The Rare Earths in Modern Science and Technology

The Rare Earths in Modern Science and TechnoIogg Volume 3 The Rare Earths in Modem Science and Technology Volume 3 Edited by Gregory J. McCarthy North Dakota State University, Fargo, North Dakota Herbert B. Silber University of Texas at San Antonio, San Antonio, Texas and James J. Rhyne National Bureau of Standards, Washington, D.C. Associate Editor Faye M. Kalina North Dakota State University, Fargo, North Dakota Editorial Assistants Linda R. Haugrud and Joyce L. Mortensen North Dakota State University, Fargo, North Dakota PLENUM PRESS· NEW YORK AND LONDON Library of Congress Cataloging in Publication Data Rare Earth Research Conference. The rare earths in modern science and technology. Vol. 3editedbyG. J. McCarthy, H. B. Silber, andJ. J. Rhyne. Includes bibliographical references and indexes. 1. Earths, Rare-Congresses. I. McCarthy, Gregory J. II. Rhyne, J. J. III. Silber, Herbert B. QD172.R2R27 1978 546'.4 78-5365 AACR1 ISBN-13: 978-1-4613-3408-8 e-ISBN-13: 978-1-4613-3406-4 DOl: 10.1007/978-1-4613-3406-4 Proceedings of the 15th Rare Earths Research Conference, held June 15-18, 1981, at the University of Missouri at Rolla ©1982 Plenum Press, New York Softcover reprint of the hardcover 1st edition 1982 A Division of Plenum Publishing Corporation 233 Spring Street, New York, N.Y. 10013 All rights reserved No part of this book may be reproduced, stored in a retrieval system, or transmitted in any form or by any means, electronic, mechanical, photocopying, microfilming, recording, or otherwise, without written permission from the Publisher FOREWORD The Fifteenth Rare Earth Research Conference was held June 15-18, 1981 on the Rolla campus of th.e University of Missouri. The conference was hosted by the Graduate Center for Materials Research, the College of Arts and Science, and the School of Mines and Metallurgy. It was expected that the conference would provide a forum for critical examination and review of the current and important trends in rare earth science and technology. To this end, over 170 papers were presented in both oral and poster sessions by researchers representing some nineteen countries. The program committee was particularly gratified to see the diversity of effort being devoted to rare earth research by different disciplines allover the world. The collection of refereed papers in this volume attests to the fact that the objectives of the program committee were indeed realized. A high point of the meeting was the presentation of the Frank n. Spedding Award to a most distinguished colleague, Professor Georg Busch, Eidgenossische Technische Hochschule, Zurich. Professor W. Edward hi"allace, University of Pittsburgh, recipient of the first Frank H. Spedding Award made the presentation to Professor Busch who then gave the Plenary Address. Oral sessions began with keynote addresses delivered by: B.D. Sykes, University of Alberta; J.E. Greedan, McMaster University; t1. Tecotzky, U.S.R. Chemicals; J.R. Jackman, Reactive Metals and Alloys; J. Owens, Harshaw· Chemical-; W. T. Carnall, Argonne National Laboratory; M.B. Maples, University of California-San Diego; R. Lemaire, Neel Laboratory, Grenoble, France; W.J. Evans, University of Chicago; E. Kaldis, ETH, Zurich, Switzerland; R.G. Barnes, Iowa State University; and P. Muntz, Universitat Konstanz/FRG. The success of any scientific meeting depends largely upon the voluntary efforts of many dedicated people. I first wish