emitter to transform the sensed thermal energy into a narrow band width optical signal that travels to a detector using a light pipe. An optical bandpass filter at the detector removes any noise signal outside of the band width of the signal from the emitter.

  13. RARE-EARTH METAL FISSION PRODUCTS FROM LIQUID U-Bi

    DOEpatents

    Wiswall, R.H.

    1960-05-10

    Fission product metals can be removed from solution in liquid bismuth without removal of an appreciable quantity of uranium by contacting the liquid metal solution with fused halides, as for example, the halides of sodium, potassium, and lithium and by adding to the contacted phases a quantity of a halide which is unstable relative to the halides of the fission products, a specific unstable halide being MgCl/sub 3/.

  14. Rare-earth metal complexes having an unusual indolyl-1,2-dianion through C-H activation with a novel η1:(μ2-η1:η1) bonding with metals.

    PubMed

    Zhu, Xiancui; Zhou, Shuangliu; Wang, Shaowu; Wei, Yun; Zhang, Lijun; Wang, Fenhua; Wang, Shaoyin; Feng, Zhijun

    2012-12-21

    Studies on the reactions of 3-(tert-butyliminomethine)indole or 3-(tert-butylaminomethylene)indole with rare-earth metal amides [(Me(3)Si)(2)N](3)RE(III)(μ-Cl)Li(THF)(3) (RE = Y, Yb) led to the discovery of different reactivity patterns with isolation of novel rare-earth metal complexes having a unique indolyl-1,2-dianion in a novel η(1):(μ(2)-η(1):η(1)) bonding mode through C-H activation.

  15. Cationic rare-earth metal trimethylsilylmethyl complexes supported by THF and 12-crown-4 ligands: synthesis and structural characterization.

    PubMed

    Elvidge, Benjamin R; Arndt, Stefan; Zeimentz, Peter M; Spaniol, Thomas P; Okuda, Jun

    2005-09-19

    To expand the limited range of rare-earth metal cationic alkyl complexes known, a series of mono- and dicationic trimethylsilylmethyl complexes supported by THF and 12-crown-4 ligands with [BPh4]-, [BPh3(CH2SiMe3)]-, [B(C6F5)4]-, [B(C6F5)3(CH2SiMe3)]-, and [Al(CH2SiMe3)4]- anions were prepared from corresponding neutral precursors [Ln(CH2SiMe3)3Ln] (Ln = Sc, Y, Lu; L = THF, n = 2 or 3; L = 12-crown-4, n = 1) as solvent-separated ion pairs. The syntheses of the monocationic derivatives [Ln(CH2SiMe3)2(12-crown-4)n(THF)m]+[A]- are all high yielding and proceed rapidly in THF solution at room temperature. A "one pot" procedure using the neutral species directly for the syntheses of a number of lutetium and yttrium dicationic derivatives [Ln(CH2SiMe3)(12-crown-4)n(THF)m]2+[A]-2 with a variety of different anions, a class of compounds previously limited to just a few examples, is presented. When BPh3 is used to generate the ion triple, the presence of 12-crown-4 is required for complete conversion. Addition of a second equiv of 12-crown-4 and a third equiv of [NMe2PhH]+[B(C6F5)4]- abstracts a third alkyl group from [Ln(CH2SiMe3)(12-crown-4)2(THF)x]2+[B(C6F5)4]-2 (Ln = Y, Lu). X-ray crystallography and variable-temperature (VT) NMR spectroscopy reveal a structural diversity within the known series of neutral 12-crown-4 supported tris(trimethylsilylmethyl) complexes [Ln(CH2SiMe3)3(12-crown-4)] (Ln = Sc, Y, Sm, Gd-Lu) in the solid and solution states. The X-ray structure of [Sc(CH2SiMe3)3(12-crown-4)] exhibits incomplete 12-crown-4 coordination. VT NMR spectroscopy indicates fluxional 12-crown-4 coordination on the NMR time scale. X-ray crystallography of only the second structurally characterized dicationic rare-earth metal alkyl complex [Y(CH2SiMe3)(12-crown-4)(THF)3]2+[BPh4]-2 shows exocyclic 12-crown-4 coordination at the 8-coordinate metal center with well separated counteranions. 11B and 19F NMR spectroscopy of all mono- and dicationic rare-earth metal complexes

  16. Catalytic addition of amine N-H bonds to carbodiimides by half-sandwich rare-earth metal complexes: efficient synthesis of substituted guanidines through amine protonolysis of rare-earth metal guanidinates.

    PubMed

    Zhang, Wen-Xiong; Nishiura, Masayoshi; Hou, Zhaomin

    2007-01-01

    Reaction of [Ln(CH(2)SiMe(3))(3)(thf)(2)] (Ln=Y, Yb, and Lu) with one equivalent of Me(2)Si(C(5)Me(4)H)NHR' (R'=Ph, 2,4,6-Me(3)C(6)H(2), tBu) affords straightforwardly the corresponding half-sandwich rare-earth metal alkyl complexes [{Me(2)Si(C(5)Me(4))(NR')}Ln(CH(2)SiMe(3))(thf)(n)] (1: Ln = Y, R' = Ph, n=2; 2: Ln = Y, R' = C(6)H(2)Me(3)-2,4,6, n=1; 3: Ln = Y, R' = tBu, n=1; 4: Ln = Yb, R' = Ph, n=2; 5: Ln = Lu, R' = Ph, n=2) in high yields. These complexes, especially the yttrium complexes 1-3, serve as excellent catalyst precursors for the catalytic addition of various primary and secondary amines to carbodiimides, efficiently yielding a series of guanidine derivatives with a wide range of substituents on the nitrogen atoms. Functional groups such as C[triple chemical bond]N, C[triple chemical bond]CH, and aromatic C--X (X: F, Cl, Br, I) bonds can survive the catalytic reaction conditions. A primary amino group can be distinguished from a secondary one by the catalyst system, and therefore, the reaction of 1,2,3,4-tetrahydro-5-aminoisoquinoline with iPrN==C==NiPr can be achieved stepwise first at the primary amino group to selectively give the monoguanidine 38, and then at the cyclic secondary amino unit to give the biguanidine 39. Some key reaction intermediates or true catalyst species, such as the amido complexes [{Me(2)Si(C(5)Me(4))(NPh)}Y(NEt(2))(thf)(2)] (40) and [{Me(2)Si(C(5)Me(4))(NPh)}Y(NHC(6)H(4)Br-4)(thf)(2)] (42), and the guanidinate complexes [{Me(2)Si(C(5)Me(4))(NPh)}Y{iPrNC(NEt(2))(NiPr)}(thf)] (41) and [{Me(2)Si(C(5)Me(4))(NPh)}Y{iPrN}C(NC(6)H(4)Br-4)(NHiPr)}(thf)] (44) have been isolated and structurally characterized. Reactivity studies on these complexes suggest that the present catalytic formation of a guanidine compound proceeds mechanistically through nucleophilic addition of an amido species, formed by acid-base reaction between a rare-earth metal alkyl bond and an amine N--H bond, to a carbodiimide, followed by amine protonolysis of the

  17. Methylidene rare-earth-metal complex mediated transformations of C=N, N=N and N-H bonds: new routes to imido rare-earth-metal clusters.

    PubMed

    Hong, Jianquan; Zhang, Lixin; Wang, Kai; Zhang, Yin; Weng, Linhong; Zhou, Xigeng

    2013-06-10

    Three new patterns of reactivity of rare-earth metal methylidene complexes have been established and thus have resulted in access to a wide variety of imido rare-earth metal complexes [L3Ln3(μ2-Me)3(μ3-Me)(μ-NR)] (L = [PhC(NC6H3iPr2-2,6)2](-); R = Ph, Ln = Y (2 a), Lu (2 b); R = 2,6-Me2C6H3, Ln = Y (3 a), Lu (3 b); R = p-ClC6H4, Ln = Y (4 a), Lu (4 b); R = p-MeOC6H4, Ln = Y (5 a), Lu (5 b); R = Me2CHCH2CH2, Ln = Y (6 a), Lu (6 b)) and [{L3Lu3(μ2-Me)3(μ3-Me)}2(μ-NR'N)] (R' = (CH2)6 (7 b), (C6H4)2 (8 b)). Complex 2 b was treated with an excess of CO2 to give the corresponding carboxylate complex [L3Lu3(μ-η(1):η(1)-O2CCH3)3(μ-η(1):η(2)-O2C-CH3)(μ-η(1):η(1):η(2)-O2CNPh)] (9 b) easily. Complex 2 a could undergo the selective μ3-Me abstraction reaction with phenyl acetylene to give the mixed imido/alkynide complex [L3Y3(μ2-Me)3(μ3-η(1):η(1):η(3)-NPh)(μ3-C≡CPh)] (10 a) in high yield. Treatment of 2 with one equivalent of thiophenol gave the selective μ3-methyl-abstracted products [L3Ln3(μ2-Me)3(μ3-η(1):η(1):η(3)-NPh)(μ3-SPh)] (Ln = Y (11 a); Lu (11 b). All new complexes have been characterized by elemental analysis, NMR spectroscopy, and most of the structures confirmed by X-ray diffraction.

  18. Self-propelled droplets for extracting rare-earth metal ions.

    PubMed

    Ban, Takahiko; Tani, Kentaro; Nakata, Hiroki; Okano, Yasunori

    2014-09-07

    We have developed self-propelled droplets having the abilities to detect a chemical gradient, to move toward a higher concentration of a specific metal ion (particularly the dysprosium ion), and to extract it. Such abilities rely on the high surface activity of di(2-ethylhexyl) phosphoric acid (DEHPA) in response to pH and the affinity of DEHPA for the dysprosium ion. We used two external stimuli as chemical signals to control droplet motion: a pH signal to induce motility and metal ions to induce directional sensing. The oil droplets loaded with DEHPA spontaneously move around beyond the threshold of pH even in a homogeneous pH field. In the presence of a gel block containing metal ions, the droplets show directional sensing and their motility is biased toward higher concentrations. The metal ions investigated can be arranged in decreasing order of directional sensing as Dy(3+)≫ Nd(3+) > Y(3+) > Gd(3+). Furthermore, the analysis of components by using an atomic absorption spectrophotometer reveals that the metal ions can be extracted from the environmental media to the interiors of the droplets. This system may offer alternative self-propelled nano/microscale machines to bubble thrust engines powered by asymmetrical catalysts.

  19. Formation of Tsai-type 1/1 approximants in In-Pd-RE (RE: rare earth metal) alloys

    NASA Astrophysics Data System (ADS)

    So, Yeong-Gi; Saruhashi, Fukuaki; Kimoto, Koji; Tamura, Ryuji; Edagawa, Keiichi

    2014-09-01

    The formation of the 1/1 crystal approximant phase (1/1 phase) to the icosahedral phase (i phase) in In-Pd-RE (RE: rare earth metal) systems has been investigated. A new series of 1/1 phases were found in In53Pd33RE14 (RE; Y, Ce, Pr, Nd, Sm, Gd, Tb, Dy, Ho, Er, and Tm) alloys. For Y, Sm, Gd, Tb, Dy, and Ho, the 1/1 phases were found in annealed alloys, indicating that they are thermodynamically stable. The atomic structure of the 1/1 phases was directly observed by high-angle annular dark-field imaging performed via scanning transmission electron microscopy, revealing that the 1/1 phases consisted of a periodic arrangement of Tsai-type icosahedral clusters. Further, the atomic size effect on i phase formation, as well as formation conditions previously reported for other Tsai-type i and 1/1 phases were examined. It was found that the ratio of the atomic radius of base metals such as In and Pd affects i phase formation. Moreover, the appropriate range of the radius ratio for i phase formation was narrower than that for 1/1 phase formation. Present address: Department of Materials Science and Engineering, Akita University, Tegata Gakuen-machi, Akita-shi, Akita 010-8502, Japan

  20. Exchange Processes in Shibasaki's Rare Earth Alkali Metal BINOLate Frameworks and Their Relevance in Multifunctional Asymmetric Catalysis.

    PubMed

    Robinson, Jerome R; Gu, Jun; Carroll, Patrick J; Schelter, Eric J; Walsh, Patrick J

    2015-06-10

    Shibasaki's rare earth alkali metal BINOLate (REMB) catalysts (REMB; RE = Sc, Y, La - Lu; M = Li, Na, K; B = 1,1-bi-2-naphtholate; RE/M/B = 1/3/3) are among the most successful enantioselective catalysts and have been employed in a broad range of mechanistically diverse reactions. Despite the phenomenal success of these catalysts, several fundamental questions central to their reactivity remain unresolved. Combined reactivity and spectroscopic studies were undertaken to probe the identity of the active catalyst(s) in Lewis-acid (LA) and Lewis-acid/Brønsted-base (LA/BB) catalyzed reactions. Exchange spectroscopy provided a method to obtain rates of ligand and alkali metal self-exchange in the RE/Li frameworks, demonstrating the utility of this technique for probing solution dynamics of REMB catalysts. Isolation of the first crystallographically characterized REMB complex with substrate bound enabled stoichiometric and catalytic reactivity studies, wherein we observed that substrate deprotonation by the catalyst framework was necessary to achieve selectivity. Our spectroscopic observations in LA/BB catalysis are inconsistent with previous mechanistic proposals, which considered only tris(BINOLate) species as active catalysts. These findings significantly expand our understanding of the catalyst structure in these privileged multifunctional frameworks and identify new directions for development of new catalysts.

  1. Precious metals and rare earth elements in municipal solid waste – Sources and fate in a Swiss incineration plant

    SciTech Connect

    Morf, Leo S.; Gloor, Rolf; Haag, Olaf; Haupt, Melanie; Skutan, Stefan; Lorenzo, Fabian Di; Böni, Daniel

    2013-03-15

    Highlights: ► We carefully addressed all the very valuable comments and suggestions of the reviewers. ► We also have shortened the size of the paper and tried simplify it substantially, as requested by the reviewers (introduction 25% reduced!). ► We have decided to take the chance and have replaced the data for the “additional” elements (Cu, Cd, Zn, Pb, Sn, Cr, Ni, Fe, Al) of the earlier MFA (Morf, 2011) with data that belong to the samples of this study. ► We are convinced that with the revision the paper has significantly improved in quality and attractiveness. - Abstract: In Switzerland many kinds of waste, e.g. paper, metals, electrical and electronic equipment are separately collected and recycled to a large extent. The residual amount of municipal solid waste (MSW) has to be thermally treated before final disposal. Efforts to recover valuable metals from incineration residues have recently increased. However, the resource potential of critical elements in the waste input (sources) and their partitioning into recyclable fractions and residues (fate) is unknown. Therefore, a substance flow analysis (SFA) for 31 elements including precious metals (Au, Ag), platinum metal group elements (Pt, Rh) and rare earth elements (La, Ce, etc.) has been conducted in a solid waste incinerator (SWI) with a state-of-the-art bottom ash treatment according to the Thermo-Re® concept. The SFA allowed the determination of the element partitioning in the SWI, as well as the elemental composition of the MSW by indirect analysis. The results show that the waste-input contains substantial quantities of precious metals, such as 0.4 ± 0.2 mg/kg Au and 5.3 ± 0.7 mg/kg Ag. Many of the valuable substances, such as Au and Ag are enriched in specific outputs (e.g. non-ferrous metal fractions) and are therefore recoverable. As the precious metal content in MSW is expected to rise due to its increasing application in complex consumer products, the results of this study are

  2. Synthesis, structure, and catalytic activity of novel trinuclear rare-earth metal amido complexes incorporating μ-η5:η1 bonding indolyl and μ3-oxo groups.

    PubMed

    Yang, Song; Zhu, Xiancui; Zhou, Shuangliu; Wang, Shaowu; Feng, Zhijun; Wei, Yun; Miao, Hui; Guo, Liping; Wang, Fenhua; Zhang, Guangchao; Gu, Xiaoxia; Mu, Xiaolong

    2014-02-14

    The reactions of different pyrrolyl-functionalized indoles with rare-earth metal(III) amides [(Me3Si)2N]3RE(III)(μ-Cl)Li(THF)3 (RE = Yb, Er, Dy, Eu, Y) produced different kinds of rare-earth metal amido complexes. Reactions of N-((1H-pyrrol-2-yl)methylene)-2-(1H-indol-3-yl)ethanamine with rare-earth metal amides [(Me3Si)2N]3RE(III)(μ-Cl)Li(THF)3 (RE = Yb, Er, Dy, Eu, Y) in toluene or THF at temperatures of 75-80 °C afforded the novel trinuclear rare-earth metal amido complexes incorporating the indolyl ligand in μ-η(5):η(1) bonding modes and a μ3-O group, which is believed to originate from cleavage of the THF ring based on experimental results. Reactions of 2-(1H-indol-3-yl)-N-((1-methyl-1H-pyrrol-2-yl)methylene)ethanamine with rare-earth metal(III) amides [(Me3Si)2N]3RE(III)(μ-Cl)Li(THF)3 (RE = Yb, Dy) produced mononuclear ytterbium and dysprosium amides having the indolyl ligand in an η(1) bonding fashion. The results indicate that substituents not only have an influence on reactivity, but also have an influence on the bonding of the indolyl ligands with metals. The catalytic activities of the novel lanthanide amido complexes for the hydrophosphonylation of both aromatic and aliphatic aldehydes and ketones were explored. The results indicate that these complexes display a high catalytic activity for the C-P bond formation under mild conditions when using low catalyst loadings (0.1 mol% for aldehydes and ketones). Thus, it provides a potential way to prepare α-hydroxy phosphonates.

  3. Trinuclear rare earth metal complexes based on 1,3,5-triamino-1,3,5-trideoxy-cis inositol as catalysts for the hydrolysis of phosphodiesters.

    PubMed

    Ramadan, Ahmed M; Calatayud Sala, José Miguel; Parac-Vogt, Tatjana N

    2011-02-14

    Trinuclear rare-earth metal complexes [M₃(taciH₋₃)₂](3+) (M = La(3+), Y(3+)), based on a rigid polyamino-polyalcohol ligand 1,3,5-triamino-1,3,5-trideoxy-cis-inositol (taci), are proven to be efficient catalysts for the hydrolysis of 2-hydroxypropyl-4-nitrophenyl phophate (HPNP), a commonly used RNA model system.

  4. Core and shallow-core d- to f-shell excitations in rare-earth metals

    NASA Astrophysics Data System (ADS)

    Bradley, J. A.; Moore, K. T.; van der Laan, G.; Bradley, J. P.; Gordon, R. A.

    2011-11-01

    We report on the results of probing the light lanthanide metals Ce, Pr, and Nd with inelastic x-ray and electron scattering. Aberration-corrected transmission electron microscope-based electron spectroscopy and nonresonant inelastic x-ray scattering are shown to be in a high degree of accord and here serve as complementary probes of electronic structure. The high resolution and high signal-to-noise electron technique allows for the measurement of the complex and subtle excitation spectra in the lanthanide metals, validating the applicability of the screened trivalent atomic model used for these materials. In addition, the momentum transfer dependence of the x-ray scattering is extracted and compared against atomic calculations for the most tightly bound excitonic resonances, which provides a direct test of the predicted atomic radial wave functions.

  5. Rare earth elements and permanent magnets (invited)

    NASA Astrophysics Data System (ADS)

    Dent, Peter C.

    2012-04-01

    Rare earth (RE) magnets have become virtually indispensible in a wide variety of industries such as aerospace, automotive, electronics, medical, and military. RE elements are essential ingredients in these high performance magnets based on intermetallic compounds RECo5, RE2TM17 (TM: transition metal), and RE2TM14B. Rare earth magnets are known for their superior magnetic properties—high induction, and coercive force. These properties arise due to the extremely high magnetocrystalline anisotropy made possible by unique 3d-4f interactions between transition metals and rare earths. For more than 40 years, these magnets remain the number one choice in applications that require high magnetic fields in extreme operating conditions—high demagnetization forces and high temperature. EEC produces and specializes in RECo5 and RE2TM17 type sintered magnets. Samarium and gadolinium are key RE ingredients in the powder metallurgical magnet production processes which include melting, crushing, jet milling, pressing, sintering, and heat treating. The magnetic properties and applications of these magnets will be discussed. We will also briefly discuss the past, current, and future of the permanent magnet business. Currently, over 95% of all pure rare earth oxides are sourced from China, which currently controls the market. We will provide insights regarding current and potential new magnet technologies and designer choices, which may mitigate rare earth supply chain issues now and into the future.

  6. Rare-earth metal hydrides supported by silicon-bridged boratabenzene fluorenyl ligands: synthesis, structure and reactivity.

    PubMed

    Wang, Chunhong; Xiang, Li; Leng, Xuebing; Chen, Yaofeng

    2017-01-24

    The reactions of rare-earth metal benzyl complexes supported by silicon-bridged boratabenzene fluorenyl ligands with PhSiH3 in toluene gave the corresponding dinuclear hydrides [{μ-[Me2Si(C13H8)(C5H4BNEt2)]}Ln(μ-H)(THF)]2 (3-Ln; Ln = La, Nd, Gd), wherein the rare-earth metal ions are linked by both silicon-bridged boratabenzene fluorenyl ligands and hydrido ligands. The reactivity of these hydrides toward unsaturated substrates was studied. Among these, alkynides [{μ-[Me2Si(C13H8)(C5H4BNEt2)]}Ln(μ-CCPh)]2 (4-Ln; Ln = La, Nd) were obtained via the σ-bond metathesis reaction, when 3-Ln (Ln = La, Nd) was treated with phenylacetylene. While reacting with 3-hexyne, the mono-addition product [{μ-[Me2Si(C13H8)(C5H4BNEt2)]}Ln]2(μ-H)[μ-C(Et)[double bond, length as m-dash]C(H)Et] (5-Ln; Ln = La, Nd) was formed. Further investigations on the reactivity of 3-La displayed that benzonitrile and tert-butyl isonitrile readily inserted into the La-H bonds, affording an azomethine complex [{μ-[Me2Si(C13H8)(C5H4BNEt2)]}La{μ-N[double bond, length as m-dash]C(H)Ph}]2 (6-La) and an N-tert-butylformimidoyl complex [{μ-[Me2Si(C13H8)(C5H4BNEt2)]}La{μ,η(2)-C(H)[double bond, length as m-dash]N(t)Bu}]2 (7-La), respectively. The reaction with N,N'-diisopropylcarbodiimide at room temperature or at 75 °C gave a dimeric complex [{μ-[Me2Si(C13H8)(C5H4BNEt2)]}La]2(μ-H)[μ-N((i)Pr)CHN((i)Pr)] (8-La) or a monomeric complex [Me2Si(C13H8)(C5H4BNEt2)]La[N((i)Pr)CHN((i)Pr)] (9-La), respectively.

  7. Determination of the Magnetic Moments of Transition Metal Complexes Using Rare Earth Magnets

    NASA Astrophysics Data System (ADS)

    de Berg, Kevin C.; Chapman, Kenneth J.

    2001-05-01

    This paper describes how powerful neodymium magnets and an electronic balance can be used to determine magnetic moments and susceptibilities of transition metal complexes. The technique is an improvement on one previously reported (J. Chem. Educ. 1998, 75, 61) and allows the effect of temperature on paramagnetism to be studied. Results consistent with the Curie law are reported and a theoretical background to the measurement of magnetic moments is given to explain why magnetic field strength and its gradient are important to the technique described.

  8. Recipe for High Moment Materials with Rare-earth and 3d Transition Metal Composites

    NASA Astrophysics Data System (ADS)

    Autieri, Carmine; Kumar, P. Anil; Walecki, Dirk; Webers, Samira; Gubbins, Mark A.; Wende, Heiko; Sanyal, Biplab

    2016-07-01

    Materials with high volume magnetization are perpetually needed for the generation of sufficiently large magnetic fields by writer pole of magnetic hard disks, especially for achieving increased areal density in storage media. In search of suitable materials combinations for this purpose, we have employed density functional theory to predict the magnetic coupling between iron and gadolinium layers separated by one to several monolayers of 3d transition metals (Sc-Zn). We demonstrate that it is possible to find ferromagnetic coupling for many of them and in particular for the early transition metals giving rise to high moment. Cr and Mn are the only elements able to produce a significant ferromagnetic coupling for thicker spacer layers. We also present experimental results on two trilayer systems Fe/Sc/Gd and Fe/Mn/Gd. From the experiments, we confirm a ferromagnetic coupling between Fe and Gd across a 3 monolayers Sc spacer or a Mn spacer thicker than 1 monolayer. In addition, we observe a peculiar dependence of Fe/Gd magnetic coupling on the Mn spacer thickness.

  9. Recipe for High Moment Materials with Rare-earth and 3d Transition Metal Composites

    PubMed Central

    Autieri, Carmine; Kumar, P. Anil; Walecki, Dirk; Webers, Samira; Gubbins, Mark A.; Wende, Heiko; Sanyal, Biplab

    2016-01-01

    Materials with high volume magnetization are perpetually needed for the generation of sufficiently large magnetic fields by writer pole of magnetic hard disks, especially for achieving increased areal density in storage media. In search of suitable materials combinations for this purpose, we have employed density functional theory to predict the magnetic coupling between iron and gadolinium layers separated by one to several monolayers of 3d transition metals (Sc-Zn). We demonstrate that it is possible to find ferromagnetic coupling for many of them and in particular for the early transition metals giving rise to high moment. Cr and Mn are the only elements able to produce a significant ferromagnetic coupling for thicker spacer layers. We also present experimental results on two trilayer systems Fe/Sc/Gd and Fe/Mn/Gd. From the experiments, we confirm a ferromagnetic coupling between Fe and Gd across a 3 monolayers Sc spacer or a Mn spacer thicker than 1 monolayer. In addition, we observe a peculiar dependence of Fe/Gd magnetic coupling on the Mn spacer thickness. PMID:27381456

  10. Alkali metal – yttrium borohydrides: The link between coordination of small and large rare-earth

    SciTech Connect

    Sadikin, Yolanda; Stare, Katarina; Schouwink, Pascal; Brix Ley, Morten; Jensen, Torben R.; Meden, Anton; Černý, Radovan

    2015-05-15

    The system Li–A–Y–BH{sub 4} (A=K, Rb, Cs) is found to contain five new compounds and four further ones known from previous work on the homoleptic borohydrides. Crystal structures have been solved and refined from synchrotron X-ray powder diffraction, thermal stability of new compounds have been investigated and ionic conductivity measured for selected samples. Significant coordination flexibility for Y{sup 3+} is revealed, which allows the formation of both octahedral frameworks and tetrahedral complex anions with the tetrahydroborate anion BH{sub 4} both as a linker and terminal ligand. Bi- and trimetallic cubic double-perovskites c-A{sub 3}Y(BH{sub 4}){sub 6} or c-A{sub 2}LiY(BH{sub 4}){sub 6} (A=Rb, Cs) form in all the investigated systems, with the exception of the Li–K–Y system. The compounds with the stoichiometry AY(BH{sub 4}){sub 4} crystallize in all investigated systems with a great variety of structure types which find their analog amongst metal oxides. In-situ formation of a new borohydride – closo-borane is observed during decomposition of all double perovskites. - Graphical abstract: The system Li–A–Y–BH{sub 4} (A=K, Rb, Cs) is found to contain five novel compounds and four further ones previously reported. Significant coordination flexibility of Y{sup 3+} is revealed, which can be employed to form both octahedral frameworks and tetrahedral complex anions, very different structural topologies. Versatility is also manifested in three different simultaneously occurring coordination modes of borohydrides for one metal cation, as proposed by DFT optimization of the monoclinic KY(BH{sub 4}){sub 4} structural model observed by powder diffraction. - Highlights: • The system Li-A-Y-BH{sub 4} (A=K, Rb, Cs) contains nine compounds in total. • Y{sup 3+} forms octahedral frameworks and tetrahedral complex anions. • Bi- and trimetallic double-perovskites crystallize in most systems. • Various AY(BH{sub 4}){sub 4} crystallize with

  11. Heteroscorpionate rare-earth metal zwitterionic complexes: syntheses, characterization, and heteroselective catalysis on the ring-opening polymerization of rac-lactide.

    PubMed

    Zhang, Zhichao; Cui, Dongmei

    2011-10-04

    Novel neutral phosphine-modified heteroscorpionate ligand (3,5-Me(2)Pz)(2)CHPPh(2) (1) and its derivatives oxophosphine (2) and iminophosphine (3) heteroscorpionates were synthesized for the first time. These neutral heteroscorpionate ligands displayed unique chemistry towards rare-earth metal tris(alkyl)s [Ln(CH(2)SiMe(3))(3)(thf)(2)] (Ln=Y, Lu, Sc). The reaction between compound 1 and [Ln(CH(2)SiMe(3))(3)(thf)(2)] afforded heteroscorpionate rare-earth metal trialkyl adduct complexes 4a-c. Compounds 2 and 3 were treated with [Ln(CH(2)SiMe(3))(3)(thf)(2)] to give the unprecedented zwitterionic heteroscorpionate rare-earth metal dialkyls 5 and 6, respectively. In the process, the heteroscorpionates transferred to the carbanions by means of methine C-H bond cleavage that was attributed to the presence of the electron-withdrawing groups. In addition the ligand and central metal showed a concerted effect on both the catalytic activity and specific selectivity of complexes 4-6 for the ring-opening polymerization (ROP) of rac-lactide (rac-LA). All the adduct complexes 4 were nonselective and gave atactic polylactide (PLA), probably due to the dissociation of ligand 1 from the active metal center during the polymerization. Strikingly, zwitterionic complexes 5 catalyzed rapid ROP of rac-LA to produce PLAs with heterotacticity up to 0.87. However, the zwitterionic complexes 6 were less active and less selective than 5, which might be on account of the stronger coordination of the tetradentate ligand. Complexes 5 represent rare examples of the selective ROP of rac-LA mediated by rare-earth metal complexes supported by non-bisphenolate ligands.

  12. Alkali metal - yttrium borohydrides: The link between coordination of small and large rare-earth

    NASA Astrophysics Data System (ADS)

    Sadikin, Yolanda; Stare, Katarina; Schouwink, Pascal; Brix Ley, Morten; Jensen, Torben R.; Meden, Anton; Černý, Radovan

    2015-05-01

    The system Li-A-Y-BH4 (A=K, Rb, Cs) is found to contain five new compounds and four further ones known from previous work on the homoleptic borohydrides. Crystal structures have been solved and refined from synchrotron X-ray powder diffraction, thermal stability of new compounds have been investigated and ionic conductivity measured for selected samples. Significant coordination flexibility for Y3+ is revealed, which allows the formation of both octahedral frameworks and tetrahedral complex anions with the tetrahydroborate anion BH4 both as a linker and terminal ligand. Bi- and trimetallic cubic double-perovskites c-A3Y(BH4)6 or c-A2LiY(BH4)6 (A=Rb, Cs) form in all the investigated systems, with the exception of the Li-K-Y system. The compounds with the stoichiometry AY(BH4)4 crystallize in all investigated systems with a great variety of structure types which find their analog amongst metal oxides. In-situ formation of a new borohydride - closo-borane is observed during decomposition of all double perovskites.

  13. Role of vacancies, light elements and rare-earth metals doping in CeO2

    NASA Astrophysics Data System (ADS)

    Shi, H.; Hussain, T.; Ahuja, R.; Kang, T. W.; Luo, W.

    2016-08-01

    The magnetic properties and electronic structures of pure, doped and defective cerium oxide (CeO2) have been studied theoretically by means of ab initio calculations based on the density function theory (DFT) with the hybrid HF/DFT technique named PBE0. Carbon (C), nitrogen (N), phosphorus (P), sulphur (S), lanthanum (La) and praseodymium (Pr) doped in CeO2 and CeO2 containing oxygen vacancies (Ov) were considered. Our spin-polarized calculations show that C, N, Pr dopants and Ov defects magnetize the non-magnetic CeO2 in different degree. The optical band gap related to photocatalysis for pure CeO2, corresponding to the ultraviolet region, is reduced obviously by C, N, S, Pr impurities and oxygen vacancies, shifting to the visible region and even further to the infrared range. Especially, N-, S- and Pr-doped CeO2 could be used to photocatalytic water splitting for hydrogen production. As the concentration of Ov increasing up to 5%, the CeO2 exhibits a half-metallic properties.

  14. Role of vacancies, light elements and rare-earth metals doping in CeO2

    PubMed Central

    Shi, H.; Hussain, T.; Ahuja, R.; Kang, T. W.; Luo, W.

    2016-01-01

    The magnetic properties and electronic structures of pure, doped and defective cerium oxide (CeO2) have been studied theoretically by means of ab initio calculations based on the density function theory (DFT) with the hybrid HF/DFT technique named PBE0. Carbon (C), nitrogen (N), phosphorus (P), sulphur (S), lanthanum (La) and praseodymium (Pr) doped in CeO2 and CeO2 containing oxygen vacancies (Ov) were considered. Our spin-polarized calculations show that C, N, Pr dopants and Ov defects magnetize the non-magnetic CeO2 in different degree. The optical band gap related to photocatalysis for pure CeO2, corresponding to the ultraviolet region, is reduced obviously by C, N, S, Pr impurities and oxygen vacancies, shifting to the visible region and even further to the infrared range. Especially, N-, S- and Pr-doped CeO2 could be used to photocatalytic water splitting for hydrogen production. As the concentration of Ov increasing up to 5%, the CeO2 exhibits a half-metallic properties. PMID:27554285

  15. Role of vacancies, light elements and rare-earth metals doping in CeO2.

    PubMed

    Shi, H; Hussain, T; Ahuja, R; Kang, T W; Luo, W

    2016-08-24

    The magnetic properties and electronic structures of pure, doped and defective cerium oxide (CeO2) have been studied theoretically by means of ab initio calculations based on the density function theory (DFT) with the hybrid HF/DFT technique named PBE0. Carbon (C), nitrogen (N), phosphorus (P), sulphur (S), lanthanum (La) and praseodymium (Pr) doped in CeO2 and CeO2 containing oxygen vacancies (Ov) were considered. Our spin-polarized calculations show that C, N, Pr dopants and Ov defects magnetize the non-magnetic CeO2 in different degree. The optical band gap related to photocatalysis for pure CeO2, corresponding to the ultraviolet region, is reduced obviously by C, N, S, Pr impurities and oxygen vacancies, shifting to the visible region and even further to the infrared range. Especially, N-, S- and Pr-doped CeO2 could be used to photocatalytic water splitting for hydrogen production. As the concentration of Ov increasing up to 5%, the CeO2 exhibits a half-metallic properties.

  16. Optical and dielectric characteristics of the rare-earth metal oxide Lu{sub 2}O{sub 3}

    SciTech Connect

    Ordin, S. V. Shelykh, A. I.

    2010-05-15

    The characteristics of the Lu{sub 2}O{sub 3} oxide and their variations controlled by compositional defects are studied. The defects are anion vacancies produced on partial reduction of the oxide. Such defects exhibit features typical of quantum objects and have a profound effect on the optical transmittance spectrum, the character of conduction (insulator or semiconductor properties) and the order of magnitude of the permittivity {epsilon} (capable of varying from 11.2 to 125). The structural features of vacancies in the oxides are considered, and the effect of vacancies on the polarization, conductivity, and lattice vibrations is studied. The studies are carried out in the temperature range 200-900 K, the wavelength range 0.03-50 {mu}m, and the current frequency range 10{sup 2}-10{sup 5} Hz. The rare-earth metal oxides attract interest for applications in microelectronics due to their high permittivity (several times higher than the permittivity of SiO{sub 2}) and, hence, the prospects for use of these oxides instead of SiO{sub 2}.

  17. Me-Si bond cleavage of anionic bis(trimethylsilyl)amide in scorpionate-anchored rare earth metal complexes.

    PubMed

    Yi, Weiyin; Zhang, Jie; Chen, Zhenxia; Zhou, Xigeng

    2012-10-15

    A novel Tp(Me2)-supported (Tp(Me2) = tri(3,5-dimethylpyrazolyl)borate) rare earth metal complex promoted Me-Si cleavage of the bis(trimethylsilyl) amide ligand ([(Me(3)Si)(2)N](-)) was observed. Reaction of Tp(Me2)LnCl(2) with 2 equiv of K[(RN)(2)CN(SiMe(3))(2)] (KGua) gave the methylamidinate complexes Tp(Me2)Ln[(RN)(2)CMe][N(SiMe(3))(2)] (R = isopropyl, Ln = Y (1(Y)), Er (1(Er)); R = cyclohexyl, Ln = Y (2(Y))) in moderate yields. In contrast, Tp(Me2)YCl(2)(THF) reacted with 1 equiv of KGua to afford a C-N cleavage product Tp(Me2)Y(Cl)N(SiMe(3))(2)(THF) (4), indicating that this guanidinate ligand is not stable in the yttrium complex with the Tp(Me2) ligand, and a carbodiimide deinsertion takes place easily. The mechanism for the formation of complexes 1 and 2 was also studied by controlling the substrate stoichiometry and the reaction sequence and revealed that the bis(trimethylsilyl)amine anion N(SiMe(3))(2)(-) can undergo two routes of γ-methyl deprotonation and Si-Me cleavage for its functionalizations. All these new complexes were characterized by elemental analysis and spectroscopic methods, and their solid-state structures were also confirmed by single-crystal X-ray diffraction.

  18. Thermal and optical properties of rare earth metal β-Diketone Bipy complexes as optical recording materials

    NASA Astrophysics Data System (ADS)

    Ma, Dongzhe; Wu, Yiqun; Jiang, Xin; Chen, Zhimin; Zuo, Xia

    2005-09-01

    Three kinds of novel rare earth metal β-diketone bipy complexes have been synthesized. Smooth films of the complexes on K9 glass substrates and single-crystal silicon substrates were prepared by spin-coating method. The absorption spectra of these new materials were measured in solution and in film. The optical constants (complex refractive index N=n+ik ) of the films on single-crystal silicon substrates at 405nm were determined with scanning ellipsometer. The thermo-gravimetric analysis (TGA) of the materials was also carried out. It is found that the absorption spectra of these films have comparatively broad band in the wavelength region 300-400nm, the peek is at ~345nm and the absorption edge is steep in the wavelength region 350-400nm, which indicates that the absorption of the films is well matched with the wavelength of GaN semiconductor laser diode (405nm). The refractive index (n) of the films is above 1.9 and the extinction coefficient (k) of is 0.1-0.3 at 405nm. The reflection peeks are located near 405nm. And also the new materials possess excellent thermal stability (their decomposition temperatures are higher than 300°C). The results imply that these novel materials are promising candidates for the recording media of blue discs.

  19. Rapid enrichment of rare-earth metals by carboxymethyl cellulose-based open-cellular hydrogel adsorbent from HIPEs template.

    PubMed

    Zhu, Yongfeng; Wang, Wenbo; Zheng, Yian; Wang, Feng; Wang, Aiqin

    2016-04-20

    A series of monolithic open-cellular hydrogel adsorbents based on carboxymethylcellulose (CMC) were prepared through high internal phase emulsions (HIPEs) and used to enrich the rare-earth metals La(3+) and Ce(3+). The changes of pore structure, and the effects of pH, contact time, initial concentration on the adsorption performance were systematically studied. The results show that the as-prepared monolithic hydrogel adsorbents possess good open-cellular framework structure and have fast adsorption kinetics and high adsorption capacity for La(3+) and Ce(3+). The involved adsorption system can reach equilibrium within 30min and the maximal adsorption capacity is determined to be 384.62mg/g for La(3+) and 333.33mg/g for Ce(3+). Moreover, these porous hydrogel adsorbents show an excellent adsorptive reusability for La(3+) and Ce(3+) through five adsorption-desorption cycles. Such a pore hierarchy structure makes this monolithic open-cellular hydrogel adsorbent be an effective adsorbent for effective enrichment of La(3+) and Ce(3+) from aqueous solution.

  20. Magnetic Resonance Imaging Distortion and Targeting Errors from Strong Rare Earth Metal Magnetic Dental Implant Requiring Revision.

    PubMed

    Seong-Cheol, Park; Chong Sik, Lee; Seok Min, Kim; Eu Jene, Choi; Do Hee, Lee; Jung Kyo, Lee

    2016-12-22

    Recently, the use of magnetic dental implants has been re-popularized with the introduction of strong rare earth metal, for example, neodymium, magnets. Unrecognized magnetic dental implants can cause critical magnetic resonance image distortions. We report a case involving surgical failure caused by a magnetic dental implant. A 62-year-old man underwent deep brain stimulation for medically insufficiently controlled Parkinson's disease. Stereotactic magnetic resonance imaging performed for the first deep brain stimulation showed that the overdenture was removed. However, a dental implant remained and contained a neodymium magnet, which was unrecognized at the time of imaging; the magnet caused localized non-linear distortions that were the largest around the dental magnets. In the magnetic field, the subthalamic area was distorted by a 4.6 mm right shift and counter clockwise rotation. However, distortions were visually subtle in the operation field and small for distant stereotactic markers, with approximately 1-2 mm distortions. The surgeon considered the distortion to be normal asymmetry or variation. Stereotactic marker distortion was calculated to be in the acceptable range in the surgical planning software. Targeting errors, approximately 5 mm on the right side and 2 mm on the left side, occurred postoperatively. Both leads were revised after the removal of dental magnets. Dental magnets may cause surgical failures and should be checked and removed before stereotactic surgery. Our findings should be considered when reviewing surgical precautions and making distortion-detection algorithm improvements.

  1. Magnetic coupling at rare earth ferromagnet/transition metal ferromagnet interfaces: A comprehensive study of Gd/Ni.

    PubMed

    Higgs, T D C; Bonetti, S; Ohldag, H; Banerjee, N; Wang, X L; Rosenberg, A J; Cai, Z; Zhao, J H; Moler, K A; Robinson, J W A

    2016-07-22

    Thin film magnetic heterostructures with competing interfacial coupling and Zeeman energy provide a fertile ground to study phase transition between different equilibrium states as a function of external magnetic field and temperature. A rare-earth (RE)/transition metal (TM) ferromagnetic multilayer is a classic example where the magnetic state is determined by a competition between the Zeeman energy and antiferromagnetic interfacial exchange coupling energy. Technologically, such structures offer the possibility to engineer the macroscopic magnetic response by tuning the microscopic interactions between the layers. We have performed an exhaustive study of nickel/gadolinium as a model system for understanding RE/TM multilayers using the element-specific measurement technique x-ray magnetic circular dichroism, and determined the full magnetic state diagrams as a function of temperature and magnetic layer thickness. We compare our results to a modified Stoner-Wohlfarth-based model and provide evidence of a thickness-dependent transition to a magnetic fan state which is critical in understanding magnetoresistance effects in RE/TM systems. The results provide important insight for spintronics and superconducting spintronics where engineering tunable magnetic inhomogeneity is key for certain applications.

  2. Magnetic coupling at rare earth ferromagnet/transition metal ferromagnet interfaces: A comprehensive study of Gd/Ni

    PubMed Central

    Higgs, T. D. C.; Bonetti, S.; Ohldag, H.; Banerjee, N.; Wang, X. L.; Rosenberg, A. J.; Cai, Z.; Zhao, J. H.; Moler, K. A.; Robinson, J. W. A.

    2016-01-01

    Thin film magnetic heterostructures with competing interfacial coupling and Zeeman energy provide a fertile ground to study phase transition between different equilibrium states as a function of external magnetic field and temperature. A rare-earth (RE)/transition metal (TM) ferromagnetic multilayer is a classic example where the magnetic state is determined by a competition between the Zeeman energy and antiferromagnetic interfacial exchange coupling energy. Technologically, such structures offer the possibility to engineer the macroscopic magnetic response by tuning the microscopic interactions between the layers. We have performed an exhaustive study of nickel/gadolinium as a model system for understanding RE/TM multilayers using the element-specific measurement technique x-ray magnetic circular dichroism, and determined the full magnetic state diagrams as a function of temperature and magnetic layer thickness. We compare our results to a modified Stoner-Wohlfarth-based model and provide evidence of a thickness-dependent transition to a magnetic fan state which is critical in understanding magnetoresistance effects in RE/TM systems. The results provide important insight for spintronics and superconducting spintronics where engineering tunable magnetic inhomogeneity is key for certain applications. PMID:27444683

  3. Magnetic coupling at rare earth ferromagnet/transition metal ferromagnet interfaces: A comprehensive study of Gd/Ni

    NASA Astrophysics Data System (ADS)

    Higgs, T. D. C.; Bonetti, S.; Ohldag, H.; Banerjee, N.; Wang, X. L.; Rosenberg, A. J.; Cai, Z.; Zhao, J. H.; Moler, K. A.; Robinson, J. W. A.

    2016-07-01

    Thin film magnetic heterostructures with competing interfacial coupling and Zeeman energy provide a fertile ground to study phase transition between different equilibrium states as a function of external magnetic field and temperature. A rare-earth (RE)/transition metal (TM) ferromagnetic multilayer is a classic example where the magnetic state is determined by a competition between the Zeeman energy and antiferromagnetic interfacial exchange coupling energy. Technologically, such structures offer the possibility to engineer the macroscopic magnetic response by tuning the microscopic interactions between the layers. We have performed an exhaustive study of nickel/gadolinium as a model system for understanding RE/TM multilayers using the element-specific measurement technique x-ray magnetic circular dichroism, and determined the full magnetic state diagrams as a function of temperature and magnetic layer thickness. We compare our results to a modified Stoner-Wohlfarth-based model and provide evidence of a thickness-dependent transition to a magnetic fan state which is critical in understanding magnetoresistance effects in RE/TM systems. The results provide important insight for spintronics and superconducting spintronics where engineering tunable magnetic inhomogeneity is key for certain applications.

  4. Magnetic coupling at rare earth ferromagnet/transition metal ferromagnet interfaces: A comprehensive study of Gd/Ni

    SciTech Connect

    Higgs, T. D. C.; Bonetti, S.; Ohldag, H.; Banerjee, N.; Wang, X. L.; Rosenberg, A. J.; Cai, Z.; Zhao, J. H.; Moler, K. A.; Robinson, J. W. A.

    2016-07-22

    Thin film magnetic heterostructures with competing interfacial coupling and Zeeman energy provide a fertile ground to study phase transition between different equilibrium states as a function of external magnetic field and temperature. A rare-earth (RE)/transition metal (TM) ferromagnetic multilayer is a classic example where the magnetic state is determined by a competition between the Zeeman energy and antiferromagnetic interfacial exchange coupling energy. Technologically, such structures offer the possibility to engineer the macroscopic magnetic response by tuning the microscopic interactions between the layers. We have performed an exhaustive study of nickel/gadolinium as a model system for understanding RE/TM multilayers using the element-specific measurement technique x-ray magnetic circular dichroism, and determined the full magnetic state diagrams as a function of temperature and magnetic layer thickness. We compare our results to a modified Stoner-Wohlfarth-based model and provide evidence of a thickness-dependent transition to a magnetic fan state which is critical in understanding magnetoresistance effects in RE/TM systems. In conclusion, the results provide important insight for spintronics and superconducting spintronics where engineering tunable magnetic inhomogeneity is key for certain applications.

  5. Solvent-free mechanochemical synthesis and magnetic properties of rare-earth based metal-organic frameworks

    DOE PAGES

    Singh, N. K.; Gupta, S.; Pecharsky, V. K.; ...

    2016-11-17

    Mechanical milling of benzene 1,3,5-tricarboxylic acid [C6H3(COOH)3], both with the single and mixed rare earth carbonates [R2(CO3)3·xH2O; R = Gd, Tb and Dy], leads to the formation of metal-organic frameworks [R{C6H3(COO)3}] that adopt MIL-78 type structure. M(T) data of the investigated MOFs do not show any apparent onset of long range magnetic ordering down to 2 K. The M(H) data for Gd{C6H3(COO)3}collected at 2 K show deviations from the magnetization behavior expected for non-interacting Gd3+ ions. For the Gd based MOF the temperature dependence of the isothermal magnetic entropy change (i.e. magnetocaloric effect, ΔSM) exhibits a monotonous increase with decreasingmore » temperature and at T = 3.5 K it reaches 34.1 J kg$-$1K$-$1 for a field change (ΔH) of 50 kOe. Finally, for the same ΔH the maximum values of ΔSM for R = Tb and Dy are 5.5 J kg$-$1K$-$1 and 8.5 J kg$-$1K$-$1 at 9.5 K and 4.5 K, respectively.« less

  6. Magnetic coupling at rare earth ferromagnet/transition metal ferromagnet interfaces: A comprehensive study of Gd/Ni

    DOE PAGES

    Higgs, T. D. C.; Bonetti, S.; Ohldag, H.; ...

    2016-07-22

    Thin film magnetic heterostructures with competing interfacial coupling and Zeeman energy provide a fertile ground to study phase transition between different equilibrium states as a function of external magnetic field and temperature. A rare-earth (RE)/transition metal (TM) ferromagnetic multilayer is a classic example where the magnetic state is determined by a competition between the Zeeman energy and antiferromagnetic interfacial exchange coupling energy. Technologically, such structures offer the possibility to engineer the macroscopic magnetic response by tuning the microscopic interactions between the layers. We have performed an exhaustive study of nickel/gadolinium as a model system for understanding RE/TM multilayers using themore » element-specific measurement technique x-ray magnetic circular dichroism, and determined the full magnetic state diagrams as a function of temperature and magnetic layer thickness. We compare our results to a modified Stoner-Wohlfarth-based model and provide evidence of a thickness-dependent transition to a magnetic fan state which is critical in understanding magnetoresistance effects in RE/TM systems. In conclusion, the results provide important insight for spintronics and superconducting spintronics where engineering tunable magnetic inhomogeneity is key for certain applications.« less

  7. Frustrated Lewis Pair-Like Reactivity of Rare-Earth Metal Complexes: 1,4-Addition Reactions and Polymerizations of Conjugated Polar Alkenes.

