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Trevor M. Riedemann Manager, MPC Rare Earth Materials Section 122 Metals Development Building Ames Laboratory Ames, IA 50011-3020 Phone: 515-294-1366 Fax:

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Presentation on theme: "Trevor M. Riedemann Manager, MPC Rare Earth Materials Section 122 Metals Development Building Ames Laboratory Ames, IA 50011-3020 Phone: 515-294-1366 Fax:"— Presentation transcript:

1 Trevor M. Riedemann Manager, MPC Rare Earth Materials Section 122 Metals Development Building Ames Laboratory Ames, IA Phone: Fax: Materials Preparation Center A US Department of Energy Specialized Research Center High Purity Rare Earth Metals Preparation

2 The Materials Preparation Center (MPC) is a U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, Division of Materials Sciences & Engineering specialized research center located at the Ames Laboratory. MPC operations are primarily funded by the Materials Discovery, Design, & Synthesis team's Synthesis & Processing Science core research activity. 2 Lawrence L. Jones Director, MPC 121 Metals Development Building Ames Laboratory Ames, IA Phone: Fax: Thomas A. Lograsso Division Director Division of Materials Science & Engineering 124 Metals Development Building Ames, IA Phone: Fax: Acknowledgements

3 The Rare Earths, F.H Spedding & A.H. Daane, eds. (1961) John Wiley & Sons. Chapter 6 – Preparation of the Rare Earth Fluorides, O.N. Carlson & F.A. Schmidt Chapter 8 – Metallothermic Preparation of Rare Earth Metals, A.H. Daane Beaudry, B.J. & P.E. Palmer, (1974) “The use of inert atmospheres in the preparation and handling of high purity rare earth metals” Haschke, J.M, and H.A. Eich, eds. Proceedings of the 11 th Rare Earth Research Conference (CONF , Part 2, NTIS, Springfield, Virginia 22151) pp Handbook on the Physics and Chemistry of Rare Earths, Vol 1 – Metals, (1978) K.A.Gschneidner, Jr. & L.R. Eyring, eds. Chapter 2 – Preparation and Basic Properties of the Rare Earth metals, B.J. Beaudry & K.A. Gschneidner A Lanthanide Lanthology, Part I & II, B.T. Kilbourn (1993) Molycorp. Inc. 3 Acknowledgements

4 1794 J. Gadolin first reports their existence 1804 M.H. Klaproth isolated ceria 1827 Preparation of first REM (Ce) … 1931 Preparation of “reasonably pure” metal by electrolysis 1937 Pure enough to determine crystal structures 1947 Separation adjacent RE by ion exchange. 1950’s Spedding and Daane – developed “Ames Process” – 1987 Two Hundred Years of Rare Earths Rare Earth Information Center IS-RIC 10 Institute for Physical Research and Technology Iowa State University K.A. Gschneidner Jr & J. Capellen, ed. The Rare Earths - A very Brief History

5 Z Symbol Name Etymology 21 Sc Scandium Latin Scandia (Scandinavia) 39 Y Yttrium Ytterby, Sweden, where the first ore was discovered. 57La Lanthanum Greek "lanthanein", meaning to be hidden. 58 Ce Cerium For the dwarf planet Ceres. 59 Pr Praseodymium Greek "prasios” leek-green, &"didymos", meaning twin. 60 Nd Neodymium Greek "neos” new, and "didymos", meaning twin. 61 Pm Promethium Titan Prometheus, who brought fire to mortals. 62 Sm Samarium Vasili Samarsky-Bykhovets, who discovered samarskite. 63 Eu Europium For the continent of Europe. 64 Gd GadoliniumJohan Gadolin (1760–1852), to honor his study of REE. 65 Tb Terbium Ytterby, Sweden. 66 Dy Dysprosium Greek "dysprositos", meaning hard to get. 67 HoHolmium Stockholm (in Latin, "Holmia”) 68 Er Erbium Ytterby, Sweden. 69 Tm Thulium For the mythological northern land of Thule. 70 Yb Ytterbium Ytterby, Sweden. 71 Lu LutetiumLutetia, the city which later became Paris – 1987 Two Hundred Years of Rare Earths Rare Earth Information Center IS-RIC 10 Institute for Physical Research and Technology Iowa State University K.A. Gschneidner Jr & J. Capellen, ed. The Rare Earths - Etymology

