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ELECTRONIC STRUCTURE AND PROPERTIES OF HYDROGEN IN METALS
NATO CONFERENCE SERIES
I Ecology II Systems Science III Human Factors IV Marine Sciences V Air-Sea Interactions VI Materials Science
VI MATERIALS SCIENCE
Volume 1
Volume 2
Volume 3
Volume 4
Volume 5
Volume 6
Molecular Metals Edited by William E. Hatfield
Materials for Advanced Batteries Edited by D. W. Murphy, J. Broadhead, and B. C. H. Steele
Adhesion in Cellulosic and Wood-Based Composites Edited by John F. Oliver
Adhesion Problems in the Recycling of Concrete Edited by Pieter C. Kreijger
Atomistics of Fracture Edited by R. M. Latanision and J. R. Pickens
Electronic Structure and Properties of Hydrogen in Metals Edited by P. Jena and C. B. Satterthwaite
ELECTRONIC STRUCTURE AND PROPERTIES OF HYDROGEN IN METALS
Edited by
P. Jena and
C. B. Satterthwaite Virginia Commonwealth University Richmond, Virginia
Published in cooperation with NATO Scientific Affairs Division
PLENUM PRESS· NEW YORK AND LONDON
Library of Congress Cataloging in Publication Data
NATO International Symposium on the Electronic Structure and Properties of Hydrogen in Metals (1982: Richmond, Va.)
Electronic structure and properties of hydrogen in metals.
(NATO conference series. VI, Materials science; v. 6) "Proceedings of a NATO International Symposium on the Electronic Structure and
Properties of Hydrogen in Metals, held March 4-6, 1982, in Richmond, Virginia"Verso t.p.
Includes bibliographical references and index. 1. Metals-Hydrogen content-Congresses. 2. Electronic structure-Congresses. 1.
Jena, P. II. Satterthwaite, C. S., 1920- . III. North Atlantic Treaty Organization. Scientific Affairs Division. IV. Title. V. Series. TN689.2.N36 1983 669/.94 82·16569 ISBN 978-1-4684-7632-3 ISBN 978-1-4684-7630-9 (eBook) DOI 10.1007/978-1-4684-7630-9
Proceedings of a NATO International Symposium on the Electronic Structure and Properties of Hydrogen in Metals, held March 4-6, 1982, in Richmond, Virginia
© 1983 Plenum Press, New York Softcover reprint of the hardcover 1 st edition 1983
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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
PREFACE
Hydrogen is the smallest impurity atom that can be implanted in a metallic host. Its small mass and strong interaction with the host electrons and nuclei are responsible for many anomalous and interesting solid state effects. In addition, hydrogen in metals gives rise to a number of technological problems such as hydrogen embrittlement, hydrogen storage, radiation hardening, first wall problems associated with nuclear fusion reactors, and degradation of the fuel cladding in fission reactors. Both the fundamental effects and applied problems have stimulated a great deal of interest in the study of metal hydrogen systems in recent years. This is evident from a growing list of publications as well as several international conferences held in this field during the past decade. It is clear that a fundamental understanding of these problems requires a firm knowledge of the basic interactions between hydrogen, host metal atoms, intrinsic lattice defects and electrons. This understanding is made particularly difficult by hyrogen's small mass and by the large lattice distortions that accompany the hydrogenation process.
The purpose of the "International Symposium on the Electronic Structure and Properties of Hydrogen in Metals" held in Richmond, Virginia, March 4-6, 1982 was to increase our fundamental understanding of hydrogen in metals. Such knowledge is essential in solving technologically important questions. The symposium consisted of twenty-two invited papers and seventy-two contributed poster presentations and attracted nearly 150 participants from thirteen countries. The proceedings of this symposium constitute this book.