to v vi FOREWORD acknowledge with much appreciation the advice and assistance given me upon assuming my duties as president of the board and conference chairman by the past conference chairman and secretary, Professor John Gruber and Faye Kalina. The success of the program is testimony to the talents of Professor Gregory Choppin and the excellent job done by his program committee and session chairpersons. Program Committee G. Barlow E. Greedan K. Gschneidner R. Haire J. Kaczmarec H. Marks H. Silber S. Taher A. Tauber Session Chairpersons J.C. Achard J.L. Atwood E. Banks B.J. Beaudry B.A. Bilal J-C. Bunzli O.N. Carlson P. Caro F.L. Carter W. T. Carnall J. Chrysochoos J. Deportes T. Donahue L. Eyring J. Gruber K. Gschneidner A. Percheron-Guegan R.G. Haire J .}I. Haschke J. Kaczmarec H. Kirchmayr S.K. Malik T.J. Marks L. Niinisto O. Serra A. Dean Sherry S.M.A. Taher W.E. Wallace G. Gorller-Walrand W.C. Weimer W. Yelon I appreciate the many hours of work contributed by those who served on the following committees: Local Committee Adrian Daane, Chairperson Harlan Anderson Gordon Lewis Thomas O'Keefe D. Vincent Roach Donald Sparlin Manfred Huttig William Yelon Selection Committee for the Frank H. Spedding Award Recipient W.E. Wallace, Chairperson Joseph Cannon Paul Caro J.B. Gruber Fred Rothwarf vii FOREWORD Arlene James, Chairperson Jean Daane Eunice French We are all deeply indebted to the co-editors of the Conference Proceedings who gave many hours to the organization and refereeing of the papers in bringing you Volume 3 of "The Rare Earths in Hodern Science and Technology". We are also very appreciative of the monetary support provided to the Conference by the following donors: National Science Foundation, Washington, D.C., U.S.A. Petroleum Research Fund (American Chemical Society), Washington, D.C., U.S.A. Modern Hetals, Union/Uolycorp, Los Angeles, California, U.S.A. Raytheon Corp., Lexington, Massachusetts, U.S.A. Reactive Uc·tals and Alloys Corp., West Pittsburgh, Pennsylvania, U.S.A. Rhone-Poulenc Industries (Chimie Fine Division), Paris, Cedex 08, France Ronson Metals Corp., New-ark, New Jersey, U.S.A. University of Hissouri-Rolla, Rolla, rUssouri, U. S .A. North Dakota State University, Fargo, North Dakota, U.S.A. I must acknowledge, especially, the invaluable help and counsel of Norma Fleming, Conference Coordinator, and her staff, and of Professor Adrian Daane, Chairman of the Local Committee. I thank very much our secrtai~: Faye Kalina for assisting the co-editors with the manuscripts and proceedings, Janet Thompson and Nina Haas, Materials Research, UMR, for assisting with all phases of the Conference activities; Jane Bunting and Audrey Thompson, Extension Office, UMR, for handling mailings and registration; and Gislaine Heneroud, Neel Laboratory, Grenoble, for assisting with registration. Lastly, I wish to thank all the conference participants for their kindness and congeniality. I look forward to seeing all of you again at the Sixteenth Rare Earth Research Conference at Florida State University in April 1983. William J. James General Conference Chairman University of Missouri-Rolla November 1981 PREFACE A coherent picture of research progress and new developments involving the rare earths can be difficult to develop due to the wide dispersal of relevant papers throughout the physics, chemistry and materials literature. We have once again taken advantage of the international gathering of scientists for a Rare Earth