    PubMed

    Xu, Pengfei; Yao, Yingming; Xu, Xin

    2017-01-26

    Three rare-earth aryloxide ion pairs {[L1REOAr](+) /[B(C6 F5 )4 ](-) ; L1=CH3 C(2,6-iPr2 C6 H3 N)CHC(CH3 )(NCH2 CH2 PPh2 ); RE=Sc, Y, Lu; Ar=2,6-tBu2 C6 H3 } were reported that feature rare-earth/phosphorus (RE/P) combinations exhibiting frustrated Lewis pair (FLP)-like 1,4-addition reactions towards conjugated carbonyl substrates (e.g., enone, ynone, and acrylic substrates). Furthermore, these RE/P complexes were found to be effective catalysts for the polymerization of conjugated polar alkene monomers. Mechanistic studies revealed that the rare-earth metal-catalyzed polymerizations were initiated by new FLP-type 1,4-additions rather than traditional and ubiquitous covalent RE-E (E=H, C, N, etc.) bond insertion or single-electron transfer.

  8. Graphene oxide-rare earth metal-organic framework composites for the selective isolation of hemoglobin.

    PubMed

    Liu, Jia-Wei; Zhang, Yue; Chen, Xu-Wei; Wang, Jian-Hua

    2014-07-09

    Graphene oxide-La(BTC)(H2O)6 (H3BTC=1,3,5-benzenetricarboxylic acid) metal organic framework composites (LaMOF-GOn, n = 1-6, corresponding to the percentage of GO at 1, 2, 3, 4, 5, and 10%) are prepared through a simple and large-scale method at room temperature. The obtained composites are characterized by ATR-FTIR spectra, SEM, XRD, TGA, and N2 adsorption-desorption isotherm. The presence of GO significantly changes the morphologies of the composites from spindly rectangular rods to irregular thick blocks and increases their surface area from 14.8 cm(2) g(-1) (LaMOFs) to 26.6 cm(2) g(-1) (LaMOF-GO3), whereas at the same time, the crystalline structure of La(BTC)(H2O)6 is maintained. As a novel solid-phase adsorbent the LaMOF-GO composite exhibits outstanding adsorption properties for proteins. The strong hydrophobic interaction, especially π-π interaction between protein and the composite, is the main driving force for protein adsorption. In particular, highly selective isolation of hemoglobin (Hb) is achieved by using LaMOF-GO3 composite as sorbent in 4 mM B-R buffer containing 0.05 mol L(-1) NaCl at pH 8. The retained Hb could be effectively recovered with a 1 mM B-R buffer at pH 10, giving rise to a recovery of 63%. The practical applicability of the LaMOF-GO3 composite is demonstrated by the selective adsorption of Hb from human whole blood, and SDS-PAGE assays indicate that Hb could be selectively isolated with high purity from biological samples of complex matrixes.

  9. Crystalline rare-earth activated oxyorthosilicate phosphor

    DOEpatents

    McClellan, Kenneth J.; Cooke, D. Wayne

    2004-02-10

    Crystalline, transparent, rare-earth activated lutetium oxyorthosilicate phosphor. The phosphor consists essentially of lutetium yttrium oxyorthosilicate activated with a rare-earth metal dopant M and having the general formula Lu(.sub.2-x-z)Y.sub.x M.sub.z SiO.sub.5, wherein 0.00.ltoreq.x.ltoreq.1.95, wherein 0.001.ltoreq.z.ltoreq.0.02, and wherein M is selected from Sm, Tb, Tm, Eu, Yb, and Pr. The phosphor also consists essentially of lutetium gadolinium oxyorthosilicate activated with a rare-earth metal dopant M and having the general formula Lu(.sub.2-x-z)Gd.sub.x M.sub.z SiO.sub.5, wherein 0.00.ltoreq.x.ltoreq.1.95, wherein 0.001.ltoreq.z.ltoreq.0.02, and wherein M is selected from Sm, Tb, Tm, Eu, Yb, and Pr. The phosphor also consists essentially of gadolinium yttrium oxyorthosilicate activated with a rare-earth metal dopant M and having the general formula Gd(.sub.2-x-z)Y.sub.x M.sub.z SiO.sub.5, wherein 0.00.ltoreq.x.ltoreq.1.95, wherein 0.001.ltoreq.z.ltoreq.0.02, and wherein M is selected from Sm, Tb, Tm, Eu, Yb, and Pr. The phosphor may be optically coupled to a photodetector to provide a radiation detector.

  10. CADMIUM-RARE EARTH BORATE GLASS AS REACTOR CONTROL MATERIAL

    DOEpatents

    Ploetz, G.L.; Ray, W.E.

    1958-11-01

    A reactor control rod fabricated from a cadmiumrare earth-borate glass is presented. The rare earth component of this glass is selected from among those rare earths having large neutron capture cross sections, such as samarium, gadolinium or europium. Partlcles of this glass are then dispersed in a metal matrix by standard powder metallurgy techniques.

  11. IUPAC-NIST Solubility Data Series. 100. Rare Earth Metal Fluorides in Water and Aqueous Systems. Part 1. Scandium Group (Sc, Y, La)

    SciTech Connect

    Mioduski, Tomasz; Gumiński, Cezary; Zeng, Dewen

    2014-03-15

    This work presents an assessment of solubility data for rare earth metal fluorides (generally of trivalent metals and of CeF{sub 4}) in water and in aqueous ternary systems. Compilations of all available experimental data are introduced for each rare earth metal fluoride with a corresponding critical evaluation. Every such evaluation contains a collection of all solubility results in water, a selection of suggested solubility data, and a brief discussion of the multicomponent systems. Because the ternary systems were seldom studied more than once, no critical evaluations of such data were possible. Only simple fluorides (no complexes or binary salts) are treated as the input substances in this report. The literature has been covered through the end of 2013.

  12. Effect of rare earth elements (Er, Ho) on semi-metallic materials (ScN) in an applied electric field

    NASA Astrophysics Data System (ADS)

    Kim, Hyunjung; Park, Yeonjoon; King, Glen C.; Lee, Kunik; Choi, Sang H.

    2012-04-01

    The development of materials and fabrication technology for field-controlled spectrally active optics is essential for applications such as membrane optics, filters for LIDARs, windows for sensors, telescopes, spectroscopes, cameras and flat-panel displays. The dopants of rare earth elements, in a host of optical systems, create a number of absorption and emission band structures and can easily be incorporated into many high quality crystalline and amorphous hosts. In wide band-gap semiconductors like ScN, the existing deep levels can capture or emit the mobile charges, and can be ionized with the loss or capture of the carriers which are the fundamental basis of concept for smart optic materials. The band gap shrinkage or splitting with dopants supports the possibility of this concept. In the present work, a semi-metallic material (ScN) was doped with rare earth elements (Er, Ho) and tested under an applied electric field to characterize spectral and refractive index shifts by either Stark or Zeeman Effect. These effects can be verified using the UV-Vis spectroscopy, the Hall Effect measurement and the ellipsometric spectroscopy. The optical band gaps of ScN doped with Er and doped with Ho were experimentally estimated as 2.33eV and 2.24eV (+/-0.2eV) respectively. This is less than that of undoped ScN (2.5+/-0.2eV). The red-shifted absorption onset is a direct evidence for the decrease of band gap energy (Eg), and the broadening of valence band states is attributable to the doping cases. A decrease in refractive index with an applied field was observed as a small shift in absorption coefficient using a variable angle spectroscopic ellipsometer. In the presence of an electric field, mobile carriers are redistributed within the space charge region (SCR) to produce this electro-refractive effect. The shift in refractive index is also affected by the density and location of deep potential wells within the SCR. In addition, the microstructure change was observed by a

  13. Effect of Rare Earth Elements (Er, Ho) on Semi-Metallic Materials (ScN) in an Applied Electric Field

    NASA Technical Reports Server (NTRS)

    Kim, Hyunjung; Park, Yeonjoon; King, Glen C.; Lee, Kunik; Choi, Sang H.

    2012-01-01

    The development of materials and fabrication technology for field-controlled spectrally active optics is essential for applications such as membrane optics, filters for LIDARs, windows for sensors, telescopes, spectroscopes, cameras and flat-panel displays. The dopants of rare earth elements, in a host of optical systems, create a number of absorption and emission band structures and can easily be incorporated into many high quality crystalline and amorphous hosts. In wide band-gap semiconductors like ScN, the existing deep levels can capture or emit the mobile charges, and can be ionized with the loss or capture of the carriers which are the fundamental basis of concept for smart optic materials. The band gap shrinkage or splitting with dopants supports the possibility of this concept. In the present work, a semi-metallic material (ScN) was doped with rare earth elements (Er, Ho) and tested under an applied electric field to characterize spectral and refractive index shifts by either Stark or Zeeman Effect. These effects can be verified using the UV-Vis spectroscopy, the Hall Effect measurement and the ellipsometric spectroscopy. The optical band gaps of ScN doped with Er and doped with Ho were experimentally estimated as 2.33eV and 2.24eV ( 0.2eV) respectively. This is less than that of undoped ScN (2.5 0.2eV). The red-shifted absorption onset is a direct evidence for the decrease of band gap energy (Eg), and the broadening of valence band states is attributable to the doping cases. A decrease in refractive index with an applied field was observed as a small shift in absorption coefficient using a variable angle spectroscopic ellipsometer. In the presence of an electric field, mobile carriers are redistributed within the space charge region (SCR) to produce this electro-refractive effect. The shift in refractive index is also affected by the density and location of deep potential wells within the SCR. In addition, the microstructure change was observed by a TEM

  14. Selective Emitter Pumped Rare Earth Laser

    NASA Technical Reports Server (NTRS)

    Chubb, Donald L. (Inventor); Patton, Martin O. (Inventor)

    2001-01-01

    A selective emitter pumped rare earth laser provides an additional type of laser for use in many laser applications. Rare earth doped lasers exist which are pumped with flashtubes or laser diodes. The invention uses a rare earth emitter to transform thermal energy input to a spectral band matching the absorption band of a rare earth in the laser in order to produce lasing.

  15. Recycling of Rare Earth Elements

    NASA Astrophysics Data System (ADS)

    Lorenz, Tom; Bertau, Martin

    2017-01-01

    Any development of an effective process for rare earth (RE) recycling has become more and more challenging, especially in recent years. Since 2011, when commodity prices of REs had met their all-time maximum, prices have dropped rapidly by more than 90 %. An economic process able to offset these fluctuations has to take unconventional methods into account beside well-known strategies like acid/basic leaching or solvent extraction. The solid-state chlorination provides such an unconventional method for mobilizing RE elements from waste streams. Instead of hydrochloric acid this kind of chlorination decomposes NH4Cl thermally to release up to 400 °C hot HCl gas. After cooling the resulting solid metal chlorides may be easily dissolved in pH-adjusted water. Without producing strongly acidic wastes and with NH4Cl as cheap source for hydrogen chloride, solid-state chlorination provides various advantages in terms of costs and disposal. In the course of the SepSELSA project this method was examined, adjusted and optimized for RE recycling from fluorescent lamp scraps as well as Fe14Nd2B magnets. Thereby many surprising influences and trends required various analytic methods to examine the reasons and special mechanisms behind them.

  16. Enhanced pinning in mixed rare earth-123 films

    DOEpatents

    Driscoll, Judith L.; Foltyn, Stephen R.

    2009-06-16

    An superconductive article and method of forming such an article is disclosed, the article including a substrate and a layer of a rare earth barium cuprate film upon the substrate, the rare earth barium cuprate film including two or more rare earth metals capable of yielding a superconductive composition where ion size variance between the two or more rare earth metals is characterized as greater than zero and less than about 10.times.10.sup.-4, and the rare earth barium cuprate film including two or more rare earth metals is further characterized as having an enhanced critical current density in comparison to a standard YBa.sub.2Cu.sub.3O.sub.y composition under identical testing conditions.

  17. Europium-activated phosphors containing oxides of rare-earth and group-IIIB metals and method of making the same

    DOEpatents

    Comanzo, Holly Ann; Setlur, Anant Achyut; Srivastava, Alok Mani

    2006-04-04

    Europium-activated phosphors comprise oxides of at least a rare-earth metal selected from the group consisting of gadolinium, yttrium, lanthanum, and combinations thereof and at least a Group-IIIB metal selected from the group consisting of aluminum, gallium, indium, and combinations thereof. A method for making such phosphors comprises adding at least a halide of at least one of the selected Group-IIIB metals in a starting mixture. The method further comprises firing the starting mixture in an oxygen-containing atmosphere. The phosphors produced by such a method exhibit improved absorption in the UV wavelength range and improved quantum efficiency.

  18. Europium-activated phosphors containing oxides of rare-earth and group-IIIB metals and method of making the same

    DOEpatents

    Comanzo, Holly Ann; Setlur, Anant Achyut; Srivastava, Alok Mani; Manivannan, Venkatesan

    2004-07-13

    Europium-activated phosphors comprise oxides of at least a rare-earth metal selected from the group consisting of gadolinium, yttrium, lanthanum, and combinations thereof and at least a Group-IIIB metal selected from the group consisting of aluminum, gallium, indium, and combinations thereof. A method for making such phosphors comprises adding at least a halide of at least one of the selected Group-IIIB metals in a starting mixture. The method further comprises firing the starting mixture in an oxygen-containing atmosphere. The phosphors produced by such a method exhibit improved absorption in the UV wavelength range and improved quantum efficiency.

  19. Quest for highly connected metal-organic framework platforms: rare-earth polynuclear clusters versatility meets net topology needs.

    PubMed

    Alezi, Dalal; Peedikakkal, Abdul Malik P; Weseliński, Łukasz J; Guillerm, Vincent; Belmabkhout, Youssef; Cairns, Amy J; Chen, Zhijie; Wojtas, Łukasz; Eddaoudi, Mohamed

    2015-04-29

    Gaining control over the assembly of highly porous rare-earth (RE) based metal-organic frameworks (MOFs) remains challenging. Here we report the latest discoveries on our continuous quest for highly connected nets. The topological exploration based on the noncompatibility of a 12-connected RE polynuclear carboxylate-based cluster, points of extension matching the 12 vertices of the cuboctahedron (cuo), with 3-connected organic ligands led to the discovery of two fascinating and highly connected minimal edge-transitive nets, pek and aea. The reduced symmetry of the employed triangular tricarboxylate ligand, as compared to the prototype highly symmetrical 1,3,5-benzene(tris)benzoic acid guided the concurrent occurrence of nonanuclear [RE9(μ3-OH)12(μ3-O)2(O2C-)12] and hexanuclear [RE6(OH)8(O2C-)8] carboxylate-based clusters as 12-connected and 8-connected molecular building blocks in the structure of a 3-periodic pek-MOF based on a novel (3,8,12)-c trinodal net. The use of a tricarboxylate ligand with modified angles between carboxylate moieties led to the formation of a second MOF containing solely nonanuclear clusters and exhibiting once more a novel and a highly connected (3,12,12)-c trinodal net with aea topology. Notably, it is the first time that RE-MOFs with double six-membered ring (d6R) secondary building units are isolated, representing therefore a critical step forward toward the design of novel and highly coordinated materials using the supermolecular building layer approach while considering the d6Rs as building pillars. Lastly, the potential of these new MOFs for gas separation/storage was investigated by performing gas adsorption studies of various probe gas molecules over a wide range of pressures. Noticeably, pek-MOF-1 showed excellent volumetric CO2 and CH4 uptakes at high pressures.

  20. Solvent-free mechanochemical synthesis and magnetic properties of rare-earth based metal-organic frameworks

    SciTech Connect

    Singh, N. K.; Gupta, S.; Pecharsky, V. K.; Balema, V. P.

    2016-11-17

    Mechanical milling of benzene 1,3,5-tricarboxylic acid [C6H3(COOH)3], both with the single and mixed rare earth carbonates [R2(CO3)3·xH2O; R = Gd, Tb and Dy], leads to the formation of metal-organic frameworks [R{C6H3(COO)3}] that adopt MIL-78 type structure. M(T) data of the investigated MOFs do not show any apparent onset of long range magnetic ordering down to 2 K. The M(H) data for Gd{C6H3(COO)3}collected at 2 K show deviations from the magnetization behavior expected for non-interacting Gd3+ ions. For the Gd based MOF the temperature dependence of the isothermal magnetic entropy change (i.e. magnetocaloric effect, ΔSM) exhibits a monotonous increase with decreasing temperature and at T = 3.5 K it reaches 34.1 J kg$-$1K$-$1 for a field change (ΔH) of 50 kOe. Finally, for the same ΔH the maximum values of ΔSM for R = Tb and Dy are 5.5 J kg$-$1K$-$1 and 8.5 J kg$-$1K$-$1 at 9.5 K and 4.5 K, respectively.

  1. Superconductivity of metal nitride chloride β-MNCl (M = Zr, Hf) with rare-earth metal RE (RE = Eu, Yb) doped by intercalation

    NASA Astrophysics Data System (ADS)

    Zhang, Shuai; Tanaka, Masashi; Onimaru, Takahiro; Takabatake, Toshiro; Isikawa, Yosikazu; Yamanaka, Shoji

    2013-04-01

    Electrons were doped into the β-form layered metal nitride chloride MNCl (M = Zr, Hf) by intercalation of rare-earth metals RE (RE = Eu, Yb) using liquid ammonia solutions. The intercalated compounds REx(NH3)yMNCl show superconductivity with transition temperatures Tc of ˜13 and 24.3 K for M = Zr and Hf, respectively, quite similar to the alkali metal intercalated analogs. The paramagnetic characteristics for Eu2+ and Yb3+ can coexist with superconductivity. The magnetic resistance measured on the uniaxially oriented Eu0.08(NH3)yHfNCl with the magnetic field parallel to the ab plane (‖ ab) and the c axis (‖ c) shows a strong anisotropic effect on the upper critical field Hc2; a large anisotropic parameter \\gamma ={H}_{{c}2}^{\\parallel a b}/{H}_{{c}2}^{\\parallel c}\\sim 4 suggests a pseudo-two-dimensional superconductivity. The Tc of Eu0.13(THF)yHfNCl is shifted toward a higher value of 25.8 K upon expansion of the interlayer spacing from 11.9 to 17.5 Å by co-intercalation of voluminous organic molecules such as tetrahydrofuran.

  2. Rare Earth Garnet Selective Emitter

    NASA Technical Reports Server (NTRS)

    Lowe, Roland A.; Chubb, Donald L.; Farmer, Serene C.; Good, Brian S.

    1994-01-01

    Thin film Ho-YAG and Er-YAG emitters with a platinum substrate exhibit high spectral emittance in the emission band (epsilon(sub lambda) approx. = 0.75, sup 4)|(sub 15/2) - (sup 4)|(sub 13/2),for Er-YAG and epsilon(sub lambda) approx. = 0.65, (sup 5)|(sub 7) - (sup 5)|(sub 8) for Ho-YAG) at 1500 K. In addition, low out-of-band spectral emittance, epsilon(sub lambda) less than 0.2, suggest these materials would be excellent candidates for high efficiency selective emitters in thermophotovoltaic (TPV) systems operating at moderate temperatures (1200-1500 K). Spectral emittance measurements of the thin films were made (1.2 less than lambda less than 3.0 microns) and compared to the theoretical emittances calculated using measured values of the spectral extinction coefficient. In this paper we present the results for a new class of rare earth ion selective emitters. These emitters are thin sections (less than 1 mm) of yttrium aluminum garnet (YAG) single crystal with a rare earth substitutional impurity. Selective emitters in the near IR are of special interest for thermophotovoltaic (TPV) energy conversion. The most promising solid selective emitters for use in a TPV system are rare earth oxides. Early spectral emittance work on rare earth oxides showed strong emission bands in the infrared (0.9 - 3 microns). However, the emittance outside the emission band was also significant and the efficiency of these emitters was low. Recent improvements in efficiency have been made with emitters fabricated from fine (5 - 10 microns) rare earth oxide fibers similar to the Welsbach mantle used in gas lanterns. However, the rare earth garnet emitters are more rugged than the mantle type emitters. A thin film selective emitter on a low emissivity substrate such as gold, platinum etc., is rugged and easily adapted to a wide variety of thermal sources. The garnet structure and its many subgroups have been successfully used as hosts for rare earth ions, introduced as substitutional

  3. Dihydrogen addition in a dinuclear rare-earth metal hydride complex supported by a metalated TREN ligand.

    PubMed

    Venugopal, Ajay; Fegler, Waldemar; Spaniol, Thomas P; Maron, Laurent; Okuda, Jun

    2011-11-09

    The dinuclear lutetium dihydride dication supported by metalated tripodal ligands undergoes facile hydrogenolysis with H(2) to form a trihydride dication. Molecular orbital analysis shows that the LUMO is a bonding Lu···Lu orbital that is poised to activate dihydrogen.

  4. Stability constants of some metal complexes of triethylenetetraminehexa-acetic acid and complexometric titration of rare earths and other metals.

    PubMed

    Soucek, D A; Cheng, K L; Droll, H A

    1968-08-01

    The stability constants of some non-protonated 1:1 metal complexes of triethylenetetraminehexa-acetic acid are reported; log K values are Cd 19.8, Co(II) 20.4, Ni 19.9, Pb 19.5, Sm(III) 24.3, Zn 20.1.

  5. Antibacterial, Antifungal and Nematicidal Activities of Rare Earth Ions.

    PubMed

    Wakabayashi, Tokumitsu; Ymamoto, Ayumi; Kazaana, Akira; Nakano, Yuta; Nojiri, Yui; Kashiwazaki, Moeko

    2016-12-01

    Despite the name, rare earth elements are relatively abundant in soil. Therefore, these elements might interact with biosphere during the history of life. In this study, we have examined the effect of rare earth ions on the growth of bacteria, fungi and soil nematode. All rare earth ions, except radioactive promethium that we have not tested, showed antibacterial and antifungal activities comparable to that of copper ions, which is widely used as antibacterial metals in our daily life. Rare earth ions also have nematicidal activities as they strongly perturb the embryonic development of the nematode, Caenorhabditis elegans. Interestingly, the nematicidal activity increased with increasing atomic number of lanthanide ions. Since the rare earth ions did not show high toxicity to the human lymphoblastoid cell line or even stimulate the growth of the cultured cells at 1 mM, it raised the possibility that we can substitute rare earth elements for the antibacterial metals usually used because of their safety.

  6. Optimization of a Molten Salt Electrolytic Bath Geometry for Rare Earth Metal Recovery using a Finite Element Method

    NASA Astrophysics Data System (ADS)

    Numata, Hiroo; Akatsuka, Hiroshi; Matsuura, Haruaki

    2013-02-01

    For a recycling procedure for rare earths from spent hydrogen absorbing alloys by rare earths electrodeposition in a molten salt, the electrolytic bath and the cathode accessories have been optimized by evaluating the appropriate secondary current distribution using finite element method (FEM) computer simulation. The desirable cathode dish as an accessory was designed to prevent drops of less adherent electrodeposits, which improved the current density distribution compared with an a priori determined one. In the bath optimization, a reciprocal proportionality of the difference between the maximum and minimum current densities vs. the ratio of volume to surface area (or electrolyte volume) was found. It was found by FEM that if a resistive floating mass is assumed on the electrolyte surface, the observed necking in the electrodeposit near the electrolyte surface can be analyzed.

  7. Neutral ligand induced methane elimination from rare-earth metal tetramethylaluminates up to the six-coordinate carbide state.

    PubMed

    Venugopal, Ajay; Kamps, Ina; Bojer, Daniel; Berger, Raphael J F; Mix, Andreas; Willner, Alexander; Neumann, Beate; Stammler, Hans-Georg; Mitzel, Norbert W

    2009-08-07

    The reaction of 1,3,5-trimethyl-1,3,5-triazacyclohexane (TMTAC) with [La{Al(CH(3))(4)}(3)] resulted in C-H activation, leading to the formation of [(TMTAC)La{Al(CH(3))(4)}{(mu(3)-CH(2))[Al(CH(3))(2)(mu(2)-CH(3))](2)}] (1) containing a bis(aluminate) dianion and subsequent extrusion of methane. A similar reaction with [Y{Al(CH(3))(4)}(3)] led to the formation of CH(4), [TMTAC{Al(CH(3))(3)}(2)] (2) and {[(TMTAC)Y][Y(2)(mu(2)-CH(3))][{(mu(6)-C)[Al(mu(2)-CH(3))(2)(CH(3))](3)}{(mu(3)-CH(2))(mu(2)-CH(3))Al(CH(3))(2)}(2)] (3), containing a six-coordinate carbide ion and two [CH(2)Al(CH(3))(3)](2)(-) anions. Compound 3 is a product of multiple C-H activation. This reaction was monitored by in situ(1)H NMR spectroscopy. The analogous reaction with [Sm{Al(CH(3))(4)}(3)] led to the formation of 2, of [(TMTAC)Sm{(mu(2)-CH(3))(CH(3))(2)Al}(2){(mu(3)-CH(2))(2)Al(CH(3))(2)}(2)] (4), which contains a tris(aluminate) trianion, and [{(TMTAC)Sm}{Sm(2)(mu(2)-CH(3))}{(mu(6)-C)[Al(mu(2)-CH(3))(2)(CH(3))](3)}{(mu(3)-CH(2))(mu(2)-CH(3))Al(CH(3))(2)}(2)] (5), which is isostructural to 3. The products were characterised by elemental analyses (except 4, 5), 1 by multinuclear NMR spectroscopy and compounds 1, 2, 3, 4 and 5 by X-ray crystallography. Quantumchemical calculations were undertaken to support the crystallographic data analysis and confirm the structure of 3 and to compare it with an analogous compound where the central six-coordinate carbon has been replaced by oxygen. The investigations point to a mechanism of sterically induced condensation of [Al(CH(3))(4)](-) groups in close proximity in the coordination spheres of the rare-earth metal atoms, which is dependent on the size of these metal atoms.

  8. Novel Fiber Preforms: Rare Earth Doping.

    DTIC Science & Technology

    1987-03-31

    proposed by the group at Southampton, and future experiments with axial laser heating of terbium metal are planned. As noted, much of the effort during...been doped with terbium , in our learning to control the doping concentration, we have observed bands of undesired microcrystailinity in some terbium ...preforms with terbium (not yet pulled into fibers), and rare earth glasses formed by sol-gel tech- niques. Future efforts will be to prepare fibers

  9. Rare Earth Optical Temperature Sensor

    NASA Technical Reports Server (NTRS)

    Chubb, Donald L.; Wolford, David S.

    2000-01-01

    A new optical temperature sensor suitable for high temperatures (greater than 1700 K) and harsh environments is introduced. The key component of the sensor is the rare earth material contained at the end of a sensor that is in contact with the sample being measured. The measured narrow wavelength band emission from the rare earth is used to deduce the sample temperature. A simplified relation between the temperature and measured radiation was verified experimentally. The upper temperature limit of the sensor is determined by material limits to be approximately 2000 C. The lower limit, determined by the minimum detectable radiation, is found to be approximately 700 K. At high temperatures 1 K resolution is predicted. Also, millisecond response times are calculated.

  10. Heterobimetallic transition metal/rare earth metal bifunctional catalysis: a Cu/Sm/Schiff base complex for syn-selective catalytic asymmetric nitro-Mannich reaction.

    PubMed

    Handa, Shinya; Gnanadesikan, Vijay; Matsunaga, Shigeki; Shibasaki, Masakatsu

    2010-04-07

    The full details of a catalytic asymmetric syn-selective nitro-Mannich reaction promoted by heterobimetallic Cu/Sm/dinucleating Schiff base complexes are described, demonstrating the effectiveness of the heterobimetallic transition metal/rare earth metal bifunctional catalysis. The first-generation system prepared from Cu(OAc)(2)/Sm(O-iPr)(3)/Schiff base 1a = 1:1:1 with an achiral phenol additive was partially successful for achieving the syn-selective catalytic asymmetric nitro-Mannich reaction. The substrate scope and limitations of the first-generation system remained problematic. After mechanistic studies on the catalyst prepared from Sm(O-iPr)(3), we reoptimized the catalyst preparation method, and a catalyst derived from Sm(5)O(O-iPr)(13) showed broader substrate generality as well as higher reactivity and stereoselectivity compared to Sm(O-iPr)(3). The optimal system with Sm(5)O(O-iPr)(13) was applicable to various aromatic, heteroaromatic, and isomerizable aliphatic N-Boc imines, giving products in 66-99% ee and syn/anti = >20:1-13:1. Catalytic asymmetric synthesis of nemonapride is also demonstrated using the catalyst derived from Sm(5)O(O-iPr)(13).

  11. Water-free rare-earth-metal ionic liquids/ionic liquid crystals based on hexanitratolanthanate(III) anion.

    PubMed

    Ji, Shun-Ping; Tang, Meng; He, Ling; Tao, Guo-Hong

    2013-04-02

    The hexanitratolanthanate anion (La(NO(3))(6)(3-)) is an interesting symmetric anion suitable to construct the component of water-free rare-earth-metal ionic liquids. The syntheses and structural characterization of eleven lanthanum nitrate complexes, [C(n)mim](3)[La(NO(3))(6)] (n=1, 2, 4, 6, 8, 12, 14, 16, 18), including 1,3-dimethylimidazolium hexanitratolanthanate ([C(1)mim](3)[La(NO(3))(6)], 1), 1-ethyl-3-methylimidazolium hexanitratolanthanate ([C(2)mim](3)[La(NO(3))(6)], 2), 1-butyl-3-methylimidazolium hexanitratolanthanate ([C(4)mim](3)[La(NO(3))(6)], 3), 1-isobutyl-3-methylimidazolium hexanetratolanthanate ([isoC(4)mim](3)[La(NO(3))(6)], 4), 1-methyl-3-(3'-methylbutyl)imidazolium hexanitratolanthanate ([MC(4)mim](3)[La(NO(3))(6)], 5), 1-hexyl-3-methylimidazolium hexanitratolanthanate ([C(6)mim](3)[La(NO(3))(6)], 6), 1-methyl-3-octylimidazolium hexanitratolanthanate ([C(8)mim](3)[La(NO(3))(6)], 7), 1-dodecyl-3-methylimidazolium hexanitratolanthanate ([C(12)mim](3)[La(NO(3))(6)], 8), 1-methyl-3-tetradecylimidazolium hexanitratolanthanate ([C(14)mim](3)[La-(NO(3))(6)], 9), 1-hexadecyl-3-methylimid-azolium hexanitratolanthanum ([C(16)dmim](3)[La(NO(3))(6)], 10), and 1-methyl-3-octadecylimidazolium hexanitratolanthanate ([C(18)mim](3)[La(NO(3))(6)], 11) are reported. All new compounds were characterized by (1)H and (13)C NMR, and IR spectroscopy as well as elemental analysis. The crystal structure of compound 1 was determined by using single-crystal X-ray diffraction, giving the following crystallographic information: monoclinic; P2(1)/c; a=15.3170 (3), b=14.2340 (2), c=13.8954(2) Å; β=94.3453(15)°, V=3020.80(9) Å(3), Z=4, ρ=1.764 g cm(-3). The coordination polyhedron around the lanthanum ion is rationalized by six nitrate anions with twelve oxygen atoms. No hydrogen-bonding network or water molecule was found in 1. The thermodynamic stability of the new complexes was investigated by using thermogravimetric analysis (TGA). The water

  12. Laboratory calibration and field testing of the Chemcatcher-Metal for trace levels of rare earth elements in estuarine waters.

    PubMed

    Petersen, Jördis; Pröfrock, Daniel; Paschke, Albrecht; Broekaert, Jose A C; Prange, Andreas

    2015-10-01

    Little knowledge is available about water concentrations of rare earth elements (REEs) in the marine environment. The direct measurement of REEs in coastal waters is a challenging task due to their ultra-low concentrations as well as the high salt content in the water samples. To quantify these elements at environmental concentrations (pg L(-1) to low ng L(-1)) in coastal waters, current analytical techniques are generally expensive and time consuming, and require complex chemical preconcentration procedures. Therefore, an integrative passive sampler was tested as a more economic alternative sampling approach for REE analysis. We used a Chemcatcher-Metal passive sampler consisting of a 3M Empore Chelating Disk as the receiving phase, as well as a cellulose acetate membrane as the diffusion-limiting layer. The effect of water turbulence and temperature on the uptake rates of REEs was analyzed during 14-day calibration experiments by a flow-through exposure tank system. The sampling rates were in the range of 0.42 mL h(-1) (13 °C; 0.25 m s(-1)) to 4.01 mL h(-1) (13 °C; 1 m s(-1)). Similar results were obtained for the different REEs under investigation. The water turbulence was the most important influence on uptake. The uptake rates were appropriate to ascertain time-weighted average concentrations of REEs during a field experiment in the Elbe Estuary near Cuxhaven Harbor (exposure time 4 weeks). REE concentrations were determined to be in the range 0.2 to 13.8 ng L(-1), where the highest concentrations were found for neodymium and samarium. In comparison, most of the spot samples measured along the Chemcatcher samples had REE concentrations below the limit of detection, in particular due to necessary dilution to minimize the analytical problems that arise with the high salt content in marine water samples. This study was among the first efforts to measure REE levels in the field using a passive sampling approach. Our results suggest that passive samplers could be

  13. Potency of (doped) rare earth oxide particles and their constituent metals to inhibit algal growth and induce direct toxic effects.

    PubMed

    Joonas, Elise; Aruoja, Villem; Olli, Kalle; Syvertsen-Wiig, Guttorm; Vija, Heiki; Kahru, Anne

    2017-03-27

    Use of rare earth elements (REEs) has increased rapidly in recent decades due to technological advances. It has been accompanied by recurring rare earth element anomalies in water bodies. In this work we (i) studied the effects of eight novel doped and one non-doped rare earth oxide (REO) particles (aimed to be used in solid oxide fuel cells and gas separation membranes) on algae, (ii) quantified the individual adverse effects of the elements that constitute the (doped) REO particles and (iii) attempted to find a discernible pattern to relate REO particle physicochemical characteristics to algal growth inhibitory properties. Green algae Raphidocelis subcapitata (formerly Pseudokirchneriella subcapitata) were used as a test species in two different formats: a standard OECD201 algal growth inhibition assay and the algal viability assay (a 'spot test') that avoids nutrient removal effects. In the 24h 'spot' test that demonstrated direct toxicity, algae were not viable at REE concentrations above 1mgmetal/L. 72-hour algal growth inhibition EC50 values for four REE salts (Ce, Gd, La, Pr) were between 1.2 and 1.4mg/L, whereas the EC50 for REO particles ranged from 1 to 98mg/L. The growth inhibition of REEs was presumably the result of nutrient sequestration from the algal growth medium. The adverse effects of REO particles were at least in part due to the entrapment of algae within particle agglomerates. Adverse effects due to the dissolution of constituent elements from (doped) REO particles and the size or specific surface area of particles were excluded, except for La2NiO4. However, the structure of the particles and/or the varying effects of oxide composition might have played a role in the observed effects. As the production rates of these REO particles are negligible compared to other forms of REEs, there is presumably no acute risk for aquatic unicellular algae.

  14. Scarcity of rare earth elements.

    PubMed

    de Boer, M A; Lammertsma, K

    2013-11-01

    Rare earth elements (REEs) are important for green and a large variety of high-tech technologies and are, therefore, in high demand. As a result, supply with REEs is likely to be disrupted (the degree of depends on the REE) in the near future. The 17 REEs are divided into heavy and light REEs. Other critical elements besides REEs, identified by the European Commission, are also becoming less easily available. Although there is no deficiency in the earth's crust of rare earth oxides, the economic accessibility is limited. The increased demand for REEs, the decreasing export from China, and geopolitical concerns on availability contributed to the (re)opening of mines in Australia and the USA and other mines are slow to follow. As a result, short supply of particularly terbium, dysprosium, praseodymium, and neodymium is expected to be problematic for at least the short term, also because they cannot be substituted. Recycling REEs from electronic waste would be a solution, but so far there are hardly any established REE recycling methods. Decreasing the dependency on REEs, for example, by identifying possible replacements or increasing their efficient use, represents another possibility.

  15. Anthropogenic Cycles of Rare Earth Elements

    NASA Astrophysics Data System (ADS)

    Du, X.; Graedel, T. E.

    2009-12-01

    This research will develop quantitatively resolved anthropogenic cycles and in-use stocks for the rare earth metals specifically cerium, lanthanum and dysprosium in Japan, China, and the U.S. for the year of 2007. Rare earth elements (REE) is a group of 17 scare metals widely used in a growing number of emerging technologies and have been in high demand for emerging technologies as raw materials during past the three decades. New market participants from newly industrializing countries, primarily China, have had strong impacts on the demand of share. Consequently, the importance to sustain a reliable, steady, uninterrupted supply on global market triggered comprehensive research to recognize and understand the life cycles of rare earths. Moreover, because China plays a dominant role in mining production since 1990, it requires the assessment for the countries, which are almost completely dependent on imports from China with respect to rare earth resources. The study aims to analyze the flows and stocks of rare earth elements individually as elemental form in spite of their natural geological co-occurrence and mixed composition in applications. By applying the method of Material Flow Analysis (MFA) work has been done on evaluating current and historical flows of specific technologically significant materials, for example, copper, zinc, nickel, etc., determining the stocks available in different types of reservoirs (e.g., lithosphere, in-use) and the flows among the reservoirs, developing scenarios of possible futures of metal use, and assessing the environmental and policy implications of the results. Therefore, REE as a new target deserves inclusion because of its potential demand-supply conflict and importance to secure the competitive advantage of technical innovation in future. This work will generate a quantitatively resolved anthropogenic life cycle and in-use stocks for REE for the main target countries for a chosen year, 2007, providing flows and stocks from

  16. Rare earth metal bis(amide) complexes bearing amidinate ancillary ligands: synthesis, characterization, and performance as catalyst precursors for cis-1,4 selective polymerization of isoprene.

    PubMed

    Luo, Yunjie; Fan, Shimin; Yang, Jianping; Fang, Jianghua; Xu, Ping

    2011-03-28

    A family of rare earth metal bis(amide) complexes bearing monoanionic amidinate [RC(N-2,6-Me(2)C(6)H(3))(2)](-) (R = cyclohexyl (Cy), phenyl (Ph)) as ancillary ligands were synthesized and characterized. One-pot salt metathesis reaction of anhydrous LnCl(3) with one equivalent of amidinate lithium [RC(N-2,6-Me(2)C(6)H(3))(2)]Li, following the introduction of two equivalents of NaN(SiMe(3))(2) in THF at room temperature afforded the neutral and unsolvated mono(amidinate) rare earth metal bis(amide) complexes [RC(N-2,6-Me(2)C(6)H(3))(2)]Y[N(SiMe(3))(2)](2) (R = Cy (1); R = Ph (2)), and the "ate" mono(amidinate) rare earth metal bis(amide) complex [CyC(N-2,6-Me(2)C(6)H(3))(2)]Lu[N(SiMe(3))(2)](2)(μ-Cl)Li(THF)(3) (3) in 61-72% isolated yields. These complexes were characterized by elemental analysis, NMR spectroscopy, FT-IR spectroscopy, and X-ray single crystal diffraction. Single crystal structural determination revealed that the central metal in complexes 1 and 2 adopts a distorted tetrahedral geometry, and in complex 3 forms a distorted trigonal bipyramidal geometry. In the presence of AlMe(3), and in combination with one equimolar amount of [Ph(3)C][B(C(6)F(5))(4)], complexes 1 and 2 showed high activity towards isoprene polymerization to give high molecular weight polyisoprene (M(n) > 10(4)) with good cis-1,4 selectivity (>90%).

  17. Rare earths, the lanthanides, yttrium and scandium

    USGS Publications Warehouse

    Hedrick, J.B.

    2006-01-01

    In 2005, rare earths were not mined in the United States. The major supplier, Molycorp, continued to maintain a large stockpile of rare-earth concentrates and compounds. Consumption decreased of refined rare-earth products. The United States remained a major importer and exporter of rare earths in 2005. During the same period, yttrium was not mined or refined in the US. Hence, supply of yttrium compounds for refined yttrium products came from China, France and Japan. Scandium was not also mined. World production was primarily in China, Russia and Ukraine. Demand for rare earths in 2006 is expected to be closely tied to economic conditions in the US.

  18. Replacing the Rare Earth Intellectual Capital

    SciTech Connect

    Gschneidner, Jr., Karl

    2011-04-01

    The rare earth crisis slowly evolved during a 10 to 15 year period beginning in the mid-1980s, when the Chinese began to export mixed rare earth concentrates. In the early 1990s, they started to move up the supply chain and began to export the individual rare earth oxides and metals. By the late 1990s the Chinese exported higher value products, such as magnets, phosphors, polishing compounds, catalysts; and in the 21st century they supplied finished products including electric motors, computers, batteries, liquid-crystal displays (LCDs), TVs and monitors, mobile phones, iPods and compact fluorescent lamp (CFL) light bulbs. As they moved to higher value products, the Chinese slowly drove the various industrial producers and commercial enterprises in the US, Europe and Japan out of business by manipulating the rare earth commodity prices. Because of this, the technically trained rare earth engineers and scientists who worked in areas from mining to separations, to processing to production, to manufacturing of semifinished and final products, were laid-off and moved to other fields or they retired. However, in the past year the Chinese have changed their philosophy of the 1970s and 1980s of forming a rare earth cartel to control the rare earth markets to one in which they will no longer supply the rest of the world (ROW) with their precious rare earths, but instead will use them internally to meet the growing demand as the Chinese standard of living increases. To this end, they have implemented and occasionally increased export restrictions and added an export tariff on many of the high demand rare earth elements. Now the ROW is quickly trying to start up rare earth mines, e.g. Molycorp Minerals in the US and Lynas Corp. in Australia, to cover this shortfall in the worldwide market, but it will take about five years for the supply to meet the demand, even as other mines in the ROW become productive. Unfortunately, today there is a serious lack of technically trained

  19. Rare earth garnet selective emitter

    NASA Technical Reports Server (NTRS)

    Lowe, Roland A.; Chubb, Donald L.; Farmer, Serene C.; Good, Brian S.

    1994-01-01

    Thin film Ho-YAG and Er-YAG emitters with a platinum substrate exhibit high spectral emittance in the emission band (epsilon(sub lambda) approximately equal to 0.74, ((4)l(sub 15/2)) - ( (4)l(sub13/2)), for Er-YAG and epsilon(sub lambda) approximately equal to 0.65, ((5)l(sub 7))-((5)l(sub 8)) for Ho-YAG) at excellent candidates for high efficiency selective emitters in the thermophotovoltaics (TPV) systems operating at moderate temperatures (1200-1500K). Spectral emittance measurements of the thin films were made (1.2 less than lambda less than 3.0 microns) and compared to the theoretical emittances calculated using measured values of the spectral extinction coefficient. In this paper we present the results for a new class of rare earth ion selective emitters. These emitters are thin sections (less than 1 mm) of yttrium aluminum garnet (YAG) single crystal with a rare earth substitutional impurity. This paper presents normal spectral emittance, epsilon(sub lambda), measurements of holmium (Ho), and erbium (Er) doped YAG thin film selective emitters at 1500 K, and compares those results with the theoretical spectral emittance.

  20. Rare earth elements: end use and recyclability

    USGS Publications Warehouse

    Goonan, Thomas G.

    2011-01-01

    Rare earth elements are used in mature markets (such as catalysts, glassmaking, lighting, and metallurgy), which account for 59 percent of the total worldwide consumption of rare earth elements, and in newer, high-growth markets (such as battery alloys, ceramics, and permanent magnets), which account for 41 percent of the total worldwide consumption of rare earth elements. In mature market segments, lanthanum and cerium constitute about 80 percent of rare earth elements used, and in new market segments, dysprosium, neodymium, and praseodymium account for about 85 percent of rare earth elements used. Regardless of the end use, rare earth elements are not recycled in large quantities, but could be if recycling became mandated or very high prices of rare earth elements made recycling feasible.

  1. Rare Earth Element Mines, Deposits, and Occurrences

    USGS Publications Warehouse

    Orris, Greta J.; Grauch, Richard I.

    2002-01-01

    Data on rare earth (including yttrium) mines, deposits, and occurrences were compiled as part of an effort by the USGS and the University of Arizona Center for Mineral Resources to summarize current knowledge on the supply and demand outlook and related topics for this group of elements. Economic competition and environmental concerns are increasingly constraining the mining and processing of rare earths from the Mountain Pass mine in California. For many years, the deposit at Mountain Pass was the world's dominant source of rare earth elements and the United States was essentially self-sufficient. Starting approximately 10 years ago, the U.S. has become increasingly dependent (> 90 percent of separated rare earths) upon imports from China, now the dominant source of rare earths. A knowledge of the known economic and noneconomic sources of rare earths is basic to evaluating the outlook for rare earth supply and associated issues.

  2. Biosorption of metal and salt tolerant microbial isolates from a former uranium mining area. Their impact on changes in rare earth element patterns in acid mine drainage.

    PubMed

    Haferburg, Götz; Merten, Dirk; Büchel, Georg; Kothe, Erika

    2007-12-01

    The concentration of metals in microbial habitats influenced by mining operations can reach enormous values. Worldwide, much emphasis is placed on the research of resistance and biosorptive capacities of microorganisms suitable for bioremediation purposes. Using a collection of isolates from a former uranium mining area in Eastern Thuringia, Germany, this study presents three Gram-positive bacterial strains with distinct metal tolerances. These strains were identified as members of the genera Bacillus, Micrococcus and Streptomyces. Acid mine drainage (AMD) originating from the same mining area is characterized by high metal concentrations of a broad range of elements and a very low pH. AMD was analyzed and used as incubation solution. The sorption of rare earth elements (REE), aluminum, cobalt, copper, manganese, nickel, strontium, and uranium through selected strains was studied during a time course of four weeks. Biosorption was investigated after one hour, one week and four weeks by analyzing the concentrations of metals in supernatant and biomass. Additionally, dead biomass was investigated after four weeks of incubation. The maximum of metal removal was reached after one week. Up to 80% of both Al and Cu, and more than 60% of U was shown to be removed from the solution. High concentrations of metals could be bound to the biomass, as for example 2.2 mg/g U. The strains could survive four weeks of incubation. Distinct and different patterns of rare earth elements of the inoculated and non-inoculated AMD water were observed. Changes in REE patterns hint at different binding types of heavy metals regarding incubation time and metabolic activity of the cells.

  3. Rare-earth metal complexes stabilized by amino-phosphine ligand. Reaction with mesityl azide and catalysis of the cycloaddition of organic azides and aromatic alkynes.

    PubMed

    Liu, Bo; Cui, Dongmei

    2009-01-21

    Stoichiometric reactions between mesityl azide (MesN3, Mes = 2,4,6-C6H2Me3) and amino-phosphine ligated rare-earth metal alkyl, LLn(CH2SiMe3)2(THF) (L = (2,6-C6H3Me2)NCH2C6H4P(C6H5)2; Ln = Lu (1a), Sc (1b)), amide, LLu(NH(2,6-C6H3iPr2))2(THF) (2) and acetylide at room temperature gave the amino-phosphazide ligated rare-earth metal bis(triazenyl) complexes, [L(MesN3)]Ln[(MesN3)(CH2SiMe3)]2 (Ln = Lu (3a); Sc (3b)), bis(amido) complex [L(MesN3)]Lu[NH(2,6-C6H3iPr2)]2 (4), and bis(alkynyl) complex (5) (L(MesN3)Lu (C[triple bond, length as m-dash]CPh)2)2, respectively. The triazenyl group in coordinates to the metal ion in a rare eta2-mode via N(beta) and N(gamma) atoms, generating a triangular metallocycle. The amino-phosphazide ligand, L(MesN3), in , and chelates to the metal ion in a eta3-mode via N(alpha) and N(gamma) atoms. In the presence of excess phenylacetylene, complex isomerized to , where the triazenyl group coordinates to the metal ion in a eta3 mode via N(alpha) and N(gamma) atoms. Complexes , , and have shown an unprecedented catalytic activity towards the cycloaddition of organic azides and aromatic alkynes to afford 1,5-disubstituted 1,2,3-triazoles selectively.

  4. Dehydrogenation of secondary amines: synthesis, and characterization of rare-earth metal complexes incorporating imino- or amido-functionalized pyrrolyl ligands.