The discussions and presentations included a number of topics: phase diagrams, spinodals, order-disorder transformations, thermodynamics, neutron scattering, elastic interactions, electronic structure, magnetic and hyperfine properties, superconductivity, diffusion, interaction with lattice defects, chemisorption, and catalysis. A variety of experimental and theoretical techniques were discussed and the complimentarity of these techniques in probing the electronic structure and properties of metal-hydrogen systems was emphasized.
v
vi PREFACE
The structure, phase diagrams; phase transitions, stabilities, stoichiometries and site occupancies were presented from an experimental viewpoint and discussed theoretically in terms of electronic and elastic interactions. The electronic structure and properties were studied with de Haas van Alphen effect, XPS/UPS and energy loss spectroscopy, M6ssbauer effect, perturbed angular correlation, muon spin rotation, and electron and nuclear spin resonance techniques. The results were analyzed theoretically using conventional jellium, cluster, and band structure models. The mechanism of trapping of hydrogen by impurities and imperfections and the effects of trapping on diffusion entered the discussion. New work on superconductivity and the status of the theory were presented. Throughout much of the program isotope effects and quantum solid effects associated with the small hydrogen mass played a role. The present understanding of hydrogen chemisorption and catalysis was reviewed. Because of the limited time available for the conference, many important areas of hydrogen in metals had to be left out.
We wish to thank the conferees for the high quality of their participation in the invited and poster presentations and exchange of ideas. We thank the members of the international steering committee: Professors G. Alefeld, B. Baranowski, H. K. Birnbaum, J. P. Burger, J. Friedel, F. D. Manchester, D. T. Peterson, J. M. Rowe, K. S. Singwi, A. M. Stoneham, W. E. Wallace and T. Yamazaki for their advice in the choice of scientific topics and organization of the symposium. We owe special gratitude to the local organizing committee: Professors C. T. Butler, T. D. Doiron, D. W. Hartman, W. J. Kossler, H. E. Schone, J. Ruvalds, C. E. Stronach, and K. R. Squire for their help during the one and half year this symposium was being planned. We are grateful to the faculty and staff of the Physics Department of Virginia Commonwealth University, in particular Professor R. H. Gowdy, Prof. G. B. Taggart, Mr. James Spivey, Ms. Kim Hulce, and Miss Belinda Ashmore for their individual help and advice.
This symposium was made possible by a generous grant from the Special Program Panel on Materials Science of the North Atlantic Treaty Organization. The symposium was hosted by the Virginia Commonwealth University. We also acknowledge with thanks the financial support of the Virginia Commonwealth University, the National Science Foundation, the Exxon Corporation, and Philip Morris, U.S.A.
P. Jena C. B. Satterthwaite
Richmond, Virginia May, 1982
CONTENTS
PHASE DIAGRAMS, SPINODALS, AND THERMODESORPTION
Metal-Hydrogen Phase Diagrams . . . . . . . . . . . . . . T. Schober
A Review of the Statistical Theory of the Phase-Change Behavior of Hydrogen in Metals . . . . . . .
Carol K. Hall
Spinodals and Spinodal Mechanisms in M-H Systems F.D. Manchester
What is the Relevance of Thermal Fluctuations for the Spinodal Decomposition in a Coherent Metal-
1
11
25
Hydrogen System? .. . . . . . . . . . . . . . . . .. 43 Joseph W. Haus and Harald King
Enthalpy of Metal-Hydrogen Systems: A Pair-Bond Model P. S. Rudman
Thermal Desorption Spectra of PdH System (O<x<O.9) in Different Samples: a Powdef, a Foil, and a Wire
A. Stern, A. Resnik, D. Shaltiel, and S.R. Kreitzman
Fundamental Aspects of Thermodesorption Spectra in Bulk Hydride Systems ......... .
S.R. Kreitzman, A. Stern, and D. Shaltiel
Thermal Desorption Spectroscopy (TDS) of Hydrogen from Niobium . • . . . . . .. ....
V.J. Ghosh, M.A. Pick, D.O. Welch, and G.J. Dienes
The Concentration Profile of Hydrogen near the Surface of Niobium . . .. ........•.•.