Research Conference to present under one cover a comprehensive update of the rare earths in modern science and technology. Authors presenting papers in Rolla were invited to submit papers or notes for this volume. All submissions were refereed. We have included three types of contributions: longer invited review papers, shorter research reports and one or two page notes. The first two are meant to have this volume as their sole publication outlet while the notes are typically from authors who have submitted, or are planning, a full publication elsewhere. Among the 120 contributions in this volume the reader will find many papers in two of the areas where rare earths have been utilized most heavily over the last two decades, luminescent and magnetic materials. Professor Busch's Spedding Award Address describes the pioneering work of his group at the ETH, Zurich, on such materials and provides us with historical insight into research on the rare earths when their complex electronic structure, spectra and interactions in solids were just beginning to be understood. The role of rare earths in steelmaking is also reviewed. This volume also has strong components in the physical and structural chemistry of rare earth compounds and in the innovative applications of rare earths in bioinorganic, organometallic and coordination chemistry. We also welcome our first contributions from scientists in the People's Republic of China. H.B. Silber, J.J. Rhyne and I would especially like to acknowledge the many referees whose efforts contributed so much to the quality of this volume. Gregory J. HcCarthy Fargo, North Dakota October, 1981 ix Presentation of the Frank H. spedding Award for Outstanding Contributions to the Science and TechnoZogy of the Rare Earths to Professor Georg Busch GEORG BUSCH Our Spedding Award recipient has had a scientific career of almost incredible depth and range. Prof. Busch's early interests lay with the phenomenon of ferroelectricity. In that, he had interests in common with the late Prof. Berndt Matthias, whose origin was also in the Eidgenossische Technische Hochschule Zurich. Prof. Busch became interested in the 1940's in semiconductor physics and in the early 1950's he began a search for a ferromagnetic semiconductor. In time he realized that his great quest led xi xii SPEDDING AWARD inexorably to the rare earths. (My feeling is that when you need a certain material property you can nearly always find it among the rare earth systems.) In his studies of rare earth-containing III-V semiconductors, such as GdN and CeP, and II-VI semiconductors, such as EuS and TmS, he found his ferromagnetic superconductor. In his work on the rare earth chalcogenides and pnictides he wrote a new chapter in the solid state sciences. Recognizing the importance of chemical control, Prof. Busch established a Solid State Chemistry Group within his Solid State Physics Institute and they produced and studied in great depth single crystals of the rare earth pnictides and chalcogenides which had been characterized in the most exhaustive detail. His work of the 60's and 70's involved synthesis and studies of the structural, thermodynamic, magnetic and optical properties of this large class of inorganic compounds. Prof. Busch's work involved classical studies such as determination of specific heats and bulk magnetization but also involved more recently introduced techniques such as ESR, XPS and spin-polarized photoemission. The latter is, I