    PubMed

    Li, Qinghai; Zhou, Shuangliu; Wang, Shaowu; Zhu, Xiancui; Zhang, Lijun; Feng, Zhijun; Guo, Liping; Wang, Fenhua; Wei, Yun

    2013-02-28

    The dehydrogenation of pyrrolyl-functionalized secondary amines initiated by rare-earth metal amides was systematically studied. Reactions of the rare-earth metal amides [(Me(3)Si)(2)N](3)RE(μ-Cl)Li(THF)(3) with pyrrolyl-functionalized secondary amines 2-(t)BuNHCH(2)-5-R-C(4)H(2)NH (R = H (1), R = (t)Bu (2)) led to dehydrogenation of the secondary amines with isolation of imino-functionalized pyrrolyl rare-earth metal complexes [2-(t)BuN=CH-5-R-C(4)H(2)N](2)REN(SiMe(3))(2) (R = H, RE = Y (3a), Dy (3b), Yb (3c), Eu (3d); R = (t)Bu, RE = Y (4a), Dy (4b), Er (4c)). The mixed ligands erbium complex [2-(t)BuNCH(2)-5-(t)Bu-C(4)H(2)N]Er[2-(t)BuN=CH-5-(t)BuC(4)H(2)N](2)ClLi(2)(THF) (4c') was isolated in a short reaction time for the synthesis of complex 4c. Reaction of the deuterated pyrrolyl-functionalized secondary amine 2-((t)BuNHCHD)C(4)H(3)NH with yttrium amide [(Me(3)Si)(2)N](3)Y(μ-Cl)Li(THF)(3) further proved that pyrrolyl-amino ligands were transferred to pyrrolyl-imino ligands. Treatment of 2-((t)BuNHCH(2))C(4)H(3)NH (1) with excess (Me(3)Si)(2)NLi gave the only pyrrole deprotonated product {[η(5):η(2):η(1)-2-((t)BuNHCH(2))C(4)H(3)N]Li(2)N(SiMe(3))(2)}(2) (5), indicating that LiN(SiMe(3))(2) could not dehydrogenate the secondary amines to imines and rare-earth metal ions had a decisive effect on the dehydrogenation. The reaction of the rare-earth metal amides [(Me(3)Si)(2)N](3)RE(μ-Cl)Li(THF)(3) with 1 equiv. of more bulky pyrrolyl-functionalized secondary amine 2-[(2,6-(i)Pr(2)C(6)H(3))NHCH(2)](C(4)H(3)NH) (6) in toluene afforded the only amine and pyrrole deprotonated dinuclear rare-earth metal amido complexes {(μ-η(5):η(1)):η(1)-2-[(2,6-(i)Pr(2)C(6)H(3))NCH(2)]C(4)H(3)N]LnN(SiMe(3))(2)}(2) (RE = Nd (7a), Sm (7b), Er (7c)), no dehydrogenation of secondary amine to imine products were observed. On the basis of experimental results, a plausible mechanism for the dehydrogenation of secondary amines to imines was proposed.

  5. Material efficiency: rare and critical metals.

    PubMed

    Ayres, Robert U; Peiró, Laura Talens

    2013-03-13

    In the last few decades, progress in electronics, especially, has resulted in important new uses for a number of geologically rare metals, some of which were mere curiosities in the past. Most of them are not mined for their own sake (gold, the platinum group metals and the rare Earth elements are exceptions) but are found mainly in the ores of the major industrial metals, such as aluminium, copper, zinc and nickel. We call these major metals 'attractors' and the rare accompanying metals 'hitch-hikers'. The key implication is that rising prices do not necessarily call forth greater output because that would normally require greater output of the attractor metal. We trace the geological relationships and the functional uses of these metals. Some of these metals appear to be irreplaceable in the sense that there are no known substitutes for them in their current functional uses. Recycling is going to be increasingly important, notwithstanding a number of barriers.

  6. Synthesis and characterization of anionic rare-earth metal amides stabilized by phenoxy-amido ligands and their catalytic behavior for the polymerization of lactide.

    PubMed

    Lu, Min; Yao, Yingming; Zhang, Yong; Shen, Qi

    2010-10-28

    A dianionic phenoxyamido ligand was the first to be used to stabilize organo-rare-earth metal amido complexes. Amine elimination reaction of Nd[N(TMS)(2)](3)(μ-Cl)Li(THF)(3) (TMS = SiMe(3)) with aminophenol [HNOH] {[HNOH] = N-p-methylphenyl(2-hydroxy-3,5-di-tert-butyl)benzylamine} in a 1 : 1 molar-ratio gave the anionic phenoxyamido neodymium amide [NO](2)Nd[N(TMS)(2)][Li(THF)](2) (2) in a low isolated yield. A further study revealed that the stoichiometric reactions of Ln[N(TMS)(2)](3)(μ-Cl)Li(THF)(3) with the lithium aminophenoxy [HNOLi(THF)](2) (1) in tetrahydrofuran (THF) gave the anionic rare-earth metal amido complexes [NO](2)Ln[N(TMS)(2)][Li(THF)](2) [Ln = Nd (2), Sm (3), Yb (4), Y (5)] in high isolated yields. All of these complexes are fully characterized. X-Ray structure determination revealed that complex 1 has a solvated dimeric structure, and complexes 2-5 are isostructural, and have solvated monomeric structures. Each of the rare-earth metal ions is coordinated by two oxygen atoms and two nitrogen atoms from two phenoxyamido ligands and one nitrogen atom from the N(TMS)(2) group to form a distorted trigonal bipyramidal geometry. Each of the lithium atoms in complexes 2-5 is coordinated with one oxygen atom and one nitrogen atom from two different phenoxyamido groups, and one oxygen atom from one THF molecule to form a trigonal planar geometry. Furthermore, the catalytic behavior of complexes 2-5 for the ring-opening polymerization of l-lactide was explored.

  7. Highly efficient stabilisation of meta-ethynylpyridine polymers with amide side chains in water by coordination of rare-earth metals.

    PubMed

    Makida, Hiroki; Abe, Hajime; Inouye, Masahiko

    2015-02-14

    An amphiphilic meta-ethynylpyridine polymer with chiral amide side chains was developed. The polymer was prepared by sequential Sonogashira reactions, and the product was soluble in polar and apolar solvents. The additive effects of metal salts on the polymer were examined in water and aqueous EtOH on the basis of UV-vis and CD spectra. The enhancement of the positive Cotton effect and hypochromism around 360 nm occurred by the addition of various metal salts, indicating the coordination of the cations to the amide side chains of the polymer to stabilise the helical structure. Among them, rare-earth metal salts, especially Sc(OTf)3 showed more efficient additive effects probably because of its strong coordination ability even in water. Positive cooperativity was observed for the coordination of Sc(OTf)3 to the polymer in aqueous EtOH.

  8. Synthesis and Characterization of Alkaline-Earth Metal (Ca, Sr, and Ba) Doped Nanodimensional LaMnO3 Rare-Earth Manganites

    NASA Astrophysics Data System (ADS)

    Asma, Khalid; Saadat, Anwar Siddiqi; Affia, Aslam

    2013-07-01

    The substitution of divalent cations of alkaline-earth elements in nanodimensional structures of rare-earth manganites produces advanced materials with potential electrical and magnetic functionalities. A systematic investigation of La0.65A0.35MnO3 (A = Ca, Sr, Ba) materials synthesized with a modified citrate route adopting ethanol dehydration has been undertaken. The structural and morphological analyses are carried out by using x-ray diffraction and scanning electron microscopy, respectively. Resistivity measurements are performed in variation with temperature to study the electrical transport properties which are found to vary with the size of the A-site cationic radius. Room temperature magnetic measurements are carried out to investigate the type of magnetic phase present in materials. The stability of the magnetic phase and coercivity are found to be dependent on the size of nanocrystallites.

  9. Phase characteristics of rare earth elements in metallic fuel for a sodium-cooled fast reactor by injection casting

    NASA Astrophysics Data System (ADS)

    Kuk, Seoung Woo; Kim, Ki Hwan; Kim, Jong Hwan; Song, Hoon; Oh, Seok Jin; Park, Jeong-Yong; Lee, Chan Bock; Youn, Young-Sang; Kim, Jong-Yun

    2017-04-01

    Uranium-zirconium-rare earth (U-Zr-RE) fuel slugs for a sodium-cooled fast reactor were manufactured using a modified injection casting method, and investigated with respect to their uniformity, distribution, composition, and phase behavior according to RE content. Nd, Ce, Pr, and La were chosen as four representative lanthanide elements because they are considered to be major RE components of fuel ingots after pyroprocessing. Immiscible layers were found on the top layers of the melt-residue commensurate with higher fuel slug RE content. Scanning electron microscopy-energy-dispersive X-ray spectroscopy (SEM-EDS) data showed that RE elements in the melt-residue were distributed uniformly throughout the fuel slugs. RE element agglomeration did not contaminate the fuel slugs but strongly affected the RE content of the slugs.

  10. Quantitative moment study and coupling of 4 f rare earth and 3 d metal by transmitted electrons

    NASA Astrophysics Data System (ADS)

    Fu, X.; Warot-Fonrose, B.; Arras, R.; Dumesnil, K.; Serin, V.

    2016-10-01

    We report a simultaneous investigation of 3 d and 4 f magnetic moments by exploring the Fe -L2 ,3 and Dy -M4 ,5 electron energy-loss edges of a DyF e2/YF e2 superlattice using the energy-loss magnetic chiral dichroism (EMCD) technique. Specific EMCD sum rules for M4 ,5 edges were established and carefully applied to the dichroic signal at Dy -M4 ,5 edges, giving an orbital to the effective spin moment ratio of 5.1 ±1.8 . With dynamic diffraction effects considered, the opposite signs of Fe -L3 and Dy -M5 dichroic peaks unambiguously indicate the antiparallel alignment of net Fe 3 d and Dy 4 f moments. The EMCD technique is shown to be an effective tool to locally characterize the 4 f moment of rare earth elements and study 3 d -4 f moment coupling.

  11. Synthesis and Characterization of Organo-Rare-Earth Metal Monoalkyl Complexes Supported by Carbon σ-Bonded Indolyl Ligands: High Specific Isoprene 1,4-Cis Polymerization Catalysts.

    PubMed

    Guo, Liping; Zhu, Xiancui; Zhang, Guangchao; Wei, Yun; Ning, Lixin; Zhou, Shuangliu; Feng, Zhijun; Wang, Shaowu; Mu, Xiaolong; Chen, Jun; Jiang, Yuzhe

    2015-06-15

    A series of N-protected 3-imino-functionalized indolyl ligands 1-R-3-(R'N═CH)C8H5N [R = Bn, R' = 2,6-(i)Pr2C6H3 (HL(1)); R = CH3, R' = 2,6-(i)Pr2C6H3 (HL(2)); R = Bn, R' = (t)Bu (HL(3))] and 1-CH3-2-(2,6-(i)Pr2C6H3N═CH)C8H5N (HL(4)) was prepared via reactions of N-protected indolyl aldehydes with corresponding amines. The C-H σ-bond metathesis followed by alkane elimination reactions between RE(CH2SiMe3)3(thf)2 and HL(1)-HL(3) afforded the carbon σ-bonded indolyl-ligated rare-earth metal monoalkyl complexes. Reactions of RE(CH2SiMe3)3(thf)2 with 2 equiv of HL(1) or HL(2) gave the carbon σ-bonded indolyl-ligated rare-earth metal monoalkyl complexes L(1)2RECH2SiMe3 (RE = Y(1), Er(2), Dy(3)) and L(2)2RECH2SiMe3 (RE = Y(5), Er(6), Dy(7), Yb(8)), while reaction of Yb(CH2SiMe3)3(thf)2 with 2 equiv of HL(1) afforded the ytterbium dialkyl complex L(1)Yb(CH2SiMe3)2(thf)2 (4). Reactions of RE(CH2SiMe3)3(thf)2 with HL(3) gave the tris(heteroaryl) rare-earth metal complexes L(3)3RE (RE = Y(9), Er(10)). In the presence of cocatalysts, the rare-earth metal monoalkyl complexes initiated isoprene polymerization with a high activity (90% conversion of 1000 equiv of isoprene in 25 min) producing polymers with high regio- and stereoselectivity (1,4-cis polymers up to 99%).

  12. Laminated rare earth structure and method of making

    DOEpatents

    Senor, David J [West Richland, WA; Johnson, Roger N [Richland, WA; Reid, Bruce D [Pasco, WA; Larson, Sandra [Richland, WA

    2002-07-30

    A laminated structure having two or more layers, wherein at least one layer is a metal substrate and at least one other layer is a coating comprising at least one rare earth element. For structures having more than two layers, the coating and metal substrate layers alternate. In one embodiment of the invention, the structure is a two-layer laminate having a rare earth coating electrospark deposited onto a metal substrate. In another embodiment of the invention, the structure is a three-layer laminate having the rare earth coating electrospark deposited onto a first metal substrate and the coating subsequently abonded to a second metal substrate. The bonding of the coating to the second metal substrate may be accomplished by hot pressing, hot rolling, high deformation rate processing, or combinations thereof. The laminated structure may be used in nuclear components where reactivity control or neutron absorption is desired and in non-nuclear applications such as magnetic and superconducting films.

  13. Ground-state oxygen holes and the metal-insulator transition in the negative charge-transfer rare-earth nickelates

    NASA Astrophysics Data System (ADS)

    Bisogni, Valentina; Catalano, Sara; Green, Robert J.; Gibert, Marta; Scherwitzl, Raoul; Huang, Yaobo; Strocov, Vladimir N.; Zubko, Pavlo; Balandeh, Shadi; Triscone, Jean-Marc; Sawatzky, George; Schmitt, Thorsten

    2016-10-01

    The metal-insulator transition and the intriguing physical properties of rare-earth perovskite nickelates have attracted considerable attention in recent years. Nonetheless, a complete understanding of these materials remains elusive. Here we combine X-ray absorption and resonant inelastic X-ray scattering (RIXS) spectroscopies to resolve important aspects of the complex electronic structure of rare-earth nickelates, taking NdNiO3 thin film as representative example. The unusual coexistence of bound and continuum excitations observed in the RIXS spectra provides strong evidence for abundant oxygen holes in the ground state of these materials. Using cluster calculations and Anderson impurity model interpretation, we show that distinct spectral signatures arise from a Ni 3d8 configuration along with holes in the oxygen 2p valence band, confirming suggestions that these materials do not obey a conventional positive charge-transfer picture, but instead exhibit a negative charge-transfer energy in line with recent models interpreting the metal-insulator transition in terms of bond disproportionation.

  14. Levels of rare earth elements, heavy metals and uranium in a population living in Baiyun Obo, Inner Mongolia, China: a pilot study.

    PubMed

    Hao, Zhe; Li, Yonghua; Li, Hairong; Wei, Binggan; Liao, Xiaoyong; Liang, Tao; Yu, Jiangping

    2015-06-01

    The Baiyun Obo deposit is the world's largest rare earth elements (REE) deposit. We aimed to investigate levels of REE, heavy metals (HMs) and uranium (U) based on morning urine samples in a population in Baiyun Obo and to assess the possible influence of rare earth mining processes on human exposure. In the mining area, elevated levels were found for the sum of the concentrations of light REE (LREE) and heavy REE (HREE) with mean values at 3.453 and 1.151 μg g(-1) creatinine, which were significantly higher than those in the control area. Concentrations of HMs and U in the population increased concomitantly with increasing REE levels. The results revealed that besides REE, HMs and U were produced with REE exploitation. Gender, age, educational level, alcohol and smoking habit were major factors contributing to inter-individual variation. Males were more exposed to these metals than females. Concentrations in people in the senior age group and those with only primary education were low. Drinking and smoking were associated with the levels of LREE, Cr, Cu, Cd and Pb in morning urine. Hence this study provides basic and useful information when addressing public and environmental health challenges in the areas where REE are mined and processed.

  15. Ground-state oxygen holes and the metal-insulator transition in the negative charge-transfer rare-earth nickelates.

    PubMed

    Bisogni, Valentina; Catalano, Sara; Green, Robert J; Gibert, Marta; Scherwitzl, Raoul; Huang, Yaobo; Strocov, Vladimir N; Zubko, Pavlo; Balandeh, Shadi; Triscone, Jean-Marc; Sawatzky, George; Schmitt, Thorsten

    2016-10-11

    The metal-insulator transition and the intriguing physical properties of rare-earth perovskite nickelates have attracted considerable attention in recent years. Nonetheless, a complete understanding of these materials remains elusive. Here we combine X-ray absorption and resonant inelastic X-ray scattering (RIXS) spectroscopies to resolve important aspects of the complex electronic structure of rare-earth nickelates, taking NdNiO3 thin film as representative example. The unusual coexistence of bound and continuum excitations observed in the RIXS spectra provides strong evidence for abundant oxygen holes in the ground state of these materials. Using cluster calculations and Anderson impurity model interpretation, we show that distinct spectral signatures arise from a Ni 3d(8) configuration along with holes in the oxygen 2p valence band, confirming suggestions that these materials do not obey a conventional positive charge-transfer picture, but instead exhibit a negative charge-transfer energy in line with recent models interpreting the metal-insulator transition in terms of bond disproportionation.

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

    SciTech Connect

    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{sup 1}P←a{sup 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 (<130 cm{sup −1}). All of the M ⋅ RG diatomics have bond lengths considerably longer than those of the 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 Sr{sub 2} while this transition is quenched in Ba{sub 2}. This behaviour is consistent with the absence of vibrational structure on the dimer absorption band in Ba{sub 2} 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.

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

    PubMed

    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 (<130 cm(-1)). All of the M ⋅ RG diatomics have bond lengths considerably longer than those of the 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.

  18. Cysteine-Functionalized Chitosan Magnetic Nano-Based Particles for the Recovery of Light and Heavy Rare Earth Metals: Uptake Kinetics and Sorption Isotherms

    PubMed Central

    Galhoum, Ahmed A.; Mafhouz, Mohammad G.; Abdel-Rehem, Sayed T.; Gomaa, Nabawia A.; Atia, Asem A.; Vincent, Thierry; Guibal, Eric

    2015-01-01

    Cysteine-functionalized chitosan magnetic nano-based particles were synthesized for the sorption of light and heavy rare earth (RE) metal ions (La(III), Nd(III) and Yb(III)). The structural, surface, and magnetic properties of nano-sized sorbent were investigated by elemental analysis, FTIR, XRD, TEM and VSM (vibrating sample magnetometry). Experimental data show that the pseudo second-order rate equation fits the kinetic profiles well, while sorption isotherms are described by the Langmuir model. Thermodynamic constants (ΔG°, ΔH°) demonstrate the spontaneous and endothermic nature of sorption. Yb(III) (heavy RE) was selectively sorbed while light RE metal ions La(III) and Nd(III) were concentrated/enriched in the solution. Cationic species RE(III) in aqueous solution can be adsorbed by the combination of chelating and anion-exchange mechanisms. The sorbent can be efficiently regenerated using acidified thiourea. PMID:28347004

  19. Cysteine-Functionalized Chitosan Magnetic Nano-Based Particles for the Recovery of Light and Heavy Rare Earth Metals: Uptake Kinetics and Sorption Isotherms.

    PubMed

    Galhoum, Ahmed A; Mafhouz, Mohammad G; Abdel-Rehem, Sayed T; Gomaa, Nabawia A; Atia, Asem A; Vincent, Thierry; Guibal, Eric

    2015-02-04

    Cysteine-functionalized chitosan magnetic nano-based particles were synthesized for the sorption of light and heavy rare earth (RE) metal ions (La(III), Nd(III) and Yb(III)). The structural, surface, and magnetic properties of nano-sized sorbent were investigated by elemental analysis, FTIR, XRD, TEM and VSM (vibrating sample magnetometry). Experimental data show that the pseudo second-order rate equation fits the kinetic profiles well, while sorption isotherms are described by the Langmuir model. Thermodynamic constants (ΔG°, ΔH°) demonstrate the spontaneous and endothermic nature of sorption. Yb(III) (heavy RE) was selectively sorbed while light RE metal ions La(III) and Nd(III) were concentrated/enriched in the solution. Cationic species RE(III) in aqueous solution can be adsorbed by the combination of chelating and anion-exchange mechanisms. The sorbent can be efficiently regenerated using acidified thiourea.

  20. Controlled synthesis of racemic indenyl rare-earth metal complexes via the cooperation between the intramolecular coordination of donor atoms and a bridge.

    PubMed

    Zhou, Shuangliu; Wu, Zhangshuan; Zhou, Lingmin; Wang, Shaowu; Zhang, Lijun; Zhu, Xiancui; Wei, Yun; Zhai, Jinhua; Wu, Jie

    2013-06-03

    The reactions of Me2Si(C9H6CH2CH2-DG)2 (DG = NMe2 (1), CH2NMe2 (2), OMe (3), and N(CH2CH2)2O (4)) with [(Me3Si)2N]3RE(μ-Cl)Li(THF)3 in toluene afforded a series of racemic divalent rare-earth metal complexes: {η(5):η(1):η(5):η(1)-Me2Si(C9H5CH2CH2-DG)2}RE (DG = NMe2, RE = Yb (6) and Eu (7); DG = CH2NMe2, RE = Yb (8), Eu (9), and Sm (10); DG = OMe, RE = Yb (11) and Eu (12); DG = N(CH2CH2)2O, RE = Yb (13) and Eu (14)). Similarly, the racemic divalent rare-earth metal complexes {η(5):η(1):η(5):η(1)-Me2Si(C9H5CH2CH2CH2NMe2)(C9H5CH2CH2OMe)}RE (RE = Yb (15) and Eu (16)) were also obtained. The reaction of Me2Si(C9H5CH2CH2OMe)2Li2 with NdCl3 gave a racemic dimeric neodymium chloride {η(5):η(1):η(5)-Me2Si(C9H5CH2CH2OMe)2NdCl}2 (17), whereas the reaction of Me2Si(C9H5CH2CH2NMe2)2Li2 with SmCl3 afforded a racemic dinuclear samarium chloride bridged by lithium chloride {η(5):η(1):η(5):η(1)-Me2Si(C9H5CH2CH2NMe2)2SmCl}2(μ-LiCl) (18). Further reaction of complex 18 with LiCH2SiMe3 provided an unexpected rare-earth metal alkyl complex {η(5):η(1):η(5):η(1):σ-Me2Si(C9H5CH2CH2NMe2)[(C9H5CH2CH2N(CH2)Me]}Sm (19) through the activation of an sp(3) C-H bond α-adjacent to the nitrogen atom. Complexes 19 and {η(5):η(1):η(5):η(1):σ-Me2Si(C9H5CH2CH2NMe2)[(C9H5CH2CH2N(CH2)Me]}Y (20) were also obtained by one-pot reactions of Me2Si(C9H5CH2CH2NMe2)2Li2 with RECl3 followed by treatment with LiCH2SiMe3. All compounds were fully characterized by spectroscopic methods and elemental analysis. Complexes 6-10 and 14-20 were further characterized by single-crystal X-ray diffraction analysis. All of the prepared rare-earth metal complexes were racemic, suggesting that racemic organo rare-earth metal complexes could be controllably synthesized by the cooperation between a bridge and the intramolecular coordination of donor atoms.

  1. Recent developments of rare-earth-free hard-magnetic materials

    NASA Astrophysics Data System (ADS)

    Li, Da; Pan, DeSheng; Li, ShaoJie; Zhang, ZhiDong

    2016-01-01

    Recent advances in rare-earth-free hard-magnetic materials including magnetic bulk, thin films, nanocomposites and nanostructures are introduced. Since the costs of the rare-earth metals boosts up the price of the high-performance rare-earth permanent magnets, there is a much revived interest in various types of hard-magnetic materials based on rare-earth-free compounds. The 3d transition metals and their alloys with large coercivity and high Curie temperatures (working temperatures) are expected to overcome the disadvantages of rare-earth magnets. Making rare-earth-free magnets with a large energy product to meet tomorrow's energy needs is still a challenge.

  2. Effect of rare earth metal Ce addition to Sn-Ag solder on interfacial reactions with Cu substrate

    NASA Astrophysics Data System (ADS)

    Yoon, Jeong-Won; Noh, Bo-In; Jung, Seung-Boo

    2014-05-01

    The effect of adding a small amount of rare earth cerium (Ce) element to low Ag containing Sn-1wt%Ag Pb-free solder on its interfacial reactions with Cu substrate was investigated. The growth of intermetallic compounds (IMCs) between three Sn-1Ag-xCe solders with different Ce contents and a Cu substrate was studied and the results were compared to those obtained for the Ce-free Sn-1Ag/Cu systems. In the solid-state reactions of the Sn-1Ag(-xCe)/Cu solder joints, the two IMC layers, Cu6Sn5 and Cu3Sn, grew as aging time increased. Compared to the Sn-1Ag/Cu joint, the growth of the Cu6Sn5 and Cu3Sn layers was depressed for the Ce-containing Sn-1Ag-xCe/Cu joint. The addition of Ce to the Sn-Ag solder reduced the growth of the interfacial Cu-Sn IMCs and prevented the IMCs from spalling from the interface. The evenly-distributed Ce elements in the solder region blocked the diffusion of Sn atoms to the interface and retarded the growth of the interfacial IMC layer.

  3. Research into processes of production of hydrides of materials containing rare-earth metals and their corrosion

    NASA Astrophysics Data System (ADS)

    Sofronov, V. L.; Kartashov, E. Y.; Molokov, P. B.; Zhiganov, A. N.; Kalaev, M. E.

    2017-01-01

    Production of permanent magnets on basis of rare earth elements (REE) is implemented by means of powder metallurgy, therefore a technologically important operation is the multistage mechanical crushing of materials to the extent of domains. The promising technique of crushing of magnetic materials is their consistent hydrogenation-dehydrogenation that allows obtaining nano-dispersed powders which are stable enough in air. Hydrogenation apparatuses, as opposed to conventional grinding machines, do not comprise motion works and their producing capacity is much higher. Hydrogenation process does not require any additional preparation of materials and it excludes undermilling and overmilling as well as material oxidation. The paper presents the results of investigation on the temperature effect on the hydrogenation process of Nd-Fe alloys. The study results on the corrosion stability of ligature hydrides under various conditions are also given. Kinetic parameters of the hydrogenation process of ligatures are determined. The phase composition of corrosion products is detected. Guidelines on hydride powder storage are given.

  4. Metals and Rare Earth Elements in polar aerosol as specific markers of natural and anthropogenic aerosol sources areas and atmospheric transport processes

    NASA Astrophysics Data System (ADS)

    Giardi, Fabio; Becagli, Silvia; Caiazzo, Laura; Cappelletti, David; Grotti, Marco; Malandrino, Mery; Salzano, Roberto; Severi, Mirko; Traversi, Rita; Udisti, Roberto

    2016-04-01

    Metals and Rare Earth Elements (REEs) in the aerosol have conservative properties from the formation to the deposition and can be useful to identify and quantify their natural and anthropic sources and to study the atmospheric transport processes. In spite of their importance relatively little is known about metals and especially REEs in the Artic atmosphere due to their low concentration in such environment. The present work reports the first attempt to determine and interpret the behaviour of metals and REEs in polar aerosol at high temporal resolution. Daily PM10 samples of arctic atmospheric particulate were collected on Teflon filters, during six spring-summer campaigns, since 2010, in the laboratory of Gruvebadet in Ny Ålesund (78°56' N, 11°56' E, Svalbard Islands, Norway). Chemical analyses were carried out through Inductively Coupled Plasma Mass Spectrometer provided with a desolvation nebulizer inlet system, allowing to reduce isobaric interferences and thus to quantify trace and ultra-trace metals in very low concentration in the Arctic aerosol samples. The results are useful in order to study sources areas, transport processes and depositional effects of natural and anthropic atmospheric particulate reaching the Arctic from southern industrialized areas; moreover, the observed seasonal trends give information about the different impact of natural and anthropic emissions driven by phenomena such as the Arctic Haze and the melting of the snow. In particular Rare Earth Elements (often in the ppt range) can be considered as soil's fingerprints of the particulate source areas and their determination, together with air-mass backtrajectory analysis, allow to identify dust source areas for the arctic mineral aerosol.

  5. Rare-earth metal bis(alkyl)s that bear a 2-pyridinemethanamine ligand: dual catalysis of the polymerizations of both isoprene and ethylene.

    PubMed

    Jian, Zhongbao; Cui, Dongmei

    2012-02-28

    New pyridinemethanamido-ligated rare-earth metal bis(alkyl) complexes [C(5)H(4)N-CH(Me)-NC(6)H(3)((i)Pr)(2)]Ln(CH(2)SiMe(3))(2)(THF) (Ln = Sc (1), Y (2), Lu (3)) have been prepared at 0 °C via a protonolysis reaction between rare-earth metal tris(alkyl)s and the corresponding 2-pyridinemethanamine ligand and fully characterized by NMR and X-ray diffraction analysis. Bis(alkyl) complexes 1-3 are analogous monomers of THF solvate, where the ligand bonds to the metal center in a κN:κN-bidentate mode. Complexes 1-3, in combination with [Ph(3)C][B(C(6)F(5))(4)], showed a good activity towards isoprene polymerization to give polyisoprene with a main 3,4-selectivity (60%-66%); in particular the yttrium catalyst system, 2/[Ph(3)C][B(C(6)F(5))(4)], displayed a living mode. By contrast, only the precatalyst 2 exhibited activity for isoprene polymerization in the presence of [PhNMe(2)H][B(C(6)F(5))(4)]. The influence of alkylaluminium (AlR(3), R = Me, Et, (i)Bu) and the metal center on the polymerization of isoprene was also studied, and it was found that addition of AlMe(3) to the catalyst systems could lead to a dramatic change in the microstructure of the polymer from 3,4-specific to 1,4-selective (89%-95%), but the ionic radius of the central metal had little influence on the selectivity. In addition, by using the 1(Sc)/[Ph(3)C][B(C(6)F(5))(4)]/10 Al(i)Bu(3), the polymerization of ethylene was also achieved with moderate activity (up to 3.2× 10(5) g (PE) mol(Sc)(-1) h(-1) bar(-1)) and narrow polydispersity (M(w)/M(n) = 1.19-1.28); while the effect of temperature on the activity was discussed. Such dual catalysis for the polymerizations of both isoprene and ethylene is rare.

  6. Ames Lab 101: Rare-Earth Recycling

    ScienceCinema

    Ryan Ott

    2016-07-12

    Recycling keeps paper, plastics, and even jeans out of landfills. Could recycling rare-earth magnets do the same? Perhaps, if the recycling process can be improved. Scientists at the U.S. Department of Energy's Ames Laboratory are working to more effectively remove the neodymium, a rare earth, from the mix of other materials in a magnet.

  7. Ames Lab 101: Rare-Earth Recycling

    SciTech Connect

    Ryan Ott

    2012-09-05

    Recycling keeps paper, plastics, and even jeans out of landfills. Could recycling rare-earth magnets do the same? Perhaps, if the recycling process can be improved. Scientists at the U.S. Department of Energy's Ames Laboratory are working to more effectively remove the neodymium, a rare earth, from the mix of other materials in a magnet.

  8. Ternary rare earth-lanthanide sulfides

    DOEpatents

    Takeshita, Takuo; Gschneidner JR., Karl A.; Beaudry, Bernard J.

    1987-01-06

    A new ternary rare earth sulfur compound having the formula: where M is a rare earth element selected from the group europium, samarium and ytterbium and x=0.15 to 0.8. The compound has good high-temperature thermoelectric properties and exhibits long-term structural stability up to 1000.degree. C.

  9. The Rare Earth Magnet Industry and Rare Earth Price in China

    NASA Astrophysics Data System (ADS)

    Ding, Kaihong

    2014-07-01

    In the past four years, the price of rare earth metal fluctuates sharply for many reasons. Currently, it has become more stable and more reasonable. This presentation is focused on the effect about the rare earth metal price. Some motor manufacturers have shifted from rare earth permanent magnet to ferrite magnet. Many motor manufacturers changed the design for the motor cooling system to make the motor function at a lower temperature. Thus the consumption of Dy can be markedly reduced. As for manufacturer of NdFeB magnet, we are also trying to optimize our process to reduce to dependence of HREE such as Dy and Tb. HS process have been introduced to solve the problem. With more and more people focusing and engaging on the REE industry, the price of REE will be more transparent without too many fluctuations. China is considering the problems of balancing the environment, energy sources, and labor sources. The application field about NdFeB such as wind turbine generator, HEV/EV, FA /OA is flourishing.

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

    SciTech Connect

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

    2007-04-15

    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.

  11. Di and trinuclear rare-earth metal complexes supported by 3-amido appended indolyl ligands: synthesis, characterization and catalytic activity towards isoprene 1,4-cis polymerization.

    PubMed

    Zhang, Guangchao; Deng, Baojia; Wang, Shaowu; Wei, Yun; Zhou, Shuangliu; Zhu, Xiancui; Huang, Zeming; Mu, Xiaolong

    2016-10-21

    Different di and trinuclear rare-earth metal complexes supported by 3-amido appended indolyl ligands were synthesized and their catalytic activities towards isoprene polymerization were investigated. Treatment of [RE(CH2SiMe3)3(thf)2] with 1 equiv. of 3-(CyN[double bond, length as m-dash]CH)C8H5NH in toluene or in THF afforded dinuclear rare-earth metal alkyl complexes having indolyl ligands in different hapticities with central metals {[η(2):η(1)-μ-η(1)-3-(CyNCH(CH2SiMe3))Ind]RE-(thf)(CH2SiMe3)}2 (Cy = cyclohexyl, Ind = Indolyl, RE = Yb (1), Er (2), Y (3)) or {[η(1)-μ-η(1)-3-(CyNCH(CH2SiMe3))Ind]RE-(thf)2(CH2SiMe3)}2 (RE = Yb (4), Er (5), Y (6), Gd (7)), respectively. These two series of dinuclear complexes could be transferred to each other easily by only changing the solvents in the process. Reaction of [Er(CH2SiMe3)3(thf)2] with 1 equiv. of 3-t-butylaminomethylindole 3-((t)BuNHCH2)C8H5NH in THF afforded the unexpected trinuclear erbium alkyl complex [η(2):η(1)-μ-η(1)-3-((t)BuNCH2)Ind]4Er3(thf)5(CH2SiMe3) (8), which can also be prepared by reaction of 3 equiv. of [Er(CH2SiMe3)3(thf)2] with 4 equiv. of 3-((t)BuNHCH2)C8H5NH in THF. Accordingly, complexes [η(2):η(1)-μ-η(1)-3-((t)BuNCH2)Ind]4RE3(thf)5(CH2SiMe3) (RE = Y (9), Dy (10)) were prepared by reactions of 3 equiv. of [RE(CH2SiMe3)3(thf)2] with 4 equiv. of 3-((t)BuNHCH2)C8H5NH in THF. Reactions of [RE(CH2SiMe3)3(thf)2] with 1 equiv. of 3-t-butylaminomethylindole 3-((t)BuNHCH2)C8H5NH in THF, followed by treatment with 1 equiv. of [(2,6-(i)Pr2C6H3)N[double bond, length as m-dash]CHNH(C6H3(i)Pr2-2,6)] afforded, after workup, the dinuclear rare-earth metal complexes [η(1)-μ-η(1):η(1)-3-((t)BuNCH2)Ind][η(1)-μ-η(1):η(3)-3-((t)BuNCH2)Ind]RE2(thf)[(η(3)-2,6-(i)Pr2C6H3)NCHN(C6H3(i)Pr2-2,6)]2(RE = Er (11), Y (12)) having the indolyl ligands bonded with the rare-earth metal in different ligations. All new complexes 1-12 were fully characterized by spectroscopic methods and elemental analyses, and

  12. Biosorption and desorption of lanthanum(III) and neodymium(III) in fixed-bed columns with Sargassum sp.: perspectives for separation of rare earth metals.

    PubMed

    Oliveira, Robson C; Guibal, Eric; Garcia, Oswaldo

    2012-01-01

    Rare earth (RE) metals are essentials for the manufacturing of high-technology products. The separation of RE is complex and expensive; biosorption is an alternative to conventional processes. This work focuses on the biosorption of monocomponent and bicomponent solutions of lanthanum(III) and neodymium(III) in fixed-bed columns using Sargassum sp. biomass. The desorption of metals with HCl 0.10 mol L(-1) from loaded biomass is also carried out with the objective of increasing the efficiency of metal separation. Simple models have been successfully used to model breakthrough curves (i.e., Thomas, Bohart-Adams, and Yoon-Nelson equations) for the biosorption of monocomponent solutions. From biosorption and desorption experiments in both monocomponent and bicomponent solutions, a slight selectivity of the biomass for Nd(III) over La(III) is observed. The experiments did not find an effective separation of the RE studied, but their results indicate a possible partition between the metals, which is the fundamental condition for separation perspectives.

  13. Features and regularities in behavior of thermoelectric properties of rare-earth, transition, and other metals under high pressure up to 20 GPa

    SciTech Connect

    Morozova, Natalia V.; Shchennikov, Vladimir V.; Ovsyannikov, Sergey V. E-mail: sergey2503@gmail.com

    2015-12-14

    We report results of systematic investigations of the thermoelectric properties of a number of rare-earth metals, transition metals, and other metals under high pressure up to 20 GPa at room temperature. We studied an effect of applied pressure on the Seebeck effect of scandium (Sc), yttrium (Y), lanthanum (La), europium (Eu), ytterbium (Yb), iron (Fe), manganese (Mn), chromium (Cr), gold (Au), tin (Sn), and CeNi alloy. We found that the high-pressure behavior of the thermopower of three rare-earth metals, namely, Sc, Y, and La, follows a general trend that has been established earlier in lanthanides, and addressed to a s → d electron transfer. Europium and ytterbium, on the contrary, showed a peculiar high-pressure behavior of the thermopower with peaks at near 0.7–1 GPa for Eu and 1.7–2.5 GPa for Yb. Chromium, manganese, and tin demonstrated a gradual and pronounced lowering of the absolute value of the thermopower with pressure. Above 9–11 GPa, the Seebeck coefficients of Mn and Sn were inverted, from n- to p-type for Mn and from p- to n-type for Sn. The Seebeck effect in iron was rather high as ∼16 μV/K and weakly varied with pressure up to ∼11 GPa. Above ∼11 GPa, it started to drop dramatically with pressure to highest pressure achieved 18 GPa. Upon decompression cycle the thermopower of iron returned to the original high values but demonstrated a wide hysteresis loop. We related this behavior in iron to the known bcc (α-Fe) → hcp (ε-Fe) phase transition, and proposed that the thermoelectricity of the α-Fe phase is mainly contributed by the spin Seebeck effect, likewise, the thermoelectricity of the ε-Fe phase—by the conventional diffusion thermopower. We compare the pressure dependencies of the thermopower for different groups of metals and figure out some general trends in the thermoelectricity of metals under applied stress.

  14. On-line collection/concentration and determination of transition and rare-earth metals in water samples using Multi-Auto-Pret system coupled with inductively coupled plasma-atomic emission spectrometry.

    PubMed

    Katarina, Rosi Ketrin; Oshima, Mitsuko; Motomizu, Shoji

    2009-05-15

    On-line preconcentration and determination of transition and rare-earth metals in water samples was performed using a Multi-Auto-Pret system coupled with inductively coupled plasma-atomic emission spectrometry (ICP-AES). The Multi-Auto-Pret AES system proposed here consists of three Auto-Pret systems with mini-columns that can be used for the preconcentration of trace metals sequentially or simultaneously, and can reduce analysis time to one-third and running cost of argon gas and labor. A newly synthesized chelating resin, ethylenediamine-N,N,N'-triacetate-type chitosan (EDTriA-type chitosan), was employed in the Multi-Auto-Pret system for the collection of trace metals prior to their measurement by ICP-AES. The proposed resin showed very good adsorption ability for transition and rare-earth metal ions without any interference from alkali and alkaline-earth metal ions in an acidic media. For the best result, pH 5 was adopted for the collection of metal ions. Only 5 mL of samples could be used for the determination of transition metals, while 20 mL of samples was necessary for the determination of rare-earth metals. Metal ions adsorbed on the resin were eluted using 1.5 M nitric acid, and were measured by ICP-AES. The proposed method was evaluated by the analysis of SLRS-4 river water reference materials for trace metals. Good agreement with certified and reference values was obtained for most of the metals examined; it indicates that the proposed method using the newly synthesized resin could be favorably used for the determination of transition and rare-earth metals in water samples by ICP-AES.

  15. Ground states of an Ising model on an extended Shastry-Sutherland lattice and the 1/2-magnetization plateau in some rare-earth-metal tetraborides.

    PubMed

    Dublenych, Yu I

    2013-08-01

    A complete solution of the ground-state problem for an Ising model on the Shastry-Sutherland lattice with an additional interaction along the diagonals of "empty" squares in an applied magnetic field is presented. A rigorous proof is given that this interaction gives rise to a plateau at one-half of the saturation magnetization. Such a fractional plateau has been observed in some rare-earth-metal tetraborides, in particular in strong Ising magnets ErB(4) (where it is the only one) and TmB(4) (where it is the broadest one), but its origin has remained unclear. Our study sheds new light on the solution of this problem.

  16. Research progress on polyoxometalate-based transition-metal-rare-earth heterometallic derived materials: synthetic strategies, structural overview and functional applications.

    PubMed

    Zhao, Jun-Wei; Li, Yan-Zhou; Chen, Li-Juan; Yang, Guo-Yu

    2016-03-25

    With the rapid development of science and technology and the trend of multidisciplinary pervasion, POM-based TM-RE heterometallic chemistry (POM = polyoxometalate, TM = transition-metal, RE = rare-earth) has become one of the most rapidly growing and challengeable areas of inorganic chemistry due to the impressive structural diversities, various chemical compositions and potential applications of these materials in magnetism, optics, electrochemistry, electrocatalysis and materials science. Over the past several years, continuous interest and persisting efforts have been dedicated to the preparation and exploration of POM-based TM-RE heterometallic derived materials (PTRHDMs), which have led to more than two hundred PTRHDMs. In this review, we summarize the structural types of reported PTRHDMs together with synthetic strategies, structural motifs and relevant functional applications. The exciting array of this emerging research theme presages continuous growth and great vitality. In the last section, some prospects of this branch are also presented and possible guidance for future work is outlined.

  17. Universal behavior of chalcogenides of rare-earth metals in the transition to a state with intermediate valence at high pressures

    SciTech Connect

    Tsiok, O. B.; Khvostantsev, L. G.; Brazhkin, V. V.

    2015-06-15

    Precision measurements of resistivity, thermopower, and volume are performed for TmS, TmSe, and TmTe under a hydrostatic pressure up to 8 GPa. Comparison of the transport properties and volume of TmTe and SmTe in the valence transition region demonstrates a complete analogy up to quantitative coincidence. It is shown that the thermopower of all thulium and samarium chalcogenides in the lattice collapse region and in subsequent rearrangement of the electron spectrum in a wide range of pressures follow a universal dependence corresponding the passage of the Fermi level through the peak of the density of states (DOS). The results are considered in the context of ideas about the exciton nature of the intermediate valence in chalcogenides of rare-earth metals.

  18. Purification of rare-earth metals as the approach to improving properties of hard magnetic Nd2Fe14B-based materials

    NASA Astrophysics Data System (ADS)

    Kolchugina, N. B.; Burkhanov, G. S.; Dormidontov, A. G.; Lukin, A. A.; Koshkid'ko, Yu S.; Skotnicová, K.; Drulis, H.; Smetana, B.

    2016-01-01

    Purification of rare-earth metals, namely, Nd, Pr, Tb, Dy used in manufacturing Nd2Fe14B-based magnets was realized. The metals were purified by vacuum distillation/sublimation. Conditions of the process were optimized and the structure of distilled metals was studied. Distilled terbium and dysprosium were used to prepare hydrides TbH2 and DyH2. Peculiarities of the decomposition of terbium and dysprosium hydrides were studied with the view of the use of the compounds as efficient additions, which allow the high- coercivity state of sintered magnets to be formed. Terbium hydride additions (to 4 wt %) favor the marked increase in the magnetization coercive force without excessive attenuation of the remanence (j H c = 1940 kA/m, (BH max) = 292 kJ/m3). Dysprosium hydride additions increase the stability of high-coercivity state (j H c = 1310 kA/m, (BH max) = 322 kJ/m3 at 2 wt% DyH2).

  19. Novel Fiber Preforms: Rare Earth Doping.

    DTIC Science & Technology

    1988-01-21

    measurements were made on a Digilab FTS-15B as KBr While there are many complex multicomponent rare pellets from 3800-4(0cm and as low density poivethvene...earth glasses, phosphates hold special interest as binary pellets t50-500cm ). Spectral resolution was 2 cm- cr rare earth glasses of variable composition...SiO- the glasses have compositions in the range x = 0.009 to 0052. w.hich corresponds to 0.9 to 5.2 molo or up to 23 wt% rare earth oxide as determruned

  20. Improved Rare-Earth Emitter Hollow Cathode

    NASA Technical Reports Server (NTRS)

    Goebel, Dan M.

    2011-01-01

    An improvement has been made to the design of the hollow cathode geometry that was created for the rare-earth electron emitter described in Compact Rare Earth Emitter Hollow Cathode (NPO-44923), NASA Tech Briefs, Vol. 34, No. 3 (March 2010), p. 52. The original interior assembly was made entirely of graphite in order to be compatible with the LaB6 material, which cannot be touched by metals during operation due to boron diffusion causing embrittlement issues in high-temperature refractory materials. Also, the graphite tube was difficult to machine and was subject to vibration-induced fracturing. This innovation replaces the graphite tube with one made out of refractory metal that is relatively easy to manufacture. The cathode support tube is made of molybdenum or molybdenum-rhenium. This material is easily gun-bored to near the tolerances required, and finish machined with steps at each end that capture the orifice plate and the mounting flange. This provides the manufacturability and robustness needed for flight applications, and eliminates the need for expensive e-beam welding used in prior cathodes. The LaB6 insert is protected from direct contact with the refractory metal tube by thin, graphite sleeves in a cup-arrangement around the ends of the insert. The sleeves, insert, and orifice plate are held in place by a ceramic spacer and tungsten spring inserted inside the tube. To heat the cathode, an insulating tube is slipped around the refractory metal hollow tube, which can be made of high-temperature materials like boron nitride or aluminum nitride. A screw-shaped slot, or series of slots, is machined in the outside of the ceramic tube to constrain a refractory metal wire wound inside the slot that is used as the heater. The screw slot can hold a single heater wire that is then connected to the front of the cathode tube by tack-welding to complete the electrical circuit, or it can be a double slot that takes a bifilar wound heater with both leads coming out

  1. Protecting the environment and public health from rare earth mining

    NASA Astrophysics Data System (ADS)

    Huang, Xiang; Zhang, Guochun; Pan, An; Chen, Fengying; Zheng, Chunli

    2016-11-01

    As increasing demand for green energy and high-tech devices grows, so does the rising prospecting of rare earth metals required for their production. Protecting the environment and public health from rare earth element (REE) mining as well as emerging pollutants is urgently required to achieve sustainable development. This study mapped Earth's hidden REE deposits to identify potential contamination hotspots with the aim of preventing its deleterious effects on the environment. We worry that there would be widespread tailing facilities concomitant with serious pollutions, such as the Bayan Obo tailings site, and argue that a tradeoff between the underground REE exploration and environment conservation should be reached as soon as possible.

  2. Tuning bad metal and non-Fermi liquid behavior in a Mott material: Rare-earth nickelate thin films.

    PubMed

    Mikheev, Evgeny; Hauser, Adam J; Himmetoglu, Burak; Moreno, Nelson E; Janotti, Anderson; Van de Walle, Chris G; Stemmer, Susanne

    2015-11-01

    Resistances that exceed the Mott-Ioffe-Regel limit (known as bad metal behavior) and non-Fermi liquid behavior are ubiquitous features of the normal state of many strongly correlated materials. We establish the conditions that lead to bad metal and non-Fermi liquid phases in NdNiO3, which exhibits a prototype bandwidth-controlled metal-insulator transition. We show that resistance saturation is determined by the magnitude of Ni eg orbital splitting, which can be tuned by strain in epitaxial films, causing the appearance of bad metal behavior under certain conditions. The results shed light on the nature of a crossover to a non-Fermi liquid metal phase and provide a predictive criterion for Anderson localization. They elucidate a seemingly complex phase behavior as a function of film strain and confinement and provide guidelines for orbital engineering and novel devices.

  3. Tuning bad metal and non-Fermi liquid behavior in a Mott material: Rare-earth nickelate thin films

    PubMed Central

    Mikheev, Evgeny; Hauser, Adam J.; Himmetoglu, Burak; Moreno, Nelson E.; Janotti, Anderson; Van de Walle, Chris G.; Stemmer, Susanne

    2015-01-01

    Resistances that exceed the Mott-Ioffe-Regel limit (known as bad metal behavior) and non-Fermi liquid behavior are ubiquitous features of the normal state of many strongly correlated materials. We establish the conditions that lead to bad metal and non-Fermi liquid phases in NdNiO3, which exhibits a prototype bandwidth-controlled metal-insulator transition. We show that resistance saturation is determined by the magnitude of Ni eg orbital splitting, which can be tuned by strain in epitaxial films, causing the appearance of bad metal behavior under certain conditions. The results shed light on the nature of a crossover to a non-Fermi liquid metal phase and provide a predictive criterion for Anderson localization. They elucidate a seemingly complex phase behavior as a function of film strain and confinement and provide guidelines for orbital engineering and novel devices. PMID:26601140

  4. Ternary rare earth-lanthanide sulfides

    DOEpatents

    Takeshita, Takuo; Gschneidner, Jr., Karl A.; Beaudry, Bernard J.

    1987-01-06

    A new ternary rare earth sulfur compound having the formula: La.sub.3-x M.sub.x S.sub.4 where M is a rare earth element selected from the group europium, samarium and ytterbium and x=0.15 to 0.8. The compound has good high-temperature thermoelectric properties and exhibits long-term structural stability up to 1000.degree. C.

  5. High mobilization of arsenic, metals and rare earth elements in seepage waters driven by respiration of old allochthonous organic carbon.

    PubMed

    Weiske, Arndt; Schaller, Jörg; Hegewald, Tilo; Machill, Susanne; Werner, Ingo; Dudel, E Gert

    2013-12-01

    Metal and metalloid mobilization processes within seepage water are of major concern in a range of water reservoir systems. The mobilization process of arsenic and heavy metals within a dam and sediments of a drinking water reservoir was investigated. Principle component analysis (PCA) on time series data of seepage water showed a clear positive correlation of arsenic with iron and DOC (dissolved organic carbon), and a negative correlation with nitrate due to respiratory processes. A relationship of reductive metal and metalloid mobilization with respiration of old carbon was shown. The system is influenced by sediment layers as well as a recent DOC input from degraded ombrotrophic peatbogs in the catchment area. The isotopic composition ((12)C, (13)C and (14)C) of DOC is altered along the path from basin to seepage water, but no significant changes in structural parameters (LC-OCD-OND, FT-IR) could be seen. DIC (dissolved inorganic carbon) in seepage water partly originates from respiratory processes, and a higher relationship of it with sediment carbon than with the DOC inventory of infiltrating water was found. This study revealed the interaction of respiratory processes with metal and metalloid mobilization in sediment water flows. In contrast to the presumption that emerging DOC via respiratory processes mainly controls arsenic and metal mobilization it could be shown that the presence of aged carbon compounds is essential. The findings emphasize the importance of aged organic carbon for DOC, DIC, arsenic and metal turnover.

