Handbook on the Physics and Chemistry of Rare Earths Volume 6 Elsevier, 1984

Handbook on the Physics and Chemistry of Rare Earths volume 6 Elsevier, 1984 Edited by: Karl A. Gschneidner, Jr. and LeRoy Eyring ISBN: 978-0-444-86592-2 by kmno4 PREFACE Karl A. GSCHNEIDNER, Jr., and LeRoy EYRING These elements perplex us in our rearches [sic], baffle us in our speculations, and haunt us in our very dreams. They streteh like an unknown sea before us-mocking, mystifying, and murmuring strange revelations and possibilities. Sir William Crookes (February 16, 1887) This lament of Sir William Crookes, which introduced the preface to the previous volumes of this series, still beckons hauntingly for satisfaction. Although many of the grea{est mysteries he contemplated have been satisfactorily solved, there still remains the need for voyages of discovery on the "unknown sea". The first five volumes of the Handbook of the Physics and Chemistry of Rare Earths served primarily as navigational guides for the "elemental sea" and the "sea of binary materials". Although some information in volumes three, four and five dealt with ternary and higher order materials, this vast "sea" is still virtually unknown. Volume six is the beginning of an intensive exploration of the "sea of ternary and higher order materials". But even with this volume only a small portion will be duly recorded in our log (Handbook), and future volumes will be needed to help map out the unknown and bring it into the realm of our knowledge. Even though our knowledge of the "elemental sea" and "sea of binary materials" is vast, it is, nevertheless, incomplete, and portions of the future volumes will help fill in these unexplored bays and inlets. The four chapters in volume six deal with ternary (and higher order) systems, compounds, etc. which contain at least one rare earth metal and at least one nonmetallic element (H, B, C or Si). The first chapter deals with hydrogen absorption by intermetallic compounds. The next two chapters are quite complementary, dealing with the crystal chemistry of ternary borides and silicides, and phase equilibria in ternary and higher order systems involving boron. A companion chapter on phase equilibria in ternary and higher order systems involving silicon is scheduled for volume seven. The last chapter of volume six is a little more specialized and is concerned with divalent samarium and ytterbium in organic chemistry. Future volumes are scheduled to contain more reviews on the organic chemistry of rare earths--a rapidly growing and dynamic "bay" in the "sea of ternary and higher order materials". It is our intent that the handbook will continue to serve as a chronicle, charts, and navigational aids to those who would explore the mysteries of this'unknown sea, the rare earths. V CONTENTS Preface v Contents vii Contents of volumes 1-5 ix 47. K.H,J. Buschow Hydrogen absorption in intermetallic compounds 1 48. E. Parth6 and B. Chabot Crystal structures and crystal chemistry of ternary rare earth-transition metal borides, silicides and homologues 113 49. P. Rogl Phase equilibria in ternary and higher order systems with rare earth elements and boron 335 50. H.B. Kagan and J.L. Namy Preparation of divalent ytterbium and samarium derivatives and their use in organic chemistry 525 Subject index 567 vii CONTENTS OF VOLUMES 1-5 VOLUME 1: METALS 1. Z.B. Goldschmidt, Atomic properties (free atom) 1 2. B.J. Beaudry and K.A. Gschneidner, Jr., Preparation and basie properties of the rare earth metals 173 3. S.H. Liu, Eleetronie structure of rare earth metals 233 4. D.C. Koskenmaki and K.A. Gschneidner, Jr., Cerium 337 5. L.J. Sundström, Low temperature heat eapaeity of the rare earth metals 379 6. K.A. McEwen, Magnetie and transport properties of the rare earths 411 7. S.K. Sinha, Magnetie struetures and inelastie neutron seattering: metals, alloys and compounds 489 8. T.E. Scott, Elastie and meehanieal properties 591 9. A. Jayaraman, High pressure studies: metals, alloys and eompounds 707 10. C. Probst and J. Wittig, Supereonduetivity: metals, alloys and eompounds 749 11. M.B. Maple, L.E. DeLong and B.C. Sales, Kondo effect: alloys and eompounds 797 12. M.P. Dariel, Diffusion in rare earth metals 847 Subject index 877 VOLUME 2: ALLOYS AND INTERMETALLICS 13. A. Iandelli and A. Palenzona, Crystal ehemistry ofintermetallic compounds 1 14. H.R. Kirchmayr and C.A. Poldy, Magnetie properties of intermetallie eompounds of rare earth metals 55 15. A.E. Clark, Magnetostrictive RFe 2 intermetallie compounds 231 16. J.J. Rhyne, Amorphous magnetie rare earth alloys 259 17. P. Fulde, Crystalfields 295 18. R.G. Barnes, NMR, EPR and Mössbauer effeet: metals, alloys and eompounds 387 19. P. Wachter, Europium ehaleogenides: EuO, EuS, EuSe and EuTe 507 20. A. Jayaraman, Valenee ehanges in eompounds 575 Subjeet index 613 VOLUME 3: NON-METALLIC COMPOUNDS- I 21. L.A. Haskin and T.P. Paster, Geochemistry and mineralogy of the rare