6 6 US Geological Survey Fact Sheet Rare Earth Elements – Critical Resources for High Technology Gordon B. Haxel, James B. Hedrick, and Greta J. Orris The Rare Earths - Abundance

7 7 Y 2 O 3 La 2 O 3 CeO 2 Pr 6 O 11 Nd 2 O 3 Sm 2 O 3 Eu 2 O 3 Gd 2 O 3 Tb 4 O 7 Dy 2 O 3 Ho 2 O 3 Er 2 O 3 Tm 2 O 3 Yb 2 O 3 Lu 2 O 3 III / IV UPDATE ON THE GLOBAL RARE EARTH INDUSTRY: Prospect for Magnetic Rare Earth Materials 2004 China Magnet Symposium Global Markets and Business Opportunities May 17-21, 2004, Xi’an, China Constantine E. Karayannopoulos High Purity Oxide Prices

8 8 Y 2 O 3 La 2 O 3 CeO 2 Pr 6 O 11 Nd 2 O 3 Sm 2 O 3 Eu 2 O 3 Gd 2 O 3 Tb 4 O 7 Dy 2 O 3 Ho 2 O 3 Er 2 O 3 Tm 2 O 3 Yb 2 O 3 Lu 2 O 3 III / IV /2010 La 99%US$/kg Ce 99%US$/kg Pr 99%US$/kg Nd 99%US$/kg Eu 99%US$/kg Tb 99%US$/kg Dy 99%US$/kg Source: Metal Pages High Purity Oxide Prices

9 9 The Rare Earths - Physical Properties

10 (1)High purity oxides from Ion-Exchange (2) Preparation of anhydrous RE-fluorides (3) Metallothermic reduction by Ca metal (4) Metallothermic reduction by La metal 10 R 2 O 3 + 6HF  2RF 3 + 3H 2 O 3Ca + 2RF 3  2R + 3CaF 2 R 2 O 3 + 2La  La 2 O 3 + 2R  The Rare Earths - Ames Process

11 Impurity Sources: Oxygen: Incomplete oxide conversion Calcium reductant Atmosphere (handling and processing) N, C, & H:Adsorbed on oxide/fluoride Calcium reductant Tantalum Crucible Atmosphere Ca & F:Reductant and incomplete reduction (10% excess Ca is used in Rx) Insufficient vacuum casting Fe, Co, Ni & Cu:Tantalum Crucible Impurities in oxide & HF Contamination of oxide during handling 11 ? Ames Process = High purity Cross Contamination in Processing Line Foundry vs Chip Fab

12 12 Ames Commercial N/T How Pure?

13 13 ImpurityIngotDistilledDistilledDistilled H Cn.a.n.a. n.a. 132 N O Fe La Ta Total mag. RE at% pure<97.5<95.6<94.2<99.81 Anlaysis of three commercial Tb samples and MPC Tb (ppm at). Source A Source D MPC Semiquantitative MS for 25 elements (H,N and O by vacuum fusion) High purity Rare Earth Metals – Do We Need Them? Proc. of the first Symposium Rare Metals Forum, Extra-High Purification Technology and New Functional Materials Creation of Rare Earth Metals, Society of Non-Traditional Technology, Tokyo, Japan (1989) pp K.A. Gschneidner, Jr.

14 Impurities affect the basic properties of pure metals (and alloys) Lattice parameters Crystal structure Melting point Hardness Strength Resistivity Susceptibility Grain growth Magnetic domain wall motion Stoichiometry of alloy is shifted Second phase can form and change the properties. Crystal Growth Oxygen as impurity in crystal growth of intermetallics, D. Souptel, W. Lo¨ ser, W. Gruner, G. Behr, Journal of Crystal Growth 307 (2007) 410– Impurities may mask the INTRINSIC behavior of the pure metal or alloy material Why do we need High Purity Metals?