M.A. Pick, A. Hanson, K.W. Jones, and A.N. Goland
vii
49
55
61
67
73
viii CONTENTS
Theory of Hydrogen Absorption in Metal Hydrides Tomoyasu Tanaka and Daniel E. Azofeifa
STRUCTURAL PROPERTIES, SITE OCCUPANCIES, AND ELASTIC INTERACTIONS
Stabilities, Stoichiometries, and Site Occupancies in
79
Hydrides of Intermeta11ic Compounds . • . • . • . . . • . 85 D.G. Westlake
Octahedral Site Occupation in Lanthanum Dihydride . • . . • • • 97 E.L. Venturini
Thermodynamic and Structural Properties of the Rare-Earth C0 3 Hydrides • • • • . • • • . . . • . . • . • . • . . . 103
Henry A. Kierstead
Measurement of Three Dimensional Distributions of Hydrogen in Thin Samples using the 15N Hydrogen Profiling Method • • • • • . • • • . . . . • . . . . • .
W.A. Lanford and C. Burman
Strain Effects in the X-ray Determination of Lattice Parameters in Pd-H. .•..•
x P.A. Hardy, I.S. Ba1baa, and F.D. Manchester
Lattice Distortions and Phase Transitions of Hydrogen in Niobium
H. Peis1
Forces, Dipole Force Tensor, and Elastic Binding Energy in a-Palladium Hydrides • • • • • • • • • • • • • .
J. Kha1ifeh, G. Moraitis, and C. Demangeat
Relaxation, Electronic, and Volume Expansion Contributions to the Elastic Constant Changes Induced by Hydrogen and Deuterium in Nb • • • • • • • • • • • • . • • • •
F.M. Mazzo1ai and H.K. Birnbaum
Low Temperature Ultrasonic Attenuation in Rapidly Cooled Niobium Containing Oxygen and Hydrogen • • • .
K.F. Huang, A.V. Granato, and H.K. Birnbaum
· 109
• 115
· 117
• 119
• 125
· 133
Ultrasonic Attenuation Measurements in Single Crystal PdH 65. . 139 T. Kanashiro, D.K. Hsu, R.G. Leisure, and P.C. Riedi .
Contribution of Optical Phonons to the Elastic Moduli of PdH and PdD ••••••••••••••••.•• • 145
B.M. G~erken, R~ Griessen, L.M. Huisman, and E. Walker
CONTENTS
NEUTRON SCATTERING
Neutron Spectroscopic Studies of Dilute Hydrogen in Pure and Defected Metals . . . . . . . . . . . . .
J.J. Rush
Structure and Phase Transitions in V2D and V2H S.C. Moss
Hydrogen Vibrations in Nickel Hydride . . . . . . . . . . . J. Eckert, C.F. Majkrzak, L. Passell, W.B. Daniels, and
T.A. Kitchens
Localized Vibrations of H in Nb and Ta at High Concentration and Low Temperatures • . . . . .
J. Eckert, J.A. Goldstone, and D. Richter
Tetrahedral and Octahedral Site Occupancy and Optic Mode
ix
· 151
· 153
· 165
· 167
Vibrations of Hydrogen in Yttrium . . . . . . 169 J.A. Goldstone, J. Eckert, E.L. Venturini, and P.M.
Richards
Influence of Substitutional and Interstitial Impurities on Local Hydrogen Modes in Nb ..•... . ..... 171
A. Magerl, J.J. Rush, J.M. Rowe, D. Richter, and H. Wipf
Quasielastic Neutron Scattering in Metal Hydrides: Effects of the Quantum Mechanical Motion of Interstitial Hydrogen Atoms •. .. •.•••......•.•.. 177
D.W. Brown and V.M. Kenkre
A Study of Hydrogen Site Occupation in the Yttrium-Hydrogen Solid Solution Phase Using Inelastic Neutron Scattering • . • • . . . . . . . . ....•..• 183
J.E. Bonnet, S.K.P. Wilson, and D.K. Ross
Neutron Scattering Studies of the Low Temperature Transition in ex' PdD . . . . . . . • . • . . • . • • . . . . .• . 189
R.A. Bond, I.S. Anderson, B.S. Bowerman, C.J. Carlile, D.J. Picton, D.K. Ross, D.G. Witchell, and J.K. Kjems
Properties of Vanadium-Alloy Dihydrides • . . . . . . . . 197 H.G. Severin and E. Wicke
Temperature Dependence of Intrinsic Disorder in LaH and YH . • . . .. . ..•...•••..• x .•..•. 205
PeterxM. Richards
x CONTENTS
ELECTRONIC STRUCTURE
Electronic Structure of Metal Hydrides: A Review of Experimental and Theoretical Progress • .
