ELECTRONIC STRUCTURE AND PROPERTIES OF HYDROGEN IN METALS

NATO CONFERENCE SERIES

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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

A Division of Plenum Publishing Corporation 233 Spring Street, New York, N.Y. 10013

AII 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

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