believe, a first in Prof. Busch's laboratory.. If you wish to know all about his rare earth chalcogenide and rare earth pnictide work, then you have the job of reading about 110 papers which he has published on these materials. Recently his attention has turned to intermetallic hydrides hydrogen storage systems -- structures of complex hydrides and surface features. In the early 1960's our group in Pittsburgh began work on rare earth nitrides. We soon encountered the stunningly brilliant work of Busch and Vogt on rare earth nitrides. And we decided upon other things to do. In our work on hydrides we recognize Busch's group at Zurich as a force to be reckoned with. Or to put it in less pejorative .language, the Zurich group under Busch is a world center of excellence in hydride research. And from this excellence I am convinced all the world will profit. It is a very great pleasure for me to present Prof. G. Busch, the 1982 Spedding Award recipient. W. E. Wallace University of Pittsburgh June, 1981 CONTENTS SPEDDING AWARD ADDRESS Rare Earth Reminiscences 1 BIOINORGANIC CHEMISTRY Magnetic Resonance Studies of Metal Cation Transport Across Biological Membranes: Use of Paramagnetic Lanthanide Ions . . . . . . J.A. Balschi, V.P. Cirillo, W.J. leNoble, M.M. Pike, E.C. Schreiber, Jr., S.R. Simon and C.S. Springer, Jr. Inter-Lanthanide Ion Energy Transfer Distance Measurements in Biological Systems . W.DeW. Horrocks, Jr., M.-J. Rhee, A.P. Snyder, T. Choosri, and V.K. Arkle Gadolinium as an EPR and NMR Probe of Ca 2+ Sites in Biological Systems ••.. E.M. Stephens and C.M. Grisham Optical Activity of Mixed-Ligand Complexes of Tb(III) with Pyridine-2,6-Dicarboxylic Acid and Hydroxycarboxylic Acids . . . . . • . . . . H.G. Brittain 15 21 25 31 Terbium Luminescence as a Probe of Lanthanide Coordination in Solution . . . . . . F.S. Richardson 35 A 160Tb (III) Probe of the Calcium Binding Sites of Muscle Calcium Binding Parvalbumin . F. Gonzalez-Fernandez and D.J. Nelson 37 x~i xiv CONTENTS The Lanthanides as Structural Probes in Peptides R.E. Lenkinski, and R.L. Stephens Multinuclear NMR Study of Three Aqueous Lanthanide Shift Reagents: Complexes with EDTA and Two Macrocyclic Ligands . . . . . . . . . . . . . . • . . . . . . . C.C. Bryden, C.N. Reilley and J.F. Desreux Structures of Dithiophosphinate Complexes of the Lanthanides in the Solid and Solution by X-Ray Diffraction and Paramagnetic NMR . . . . . . . . . . . . . . . . . . A.A. Pinkerton 45 53 59 ORGANOMETALLIC AND COORDINATION CHEMISTRY Recent Advances in the Low Valent Approach to f-Element Organometallic Chemistry W.J. Evans Laser Photochemistry of a Uranium Compound Tailored for lO~ Absorption: U(OCH 3 )6 . . . . . . . . . . . E.A. Cuellar, S.S. Miller, R.C. Teitelbaum, T.J. Marks, and E. Weitz New Stoichiometric and Catalytic Pentamethylcyclopentadienyl Organoactinide Chemistry . . . . ....... . P.J. Fagan, E.A. Maatta, A.M. Seyam, and T.J. Marks Choosing a Coordination Number for Ln(III): 1:1, 1:2, 2:1, 3:2 and 4:3 Complexes with Crown Ethers . . . . . J.-C.G. Bunzli, D. Wessner, A. Giorgetti and Y. Fr~sat A Systematic Study of the Complexation of DI- and TRI-Valent Lanthanide Ions by Macrocycles of Varying Size J.F. Desreux and J. Massaux Octahedral Compounds of Lanthanides: Oxide (tmpo) as Ligand O.A. Serra and M. Moraes 61 71 77 85 87 Trimethylphosphine 91 Amine Complexes of Divalent Europium F.A. Hart, and W. Zhu 95 High Coordination Polyhedra of Trivalent Rare Earth Ions J.