earths 1 22. J.E. Powell, Separation ehemistry 81 23. C.K. Jorgensen, Theoretieal ehemistry of rare earths 111 24. W.T. Carnall, The absorption and fluoreseenee speetra of rare earth ions in solution 171 25. L.C. Thompson, Complexes 209 26. G.G. Libowitz and A.J. Maeland, Hydrides 299 27. L. Eyring, The binary rare earth oxides 337 28. D.J.M. Bevan and E. Summerville, Mixed rare earth oxides 401 29. C.P. Khattak and F.F.Y. Wang, Perovskites and garnets 525 30. L.H. Brixner, J.R. Barkley and W. Jeitschko, Rare earth molybdates (VI) 609 Subject index 655 ix x CONTENTS OF VOLUMES 1-5 VOLUME 4: NON-METALLIC COMPOUNDS- II 31. J. Flahaut, Sulfides, selenides and tellurides 1 32. J.M. Haschke, Halides 89 33. F. Hulliger, Rare earth pnictides 153 34. G. Blasse, Chemistry and physics of R-activated phosphors 237 35. M.J. Weber, Rare earth lasers 275 36. F.K. Fong, Nonradiative processes of rare-earth ions in crystals 317 37A. J.W. O'Laughlin, Chemical spectrophotometric and polarographic methods 341 37B. S.R. Taylor, Trace element analysis of rare earth elements by spark source mass spectrometry 359 37C. R.J. Conzemius, Analysis of rare earth matrices by spark source mass spectrometry 377 37D. E.L. DeKalb and V.A. Fassel, Optical atomic emission and absorption methods 405 37E. A.P. D'Silva and V.A. Fassel, X-ray excited optical luminescence of the rare earths 441 37F. W.V. Boynton, Neutron activation analysis 457 37G. S. Schuhmann and J.A. Philpotts, Mass-spectrometric stable-isotope dilution analysisfor lanthanides in geochemical materials 471 38. J. Reuben and G.A. Elgavish, Shift reagents and NMR of paramagnetic lanthanide complexes 483 39. J. Reuben, Bioinorganic chemistry: lanthanides as probes in systems of biological interest 515 40. T.J. Haley, Toxicity 553 Subjeet index 587 VOLUME 5 41. M. Gasgnier, Rare earth alloys and compounds as thin films 1 42. E. Gratz and M.J. Zuckermann, Transport properties (electrical resistivity, thermoelectric power and thermal conductivity ) of rare earth intermetallic compounds 117 43. F.P. Netzer and E. Bertel, Adsorption and catalysis on rare earth surfaces 217 44. C. Boulesteix, Defects and phase transformation near room temperature in rare earth sesquioxides 321 45. O. Greis and J.M. Haschke, Rare earthfluorides 387 46. C.A. Morrison and R.P. Leavitt, Spectroscopic properties of triply ionized lanthanides in transparent host crystals 461 Subjeet index 693 Handbook on the Physics and Chemistry of Rare Earths, edited by K.A. Gschneidner, Jr. and L. Eyring © Elsevier Science Publishers B.V., 1984 Chapter 47 HYDROGEN ABSORPTION IN INTERMETALLIC COMPOUNDS K.H.J. BUSCHOW Philips Research Laboratories, Eindhoven, The Netherlands Contents 4.4. Metastable character of ternary 1. Introduction 1 hydrides 44 2. Intermetallic compounds 4 5. Physical properties 47 2.1. Preparation, phase diagrams, 5.1. Crystal structures 48 composition, structure and relative 5.2. Magnetic properties 53 stability 4 5.3. Miscellaneous properties 78 2.2. Magnetic properties 10 6. Technical applications 80 3. Hydrogen sorption in intermetallic 6.1. Hydrogen storage 80 compounds 17 6.2. Hydrogen purification and 3.1. Pressure-composition isotherms 17 hydrogen getters 82 3.2. Activation 18 6.3. Heat pumps 82 3.3. Hydriding kinetics 20 6.4. Energy storage 84 3.4. Surface effects and poisoning 24 6.5. Electrochemical cells 85 3.5. Sorption hysteresis 26 6.6. Thermal compressors and heat 3.6. Diffusion of hydrogen atoms 28 engines 86 4. Thermodynamic aspects 32 6.7. H and D isotope separation 87 4.1. Pressure-composition isotherms 32 6.8. Neutron moderators 4.2. Experimental values of AH and neutron generators 88 and AS 35 7. Concluding remarks 88 4.3. Empirical relations for Appendix 90 estimating AH of the hydrides of References 104 intermetallic compounds 37 1. Introduction It cannot be said that research on metal hydrides has had a history of continuous growth. Prior to 1950 the relatively small amount of interest was confined to binary hydrides, at that time usually referred to as solid solutions of hydrogen in metals. Activity in the field of metal hydride research intensified in the 1950s, mainly stimulated by the possibility of using stable hydrides for neutron moderators. After another period of relatively little activity, research on metal hydrides started to grow again in the 1970s and has since then been experiencing a period of proliferation. This second time, too, the renewed interest in metal hydride research was triggered 2 K.HJ. BUSCHOW by a potential application of these materials, namely as an energy carrier. The energy crisis in the early 1970s led to a search for alternative energy sources and to a search for methods which would enable more effective use to be made of the energy available, The use of metal hydrides comprises heat pumping and energy storage in conjunction with the generation of hydrogen by electrolysis and thermolysis of water.

Load more