15 15 Why do we need High Purity Metals? Temperature (K) - Δ S m (J/kg K) Gd 5 Si 2 Ge 2 : 0 – 5 T V. K. Pecharsky and K. A. Gschneidner, Jr. Giant Magnetocaloric Effect in Gd 5 Si 2 Ge 2 Physical Review Letters 78 (1997) No. 23 T. Zhang, et. Al (Sichuan University) The structure and magnetocaloric effect of rapidly quenched Gd 5 Si 2 Ge 2 alloy with low-purity gadolinium Materials Letters 61 (2007) 440–443 K. A. Gschneidner, Jr., et al. Method of Making Active Magentic Refrigerant, Colossal Magnetostriction and Giant Magentoresistive Materials Based on Gd-Si-Ge Alloys US Patent: 6,589,366 B1 (2003) Impurities are suppressing a structural transition from orthorhombic to monoclinic

16 16 Y. Matsumoto, et al. Quantum Criticality Without Tuning in the Mixed Valence Compound -YbAlB4. Science, 2011; 331 (6015) S. Nakatsuji, et al. Superconductivity and quantum criticality in the heavy-fermion system –YbAlB 4 Nature Physics 4, (2008) Robin T. Macaluso, et. al Crystal Structure and Physical Properties of Polymorphs of LnAlB 4 (Ln = Yb, Lu) Chem. Mater., 2007, 19 (8), pp 1918–1922 An exotic new superconductor based on the element ytterbium displays unusual properties that could change how scientists understand and create materials for superconductors and electronics. Beta-YbAlB4, can reach a quantum critical, without being subject to massive changes in pressure, magnetic fields, or chemical impurities. Why do we need High Purity Metals?

17 High Purity Oxides 17 Praseodymium Oxide Pr 6 O % pure <10 ppm REM GARBAGE IN = GARBAGE OUT Y 2 O 3 La 2 O 3 CeO 2 Pr 6 O 11 Nd 2 O 3 Sm 2 O 3 Eu 2 O 3 Gd 2 O 3 Tb 4 O 7 Dy 2 O 3 Ho 2 O 3 Er 2 O 3 Tm 2 O 3 Yb 2 O 3 Lu 2 O 3 III / IV Inputs: Oxides

18 18 Triple Distilled commercial Ca has ~2000 – 5000 ppm oxygen Inputs: Calcium Reductant

19 19 Oxygen content is lowered <10 ppm Glove box protected Ca readily picks up O from H 2 O >1000 ppm from air in 5 minutes The effect of handing the Ca in air results in a 30-fold increase in O content in Cerium metal (BJB) Oxygen content is lowered <10 ppm Glove box protected Ca readily picks up O from H 2 O >1000 ppm from air in 5 minutes The effect of handing the Ca in air results in a 30-fold increase in O content in Cerium metal (BJB) 6 Days 900 g/run Ce 1900g Ca Lu 505g Ca

20 20 Alumina Magnesia Quartz Zirconia Graphite Iron X X X X X X Inputs: Tantalum 10” x 14” x 0.030” = $

21 21 ASTM B708 – 05 R05200, unalloyed tantalum, electron-beam furnace or vacuum-arc melt, or both ASTM B708 – 05 R05400, unalloyed tantalum, powder-metallurgy consolidation Element R05200 R05400 C O N H Fe Mo Nb Ni Si Ti W Cleanest Ta: Pickled Annealed 2000ºC degassed Inputs: Tantalum

22 22 Purity range from 99% to 99.99% Parameter Level † HF99.95 wt% H 2 SO wt ppm SO 2 50 wt ppm H 2 O 200 wt ppm As 25 wt ppm Hydrofluosilicic 0.05mol %* †Honeywell Specifications *Handbook of Compressed Gasses, 4 th ed. (1999) H 2 SiF 6 Not a lot of impurities to worry about…but….. Nasty Stuff Inputs: Hydrofluoric Acid (HF)

23 23 The Rare Earths - Physical Properties 1234 Vapor Pressure at Melting Point Tm 73.4 mm Hg Ce 3.6(10) -12 mm Hg

24 24 Ames Process – Flow Diagram

25 25 Sm, Eu, Tm and Yb Low Boiling Points Reduction by Lanthanum from Oxide Easily purified by Sublimation Sm, Eu, Tm and Yb can be melted in Ta crucibles without Ta contamination Tm is very difficult to arc melt due to ~74mm vapor pressure at its melting point Ames Process – Flow Diagram

26 26 Sm, Eu, Tm and Yb ① Dry Oxide Removes H 2 O and CO 2 ② Machine lanthanum chips ③ Mix oxide and La chips (in dry box) ④ Pack in crucible (in dry box) ⑤ Load into induction furnace ⑥ Heat under vacuum. ⑦ Hold for 8 hours ⑧ Perform a low temp sublimation. ⑨ Strip Ta from sublimate mass ⑩ Europium is extruded. Ames Process – Procedure