-C.G. Bunzli, and B. Klein 97 CONTENTS xv Erbium Chloride Complexation in Aqueous DMF • . • . . • . . . • H.B. Silber, and M.R. Riddle 99 Lanthanide Hexafluoroantimonate Complexes of Hexamethylphosphoramide . . . • • . . . . • • . 105 S.M. Melo and N.M.P.S. Ricardo SPECTROSCOPY Parametrisation of the MCD-Spectra of Rare Earths: Example of Pr 3+ in PVA-Matrix • . . . • . . • . . 109 C. Gorller-Walrand, N. De Moitie-Neyt, and Y. Beyens Ab-Initio Calculation of Lanthanide Crystal Field Parameters and Transition Probabilities • . . . . • . 115 M. Faucher and 0. Malta On the Origin of Resonance Lines in 3d Emission Spectra of Rare Earths . • . • . . . . . . • . • . 121 J. Kanski Transition Intensities for Nd 3+ in Crystals . • • • . . . • • . 125 A.A.S. da Gama and G.F. de Sa Truncation Effects on Crystal Field Calculations for the 4f 6 (Eu 3+) Configuration in Solids G.T. de Sagey, P. Porcher, G. Garon and P. Caro • • . . . 127 Study of M4 5_Level Soft X-Ray Appearance Potential Spectra of Selected Rare Earths . . . . • • • . . . . 131 D. Chopra and G. Martin The Effect of Multiplet Splitting of the 4d Levels in Rare Earth Elements on Their X-Ray Spectra S.1. Salem . . . . . 135 Optical Spectra, Energy Levels, and Crystal-Field Analysis of Tripositive Rare Earth Ions in • 139 Y203: I. Kramers Ions in C? Sites • N.C. Chang, J.B. Gruber, R.P. Leavitt, and C.A. Morrison Sm 2+ Activated Mixed Fluorides: Synthesis and Fluorescence . . . . . . . . • . F. Gaume, A. Gros and J.C. Bourcet . • • . . • . • 143 Electric and Magnetic Dipole Strengths of f-f Transitions in Cubic CS2NaYC16:Ln3+ Systems F.S. Richardson . . . . . . 147 xvi CONTENTS Absorption Spectrophotometric Characterization of Smell), Sm(lll), and Sm(ll/lll) Bromides and Sm(lll) Oxybromide in the Solid State • • .• A.B. Wood, J.P. Young, J.R. Peterson and J.M. Haschke Cascade Laser Action in Tm3+: YLF L. Esterowitz, R. Allen and R. Eckardt Laser Induced Luminescence of Pr3+ in CaF2 Attributed to Different Local Site Symmetries . . . . . . J. Chrysochoos, J.M. Stillman and P.W.M. Jacobs Photoconductivity Due to Autoionization of Divalent Rare Earth Impurities in Crystals Having the Fluorite Structure . . . . • . . . . . . C. Pedrini, F. Gaume-Mahn and D.S. McClure The Effect of Structural Environment on the Absorption Spectra of Selected Lanthanide Sesquioxides R.G. Haire, J.P. Young and J.R. Peterson The Ce 3+ + Tb3+ Transfer in Phosphate Host Lattices P. Bochu, C. Parent, A. Daoudi, G. Le Flem and P. Hagenmuller 153 159 161 165 171 177 Laser Excited Luminescence of Tb3+, Eu3+-Activated Ferroelectric Gadolinium Molybdate (GMO) B.K. Chandrasekhar and W.B. White 179 Luminescence of High-Pressure Phases of Eu 2+ Activated Alkaline Earth Borates and Silicates • . • • . . G. Adachi,. K. Machida and J. Shiokawa 183 PMR Spectroscopic Studies of Lanthanide Aminocarboxylate Complexes • . .• .••...•.•.. G.R. Choppin, P.A. Baisden and E.N. Rizkalla 187 The Interaction of 1:1 and 1:2 Lanthanids-EDTA Chelates with Alkali Cations: Aqueous Relaxation Reagents for Metal Nuclide NMR G.A. Elgavish 193 Luminescence of L-(-)-Tryptophan in DMSO at 77 K in the Presence of Tb3+ • . • • • ... V. Anantharaman and J. Chrysochoos 199 Hypersensitivity i~the 4f-4f Absorption Spectra of Er 3- and Ho Complexes • . • . . • . . . . S.A. Davis and F.S. Richardson 203 xvii CONTENTS Possible Symmetries of the Coordination Sphere of Eu 3+ in DMSO via a Correlation of Magnetic Circular Dichroism (MCD) with