  6. Charge disproportionation without charge transfer in the rare-earth nickelates as a possible mechanism for the metal-insulator transition

    NASA Astrophysics Data System (ADS)

    Johnston, Steven; Mukherjee, Anamitra; Elfimov, Ilya; Berciu, Mona; Sawatzky, George

    2014-03-01

    We study a model for the metal-insulator (MI) transition in the rare-earth nickelates RNiO3, based upon a negative charge transfer energy and coupling to a rock-salt like lattice distortion of the NiO6 octahedra. Using exact diagonalization and the Hartree-Fock approximation we demonstrate that electrons couple strongly to these distortions. For small distortions the system is metallic, with ground state of predominantly d8 ligand character, where ligand denotes a ligand hole. For sufficiently large distortions (δdNi - O ~ 0 . 05 - 0 . 10 Å), however, a gap opens at the Fermi energy as the system enters a periodically distorted state alternating along the three crystallographic axes, with (d8 ligand2) S = 0(d8) S = 1 character, where S is the total spin. Thus the MI transition may be viewed as being driven by an internal volume ``collapse'' where the NiO6 octahedra with two ligand holes shrink around their central Ni, while the remaining octahedra expand accordingly, resulting in the superstructure observed in x-ray diffraction in the insulating phase. This insulating state is an example of charge ordering achieved without any actual movement of the charge, similar to that reported in a prior DMFT study.

  7. Charge Disproportionation without Charge Transfer in the Rare-Earth-Element Nickelates as a Possible Mechanism for the Metal-Insulator Transition

    NASA Astrophysics Data System (ADS)

    Johnston, Steve; Mukherjee, Anamitra; Elfimov, Ilya; Berciu, Mona; Sawatzky, George A.

    2014-03-01

    We study a model for the metal-insulator (M-I) transition in the rare-earth-element nickelates RNiO3, based upon a negative charge transfer energy and coupling to a rocksaltlike lattice distortion of the NiO6 octahedra. Using exact diagonalization and the Hartree-Fock approximation we demonstrate that electrons couple strongly to these distortions. For small distortions the system is metallic, with a ground state of predominantly d8L character, where L_ denotes a ligand hole. For sufficiently large distortions (δdNi-O˜0.05-0.10 Å), however, a gap opens at the Fermi energy as the system enters a periodically distorted state alternating along the three crystallographic axes, with (d8L_2)S =0(d8)S=1 character, where S is the total spin. Thus the M-I transition may be viewed as being driven by an internal volume "collapse" where the NiO6 octahedra with two ligand holes shrink around their central Ni, while the remaining octahedra expand accordingly, resulting in the (1/2, 1/2, 1/2) superstructure observed in x-ray diffraction in the insulating phase. This insulating state is an example of charge ordering achieved without any actual movement of the charge.

  8. Current Status on Resource and Recycling Technology for Rare Earths

    NASA Astrophysics Data System (ADS)

    Takeda, Osamu; Okabe, Toru H.

    2014-06-01

    The development of recycling technologies for rare earths is essential for resource security and supply stability because high-quality rare earth mines are concentrated in China and the demand for rare earth metals such as neodymium and dysprosium, used as raw materials in permanent magnets (neodymium magnet), is expected to increase rapidly in the near future. It is also important to establish a recycling-based society from the perspective of the conservation of finite and valuable mineral resources and the reduction of the environmental load associated with mining and smelting. In this article, the current status of rare earth resource as well as that of recycling technology for the magnets is reviewed. The importance of establishing an efficient recycling process for rare earths is discussed from the characteristics of supply chain of rare earths, and the technological bases of the recycling processes for the magnet are introduced. Further, some fundamental researches on the development of new recycling processes based on pyrometallurgical process are introduced, and the features of the recycling processes are evaluated.

  9. Rare earth element scavenging in seawater

    NASA Astrophysics Data System (ADS)

    Byrne, Robert H.; Kim, Ki-Hyun

    1990-10-01

    Examinations of rare earth element (REE) adsorption in seawater, using a variety of surface-types, indicated that, for most surfaces, light rare earth elements (LREEs) are preferentially adsorbed compared to the heavy rare earths (HREEs). Exceptions to this behavior were observed only for silica phases (glass surfaces, acid-cleaned diatomaceous earth, and synthetic SiO 2). The affinity of the rare earths for surfaces can be strongly affected by thin organic coatings. Glass surfaces which acquired an organic coating through immersion in Tampa Bay exhibited adsorptive behavior typical of organic-rich, rather than glass, surfaces. Models of rare earth distributions between seawater and carboxylate-rich surfaces indicate that scavenging processes which involve such surfaces should exhibit a strong dependence on pH and carbonate complexation. Scavenging models involving carboxylate surfaces produce relative REE abundance patterns in good general agreement with observed shale-normalized REE abundances in seawater. Scavenging by carboxylate-rich surfaces should produce HREE enrichments in seawater relative to the LREEs and may produce enrichments of lanthanum relative to its immediate trivalent neighbors. Due to the origin of distribution coefficients as a difference between REE solution complexation (which increases strongly with atomic number) and surface complexation (which apparently also increases with atomic number) the relative solution abundance patterns of the REEs produced by scavenging reactions can be quite complex.

  10. New rare earth metal-rich indides RE14Ni 3In 3 ( RE=Sc, Y, Gd-Tm, Lu)—synthesis and crystal chemistry

    NASA Astrophysics Data System (ADS)

    Lukachuk, Mar'yana; Galadzhun, Yaroslav V.; Zaremba, Roman I.; Dzevenko, Mariya V.; Kalychak, Yaroslav M.; Zaremba, Vasyl I.; Rodewald, Ute Ch.; Pöttgen, Rainer

    2005-09-01

    The rare earth-nickel-indides RE14Ni 3In 3 ( RE=Sc, Y, Gd-Tm, Lu) were synthesized from the elements by arc-melting and subsequent annealing. The compounds were investigated on the basis of X-ray powder and single crystal data: Lu 14Co 2In 3 type, P4 2/ nmc, Z=4, a=888.1(1), c=2134.7(4), wR2=0.0653, 1381 F2 values, 63 variables for Sc 13.89Ni 3.66In 2.45; a=961.2(1), c=2316.2(5), wR2=0.0633, 1741 F2 values, 64 variables for Y 13.84Ni 3.19In 2.97; a=965.3(1), c=2330.5(5), wR2=0.0620, 1765 F2 values, 63 variables for Gd 14Ni 3.29In 2.71; a=956.8(1), c=2298.4(5), wR2=0.0829, 1707 F2 values, 64 variables for Tb 13.82Ni 3.36In 2.82; a=951.7(1), c=2289.0(5), wR2=0.0838, 1794 F2 values, 64 variables for Dy 13.60Ni 3.34In 3.06; a=948.53(7), c=2270.6(1), wR2=0.1137, 1191 F2 values, 64 variables for Ho 13.35Ni 3.17In 3.48; a=943.5(1), c=2269.1(5), wR2=0.0552, 1646 F2 values, 64 variables for Er 13.53Ni 3.14In 3.33; a=938.42(7), c=2250.8(1), wR2=0.1051, 1611 F2 values, 64 variables for Tm 13.47Ni 3.28In 3.25; a=937.3(1), c=2249.6(5), wR2=0.0692, 1604 F2 values, 64 variables for Tm 13.80Ni 3.49In 2.71; and a=933.4(1), c=2263.0(5), wR2=0.0709, 1603 F2 values, 64 variables for Lu 13.94Ni 3.07In 2.99. The RE14Ni 3In 3 indides show significant Ni/In mixing on the 4 c In1 site. Except the gadolinium compound, the RE14Ni 3In 3 intermetallics also reveal RE/In mixing on the 4 c RE1 site, leading to the refined compositions. Due to the high rare earth metal content, the seven crystallographically independent RE sites have between 9 and 10 nearest RE neighbors. The RE14Ni 3In 3 structures can be described as a complex intergrowth of rare earth-based polyhedra. Both nickel sites have a distorted trigonal-prismatic rare earth coordination. An interesting feature is the In2-In2 dumb-bell at an In2-In2 distance of 304 pm (for Gd 14Ni 3.29In 2.71). The crystal chemical peculiarities of the RE14Ni 3In 3 indides are briefly discussed.

  11. Rare-earth metal halogenide encapsulation-induced modifications in Raman spectra of single-walled carbon nanotubes

    NASA Astrophysics Data System (ADS)

    Kharlamova, M. V.

    2015-01-01

    In the present work, a detailed Raman spectroscopy investigation on the single-walled carbon nanotubes (SWCNTs) filled with praseodymium chloride, terbium chloride and thulium chloride was performed. The salts were incorporated inside the SWCNTs by a capillary filling method using melts, and the high-resolution transmission electron microscopy data proved the high filling degree of the nanotube channels. A thorough analysis of the radial breathing mode and G-band of the Raman spectra of the pristine and filled SWCNTs showed that the encapsulated salts cause acceptor doping of the host nanotubes, and the doping efficiency depends on the compound. The incorporated thulium chloride has the strongest doping effect on the SWCNTs, whereas praseodymium chloride has the weakest effect. It was found that the encapsulated salts modify more significantly the electronic structure of metallic nanotubes than semiconducting SWCNTs.

  12. Byproduct metals and rare-earth elements used in the production of light-emitting diodes—Overview of principal sources of supply and material requirements for selected markets

    USGS Publications Warehouse

    Wilburn, David R.

    2012-01-01

    The use of light-emitting diodes (LEDs) is expanding because of environmental issues and the efficiency and cost savings achieved compared with use of traditional incandescent lighting. The longer life and reduced power consumption of some LEDs have led to annual energy savings, reduced maintenance costs, and lower emissions of carbon dioxide, sulfur dioxide, and nitrogen oxides from powerplants because of the resulting decrease in energy consumption required for lighting applications when LEDs are used to replace less-energy-efficient sources. Metals such as arsenic, gallium, indium, and the rare-earth elements (REEs) cerium, europium, gadolinium, lanthanum, terbium, and yttrium are important mineral materials used in LED semiconductor technology. Most of the world's supply of these materials is produced as byproducts from the production of aluminum, copper, lead, and zinc. Most of the rare earths required for LED production in 2011 came from China, and most LED production facilities were located in Asia. The LED manufacturing process is complex and is undergoing much change with the growth of the industry and the changes in demand patterns of associated commodities. In many respects, the continued growth of the LED industry, particularly in the general lighting sector, is tied to its ability to increase LED efficiency and color uniformity while decreasing the costs of producing, purchasing, and operating LEDs. Research is supported by governments of China, the European Union, Japan, the Republic of Korea, and the United States. Because of the volume of ongoing research in this sector, it is likely that the material requirements of future LEDs may be quite different than LEDs currently (2011) in use as industry attempts to cut costs by reducing material requirements of expensive heavy rare-earth phosphors and increasing the sizes of wafers for economies of scale. Improved LED performance will allow customers to reduce the number of LEDs in automotive, electronic

  13. Mechanistic Investigations of the Stereoselective Rare Earth Metal-Mediated Ring-Opening Polymerization of β-Butyrolactone.

    PubMed

    Altenbuchner, Peter T; Kronast, Alexander; Kissling, Stefan; Vagin, Sergei I; Herdtweck, Eberhardt; Pöthig, Alexander; Deglmann, Peter; Loos, Robert; Rieger, Bernhard

    2015-09-21

    Poly(3-hydroxybutyrate) (PHB) is produced by numerous bacteria as carbon and energy reserve storage material. Whereas nature only produces PHB in its strictly isotactic (R) form, homogeneous catalysis, when starting from racemic (rac) β-butyrolactone (BL) as monomer, can in fact produce a wide variety of tacticities. The variation of the metal center and the surrounding ligand structure enable activity as well as tacticity tuning. However, no homogeneous catalyst exists to date that is easy to modify, highly active, and able to produce PHB with high isotacticities from rac-β-BL. Therefore, in this work, the reaction kinetics of various 2-methoxyethylamino-bis(phenolate) lanthanide (Ln=Sm, Tb, Y, Lu) catalysts are examined in detail. The order in monomer and catalyst are determined to elucidate the reaction mechanism and the results are correlated with DFT calculations of the catalytic cycle. Furthermore, the enthalpies and entropies of the rate-determining steps are determined through temperature-dependent in situ IR measurements. Experimental and computational results converge in one specific mechanism for the ring-opening polymerization of BL and even allow us to rationalize the preference for syndiotactic PHB.

  14. Rare earth phosphors and phosphor screens

    DOEpatents

    Buchanan, Robert A.; Maple, T. Grant; Sklensky, Alden F.

    1981-01-01

    This invention relates to rare earth phosphor screens for converting image carrying incident radiation to image carrying visible or near-visible radiation and to the rare earth phosphor materials utilized in such screens. The invention further relates to methods for converting image carrying charged particles to image carrying radiation principally in the blue and near-ultraviolet region of the spectrum and to stabilized rare earth phosphors characterized by having a continuous surface layer of the phosphors of the invention. More particularly, the phosphors of the invention are oxychlorides and oxybromides of yttrium, lanthanum and gadolinium activated with trivalent cerium and the conversion screens are of the type illustratively including x-ray conversion screens, image amplifier tube screens, neutron imaging screens, cathode ray tube screens, high energy gamma ray screens, scintillation detector screens and screens for real-time translation of image carrying high energy radiation to image carrying visible or near-visible radiation.

  15. Local magnetic moment formation at 119Sn Mössbauer impurity in RFe2 ( R=rare-earth metals) Laves phases compounds

    NASA Astrophysics Data System (ADS)

    de Oliveira, A. L.; de Oliveira, N. A.; Troper, A.

    2010-05-01

    The purpose of the present work is to theoretically study the local magnetic moment formation and the systematics of the magnetic hyperfine fields at a non-magnetic s-p Mössbauer 119Sn impurity diluted on R sites ( R=rare-earth metals) of the cubic Laves phases intermetallic compounds RFe2. One considers that the magnetic hyperfine field has two contributions (i) the contribution from R ions, calculated via an extended Daniel-Friedel [J. Phys. Chem. Solids 24 (1963) 1601] model and (ii) the contribution from the induced magnetic moments arising from the Fe neighboring sites. We have in this case a two-center Blandin-Campbell-like [Phys. Rev. Lett. 31 (1973) 51; J. Magn. Magn. Mater. 1 (1975) 1] problem, where a magnetic 3d-element located at a distance from the 119Sn impurity gives an extra magnetization to a polarized electron gas which is strongly charge perturbed at the 119Sn impurity site. We also include in the model, the nearest-neighbor perturbation due to the translational invariance breaking introduced by the impurity. Our self-consistent total magnetic hyperfine field calculations are in a very good agreement with recent experimental data.

  16. Co-based alloys design based on first-principles calculations: Influence of transition metal and rare-earth alloying element on stacking fault energy

    NASA Astrophysics Data System (ADS)

    Achmad, Tria Laksana; Fu, Wenxiang; Chen, Hao; Zhang, Chi; Yang, Zhi-Gang

    2017-01-01

    The main idea of alloy design is to reduce costs and time required by the traditional (trial and error) method, then finding a new way to develop the efficiency of the alloy design is necessary. In this study, we proposed a new approach to the design of Co-based alloys. It is based on the concept that lowering the ratio of stable and unstable stacking fault energy (SFE) could bring a significant increase in the tendency of partial dislocation accumulation and FCC to HCP phase transformation then enhance mechanical properties. Through the advance development of the computing techniques, first-principles density-functional-theory (DFT) calculations are capable of providing highly accurate structural modeling at the atomic scale without any experimental data. The first-principles calculated results show that the addition of some transition metal (Cr, Mo, W, Re, Os, Ir) and rare-earth (Sc, Y, La, Sm) alloying elements would decrease both stable and unstable SFE of pure Co. The dominant deformation mechanism of binary Co-4.5 at.% X (X = alloying element) is extended partial dislocation. Our study reveals Re, W, Mo and La as the most promising alloying additions for the Co-based alloys design with superior performances. Furthermore, the underlying mechanisms for the SFE reduction can be explained regarding the electronic structure.

  17. Chiral 2,6-bis(oxazolinyl)pyridine-rare earth metal complexes as catalysts for highly enantioselective 1,3-dipolar cycloaddition reactions of 2-benzopyrylium-4-olates.

    PubMed

    Suga, Hiroyuki; Inoue, Kei; Inoue, Shuichi; Kakehi, Akikazu; Shiro, Motoo

    2005-01-07

    Significant levels of enantioselectivity were obtained in 1,3-dipolar cycloadditions of 2-benzopyrylium-4-olate generated from the Rh(2)(OAc)(4)-catalyzed decomposition of o-methoxycarbonyl-alpha-diazoacetophenone. This reaction utilized chiral 2,6-bis(oxazolinyl)pyridine (Pybox)--rare earth metal triflate complexes as chiral Lewis acid catalysts. The reactions with several benzyloxyacetaldehyde derivatives catalyzed by a Sc(III)--Pybox-i-Pr complex (10 mol %) proceeded smoothly to yield endo-adducts selectively with high enantioselectivity (up to 93% ee). For the reaction with benzyl pyruvate, the Sc(III)-Pybox-i-Pr complex (10 mol %) catalyzed the reaction effectively in the presence of trifluoroacetic acid (10 mol %) to yield an exo-adduct with both high diastereo- and enantioselectivity (94% ee). This catalytic system was efficiently applied to the reactions with several other alpha-keto esters with high exo- and enantioselectivities (up to 95% ee). In contrast to the reaction with carbonyl compounds, Yb(III)--Pybox-Ph complex (10 mol %) was found to be effective to obtain high enantioselectivity (96% ee) of diastereoselectively produced exo-cycloadduct in the reaction with 3-acryloyl-2-oxazolidinone.

  18. IUPAC-NIST Solubility Data Series. 100. Rare Earth Metal Fluorides in Water and Aqueous Systems. Part 2. Light Lanthanides (Ce–Eu)

    SciTech Connect

    Mioduski, Tomasz; Gumiński, Cezary; Zeng, Dewen

    2015-03-15

    This is the second part of the volume devoted to the evaluation of experimental solubility data for rare earth metal (REM) fluorides in water as well as in aqueous ternary and multicomponent systems. Fluorides of Ce, Pr, Nd, Pm, Sm, and Eu (so-called light lanthanides), as the main solutes, are covered in the present part, which has thorough coverage of the experimental literature through the end of 2012. The experimentally unknown solubility value for PmF{sub 3} in water was predicted by an interpolation of the solubility values for NdF{sub 3} and SmF{sub 3} at 298 K. General features of the systems, such as the nature of the equilibrium solid phases, solubility as a function of temperature, influence of ionic strength, pH, mixed solvent medium on the solubility, quality of the solubility results, and solubility as a function of REM atomic number, have already been presented in Part 1 of the volume.

  19. Rare-earth metal allyl and hydrido complexes supported by an (NNNN)-type macrocyclic ligand: synthesis, structure, and reactivity toward biomass-derived furanics.

    PubMed

    Abinet, Elise; Martin, Daniel; Standfuss, Sabine; Kulinna, Heiko; Spaniol, Thomas P; Okuda, Jun

    2011-12-23

    The preparation and characterization of a series of neutral rare-earth metal complexes [Ln(Me(3)TACD)(η(3)-C(3)H(5))(2)] (Ln=Y, La, Ce, Pr, Nd, Sm) supported by the 1,4,7-trimethyl-1,4,7,10-tetraazacyclododecane anion (Me(3)TACD(-)) are reported. Upon treatment of the neutral allyl complexes [Ln(Me(3)TACD)(η(3)-C(3)H(5))(2)] with Brønsted acids, monocationic allyl complexes [Ln(Me(3)TACD)(η(3)-C(3)H(5))(thf)(2)][B(C(6)X(5))(4)] (Ln=La, Ce, Nd, X=H, F) were isolated and characterized. Hydrogenolysis gave the hydride complexes [Ln(Me(3)TACD)H(2)](n) (Ln=Y, n=3; La, n=4; Sm). X-ray crystallography showed the lanthanum hydride to be tetranuclear. Reactivity studies of [Ln(Me(3)TACD)R(2)](n) (R=η(3)-C(3)H(5), n=0; R=H, n=3,4) towards furan derivatives includes hydrosilylation and deoxygenation under ring-opening conditions.

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

    SciTech Connect

    Mioduski, Tomasz; Gumiński, Cezary; Zeng, Dewen

    2015-06-15

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

  1. Rare-earth-metal alkylaluminates supported by N-donor-functionalized cyclopentadienyl ligands: C-H bond activation and performance in isoprene polymerization.

    PubMed

    Jende, Lars N; Maichle-Mössmer, Cäcilia; Anwander, Reiner

    2013-11-25

    Homoleptic tetramethylaluminate complexes [Ln(AlMe4)3] (Ln=La, Nd, Y) reacted with HCp(NMe2) (Cp(NMe2) =1-[2-(N,N-dimethylamino)-ethyl]-2,3,4,5-tetramethyl-cyclopentadienyl) in pentane at -35 °C to yield half-sandwich rare-earth-metal complexes, [{C5 Me4CH2CH2NMe2 (AlMe3)}Ln(AlMe4)2]. Removal of the N-donor-coordinated trimethylaluminum group through donor displacement by using an equimolar amount of Et2O at ambient temperature only generated the methylene-bridged complexes [{C5Me4CH2CH2NMe(μ-CH2)AlMe3}Ln(AlMe4)] with the larger rare-earth-metal ions lanthanum and neodymium. X-ray diffraction analysis revealed the formation of isostructural complexes and the C-H bond activation of one aminomethyl group. The formation of Ln(μ-CH2)Al moieties was further corroborated by (13)C and (1)H-(13)C HSQC NMR spectroscopy. In the case of the largest metal center, lanthanum, this C-H bond activation could be suppressed at -35 °C, thereby leading to the isolation of [(Cp(NMe2))La(AlMe4)2], which contains an intramolecularly coordinated amino group. The protonolysis reaction of [Ln(AlMe4)3] (Ln=La, Nd) with the anilinyl-substituted cyclopentadiene HCp(AMe2) (Cp(AMe2) =1-[1-(N,N-dimethylanilinyl)]-2,3,4,5-tetramethylcyclopentadienyl) at -35 °C generated the half-sandwich complexes [(Cp(AMe2))Ln(AlMe4)2]. Heating these complexes at 75 °C resulted in the C-H bond activation of one of the anilinium methyl groups and the formation of [{C5Me4C6H4NMe(μ-CH2)AlMe3}Ln(AlMe4)] through the elimination of methane. In contrast, the smaller yttrium metal center already gave the aminomethyl-activated complex at -35 °C, which is isostructural to those of lanthanum and neodymium. The performance of complexes [{C5Me4CH2CH2NMe(μ-CH2 )AlMe3}-Ln(AlMe4)], [(Cp(AMe2))Ln(AlMe4)2], and [{C5Me4C6H4NMe(μ-CH2)AlMe3}Ln(AlMe4)] in the polymerization of isoprene was investigated upon activation with [Ph3C][B(C6F5)4], [PhNMe2 H][B(C6F5)4], and B(C6F5)3. The highest stereoselectivities were observed

  2. Synthesis, structure and reactivity of dinuclear rare earth metal bis(o-aminobenzyl) complexes bearing a 1,4-phenylenediamidinate co-ligand.

    PubMed

    Li, Meng; Hong, Jianquan; Chen, Zhenxia; Zhou, Xigeng; Zhang, Lixin

    2013-06-21

    A series of phenylenediamidinate rare earth metal complexes 1,4-C6H4[C(NR)2Ln(o-CH2C6H4NMe2)2]2 (R = 2,6-(i)Pr2-C6H3, Ln = Y (2a), Lu (2b), Sc (2c)) were synthesized by deprotonation of 1,4-C6H4[C(NR)(NHR)]2 (1) with two equivalents of n-BuLi followed by reacting with two equivalents of anhydrous LnCl3 and subsequently four equivalents of Li(o-CH2C6H4NMe2), or by protolysis of [Ln(o-CH2C6H4NMe2)3] with 0.5 equivalent of 1 in THF or toluene. Treatment of complexes 2a and 2b with four equivalents of phenyl isocyanate and phenyl isothiocyanate gave the corresponding insertion products 1,4-C6H4[C(NR)2Ln{OC(CH2C6H4NMe2-o)NPh}2(THF)]2 (Ln = Y (3a), Lu (3b)) and 1,4-C6H4[C(NR)2Ln{SC(CH2C6H4NMe2-o)NPh}2]2 (Ln = Y (4a), Lu (4b)), respectively. The structures of 1, 3b, and 4a were established by X-ray diffraction studies. Complexes 2 show high activity for rac-lactide and ε-caprolactone polymerization; for the former a synergistic effect between two metal centers is observed.

  3. Synergistic effects in solvent-extraction systems based on alkylsalicylic acids. I. Extraction of trivalent rare-earth metals in the presence of aliphatic amides

    SciTech Connect

    Preston, J.S.; Preez, A.C. du

    1995-07-01

    Aliphatic carboxylic acid amides were found to cause synergistic shifts in the pH{sub 50} values for the extraction of the trivalent rare-earth metals from chloride media by solutions of alkylsalicylic acids in xylene. For the different types of amide examined, the synergistic shifts for the extraction of neodymium by 3,5-diisopropylsalicylic acid (DIPSA) generally decrease in the order: R.CO.NR{sub 2}` > R.CO.NHR` > R.CO.NH{sub 2}, where R and R` are alkyl groups. With the N,N-dialkyl amides (R.CO.NR{sub 2}`) and the N-alkyl amides (R.CO.NHR`), the extent of the synergistic effect decreases with increasing chain-branching in either of the alkyl groups R and R`. For additions to 0.25 M alkylsalicylic acid, the synergistic effect increases with concentrations of up to 0.1 M amide, and decreases with higher concentrations. The extent of the synergistic shift produced by a given amide, as well as the separation in pH{sub 50} values from lanthanum to lutetium, increases with increasing steric bulk of the alkylsalicylic acid used. The separations between adjacent lanthanides are too small to be of any practical interest, however. Measurement of the solubility of salicylic acids (HA) in xylene containing various amounts of N,N-dialkyl amide (L) indicate that essentially complete formation of the HA.L adduct takes place. Treatment of metal-distribution data by slope analysis, and measurement of the solubility of the neodymium-DIPSA complex in xylene in the presence of amide suggest that the mixed-ligand complex has the stoichiometry NdA{sub 3}L{sub 2}. 18 refs., 6 figs., 3 refs.

  4. Rare-earth metal complexes supported by 1,omega-dithiaalkanediyl-bridged bis(phenolato) ligands: synthesis, structure, and heteroselective ring-opening polymerization of rac-lactide.

    PubMed

    Ma, Haiyan; Spaniol, Thomas P; Okuda, Jun

    2008-04-21

    Monomeric yttrium and lutetium bis(phenolato) complexes [Ln(OSSO){N(SiHMe 2) 2}(THF)] (Ln = Y, Lu) were prepared from the reaction of silylamido complexes [Ln{N(SiHMe 2) 2} 3(THF) 2] with 1 equiv of tetradentate 1,omega-dithiaalkanediyl-bridged bis(phenol) (OSSO)H 2 1- 9 in moderate to high yields. In contrast to the rigid configuration of scandium analogues, the yttrium complexes 2b and 3b and the lutetium complex 3c that contain a C 2 bridge between the two sulfur donors of the ligand are symmetric in solution. The monomeric nature of these complexes was indicated by an X-ray diffraction study of the yttrium complex 6b. The yttrium center in 6b is coordinated to the tetradentate [OSSO]-type ligand, one silylamido group and one THF ligand with the two oxygen donors of the [OSSO]-type ligand located trans. Corresponding bis(phenolato) silylamido complexes of larger rare-earth metals could not be obtained from similar reactions: Reaction of [La{N(SiHMe 2) 2} 3(THF) 2] with 1,2-xylylene-linked bis(phenol) gave a dinuclear lanthanum complex 6d of the formula [La 2(OSSO) 3] with two inequivalent eight-coordinate metal centers. The yttrium and lutetium complexes efficiently initiated the ring-opening polymerization (ROP) of lactides in THF. The heteroselectivity during the ROP of rac-lactide was enhanced when the steric demand of the bis(phenolato) ligand was increased, either by extending the bridge length or by introducing bulky ortho-substituents in the phenoxy units. A C 3 bridge within the ligand backbone is essential to allow configurational interconversion of the active site between Lambda and Delta configuration during polymerization, allowing accommodation of both enantiomers of the monomer in an alternating fashion.

  5. Rare-earth metal alkyl, amido, and cyclopentadienyl complexes supported by imidazolin-2-iminato ligands: synthesis, structural characterization, and catalytic application.

    PubMed

    Trambitas, Alexandra G; Panda, Tarun K; Jenter, Jelena; Roesky, Peter W; Daniliuc, Constantin; Hrib, Cristian G; Jones, Peter G; Tamm, Matthias

    2010-03-01

    The rare earth metal dichlorides [(1)MCl(2)(THF)(3)] (2a, M = Sc; 2b, M = Y; 2c, M = Lu) and the gadolinium complex [(1)GdCl(2)(THF)(2)] x [LiCl(THF)(2)] (2d), containing the 1,3-bis(2,6-diisopropylphenyl)imidazolin-2-iminato ligand 1, proved to be versatile starting materials for the preparation of trimethylsilylmethyl ("neosilyl") and bis(trimethylsilyl)amido complexes [(1)M(CH(2)SiMe(3))(2)(THF)(2)] (3a-3d) and [(1)M(HMDS)(2)(THF)] [4a-4d, HMDS = hexamethyldisilazide, N(SiMe(3))(2)] and for the preparation of the benzyl complex [(1)Lu(CH(2)Ph)(2)(THF)(2)] (5c) by the reaction with LiCH(2)SiMe(3), Na[N(SiMe(3))(2)], and KCH(2)Ph, respectively. Treatment of 2a-2c with KCp* afforded the mono(pentamethylcyclopentadienyl) complexes [(1)Sc(Cp*)Cl(THF)] (6a), [(1)Y(Cp*)Cl(THF)(2)] (6b), and [(1)Lu(Cp*)Cl(THF)] (6c). In contrast, the gadolinocene complex [(1)Gd(Cp*)(2)(THF)] (7) was isolated from the reaction of 2d with 2 equiv of KCp*. The molecular structures of 3a-3d, 4b.THF, 4d, 5c, 6a, 6c, and 7 x THF were determined by X-ray diffraction analyses, revealing the presence of exceptionally short metal-nitrogen bonds. The neosilyl complexes 3b and 3c showed high catalytic activity in the intramolecular hydroamination of aminoalkenes and aminoalkynes and in the hydrosilylation of 1-hexene and 1-octene with PhSiH(3).

  6. Synthesis of main group, rare-earth, and d{sup 0} metal complexes containing beta-hydrogen

    SciTech Connect

    Yan, Ka King

    2013-01-01

    >F5)3 give the expected dicationic M{HB(C6F5)3}2L (M = Ca, Yb; L = THF2 or TMEDA) and dicationic mono(silylalkyl) LnC(SiHMe2)3{HB(C6F5)3}2 (Ln = Y, Lu, La), respectively. Salt metathesis reactions of Cp2(NR2)ZrX (X = Cl, I, OTf; R = t-Bu, SiHMe2) and lithium hydrosilazide ultimately afford hydride products Cp2(NR2)ZrH that suggest unusual β-hydrogen elimination processes. A likely intermediate in one of these reactions, Cp2Zr[N(SiHMe2)t-Bu][N(SiHMe2)2], is isolated under controlled synthetic conditions. Addition of alkali metal salts to this zirconium hydrosilazide compound produces the corresponding zirconium hydride. However as conditions are varied, a number of other pathways are also accessible, including C-H/Si-H dehydrocoupling, γ-abstraction of a CH, and β-abstraction of a SiH. Our observations suggest that the conversion of (hydrosilazido)zirconocene to zirconium hydride does not follow the classical four-center β- elimination mechanism.

  7. Dinuclear rare-earth metal alkyl complexes supported by indolyl ligands in μ-η(2) :η(1) :η(1) hapticities and their high catalytic activity for isoprene 1,4-cis-polymerization.

    PubMed

    Zhang, Guangchao; Wei, Yun; Guo, Liping; Zhu, Xiancui; Wang, Shaowu; Zhou, Shuangliu; Mu, Xiaolong

    2015-02-02

    Two series of new dinuclear rare-earth metal alkyl complexes supported by indolyl ligands in novel μ-η(2) :η(1) :η(1) hapticities are synthesized and characterized. Treatment of [RE(CH2 SiMe3 )3 (thf)2 ] with 1 equivalent of 3-(tBuN=CH)C8 H5 NH (L1 ) in THF gives the dinuclear rare-earth metal alkyl complexes trans-[(μ-η(2) :η(1) :η(1) -3-{tBuNCH(CH2 SiMe3 )}Ind)RE(thf)(CH2 SiMe3 )]2 (Ind=indolyl, RE=Y, Dy, or Yb) in good yields. In the process, the indole unit of L1 is deprotonated by the metal alkyl species and the imino C=N group is transferred to the amido group by alkyl CH2 SiMe3 insertion, affording a new dianionic ligand that bridges two metal alkyl units in μ-η(2) :η(1) :η(1) bonding modes, forming the dinuclear rare-earth metal alkyl complexes. When L1 is reduced to 3-(tBuNHCH2 )C8 H5 NH (L2 ), the reaction of [Yb(CH2 SiMe3 )3 (thf)2 ] with 1 equivalent of L2 in THF, interestingly, generated the trans-[(μ-η(2) :η(1) :η(1) -3-{tBuNCH2 }Ind)Yb(thf)(CH2 SiMe3 )]2 (major) and cis-[(μ-η(2) :η(1) :η(1) -3-{tBuNCH2 }Ind)Yb(thf)(CH2 SiMe3 )]2 (minor) complexes. The catalytic activities of these dinuclear rare-earth metal alkyl complexes for isoprene polymerization were investigated; the yttrium and dysprosium complexes exhibited high catalytic activities and high regio- and stereoselectivities for isoprene 1,4-cis-polymerization.

  8. What about the rare-earth elements

    Technology Transfer Automated Retrieval System (TEKTRAN)

    There is insufficient understanding of the nutritional physiology of pecan trees and orchards; thus, affecting nutmeat yield and quality, disease resistance and alternate bearing. An analysis of the rare-earth element composition of pecan and related hickory cousins found that they hyperaccumulate ...

  9. Decomposition of Rare Earth Loaded Resin Particles

    SciTech Connect

    Voit, Stewart L; Rawn, Claudia J

    2010-09-01

    resin is made of sulfonic acid functional groups attached to a styrene divinylbenzene copolymer lattice (long chained hydrocarbon). The metal cation binds to the sulfur group, then during thermal decomposition in air the hydrocarbons will form gaseous species leaving behind a spherical metal-oxide particle. Process development for resin applications with radioactive materials is typically performed using surrogates. For americium and curium, a trivalent metal like neodymium can be used. Thermal decomposition of Nd-loaded resin in air has been studied by Hale. Process conditions were established for resin decomposition and the formation of Nd{sub 2}O{sub 3} particles. The intermediate product compounds were described using x-ray diffraction (XRD) and wet chemistry. Leskela and Niinisto studied the decomposition of rare earth (RE) elements and found results consistent with Hale. Picart et al. demonstrated the viability of using a resin loading process for the fabrication of uranium-actinide mixed oxide microspheres for transmutation of minor actinides in a fast reactor. For effective transmutation of actinides, it will be desirable to extend the in-reactor burnup and minimize the number of recycles of used actinide materials. Longer burn times increases the chance of Fuel Clad Chemical or Mechanical Interaction (FCCI, FCMI). Sulfur is suspected of contributing to Irradiation Assisted Stress Corrosion Cracking (IASCC) thus it is necessary to maximize the removal of sulfur during decomposition of the resin. The present effort extends the previous work by quantifying the removal of sulfur during the decomposition process. Neodymium was selected as a surrogate for trivalent actinide metal cations. As described above Nd was dissolved in nitric acid solution then contacted with the AG-50W resin column. After washing the column, the Nd-resin particles are removed and dried. The Nd-resin, seen in Figure 1 prior to decomposition, is ready to be converted to Nd oxide microspheres.

  10. Calcium substitution in rare-earth metal germanides with the hexagonal Mn{sub 5}Si{sub 3} structure type. structural characterization of the extended series RE{sub 5–x}Ca{sub x}Ge{sub 3} (RE=Rare-earth metal)

    SciTech Connect

    Suen, Nian-Tzu; Broda, Matthew; Bobev, Svilen

    2014-09-15

    Reported are the synthesis and the structural characterization of an extended family of rare-earth metal–germanides with a general formula RE{sub 5–x}Ca{sub x}Ge{sub 3} (RE=Y, Ce–Nd, Sm, Gd–Tm and Lu; x<2). All twelve phases are isotypic, crystallizing with the Mn{sub 5}Si{sub 3} structure type (Pearson index hP16, hexagonal space group P6{sub 3}/mcm); they are the Ca-substituted variants of the corresponding RE{sub 5}Ge{sub 3} binaries. Across the series, despite some small variations in the Ca-uptake, the unit cell volumes decrease monotonically, following the lanthanide contraction. Temperature dependent DC magnetization measurements reveal paramagnetic behavior in the high temperature range, and the obtained effective moments are consistent with free-ion RE{sup 3+} ground state, as expected from prior studies of the binary RE{sub 5}Ge{sub 3} phases. The onset of magnetic ordering is observed in the low temperature range, and complex magnetic interactions (ferromagnetic/ferrimagnetic) can be inferred, different from the binary phases RE{sub 5}Ge{sub 3}, which are known as antiferromagnetic. In order to understand the role of Ca in the bonding, the electronic structures of the La{sub 5}Ge{sub 3} and the hypothetical compounds La{sub 2}Ca{sub 3}Ge{sub 3} and La{sub 3}Ca{sub 2}Ge{sub 3} with ordered metal atoms are compared and discussed. - Graphical abstract: The family of rare-earth metal–calcium–germanides with the general formula RE{sub 5–x}Ca{sub x}Ge{sub 3} (RE=Y, Ce–Nd, Sm, Gd–Tm and Lu) crystallize in the hexagonal space group P6{sub 3}/mcm (No. 193, Pearson symbol hP16) with a structure that is a variant of the Mn{sub 5}Si{sub 3} structure type. - Highlights: • The newly synthesized RE{sub 5–x}Ca{sub x}Ge{sub 3} (RE=Y, Ce–Nd, Sm, Gd–Tm and Lu) constitute an extended family. • The structure is a substitution variant of the hexagonal Mn{sub 5}Si{sub 3} structure type. • Ca-uptake is the highest in the early members, and

  11. Multilayer Thermal Barrier Coating (TBC) Architectures Utilizing Rare Earth Doped YSZ and Rare Earth Pyrochlores

    NASA Technical Reports Server (NTRS)

    Schmitt, Michael P.; Rai, Amarendra K.; Bhattacharya, Rabi; Zhu, Dongming; Wolfe, Douglas E.

    2014-01-01

    To allow for increased gas turbine efficiencies, new insulating thermal barrier coatings (TBCs) must be developed to protect the underlying metallic components from higher operating temperatures. This work focused on using rare earth doped (Yb and Gd) yttria stabilized zirconia (t' Low-k) and Gd2Zr2O7 pyrochlores (GZO) combined with novel nanolayered and thick layered microstructures to enable operation beyond the 1200 C stability limit of current 7 wt% yttria stabilized zirconia (7YSZ) coatings. It was observed that the layered system can reduce the thermal conductivity by approximately 45 percent with respect to YSZ after 20 hr of testing at 1316 C. The erosion rate of GZO is shown to be an order to magnitude higher than YSZ and t' Low-k, but this can be reduced by almost 57 percent when utilizing a nanolayered structure. Lastly, the thermal instability of the layered system is investigated and thought is given to optimization of layer thickness.

  12. Magnesium substitutions in rare-earth metal germanides with the Gd5Si4 type. Synthesis, structure determination and magnetic properties of RE5-xMgxGe4 (RE=Gd-Tm, Lu and Y)

    SciTech Connect

    Sarrao, J L; Thompson, Joe D; Tobash, P H; Bobev, S

    2009-01-01

    A series of magnesium-substituted rare-earth metal germanides with a general formula RE{sub 5-x}Mg{sub x}Ge{sub 4} (x {approx} 1.0-2.3; RE =Gd-Tm, Lu, Y) have been synthesized by high-temperature reactions and structurally characterized by single-crystal X-ray diffraction. These compounds crystallize with the common Gd{sub 5}Si{sub 4} type in the orthorhombic space group Pnma (No. 62; Z =4; Pearson's code oP36) and do not appear to undergo temperature-induced crystallographic phase transitions down to 120 K. Replacing rare-earth metal atoms with Mg, up to nearly 45 % at., reduces the valence electron count and is clearly expressed in the subtle changes of the Ge-Ge and metal-metal bonding. Magnetization measurements as a function of the temperature and the applied field reveal complex magnetic structures at cryogenic temperatures, and Curie-Weiss paramagnetic behavior at higher temperatures. The observed local moment magnetism is consistent with RE+ ground states in all cases. In the magnetically ordered phases, the magnetization cannot reach saturation in fields up to 50 kOe. The structural trends across the series and the variations of hte magnetic properties as a function of the Mg content are also discussed. KEYWORDS: Rare-earth intermetallics, germanides, crystal structure,Gd{sub 5}Si{sub 4} type.

  13. Rare-earth-metal-hydrocarbyl complexes bearing linked cyclopentadienyl or fluorenyl ligands: synthesis, catalyzed styrene polymerization, and structure-reactivity relationship.

    PubMed

    Jian, Zhongbao; Cui, Dongmei; Hou, Zhaomin

    2012-02-27

    A series of rare-earth-metal-hydrocarbyl complexes bearing N-type functionalized cyclopentadienyl (Cp) and fluorenyl (Flu) ligands were facilely synthesized. Treatment of [Y(CH(2)SiMe(3))(3)(thf)(2)] with equimolar amount of the electron-donating aminophenyl-Cp ligand C(5)Me(4)H-C(6)H(4)-o-NMe(2) afforded the corresponding binuclear monoalkyl complex [({C(5)Me(4)-C(6)H(4)-o-NMe(μ-CH(2))}Y{CH(2)SiMe(3)})(2)] (1a) via alkyl abstraction and C-H activation of the NMe(2) group. The lutetium bis(allyl) complex [(C(5)Me(4)-C(6)H(4)-o-NMe(2))Lu(η(3)-C(3)H(5))(2)] (2b), which contained an electron-donating aminophenyl-Cp ligand, was isolated from the sequential metathesis reactions of LuCl(3) with (C(5)Me(4)-C(6)H(4)-o-NMe(2))Li (1 equiv) and C(3)H(5)MgCl (2 equiv). Following a similar procedure, the yttrium- and scandium-bis(allyl) complexes, [(C(5)Me(4)-C(5)H(4)N)Ln(η(3)-C(3)H(5))(2)] (Ln=Y (3a), Sc (3b)), which also contained electron-withdrawing pyridyl-Cp ligands, were also obtained selectively. Deprotonation of the bulky pyridyl-Flu ligand (C(13)H(9)-C(5)H(4)N) by [Ln(CH(2)SiMe(3))(3)(thf)(2)] generated the rare-earth-metal-dialkyl complexes, [(η(3)-C(13)H(8)-C(5)H(4)N)Ln(CH(2)SiMe(3))(2)(thf)] (Ln=Y (4a), Sc (4b), Lu (4c)), in which an unusual asymmetric η(3)-allyl bonding mode of Flu moiety was observed. Switching to the bidentate yttrium-trisalkyl complex [Y(CH(2)C(6)H(4)-o-NMe(2))(3)], the same reaction conditions afforded the corresponding yttrium bis(aminobenzyl) complex [(η(3)-C(13)H(8)-C(5)H(4)N)Y(CH(2)C(6)H(4)-o-NMe(2))(2)] (5). Complexes 1-5 were fully characterized by (1)H and (13)C NMR and X-ray spectroscopy, and by elemental analysis. In the presence of both [Ph(3)C][B(C(6)F(5))(4)] and AliBu(3), the electron-donating aminophenyl-Cp-based complexes 1 and 2 did not show any activity towards styrene polymerization. In striking contrast, upon activation with [Ph(3)C][B(C(6)F(5))(4)] only, the electron-withdrawing pyridyl-Cp-based complexes 3, in

  14. Effect of rare earth oxides for improvement of MCFC

    NASA Astrophysics Data System (ADS)

    Ota, Ken-ichiro; Matsuda, Yoshiyuki; Matsuzawa, Koichi; Mitsushima, Shigenori; Kamiya, Nobuyuki

    The solubility of rare earth metal oxides and their effect on the NiO solubility have been discussed to stabilize the cathode of molten carbonate fuel cells. The solubility of Ho, Yb, and Nd oxides were 4.4 × 10 -4, 3.4 × 10 -4, and 1.3 × 10 -3 (mole fraction) at 923 K, respectively. The solubilities of NiO in (Li 0.52/Na 0.48) 2CO 3 with the saturated Ho, Yb, and Nd were 1.57 × 10 -5, 1.41 × 10 -5, and 9.5 × 10 -6, respectively. Among these three, Nd, which has the highest solubility in the carbonates, reduced the NiO solubility most; although, the La reduced the NiO solubility more than Nd. The logarithm of the solubility of the rare earth metal oxides has a linear relation to the Coulomb force ratio between the rare earth metal and the alkaline metal. Following this relation, the La should have the highest solubility among all the lanthanides. The basicity which NiO solubility closely relates has a linear relationship to the Coulomb force parameter of the melts. Based on these two models, the La would be the best additive to reduce the NiO solubility in Li/Na eutectic carbonate melt, among all the lanthanides.

  15. Rare-earth-transition-metal organic-inorganic hybrids based on Keggin-type polyoxometalates and pyrazine-2,3-dicarboxylate.

    PubMed

    Zhang, Shaowei; Zhao, Junwei; Ma, Pengtao; Niu, Jingyang; Wang, Jingping

    2012-05-01

    Five rare-earth-transition-metal (RE-TM) heterometal organic-inorganic hybrids based on Keggin-type silicotungstates and mixed ligands H2pzda (pzda=pyrazine-2,3-dicarboxylate) and en (en=ethylenediamine) (enH2)[Cu(en)2(H2O)]2{[Cu(en)2][Cu(en)2(H2O)][(α-SiW11 O39)RE(H2O)(pzda)]}2·n H2O (n≈4; RE=YIII (1), DyIII (2), YbIII (3), and LuIII (4)) and [Cu(en)2(H2O)]2{[Cu(en)2]2[Cu(pzda)2][(α-H2SiW11O39)Ce(H2O)]2}·n H2O (5; n≈8) have been hydrothermally synthesized and structurally characterized. Compounds 1-5 all contain the dimeric mono-RE substituted Keggin [RE(α-SiW11O39)]210- subunits linked by H2pzda ligands. Interestingly, 1-4 exhibit discrete structures, in which the H2pzda ligand acts as a tetradentate ligand to bind the RE and Cu cations, whereas 5 displays a 1D double-chain architecture, in which the H2pzda ligand adopts a new pentadentate mode to connect the Ce and Cu cations. To our knowledge, 1-5 represent the first monovacant Keggin-type silicotungstates containing both RE-TM heterometals and mixed ligands. The luminescence of 2 is derived from the combination of the DyIII cations and H2pzda ligands, whereas the luminescence properties of 1 and 3-5 are attributable to the H2pzda ligands.

  16. Investigating Heavy Metal Pollution in Mining Brownfield and Its Policy Implications: A Case Study of the Bayan Obo Rare Earth Mine, Inner Mongolia, China.

    PubMed

    Pan, Yuxue; Li, Haitao

    2016-04-01

    The rapid urbanization of China and associated demand for land resources necessitates remediation, redevelopment, and reclamation of contaminated soil. Before these measures are taken, a basic investigation and inventory of heavy metal (HM) pollution levels in contaminated soil is necessary for establishing and implementing the redevelopment plan. In the present study, to identify the policy implications of inventorying and mapping HM pollution of soil in brownfields throughout China, the Bayan Obo giant rare earth element (REE)-Nb-Fe ore deposit of Baotou in Inner Mongolia, China, which is the largest REE mineral deposit in the world, was taken as a case study. Soil samples from 24 sites in Bayan Obo mining area (MA) and 76 sites in mine tailing area (TA) were collected for determining contents of soil HMs (Cr, Cd, Pb, Cu, and Zn). The results showed that the average concentrations of Cr, Cd, Pb, Cu, and Zn in both MA and TA were all higher than their corresponding background values for Inner Mongolia but lower than the Class II criteria of the National Soil Quality Standards of China (GB 15618-1995). Enrichment factor (EF) analysis of the soil samples indicated that the soil in the brownfield sites was highly enriched with Cr, Cd, Pb, Cu, and Zn compared to the corresponding background values. In MA, the EF for Cd was the highest among the studied elements, while in TA, the EF for Cr (3.45) was the highest, closely followed by the EF for Cd (3.34). The potential ecological risk index (RI) indicated a moderate potential ecological risk from the studied HMs in MA and a low potential ecological risk in TA, and the results of RI also suggested that the soil was most heavily polluted by Cd. According to the spatial distribution maps of HM, contamination hot-spots were primarily located near mining-related high-pollution plants. Based on the results, policy recommendations are proposed related to brownfield management in urban planning.