27 27 Ames Process

28 28

29 29 La, Ce, Nd and Pr Low Melting but high Boiling Points Volatile impurities (Ca & F) can be quantitatively removed by vacuum casting without loss of metal Ta solubility at M.P. is low therefore Ta dissolved during vacuum casting can be removed by precipitation. Ames Process – Flow Diagram

30 30 La, Ce, Nd and Pr ① Dry Oxide ② LT/HT Fluorination of oxide ③ Heat mixture of Ca & REF 3 ④ Cool, remove slag ⑤ Total of three reductions in same crucible ⑥ Vacuum cast at high temperature ⑦ Cool to just above melting point. Hold to precipitate tantalum ⑧ Decant or “pour” RE into thin wall crucible ⑨ Machine off crucible ⑩ Arc cast into ingots Ames Process – Procedure

31 31 Ames Process: Low Temp Fluorination

32 32 Ames Process Reduction Step

33 33 Ames Process Post Reduction

34 34 Ames Process Pour/Decant Step

35 35

36 36 Sc, Dy, Ho and Er High Melting and low to intermediate Boiling Points. To remove F impurity thru vacuum casting, must loose up to 30% of metal Easily purified with respect to O, N, C, Ta and other non-volatile impurities by sublimation. Ames Process – Flow Diagram

37 37 Sc, Dy, Ho and Er ① Dry oxide ② LT Fluorination of oxide ③ Heat mixture of Ca & REF 3 ④ Cool, remove slag ⑤ Total of three reductions in same crucible Excluding Sc ⑥ Vacuum cast Metal loss occurs ⑦ Sublimate to purify ⑧ Machine off crucible ⑨ Arc cast into ingots Ames Process – Procedure

38 38 Ames Process Reduction Step

39 39 Dysprosium metal (as Reduced)

40 40 Ames Process Sublimation Step

41 41

42 42 Y, Gd, Tb and Lu High Melting and High Boiling Points. Volatile impurities (Ca & F) can be removed by vacuum casting without significant loss of metal Ta solubility at MP is high, but can be removed by distillation. Slow distillations will reduce O, N, C slightly Ames Process – Flow Diagram

43 43

44 44 Scandium At MP ~ 3.2 at.% Ta (11.8 wt%) Cerium, At MP ~ 0.10 at% Ta

45 45 Hey! What about me! Ames Process – Flow Diagram

46 High Purity Fluorides 46 Praseodymium Fluoride PrF 3 “Topped” YF 3 LaF 3 CeF 3 PrF 3 NdF 3 SmF 3 EuF 3 GdF 3 TbF 3 DyF 3 HoF 3 ErF 3 TmF 3 YbF 3 LuF 3

47 47 Commercial: R 2 O 3 + 6NH 4 HF 2  2RF 3 + 3NH 3 + 3H 2 O 450ºC 1000 to 5000 ppm residual O Also a source of N impurity Ames LT: R 2 O 3 + 6HF (anhydrous) + Ar  2RF 3 + 3H 2 O + Ar 650ºC 10 to 1000 ppm residual O Pt lined furnace eliminated source of transition metal impurities. RF 3 + HF (anhydrous)  RF 3 + H 2 O Ames HT “Topped”: <10 ppm residual O Some reduction of transition metals La – Nd, Gd, Tb, Lu M.P. High Purity Fluorides

48 48 RF 3 + HF (anhydrous)  RF 3 + (H 2 O, other trace) MetalTAlSiCrFeNiCu La Yes Ce Yes0.5< Tb Yes0.5< M.P. High Purity Fluorides Beaudry, B.J. & P.E. Palmer

49 49

50 50 LaCePrNdGdTbLuY (1) (2) (3) (4) (5) Oxygen content in AT PPM of selected REM prepared from various grades of fluorides and calcium. (1) Typical commercial purity (2) Fluoride prepared by NH 4 HF 2 and reduced with purified calcium (4) Low-temp fluoride, purified calcium, handled in glove box (5) Topped fluoride, purified calcium, handled in glove box (3) Topped fluoride, purified calcium, handled in air Beaudry, B.J. & P.E. Palmer

51 Ames Process = High Purity 51 Start with pure inputs Keep them pure Semper Fidelis


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