Absorption and Emission Spectra . . . . . . . . . J. Chrysochoos, M.J. Stillman and P.W.M. Jacobs 207 Diphenyl-Phosphinyl-Morpholide (DPPM) Lanthanide Salt Adducts: Nd 3+ and Eu 3+ Spectra . . . G. Vicentini and L.R.F. Carvalho 213 Adducts of Lanthanide Trifluoromethanesulfonates and Tetramethylene Sulfoxide (TMSO) L.B. Zinner and F.A. Araujo 217 Photoreduction of Ytterbium and Samarium T. Donohue 223 PHASE EQUILIBRIA AND THERMODYNAMICS CeN: Phase Relationships and Enthalpies of Solution E. Kaldis, B. Steinmann, B. Fritzler E. Jilek and A. Wisard 227 Enthalpies of Solution and Lattice Constant Anomalies of Sm3S4 - Sm2S3 Solid Solutions . ...• E. Kaldis, H. Spychiger, B. Fritzler and E. Jelek 237 High Temperature Phase Diagram and Enthalpies of Solution of TmSe . . ..... B. Fritzler, E. Kaldis and E. Jilek 243 Densities and Concentration of Defects in TmSe B. Fritzler, E. Kaldis, B. Steinmann, E. Jilek and A. Wisard 249 Preparation and Thermoelectric Properties of Some Rare Earth Chalcogenides ....... T. Takeshita, B.J. Beaudry and K.A. Gschneidner, Jr. 255 Thermal Decomposition of Rare Earth Sulfate and Selenate Hydrates . . . . . ..... L. Niinisto, P. Saikkonen and R. Sonninen 257 Rare Earth Oxysulfide/Oxysulfate Equilibria at 1100-1500K .......... . R.K. Dwivedi and D.A.R. Kay 265 xviii CONTENTS Phase Studies and Selective Oxidation in Rare Earth~ Molybdenum-Oxide Systems, Ln203-Mo02-Mo03 H. Prevost-Czesk1eba and G. Tourne 271 Correlation of Spectral and Heat-Capacity Schottky Contributions for DY203, Er203 and Yb203 • • E.F. Westrum, Jr., R.D. Chirico and J.B. Gruber 275 Enthalpy of Formation of Barium Lanthanide(IV) Oxides: BaCe03, BaPr03' and BaTb0 3 ..•.•..•.. L.R. MOrss and N. Mensi 279 On Mixed Crystals of Pr1_yTbyOx Grown Under High Oxygen Pressures • . • . . B. Chang, M. McKelvy and L. Eyring 283 A Kinetic Study of the Oxidation of Zeta Phase 1 O2 Pr10018 Praseodymium Oxide: 51 10 Pr9 16 +-9 + . . • . ° 289 T. Sugihara, S.H. Lin and L. Eyring Predicted Stabilities of Rare Earth Diha1ides S. Bratsch and H.B. Silber Vaporization and Thermodynamic Properties of Samarium Dicarbide and Nonstoichiometric Disamarium Tricarbide • • • . • . . J.M. Haschke and T.A. Deline Complexity of Phase Equilibria in the MM-Co-Fe System Between 2:7 and 1:5 Stoichiometries . . . • . E.M.T. Ve1u, S. Laha, E.C. Subbarao, K.P. Gupta, A.K. Majumdar, T.A.P. Sankar, S. Pandian and U. Ramakrishna Low Temperature-High Magnetic Field Heat Capacity Studies of Weakly and Nearly Ferromagnetic and Mixed Valence Rare Earth Materials . . K.A. Gschneidner, Jr., K. Ikeda and O.D. McMasters 291 293 295 299 STRUCTURAL AND SOLID STATE CHEMISTRY Anomalous Behavior of Cerium and Europium Ions in Ternary Molybdenum Cha1cogenides (Chevre1 Phases). M.B. Maple, M.S. Torikachvi1i, R.P. Guertin and S. Foner New Fluorides with Ce IV , Pr IV , Nd IV , Tb IV , and DyIV . • • . . R. Hoppe 301 315 xix CONTENTS Ternary Halides of the Rare Earth Elements: Phases and Structures . . . . . G. Meyer Investigation of the "Diadochic" Incorporation of the Rare Earth Elements in CaF2 at Elevated Temperature and Pressure . . .... B.A. Bilal, P. Becker, V. Koss and H. Nies 317 . . . . . 323 Crystal Structures of EuMgF4, SmMgF4, and SrMgF4 E. Banks, R. Jenkins and B. Post 329 Structural Phase Transitions in CS2NaLnC16 . . . . . . . . G.P. Knudsen, F.W. Voss, R. Nevald and H.