J.H. Weaver, D.J. Peterman and D.T. Peterson
The Electronic Structure of PdH Studied with Photoemission and Electron Energy Loss Spectroscopy . . • . . . . .
P. Bennett and J.C. Fuggle
· 207
· 223
XPS/UPS Study of the Electronic Structure of PdHO. 6 ...... 229 L. Schlapbach and J.P. Burger
Electronic Structure of Metal Hydrides and Deuterides from de Haas van Alphen Measurements • . . . . • . .
R. Griessen and L.M. Huisman
Electronic Structure of Non-Stoichiometric Transition Metal Hydrides . . .• ......... . . . .
A. Bansil, R. Prasad and L. Schwartz
A Simple Tight Binding Description of the Electronic Structure of a Single and a Pair of Hydrogen Atoms in fcc Transi-
· 235
· 249
tion Metals . • . . • . . . . . . • . . . . . . . . . . • 265 M.A. Khan, J.C. Parlebas, and C. Demangeat
Theoretical Studies of Dilute Hydrogen Impurities in Palladium . ••.. . • . . . . . . .. ..... 277
Barry M. Klein and Warren E. Pickett
Electronic Structure of Interstitial Hydrogen in Aluminum . . . 283 Raju P. Gupta
Calculation of the Ground State Energy of Hydrogen at Interstitial Sites in a Lithium Cluster . . • . . . • • . 291
D.D. Schillady, T. Nguyen, and P. Jena
Parametrization of the Self-consistently Calculated Electronic Densities Around a Proton in Jellium • • . • . . • . • . 299
S. Estreicher and P.F. Meier
Electronic Structure of Vanadium-Hydrogen Clusters . • • • . . 307 G. Bambakidis, M.P. Guse, and G.C. Abell
SUPERCONDUCTIVITY
Superconductivity in Metal-Hydrogen Systems • • • • • • . . • . 309 B. Stritzker
CONTENTS
Superconductivity in Metal Hyrides Michele Gupta
xi
3Z1
Effect of Structural Phase Transitions on the Superconductivity of PdH (D ) . • • . . . . . . . .. ......... 335
R.W. Stanale~ and C. B. Satterthwaite
Superconductivity and Hydrogen Depth Profiles in Electrolytically Charged Cu-Implanted Pd . . •
W.J. Standish, A. Leiberich, W. Scholz, and C.G. Homan
Super conducting Tunneling into Pd-Ni-D Alloys P. Nedellec, L. Dumoulin, and J.P. Burger
Resistivity and Electron-Phonon Coupling in Palladium Alloy Hydrides . . . . . . . . . . . .. ....
A.F. Rex, J. Ruvalds, and B.S. Deaver, Jr.
Superconductivity of Pd-H and its Connection with the Phase
· 341
· 347
· 353
D' x lagram . . . . . . . . . . . . , . . . . . . . . . . . · 359 I.S. Balbaa and F.D. Manchester
MAGNETIC PROPERTIES
Magnetism of Mn, Fe, Co Impurities in PdH as a Hydrogen Concentration; Relation wifh the Structure of the Host . . . . . . . . . .
B. Souffache and J.P. Burger
Function of Electronic
• . 361
The Magnetic Properties of Gd Y6- FeZ3 (x=O,1,Z,3) Compounds and Their Hyrides . . .x. .x. . . . . . • . 367
A.T. Pedziwiatr, E.B. Boltich, W.E. Wallace, and R.S. Craig
Measurements of the Magnetization of Activated FeTi . . . . . . 373 D. Khatamian, F.D. Manchester, G.C. Weatherly, and
C.B. Alcock
Jahn-Teller Resonance States in the Vb Metal Hydrides . . . . . 379 G.C. Abell
Hydrogenation Entropies of the zrMnZt System. . . . • . . F. Pourarian, V.K. Sinha, W.E. Wa race, A.T. Pedziwiatr,
and R.S. Craig
HYPERFINE INTERACTION
On the Electronic Structure of Hydrogen in Metals in the Light of Muon Knight Shift Measurements . . . . . .