  17. Investigating Heavy Metal Pollution in Mining Brownfield and Its Policy Implications: A Case Study of the Bayan Obo Rare Earth Mine, Inner Mongolia, China

    NASA Astrophysics Data System (ADS)

    Pan, Yuxue; Li, Haitao

    2016-04-01

    The rapid urbanization of China and associated demand for land resources necessitates remediation, redevelopment, and reclamation of contaminated soil. Before these measures are taken, a basic investigation and inventory of heavy metal (HM) pollution levels in contaminated soil is necessary for establishing and implementing the redevelopment plan. In the present study, to identify the policy implications of inventorying and mapping HM pollution of soil in brownfields throughout China, the Bayan Obo giant rare earth element (REE)-Nb-Fe ore deposit of Baotou in Inner Mongolia, China, which is the largest REE mineral deposit in the world, was taken as a case study. Soil samples from 24 sites in Bayan Obo mining area (MA) and 76 sites in mine tailing area (TA) were collected for determining contents of soil HMs (Cr, Cd, Pb, Cu, and Zn). The results showed that the average concentrations of Cr, Cd, Pb, Cu, and Zn in both MA and TA were all higher than their corresponding background values for Inner Mongolia but lower than the Class II criteria of the National Soil Quality Standards of China (GB 15618—1995). Enrichment factor (EF) analysis of the soil samples indicated that the soil in the brownfield sites was highly enriched with Cr, Cd, Pb, Cu, and Zn compared to the corresponding background values. In MA, the EF for Cd was the highest among the studied elements, while in TA, the EF for Cr (3.45) was the highest, closely followed by the EF for Cd (3.34). The potential ecological risk index (RI) indicated a moderate potential ecological risk from the studied HMs in MA and a low potential ecological risk in TA, and the results of RI also suggested that the soil was most heavily polluted by Cd. According to the spatial distribution maps of HM, contamination hot-spots were primarily located near mining-related high-pollution plants. Based on the results, policy recommendations are proposed related to brownfield management in urban planning.

  18. New rare-earth metal germanides with bismuth substitution. Synthesis, structural variations, and magnetism of the RE[Bi{sub x}Ge{sub 1-x}]{sub 2} (RE=Y, Pr, Nd, Sm, Gd-Tm, Lu) compounds

    SciTech Connect

    Zhang, Jiliang; Hmiel, Benjamin; Antonelli, Anthony; Tobash, Paul H.; Bobev, Svilen; Saha, Shanta; Kirshenbaum, Kevin; Greene, Richard L.; Paglione, Johnpierre

    2012-12-15

    Single-crystals of the novel rare-earth metal-bismuth digermanides with idealized formula RE[Bi{sub x}Ge{sub 1-x}]{sub 2} (RE=Y, Pr, Nd, Sm, Gd-Tm, Lu; x<0.16(1)) have been obtained using the Bi-flux technique. Their structures have been established by single-crystal X-ray diffraction; they can be divided into three classes, closely related to the ZrSi{sub 2} structure with the space group Cmcm (no. 63). The structural relationship and the variations with the type of the rare-earth metal have been explored and discussed. Temperature-dependent magnetization measurements on the single-crystals reveal magnetic behavior, which have been rationalized based on the mean-field theory. At cryogenic temperatures, the localized 4f electrons in most of the compounds exhibit antiferromagnetic ordering, mediated by the conduction electrons via Ruderman-Kittel-Kasuya-Yosida (RKKY) exchange interactions. - Graphical abstract: This paper details the synthesis and the structural characterization of an extended series of rare-earth metal-bismuth-germanides RE[Bi{sub x}Ge{sub 1-x}]{sub 2} (RE=Y, Pr-Sm, Gd-Tm, Lu). They crystallize with the same extended symmetry (space group Cmcm), but with three distinct structures, which are closely related. Magnetization measurements show low-temperature antiferromagnetic ordering. RE[Bi{sub x}Ge{sub 1-x}]{sub 2} are the first compounds between these elements. Highlights: Black-Right-Pointing-Pointer RE[Bi{sub x}Ge{sub 1-x}]{sub 2} (RE=rare-earth metal) are the first compounds of the respective elements. Black-Right-Pointing-Pointer Their structures are closely related. Black-Right-Pointing-Pointer Three structures can be distinguished based on the packing of the REGe{sub 6} triangular prisms. Black-Right-Pointing-Pointer All compounds show low-temperature antiferromagnetic ordering.

  19. Rare-earth oxide nanostructures: rules of rare-earth nitrate thermolysis in octadecylamine.

    PubMed

    Wang, Dingsheng; Wang, Zhongying; Zhao, Peng; Zheng, Wen; Peng, Qing; Liu, Liqin; Chen, Xueyuan; Li, Yadong

    2010-04-01

    The decomposed regularity of rare-earth nitrates in octadecylamine (ODA) is discussed. The experimental results show that these nitrates can be divided into four types. For rare-earth nitrates with larger RE(3+) ions (RE=rare earth, La, Pr, Nd, Sm, Eu, Gd), the decomposed products exhibited platelike nanostructures. For those with smaller RE(3+) ions (RE=Y, Dy, Ho, Er, Tm, Yb), the decomposed products exhibited beltlike nanostructures. For terbium nitrate with a middle RE(3+) ion, the decomposed product exhibited a rodlike nanostructure. The corresponding rare-earth oxides, with the same morphologies as their precursors, could be obtained when these decomposed products were calcined. For cerium nitrate, which showed the greatest differences, flowerlike cerium oxide could be obtained directly from decomposition of the nitrate without further calcination. This regularity is explained on the basis of the lanthanide contraction. Owing to their differences in electron configuration, ionic radius, and crystal structure, such a nitrate family therefore shows different thermolysis properties. In addition, the potential application of these as-obtained rare-earth oxides as catalysts and luminescent materials was investigated. The advantages of this method for rare-earth oxides includes simplicity, high yield, low cost, and ease of scale-up, which are of great importance for their industrial applications.

  20. Syntheses, characterization and biological activities of rare earth metal complexes with curcumin and 1,10-phenanthroline-5,6-dione.

    PubMed

    Song, Yu-Min; Xu, Jun-Peng; Ding, Lan; Hou, Qian; Liu, Jing-Wang; Zhu, Zao-Long

    2009-03-01

    Three new solid complexes have been synthesized by the reaction of rare earth(III) nitrate with the first ligand curcumin (HL) and the second ligand 1,10-phenanthroline-5,6-dione (L') in alcohol solution (pH=6.5-7.0). The composition of the complexes has been characterized by elemental analysis, molar conductivity, thermogravimetric analysis, IR, UV-vis methods. The results reveal that beta-diketone group of the first ligand to coordinates with rare earth ions in bidentate mode after deprotonated. But the second ligand uses its two N atoms coordinates with rare earth ions in bidentate mode. The general formula of the complexes is REL(3)L' (RE=Sm, Eu, Dy). The results of antibacterial activity indicated that the complexes have excellent antibacterial ability for the testing bacterium than that of curcumin. The result of agarose gel electrophoresis suggested that the complex of SmL(3)L' can cleave the plasmid DNA at physiological pH and temperature. And it was found that the cleavage process of plasmid DNA was sensitive to pH, however, adding radical scavengers almost had no effect on the DNA cleavage reaction, therefore, the cleavage of DNA by SmL(3)L' does not produce diffusible hydroxyl radicals via the Fenton reaction.

  1. An Operationally Simple Method for Separating the Rare-Earth Elements Neodymium and Dysprosium.

    PubMed

    Bogart, Justin A; Lippincott, Connor A; Carroll, Patrick J; Schelter, Eric J

    2015-07-06

    Rare-earth metals are critical components of electronic materials and permanent magnets. Recycling of consumer materials is a promising new source of rare earths. To incentivize recycling there is a clear need for simple methods for targeted separations of mixtures of rare-earth metal salts. Metal complexes of a tripodal nitroxide ligand [{(2-(t) BuNO)C6 H4 CH2 }3 N](3-) (TriNOx(3-) ), feature a size-sensitive aperture formed of its three η(2) -(N,O) ligand arms. Exposure of metal cations in the aperture induces a self-associative equilibrium comprising [M(TriNOx)thf]/ [M(TriNOx)]2 (M=rare-earth metal). Differences in the equilibrium constants (Keq ) for early and late metals enables simple Nd/Dy separations through leaching with a separation ratio SNd/Dy =359.

  2. Systematic variation of rare earths in monazite

    USGS Publications Warehouse

    Murata, K.J.; Rose, H.J.; Carron, M.K.

    1953-01-01

    Ten monazites from widely scattered localities have been analyzed for La, Ce, Pr, Nd, Sm, Gd, Y and Th by means of a combined chemical and emission spectrographic method. The analytical results, calculated to atomic percent of total rare earths (thorium excluded), show a considerable variation in the proportions of every element except praseodymium, which is relatively constant. The general variation trends of the elements may be calculated by assuming that the monazites represent different stages in a fractional precipitation process, and by assuming that there is a gradational increase in the precipitability of rare earth elements with decreasing ionic radius. Fractional precipitation brings about an increase in lanthanum and cerium, little change in praseodymium, and a decrease in neodymium, samarium, gadolinium, and yttrium. Deviations from the calculated lines of variation consist of a simultaneous, abnormal increase or decrease in the proportions of cerium, praseodymium, and neodymium with antipathetic decrease or increase in the proportions of the other elements. These deviations are ascribed to abnormally high or low temperatures that affect the precipitability of the central trio of elements (Ce, Pr, Nd) relatively more than that of the other elements. The following semiquantitative rules have been found useful in describing the composition of rare earths from monazite: 1. 1. The sum of lanthanum and neodymium is very nearly a constant at 42 ?? 2 atomic percent. 2. 2. Praseodymium is very nearly constant at 5 ?? 1 atomic percent. 3. 3. The sum of Ce, Sm, Gd, and Y is very nearly a constant at 53 ?? 3 atomic percent. No correlation could be established between the content of Th and that of any of the rare earth elements. ?? 1953.

  3. SEPARATION OF RARE EARTHS BY SOLVENT EXTRACTION

    DOEpatents

    Peppard, D.F.; Mason, G.W.

    1960-10-11

    A process is given for separating lanthanide rare earths from each other from an aqueous mineral acid solution, e.g., hydrochloric or nitric acid of a concentration of above 3 M, preferably 12 to 16 M, by extraction with a water- immiscible alkyl phosphate, such as tributyl phosphate or a mixture of mono-, di- and tributyl phosphate, and fractional back-extraction with mineral acid whereby the lanthanides are taken up by the acid in the order of increasing atomic number.

  4. High-capacity chitosan-based chelating resin for on-line collection of transition and rare-earth metals prior to inductively coupled plasma-atomic emission spectrometry measurement.

    PubMed

    Katarina, Rosi Ketrin; Oshima, Mitsuko; Motomizu, Shoji

    2009-10-15

    High-capacity chitosan-based chelating resin, N-(2-hydroxyethyl)glycine-type chitosan, was synthesized using chloromethyloxirane (CMO) as a cross-linker and a coupling arms and hydroxylethylamine and bromoacetic acid as a synthesizer for the N-(2-hydroxyethyl)glycine chelating moiety. The CMO could bind with both of hydroxyl and amino group of the chitosan resin, and then couple with the chelating moiety. Increasing the amounts of chelating moiety could increase the capacity of the resin toward metal ions. Most transition and rare-earth metals could adsorb quantitatively on the resin at wide pH ranges and could be separated from alkaline and alkaline-earth metals. The resin was packed in a mini-column (40 mm length x 2 mm i.d.) which was installed in a Multi-Auto-Pret system. The Multi-Auto-Pret system coupled with ICP-AES was successfully applied to the determination of transition and rare-earth metals in river water samples.

  5. Synchrotron radiation studies of local structure and bonding in transition metal aluminides and rare earth transition metal magnetic nitrides. Final report, August 1, 1990--July 14, 1993

    SciTech Connect

    Budnick, J.I.; Pease, D.M.

    1995-05-01

    The following areas of study are reported on: bonding and near neighbor force constants in NiAl, CoAl, FeAl via temperature dependent EXAFS; alloys formed when Fe or Ga is microalloyed into a NiAl matrix; EXAFS studies of nitrided versus non nitrided Y{sub 2}Fe{sub 17}; and transition metal x-ray spectra as related to magnetic moments.

  6. Rare-earth metal gallium silicides via the gallium self-flux method. Synthesis, crystal structures, and magnetic properties of RE(Ga1-xSix)2 (RE=Y, La-Nd, Sm, Gd-Yb, Lu)

    NASA Astrophysics Data System (ADS)

    Darone, Gregory M.; Hmiel, Benjamin; Zhang, Jiliang; Saha, Shanta; Kirshenbaum, Kevin; Greene, Richard; Paglione, Johnpierre; Bobev, Svilen

    2013-05-01

    Fifteen ternary rare-earth metal gallium silicides have been synthesized using molten Ga as a molten flux. They have been structurally characterized by single-crystal and powder X-ray diffraction to form with three different structures—the early to mid-late rare-earth metals RE=La-Nd, Sm, Gd-Ho, Yb and Y form compounds with empirical formulae RE(GaxSi1-x)2 (0.38≤x≤0.63), which crystallize with the tetragonal α-ThSi2 structure type (space group I41/amd, No. 141; Pearson symbol tI12). The compounds of the late rare-earth crystallize with the orthorhombic α-GdSi2 structure type (space group Imma, No. 74; Pearson symbol oI12), with refined empirical formula REGaxSi2-x-y (RE=Ho, Er, Tm; 0.33≤x≤0.40, 0.10≤y≤0.18). LuGa0.32(1)Si1.43(1) crystallizes with the orthorhombic YbMn0.17Si1.83 structure type (space group Cmcm, No. 63; Pearson symbol oC24). Structural trends are reviewed and analyzed; the magnetic susceptibilities of the grown single-crystals are presented.

  7. 40 CFR 721.6005 - Rare earth phosphate (generic).

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Rare earth phosphate (generic). 721... Substances § 721.6005 Rare earth phosphate (generic). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substances identified generically as rare earth phophate (PMNs...

  8. 40 CFR 721.6005 - Rare earth phosphate (generic).

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Rare earth phosphate (generic). 721... Substances § 721.6005 Rare earth phosphate (generic). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substances identified generically as rare earth phophate (PMNs...

  9. 40 CFR 721.6005 - Rare earth phosphate (generic).

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Rare earth phosphate (generic). 721... Substances § 721.6005 Rare earth phosphate (generic). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substances identified generically as rare earth phophate (PMNs...

  10. 40 CFR 721.6005 - Rare earth phosphate (generic).

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Rare earth phosphate (generic). 721... Substances § 721.6005 Rare earth phosphate (generic). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substances identified generically as rare earth phophate (PMNs...

  11. 40 CFR 721.6005 - Rare earth phosphate (generic).

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Rare earth phosphate (generic). 721... Substances § 721.6005 Rare earth phosphate (generic). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substances identified generically as rare earth phophate (PMNs...

  12. Magnetomigration of rare-earth ions in inhomogeneous magnetic fields.

    PubMed

    Franczak, Agnieszka; Binnemans, Koen; Jan Fransaer

    2016-10-05

    The effects of external inhomogenous (gradient) magnetic fields on the movement of the rare-earth ions: Dy(3+), Gd(3+) and Y(3+), in initially homogeneous aqueous solutions have been investigated. Differences in the migration of rare-earth ions in gradient magnetic fields were observed, depending on the magnetic character of the ions: paramagnetic ions of Dy(3+) and Gd(3+) move towards regions of the sample where the magnetic field gradient is the strongest, while diamagnetic ions of Y(3+) move in the opposite direction. It has been showed that the low magnetic field gradients, such the ones generated by permanent magnets, are sufficient to observe the magnetomigration effects of the ions in solution. The present work clearly establishes the behavior of magnetically different ions in initially homogeneous aqueous solutions exposed to magnetic field gradients. To this avail, a methodology for measuring the local concentration differences of metal ions in liquid samples was developed.

  13. Raman Investigations of Rare-Earth Orthovanadates

    SciTech Connect

    Santos, C. C.; Silva, E. N.; Ayala, A. P.; Guedes, I.; Pizani, P. S.; Loong, C. K.; Boatner, Lynn A

    2007-01-01

    Polarized Raman spectroscopy has been used to obtain the room-temperature phonon spectra of the series of rare earth orthovanadate single crystals: SmVO4, HoVO4, YbVO4 and LuVO4. The observed Raman frequencies follow the overall mode distribution expected for RVO4 compounds with the tetragonal zircon structure. The variation of the mode frequency with atomic number across the lanthanide orthovanadate series was investigated, and the trend exhibited by the internal modes was explained by considering the force constants of VO4 tetrahedron.

  14. Rare-Earth-Free Traction Motor: Rare Earth-Free Traction Motor for Electric Vehicle Applications

    SciTech Connect

    2012-01-01

    REACT Project: Baldor will develop a new type of traction motor with the potential to efficiently power future generations of EVs. Unlike today’s large, bulky EV motors which use expensive, imported rare-earth-based magnets, Baldor’s motor could be light, compact, contain no rare earth materials, and have the potential to deliver more torque at a substantially lower cost. Key innovations in this project include the use of a unique motor design, incorporation of an improved cooling system, and the development of advanced materials manufacturing techniques. These innovations could significantly reduce the cost of an electric motor.

  15. Note: Portable rare-earth element analyzer using pyroelectric crystal

    SciTech Connect

    Imashuku, Susumu Fuyuno, Naoto; Hanasaki, Kohei; Kawai, Jun

    2013-12-15

    We report a portable rare-earth element analyzer with a palm-top size chamber including the electron source of a pyroelectric crystal and the sample stage utilizing cathodoluminescence (CL) phenomenon. The portable rare-earth element analyzer utilizing CL phenomenon is the smallest reported so far. The portable rare-earth element analyzer detected the rare-earth elements Dy, Tb, Er, and Sm of ppm order in zircon, which were not detected by scanning electron microscopy-energy dispersive X-ray spectroscopy analysis. We also performed an elemental mapping of rare-earth elements by capturing a CL image using CCD camera.

  16. Characterization of a rare earth oxide obtained from xenotime mineral

    SciTech Connect

    Vernilli, Fernando . E-mail: fernando.vernilli@demar.faenquil.br; Camargo Vernilli, Daniela; Ferreira, Bento; Silva, Gilbert

    2007-01-15

    This paper reports on the characterization of a rare earth oxide obtained by hydrometallurgy of the mineral xenotime, an yttrium phosphate containing other rare earths, and comparison with mixtures of rare earth oxides prepared in different ways. The results indicated that hydrometallurgy from xenotime yielded a solid solution of the rare earth oxides. However, when the pure rare earth oxides were simply mixed physically then heat-treated at 1000 deg. C, a similar solid solution was not obtained. On the other hand, when the mixtures were prepared using a co-precipitation process, subsequent heat treatment did produce oxide solid solutions similar to that produced by hydrometallurgy of xenotime.

  17. Reflectives: Phosphors and lasers - shedding light on rare earths

    SciTech Connect

    Tonneson, L.C.; Fox, G.J.

    1996-04-01

    The first powder electroluminescent phosphor was introduced in 1936. Today, phosphors, particularly those made of high-purity rare earths, have found their way into a variety of products: industrial, commercial, and consumer, alike. The fluorescent lamp industry which remains the leading market for the use of high-purity rare earths, lit the way for the future of rare earths in the optical, x-ray, and display screen applications. Light combined with rare earth materials is also a successful recipe for reflectivity needed in filtering applications such as optics, lasers, and conductors. This article discusses the applications and markets for phosphors and rare earths.

  18. Atomic Transition Probabilities for Rare Earths

    NASA Astrophysics Data System (ADS)

    Curry, J. J.; Anderson, Heidi M.; den Hartog, E. A.; Wickliffe, M. E.; Lawler, J. E.

    1996-10-01

    Accurate absolute atomic transition probabilities for selected neutral and singly ionized rare earth elements including Tm, Dy, and Ho are being measured. The increasing use of rare earths in high intensity discharge lamps provides motivation; the data are needed for diagnosing and modeling the lamps. Radiative lifetimes, measured using time resolved laser induced fluorescence (LIF), are combined with branching fractions, measured using a large Fourier transform spectrometer (FTS), to determine accurate absolute atomic transition probabilities. More than 15,000 LIF decay curves from Tm and Dy atoms and ions in slow beams have been recorded and analyzed. Radiative lifetimes for 298 levels of TmI and TmII and for 450 levels of DyI and DyII are determined. Branching fractions are extracted from spectra recorded using the 1.0 m FTS at the National Solar Observatory. Branching fractions and absolute transition probabilities for 500 of the strongest TmI and TmII lines are complete. Representative lifetime and branching fraction data will be presented and discussed. Supported by Osram Sylvania Inc. and the NSF.

  19. Alkaline earth metal catalysts for asymmetric reactions.

    PubMed

    Kobayashi, Shū; Yamashita, Yasuhiro

    2011-01-18

    earth metal catalyst. We found that pyridinebisoxazolines (Pybox) worked well: they served as excellent ligands for calcium compounds in 1,4-addition reactions and Mannich reactions. Moreover, they were successful in 1,4-additions in concert with enantioselective protonation, affording the desired products in good to high enantioselectivities. Our results demonstrate that alkaline earth metals are very useful and attractive catalysts in organic synthesis. Moreover, their ubiquity in the environment is a distinct advantage over rare metals for large-scale processes, and their minimal toxicity is beneficial in both handling and disposal.

  20. Rare Earth Doped Silica Nanoparticles via Thermolysis of a Single Source Metallasilsesquioxane Precursor

    PubMed Central

    Davies, Gemma-Louise; O’Brien, John; Gun’ko, Yurii K.

    2017-01-01

    Rare earth metal doped silica nanoparticles have significant advantages over traditional organic dyes and quantum dots. Silsesquioxanes are promising precursors in the production of silica nanoparticles by thermolysis, due to their structural similarities with silica materials. This manuscript describes the production of a new Eu3+-based metallasilsesquioxane species and its use as a single source precursor in the thermolytic production of luminescent rare earth metal doped silica nanoparticles with characteristic emission in the visible region of the spectrum. PMID:28378754

  1. A COMPARISON OF FAR INFRARED AND RAMAN SPECTRA OF SOME RARE EARTH GARNET SINGLE CRYSTALS,

    DTIC Science & Technology

    RARE EARTH COMPOUNDS, *INFRARED SPECTRA), (*GARNET, RARE EARTH COMPOUNDS), (* RAMAN SPECTROSCOPY, RARE EARTH COMPOUNDS), SINGLE CRYSTALS, ALUMINATES...PHONONS, YTTRIUM COMPOUNDS, YTTERBIUM COMPOUNDS, TERBIUM COMPOUNDS, DYSPROSIUM COMPOUNDS, CANADA

  2. The formation of crystals in glasses containing rare earth oxides

    NASA Astrophysics Data System (ADS)

    Fadzil, Syazwani Mohd; Hrma, Pavel; Crum, Jarrod; Siong, Khoo Kok; Ngatiman, Mohammad Fadzlee; Said, Riduan Mt

    2014-02-01

    Korean spent nuclear fuel will reach the capacity of the available temporary storage by 2016. Pyroprocessing and direct disposal seems to be an alternative way to manage and reuse spent nuclear fuel while avoiding the wet reprocessing technology. Pyroprocessing produces several wastes streams, including metals, salts, and rare earths, which must be converted into stabilized form. A suitable form for rare earth immobilization is borosilicate glass. The borosilicate glass form exhibits excellent durability, allows a high waste loading, and is easy to process. In this work, we combined the rare earths waste of composition (in wt%) 39.2Nd2O3-22.7CeO2-11.7La2O3-10.9PrO2-1.3Eu2O3-1.3Gd2O3-8.1Sm2O3-4.8Y2O3 with a baseline glass of composition 60.2SiO2-16.0B2O3-12.6Na2O-3.8Al2O3-5.7CaO-1.7ZrO2. Crystallization in waste glasses occurs as the waste loading increases. It may produce complicate glass processing and affect the product quality. To study crystal formation, we initially made glasses containing 5%, 10% and 15% of La2O3 and then glasses with 5%, 10% and 15% of the complete rare earth mix. Samples were heat-treated for 24 hours at temperatures 800°C to 1150°C in 50°C increments. Quenched samples were analyzed using an optical microscope, scanning electron microscope with energy dispersive spectroscopy, and x-ray diffraction. Stillwellite (LaBSiO5) and oxyapatite (Ca2La8Si6O26) were found in glasses containing La2O3, while oxyapatite (Ca2La8Si6O26 and NaNd9Si6O26) precipitated in glasses with additions of mixed rare earths. The liquidus temperature (TL) of the glasses containing 5%, 10% and 15% La2O3 were 800°C, 959°C and 986°C, respectively; while TL was 825°C, 1059°C and 1267°C for glasses with 5%, 10% and 15% addition of mixed rare earth oxides. The component coefficients TB2O3, TSiO2, TCaO, and TRE2O3 were also evaluated using a recently published study.

  3. Exposure, metabolism, and toxicity of rare earths and related compounds.

    PubMed Central

    Hirano, S; Suzuki, K T

    1996-01-01

    For the past three decades, most attention in heavy metal toxicology has been paid to cadmium, mercury, lead, chromium, nickel, vanadium, and tin because these metals widely polluted the environment. However, with the development of new materials in the last decade, the need for toxicological studies on those new materials has been increasing. A group of rare earths (RE) is a good example. Although some RE have been used for superconductors, plastic magnets, and ceramics, few toxicological data are available compared to other heavy metals described above. Because chemical properties of RE are very similar, it is plausible that their binding affinities to biomolecules, metabolism, and toxicity in the living system are also very similar. In this report, we present an overview of the metabolism and health hazards of RE and related compounds, including our recent studies. Images Figure 1. A Figure 1. B Figure 1. C PMID:8722113

  4. Gaps and pseudogaps in perovskite rare earth nickelates

    SciTech Connect

    Allen, S. James; Ouellette, Daniel G.; Kally, James; Kozhanov, Alex; Hauser, Adam J.; Mikheev, Evgeny; Zhang, Jack Y.; Moreno, Nelson E.; Son, Junwoo; Stemmer, Susanne; Balents, Leon

    2015-06-01

    We report on tunneling measurements that reveal the evolution of the quasiparticle state density in two rare earth perovskite nickelates, NdNiO{sub 3} and LaNiO{sub 3}, that are close to a bandwidth controlled metal to insulator transition. We measure the opening of a sharp gap of ∼30 meV in NdNiO{sub 3} in its insulating ground state. LaNiO{sub 3}, which remains a correlated metal at all practical temperatures, exhibits a pseudogap of the same order. The results point to both types of gaps arising from a common origin, namely, a quantum critical point associated with the T = 0 K metal-insulator transition. The results support theoretical models of the quantum phase transition in terms of spin and charge instabilities of an itinerant Fermi surface.

  5. Anomalous Hall Effect in a Feromagnetic Rare-Earth Cobalite

    NASA Technical Reports Server (NTRS)

    Samoilov, A. V.; Yeh, N. C.; Vasquez, R. P.

    1996-01-01

    Rare-Earth manganites and cobalites with the perovskite structure have been a subject of great recent interest because their electrical resistance changes significantly when a magnetic field is applied...we have studied the Hall effect in thin film La(sub 0.5)Ca(sub 0.5)CoO(sub 3) material and have obtained convincing evidence fo the so called anomalous Hall effect, typical for magnetic metals...Our results suggest that near the ferromagnetic ordering temperature, the dominant electron scattering mechanism is the spin fluctuation.

  6. Rare earth elements in river waters

    NASA Technical Reports Server (NTRS)

    Goldstein, Steven J.; Jacobsen, Stein B.

    1988-01-01

    To characterize the input to the oceans of rare earth elements (REE) in the dissolved and the suspended loads of rivers, the REE concentrations were measured in samples of Amazon, Indus, Mississippi, Murray-Darling, and Ohio rivers and in samples of smaller rivers that had more distinct drainage basin lithology and water chemistry. It was found that, in the suspended loads of small rivers, the REE pattern was dependent on drainage basin geology, whereas the suspended loads in major rivers had relatively uniform REE patterns and were heavy-REE depleted relative to the North American Shale composite (NASC). The dissolved loads in the five major rivers had marked relative heavy-REE enrichments, relative to the NASC and the suspended material, with the (La/Yb)N ratio of about 0.4 (as compared with the ratio of about 1.9 in suspended loads).

  7. BOREHOLE NEUTRON ACTIVATION: THE RARE EARTHS.

    USGS Publications Warehouse

    Mikesell, J.L.; Senftle, F.E.

    1987-01-01

    Neutron-induced borehole gamma-ray spectroscopy has been widely used as a geophysical exploration technique by the petroleum industry, but its use for mineral exploration is not as common. Nuclear methods can be applied to mineral exploration, for determining stratigraphy and bed correlations, for mapping ore deposits, and for studying mineral concentration gradients. High-resolution detectors are essential for mineral exploration, and by using them an analysis of the major element concentrations in a borehole can usually be made. A number of economically important elements can be detected at typical ore-grade concentrations using this method. Because of the application of the rare-earth elements to high-temperature superconductors, these elements are examined in detail as an example of how nuclear techniques can be applied to mineral exploration.

  8. Rare-earth abundances in chondritic meteorites

    NASA Technical Reports Server (NTRS)

    Evensen, N. M.; Hamilton, P. J.; Onions, R. K.

    1978-01-01

    Fifteen chondrites, including eight carbonaceous chondrites, were analyzed for rare earth element abundances by isotope dilution. Examination of REE for a large number of individual chondrites shows that only a small proportion of the analyses have flat unfractionated REE patterns within experimental error. While some of the remaining analyses are consistent with magmatic fractionation, many patterns, in particular those with positive Ce anomalies, can not be explained by known magmatic processes. Elemental abundance anomalies are found in all major chondrite classes. The persistence of anomalies in chondritic materials relatively removed from direct condensational processes implies that anomalous components are resistant to equilibrium or were introduced at a late stage of chondrite formation. Large-scale segregation of gas and condensate is implied, and bulk variations in REE abundances between planetary bodies is possible.

  9. Rare earth doped zinc oxide varistors

    DOEpatents

    McMillan, A.D.; Modine, F.A.; Lauf, R.J.; Alim, M.A.; Mahan, G.D.; Bartkowiak, M.

    1998-12-29

    A varistor includes a Bi-free, essentially homogeneous sintered body of a ceramic composition including, expressed as nominal weight %, 0.2--4.0% oxide of at least one rare earth element, 0.5--4.0% Co{sub 3}O{sub 4}, 0.05--0.4% K{sub 2}O, 0.05--0.2% Cr{sub 2}O{sub 3}, 0--0.2% CaO, 0.00005--0.01% Al{sub 2}O{sub 3}, 0--2% MnO, 0--0.05% MgO, 0--0.5% TiO{sub 3}, 0--0.2% SnO{sub 2}, 0--0.02% B{sub 2}O{sub 3}, balance ZnO. 4 figs.

  10. Rare earth doped zinc oxide varistors

    DOEpatents

    McMillan, April D.; Modine, Frank A.; Lauf, Robert J.; Alim, Mohammad A.; Mahan, Gerald D.; Bartkowiak, Miroslaw

    1998-01-01

    A varistor includes a Bi-free, essentially homogeneous sintered body of a ceramic composition including, expressed as nominal weight %, 0.2-4.0% oxide of at least one rare earth element, 0.5-4.0% Co.sub.3 O.sub.4, 0.05-0.4% K.sub.2 O, 0.05-0.2% Cr.sub.2 O.sub.3, 0-0.2% CaO, 0.00005-0.01% Al.sub.2 O.sub.3, 0-2% MnO, 0-0.05% MgO, 0-0.5% TiO.sub.3, 0-0.2% SnO.sub.2, 0-0.02% B.sub.2 O.sub.3, balance ZnO.

  11. Parity Violation Experiments with Rare Earth Atoms

    NASA Astrophysics Data System (ADS)

    Budker, Dmitry

    1997-10-01

    Since the first suggestions (V. A. Dzuba, V. V. Flambaum, and I. B. Khriplovich, Z. Phys. D1, 243 (1986).), (A. Gongora and P. G. H. Sandars, J. Phys. B 19, L291 (1986).) to search for parity violation in the rare earth atoms, experiments have been carried out by groups in Novosibirsk, Oxford, Hiroshima and Berkeley with Sm, Yb and Dy. The status of these experiments will be reviewed, with some details given on recent Berkeley Dy results ( A.-T. Nguyen, D. Budker, D. DeMille, and M. Zolotorev, Submitted to Phys. Rev. A.). Progress of the Berkeley Yb experiment ( D. DeMille, Phys. Rev. Lett. 74, 4165 (1995).), ( C.J. Bowers, D. Budker, E.D. Commins, D. DeMille, S.J. Freedman, A.-T. Nguyen, S.-Q. Shang, and M. Zolotorev, Phys. Rev. A 53, 3103-9(1996). ) will be described elsewhere at this meeting by C. J. Bowers et al.

  12. Ferritin protein encapsulated photoluminescent rare earth nanoparticle

    NASA Astrophysics Data System (ADS)

    Harada, T.; Yoshimura, H.

    2013-07-01

    Rare earth (yttrium (Y), europium (Eu), and terbium (Tb)) nanoparticles and Eu and Tb doped Y nanoparticles are synthesized in an apoferritin cavity. They exhibit a narrow size distribution and a high stability in an aqueous solution at pH 8.5. Eu and Eu doped Y (Y:Eu) nanoparticles exhibit red photoluminescence (emission peaks: 590 and 614 nm), while Tb and Tb doped Y (Y:Tb) nanoparticles exhibit green photoluminescence (emission peaks: 488, 544, 582, and 618 nm). High-resolution electron microscopy observations reveal that about 5% of the nanoparticles have a lattice structure, while the remaining nanoparticles are amorphous. Electron diffraction of the Y nanoparticles gives lattice spacings corresponding to the cubic structure of yttrium oxide (Y2O3). The most optimal dopant content for luminescence of Y:Eu and Y:Tb nanoparticles in apoferritin cavity are about 60% and 40%, respectively.

  13. Mechanical properties of rare earth stannate pyrochlores

    NASA Astrophysics Data System (ADS)

    Feng, J.; Xiao, B.; Qu, Z. X.; Zhou, R.; Pan, W.

    2011-11-01

    The RE2Sn2O7 series compounds (RE = La, Nb, Sm, Gd, Er, Yb) with a pyrochlore structure are prepared by co-precipitation method. The bulk, shear, Young's moduli, B/G, and Poisson's ratios are calculated using density functional theory and also measured by ultrasonic resonance method. The theoretical values of lattice constants and mechanical moduli are smaller than experimental results. The electronic structures of RE2Sn2O7 are analogous to RE2Zr2O7. La2Sn2O7 exhibits stronger ionic bonds than others. The covalent interactions are slightly enhanced in the heavy rare earth stannate pyrochlores. The Vickers harnesses of RE2Sn2O7 are measured experimentally, which are smaller than theoretical predictions.

  14. Thermoelectric properties of rare earth chalcogenides

    NASA Technical Reports Server (NTRS)

    Danielson, L. R.; Raag, V.; Wood, C.

    1985-01-01

    The rare earth chalcogenides are important thermoelectric materials due to their high melting points, self-doping capabilities, and low thermal conductivities. Lanthanum sulfides and lanthanum tellurides have been synthesized in quartz ampules, hot-pressed into samples, and measured. The n-type Seebeck coefficients, electrical resistivities, and power factors generally all increased as the temperature increased from 200 to 1000 C. The figure-of-merit for nonstoichiometric lanthanum telluride was 0.001/deg C at 1000 C, considerably higher than for silicon-germanium. Thermoelectric measurements were made for LaTe(2) and YbS(1.4), and p-type behavior was observed for these compounds from 300 to 1100 C.

  15. Rare earths and other trace elements in Luna 16 soil.

    NASA Technical Reports Server (NTRS)

    Helmke, P. A.; Haskin, L. A.

    1972-01-01

    An analysis has been made of four small samples of material brought to earth by the Luna 16 mission, with the aim to determine rare earths and other trace elements in these samples. The analytical results are tabulated, and the rare earth abundances are compared with the average for chondrites. A comparison is also made with the results of similar analyses of Apollo samples.

  16. Rare Earth Elements in National Defense: Background, Oversight Issues, and Options for Congress

    DTIC Science & Technology

    2011-03-31

    light rare earths (lanthanum, cerium, praseodymium , neodymium, promethium, samarium) and heavy rare earths (europium, gadolinium, terbium, dysprosium...rare earth elements cerium, lanthanum, praseodymium , and neodymium. However, the Mountain Pass mine will not immediately be able to refine rare earth

  17. Electronic and magnetic coupling between rare-earth adatoms and the Fe(001) surface

    SciTech Connect

    Carbone, C. ); Rochow, R. ); Braicovich, L. ); Jungblut, R. ); Kachel, T. ); Tillmann, D.; Kisker, E. )

    1990-02-15

    The spin-dependent electronic structure of monolayer coverages of rare-earth metals on Fe(001) has been studied by spin-resolved photoelectron spectroscopy with synchrotron radiation. The highly spin-polarized photoemission from the localized 4{ital f} levels of Gd, Tb, and Dy on Fe(001) reveals the antiparallel coupling between these heavy rare earths and the Fe spin moment. Exchange-split final-state multiplet terms of the 4{ital f} spectra of the heavy rare earths are explicitly distinguished by direct observation of opposite polarization. For 1 monolayer of the light rare-earth Nd on Fe(001) the rare-earth magnetic moment couples parallel to the Fe magnetic moment.

  18. SALICYLATE PROCESS FOR THORIUM SEPARATION FROM RARE EARTHS

    DOEpatents

    Cowan, G.A.

    1959-08-25

    The separation of thorium from rare earths is accomplished by forming an aqueous solution of salts of thorium and rare earths and sufficient acetate buffer to provide a pH of between 2 and 5, adding an ammonium salicylate to the aqueous buffered solution, contacting the resultant solution with a substantially water-immiscible organic solvent mixture of an ether and an ester, and separating the solvent extract phase containing thorium salicylate from the aqueous phase containing the rare earths.

  19. China’s Rare Earth Policies: Economic Statecraft or Interdependence?

    DTIC Science & Technology

    2012-12-01

    Ministry of Land and Resources MOC Ministry of Commerce NdFeB Neodymium Iron Boron NDRC National Development and Reform...SmCo) and neodymium iron boron (NdFeB). NdFeB magnets, known to be the world’s strongest permanent magnets, monopolize rare earth magnet usage in...that there will likely be shortages of other light rare earths and many heavy rare earths (i.e., dysprosium, terbium, neodymium , europium and erbium

  20. Syntheses and crystal structures of the rare-earth metal(III) bromide ortho-oxidotungstates(VI) with the formula REBr[WO4] (RE = Y, Gd-Yb)

    NASA Astrophysics Data System (ADS)

    Schustereit, Tanja; Schleid, Thomas; Hartenbach, Ingo

    2015-10-01

    The rare-earth metal(III) bromide ortho-oxidotungstates(VI) with the formula REBr[WO4] crystallize triclinically in space group P 1 bar (a = 689-693, b = 715-728, c = 1074-1107 pm, α = 103-106, β ≈ 108 and γ = 93-95°, Z = 4) for RE = Y, Gd-Yb. Their crystal structure is isotypic with the most examples of the formally analogous lanthanoid(III) bromide oxidomolybdates(VI) REBr[MoO4] with RE = Y, Pr, Nd, Sm, Gd-Lu. It contains two crystallographically different rare-earth metal(III) cations with coordination numbers of seven plus one for (RE1)3+ and seven for (RE2)3+. The (RE1)3+ cations are surrounded by three Br- and four plus one O2- anions forming distorted trigonal dodecahedra, while the (RE2)3+ cations exhibit a coordination environment of one Br- and six O2- anions in the shape of a monocapped trigonal prism. Furthermore, the structure contains two crystallographically independent, isolated tetrahedral [WO4]2- units. All these polyhedra are fused together to form 1 ∞ {REBr[WO4]} chains running along [012]. Since the title compounds, synthesized by solid-state reactions from the underlying binaries, emerge as pure phases according to X-ray powder diffractometry, spectroscopic and magnetic measurements were performed.

  1. Bis(imino)diphenylamido rare-earth metal dialkyl complexes: synthesis, structure, and catalytic activity in living ring-opening ε-caprolactone polymerization and copolymerization with γ-butyrolactone.

    PubMed

    Du, Gaixia; Wei, Yanling; Zhang, Wei; Dong, Yuping; Lin, Zhengguo; He, Huan; Zhang, Shaowen; Li, Xiaofang

    2013-01-28

    Bis(imino)diphenylamido rare-earth metal dialkyl complexes [o-(2,6-(i)Pr(2)-C(6)H(3)-N=C-C(6)H(4))(2)-N]Ln(CH(2)SiMe(3))(2) (1: Ln = Sc; 2: Ln = Lu; 3: Ln = Y) have been synthesized in good yields and structurally characterized by elemental analysis, NMR spectroscopy, and single-crystal X-ray diffraction studies. They serve as highly efficient single-component catalysts both for the living ring-opening ε-caprolactone polymerization and random copolymerization with γ-butyrolactone, with the activity being dependent on the steric hindrance around the metal center, yielding high molecular weight PCLs or P(CL-co-BL)s with narrow molecular weight distributions.

  2. Half-sandwich rare-earth-catalyzed olefin polymerization, carbometalation, and hydroarylation.

    PubMed

    Nishiura, Masayoshi; Guo, Fang; Hou, Zhaomin

    2015-08-18

    The search for new catalysts for more efficient, selective chemical transformations and for the synthesis of new functional materials has been a long-standing research subject in both academia and industry. To develop new generations of catalysts that are superior or complementary to the existing ones, exploring the potential of untapped elements is an important strategy. Rare-earth elements, including scandium, yttrium, and the lanthanides (La-Lu), constitute one important frontier in the periodic table. Rare-earth elements possess unique chemical and physical properties that are different from those of main-group and late-transition metals. The development of rare-earth-based catalysts by taking the advantage of these unique properties is of great interest and importance. The most stable oxidation state of rare-earth metals is 3+, which is difficult to change under many reaction conditions. The oxidative addition and reductive elimination processes often observed in catalytic cycles involving late transition metals are generally difficult in the case of rare-earth complexes. The 18-electron rule that is applicable to late-transition-metal complexes does not fit rare-earth complexes, whose structures are mainly governed by the sterics (rather than the electron numbers) of the ligands. In the lanthanide series (La-Lu), the ionic radius gradually decreases with increasing atomic number because of the influence of the 4f electrons, which show poor shielding of nuclear charge. Rare-earth metal ions generally show strong Lewis acidity and oxophilicity. Rare-earth metal alkyl and hydride species are highly reactive, showing both nucleophilicity and basicity. The combination of these features, such as the strong nucleophilicity and moderate basicity of the alkyl and hydride species and the high stability, strong Lewis acidity, and unsaturated C-C bond affinity of the 3+ metal ions, can make rare-earth metals unique candidates for the formation of excellent single

  3. Multicomponent, Rare-Earth-Doped Thermal-Barrier Coatings

    NASA Technical Reports Server (NTRS)

    Miller, Robert A.; Zhu, Dongming

    2005-01-01

    Multicomponent, rare-earth-doped, perovskite-type thermal-barrier coating materials have been developed in an effort to obtain lower thermal conductivity, greater phase stability, and greater high-temperature capability, relative to those of the prior thermal-barrier coating material of choice, which is yttria-partially stabilized zirconia. As used here, "thermal-barrier coatings" (TBCs) denotes thin ceramic layers used to insulate air-cooled metallic components of heat engines (e.g., gas turbines) from hot gases. These layers are generally fabricated by plasma spraying or physical vapor deposition of the TBC materials onto the metal components. A TBC as deposited has some porosity, which is desirable in that it reduces the thermal conductivity below the intrinsic thermal conductivity of the fully dense form of the material. Undesirably, the thermal conductivity gradually increases because the porosity gradually decreases as a consequence of sintering during high-temperature service. Because of these and other considerations such as phase transformations, the maximum allowable service temperature for yttria-partially stabilized zirconia TBCs lies in the range of about 1,200 to 1,300 C. In contrast, the present multicomponent, rare-earth-doped, perovskite-type TBCs can withstand higher temperatures.

  4. Data fusion for food authentication. Combining rare earth elements and trace metals to discriminate "Fava Santorinis" from other yellow split peas using chemometric tools.

    PubMed

    Drivelos, Spiros A; Higgins, Kevin; Kalivas, John H; Haroutounian, Serkos A; Georgiou, Constantinos A

    2014-12-15

    "Fava Santorinis", is a protected designation of origin (PDO) yellow split pea species growing only in the island of Santorini in Greece. Due to its nutritional quality and taste, it has gained a high monetary value. Thus, it is prone to adulteration with other yellow split peas. In order to discriminate "Fava Santorinis" from other yellow split peas, four classification methods utilising rare earth elements (REEs) measured through inductively coupled plasma-mass spectrometry (ICP-MS) are studied. The four classification processes are orthogonal projection analysis (OPA), Mahalanobis distance (MD), partial least squares discriminant analysis (PLS-DA) and k nearest neighbours (KNN). Since it is known that trace elements are often useful to determine geographical origin of food products, we further quantitated for trace elements using ICP-MS. Presented in this paper are results using the four classification processes based on the fusion of the REEs data with the trace element data. Overall, the OPA method was found to perform best with up to 100% accuracy using the fused data.

  5. Accumulation of rare earth elements by siderophore-forming Arthrobacter luteolus isolated from rare earth environment of Chavara, India.

    PubMed

    Emmanuel, E S Challaraj; Ananthi, T; Anandkumar, B; Maruthamuthu, S

    2012-03-01

    In this study, Arthrobacter luteolus, isolated from rare earth environment of Chavara (Quilon district, Kerala, India), were found to produce catechol-type siderophores. The bacterial strain accumulated rare earth elements such as samarium and scandium. The siderophores may play a role in the accumulation of rare earth elements. Catecholate siderophore and low-molecular-weight organic acids were found to be present in experiments with Arthrobacter luteolus. The influence of siderophore on the accumulation of rare earth elements by bacteria has been extensively discussed.

  6. Precise rare earth analysis of geological materials

    SciTech Connect

    Laul, J.C.; Wogman, N.A.

    1982-01-01

    Rare earth element (REE) concentrations are very informative in revealing chemical fractionation processs in geological systems. The REE's (La-Lu) behavior is characteristic of various primary and secondary minerals which comprise a rock. The REE's contents and their patterns provide a strong fingerprint in distinguishing among various rock types and in understanding the partial melting and/or fractional crystallization of the source region. The REE contents in geological materials are usually at trace levels. To measure all the REE at such levels, radiochemical neutron activation analysis (RNAA) has been used with a REE group separation scheme. To maximize detection sensitivites for individual REE, selective ..gamma..-ray/x-ray measurements have been made using normal Ge(Li) and low-energy photon detectors (LEPD), and Ge(Li)-NaI(Tl) coincidence-noncoincidence spectrometer systems. Using these detection methods an individual REE can be measured at or below the ppB levels; chemical yields of the REE are determined by reactivation.

  7. Monolithic integration of rare-earth oxides and semiconductors for on-silicon technology

    SciTech Connect

    Dargis, Rytis Clark, Andrew; Erdem Arkun, Fevzi; Grinys, Tomas; Tomasiunas, Rolandas; O'Hara, Andy; Demkov, Alexander A.

    2014-07-01

    Several concepts of integration of the epitaxial rare-earth oxides into the emerging advanced semiconductor on silicon technology are presented. Germanium grows epitaxially on gadolinium oxide despite lattice mismatch of more than 4%. Additionally, polymorphism of some of the rare-earth oxides allows engineering of their crystal structure from hexagonal to cubic and formation of buffer layers that can be used for growth of germanium on a lattice matched oxide layer. Molecular beam epitaxy and metal organic chemical vapor deposition of gallium nitride on the rare-earth oxide buffer layers on silicon is discussed.

  8. Research on new rare-earth half-metallic ferromagnets X0.75Eu0.25O (X=Ca, Sr and Ba) based on the first-principles calculations

    NASA Astrophysics Data System (ADS)

    Jun, Liu; Xiao-Lan, Yang; Wei, Kang

    2016-09-01

    New rare-earth half-metallic ferromagnets X0.75Eu0.25O (X=Ca, Sr and Ba) with the NaCl structure are predicted based on the first-principles calculations. These materials only have up-spin subbands at the Fermi level and their net magnetic moments are all 7.00 μB per unit cell, which exhibits the evident half-metallic characteristics. Their energy gaps and half-metallic gaps are both wide so that they all have high Curie temperatures and stable half-metallicity, holding great potential applications in spintronics. From the calculated formation energies, it is possible to prepare Sr0.75Eu0.25O and Ba0.75Eu0.25O experimentally. However, it may be difficult to prepare Ca0.75Eu0.25O in experiments. The magnetic moments and the half-metallicity of X0.75Eu0.25O mainly originate from the spin-polarization of Eu 4f-orbitals, which are caused by the strong octahedral crystal field in the ligand compound ML6 consisting of the Eu-ion and six O-ions around it.