-D. Amberger 335 Synthesis and Crystal Data for Alkaline EarthLanthanide Phosphates with the Eulytite Structure G.J. McCarthy, D. Krabbenhoft, R.G. Garvey and C. Roob 339 The Crystal Structure and Stoichiometry of the Ca2+xNd8-x(Si04)602-l/2x System . . . . J.A. Fahey and W.J. Weber 341 Electron Beam-Induced Reduction of Tb0 2 _ o: A High Resolution Electron Microscope Study . . . L. Eyring and R.T. Tuenge 345 Crystal Structure and Properties of (LaO) CuS and (LaO)Ags . . . . . . . . . . . . . . . . . M. Palazzi, C. Carcaly, P. Laruelle and J. Flahaut 347 The Crystal Chemistry of the Europium Arsenides . . . . F.L. Carter and L.D. Calvert 351 Crystal Structures and Phase Relationships within Ternary Systems: Rare Earth Metal-Noble Metal-Boron . . . P. Rogl and H. Nowotny 353 Fast Diffusion and Electrotransport of Cobalt, Iron and Nickel in a-Yttrium . . . . . . . . I.C.I. Okafor and O.N. Carlson 357 Ternary Compounds in RE(Au,Ga)2 and RE(Ag,Ga)2 Alloys. . . . A.E. Dwight 359 MAGNETIC PROPERTIES Magnetic Properties of ErM3' M = (Ni, Fe, Co) ...... B. Decrop, J. Deportes, B. Kebe, C. Crowder, W.J. James and W. Yelon 361 xx CONTENTS Transport and Magnetic Properties of the Gd4(Col_~ix)3 Series (0 < x < 0.2) •••.• . •..• E. Gratz, G. Hilscher, H. Kirchmayr and H. Sassik 367 Structures and Magnetism of Some Polycomponent 2:7 Rare Earth-Transition Metal Systems • W.E. Wallace, M. Merches and R.S. Craig 373 Evidence for the Noncollinearity of the Magnetic Structure of Er6Mn23 ..••.•••• B. Kebe, C. Crowder, W.J. James, J. Deportes, R. Lemaire and W. Yelon Mossbauer Investigation of the Effect of Annealing on the Ordering Temperature of Amorphous DyFe2 C. Bucci, E. Bauminger and H. Savage 377 .••• Magnetization and SSMn Hyperfine Field in RMn2 (R = Rare Earth) Intermetallic Compounds S.K. Malik, S.K. Dhar, R. Vijayaraghavan, K. Shimizu and W.E. Wallace Magnetic Properties of Cubic and Hexagonal HoMn2 • J. Rhyne, K. Hardman, S. Malik and W. Wallace Susceptibility Densities in the Pauli Paramagnets YNiS and CeNiS . • . • . . • . • • • . . . . D. Gignoux, D. Givord, F. Givord, R. Lemaire and F. Tasset Thermal Variation of Anisotropies of Cobalt in YCos and NdCo S Up to 450 K • . . • . • • • . J.M. Alameaa, D.Givord, R. Lemaire and Q. Lu The Magnetic Structure of Y(Mnl-xFe x )12 Y.C. Yang, G.J. Long, B. Kebe, W.J. James and J. Deportes Magnetic Characteristics of the Intermetallic Compounds R2Ni17-xAlx (R = Gd, Tb) • • • • • . . . • . . . • M. Coldea and I. Pop Observation of Spiral Spin Antiferromagnetic Domains in Single Crystal Terbium • • • . . S.B. Palmer, J. Baruchel, S. Farrant, D. Jones and M. Schlenker Crystal Field and Quadrupolar Effects on the Third-Order Magnetic Susceptibility • • • •• • • . . • . P. Morin and D. Schmitt 381 385 391 393 399 403 407 413 419 xxi CONTENTS Magnetic Properties of Some Single Crystal Rare Earth Tetraborides . • . • • . . . . . . J. Etourneau, B. Chevalier, R. Georges, G. Will, W. Schaffer and J.C. Gianduzzo 423 Transferred Hyperfine Interactions and Quadrupole Effects for the Diamagnetic Ions in Rare-Earth Elpasolites, CS2NaLnC16 . . . . . . . . . . . F.W. Voss, R. Nevald, G.P. Knudsen., and H.-D. Amberger 427 Structure-Property Interplay in the System RTi0 3 : . .....