Alexander Schenck
· 385
· 391
xii CONTENTS
Anomalous Muon Knight Shift Behavior in a Cd Single Crystal . . 407 F.N. Gygax, A. Hintermann, W. Ruegg, A. Schenck, W.
Studer, A.J. van der Wal, and H. Wehr
The Hyperfine Field of the Positive Muons in the Ferromagnetic Transition Metals . . • . . . • . . . . . . . . 413
Kiyoyuki Terakura, Hisazumi Akai, Masako Akai, and Junjiro Kanamori
Hyperfine Field of Positive Muons Trapped at Monovacancies in Iron . • . •. ..... ....... . . 425
H. Graf, A. Moslang, E. Recknagel, and A. Weidinger
Pulsed ~SR Studies on ~+ in Metals . 431 K. Nagamine, K. Nishiyama, T. Natsui, Y. Kuno, J. Imazato,
H. Nakayama, and T. Yamazaki
Magnetic Susceptibility and Proton NMR Study of TiCr l SHx . 437 James F. Lynch, John R. Johnson, and Robert C. Bowman, Jr.
Proton NMR Studies of the Electronic Structure of ZrH .... 443 A. Attalla, R.C. Bowman, Jr., B.D. Craft, E.L. Venturini,
and W.-K. Rhim
Nuclear Magnetic Resonance of Hydrogen in CeH for x>2 . " 449 D. Zamir, N. Salibi, R.M. Cotts, Tan-Tee PBua, and R.G.
Barnes
DIFFUSION
Use of Nuclear Magnetic Resonance to Observe Diffusion of Hydrogen in Metals . . • . • . . . . . • . • . . . . . . 451
Robert M. Cotts
Diffusion of Hydrogen in Vanadium-Based Bcc Alloys • . . . . . 465 D.J. Pine and R.M. Cotts
The Effect of Magnetic Impurities on the Apparent Diffusion Coefficient of Hydrogen in Metal Hydrides Deduced from NMR . . . • . . . • . . . . • . . . . . . .. ., 467
T-T. Phua, R.G. Barnes, D.R. Torgeson, D.T. Peterson, M. Belhoul and G.A. Styles
NMR Studies of Hydrogen Diffusion in Palladium and S-LaNi5 Hydrides ...... . . . . . . . . . . . . . 473
K.L. Ngai, A.K. Rajagopal, and R.W. Rendell'
Hydrogen Diffusion and Electronic Structure in Crystalline and Amorphous Ti CuH . . . . . • • . . . . .. . 479
R.C. Bowman, Jr., A~J. gaeland, W.-K. Rhim, and J.F. Lynch
CONTENTS xiii
Local Diffusion and Tunnelling of Trapped Hydrogen in Metals . • • . . .. .......••. . 485
H. Wipf and K. Neumaier
Extracting Maximal Information on Positive Muon Diffusion in Metals ...•....•........... . 499
M. Leon
Effects of Impurities on the Diffusion of Positive Muons in Niobium . . . . . . . . . . . . . . . . . . . .. ., 50S
O. Hartmann, E. Karlsson, R. Wappling, E. Holzschuh, W. Kundig, B.D. Patterson, K. Schulze, D. Richter, R. Hempelmann, and S. Cox
Muon Diffusion in Noble Metals ................. 507 M.E. Schillaci, C. Boekema, R.H. Heffner, R.L. Hutson,
M. Leon, C.E. Olsen, S.A. Dodds, D.E. MacLaughlin, and P.M. Richards
Diffusion of Positive Muons in Aluminum and Aluminum-Based Alloys. . . . . . . . . . . . . . . . . . . . . .. .' 513
K.W. Kehr, D. Richter, J.M. Welter, O. Hartmann, E. Karlsson, L.O. Norlin, T.O. Niinikoski, and A. Yaouanc
Anomalous Behavior of Diffusion Coefficients of Hydrogen and Deuterium in High Content Palladium Hydride and Deuteride • . . . . . . . . . . . . . . . .. .' 519