  9. Rare earth element diffusion in natural enstatite

    NASA Astrophysics Data System (ADS)

    Cherniak, Daniele J.; Liang, Yan

    2007-03-01

    Chemical diffusion coefficients of La, Nd, Eu, Gd, and Yb in natural enstatite have been measured at 850-1250 °C and 1 atm. Anhydrous diffusion experiments were run in Pt capsules in air, or in sealed silica glass capsules under an iron-wüstite (IW) solid buffer. The sources of diffusant were pre-reacted mixtures of synthetic enstatite powder and microcrystalline rare-earth aluminate garnet. Rutherford Backscattering Spectrometry (RBS) was used to measure diffusion profiles. For Gd diffusion in air over the temperature range 1000-1250 °C, the following Arrhenius relation is found for diffusion normal to (210): D=2.55×10-9exp(321±85mol /RT)ms-1. There is no significant difference between Gd diffusion in air and under IW-buffered conditions. Behavior similar to Gd is also noted for Nd. The Arrhenius relationship for Eu diffusion in enstatite, normal to (210) and at 850-1150 °C and IW-buffered conditions, is D=6.93×10-6exp(-384±29mol /RT)ms-1. For Eu diffusion in air over the temperature range 1000-1200 °C for the same orientation, the following Arrhenius relation is found: D=1.70×10-8exp(-350±42mol /RT)ms-1. For Eu diffusion under IW-buffered conditions and for experiments run in air, diffusivities normal to (001) are similar to those for diffusion normal to (210). Eu diffusion under IW-buffered conditions is more than an order of magnitude faster than Eu diffusion in air. It is likely that majority of Eu is in the divalent state for diffusion under IW-buffered conditions, but Eu is in the trivalent state for diffusion in air. In the case of Nd and Gd, where valence state does not change under the investigated fO 2 conditions, diffusivities measured for experiments run both in air and under IW-buffered conditions are comparable to those obtained for trivalent Eu. Further, measurements of La, Nd, Eu +3, Gd, and Yb diffusion suggest that diffusion of trivalent REE in enstatite is not sensitive to ionic size, in contrast to that observed for REE diffusion in

  10. Google Earth locations of USA and seafloor hydrothermal vents with associated rare earth element data

    SciTech Connect

    Andrew Fowler

    2016-02-10

    Google Earth .kmz files that contain the locations of geothermal wells and thermal springs in the USA, and seafloor hydrothermal vents that have associated rare earth element data. The file does not contain the actual data, the actual data is available through the GDR website in two tier 3 data sets entitled "Compilation of Rare Earth Element Analyses from US Geothermal Fields and Mid Ocean Ridge (MOR) Hydrothermal Vents" and "Rare earth element content of thermal fluids from Surprise Valley, California"

  11. Trace Metals, Rare Earths, Carbon and Pb Isotopes as Proxies of Environmental Catastrophe at the Permian - Triassic Boundary in Spiti Himalayas, India

    NASA Astrophysics Data System (ADS)

    Ghosh, N.; Basu, A. R.; Garzione, C. N.; Ghatak, A.; Bhargava, O. N.; Shukla, U. K.; Ahluwalia, A. D.

    2015-12-01

    Himalayan sediments from Spiti Valley, India preserve geochemical signatures of the Permian - Triassic (P-Tr) mass extinction in the Neo-Tethys Ocean. We integrate new sedimentological and fossil record with high-resolution geochemical-isotopic data from Spiti that reveals an ecological catastrophe of global proportions. Trace elements of U, Th, Nb, Ta, Zr, Hf, the rare earths (REE) and carbon, oxygen and lead isotopes measured across the P-Tr boundary in Spiti are used as proxies for evaluating abrupt changes in this continental shelf environment. δ13Corg excursions of 2.4‰ and 3.1‰ in Atargu and Guling P-Tr sections in Spiti Valley are associated with an abrupt fall of biological productivity while δ13Ccarb and δ18Ocarb record of these sediments shows effects of diagenesis. Here, the P-Tr boundary is compositionally distinct from the underlying Late Permian gray shales, as a partly gypsiferous ferruginous layer that allows additional geochemical-isotopic investigation of sedimentary sources. Conspicuous Ce - Eu anomalies in the light REE-enriched Late Permian shales reflect the source composition of the adjacent Panjal Trap basalts of Kashmir. An abrupt change of this source to continental crust is revealed by Nb - Ta and Zr - Hf anomalies at the P-Tr ferruginous layer and continuing through the overlying Early Triassic carbonate rocks. Pb concentration and isotope ratios of 206Pb/204Pb, 207Pb/204Pb and 208Pb/204Pb identify changes in the sedimentary element flux, distinguishing the Late Permian shales from the distinct siliciclastic continental crustal signature in the Early Triassic carbonates. These geochemical-isotopic constraints on the sedimentary geochemistry of one of the most critical transitions in geological record establish the utility of multi-proxy datasets for paleoenvironmental reconstructions.

  12. Rare earth element enrichment using membrane based solvent extraction

    NASA Astrophysics Data System (ADS)

    Makertiharta, I. G. B. N.; Dharmawijaya, P. T.; Zunita, M.; Wenten, I. G.

    2017-01-01

    The chemical, catalytic, electrical, magnetic, and optical properties of rare earth elements are required in broad applications. Rare earth elements have similar physical and chemical properties thus it is difficult to separate one from each other. Rare earth element is relatively abundant in earth's crust but rarely occur in high concentrated deposits. Traditionally, ion-exchange and solvent extraction techniques have been developed to separate and purify single rare earth solutions or compounds. Recently, membrane starts to gain attention for rare earth separation by combining membrane and proven technologies such as solvent extraction. Membrane-based process offers selective, reliable, energy efficient and easy to scale up separation. During membrane-based separation process, one phase passes through membrane pores while the other phase is rejected. There is no direct mixing of two phases thus the solvent loss is very low. Membrane can also lower solvent physical properties requirement (viscosity, density) and backmixing, eliminate flooding phenomenon and provide large interfacial area for mass transfer. This paper will summarize research efforts in developing membrane technology for rare earth element separation. Special attention will be given to solvent extraction related process as the commonly used method for rare earth element separation. Furthermore, membrane configuration and its potentials will also be discussed.

  13. Optical Properties of Nd Doped Rare Earth Vanadates (Preprint)

    DTIC Science & Technology

    2010-07-01

    common of these is yttrium orthovanadate, other rare earth vanadates such as lutetium vanadate and gadolinium vanadate are being used for their...state laser hosts such as YAG. While the most common of these is yttrium orthovanadate, other rare earth vanadates such as lutetium vanadate and

  14. How PNNL Extracts Rare Earth Elements from Geothermal Brine

    SciTech Connect

    2016-07-12

    By looking at a problem at a nanoscale level, PNNL researchers are developing an economic way to extract valuable rare earth elements from geothermal fluids. This novel approach may help meet the high demand for rare earth elements that are used in many clean energy technologies.

  15. Tunable, rare earth-doped solid state lasers

    DOEpatents

    Emmett, John L.; Jacobs, Ralph R.; Krupke, William F.; Weber, Marvin J.

    1980-01-01

    Laser apparatus comprising combinations of an excimer pump laser and a rare earth-doped solid matrix, utilizing the 5d-4f radiative transition in a rare earth ion to produce visible and ultra-violet laser radiation with high overall efficiency in selected cases and relatively long radiative lifetimes.

  16. Rare-earth occurrences in the Pea Ridge tailings

    SciTech Connect

    Vierrether, C.W.; Cornell, W.I.

    1993-01-01

    Tailings from the Pea Ridge iron mine contain significant amounts of apatite, which has rare-earth element values associated with it. In association with the recovery of rare-earth minerals as a secondary resource, the US Bureau of Mines conducted an investigation on the recoverability of the rare-earth minerals from the tailings. The mill tailings were subjected to a phosphate flotation to separate the apatite from other constituents. More than 70-pct recovery of the rare-earth values was achieved. Based on mineralogical characterization and prior analysis of rare-earth-bearing breccia pipe material at Pea Ridge, it is proposed that processing this phosphate concentrate on a vanner table would yield up to a 95-pct recovery of the rare earths in the concentrate, with the apatite reporting to the tailings. Intensive ore microscopy studies of the original tailings to the flotation products led to the identification of monazite, xenotime, and rare-earth-enriched apatite as the major rare-earth-bearing minerals in the tailings.

  17. Condensation and fractionation of rare earths in the solar nebula

    NASA Technical Reports Server (NTRS)

    Davis, A. M.; Grossman, L.

    1979-01-01

    The condensation behavior of the rare earth elements in the solar nebula is calculated on the basis of the most recent thermodynamic data in order to construct a model explaining group II rare earth element patterns in Allende inclusions. Models considered all involve the removal of large fractions of the more refractory heavy rare earth elements in an early condensate, followed by the condensation of the remainder at a lower temperature. It is shown that the model of Boynton (1975) in which one rare earth element component is dissolved nonideally in perovskite according to relative activity coefficients can not reasonably be made to fit the observed group II patterns. A model in which two rare earth components control the patterns and dissolve ideally in perovskite is proposed and shown to be able to account for the 20 patterns by variations of the perovskite removal temperature and the relative proportions of the two components.

  18. PROCESS FOR SEPARATING AMERICIUM AND CURIUM FROM RARE EARTH ELEMENTS

    DOEpatents

    Baybarz, R.D.; Lloyd, M.H.

    1963-02-26

    This invention relates to methods of separating americium and curium values from rare earth values. In accordance with the invention americium, curium, and rare earth values are sorbed on an anion exchange resin. A major portion of the rare earth values are selectively stripped from the resin with a concentrated aqueous solution of lithium chloride, and americium, curium, and a minor portion of rare earth values are then stripped from the resin with a dilute aqueous solution of lithium chloride. The americium and curium values are further purified by increasing the concentration of lithium chloride in the solution to at least 8 molar and selectively extracting rare earth values from the resulting solution with a monoalkylphosphoric acid. (AEC)

  19. Rare earth elements in Hamersley BIF minerals

    NASA Astrophysics Data System (ADS)

    Alibert, Chantal

    2016-07-01

    Minerals from the Hamersley banded iron formation, Western Australia, were analyzed for Y and rare earth elements (YREEs) by laser ablation ICP-MS to investigate diagenetic pathways, from precursor phases to BIF minerals. One group of apatites carries the seawater REE signature, giving evidence that P and REEs, thoroughly scavenged from the water column by Si-ferrihydrite particles, were released upon microbial Fe3+ reductive dissolution of Si-ferrihydrite in pore-water and finally sequestered mainly in authigenic apatite. The absence of fractionation between apatite and seawater suggests that REE were first incorporated into an amorphous calcium phosphate as fully hydrated cations, i.e. as outer-sphere complexes. The iron oxides and carbonates carry only a small fraction of the whole-rock REE budget. Their REE patterns are distinctly enriched in Yb and show some M-type tetrad effect consistent with experimental Kd(REE) between solid and saline solution with low carbonate ion concentrations. It is deduced that hematite formed at an incipient stage of Fe2+-catalyzed dissolution of Si-ferrihydrite, via a dissolution-reprecipitation pathway. The REE pattern of greenalite, found as sub-micron particles in quartz in a chert-siderite sample, is consistent with its authigenic origin by precipitation in pore-water after dissolution of a small amount of Si-ferrihydrite. Magnetite carries very low YREEs (ppb-level), has an homogeneous pattern distinctly enriched in the mid-REEs compared to hematite, and includes a late population depleted in light-REEs, Ba and As. Magnetite forming aggregates and massive laminae is tentatively interpreted as reflecting some fluid-aided hematite-magnetite re-equilibration or transformation at low-grade metamorphic temperatures.

  20. [Effects of arbuscular mycorrhizal fungi on the growth and rare earth elements uptake of soybean grown in rare earth mine tailings].

    PubMed

    Guo, Wei; Zhao, Ren-xin; Zhao, Wen-jing; Fu, Rui-ying; Guo, Jiang-yuan; Zhang, Jun

    2013-05-01

    A greenhouse pot experiment was conducted to investigate the influence of arbuscular mycorrhizal (AM) fungi Glomus versiforme on the plant growth, nutrient uptake, C: N: P stoichiometric, uptake of heavy metals and rare earth elements by soybean (Glycine max) grown in rare earth mine tailings. The aim was to provide a basis for the revegetation of rare earth mine tailings. The results indicated that soybean had a high mycorrhizal colonization and symbiotic associations were successfully established with G. versiforme, with an average rate of approximately 67%. The colonization of G. versiforme significantly promoted the growth of soybean, increased P, K contents, and decreased C: N: P ratios, supporting the growth rate hypothesis. Inoculation with G. versiforme significantly decreased shoots and roots La, Ce, Pr and Nd concentrations of soybean compared to the control treatment. However, inoculation with G. versiforme had no significant effect on the heavy metal concentrations, except for significantly decreased shoot Fe and Cr concentrations and increased root Cd concentrations. The experiment demonstrates that AM fungi have a potential role for soybean to adapt the composite adversity of rare earth tailings and play a positive role in revegetation of rare earth mine tailings. Further studies on the role of AM fungi under natural conditions should be conducted.

  1. Bacterial Cell Surface Adsorption of Rare Earth Elements

    NASA Astrophysics Data System (ADS)

    Jiao, Y.; Park, D.; Reed, D.; Fujita, Y.; Yung, M.; Anderko, A.; Eslamimanesh, A.

    2015-12-01

    Rare earth elements (REE) play a critical role in many emerging clean energy technologies, including high-power magnets, wind turbines, solar panels, hybrid/electric vehicle batteries and lamp phosphors. In order to sustain demand for such technologies given current domestic REE shortages, there is a need to develop new approaches for ore processing/refining and recycling of REE-containing materials. To this end, we have developed a microbially-mediated bioadsorption strategy with application towards enrichment of REE from complex mixtures. Specifically, the bacterium Caulobacter crescentus was genetically engineered to display lanthanide binding tags (LBTs), short peptides that possess high affinity and specificity for rare earth elements, on its cell surface S-layer protein. Under optimal conditions, LBT-displayed cells adsorbed greater than 5-fold more REE than control cells lacking LBTs. Competition binding experiments with a selection of REEs demonstrated that our engineered cells could facilitate separation of light- from heavy- REE. Importantly, binding of REE onto our engineered strains was much more favorable compared to non-REE metals. Finally, REE bound to the cell surface could be stripped off using citrate, providing an effective and non-toxic REE recovery method. Together, this data highlights the potential of our approach for selective REE enrichment from REE containing mixtures.

  2. Mines, prospects, and occurrences of metallic (excluding gold), pegmatite, and rare-earth mineral commodities in the Greenville 1 degree by 2 degrees Quadrangle, South Carolina, Georgia, and North Carolina

    USGS Publications Warehouse

    D'Agostino, John P.; Zupan, Alan Jon; Maybin, Arthur H.; Abrams, Charlotte E.; German, Jerry M.

    1994-01-01

    All of the known mines, prospects, and occurrences of metallic (excluding gold, pegmatite, and rare-earth mineral commodities for the Greenville 1° x 2° quadrangle are tabulated in this report. The table lists, in consecutive order for each county (fig. 1), the map number of each item, which correlates and locates the item on the accompanying Greenville 1° x 2° quadrangle map. The known name of the feature; the 7.5' topographic map on the which the commodity site is located; the Universal Transverse Mercator (UTM) northing and easting grid coordinates from the appropriate 7.5' topographic map; the commodity; remarks; and references are also listed. Some locations are known, but many sites are not verified and their locations are only approximate. References are listed in References Cited and referred to by number to save space.

  3. The formation of crystals in glasses containing rare earth oxides

    SciTech Connect

    Fadzil, Syazwani Mohd; Hrma, Pavel; Crum, Jarrod; Siong, Khoo Kok; Ngatiman, Mohammad Fadzlee; Said, Riduan Mt

    2014-02-12

    Korean spent nuclear fuel will reach the capacity of the available temporary storage by 2016. Pyroprocessing and direct disposal seems to be an alternative way to manage and reuse spent nuclear fuel while avoiding the wet reprocessing technology. Pyroprocessing produces several wastes streams, including metals, salts, and rare earths, which must be converted into stabilized form. A suitable form for rare earth immobilization is borosilicate glass. The borosilicate glass form exhibits excellent durability, allows a high waste loading, and is easy to process. In this work, we combined the rare earths waste of composition (in wt%) 39.2Nd{sub 2}O{sub 3}–22.7CeO{sub 2}–11.7La{sub 2}O{sub 3}–10.9PrO{sub 2}–1.3Eu{sub 2}O{sub 3}–1.3Gd{sub 2}O{sub 3}–8.1Sm{sub 2}O{sub 3}–4.8Y{sub 2}O{sub 3} with a baseline glass of composition 60.2SiO{sub 2}–16.0B{sub 2}O{sub 3}–12.6Na{sub 2}O–3.8Al{sub 2}O{sub 3}–5.7CaO–1.7ZrO{sub 2}. Crystallization in waste glasses occurs as the waste loading increases. It may produce complicate glass processing and affect the product quality. To study crystal formation, we initially made glasses containing 5%, 10% and 15% of La{sub 2}O{sub 3} and then glasses with 5%, 10% and 15% of the complete rare earth mix. Samples were heat-treated for 24 hours at temperatures 800°C to 1150°C in 50°C increments. Quenched samples were analyzed using an optical microscope, scanning electron microscope with energy dispersive spectroscopy, and x-ray diffraction. Stillwellite (LaBSiO{sub 5}) and oxyapatite (Ca{sub 2}La{sub 8}Si{sub 6}O{sub 26}) were found in glasses containing La{sub 2}O{sub 3}, while oxyapatite (Ca{sub 2}La{sub 8}Si{sub 6}O{sub 26} and NaNd{sub 9}Si{sub 6}O{sub 26}) precipitated in glasses with additions of mixed rare earths. The liquidus temperature (T{sub L}) of the glasses containing 5%, 10% and 15% La{sub 2}O{sub 3} were 800°C, 959°C and 986°C, respectively; while T{sub L} was 825°C, 1059°C and 1267°C for glasses

  4. Dissolution of functional materials and rare earth oxides into pseudo alveolar fluid.

    PubMed

    Takaya, Mitsutoshi; Shinohara, Yasushi; Serita, Fumio; Ono-Ogasawara, Mariko; Otaki, Noriko; Toya, Tadao; Takata, Ayako; Yoshida, Katsumi; Kohyama, Norihiko

    2006-10-01

    The dissolution rates of rare earth oxides and two types of rare earth containing functional materials into water, saline solution, and Gamble's fluid were measured in order to evaluate the biological effects of rare earth-containing functional materials. The tested materials were yttrium, lanthanum, cerium and neodymium oxides, and neodymium-boron-iron magnet alloy (NdBFe) and lanthanum-mish-metal-nickel-cobalt (LmNiCo) hydrogen-containing alloy. The dissolution rates of the rare earth oxides were very low, resulting in concentrations of rare earth elements in the test solutions of the order of ppb. In the most extreme case, Gamble's fluid dissolved 1,400 times more of the rare earth oxides than pure water. Fairly high concentration of neodymium were found in the dissolving fluids, which means that trace neodymium present as an impurity in each rare earth oxide dissolved preferentially. For yttrium oxide, the ratio of neodymium to yttrium that dissolved in the saline solution was greater than 78,000 to 1, taking into account the amount of each that was originally present in the yttrium oxide.

  5. Effects of spraying rare earths on contents of rare Earth elements and effective components in tea.

    PubMed

    Wang, Dongfeng; Wang, Changhong; Ye, Sheng; Qi, Hongtao; Zhao, Guiwen

    2003-11-05

    Rare earth (RE) fertilizer is widely applied in China to increase the yield and the quality of crops including tea. However, the effects of spraying RE fertilizer on the contents of rare earth elements (REE) and effective components in tea are unknown. The results from basin and field experiments show that the values of the REE concentrations in new shoots of tea plants and the concentration of REE in the soil (REE/REEs) either from control basins or from treatment basins were smaller than those in other parts of tea plant and similar between control and treatment. The longer the interval between spraying RE fertilizer and picking the shoots of tea plants, the less the effects from spraying. About 80% summation operator REE (the sum of the concentrations of 15 REE) in tea, whether it came from spraying or not, was insoluble in the infusion. About 10% the soluble REE of summation operator REE in tea infusion was bound to polysaccharide, and the amount of REE bound polysaccharide decreased over time. At least a 25 day safety interval is needed between spraying and picking if the microelement fertilizer is used, in order to enhance tea output and to ensure tea safety.

  6. Rare Earth Elements in Global Aqueous Media

    NASA Astrophysics Data System (ADS)

    Noack, C.; Karamalidis, A.; Dzombak, D. A.

    2012-12-01

    We are examining the occurrence and abundance of rare earth elements (REE) associated with produced waters from shale gas development, and factors controlling aqueous REE concentrations in geochemical environments, to provide information for: (1) potential recovery of REE as a valuable byproduct, and (2) utilization of unique REE signatures as a risk assessment tool. REE include the lanthanide series of elements - excluding short-lived, radioactive promethium - and yttrium. These elements are critical to a wide variety of high-tech, energy efficient applications such as phosphors, magnets, and batteries. Escalating costs of REE resulting from divergent supply and demand patterns motivates the first goal. The second goal relates to the search for a reliable, naturally occurring tracer to improve understanding of fluid migration and water-rock interactions during hydraulic fracturing and natural gas recovery. We compiled data from 100 studies of REE occurrence and concentrations in groundwaters, ocean waters, river waters, and lake waters. In the groundwater systems documented, total dissolved REE concentrations ranged over eight orders of magnitude; however the average concentrations across the lanthanides varied by less than two orders of magnitude. This leads to exceptional inter-element correlations, with a median correlation coefficient greater than 0.98, implying potential usefulness of REE ratios for groundwater signatures. Reports describing reactions governing REE solubilization were also investigated. We assembled information about important solution chemistries and performed equilibrium modeling using PHREEQC to examine common hypotheses regarding the factors controlling REE compositions. In particular, effects of pH, Eh, and common complexing ligands were evaluated. Produced and connate waters of the Marcellus shale are well characterized for their major chemical elements. There is a dearth of knowledge, however, regarding the occurrence of REE in

  7. [Content of rare earth elements in wild Hypericum japonicum Thunb].

    PubMed

    Wei, Zhen-Lin; Rui, Yu-Kui; Tian, Zhi-Huan

    2009-06-01

    Rare earth elements are important nutritional elements for human health, and today more and more attention has been paid to the effective components in Chinese traditional medicine, especially to rare earth elements. Fifteen rare earth elements in wild hypericum japonicum Thunb were analyzed by the methods of ICP-MS. The results showed that the concentrations of La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Yb, Tm, Lu and Y ranged from 6 ng x g(-1) x DW to 14 522 ng x g(-1) x DW, and among them the concentrations of La, Ce and Nd were higher than 2 000 ng x g(-1) x DW. Compared with the concentration of rare earth elements in rice, corn, wheat and barley, the total concentration of rare earth elements in hypericum japonicum Thunb was much higher, which could be the mechanism of curative effect of hypericum japonicum Thunb on liverish diseases. The character of elements and the content of rare earth elements in soil should be responsible for the difference, but the distributive mechanism of rare earth elements in hypericum japonicum Thunb should be further studied.

  8. Bioleaching of rare earth elements from monazite sand.

    PubMed

    Brisson, Vanessa L; Zhuang, Wei-Qin; Alvarez-Cohen, Lisa

    2016-02-01

    Three fungal strains were found to be capable of bioleaching rare earth elements from monazite, a rare earth phosphate mineral, utilizing the monazite as a phosphate source and releasing rare earth cations into solution. These organisms include one known phosphate solubilizing fungus, Aspergillus niger ATCC 1015, as well as two newly isolated fungi: an Aspergillus terreus strain ML3-1 and a Paecilomyces spp. strain WE3-F. Although monazite also contains the radioactive element Thorium, bioleaching by these fungi preferentially solubilized rare earth elements over Thorium, leaving the Thorium in the solid residual. Adjustments in growth media composition improved bioleaching performance measured as rare earth release. Cell-free spent medium generated during growth of A. terreus strain ML3-1 and Paecilomyces spp. strain WE3-F in the presence of monazite leached rare earths to concentrations 1.7-3.8 times those of HCl solutions of comparable pH, indicating that compounds exogenously released by these organisms contribute substantially to leaching. Organic acids released by the organisms included acetic, citric, gluconic, itaconic, oxalic, and succinic acids. Abiotic leaching with laboratory prepared solutions of these acids was not as effective as bioleaching or leaching with cell-free spent medium at releasing rare earths from monazite, indicating that compounds other than the identified organic acids contribute to leaching performance.

  9. Structure and Properties of Rare Earth Aluminosilicate Glasses.

    NASA Astrophysics Data System (ADS)

    Kohli, Jeffrey Todd

    1991-02-01

    Rare earth aluminosilicate (REAS) glasses have been formed using conventional melting techniques. The glass-forming regions of six different ternary systems have been defined with praseodymium, neodymium, samarium, terbium, erbium, or ytterbium oxides, with alumina and silica. The glass-forming regions systematically decreased in size as the atomic number of the particular rare earth in the ternary systems increased. Glasses, of the molar composition 2R_2O_3 -2Al_2O_3 -6SiO_2, were formed with twelve of the fourteen true rare earth oxides in order to investigate further effects related to the identity of the rare earth ion in the glasses. Several properties of the rare earth aluminosilicate glasses were measured. These properties include: thermal expansion, glass transformation temperature, dilatometric softening point, density, molar volume, index of refraction, Vicker's hardness, magnetic susceptibility and the Faraday rotatory response. The structures of rare earth aluminosilicate glasses were investigated using infrared and Raman spectroscopies as well as magic angle spinning nuclear magnetic resonance (MAS-NMR). MAS-NMR provided information regarding the local environments of silicon and aluminum ions in yttrium aluminosilicate (YAS) glasses. Since the size and valence of the yttrium ion are similar to the true rare earth ions, and the properties of the REAS and YAS glasses are similar, it is believed that the structures of yttrium aluminosilicate glasses are similar to those of the true rare earth aluminosilicate glasses. Several rare earth aluminogermanate glasses, having the molar formula 2R_2O _3-2Al_2O _3-6GeO_2, were also formed using conventional melting techniques. The properties of these glasses were compared and contrasted with those of the REAS glasses. Finally, a chapter on the study of magnetic susceptibility in common insulator glasses was added to the thesis. Several techniques used to measure magnetic susceptibility are reviewed in this chapter

  10. Bioavailability of heavy metals, germanium and rare earth elements at Davidschacht dump-field in mine affected area of Freiberg (Saxony)

    NASA Astrophysics Data System (ADS)

    Midula, Pavol; Wiche, Oliver

    2016-04-01

    with the other elements from this group. High amounts of As, Cd, Pb in mould horizons were proved. The surprisingly highest concentrations were determined for As (in average 3328 mg kg-1). The results of the pH measurement indicates acid conditions (in average 4.86, min. 3.89) for whole mine heap. Due to the mobility of Cd and Pb in acid environment, a high mobility of Cd in mobile soil fractions (in average 0.58 mg kg-1) was found, that seems to be responsible for the Cd pollution of Freiberger Mulde river, situated near the dump-field in the East direction from the studied area. The Pb content was in the average 1513 mg kg-1. SE analyses shows, that only the minor amounts of these metals were accounted in fractions I - IV (As: 7.75 %, Pb: 5.48 %, Cd: 26.77 %). The total Ge content in soil samples was 2.7 mg.kg-1in average. The concentrations of Nd and Ce were 17.7 mg kg-1and 38.5 mg kg-1, which is even lower than the average Nd and Ce contents in the Earth crust. However, the concentration of Ge was roughly a factor of two higher, than this average showing a large pool of Ge that could be accessed by phytoextraction. The SE analyses shows, that the average in fractions I - IV is even much lower, than in the case of the above mentioned heavy metals in comparison with Ge (1.75 %), Nd (3.28 %) and Ce (3.12 %). The BCF calculated for plants shows, that the only element, which could be possibly used as the object of phytoaccumulation is Cd (the BCF > 1) in species Populus tremula (3.0, 1.7), Spirea douglasii (1.4, 2.2) and Tanacetum vulgare (3.2, 1.3) at the most sampling places. Since these species represent the natural occurring vegetation of the dump, the use of these species together with soil amendments enhancing the plant availability of elements in soil fractions hold promise for phytoextraction of economically valuable metalloids and consequently an in situ bioremediation of the dump field. This work was realised with the support of Christin Jahns on behalf of the

  11. The Effect of Rare Earth on the Structure and Performance of Laser Clad Coatings

    NASA Astrophysics Data System (ADS)

    Bao, Ruiliang; Yu, Huijun; Chen, Chuanzhong; Dong, Qing

    Laser cladding is one kind of advanced surface modification technology and has the abroad prospect in making the wear-resistant coating on metal substrates. However, the application of laser cladding technology does not achieve the people's expectation in the practical production because of many defects such as cracks, pores and so on. The addiction of rare earth can effectively reduce the number of cracks in the clad coating and enhance the coating wear-resistance. In the paper, the effects of rare earth on metallurgical quality, microstructure, phase structure and wear-resistance are analyzed in turns. The preliminary discussion is also carried out on the effect mechanism of rare earth. At last, the development tendency of rare earth in the laser cladding has been briefly elaborated.

  12. Pressure-induced exotic states in rare earth hexaborides

    NASA Astrophysics Data System (ADS)

    Sun, Liling; Wu, Qi

    2016-08-01

    Finding the exotic phenomena in strongly correlated electron systems (SCESs) and understanding the corresponding microphysics have long been the research frontiers of condensed matter physics. The remarkable examples for the intriguing phenomena discovered in past years include unconventional superconductivity, heavy Fermion behaviors, giant magneto-resistance and so on. A fascinating type of rare earth hexaboride RB6 (R  =  Sm, Yb, Eu and Ce) belongs to a strongly correlated electron system (SCES), but shows unusual ambient-pressure and high-pressure behaviors beyond the phenomena mentioned above. Particularly, the recent discovery of the coexistence of an unusual metallic surface state and an insulating bulk state in SmB6, known to be a Kondo insulator decades ago, by theoretical calculations and many experimental measurements creates new interest for the investigation of the RB6. This significant progress encourages people to revisit the RB6 with an attempt to establish a new physics that links the SCES and the unusual metallic surface state which is a common feature of a topological insulator (TI). It is well known that pressure has the capability of tuning the electronic structure and modifying the ground state of solids, or even inducing a quantum phase transition which is one of the kernel issues in studies of SCESs. In this brief review, we will describe the progress in high pressure studies on the RB6 based on our knowledge and research interests, mainly focusing on the pressure-induced phenomena in YbB6 and SmB6, especially on the quantum phase transitions and their connections with the valence state of the rare earth ions. Moreover, some related high-pressure results obtained from CeB6 and EuB6 are also included. Finally, a summary is given in the conclusions and perspectives section.

  13. Pressure-induced exotic states in rare earth hexaborides.

    PubMed

    Sun, Liling; Wu, Qi

    2016-08-01

    Finding the exotic phenomena in strongly correlated electron systems (SCESs) and understanding the corresponding microphysics have long been the research frontiers of condensed matter physics. The remarkable examples for the intriguing phenomena discovered in past years include unconventional superconductivity, heavy Fermion behaviors, giant magneto-resistance and so on. A fascinating type of rare earth hexaboride RB6 (R  =  Sm, Yb, Eu and Ce) belongs to a strongly correlated electron system (SCES), but shows unusual ambient-pressure and high-pressure behaviors beyond the phenomena mentioned above. Particularly, the recent discovery of the coexistence of an unusual metallic surface state and an insulating bulk state in SmB6, known to be a Kondo insulator decades ago, by theoretical calculations and many experimental measurements creates new interest for the investigation of the RB6. This significant progress encourages people to revisit the RB6 with an attempt to establish a new physics that links the SCES and the unusual metallic surface state which is a common feature of a topological insulator (TI). It is well known that pressure has the capability of tuning the electronic structure and modifying the ground state of solids, or even inducing a quantum phase transition which is one of the kernel issues in studies of SCESs. In this brief review, we will describe the progress in high pressure studies on the RB6 based on our knowledge and research interests, mainly focusing on the pressure-induced phenomena in YbB6 and SmB6, especially on the quantum phase transitions and their connections with the valence state of the rare earth ions. Moreover, some related high-pressure results obtained from CeB6 and EuB6 are also included. Finally, a summary is given in the conclusions and perspectives section.

  14. New rare earth metal complexes with nitrogen-rich ligands: 5,5'-bitetrazolate and 1,3-bis(tetrazol-5-yl)triazenate-on the borderline between coordination and the formation of salt-like compounds.

    PubMed

    Eulgem, Patrick J; Klein, Axel; Maggiarosa, Nicola; Naumann, Dieter; Pohl, Roland W H

    2008-01-01

    From the two nitrogen-rich ligands BT(2-) (BT=5,5'-bitetrazole) and BTT(3-) (BTT=1,3-bis(1H-tetrazol-5-yl)triazene), a series of novel rare earth metal complexes were synthesised. For the BT ligand, a vast number of these complexes could be structurally characterised by single-crystal XRD, revealing structures ranging from discrete molecular aggregates to salt-like compounds. The isomorphous complexes [La2(BT)3]14 H2O (1) and [Ce2(BT)3]14 H2O (2) reveal discrete molecules in which one BT(2-) acts as a bridging ligand and two BT groups as chelating ligands. The complexes, [M(BT)(H2O)7]2[BT] x (x) H2O (3-5), (M=Nd (3), Sm (4), and Eu (5)), are also isomorphous and consist of [M(BT)(H2O)7]+ ions in which only one BT(2-) acts as a chelate ligand for each metal centre. [Tb(H2O)8]2[BT]3 x H2O (6) and [Er(H2O)8](2)[BT](3)x H2O (7) are salt-like compounds that do not exhibit any significant metal-nitrogen contacts. In the BTT-samarium compound 9, discrete molecules were found in which BTT(3-) acts as a tridentate ligand with three Sm--N bonds.

  15. Evolution of the atomic order and valence state of rare-earth atoms and uranium in a new carbon-metal composite—diphthalocyanine pyrolysate C64H32N16 Me ( Me = Y, La, Ce, Eu, and U)

    NASA Astrophysics Data System (ADS)

    Sovestnov, A. E.; Kapustin, V. K.; Tikhonov, V. I.; Fomin, E. V.; Chernenkov, Yu. P.

    2014-08-01

    The structure of a metal-carbon composite formed by the pyrolysis of diphthalocyanine of some rare-earth elements (Y, La, Ce, Eu) and uranium in the temperature range T ann = 800-1700°C has been investigated for the first time by the methods of X-ray diffraction analysis and X-ray line shift. It has been shown that, in the general case, the studied pyrolysates consist of three phases. One phase corresponds to the structure of graphite. The second phase corresponds to nitrides, carbides, and oxides of basic metal elements with a crystallite size ranging from 5 to 100 nm. The third phase is amorphous or consisting of crystallites with a size of ˜1 nm. It has been found that all the basic elements (Y, La, Ce, Eu, U) and incorporated iodine atoms in the third phase are in a chemically bound state. The previously unobserved electronic configurations have been revealed for europium. The possibility of including not only atoms of elements forming diphthalocyanine but also other elements (for example, iodine) in the composite structure is of interest, in particular, for the creation of a thermally, chemically, and radiation resistant metal-carbon matrix for the radioactive waste storage.

  16. Crystallographic X-ray analyses of Yb@C(2v)(3)-C80 reveal a feasible rule that governs the location of a rare earth metal inside a medium-sized fullerene.

    PubMed

    Lu, Xing; Lian, Yongfu; Beavers, Christine M; Mizorogi, Naomi; Slanina, Zdenek; Nagase, Shigeru; Akasaka, Takeshi

    2011-07-20

    Single crystal X-ray diffraction studies of Yb@C(2v)(3)-C(80)·Ni(II)(OEP)·CS(2)·1.5C(6)H(6) (OEP = octaethylporphinate) reveal that a relatively flat region of the fullerene interacts with the Ni(II)(OEP) molecule, featuring shape-matching interactions. Surprisingly, it is found that the internal metal is located under a hexagonal carbon ring apart from the 2-fold axis of the C(2v)(3)-C(80) cage, presenting the first example of metallofullerenes with an asymmetrically positioned metal. Such an anomalous location of Yb(2+) is associated with its strong ability to pursue a large coordination number and the lack of hexagon along the C(2) axis of C(2v)(3)-C(80). It is accordingly assumed that a suitable cage hexagon is most likely to be preferred by the single rare earth metal to stay behind inside a medium-sized fullerene, such as C(80) and C(82).

  17. Prospective analysis of the flows of certain rare earths in Europe at the 2020 horizon.

    PubMed

    Rollat, Alain; Guyonnet, Dominique; Planchon, Mariane; Tuduri, Johann

    2016-03-01

    This paper proposes a forecast of certain rare earth flows in Europe at the 2020 horizon, based on an analysis of trends influencing various actors of the rare earth industry along the value chain. While 2020 is indicated as the forecast horizon, the analysis should be considered as more representative of the next decade. The rare earths considered here are used in applications that are important for a low-carbon energy transition and/or have a significant recycling potential: NdFeB magnets (Pr, Nd, Dy), NiMH batteries (Pr, Nd) and fluorescent lamp phosphors (Eu, Tb, Y). An analysis of major trends affecting the rare earth industry in Europe along the value chain (including extraction, separation, fabrication, manufacture, use and recycling), helps to build a scenario for a material flow analysis of these rare earths in Europe. The scenario assumes in particular that during the next decade, there exists a rare earth mine in production in Europe (with Norra Kärr in Sweden as a most likely candidate) and also that recycling is in line with targets proposed in recent European legislation. Results are presented in the form of Sankey diagrams which help visualize the various flows for the three applications. For example, calculations forecast flows from extraction to separation of Pr, Nd and Dy for magnet applications in Europe, on the order of 310 tons, 980 tons and 80 tons rare earth metal resp., while recycled flows are 35 tons, 110 tons and 30 tons resp. Calculations illustrate how the relative contribution of recycling to supply strongly depends on the situation with respect to demand. Considering the balance between supply and demand, it is not anticipated any significant shortage of rare earth supply in Europe at the 2020 horizon, barring any new geopolitical crisis involving China. For some heavy rare earths, supply will in fact largely outweigh demand, as for example Europium due to the phasing out of fluorescent lights by LEDs.

  18. Complex magnetic properties in multilayer rare earth oxypnictides

    NASA Astrophysics Data System (ADS)

    Wang, Jiakui; Marcinkova, Andrea; Chen, Chih-Wei; Morosan, Emilia; Morosan Group Team

    2014-03-01

    Intensive research interest on layered transition metal pnictide materials was stimulated by the discovery of high temperature superconductivity in Fe-pnictides a few years ago. To study the relationship between superconductivity, crystal structure and magnetism, and to search for novel superconductors of better application potential, more transition metal pnictides are worth investigating. In this talk, I will discuss physical properties of members of a particular class of layered oxypnictides, with four transition metal pnictogen layers per unit cell. While varying the rare earth ion, we find that one compound is a low temperature superconductor (Tc 1.7 K), and others show diverse magnetic properties, including ferromagnetic or antiferromagnetic order, or spin glass behavior. I will show our observation from measurements of DC and AC magnetization, specific heat and resistivity. The understanding of the physical properties of these isostructual compounds may serve as a guide in the search for superconductivity in these systems. This work is supported by MURI-AFOSR and Rice University.

  19. Compact Rare Earth Emitter Hollow Cathode

    NASA Technical Reports Server (NTRS)

    Watkins, Ronald; Goebel, Dan; Hofer, Richard

    2010-01-01

    A compact, high-current, hollow cathode utilizing a lanthanum hexaboride (LaB6) thermionic electron emitter has been developed for use with high-power Hall thrusters and ion thrusters. LaB6 cathodes are being investigated due to their long life, high current capabilities, and less stringent xenon purity and handling requirements compared to conventional barium oxide (BaO) dispenser cathodes. The new cathode features a much smaller diameter than previously developed versions that permit it to be mounted on axis of a Hall thruster ( internally mounted ), as opposed to the conventional side-mount position external to the outer magnetic circuit ("externally mounted"). The cathode has also been reconfigured to be capable of surviving vibrational loads during launch and is designed to solve the significant heater and materials compatibility problems associated with the use of this emitter material. This has been accomplished in a compact design with the capability of high-emission current (10 to 60 A). The compact, high-current design has a keeper diameter that allows the cathode to be mounted on the centerline of a 6- kW Hall thruster, inside the iron core of the inner electromagnetic coil. Although designed for electric propulsion thrusters in spacecraft station- keeping, orbit transfer, and interplanetary applications, the LaB6 cathodes are applicable to the plasma processing industry in applications such as optical coatings and semiconductor processing where reactive gases are used. Where current electrical propulsion thrusters with BaO emitters have limited life and need extremely clean propellant feed systems at a significant cost, these LaB6 cathodes can run on the crudest-grade xenon propellant available without impact. Moreover, in a laboratory environment, LaB6 cathodes reduce testing costs because they do not require extended conditioning periods under hard vacuum. Alternative rare earth emitters, such as cerium hexaboride (CeB6) can be used in this

  20. Rare earths: Market disruption, innovation, and global supply chains

    USGS Publications Warehouse

    Eggert, Roderick; Wadia, Cyrus; Anderson, Corby; Bauer, Diana; Fields, Fletcher; Meinert, Lawrence D.; Taylor, Patrick

    2016-01-01

    Rare earths, sometimes called the vitamins of modern materials, captured public attention when their prices increased more than ten-fold in 2010 and 2011. As prices fell between 2011 and 2016, rare earths receded from public view—but less visibly they became a major focus of innovative activity in companies, government laboratories and universities. Geoscientists worked to better understand the resource base and improve our knowledge about mineral deposits that will be mines in the future. Process engineers carried out research that is making primary production and recycling more efficient. Materials scientists and engineers searched for substitutes that will require fewer or no rare earths while providing properties comparable or superior to those of existing materials. As a result, even though global supply chains are not significantly different now than they were before the market disruption, the innovative activity motivated by the disruption likely will have far-reaching, if unpredictable, consequences for supply chains of rare earths in the future.

  1. Magneto-Optical Experiments on Rare Earth Garnet Films.

    ERIC Educational Resources Information Center

    Tanner, B. K.

    1980-01-01

    Describes experiments in which inexpensive or standard laboratory equipment is used to measure several macroscopic magnetic properties of thin rare earth garnet films used in the manufacture of magnetic bubble devices. (Author/CS)

  2. Growth of rare-earth monolayers on synthetic fluorine mica

    NASA Astrophysics Data System (ADS)

    Tsui, F.; Han, P. D.; Flynn, C. P.

    1993-05-01

    We have grown single-crystal rare-earth films on cleaved faces of synthetic fluorine mica fluorophlogopite by molecular-beam-epitaxy techniques. This has made it possible to measure material properties such as magnetism in monolayer structures.

  3. Magnetoelastic contribution to thermal expansion of rare-earth zircons

    NASA Astrophysics Data System (ADS)

    Kazei, Z. A.; Kolmakova, N. P.; Shishkina, O. A.

    1998-02-01

    Comparative analysis is performed for the magnetoelastic contributions to thermal expansion of two groups of rare-earth zircons: phosphates RPO 4 (R=Y,Tb-Yb) and vanadates RVO 4 (R=Pr, Nd, Gd-Yb). Significant magnetoelastic anomalies of thermal expansion are observed and magnetoelastic contributions are found in regard to the corrections for the changes of the phonon contributions throughout the series of RPO 4 and RVO 4. Magnetoelastic contributions to thermal expansion are demonstrated to be well accounted for by the temperature dependences of the quadrupole moments of rare-earth ions both in phosphates and vanadates. The fully symmetric magnetoelastic coefficients are determined for all the rare-earth compounds under investigation; they are of the same sign and comparable magnitude in vanadates and phosphates, whereas the magnetoelastic contributions are opposite in sign for two isomorphous groups of rare-earth zircons.

  4. METHOD OF SEPARATING RARE EARTHS BY ION EXCHANGE

    DOEpatents

    Spedding, F.H.; Powell, J.E.

    1960-10-18

    A process is given for separating yttrium and rare earth values having atomic numbers of from 57 through 60 and 68 through 71 from an aqueous solution whose pH value can range from 1 to 9. All rare earths and yttrium are first adsorbed on a cation exchange resin, and they are then eluted with a solution of N-hydroxyethylethylenediaminetriacetic acid (HEDTA) in the order of decreasing atomic number, yttrium behaving like element 61; the effluents are collected in fractions. The HEDTA is recovered by elution with ammonia solution and the resin is regenerated with sulfuric acid. Rare earths are precipitated from the various effluents with oxalic acid, and each supernatant is passed over cation exchange resin for adsorption of HEDTA and nonprecipitated rare earths: the oxalic acid is not retained by the resin.

  5. Rare Earth Doped High Temperature Ceramic Selective Emitters

    NASA Technical Reports Server (NTRS)

    Chubb, Donald L.; Pal, AnnaMarie; Patton, Martin O.; Jenkins, Phillip P.

    1999-01-01

    As a result of their electron structure, rare earth ions in crystals at high temperature emit radiation in several narrow bands rather than in a continuous blackbody manner. This study develops a spectral emittance model for films of rare earth containing materials. Although there are several possible rare earth doped high temperature materials, this study was confined to rare earth aluminum garnets. Good agreement between experimental and theoretical spectral emittances was found for erbium, thulium and erbium-holmium aluminum garnets. Spectral emittances of these films are sensitive to temperature differences across the film. Emitter efficiency is also a sensitive function of temperature. For thulium aluminum garnet the efficiency is 0.38 at 1700 K but only 0.19 at 1262 K.

  6. Rare earths: An industry review and market outlook

    SciTech Connect

    Major-Sosias, M.A.

    1997-03-01

    A review of the global rare earths industry from production and trade, to the established and new applications that drive this unique market. The industry has been spurred by increased demand during the 1990`s, which is expected to continue into the twenty-first century. The forecast indicates additional growth, as well as the potential for the rare earths market to evolve slowly into one with a more fundamental structure.

  7. Implications of Competition for Rare Earth Elements (REE) in Africa

    DTIC Science & Technology

    2011-03-15

    Information Operations and Reports (0704-0188), 1215 Jefferson Davis Highway, Suite 1204, Arlington, VA 22202- 4302. Respondents should be aware that...2010). 3 Marc Humphries , ―Rare Earth Elements: The Global Supply Chain,‖ Congressional Research Service Report for Congress R41347 (September 30...101026_Verrastro_Geopolitics_web.pdf (accessed October 14, 2010). 10 Humphries , ―Rare Earth Elements: The Global Supply Chain,‖ (September 30, 2010): 4

  8. Ferroelectricity of domain walls in rare earth iron garnet films

    NASA Astrophysics Data System (ADS)

    Popov, A. I.; Zvezdin, K. A.; Gareeva, Z. V.; Mazhitova, F. A.; Vakhitov, R. M.; Yumaguzin, A. R.; Zvezdin, A. K.

    2016-11-01

    In this paper, we report on electric polarization arising in a vicinity of Bloch-like domain walls in rare-earth iron garnet films. The domain walls generate an intrinsic magnetic field that breaks an antiferroelectric structure formed in the garnets due to an exchange interaction between rare earth and iron sublattices. We explore 180° domain walls whose formation is energetically preferable in the films with perpendicular magnetic anisotropy. Magnetic and electric structures of the 180° quasi-Bloch domain walls have been simulated at various relations between system parameters. Singlet, doublet ground states of rare earth ions and strongly anisotropic rare earth Ising ions have been considered. Our results show that electric polarization appears in rare earth garnet films at Bloch domain walls, and the maximum of magnetic inhomogeneity is not always linked to the maximum of electric polarization. A number of factors including the temperature, the state of the rare earth ion and the type of a wall influence magnetically induced electric polarization. We show that the value of polarization can be enhanced by the shrinking of the Bloch domain wall width, decreasing the temperature, and increasing the deviations of magnetization from the Bloch rotation that are regulated by impacts given by magnetic anisotropies of the films.

  9. An Overview of Rare Earth Science and Technology

    NASA Astrophysics Data System (ADS)

    Gschneidner, Karl, Jr.

    2012-02-01

    Currently rare earth science and technology is robust: this includes all the major branches of science -- biochemistry, chemistry, materials and physics. There are, however, currently some anomalies and distortions especially in the technology and applications sector of the rare earth field, which is caused by the dominance of China on the sales of rare earths and rare earth containing products. For the past 5 to 10 years ˜95% of rare earths utilized in commerce came from China. Although Chinese actions have lead to sudden and large price spikes and export embargoes, the rare earths are still available but at a higher cost. The start up of production in 2011 at mines in the USA and Australia will alleviate this situation in about two years. Basic and applied research on the condensed matter physics/materials science has hardly been impacted by these events, but new research opportunities are opening up especially with regard to the USA's military and energy security. Magnets seems to be the hottest topic, but research on battery materials, phosphors and catalysts are also (or should be) strongly considered.

  10. Ferroelectricity of domain walls in rare earth iron garnet films.

    PubMed

    Popov, A I; Zvezdin, K A; Gareeva, Z V; Mazhitova, F A; Vakhitov, R M; Yumaguzin, A R; Zvezdin, A K

    2016-11-16

    In this paper, we report on electric polarization arising in a vicinity of Bloch-like domain walls in rare-earth iron garnet films. The domain walls generate an intrinsic magnetic field that breaks an antiferroelectric structure formed in the garnets due to an exchange interaction between rare earth and iron sublattices. We explore 180° domain walls whose formation is energetically preferable in the films with perpendicular magnetic anisotropy. Magnetic and electric structures of the 180° quasi-Bloch domain walls have been simulated at various relations between system parameters. Singlet, doublet ground states of rare earth ions and strongly anisotropic rare earth Ising ions have been considered. Our results show that electric polarization appears in rare earth garnet films at Bloch domain walls, and the maximum of magnetic inhomogeneity is not always linked to the maximum of electric polarization. A number of factors including the temperature, the state of the rare earth ion and the type of a wall influence magnetically induced electric polarization. We show that the value of polarization can be enhanced by the shrinking of the Bloch domain wall width, decreasing the temperature, and increasing the deviations of magnetization from the Bloch rotation that are regulated by impacts given by magnetic anisotropies of the films.