• R = Lanthanide (III) . . J.E. Greedan 431 Some Magnetic Properties of the System La x Gd 1_ xTi0 3 . . . . . J.P. Goral and J.E. Greedan Zero Field Temperature Dependence of the Rare Earth Sublattice Magnetization in RTi0 3 ; R = Tb, Dy, Ho, Er and Tm • . . . . . . C.W. Turner, M.F. Collins and J.E. Greedan 441 443 Magnetic and Structural Properties of CeSbl-xTex Mixed Compounds . . . . . . . . . D. Ravot, J.C. Achard, J. Rossat-Mignod 445 Effects of the Non-Stoichiometry on the Transport Properties of CeSb . . . . . . D. Ravot, J.C. Achard, M. Escorne and A. Mauger 451 Low-Temperature Behavior of DyS, DySe, HoS and HoSe. F. Hulliger, M. Landolt and R. Schmelczer Electrical Resistivity and Magnetic Field Effects of NdS3-xVxS4 . . . . . . . . . . S.M.A. Taher and J.B. Gruber Faraday Rotation of Rare Earth Alkali Germenate Glasses . • . S.C. Cherukuri and L.D. Pye 455 459 465 HYDRIDES Using NMR to Study the Properties of Rare-Earth Materials Containing Hydrogen. . . . . . R.G. Barnes Magnetic and Structural Properties of Y6Mn23D23 . . . . . . . C. Crowder, B. Kebe, W.J. James and W. Yelon 471 473 xxii CONTENTS Magnetic and Structural Properties of Th6MnZ3Dx and Y6MnZ3Dx . • • • . • . • . . . . . • K. Hardman, J.J. Rhyne, E. Prince, H.K. Smith, S.K. Malik and W.E. Wallace Valence Bonding, Atomic Volumes, and Coordination, Numbers for Y6Mn Z3 ' Th 6Mn Z3 ' and Their Hydrides F.L·.. Carter Structure of A1, Cu and Si Substituted LaNi 5 and of the Corresponding S-Deuterides from Powder Neuton Diffraction. Localized Diffusion Mode of Hydrogen in LaNi5 and A1 and Mn Substituted Compounds from Quasie1astic Neutron Scattering . . . . . . . J.C. Achard, A.J. Dianoux, C. Lartigue, A. Percheron-Guegan and F. Tasset Thermodynamic and Magnetic Properties of LaNi 5_ xFe x Compounds and Their Hydrides ....•.. J. Lam1ouni, C. Lartique, A. Percheron-Guegan, J.C. Achard and G. Jehanno Thermodynamic Properties of LaNi4rt Compounds and Their Hydrides . . . • . • . . . . • • . • • . • . . A. Pasture1, C. Chati11on, A. Percheron-Guegan, and J. C. Achard Hydrogen Desorption Rates in LaNi5_xA1x-H Arthur Tauber and Robert D. Finnegan 477 479 481 487 489 493 PURIFICATION AND ANALYSIS Structure-Reactivity Studies on the Extraction of Lanthanides by Dia1ky1 Isopropy1phosphonates C. Yuan, W. Ye, E. Ma, F. Wu and X. Yan Separation of The Rare Earths and Some Polyvalent Cations on Inorganic Ion Exchangers J.-K. Cheng, R. Cai, X. Zhao, S. Shi and Y Tseng 499 505 Solvent Extration Behavior of Lanthanides with Di(Z-Ethy1hexy1) Isopropy1phosphonate E. Ma, S. Wa?g, F. Wu and C. Yuan 507 Spectrophotometric Determination of Rare Earths in Ligand Buffer Masking Systems . • J. Cheng, Q. Luo, R. Cai, X. Li and Y. Tseng 513 xxiii CONTENTS Spectrophotometric Determination of Trace Amounts of Copper in High-Purity Rare Earth with a,S,y,oTetra-(4-trimethylammonium-phenyl) Porphine J.Cheng, K. Yang and Q. Chang 517 Rare Earth Ion Selective Electrodes: II. Europium and Praseodymium Compound Membranes Y. Suzuki, H. Itoh and T. Nakano 521 Analysis of Rare Earth Elements in Ore Concentrate Samples using Direct Current Plasma Spectrometry G.W. Johnson and T.E. Sisneros 525 Behavior of REE in Geological and Biological Systems J.C. Laul and W.C. Weimer 531 NEW APPLICATIONS Trends in Rare Earth Metal Consumption for Steel Applications in the 1980's . . . . . . . . J.R. Jackman and W.H. Trethewey 537 The Use of Rare Earths in Photovoltaics P. Munz and E. Bucher 547 Preparing Rare Earth Silicon Iron Alloys E. Morrice and M.M. Wong 557 Catalysis Using Rare Earth and Actinide Intermetallics Containing Fe, Co, Ni and Cu . . . . . . . . . . W.E. Wallace, J. France and A. Shamsi 561 Electrochemical Corrosion of Lanthanum Chromite and Yttrium Chromite in Coal Slag D.D. Marchant and J.L. Bates 569 AUTHOR INDEX 577 SUBJECT INDEX 581