S. Majorowski and B. Baranowski
Proton Jump Rates in Palladium-Hydride SO-lOOK . . . . . . . . . 525 S.R. Kreitzman and R.L. Armstrong
Theory of the Diffusion of Hydrogen in Metals • . . . • . . . . 531 K.W. Kehr
Simple Small Polaron Model for the Hydrogen Concentration Dependence of Hydrogen Diffusion in Nb . . . . . . . . . . 543
D.L. Tonks and R.N. Silver
Transport Behavior of Dense Protons in a Slab . . . . . . . . . 549 M.H. Lee and J. Hong
Analysis of Hydrogen Permeation Experiments in 403 Stainless Steel ..................... 555
Barbara Okray Hall, Richard J. Jacko and James A. Begley
Thermopower of S-Phase PdH C.L. Foiles y
.. 561
xiv
INTERACTION WITH DEFECTS, CHEMISORPTION
Direct Evidence for Interstitial and Vacancy-Associated Hydrogen Trapping Near Impurity Atoms in F.C.C.
CONTENTS
Metals • • .• ••. . .. •.•. . . . . 567 P. Boolchand, C.T. Ma, M. Marcuso, and P. Jena
Interaction of Hydrogen with Substitutional Solute Metals in the S-Phase of the Palladium-Hydrogen System . 581
F.E. Wagner, M. Karger, F. Probst, and B. Schuttler
Deuterium Desorption and Host Interstitial Clustering in d-Irradiated Ni • . . • . • . . . . . . . . . .. •.. 589
Carl Allard, Gary S. Collins and Christoph Hohenemser
Trapping by Dislocations in a~-PdD Observed by NMR ••.... 595 A.J. Holley, W.A. Barton, and E~F.W. Seymour
Positive PI-Mesons and Positive Muons as Light Isotopes of Hydrogen . • . . . . . . . • . . . . . . . 601
K. Maier and A. Seeger
Behavior of Positive Muons Implanted in Iron Alloys ...... 617 C.E. Stronach, K.R. Squire, A.S. Arrott, B. Heinrich,
W.F. Lankford, W.J. Kossler, and J.J. Singh
Hydrogen Traps in Cold-Worked Palladium Ted B. Flanagan and S. Kishimoto
. . . . . . . 623
Influence of Hydrogen on the Direction of Crack Propagation in Iron Using Computer Simulation . . . . . . . . . 629
Mayes Mullins
Theory of Hydrogen Chemisorption on Ferromagnetic Transition Metals . . • . . . • . • . . • . . . . . . . . 635
J.L. Moran-Lopez and L.M. Falicov
Hydrogen Chemisorption on Closed-Packed Surfaces • . . • . • . 641 F. Mejia-Lira and J.L. Moran-Lopez
~Jagnetic Susceptibility, Proton NMR, and Muon Spin Rotation (~SR) Studies of an Unsupported Platinum Catalyst with Absorbed Hand 0 . • • . . . • .. ... 647
R.F. Marzke, W.S. Glaunsinger, K.B. Rawlings, P. Van Rheenen, M. McKelvy, J.H. Brewer, D. Harshman, and R. F. Kiefl
CONTENTS xv
Influence of Interstitial Hydrogen on Temperature Dependence of Electrical Resistance of Disordered Ni-Mn Alloys . • . • . • • . • • • . • • • . • • • • . • 653
I. Csuzda and H.J. Bauer
Hydrogen Absorption and Critical Point Lowering in Thin PdH Films. • • • • . . • . . . . • . • • • •• ••• 659
H.L.M.xBakker, G.J. de Bruin-Hordijk, R. Feenstra, R. Griessen, D.G. de Groot, and J. Rector
SUMMARY
Hydrogen in Metals 1982 A.M. Stoneham
...••••.•••• 665
PARTICIPANTS 677
INDEX 691