  11. New examples of ternary rare-earth metal boride carbides containing finite boron carbon chains: The crystal and electronic structure of RE15B6C20 (RE=Pr, Nd)

    NASA Astrophysics Data System (ADS)

    Babizhetskyy, Volodymyr; Mattausch, Hansjürgen; Simon, Arndt; Hiebl, Kurt; Ben Yahia, Mouna; Gautier, Régis; Halet, Jean-François

    2008-08-01

    The ternary rare-earth metal boride carbides RE15B6C20 (RE=Pr, Nd) were synthesized by co-melting the elements. They exist above 1270 K. Their crystal structures were determined from single-crystal X-ray diffraction data. Both crystallize in the space group P1¯, Z=1, a=8.3431(8) Å, b=9.2492(9) Å, c=8.3581(8) Å, α=84.72(1)°, β=89.68(1)°, γ =84.23(1)° (R1=0.041 (wR2=0.10) for 3291 reflections with Io>2σ(Io)) for Pr15B6C20, and a=8.284(1) Å, b=9.228(1) Å, c=8.309(1) Å, α=84.74(1)°, β=89.68(1)°, γ=84.17(2)° (R1=0.033 (wR2=0.049) for 2970 reflections with Io>2σ(Io)) for Nd15B6C20. Their structure consists of a three-dimensional framework of rare-earth metal atoms resulting from the stacking of slightly corrugated and distorted square nets, leading to cavities filled with unprecedented B2C4 finite chains, disordered C3 entities and isolated carbon atoms, respectively. Structural and theoretical analyses suggest the ionic formulation (RE3+)15([B2C4]6-)3([C3]4-)2(C4-)2·11ē. Accordingly, density functional theory calculations indicate that the compounds are metallic. Both structural arguments as well as energy calculations on different boron vs. carbon distributions in the B2C4 chains support the presence of a CBCCBC unit. Pr15B6C18 exhibits antiferromagnetic order at TN=7.9 K, followed by a meta-magnetic transition above a critical external field B>0.03 T. On the other hand, Nd15B6C18 is a ferromagnet below TC≈40 K.

  12. Real World of Industrial Chemistry: Technology of the Rare Earths.

    ERIC Educational Resources Information Center

    Kremers, Howard E.

    1985-01-01

    The 17 rare earth elements account for one-fifth of the 83 naturally occurring elements and collectively rank as the 22nd most abundant "element." Properties of these elements (including their chemical similarity), their extraction from the earth, and their uses are discussed. (JN)

  13. Electronic, structural and transport properties of (almost) rare-earth-like actinide hydrides

    SciTech Connect

    Ward, J.W.; Cort, B.; Goldstone, J.A.; Lawson, A.C.; Cox, L.E. ); Haire, R.G. )

    1990-01-01

    By the virtue of broad-band, hybridized 5f-electron behavior, the hydride systems for Pa and U exhibit unique properties and structures, the actinide metal atoms existing in different states. A sudden change at Np to more rare-earth-like behavior implies a major change in electronic structure. There are both many parallels but also enigmas for the Np + H and Pu + H systems. Electrical resistivities are large and complex with temperature. Low-temperature structural transitions as studied by neutron diffraction help elucidate some of these effects. Phonon spectra are quite rare-earth-like, and XPS data imply a metal atom with mostly d-screened core levels. Then it is at americium, where fully localized and corelike 5f electrons are found, that we look finally for true rare-earth-like behavior, which should include a large drop in electrical resistivity. 33 refs., 7 figs., 1 tab.

  14. Method for preparing high cure temperature rare earth iron compound magnetic material

    DOEpatents

    Huang, Yuhong; Wei, Qiang; Zheng, Haixing

    2002-01-01

    Insertion of light elements such as H,C, or N in the R.sub.2 Fe.sub.17 (R=rare earth metal) series has been found to modify the magnetic properties of these compounds, which thus become prospective candidates for high performance permanent magnets. The most spectacular changes are increases of the Curie temperature, T.sub.c, of the magnetization, M.sub.s, and of coercivity, H.sub.c, upon interstitial insertion. A preliminary product having a component R--Fe--C,N phase is produced by a chemical route. Rare earth metal and iron amides are synthesized followed by pyrolysis and sintering in an inert or reduced atmosphere, as a result of which, the R--Fe--C,N phases are formed. Fabrication of sintered rare earth iron nitride and carbonitride bulk magnet is impossible via conventional process due to the limitation of nitridation method.

  15. Thermochemical study of rare earth and nitrogen incorporation in glasses

    NASA Astrophysics Data System (ADS)

    Zhang, Yahong

    Rare earth containing aluminosilicate, borosilicate, aluminate and nitrogen containing aluminosilicate glasses are technically important materials. They have extraordinary physical and chemical properties such as high glass transition temperature, very low electrical conductivity, and excellent chemical stability. These unique properties lead to applications as coatings on metals and ceramics, optical fibers, semiconductors, and nuclear waste containment materials. In addition, such systems contain the most widely used additives for sintering of Si3N4, SiAlON and SiC ceramics for high temperature applications. Thermodynamic properties and the relations among energetics, structure and bonding are essential to controlling processing parameters to synthesize, at lower cost, materials having better properties. Earlier investigations mainly pertained to specific physical properties of rare-earth doped oxide and oxynitride glasses. Work on the thermodynamic stability and materials compatibility has been very sparse. High temperature solution calorimetry in molten oxide solvents is a powerful tool for the thermodynamic study of refractory materials. With implementation and improvement, this technique has been applied to the first measurement of enthalpies of formation of RE-Si-Al-O glasses, REAlO3 glasses, RE-Si-Al-O-N glasses, and Si3N 4 and Ge3N4 with high pressure spinel structure. The first successful synthesis of REAlO3 glasses has been achieved by containerless melting. Their large enthalpies of crystallization confirm that they are reluctant glass formers. For glasses along the 2REAlO3 -3SiO2 join, the strongly negative heats of mixing support the absence of miscibility gaps except possibly at very high silica content. Energetic evidence has been presented for incipient phase-ordered regions in Gd- or Hf-containing sodium alumino-borosilicate glasses for plutonium immobilization. Linear relations between enthalpies of formation of RESiAlON glasses from elements and

  16. High-Tc Superconductivity and Raman Scattering Study of the phonon properties of electron doped (transition metal, rare-earth) - Oxygen-Free CaFeAsF and compared with RFeAsO system

    NASA Astrophysics Data System (ADS)

    Sasmal, Kalyan; Hadjiev, Viktor; Chu, C. W.(Paul)

    Quaternary CaFeAsF has ZrCuSiAs-type structure,(RO)δ+ layer in RFeAsO replaced by (CaF)δ+ layer,with tetragonal (P4/nmm)-orthorhombic (Cmma) phase transition at 134K,while magnetic order,SDW sets in at 114K. Partial replacement of Fe with Co/Ni is direct electron doping to (FeAs)δ+ layer.Tc ~15K in CaFe0.9Ni0.1AsF.Substitution of rare earth metal for alkaline earth metal suppresses anomaly in resistivity & induces superconductivity.Tc ~52K in Ca0.5Pr0.5FeAsF.Characterized by resistivity, susceptibility,XRD & EDX-SEM.Upper critical field estimated from magneto resistance.Bulk superconductivity proved by DC magnetization. Hall coefficient RH revealed hole-like charge carriers in parent compound CaFeAsF, while electron-type (RH in normal state is -Ve) for Ca0.5Pr0.5FeAsF.Evolution of Raman active phonons of Ca1-xPrxFeAsF measured with polarized Raman spectroscopy at room temperature from absurfaces of impurity-free microcrystals.Spectra exhibit sharp phonon lines on very weak electronic scattering background.Frequency and symmetry of Raman phonons involving out-of-plane atomic vibrations are found at 162.5 cm-1 (A1 g, Pr), 201 cm-1 (A1 g, As), 215.5 cm-1 (B1 g, Fe), 265 cm-1 (Eg, Fe) and 334 cm-1 (B1 g, F) for Ca0.5Pr0.5FeAsF.Observations are compared with RFeAsO unconventional superconductors also possibly related to magnetic fluctuations

  17. A novel sequential process for remediating rare-earth wastewater.

    PubMed

    Cui, Mingcan; Jang, Min; Kang, Kyounglim; Kim, Dukmin; Snyder, Shane A; Khim, Jeehyeong

    2016-02-01

    A novel and economic sequential process consisting of precipitation, adsorption, and oxidation was developed to remediate actual rare-earth (RE) wastewater containing various toxic pollutants, including radioactive species. In the precipitation step, porous air stones (PAS) containing waste oyster shell (WOS), PASWOS, was prepared and used to precipitate most heavy metals with >97% removal efficiencies. The SEM-EDS analysis revealed that PAS plays a key role in preventing the surface coating of precipitants on the surface of WOS and in releasing the dissolved species of WOS successively. For the adsorption step, a polyurethane (PU) impregnated by coal mine drainage sludge (CMDS), PUCMDS, was synthesized and applied to deplete fluoride (F), arsenic (As), uranium (U), and thorium (Th) that remained after precipitation. The continuous-mode sequential process using PAS(WOS), PU(CMDS), and ozone (O3) had 99.9-100% removal efficiencies of heavy metals, 99.3-99.9% of F and As, 95.8-99.4% of U and Th, and 92.4% of COD(Cr) for 100 days. The sequential process can treat RE wastewater economically and effectively without stirred-tank reactors, pH controller, continuous injection of chemicals, and significant sludge generation, as well as the quality of the outlet met the EPA recommended limits.

  18. Irradiation of Metallic Fuels with Rare Earth Additions for Actinide Transmutation in the ATR. Experiment Description for AFC-2A and AFC-2B

    SciTech Connect

    S. L. Hayes; D. J. Utterbeck; T. A. Hyde

    2007-03-01

    The U.S. Advanced Fuel Cycle Initiative (AFCI), now within the broader context of the Global Nuclear Energy Partnership (GNEP), seeks to develop and demonstrate the technologies needed to transmute the long-lived transuranic actinide isotopes contained in spent nuclear fuel into shorter-lived fission products, thereby dramatically decreasing the volume of material requiring disposal and the long-term radio-toxicity and heat load of high-level waste sent to a geologic repository. One important component of the technology development is actinide-bearing metallic transmutation fuel forms containing plutonium, neptunium, americium (and possibly curium) isotopes. The proposed AFC-2A and AFC-2B irradiation experiments are a continuation of the metallic fuel test series in progress in the ATR. This report documents the experiment description and test matrix of the proposed experiments and the Post Irradiation Examination (PIE) and fabrication schedule.

  19. Irradiation of Metallic Fuels with Rare Earth Additions for Actinide Transmutation in the Advanced Test Reactor. Experiment Description for AFC-2A and AFC-2B

    SciTech Connect

    Hayes, Steven L.

    2006-12-01

    The U.S. Advanced Fuel Cycle Initiative (AFCI), now within the broader context of the Global Nuclear Energy Partnership (GNEP), seeks to develop and demonstrate the technologies needed to transmute the long-lived transuranic actinide isotopes contained in spent nuclear fuel into shorter-lived fission products, thereby dramatically decreasing the volume of material requiring disposal and the long-term radio-toxicity and heat load of high-level waste sent to a geologic repository. One important component of the technology development is actinide-bearing metallic transmutation fuel forms containing plutonium, neptunium, americium (and possibly curium) isotopes. The proposed AFC-2A and AFC-2B irradiation experiments are a continuation of the metallic fuel test series in progress in the ATR. This report documents the experiment description and test matrix of the proposed experiments and the Post Irradiation Examination (PIE) and fabrication schedule.

  20. Irradiation of Metallic Fuels with Rare Earth Additions for Actinide Transmutation in the ATR. Experiment Description for AFC-2A and AFC-2B

    SciTech Connect

    S. L. Hayes; D. J. Utterbeck; T. A. Hyde

    2006-11-01

    The U.S. Advanced Fuel Cycle Initiative (AFCI), now within the broader context of the Global Nuclear Energy Partnership (GNEP), seeks to develop and demonstrate the technologies needed to transmute the long-lived transuranic actinide isotopes contained in spent nuclear fuel into shorter-lived fission products, thereby dramatically decreasing the volume of material requiring disposal and the long-term radio-toxicity and heat load of high-level waste sent to a geologic repository. One important component of the technology development is actinide-bearing metallic transmutation fuel forms containing plutonium, neptunium, americium (and possibly curium) isotopes. The proposed AFC-2A and AFC-2B irradiation experiments are a continuation of the metallic fuel test series in progress in the ATR. This report documents the experiment description and test matrix of the proposed experiments and the Post Irradiation Examination (PIE) and fabrication schedule.

  1. Different Adsorption Behavior of Rare Earth and Metallic Ion Complexes on Langmuir Mono layers Probed by Sum-Frequency Generation Spectroscopy

    SciTech Connect

    Song, Woongmo; Vaknin, David; Kim, Doseok

    2013-02-25

    Adsorption behavior of counterions under a Langmuir monolayer was investigated by sum-frequency generation (SFG) spectroscopy. By comparing SFG spectra of arachidic acid (AA) Langmuir monolayer/water interface with and without added salt, it was found that the simple trivalent cation La3+ adsorbed on AA monolayer only when the carboxylic headgroups are charged (deprotonated), implying that counterion adsorption is induced by Coulomb interaction. On the other hand, metal hydroxide complex Fe(OH)3 adsorbed even on a charge-neutral AA monolayer, indicating that the adsorption of iron hydroxide is due to chemical interaction such as covalent or hydrogen bonding to the headgroup of the molecules at the monolayer.

  2. Rare earth elements in synthetic zircon. 1. synthesis, and rare earth element and phosphorus doping.

    SciTech Connect

    Hanchar, J. M.; Finch, R. J.; Hoskin, W. O.; Watson, E. B.; Cherniak, D. J.; Mariano, A. N.; Chemical Engineering; George Washington Univ.; Univ. of Canterbury; Australian National Univ.; Rensselaer Polytechnic Inst.

    2001-05-01

    Sedimentary mineral assemblages commonly contain detrital zircon crystals as part of the heavy-mineral fraction. Age spectra determined by U-Pb isotopic analysis of single zircon crystals within a sample may directly image the age composition--but not the chemical composition--of the source region. Rare earth element (REE) abundances have been measured for zircons from a range of common crustal igneous rock types from different tectonic environments, as well as kimberlite, carbonatite, and high-grade metamorphic rocks, to assess the potential of using zircon REE characteristics to infer the rock types present in sediment source regions. Except for zircon with probable mantle affinities, zircon REE abundances and normalized patterns show little intersample and intrasample variation. To evaluate the actual variation in detrital zircon REE composition in a true sediment of known mixed provenance, zircons from a sandstone sample from the Statfjord Formation (North Sea) were analyzed. Despite a provenance including high-grade metasediment and granitoids and a range in zircon age of 2.82 b.y., the zircon REEs exhibit a narrow abundance range with no systematic differences in pattern shape. These evidences show zircon REE patterns and abundances are generally not useful as indicators of provenance.

  3. Synthesis, characterization and cytotoxicity of rare earth metal ion complexes of N,N‧-bis-(2-thiophenecarboxaldimine)-3,3‧-diaminobenzidene, Schiff base ligand

    NASA Astrophysics Data System (ADS)

    Shakir, Mohammad; Abbasi, Ambreen; Faraz, Mohammad; Sherwani, Asif

    2015-12-01

    Lanthanide complexes of La3+, Pr3+, Nd3+, Gd3+, Er3+ of general formula [Ln2 L(H2O)4(NO3)4](NO3)2·2H2O have been synthesized from Schiff base, N,N‧-bis-(2-thiophenecarboxaldimine)-3,3‧-diaminobenzidene. The complexes were characterized by elemental analysis, molar conductance, UV-Vis, fluorescence, FT-IR,1H NMR, mass spectroscopy, EDX, SEM and thermal analysis. FT-IR spectral data suggested that ligand coordinate with metal ions through azomethine nitrogen and uncondensed amino group. Molar conductance data revealed 1:2 electrolytic nature of complexes. From the analytical data, the stoichiometry of the complexes was found to be 1:2 (ligand:metal). Thephysico-chemical data suggested eight coordination number for Ln(III)Schiffbase complexes. SEM analysis shows morphological changes in the surfaces of complexes as compared to free ligand. Thermal decomposition profiles were consistent with proposed formulations. The anticancer activity of the complexes and theSchiffbase ligand has been studied towards human cervical cancer celllines (HeLa) and human breast cancer cell lines (MCF-7) and it was found that complexes exhibited greater activity than theSchiffbase.

  4. High-precision analysis on annual variations of heavy metals, lead isotopes and rare earth elements in mangrove tree rings by inductively coupled plasma mass spectrometry

    NASA Astrophysics Data System (ADS)

    Yu, Ke-Fu; Kamber, Balz S.; Lawrence, Michael G.; Greig, Alan; Zhao, Jian-Xin

    2007-02-01

    Annual variations from 1982 to 1999 of a wide range of trace elements and reconnaissance Pb isotopes ( 207Pb/ 206Pb and 208Pb/ 206Pb) were analyzed by solution ICP-MS on digested ash from mangrove Rhizophora apiculata, obtained from Leizhou Peninsula, along northern coast of South China Sea. The concentrations of the majority of elements show a weak declining trend with growth from 1982 to 1999, punctuated by several high concentration spikes. The declining trends are positively correlated with ring width and negatively correlated with inferred water-use efficiency, suggesting a physiological control over metal-uptake in this species. The episodic metal concentration-peaks cannot be interpreted with lateral movement or growth activities and appear to be related to environmental pollution events. Pb isotope ratios for most samples plot along the 'Chinese Pb line' and clearly document the importance of gasoline Pb as a source of contaminant. Shale-normalised REE + Y patterns are relatively flat and consistent across the growth period, with all patterns showing a positive Ce anomaly and elevated Y/Ho ratio. The positive Ce anomaly is observed regardless of the choice of normaliser, in contrast to previously reported REE patterns for terrestrial and marine plants. This pilot study of trace element, REE + Y and Pb isotope distribution in mangrove tree rings indicates the potential use of mangroves as monitors of historical environmental change.

  5. Rare-earth metals in nickel aluminide-based alloys: III. Structure and properties of multicomponent Ni3Al-based alloys

    NASA Astrophysics Data System (ADS)

    Bazyleva, O. A.; Povarova, K. B.; Kazanskaya, N. K.; Drozdov, A. A.

    2009-04-01

    The possibility of increasing the life of heterophase cast light Ni3Al-based superalloys at temperatures higher than 0.8 T m of Ni3Al is studied when their directional structure is additionally stabilized by nanoprecipitates, which form upon additional alloying of these alloys by refractory and active metals, and using special methods for preparing and melting of an alloy charge. The effect of the method of introducing the main components and refractory reaction-active and surface-active alloying elements into Ni3Al-based cast superalloys, which are thermally stable natural composite materials of the eutectic type, on the structure-phase state and the life of these alloys is studied. When these alloys are melted, it is necessary to perform a set of measures to form particles of refractory oxide cores covered with the β-NiAl phase and, then, γ'prim-Ni3Al phase precipitates during solidification. The latter phase forms the outer shell of grain nuclei, which provides high thermal stability and hot strength of an intermetallic compound-based alloy. As a result, a modified structure that is stabilized by the nanoprecipitates of nickel and aluminum lanthanides and the nanoprecipitates of phases containing refractory metals is formed. This structure enhances the life of the alloy at 1000 °C by a factor of 1.8-2.5.

  6. Instability of some divalent rare earth ions and photochromic effect

    NASA Astrophysics Data System (ADS)

    Egranov, A. V.; Sizova, T. Yu.; Shendrik, R. Yu.; Smirnova, N. A.

    2016-03-01

    It was shown that the divalent rare earth ions (La, Ce, Gd, Tb, Lu, and Y) in cubic sites in alkaline earth fluorides are unstable with respect to electron autodetachment since its d1(eg) ground state is located in the conduction band which is consistent with the general tendency of these ions in various compounds. The localization of doubly degenerate d1(eg) level in the conduction band creates a configuration instability around the divalent rare earth ion that leading to the formation of anion vacancy in the nearest neighborhood, as was reported in the previous paper [A. Egranov, T. Sizova, Configurational instability at the excited impurity ions in alkaline earth fluorites, J. Phys. Chem. Solids 74 (2013) 530-534]. Thus, the formation of the stable divalent ions as La, Ce, Gd, Tb, Lu, and Y (PC+ centers) in CaF2 and SrF2 crystals during x-ray irradiation occurs via the formation of charged anion vacancies near divalent ions (Re2+va), which lower the ground state of the divalent ion relative to the conductivity band. Photochromic effect occurs under thermally or optically stimulated electron transition from the divalent rare earth ion to the neighboring anion vacancy and reverse under ultraviolet light irradiation. It is shown that the optical absorption of the PC+ centers due to d → d and d → f transitions of the divalent rare-earth ion.

  7. Attenuation of rare earth elements in a boreal estuary

    NASA Astrophysics Data System (ADS)

    Åström, Mats E.; Österholm, Peter; Gustafsson, Jon Petter; Nystrand, Miriam; Peltola, Pasi; Nordmyr, Linda; Boman, Anton

    2012-11-01

    This study focuses on attenuation of rare earth elements (REE) when a boreal creek, acidified and loaded with REE and other metals as a result of wetland drainage, empties into a brackish-water estuary (salinity < 6‰). Surface water was collected in a transect from the creek mouth to the outer estuary, and settling (particulate) material in sediment traps moored at selected locations in the estuary. Ultrafiltration, high-resolution ICP-MS and modeling were applied on the waters, and a variety of chemical reagents were used to extract metals from the settling material. Aluminium, Fe and REE transported by the acidic creek were extensively removed in the inner/central estuary where the acidic water was neutralised, whereas Mn was relatively persistent in solution and thus redistributed to particles and deposited further down the estuary. The REE removal was caused by several contemporary mechanisms: co-precipitation with oxyhydroxides (mainly Al but also Fe), complexation with flocculating humic substances and sorption to suspended particles. Down estuary the dissolved REE pool, remaining after removal, was fractionated: the <1 kDa pool became depleted in the middle REE and the colloidal (0.45 μm-1 kDa) pool depleted in the middle and heavy REE. This fractionation was controlled by the removal process, such that those REE with highest affinity for the settling particles became most depleted in the remaining dissolved pool. Modeling, based on Visual MINTEQ version 3.0 and the Stockholm Humic Model after revision and updating, predicted that the dissolved (<0.45 μm) REE pool in the estuary is bound almost entirely to humic substances. Acid sulphate soils, the source of the REE and other metals in the creek water, are widespread on coastal plains worldwide and therefore the REE attenuation patterns and mechanisms identified in the studied estuary are relevant for recognition of similar geochemical processes and conditions in a variety of coastal locations.

  8. HPTLC and magnetochromatography of new complexes of carboxylates with transition metals or rare earth elements and their ligands - study of lipophilicity.

    PubMed

    Malinowska, Irena; Wronka, Agnieszka; Ferenc, Wiesława

    2017-05-01

    Nineteen new complexes of carboxylates with transition and rare elements as central ions and their ligands were characterized by chromatographic analyses. The parameter of relative lipophilicity (RM0 ) of the tested compounds was determined experimentally by the reversed-phase high-performance thin layer chromatography method with mixtures of various organic modifiers (acetonitrile, acetone, dioxane) and water as a mobile phase. The extrapolated RM0 values were compared with the logP values calculated from the molecular structures of tested solutes. Similarities between the lipophilicity indices were analysed by principal component analysis and linear regression. Thin-layer chromatography combined with a magnetic field has been proposed as a complementary method for determination of lipophilicity of the investigated compounds. The chromatograms in the field and outside it were developed simultaneously in two identical chromatographic chambers. One of them was placed in the external magnetic field of 0.4 T inductivity. We proved that chelation causes a drastic change in compound lipophilicity, but all complexes did not exhibit enhanced activity as compared with the parent ligand. Also in the magnetic field the retention of some complexes changed, which means that the presence of the field influences the physicochemical properties of the compounds and their interactions with the stationary phase.

  9. Enhanced Laser Cooling of Rare-Earth-Ion-Doped Composite Material

    NASA Astrophysics Data System (ADS)

    Jia, You-Hua; Zhong, Biao; Ji, Xian-Ming; Yin, Jian-Ping

    2008-10-01

    We predict enhanced laser cooling performance of rare-earth-ions-doped glasses containing nanometre-sized ul-traBne particles, which can be achieved by the enhancement of local Geld around rare earth ions, owing to the surface plasma resonance of small metallic particles. The influence of energy transfer between ions and the particle is theoretically discussed. Depending on the particle size and the ion emission quantum efficiency, the enhancement of the absorption is predicted. It is concluded that the absorption are greatly enhanced in these composite materials, the cooling power is increased as compared to the bulk material.

  10. Interactions of microorganisms with rare earth ions and their utilization for separation and environmental technology.

    PubMed

    Moriwaki, Hiroshi; Yamamoto, Hiroki

    2013-01-01

    In recent years, rare earth elements (REEs) have been widely used in various modern technological devices and the global demand for REE has been increasing. The increased demand for REEs has led to environmental exposure or water pollution from rare earth metal mines and various commercial products. Therefore, the development of a safe technology for the separation and adsorption of REEs is very important from the perspective of green chemistry and environmental pollution. In this review, the application and mechanisms of microorganisms for the removal and extraction of REEs from aqueous solutions are described. In addition, the advantages in using microorganisms for REE adsorption and future studies on this topic are discussed.

  11. Quantization of electronic states in a rare-earth film: Gd/W(110)

    NASA Astrophysics Data System (ADS)

    Rader, O.; Shikin, A. M.

    2001-11-01

    A variety of distinct peaks occurs in photoemission spectra of ultrathin Gd on W(110) depending on the overlayer thickness, in particular a series of sharp peaks inside of a symmetry gap of the W band structure. Our phase-accumulation analysis assigns these structures to quantum-well states hitherto undetected in rare earths. This is of considerable importance since valence electrons mediate the magnetic coupling and determine the magnetic structure of rare-earth metals. As a first example of its impact, we demonstrate how the new quantum-well data help to resolve a current controversy concerning the nature of the Gd electronic structure.

  12. METHOD OF SEPARATING TETRAVALENT PLUTONIUM VALUES FROM CERIUM SUB-GROUP RARE EARTH VALUES

    DOEpatents

    Duffield, R.B.; Stoughton, R.W.

    1959-02-01

    A method is presented for separating plutonium from the cerium sub-group of rare earths when both are present in an aqueous solution. The method consists in adding an excess of alkali metal carbonate to the solution, which causes the formation of a soluble plutonium carbonate precipitate and at the same time forms an insoluble cerium-group rare earth carbonate. The pH value must be adjusted to bctween 5.5 and 7.5, and prior to the precipitation step the plutonium must be reduced to the tetravalent state since only tetravalent plutonium will form the soluble carbonate complex.

  13. Refining and Mutual Separation of Rare Earths Using Biomass Wastes

    NASA Astrophysics Data System (ADS)

    Inoue, Katsutoshi; Alam, Shafiq

    2013-10-01

    Two different types of adsorption gels were prepared from biomass wastes. The first gel was produced from astringent persimmon peel rich in persimmon tannin, a polyphenol compound, which was prepared by means of simple dehydration condensation reaction using concentrated sulfuric acid for crosslinking. This adsorption gel was intended to be employed for the removal of radioactive elements, uranium (U(VI)) and thorium (Th(IV)), from rare earths. The second gel was prepared from chitosan, a basic polysaccharide, produced from shells of crustaceans such as crabs, shrimps, prawns, and other biomass wastes generated in marine product industry, by immobilizing functional groups of complexanes such as ethylendiaminetetraacetic acid and diethylentriaminepentaacetic acid (DTPA). This gel was developed for the mutual separation of rare earths. Of the two adsorption gels evaluated, the DTPA immobilized chitosan exhibited the most effective mutual separation among light rare earths.

  14. High efficiency rare-earth emitter for thermophotovoltaic applications

    SciTech Connect

    Sakr, E. S.; Zhou, Z.; Bermel, P.

    2014-09-15

    In this work, we propose a rare-earth-based ceramic thermal emitter design that can boost thermophotovoltaic (TPV) efficiencies significantly without cold-side filters at a temperature of 1573 K (1300 °C). The proposed emitter enhances a naturally occurring rare earth transition using quality-factor matching, with a quarter-wave stack as a highly reflective back mirror, while suppressing parasitic losses via exponential chirping of a multilayer reflector transmitting only at short wavelengths. This allows the emissivity to approach the blackbody limit for wavelengths overlapping with the absorption peak of the rare-earth material, while effectively reducing the losses associated with undesirable long-wavelength emission. We obtain TPV efficiencies of 34% using this layered design, which only requires modest index contrast, making it particularly amenable to fabrication via a wide variety of techniques, including sputtering, spin-coating, and plasma-enhanced chemical vapor deposition.

  15. Trimethylsilylmethyl complexes of the rare-earth metals with sterically hindered N-heterocyclic carbene ligands: adduct formation and C-H bond activation.

    PubMed

    Fegler, Waldemar; Spaniol, Thomas P; Okuda, Jun

    2010-08-07

    Tris(trimethylsilylmethyl) complexes of yttrium and lutetium [LnR(3)(THF)(2)] (R = CH(2)SiMe(3)) were treated with sterically bulky N-heterocyclic carbenes (NHC) 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene (IPr) and 1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene (IMes). IPr gave labile mono-adducts [LnR(3)(NHC)], isolated as thermally robust crystals and fully characterized by NMR spectroscopy and X-ray diffraction. IMes gave a similar lutetium mono-adduct [LuR(3)(IMes)] with the lutetium alkyl [LuR(3)(THF)(2)], whereas the yttrium alkyl [YR(3)(THF)(2)] resulted in the formation of an ortho-metalated product. This compound, isolated as a crystalline bis(THF) adduct, contains a strained six-membered chelate ring that has been formed by the C-H bond activation of one of the ortho-methyl groups of the mesityl group. In contrast [LuR(3)(IMes)] only slowly underwent a similar C-H bond activation.

  16. Combinatorial investigation of rare-earth free permanent magnets

    NASA Astrophysics Data System (ADS)

    Fackler, Sean Wu

    The combinatorial high throughput method allows one to rapidly study a large number of samples with systematically changing parameters. We apply this method to study Fe-Co-V alloys as alternatives to rare-earth permanent magnets. Rare-earth permanent magnets derive their unmatched magnetic properties from the hybridization of Fe and Co with the f-orbitals of rare-earth elements, which have strong spin-orbit coupling. It is predicted that Fe and Co may also have strong hybridization with 4d and 5d refractory transition metals with strong spin-orbit coupling. Refractory transition metals like V also have the desirable property of high temperature stability, which is important for permanent magnet applications in traction motors. In this work, we focus on the role of crystal structure, composition, and secondary phases in the origin of competitive permanent magnetic properties of a particular Fe-Co-V alloy. Fe38Co52V10, compositions are known as Vicalloys. Fe-CoV composition spreads were sputtered onto three-inch silicon wafers and patterned into discrete sample pads forming a combinatorial library. We employed highthroughput screening methods using synchrotron X-rays, wavelength dispersive spectroscopy, and magneto-optical Kerr effect (MOKE) to rapidly screen crystal structure, composition, and magnetic properties, respectively. We found that in-plane magnetic coercive fields of our Vicalloy thin films agree with known bulk values (300 G), but found a remarkable eight times increase of the out-of-plane coercive fields (˜2,500 G). To explain this, we measured the switching fields between in-plane and out-of-plane thin film directions which revealed that the Kondorsky model of 180° domain wall reversal was responsible for Vicalloy's enhanced out-of-plane coercive field and possibly its permanent magnetic properties. The Kondorsky model suggests that domain-wall pinning is the origin of Vicalloy's permanent magnetic properties, in contrast to strain, shape, or

  17. Development of Electronic Tongue for Detection of Rare Earth Elements in Natural Surroundings

    NASA Astrophysics Data System (ADS)

    Sarkar, Subrata; Purkait, Monirul; Roy, Jayanta Kumar; Datta, C.; Bhattacharyya, Nabarun; Sarkar, D.; Datta, Jagannath; Chowdhury, D. P.

    2011-09-01

    The rare earth elements (like lanthanum) and other metals like zirconium, arsenic, potassium, copper etc. are some of the elements, which are found in the natural surrounding. Since these metals have immense utility in the field of medical science, energy efficient electronic devices, nuclear energy domain, early and easy detection of such metals is very important. In the present work, voltammetric electronic tongue for detection and quantitative determination of these elements has been explored. A sensor array comprising of noble metals (like gold, iridium, rhodium etc) has been developed and it exhibits remarkable sensitivity and promising results for detection and analysis of these elements.

  18. Rare-earth metals (REMs) in nickel aluminide-based alloys: I. Physicochemical laws of interaction in the Ni-Al-REM and Ni x Al y -REM-AE (alloying element) systems

    NASA Astrophysics Data System (ADS)

    Povarova, K. B.; Kazanskaya, N. K.; Drozdov, A. A.; Morozov, A. E.

    2008-02-01

    The data on the Ni-Al- R ( R = REM Sc, Y, La, lanthanides) binary and ternary systems and the interactions of three rare-earth metals (yttrium, lanthanum, cerium) with the main alloying elements (Ti (Zr, Hf), Cr (Mo, W) that are introduced into Ni3Al-based VKNA alloys are analyzed. The binary aluminides of REMs in the Ni-Al- R ternary systems are shown to be in equilibrium with neither NiAl nor Ni3Al. The solid solution of aluminum in RNi5, which penetrates deep into these ternary systems, is the most stable phase in equilibrium with Ni3Al. In the NiAl (Ni3Al)-AE- R systems, REM precipitation (segregation) on various defects and interfaces in nickel aluminides is likely to be the most probable, and REMs are thought to interact with the most active impurities in real alloys (C, O, N), since REMs have a large atomic radius and, thus, are virtually undissolved in nickel, aluminum, and nickel aluminides.

  19. Au/MxOy/TiO2 catalysts for CO oxidation: promotional effect of main-group, transition, and rare-earth metal oxide additives.

    SciTech Connect

    Ma, Zhen; Overbury, Steven {Steve} H; Dai, Sheng

    2007-01-01

    Au/TiO2 catalysts are active for CO oxidation, but they suffer from high-temperature sintering of the gold particles, and few attempts have been made to promote or stabilize Au/TiO2. Our recent communication addressed these issues by loading gold onto Al2O3/TiO2 prepared via surface-sol-gel processing of Al(sec-OC4H9)3 on TiO2. In our current full paper, Au/Al2O3/TiO2 catalysts were prepared alternatively by thermal decomposition of Al(NO3)3 on TiO2 followed by loading gold, and the influences of the decomposition temperature and Al2O3 content were systematically surveyed. This facile method was subsequently extended to the preparation of a battery of metal oxide-modified Au/TiO2 catalysts virtually not reported. It was found that Au/TiO2 modified by CaO, NiO, ZnO, Ga2O3, Y2O3, ZrO2, La2O3, Pr2O3, Nd2O3, Sm2O3, Eu2O3, Gd2O3, Dy2O3, Ho2O3, Er2O3, or Yb2O3 could retain significant activity at ambient temperature even after aging in O2-He at 500 C, whereas unmodified Au/TiO2 lost its activity. Moreover, some 200 C-calcined promoted catalysts showed high activity even at about -100 C. The deactivation and regeneration of some of these new catalysts were studied. This work furnished novel catalysts for further fundamental and applied research.

  20. Process to remove rare earth from IFR electrolyte

    DOEpatents

    Ackerman, J.P.; Johnson, T.R.

    1992-01-01

    The invention is a process for the removal of rare earths from molten chloride electrolyte salts used in the reprocessing of integrated fast reactor fuel (IFR). The process can be used either continuously during normal operation of the electrorefiner or as a batch process. The process consists of first separating the actinide values from the salt before purification by removal of the rare earths. After replacement of the actinides removed in the first step, the now-purified salt electrolyte has the same uranium and plutonium concentration and ratio as when the salt was removed from the electrorefiner.

  1. Process to remove rare earth from IFR electrolyte

    DOEpatents

    Ackerman, J.P.; Johnson, T.R.

    1994-08-09

    The invention is a process for the removal of rare earths from molten chloride electrolyte salts used in the reprocessing of integrated fast reactor fuel (IFR). The process can be used either continuously during normal operation of the electrorefiner or as a batch process. The process consists of first separating the actinide values from the salt before purification by removal of the rare earths. After replacement of the actinides removed in the first step, the now-purified salt electrolyte has the same uranium and plutonium concentration and ratio as when the salt was removed from the electrorefiner. 1 fig.

  2. Thermal Expansion and Thermal Conductivity of Rare Earth Silicates

    NASA Technical Reports Server (NTRS)

    Zhu, Dongming; Lee, Kang N.; Bansal, Narottam P.

    2006-01-01

    Rare earth silicates are considered promising candidate materials for environmental barrier coatings applications at elevated temperature for ceramic matrix composites. High temperature thermophysical properties are of great importance for coating system design and development. In this study, the thermal expansion and thermal conductivity of hot-pressed rare earth silicate materials were characterized at temperatures up to 1400 C. The effects of specimen porosity, composition and microstructure on the properties were also investigated. The materials processing and testing issues affecting the measurements will also be discussed.

  3. THE RARE EARTH PEAK: AN OVERLOOKED r-PROCESS DIAGNOSTIC

    SciTech Connect

    Mumpower, Matthew R.; McLaughlin, G. C.; Surman, Rebecca E-mail: gail_mclaughlin@ncsu.edu

    2012-06-20

    The astrophysical site or sites responsible for the r-process of nucleosynthesis still remains an enigma. Since the rare earth region is formed in the latter stages of the r-process, it provides a unique probe of the astrophysical conditions during which the r-process takes place. We use features of a successful rare earth region in the context of a high-entropy r-process (S {approx}> 100k{sub B} ) and discuss the types of astrophysical conditions that produce abundance patterns that best match meteoritic and observational data. Despite uncertainties in nuclear physics input, this method effectively constrains astrophysical conditions.

  4. Size distribution of rare earth elements in coal ash

    USGS Publications Warehouse

    Scott, Clinton T.; Deonarine, Amrika; Kolker, Allan; Adams, Monique; Holland, James F.

    2015-01-01

    Rare earth elements (REEs) are utilized in various applications that are vital to the automotive, petrochemical, medical, and information technology industries. As world demand for REEs increases, critical shortages are expected. Due to the retention of REEs during coal combustion, coal fly ash is increasingly considered a potential resource. Previous studies have demonstrated that coal fly ash is variably enriched in REEs relative to feed coal (e.g, Seredin and Dai, 2012) and that enrichment increases with decreasing size fractions (Blissett et al., 2014). In order to further explore the REE resource potential of coal ash, and determine the partitioning behavior of REE as a function of grain size, we studied whole coal and fly ash size-fractions collected from three U.S commercial-scale coal-fired generating stations burning Appalachian or Powder River Basin coal. Whole fly ash was separated into , 5 um, to 5 to 10 um and 10 to 100 um particle size fractions by mechanical shaking using trace-metal clean procedures. In these samples REE enrichments in whole fly ash ranges 5.6 to 18.5 times that of feedcoals. Partitioning results for size separates relative to whole coal and whole fly ash will also be reported. 

  5. Revisiting the rare earth elements in foraminiferal tests [rapid communication

    NASA Astrophysics Data System (ADS)

    Haley, Brian A.; Klinkhammer, Gary P.; Mix, Alan C.

    2005-10-01

    Are the rare earth elements (REEs) in foraminifera a valuable proxy for use in paleoceanographic and climate change studies? In order to investigate this, we attempted a comprehensive study of REEs in planktonic and benthic foraminifera. Several different cleaning protocols were tested. Although the hydroxylamine used to clean all foraminifera in this study removes an unidentified source of REE contamination, it seems to remobilize metal oxides that are otherwise unaffected in flow-through dissolution. The calculated REE distribution coefficients, KD(REE)s, are between 100 and 500 for both planktonic and benthic foraminifera. These KDs are high compared to other elements in biogenic calcite but can be explained through a general model of element incorporation during foraminiferal calcification. From data taken from eight core tops in the southeast Pacific, we conclude that the REEs in planktonic foraminifera are, indeed, useful as a proxy for upper ocean water mass and mixed layer biogenic productivity. Alternatively, the REEs in benthic foraminifera are useful as a proxy for carbon flux to the sea floor. These proxies should be robust down core unless the sediments have undergone anoxic diagenesis, which stabilizes Fe carbonate thus overprinting the primary REE signature. However, it is clear from REE distributions in foraminiferal tests if anoxic conditions have occurred.

  6. Spin Hall torques generated by rare-earth thin films

    NASA Astrophysics Data System (ADS)

    Reynolds, Neal; Jadaun, Priyamvada; Heron, John T.; Jermain, Colin L.; Gibbons, Jonathan; Collette, Robyn; Buhrman, R. A.; Schlom, D. G.; Ralph, D. C.

    2017-02-01

    We report an initial experimental survey of spin Hall torques generated by the rare-earth metals Gd, Dy, Ho, and Lu, along with comparisons to first-principles calculations of their spin Hall conductivities. Using spin torque ferromagnetic resonance (ST-FMR) measurements and dc-biased ST-FMR, we estimate lower bounds for the spin Hall torque ratio, ξSH, of ≈0.04 for Gd, ≈0.05 for Dy, ≈0.14 for Ho, and ≈0.014 for Lu. The variations among these elements are qualitatively consistent with results from first principles [density-functional theory (DFT) in the local density approximation with a Hubbard-U correction]. The DFT calculations indicate that the spin Hall conductivity is enhanced by the presence of the partially filled f orbitals in Dy and Ho, which suggests a strategy to further strengthen the contribution of the f orbitals to the spin Hall effect by shifting the electron chemical potential.

  7. X-ray Absorption Spectroscopy of the Rare Earth orthophosphates

    SciTech Connect

    Shuh, D.K.; Terminello, L.J.; Boatner, L.A.; Abraham, M.M.

    1993-06-01

    X-ray Absorption Spectroscopy (XAS) of the Rare Earth (RE) 3d levels yields sharp peaks near the edges as a result of strong, quasi-atomic 3d{sup 10}4f{sup n} {yields} 3d-{sup 9}4f{sup n+1} transitions and these transitions exhibit a wealth of spectroscopic features. The XAS measurements of single crystal REPO{sub 4} (RE = La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Er) at the 3d edge were performed in the total yield mode at beam line 8-2 at the Stanford Synchrotron Radiation Laboratory (SSRL). The XAS spectra of the RE ions in the orthophosphate matrix generally resemble the XAS of the corresponding RE metal. This is not unexpected and emphasizes the major contribution of the trivalent state to the electronic transitions at the RE 3d edges. These spectra unequivocally identify the transitions originating from well-characterized RE cores and correlate well with previous theoretical investigations.

  8. Visible light induced oxidation of water by rare earth manganites, cobaltites and related oxides

    NASA Astrophysics Data System (ADS)

    Naidu, B. S.; Gupta, Uttam; Maitra, Urmimala; Rao, C. N. R.

    2014-01-01

    A study of the visible light induced oxidation of water by perovskite oxides of the formula LaMO3 (M = transition metal) has revealed the best activity with LaCoO3 which contains Co3+ in the intermediate-spin (IS) with one eg electron. Among the rare earth manganites, only orthorhombic manganites with octahedral Mn3+ ions exhibit good catalytic activity, but hexagonal manganites are poor catalysts. Interestingly, not only the perovskite rare earth cobaltites but also solid solutions of Co3+ in cubic rare earth sesquioxides exhibit catalytic activity comparable to LaCoO3, the Co3+ ion in all these oxides also being in the IS t2g5 e g 1 state.

  9. Magnetic Nanofluid Rare Earth Element Extraction Process Report, Techno Economic Analysis, and Results for Geothermal Fluids

    SciTech Connect

    Pete McGrail

    2016-03-14

    This GDR submission is an interim technical report and raw data files from the first year of testing on functionalized nanoparticles for rare earth element extraction from geothermal fluids. The report contains Rare Earth Element uptake results (percent removal, mg Rare Earth Element/gram of sorbent, distribution coefficient) for the elements of Neodymium, Europium, Yttrium, Dysprosium, and Cesium. A detailed techno economic analysis is also presented in the report for a scaled up geothermal rare earth element extraction process. All rare earth element uptake testing was done on simulated geothermal brines with one rare earth element in each brine. The rare earth element uptake testing was conducted at room temperature.

  10. Magneto-structural correlations in rare-earth cobalt pnictides

    NASA Astrophysics Data System (ADS)

    Thompson, Corey Mitchell

    Magnetic materials are used in many applications such as credit cards, hard drives, electric motors, sensors, etc. Although a vast range of magnetic solids is available for these purposes, our ability to improve their efficiency and discover new materials remains paramount to the sustainable progress and economic profitability in many technological areas. The search for magnetic solids with improved performance requires fundamental understanding of correlations between the structural, electronic, and magnetic properties of existing materials, as well as active exploratory synthesis that targets the development of new magnets. Some of the strongest permanent magnets, Nd 2Fe14B, SmCo5, and Sm2Co17, combine transition and rare-earth metals, benefiting from the strong exchange between the 4f and 3d magnetic sublattices. Although these materials have been studied in great detail, the development of novel magnets requires thorough investigation of other 3d-4 f intermetallics, in order to gain further insights into correlations between their crystal structures and magnetic properties. Among many types of intermetallic materials, ternary pnictides RCo 2Pn2 (R = La, Ce, Pr, Nd; Pn = P, As) are of interest because, despite their simple crystal structures, they contain two magnetic sublattices, exchange interactions between which may lead to rich and unprecedented magnetic behavior. Nevertheless, magnetism of these materials was studied only to a limited extent, especially as compared to the extensive studies of their silicide and germanide analogues. The ThCr2Si2 structure type, to which these ternary pnictides belong, is one of the most ubiquitous atomic arrangements encountered among intermetallic compounds. It accounts for over 1000 known intermetallics and has received increased attention due to the recently discovered FeAs-based superconductors. This dissertation is devoted to the investigation of

  11. Rare earth elements in scleractinian cold-water corals

    NASA Astrophysics Data System (ADS)

    Raddatz, J.; Liebetrau, V.; Hathorne, E. C.; Rüggeberg, A.; Dullo, W.; Frank, M.

    2012-12-01

    The Rare Earth Elements (REE) have a great potential to trace continental input, particle scavenging and the oxidation state of seawater. These REE are recorded in the skeleton of the cosmopolitan cold-water corals Lophelia pertusa. Here we use an online preconcentration ICP-MS method (Hathorne et al. 2012) to measure REE concentrations in seawater and associated cold-water coral carbonates in order to investigate their seawater origin. Scleractinian cold-water corals were collected in-situ and alive and with corresponding seawater samples covering from the European Continental Margin. The seawater REE patterns are characterized by the typical negative cerium anomaly of seawater, but are distinct for the northern Norwegian Margin and the Oslo Fjord, probably related to continental input. Initial results for the corresponding coral samples suggest that these distinct REE patterns of ambient seawater are recorded by the coral skeletons although some fractionation during incorporation into the aragonite occurs. This indicates that scleractinian cold-water corals can serve as a valuable archive for seawater derived REE signatures, as well radiogenic Nd isotope compositions. In a second step we analysed fossil coral samples from various locations, which were oxidatively and reductively cleaned prior to analysis. Initial results reveal that sediment-buried fossil (early Pleistocene to Holocene) coral samples from the Norwegian Margin and the Porcupine Seabight (Challenger Mound, IODP Site 1317) do not show the expected seawater REE patterns. In particular, the fossil coral-derived REE patterns lack a negative cerium anomaly suggesting that fossil coral-REE patterns do not represent ambient seawater. Thus, we suggest that the oxidative-reductive cleaning method widely used for cleaning of marine carbonates such as foraminifera prior to measurements of seawater-derived trace metal and isotope compositions are not sufficient for REE and Nd isotopes in sediment-buried coral

  12. Determination of thorium and of rare earth elements in cerium earth minerals and ores

    USGS Publications Warehouse

    Carron, M.K.; Skinner, D.L.; Stevens, R.E.

    1955-01-01

    The conventional oxalate method for precipitating thorium and the rare earth elements in acid solution exhibits definite solubilities of these elements. The present work was undertaken to establish conditions overcoming these solubilities and to find optimum conditions for precipitating thorium and the rare earth elements as hydroxides and sebacates. The investigations resulted in a reliable procedure applicable to samples in which the cerium group elements predominate. The oxalate precipitations are made from homogeneous solution at pH 2 by adding a prepared solution of anhydrous oxalic acid in methanol instead of the more expensive crystalline methyl oxalate. Calcium is added as a carrier. Quantitative precipitation of thorium and the rare earth elements is ascertained by further small additions of calcium to the supernatant liquid, until the added calcium precipitates as oxalate within 2 minutes. Calcium is removed by precipitating the hydroxides of thorium and rare earths at room temperature by adding ammonium hydroxide to pH > 10. Thorium is separated as the sebacate at pH 2.5, and the rare earths are precipitated with ammonium sebacate at pH 9. Maximum errors for combined weights of thorium and rare earth oxides on synthetic mixtures are ??0.6 mg. Maximum error for separated thoria is ??0.5 mg.

  13. Electrical Relaxation in Rare Earth Doped Cubic Lead Fluoride.

    DTIC Science & Technology

    1982-11-01

    PAGE (W v,. Data Fleted ) READ INSTRUCTIONSREPORT DOCUMENTATION PAGE BEFRE CMPETINGFORSORE OMPLETIN FO M 1. REPORT NUMBER j2. GOVT ACCESSION NO. 3...For the smallest rare earths, however, at least nine .* relaxations are found. The concentration studies indicate multiple relaxations for certain...relaxations are found. The concentration studies indicate multiple relaxations for certain sites. Both simple sites and clusters are observed for

  14. Complex Electronic Structure of Rare Earth Activators in Scintillators

    SciTech Connect

    Aberg, D.; Yu, S. W.; Zhou, F.

    2015-10-27

    To aid and further the understanding of the microscopic mechanisms behind the scintillator nonproportionality that leads to degradation of the attainable energy resolution, we have developed theoretical and experimental algorithms and procedures to determine the position of the 4f energy levels of rare earth dopants relative to the host band edge states.

  15. Potential synergy: the thorium fuel cycle and rare earths processing

    SciTech Connect

    Ault, T.; Wymer, R.; Croff, A.; Krahn, S.

    2013-07-01

    The use of thorium in nuclear power programs has been evaluated on a recurring basis. A concern often raised is the lack of 'thorium infrastructure'; however, for at least a part of a potential thorium fuel cycle, this may less of a problem than previously thought. Thorium is frequently encountered in association with rare earth elements and, since the U.S. last systematically evaluated the large-scale use of thorium (the 1970's,) the use of rare earth elements has increased ten-fold to approximately 200,000 metric tons per year. Integration of thorium extraction with rare earth processing has been previously described and top-level estimates have been done on thorium resource availability; however, since ores and mining operations differ markedly, what is needed is process flowsheet analysis to determine whether a specific mining operation can feasibly produce thorium as a by-product. Also, the collocation of thorium with rare earths means that, even if a thorium product stream is not developed, its presence in mining waste streams needs to be addressed and there are previous instances where this has caused issues. This study analyzes several operational mines, estimates the mines' ability to produce a thorium by-product stream, and discusses some waste management implications of recovering thorium. (authors)

  16. Multi-objective optimization of chromatographic rare earth element separation.

    PubMed

    Knutson, Hans-Kristian; Holmqvist, Anders; Nilsson, Bernt

    2015-10-16

    The importance of rare earth elements in modern technological industry grows, and as a result the interest for developing separation processes increases. This work is a part of developing chromatography as a rare earth element processing method. Process optimization is an important step in process development, and there are several competing objectives that need to be considered in a chromatographic separation process. Most studies are limited to evaluating the two competing objectives productivity and yield, and studies of scenarios with tri-objective optimizations are scarce. Tri-objective optimizations are much needed when evaluating the chromatographic separation of rare earth elements due to the importance of product pool concentration along with productivity and yield as process objectives. In this work, a multi-objective optimization strategy considering productivity, yield and pool concentration is proposed. This was carried out in the frame of a model based optimization study on a batch chromatography separation of the rare earth elements samarium, europium and gadolinium. The findings from the multi-objective optimization were used to provide with a general strategy for achieving desirable operation points, resulting in a productivity ranging between 0.61 and 0.75 kgEu/mcolumn(3), h(-1) and a pool concentration between 0.52 and 0.79 kgEu/m(3), while maintaining a purity above 99% and never falling below an 80% yield for the main target component europium.

  17. Pitfalls of rare earth imaging: conquering the three Ps.

    PubMed

    Lam, R W; Price, S C

    1992-01-01

    Rare earth technology has become the standard in radiographic imaging, but misapplication and insufficient comprehension of the variables of usage create practical problems. Special problem areas are pediatrics, portable radiography and phototimed exposures. These problems, as well as possible solutions, are addressed in this article.

  18. Rare earth elements exploitation, geopolitical implications and raw materials trading

    NASA Astrophysics Data System (ADS)

    Chemin, Marie-Charlotte

    2015-04-01

    Rare earth elements (REE) correspond to seventeen elements of the periodic table. They are used in high technology, cracking, electric cars' magnet, metal alloy for batteries, and also in phone construction or ceramics for electronic card. REEs are an important resource for high technology. This project targets 16 years old students in the subject "personalized aid" and will last six weeks. The purpose of this project is to develop autonomy and research in groups for a transdisciplinary work. This project gathers knowledge in geology, geography and economics. During the first session students analyze the geology applications of the REE. They begin the analysis with learning the composition in different rocks such as basalt and diorite to make the link with crystallization. Then they compare it with adakite to understand the formation of these rocks. In the second session, they study REE exploitation. We can find them as oxides in many deposits. The principal concentrations of rare earth elements are associated with uncommon varieties of igneous rocks, such as carbonatites. They can use Qgis, to localize this high concentration. In the third session, they study the environmental costs of REE exploitation. Indeed, the exploitation produces thorium and carcinogenic toxins: sulphates, ammonia and hydrochloric acid. Processing one ton of rare earths produces 2,000 tons of toxic waste. This session focuses, first, on Baotou's region, and then on an example they are free to choose. In the fourth session, they study the geopolitical issues of REE with a focus on China. In fact this country is the largest producer of REE, and is providing 95% of the overall production. REE in China are at the center of a geopolitical strategy. In fact, China implements a sort of protectionism. Indeed, the export tax on REE is very high so, as a foreign company, it is financially attractive to establish a manufacturing subsidiary in China in order to use REE. As a matter of fact

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

    USGS Publications Warehouse

    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

  20. Value analysis of neodymium content in shredder feed: toward enabling the feasibility of rare earth magnet recycling.

    PubMed

    Bandara, H M Dhammika; Darcy, Julia W; Apelian, Diran; Emmert, Marion H

    2014-06-17

    In order to facilitate the development of recycling technologies for rare earth magnets from postconsumer products, we present herein an analysis of the neodymium (Nd) content in shredder scrap. This waste stream has been chosen on the basis of current business practices for the recycling of steel, aluminum, and copper from cars and household appliances, which contain significant amounts of rare earth magnets. Using approximations based on literature data, we have calculated the average Nd content in the ferrous shredder product stream to be between 0.13 and 0.29 kg per ton of ferrous scrap. A value analysis considering rare earth metal prices between 2002 and 2013 provides values between $1.32 and $145 per ton of ferrous scrap for this material, if recoverable as pure Nd metal. Furthermore, we present an analysis of the content and value of other rare earths (Pr, Dy, Tb).

  1. Trends in Syntheses, Structures, and Properties for Three Series of Ammine Rare-Earth Metal Borohydrides, M(BH4)3·nNH3 (M = Y, Gd, and Dy).

    PubMed

    Jepsen, Lars H; Ley, Morten B; Černý, Radovan; Lee, Young-Su; Cho, Young Whan; Ravnsbæk, Dorthe; Besenbacher, Flemming; Skibsted, Jørgen; Jensen, Torben R

    2015-08-03

    Fourteen solvent- and halide-free ammine rare-earth metal borohydrides M(BH4)3·nNH3, M = Y, Gd, Dy, n = 7, 6, 5, 4, 2, and 1, have been synthesized by a new approach, and their structures as well as chemical and physical properties are characterized. Extensive series of coordination complexes with systematic variation in the number of ligands are presented, as prepared by combined mechanochemistry, solvent-based methods, solid-gas reactions, and thermal treatment. This new synthesis approach may have a significant impact within inorganic coordination chemistry. Halide-free metal borohydrides have been synthesized by solvent-based metathesis reactions of LiBH4 and MCl3 (3:1), followed by reactions of M(BH4)3 with an excess of NH3 gas, yielding M(BH4)3·7NH3 (M = Y, Gd, and Dy). Crystal structure models for M(BH4)3·nNH3 are derived from a combination of powder X-ray diffraction (PXD), (11)B magic-angle spinning NMR, and density functional theory (DFT) calculations. The structures vary from two-dimensional layers (n = 1), one-dimensional chains (n = 2), molecular compounds (n = 4 and 5), to contain complex ions (n = 6 and 7). NH3 coordinates to the metal in all compounds, while BH4(-) has a flexible coordination, i.e., either as a terminal or bridging ligand or as a counterion. M(BH4)3·7NH3 releases ammonia stepwise by thermal treatment producing M(BH4)3·nNH3 (6, 5, and 4), whereas hydrogen is released for n ≤ 4. Detailed analysis of the dihydrogen bonds reveals new insight about the hydrogen elimination mechanism, which contradicts current hypotheses. Overall, the present work provides new general knowledge toward rational materials design and preparation along with limitations of PXD and DFT for analysis of structures with a significant degree of dynamics in the structures.

  2. Separation of the rare-earth fission product poisons from spent nuclear fuel

    SciTech Connect

    Christian, Jerry D.; Sterbentz, James W.

    2016-08-30

    A method for the separation of the rare-earth fission product poisons comprising providing a spent nuclear fuel. The spent nuclear fuel comprises UO.sub.2 and rare-earth oxides, preferably Sm, Gd, Nd, Eu oxides, with other elements depending on the fuel composition. Preferably, the provided nuclear fuel is a powder, preferably formed by crushing the nuclear fuel or using one or more oxidation-reduction cycles. A compound comprising Th or Zr, preferably metal, is provided. The provided nuclear fuel is mixed with the Th or Zr, thereby creating a mixture. The mixture is then heated to a temperature sufficient to reduce the UO.sub.2 in the nuclear fuel, preferably to at least to 850.degree. C. for Th and up to 600.degree. C. for Zr. Rare-earth metals are then extracted to form the heated mixture thereby producing a treated nuclear fuel. The treated nuclear fuel comprises the provided nuclear fuel having a significant reduction in rare-earths.

  3. High pressure phase transformations in yttrium and scandium: Relation to rare earths and actinides crystal structures

    NASA Astrophysics Data System (ADS)

    Grosshans, W. A.; Vohra, Y. K.; Holzapfel, W. B.

    1982-10-01

    The phase transformations in the 4d transition metal yttrium (Y) and the 3d transition metal scandium (Sc) have been studied under pressures up to 45 GPa by energy dispersive X-ray diffraction. The metal Y shows the complete rare earth crystal structure sequence i.e. hcp→Sm-type→dhcp→fcc with increasing pressure. This establishes experimentally the similarity of Y with heavy lanthanides, and that the rare earth crystal structure sequence is driven by s→d transfer without any significant contribution from 4f electrons. The metal Sc does not undergo the rare earth crystal structure sequence with pressure but shows above 20 GPa β-Neptunium (Np) structure (tetragonal, 4 atoms/cell). This structure remains stable up to the highest pressure of 45 GPa. The occurence of the high temperature β-Np structure in trivalent Sc combined with large thermal expansions of Np and plutonium (Pu) suggest that itinerant 5f electrons become localized at high temperature in Np and Pu close to melting. This Mott transition with temperature is similar to the one observed between Pu and americium (Am).

  4. Systematic variation of rare-earth elements in cerium-earth minerals

    USGS Publications Warehouse

    Murata, K.J.; Rose, H.J.; Carron, M.K.; Glass, J.J.

    1957-01-01

    In a continuation of a study reported previously, rare-earth elements and thorium have been determined in monazite, allanite, cerite, bastnaesite, and a number of miscellaneous cerium-earth minerals. A quantity called sigma (???), which is the sum of the atomic percentages of La, Ce, and Pr, is proposed as an index of composition of all cerium-earth minerals with respect to the rare-earth elements. The value of ??? for all of the minerals analysed falls between 58 and 92 atomic per cent. Monazites, allanites, and cerites cover the entire observed range, whereas bastnaesites are sharply restricted to the range between 80 and 92 atomic per cent. The minimum value of ??? for a cerium-earth mineral corresponds to the smallest possible unit-cell size of the mineral. In monazite, this structurally controlled minimum value of ??? is estimated to be around 30 atomic per cent. Neodymium, because of its abundance, and yttrium, because of its small size, have dominant roles in contraction of the structure. In the other direction, the limit of variation in composition will be reached when lanthanum becomes the sole rare-earth element in a cerium-earth mineral. Cerium-earth minerals from alkalic rocks are all characterized by values of ??? greater than 80 atomic per cent, indicating that the processes that formed these rocks were unusually efficient in fractionating the rare-earth elements-efficient in the sense that a highly selected assemblage is produced without eliminating the bulk of these elements. Analyses of inner and outer parts of two large crystals of monazite from different deposits show no difference in ??? in one crystal and a slightly smaller value of ??? in the outer part of the other crystal compared to the inner part. The ??? of monazites from pegmatites that intrude genetically related granitic rocks in North Carolina is found to be either higher or lower than the ??? of monazites in the intruded host rock. These results indicate that the fractionation of the

  5. Recovery of rare earth elements from the sulfothermophilic red alga Galdieria sulphuraria using aqueous acid.

    PubMed

    Minoda, Ayumi; Sawada, Hitomi; Suzuki, Sonoe; Miyashita, Shin-ichi; Inagaki, Kazumi; Yamamoto, Takaiku; Tsuzuki, Mikio

    2015-02-01

    The demand for rare earth elements has increased dramatically in recent years because of their numerous industrial applications, and considerable research efforts have consequently been directed toward recycling these materials. The accumulation of metals in microorganisms is a low-cost and environmentally friendly method for the recovery of metals present in the environment at low levels. Numerous metals, including rare earth elements, can be readily dissolved in aqueous acid, but the efficiency of metal biosorption is usually decreased under the acidic conditions. In this report, we have investigated the use of the sulfothermophilic red alga Galdieria sulphuraria for the recovery of metals, with particular emphasis on the recovery of rare earth metals. Of the five different growth conditions investigated where G. sulphuraria could undergo an adaptation process, Nd(III), Dy(III), and Cu(II) were efficiently recovered from a solution containing a mixture of different metals under semi-anaerobic heterotrophic condition at a pH of 2.5. G. sulphuraria also recovered Nd(III), Dy(III), La(III), and Cu(II) with greater than 90% efficiency at a concentration of 0.5 ppm. The efficiency remained unchanged at pH values in the range of 1.5-2.5. Furthermore, at pH values in the range of 1.0-1.5, the lanthanoid ions were collected much more efficiently into the cell fractions than Cu(II) and therefore successfully separated from the Cu(II) dissolved in the aqueous acid. Microscope observation of the cells using alizarin red suggested that the metals were accumulating inside of the cells. Experiments using dead cells suggested that this phenomenon was a biological process involving specific activities within the cells.

  6. Mono-, di-, tri- and tetranuclear rare earth complexes obtained using a moderately bulky aryloxide ligand.

    PubMed

    Deacon, Glen B; Junk, Peter C; Moxey, Graeme J

    2009-11-02

    Redox transmetallation ligand exchange reactions involving a rare earth metal, 2,4,6-trimethylphenol (HOmes), and a diarylmercurial afford rare earth aryloxo complexes, which are structurally characterized. Both the lanthanoid contraction and the identity of the reaction solvent are found to influence the outcome of the reactions. Using THF in the reaction affords a dinuclear species [Ln2(Omes)6(thf)4].2THF (Ln=La 1, Nd 2) for the lighter rare earth metals, while a mononuclear species [Ln(Omes)3(thf)3] (Ln=Sm 3, Tb 5, Er 6, Yb 7, Y 8) is obtained for the heavier rare earth elements. Surprisingly, there is no change in metal coordination number between the two structural motifs. A divalent trinuclear linear complex [Eu3(Omes)6(thf)6] 4 is obtained for Eu, and features solely bridging aryloxide ligands. Using DME as the reaction solvent affords [La(Omes)3(dme)2] 9 from the reaction mixture, and [Ln2(Omes)6(dme)2].PhMe (La 10, Nd 11) and [Y(Omes)3(dme)2] 14 following crystallization of the crude product from toluene. The dinuclear species [Eu2(Omes)4(dme)4] 12 contains two unidentate and two chelating DME ligands, and contrasts the linear structure of 4. Treatment of HOmes and HgPh2 with Yb metal in DME affords the mixed valent Yb(II/III) complex [Yb2(Omes)5(dme)2] 13, which is stabilized by an intramolecular pi-Ph-Yb interaction, and is a rare example of a mixed valent rare earth aryloxide. Treatment of Er metal with HOmes at elevated temperature (solvent free) affords the homoleptic [Er4(Omes)12] 15, which consists of a tetranuclear array of Er atoms arranged in a 'herringbone' fashion; the structure is stabilized by intramolecular pi-Ph-Er interactions. Reaction of La metal with HOmes under similar conditions yields toluene insoluble "La(Omes)3", which affords 1 following extraction with THF.

  7. Rare earth modified silica-aluminas as supports for bifunctional catalysis

    SciTech Connect

    Soled, S.L.; McVicker, G.; Miseo, S.

    1996-12-31

    We have explored rare earth oxide-modified amorphous silica-aluminas as {open_quotes}permanent{close_quotes} intermediate strength acids used as supports for bifunctional catalysts. The addition of well dispersed weakly basic rare earth oxides {open_quotes}titrates{close_quotes} the stronger acid sites of amorphous silica-alumina and lowers the acid strength to the level shown by halided aluminas. Physical and chemical probes, as well as model olefin and paraffin isomerization reactions show that acid strength can be adjusted close to that of chlorided and fluorided aluminas. Metal activity is inhibited relative to halided alumina catalysts, which limits the direct metal-catalyzed dehydrocyclization reactions during paraffin reforming but does not interfere with hydroisomerization reactions.

  8. U.S. trade dispute with China over rare earth elements

    NASA Astrophysics Data System (ADS)

    Showstack, Randy

    2012-03-01

    The U.S. government has brought a new trade case against China over rare earth elements (REE) as well as tungsten and molybdenum, President Barack Obama announced on 13 March. Japan and the European Union also have taken similar actions against China about REEs, which are a group of 17 chemically similar metallic elements that are used in a variety of electronic, optical, magnetic, and catalytic applications. REEs are plentiful in the Earth's crust, although China currently has about 37% of the world's reserves and accounts for more than 95% of the world's production of the elements, according to the British Geological Survey. The United States has requested consultations with China at the World Trade Organization (WTO) concerning "China's unfair export restraints on rare earths, as well as tungsten and molybdenum," the Office of the United States Trade Representative announced in a 13 March statement.

  9. New data on mineral forms of rare metals in phosphogypsum wastes

    NASA Astrophysics Data System (ADS)

    Samonov, A. E.

    2011-09-01

    Phosphogypsum is an industrial waste of the processing of Khibiny apatite concentrate into chemical fertilizers by sulfurous technology. This is a valuable and promising technogenous rare-metal feedstock. The samples of fresh and old phosphogypsum were studied using precision physical techniques of analytical electron microscopy and X-ray spectral microanalysis. These studies allowed the discovery of new and unusual mineral compositions including strontium and rare earth metals in mineral fractions of phosphogypsum. The appearance of a new generation of technogenous rare-metal raw material permits us to characterize the prospects of its industrial use and to develop nonwaste technologies of its complex treatment.

  10. Rare Earth Nanoprobes for Functional Biomolecular Imaging and Theranostics

    PubMed Central

    Naczynski, Dominik J.; Tan, Mei Chee; Riman, Richard E.; Moghe, Prabhas V.

    2014-01-01

    Contrast agents designed to visualize the molecular mechanisms underlying cancer pathogenesis and progression have deepened our understanding of disease complexity and accelerated the development of enhanced drug strategies targeted to specific biochemical pathways. For the next generation probes and imaging systems to be viable, they must exhibit enhanced sensitivity and robust quantitation of morphologic and contrast features, while offering the ability to resolve the disease-specific molecular signatures that may be critical to reconstitute a more comprehensive portrait of pathobiology. This feature article provides an overview on the design and advancements of emerging biomedical optical probes in general and evaluates the promise of rare earth nanoprobes, in particular, for molecular imaging and theranostics. Combined with new breakthroughs in nanoscale probe configurations, and improved dopant compositions, and multimodal infrared optical imaging, rare-earth nanoprobes can be used to address a wide variety of biomedical challenges, including deep tissue imaging, real-time drug delivery tracking and multispectral molecular profiling. PMID:24921049

  11. Electronic and vibrational spectra of some rare earth trifluoromethanesulfonates crystals.

    PubMed

    Paul, P; Ghosh, M; Neogy, D; Mallick, P K

    2011-01-01

    The Raman and infrared spectra of some rare earth (dysprosium and terbium) trifluoromethanesulfonates crystals have been analyzed. Different vibrational frequencies of trifluoromethanesulfonate ions (CF3SO3-) are identified and assigned to different vibrations of the SO3 and CF3 groups. Electronic transitions of R3+ ions (R=Dy, Tb) in these salts have been assigned to transitions from the ground to different energy levels of the ground multiplet. The electronic energy levels of the rare earth ions are also determined theoretically with the help of single electron crystal field theory. They are found to yield results not only in good agreement with the observed spectral data but also in good conformity with those obtained previously from magnetic measurements.

  12. Electronic and vibrational spectra of some rare earth trifluoromethanesulfonates crystals

    NASA Astrophysics Data System (ADS)

    Paul, P.; Ghosh, M.; Neogy, D.; Mallick, P. K.

    2011-01-01

    The Raman and infrared spectra of some rare earth (dysprosium and terbium) trifluoromethanesulfonates crystals have been analyzed. Different vibrational frequencies of trifluoromethanesulfonate ions (CF 3SO 3-) are identified and assigned to different vibrations of the SO 3 and CF 3 groups. Electronic transitions of R 3+ ions (R = Dy, Tb) in these salts have been assigned to transitions from the ground to different energy levels of the ground multiplet. The electronic energy levels of the rare earth ions are also determined theoretically with the help of single electron crystal field theory. They are found to yield results not only in good agreement with the observed spectral data but also in good conformity with those obtained previously from magnetic measurements.

  13. Contamination in the Rare-Earth Element Orthophosphate Reference Samples

    PubMed Central

    Donovan, John J.; Hanchar, John M.; Picolli, Phillip M.; Schrier, Marc D.; Boatner, Lynn A.; Jarosewich, Eugene

    2002-01-01

    Several of the fourteen rare-earth element (plus Sc and Y) orthophosphate standards grown at Oak Ridge National Laboratory in the 1980s and widely distributed by the Smithsonian Institution’s Department of Mineral Sciences, are significantly contaminated by Pb. The origin of this impurity is the Pb2P2O7 flux that is derived from the thermal decomposition of PbHPO4. The lead pyrophosphate flux is used to dissolve the oxide starting materials at elevated temperatures (≈1360 °C) prior to the crystal synthesis. Because these rare-earth element standards are extremely stable under the electron beam and considered homogenous, they have been of enormous value to electron probe micro-analysis (EPMA). The monoclinic, monazite structure, orthophosphates show a higher degree of Pb incorporation than the tetragonal xenotime structure, orthophosphates. This paper will attempt to describe and rationalize the extent of the Pb contamination in these otherwise excellent materials. PMID:27446762

  14. Thermochemistry of Rare Earth Silicates for Environmental Barrier Coatings

    NASA Technical Reports Server (NTRS)

    Costa, Gustavo; Jacobson, Nathan

    2015-01-01

    Rare earth silicates are promising candidates as environmental protective coatings (EBCs) for silica-forming ceramics and composites in combustion environments since they are predicted to have lower reactivity with the water vapor combustion products. The reactivity of rare earth silicates is assessed by the thermodynamic activity of the silica component which is best measured by Knudsen effusion mass spectrometry (KEMS). Here, we discuss a novel method based on a reducing agent to increase the partial pressure of SiO(g) which is then used to calculate thermodynamic activity of silica in Y2O3-SiO2 and Yb2O3-SiO2 systems. After the KEMS measurements, samples were probed by X-ray diffraction and their phase content was calculated from Rietveld refinement.

  15. Rare-earth magnet ingestion: a childhood danger reaches adolescence.

    PubMed

    Agha, Beesan Shalabi; Sturm, Jesse J; Costello, Brian E

    2013-10-01

    Ingestion of multiple magnets may cause serious gastrointestinal morbidity, such as pressure necrosis, perforation, fistula formation, or intestinal obstruction due to forceful attraction across bowel wall. Although the consequences of multiple magnet ingestion are well documented in young children, the current popularity of small, powerful rare-earth magnets marketed as "desk toys" has heightened this safety concern in all pediatric age groups. A recent US Consumer Product Safety Commission product-wide warning additionally reports the adolescent practice of using toy high-powered, ball-bearing magnets to simulate tongue and lip piercings, a behavior that may increase risk of inadvertent ingestion. We describe 2 cases of older children (male; aged 10 and 13 years, respectively) with unintentional ingestion of multiple rare-earth magnets. Health care providers should be alerted to the potential for misuse of these high-powered, ball-bearing magnets among older children and adolescents.

  16. Rare Earth Doped Yttrium Aluminum Garnet (YAG) Selective Emitters

    NASA Technical Reports Server (NTRS)

    Chubb, Donald L.; Pal, AnnaMarie T.; Patton, Martin O.; Jenkins, Phillip P.

    1999-01-01

    As a result of their electron structure, rare earth ions in crystals at high temperature emit radiation in several narrow bands rather than in a continuous blackbody manner. This study presents a spectral emittance model for films and cylinders of rare earth doped yttrium aluminum garnets. Good agreement between experimental and theoretical film spectral emittances was found for erbium and holmium aluminum garnets. Spectral emittances of films are sensitive to temperature differences across the film. For operating conditions of interest, the film emitter experiences a linear temperature variation whereas the cylinder emitter has a more advantageous uniform temperature. Emitter efficiency is also a sensitive function of temperature. For holminum aluminum garnet film the efficiency is 0.35 at 1446K but only 0.27 at 1270 K.

  17. A divalent rare earth oxide semiconductor: Yttrium monoxide

    NASA Astrophysics Data System (ADS)

    Kaminaga, Kenichi; Sei, Ryosuke; Hayashi, Kouichi; Happo, Naohisa; Tajiri, Hiroo; Oka, Daichi; Fukumura, Tomoteru; Hasegawa, Tetsuya

    2016-03-01

    Rare earth oxides are usually widegap insulators like Y2O3 with closed shell trivalent rare earth ions. In this study, solid phase rock salt structure yttrium monoxide, YO, with unusual valence of Y2+ (4d1) was synthesized in a form of epitaxial thin film by pulsed laser deposition method. YO has been recognized as gaseous phase in previous studies. In contrast with Y2O3, YO was dark-brown colored and narrow gap semiconductor. The tunable electrical conductivity ranging from 10-1 to 103 Ω-1 cm-1 was attributed to the presence of oxygen vacancies serving as electron donor. Weak antilocalization behavior observed in magnetoresistance indicated significant role of spin-orbit coupling as a manifestation of 4d electron carrier.

  18. Alkali metal and rare earth element evolution of rock-forming minerals from the Gatumba area pegmatites (Rwanda): Quantitative assessment of crystal-melt fractionation in the regional zonation of pegmatite groups

    NASA Astrophysics Data System (ADS)

    Hulsbosch, Niels; Hertogen, Jan; Dewaele, Stijn; André, Luc; Muchez, Philippe

    2014-05-01

    This study presents a general model for the evaluation of Rayleigh fractional crystallisation as the principal differentiation mechanism in the formation of regionally zoned common and rare-element pegmatites. The magmatic evolution of these systems from a granitic source is reconstructed by means of alkali element and rare earth element (REE) analyses of rock-forming minerals (feldspars, micas and tourmaline), which represent a whole sequence of regional pegmatite zonation. The Gatumba pegmatite field (Rwanda, Central Africa) is chosen as case study area because of its well-developed regional zonation sequence. The pegmatites are spatially and temporally related to peraluminous G4-granites (986 ± 10 Ma). The regional zonation is developed around a G4-granite and the proximal pegmatites grade outwardly into biotite, two-mica and muscovite pegmatites. Rare-element (Nb-Ta-Sn) pegmatites occur most distal from the granite.

  19. Compositional and phase relations among rare earth element minerals

    NASA Technical Reports Server (NTRS)

    Burt, D. M.

    1990-01-01

    This paper discusses the compositional and phase relationships among minerals in which rare earth elements (REE) occur as essential constituents (e.g., bastnaesite, monazite, xenotime, aeschynite, allanite). Particular consideration is given to the vector representation of complex coupled substitutions in selected REE-bearing minerals and to the REE partitioning between minerals as related to the acid-base tendencies and mineral stabilities. It is shown that the treatment of coupled substitutions as vector quantities facilitates graphical representation of mineral composition spaces.

  20. Temperature-dependent Sellmeier equations for rare-earth sesquioxides.

    PubMed

    Zelmon, David E; Northridge, Jessica M; Haynes, Nicholas D; Perlov, Dan; Petermann, Klaus

    2013-06-01

    High-power lasers are making increasing demands on laser hosts especially in the area of thermal management. Traditional hosts, such as YAG, are unsuitable for many high-power applications and therefore, new hosts are being developed including rare-earth sesquioxides. We report new measurements of the refractive indices of these materials as functions of wavelength and temperature, which will aid in the design of laser cavities and other nonlinear optical elements.

  1. Are rare-earth nanoparticles suitable for in vivo applications?

    PubMed

    Liu, Chunyan; Hou, Yi; Gao, Mingyuan

    2014-10-29

    Rare earth (RE) nanoparticles have attracted considerable attention due to their unique optical and magnetic properties associated with f-electrons. The recent accomplishments in RE nanoparticle synthesis have aroused great interest of scientists to further explore their biomedical applications. This Research News summarizes recent achievements in controlled synthesis of magnetic and luminescent RE nanoparticles, surface modification, and toxicity studies of RE nanomaterials, and highlights state-of-the-art in in vivo applications of RE nanoparticles.

  2. An Integrated Rare Earth Elements Supply Chain Strategy

    DTIC Science & Technology

    2011-02-24

    Disruption in the global supply of rare earths poses a significant concern for America‘s energy security and clean energy objectives, its future defense...World Trade Organization rules by limiting clean energy imports, while incentivizing clean energy exports.54 If accurate, this speculation supports...resource scarcity and secure our supply chains. The NSS further declares the U.S. ―has a window of opportunity to lead in the development of clean energy technology

  3. Magnetostatic Effects in the Nucleation of Rare Earth Ferromagnetic Phases

    SciTech Connect

    Durfee, C. S.; Flynn, C. P.

    2001-07-30

    It has been reported that superheating, supercooling, and explosive kinetics coupled to other degrees of freedom occur at the ferromagnetic transitions of Er and Dy, and that metastable phases occur during the transition kinetics of Er. We explain these observations in terms of magnetostatic energy, which requires highly eccentric nuclei in the homogeneous nucleation of magnetic transitions in heavy rare earths. The magnetostatics favor transitions through ferrimagnetic intermediaries. The unusual kinetics derive from effective spin lattice relaxation.

  4. Distribution coefficients of rare earth ions in cubic zirconium dioxide

    NASA Astrophysics Data System (ADS)

    Romer, H.; Luther, K.-D.; Assmus, W.

    1994-08-01

    Cubic zirconium dioxide crystals are grown with the skull melting technique. The effective distribution coefficients for Nd(exp 3+), Sm(exp 3+) and Er(sup 3+) as dopants are determined experimentally as a function of the crystal growth velocity. With the Burton-Prim-Slichter theory, the equilibrium distribution coefficients can be calculated. The distribution coefficients of all other trivalent rare earth ions can be estimated by applying the correlation towards the ionic radii.

  5. The Synthesis and Characterization of Some Rare Earth Arsenides.

    DTIC Science & Technology

    1987-09-10

    Kobzenko, V. B. Chernogorenko, S. N. L’vov, M. I. Lesnaya, and K. A. Lynchak, "Equilibrium Diagram and Properties of Alloys of the As-Nd System...Stolchiometry and Structure on Physical Properties of the Rare Earth Arsen des .................................... 24 CHAPTER 3 OBJECTIVE AND TECHNICAL...Scanning Calorimetry (DSC) ..... ........ ... .......... . 67 CHAPTER 6 DISCUSSION..... ........... - .... .... . .... .. ..... 71 6.1 Properties of HoAs(Nd

  6. Process for separation of the rare earths by solvent extraction

    DOEpatents

    Mason, George W.; Lewey, Sonia

    1977-04-05

    Production rates for solvent extraction separation of the rare earths and yttrium from each other can be improved by the substitution of di(2-ethylhexyl) mono-thiophosphoric acid for di(2-ethylhexyl) phosphoric acid. The di(2-ethylhexyl) mono-thiophosphoric acid does not form an insoluble polymer at approximately 50% saturation as does the former extractant, permitting higher feed solution concentration and thus greater throughput.

  7. Trade Group Rules Against China in Rare Earths Dispute

    NASA Astrophysics Data System (ADS)

    Showstack, Randy

    2014-04-01

    The World Trade Organization (WTO) has ruled against China in a trade dispute over rare earth elements (REE) as well as tungsten and molybdenum, the group announced on 26 March. The European Union, Japan, and the United States brought trade cases against China in March 2012 concerning alleged unfair export restraints on the materials (see Eos, 93(13), 134-135, doi:10.1029/2012EO130002).

  8. Infrared spectroscopy of rare-earth-doped CaFe2As2

    NASA Astrophysics Data System (ADS)

    Xing, Zhen; Huffman, T. J.; Xu, Peng; Qazilbash, M. M.; Saha, S. R.; Drye, Tyler; Paglione, J.

    2014-03-01

    Recently, rare-earth doping in CaFe2As2 has been used to tune its electronic, magnetic, and structural properties. The substitution of rare-earth ions at the alkaline-earth sites leads to the suppression of the spin-density wave (SDW) phase transition in CaFe2As2. For example, Pr substitution results in a paramagnetic metal in the tetragonal phase that is susceptible to a low temperature structural transition to a collapsed tetragonal phase. However, La-doped CaFe2As2 remains in the uncollapsed tetragonal structure down to the lowest measured temperatures. Both the uncollapsed and collapsed tetragonal structures exhibit superconductivity with maximum Tc reaching 47 K, the highest observed in inter-metallics albeit with a small superconducting volume fraction. In this work, we perform ab-plane infrared spectroscopy of rare-earth-doped CaFe2As2 at different cryogenic temperatures. Our aim is to ascertain the contributions of electron doping and chemical pressure to the charge and lattice dynamics of this iron-arsenide system.

  9. The behavior of pyrrolyl ligands within the rare-earth metal alkyl complexes. Insertion of C=N and C=O double bonds into Ln-sigma-C bonds.

    PubMed

    Yang, Yi; Cui, Dongmei; Chen, Xuesi

    2010-04-28

    This paper presents some unusual reactions of lanthanide tris(alkyl)s or lanthanide mono-Cp' (Cp' = (C(5)Me(4))SiMe(3)) bis(alkyl)s with pyrrolyl ligands, and the eta(5)- or eta(1)-coordination mode of the pyrrolyl ring, as well as C=N and C=O double bonds insertion into Ln-sigma-C moities. N,N,O-tridentate ligand HL(1), 2-(2-CH(3)OC(6)H(3)N=CH)-C(4)H(3)NH, was prepared. Treatment of HL(1) with rare-earth metal tris(alkyl)s, Ln(CH(2)SiMe(3))(3)(THF)(2), generated centrosymmetric bimetallic (pyrrolylaldiminato)lanthanide mono(alkyl) complexes [{2-(2-CH(3)OC(6)H(3)NC(H)R)-C(4)H(3)N}LnR](2) (1a: Ln = Y; 1b: Ln = Lu) (R = CH(2)SiMe(3)). In this process, HL(1) was deprotonated by the metal alkyl and its imino C=N group was deactivated by the intramolecular alkylation, generating dianionic species that bridged the two metal alkyl units in eta(5)/eta(1):kappa(1) modes. When the reaction was carried out in dimethoxyethane (DME), asymmetric complex [2-(2-CH(3)OC(6)H(3)NC(H)R)-C(4)H(3)N](2)Y(2)R(2)(DME) (2) was given. Furthermore, the reaction of alkyl complex 1b and benzophenone (Ph(2)C=O) afforded alkyl-insertion product [{2-(2-CH(3)OC(6)H(3)NC(H)R)-C(4)H(3)N}LuOC(R)Ph(2)](2) (3). Both the intermolecular alkylation and the pyrrole's behavior as the hetero-cyclopentadienyl ligand were also observed in complexes 2 and 3. HL(1) reacted with (eta(5)-Cp')Y(CH(2)SiMe(3))(2)(THF) (E) to form a mixed ligands supported alkyl complex [(eta(5)-Cp')(L(1))]Y(CH(2)SiMe(3))(THF) (4), whilst complex E was treated with 2-(2,6-iPr(2)C(6)H(3)N=CH)-C(4)H(3)NH (HL(2)) to yield [(eta(5)-Cp')(L(2))]Y(CH(2)SiMe(3))(THF) (5). However, reaction of E and 2-(Me(2)NCH(2))-C(4)H(3)NH (HL(3)) afforded Y[(eta(5)-Cp')(L(3))(2)] (6), and ligand redistribution was found in this process. The molecular structures of complexes 5 and 6 were confirmed by X-ray diffraction, which indicated that the C=N double bond survived and the pyrrolyl ring coordinated to the metal center in eta(1)-mode.

  10. Properties of rare-earth iron garnets from first principles

    NASA Astrophysics Data System (ADS)

    Nakamoto, Ryan; Xu, Bin; Xu, Changsong; Xu, Hu; Bellaiche, L.

    2017-01-01

    Structural and magnetic properties of rare-earth iron garnets (RIG), which contain 160 atoms per unit cell, are systematically investigated for rare-earth elements varying from La to Lu (and including Y), by performing spin polarized density-functional calculations. The effects of 4 f electrons (as core or as valence electrons) on the lattice constant, internal coordinates, and bond lengths are found to be rather small, with these predicted structural properties agreeing rather well with available experiments. On the other hand, treating such electrons as valence electrons is essential to interpret the total magnetization measured in some RIG at low temperature, the different orientation and magnitude of the magnetizations that Fe and rare-earth ions can adopt and to also explain why some RIG have a compensation temperature while others do not. The magnetic exchange couplings and orbital-projected density of states are also reported for two representative materials, namely Gd3Fe5O12 and Nd3Fe5O12 , when accounting for their 4 f electrons.

  11. Alternatives to Rare Earth Permanent Magnets for Energy Harvesting Applications

    NASA Astrophysics Data System (ADS)

    Khazdozian, Helena; Hadimani, Ravi; Jiles, David

    Direct-drive permanent magnet generators (DDPMGs) offer increased reliability and efficiency over the more commonly used geared doubly-fed induction generator, yet are only employed in less than 1 percent of utility scale wind turbines in the U.S. One major barrier to increased deployment of DDPMGs in the U.S. wind industry is NdFeB permanent magnets (PMs), which contain critical rare earth elements Nd and Dy. To allow for the use of rare earth free PMs, the magnetic loading, defined as the average magnetic flux density over the rotor surface, must be maintained. Halbach cylinders are employed in 3.5kW Halbach PMGs (HPMGs) of varying slot-to-pole ratio to concentrate the magnetic flux output by a lower energy density PM over the rotor surface. We found that for high pole and slot number, the increase in magnetic loading is sufficient to allow for the use of strontium iron oxide hard ferrite PMs and achieved rated performance. Joule losses in the stator windings were found to increase for the hard ferrite PMs due to increased inductance in the stator windings. However, for scaling of the HPMG designs to 3MW, rated performance and high efficiency were achieved, demonstrating the potential for elimination for rare earth PMs in commercial scale wind turbines. This work was supported by the National Science Foundation under Grant No. 1069283 and a Barbara and James Palmer Endowment at Iowa State University.

  12. Restoration of rare earth mine areas: organic amendments and phytoremediation.

    PubMed

    Zhou, Lingyan; Li, Zhaolong; Liu, Wen; Liu, Shenghong; Zhang, Limin; Zhong, Liyan; Luo, Ximei; Liang, Hong

    2015-11-01

    Overexploitation of rare earth mine has caused serious desertification and various environmental issues, and ecological restoration of a mining area is an important concern in China. In this study, experiments involving dry grass landfilling, chicken manure broadcasting, and plant cultivation were carried out to reclaim a rare earth mine area located in Heping County, Guangdong Province, China. The prime focus was to improve soil quality in terms of nutrients, microbial community, enzyme activity, and physicochemical properties so as to reclaim the land. After 2 years of restoration, an increase of organic matter (OM), available potassium (K), available phosphorus (P) levels, and acid phosphatase (ACP) activity and a reduction of the available nitrogen (N) level and urease (URE) activity in soil were achieved compared to the original mined land. The nutrients and enzyme activities in soil with 5 years of restoration were close to or surpass those in the unexploited land as control. The bulk density, total porosity, water holding capacity, pH, and electrical conductivity (EC) of soil were improved, and the number of cultivable microorganisms and the bacterial diversity in soil were greatly increased with time during ecological restoration, especially for surface soil. Furthermore, the artificial vegetation stably grew at the restored mining sites. The results indicated that organic amendments and phytoremediation could ecologically restore the rare earth mining sites and the mined land could finally be planted as farmland.

  13. Uncovering the end uses of the rare earth elements.

    PubMed

    Du, Xiaoyue; Graedel, T E

    2013-09-01

    The rare earth elements (REE) are a group of fifteen elements with unique properties that make them indispensable for a wide variety of emerging and conventional established technologies. However, quantitative knowledge of REE remains sparse, despite the current heightened interest in future availability of the resources. Mining is heavily concentrated in China, whose monopoly position and potential restriction of exports render primary supply vulnerable to short term disruption. We have drawn upon the published literature and unpublished materials in different languages to derive the first quantitative annual domestic production by end use of individual rare earth elements from 1995 to 2007. The information is illustrated in Sankey diagrams for the years 1995 and 2007. Other years are available in the supporting information. Comparing 1995 and 2007, the production of the rare earth elements in China, Japan, and the US changed dramatically in quantities and structure. The information can provide a solid foundation for industries, academic institutions and governments to make decisions and develop strategies.

  14. Magnetism of perovskite cobaltites with Kramers rare-earth ions

    SciTech Connect

    Jirák, Z. Hejtmánek, J.; Knížek, K.; Novák, P.; Šantavá, E.; Fujishiro, H.

    2014-05-07

    The band-gap insulators RECoO{sub 3} (RE = Nd{sup 3+}, Sm{sup 3+}, and Dy{sup 3+}) with Co{sup 3+} ions stabilized in the non-magnetic low-spin state have been investigated by specific heat measurements. The experiments evidence an antiferromagnetic ordering of the rare earths with Néel temperature of T{sub N} = 1.25, 1.50, and 3.60 K for NdCoO{sub 3}, SmCoO{sub 3}, and DyCoO{sub 3}, respectively. With increasing external field, the lambda peak in specific heat, indicative of the transition, shifts to lower temperatures and vanishes for field of about 3 T. Starting from this point, a broader Schottky peak is formed, centered in 1 K range, and its position is moved to higher temperatures proportionally to applied field. The origin of the peak is in Zeeman splitting of the ground Kramers doublet, and the gradual shift with field defines effective g-factors for the rare-earth pseudospins in studied compounds. The results obtained are confronted with the calculations of crystal field splitting of the rare-earth multiplets.

  15. Mimicking the magnetic properties of rare earth elements using superatoms.

    PubMed

    Cheng, Shi-Bo; Berkdemir, Cuneyt; Castleman, A W

    2015-04-21

    Rare earth elements (REs) consist of a very important group in the periodic table that is vital to many modern technologies. The mining process, however, is extremely damaging to the environment, making them low yield and very expensive. Therefore, mimicking the properties of REs in a superatom framework is especially valuable but at the same time, technically challenging and requiring advanced concepts about manipulating properties of atom/molecular complexes. Herein, by using photoelectron imaging spectroscopy, we provide original idea and direct experimental evidence that chosen boron-doped clusters could mimic the magnetic characteristics of REs. Specifically, the neutral LaB and NdB clusters are found to have similar unpaired electrons and magnetic moments as their isovalent REs (namely Nd and Eu, respectively), opening up the great possibility in accomplishing rare earth mimicry. Extension of the superatom concept into the rare earth group not only further shows the power and advance of this concept but also, will stimulate more efforts to explore new superatomic clusters to mimic the chemistry of these heavy atoms, which will be of great importance in designing novel building blocks in the application of cluster-assembled nanomaterials. Additionally, based on these experimental findings, a novel "magic boron" counting rule is proposed to estimate the numbers of unpaired electrons in diatomic LnB clusters.

  16. Synthesis and characterization of rare-earth-free magnetic manganese bismuth nanocrystals

    SciTech Connect

    Shen, J; Cui, HZ; Huang, XP; Gong, MG; Qin, W; Kirkeminde, A; Cui, J; Ren, SQ

    2015-01-01

    Earth abundant manganese bismuth (MnBi) has long been of interest due to its largemagnetocrystalline anisotropy and high energy density for advanced permanent magnet applications. However, solution synthesis of MnBi phase is challenging due to the reduction potential mismatch between Mn and Bi elements. In this study, we show a versatile MnBi synthesis method involving the metal co-reduction followed by thermal annealing. The magnetically hard MnBi crystalline phase is then exchange coupled with magnetically soft cobalt coating. Our processing approach offers a promising strategy for manufacturing rare-earth-free magnetic nanocrystals.

  17. Synthesis and Characterization of Rare-earth-free Magnetic Manganese Bismuth Nanocrystals

    SciTech Connect

    Shen, Jian Q.; Cui, Huizhong; Huang, Xiaopeng; Gong, Maogang; Qin, Wei; Kirkeminde, Alec; Cui, Jun; Ren, Shenqiang

    2015-01-01

    Earth abundant manganese bismuth (MnBi) has long been of interest due to its large magnetocrystalline anisotropy and high energy density for advanced permanent magnet applications. However, solution synthesis of MnBi phase is challenging due to the reduction potential mismatch between Mn and Bi elements. In this study, we show a versatile MnBi synthesis method involving the metal co-reduction followed by thermal annealing. The magnetically hard MnBi crystalline phase is then exchange coupled with magnetically soft cobalt coating. Our processing approach offers a promising strategy for manufacturing rare-earth-free magnetic nanocrystals.

  18. Rare-earth distribution behaviour and lattice parameter changes on rare-earth substituted garnet single crystals

    NASA Astrophysics Data System (ADS)

    Kimura, H.; Numazawa, T.; Sato, M.

    1994-08-01

    The selection of rare-earth substituted Ga and Al garnets in solid solution and their growth to single crystals using the conventional Czochralski technique is described. The crystals grown were investigated for their distribution behavior and lattice parameter changes in order to understand their characteristics in the solid solution. Investigation was by means of an ICP chemical analysis and X-ray diffraction analysis with powdered samples ground from wafers taken from both the tops and tails of the crystals grown.

  19. Syntheses of new rare earth complexes with carboxymethylated polysaccharides and evaluation of their in vitro antifungal activities.

    PubMed

    Sun, Xiaobo; Jin, Xiaozhe; Pan, Wei; Wang, Jinping

    2014-11-26

    In the present paper, La, Eu and Yb were selected to represent light, middle and heavy rare earths to form complexes with polysaccharides through chelating coordination of carboxyl groups, which were added into polysaccharide chains by means of carboxymethylation. Their antifungal activities against plant pathogenic fungi were evaluated using growth rate method. These rare earth complexes exhibited various antifungal activities against the tested fungi, depending on rare earth elements, polysaccharide types and fungal species. Among these three metal elements (i.e. La, Eu and Yb), Yb formed the complexes with the most effective antifungal properties. Furthermore, the results showed that ligands of carboxymethylated polysaccharides played a key role in promoting cytotoxicity of the rare earth complexes. Carboxymethylated Ganoderma applanatum polysaccharide (CGAP) was found to be the most effective ligand to form complexes with antifungal activities, followed by carboxymethylated lentinan (CLNT) and carboxymethylated Momordica charantia polysaccharide (CMCP).

  20. Investigations into Rare Earth Oxide Use and Behaviour

    NASA Astrophysics Data System (ADS)

    Pryce, Owen

    2010-05-01

    The use of tracers which are applied to soils (distinguishable from tracers naturally present in soils) is increasing. Rare earth oxides (REOs) are the most prevalent of the sediment tracers used to tag soils in this manner. REOs have been applied in a host of different countries, at a range of scales e.g. over watersheds in the USA (Polyakov and Nearing, 2004; Kimoto et al., 2006); to examine rill erosion in China (Li et al., 2006); and to investigate the importance of topographical features in arable fields in the EU (Stevens and Quinton, 2008). Many successful experiments have been conducted using the suit of REO tracers, yielding important information on the behaviour of eroding sediments. However, the majority of publications have focused upon application of REO tracers, applying the tagging and extraction methods developed by Zhang et al., (2001, 2003). Furthermore, the techniques presently being used are known to generate methodological inaccuracies, such as tracer enrichment and non-uniform REO distributions on experimental plots, and analytical interferences when ICP-MS is used for tracer quantification. Unanswered questions regarding the use of REO tracers include: i) what is the effect upon soil of REO tagging?; ii) how is a uniform distribution of REOs in tagged soil achieved? iii) which is the most suitable way of applying REOs, to experimental plots of different scale, and to meet different objectives?; iv) which REOs are unsuitable for sediment tracing?; v) what is the most precise and efficient method of extracting REO tracers from sediments? vi) is the transport behaviour of REO tracers comparable to untagged soils? In an attempt to answer some of these questions, investigations have been conducted into the effect upon soil particle size of different methods of REO tagging. The ability of these methods to provide uniform distributions of REOs in the tagged soil was calculated. The accuracy and precision of published (Zhang et al., 2003; Stevens and