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Physical Metallurgy

Fifth Edition

Editors

David E. Laughlin

ALCOA Professor of Physical Metallurgy, Materials Science and Engineering, Carnegie Mellon University, Pittsburgh, PA, USA

Kazuhiro Hono

Magnetic Materials Unit, National Institute for Materials Science, Tsukuba-city Ibaraki, Japan

Table of Contents

Cover image

Title page

Copyright of Volume I

Copyright of Volume II

Copyright of Volume III

List of Contributors to Volume I

List of Contributors to Volume II

List of Contributors to Volume III

Preface to the Fifth Edition

Preface to the Fourth Edition

Preface to the Third Edition

Preface to the First and Second Editions

About the Editors

Volume I

1. Crystal Structures of Metallic Elements and Compounds

1.1. Introduction

1.2. Factors Governing Formation and Stability of Crystal Structures

1.3. Crystal Structures of the Metallic Elements

1.4. Crystal Structures of Intermetallic Phases

1.5. Crystal Structures of Quasicrystals

2. Electron Theory of Complex Metallic Alloys

2.1. Introduction

2.2. Fundamentals in Alloy Phase Stability

2.3. Structure of Complex Metallic Alloys

2.4. Electron Theory of Complex Metallic Alloys

2.5. Stabilization Mechanism in a Series of Gamma-Brasses

2.6. Stabilization Mechanism in 1/1–1/1–1/1 Approximants

2.7. Hume-Rothery Electron Concentration Rule

3. Thermodynamics and Phase Diagrams

3.1. Introduction

3.2. Thermodynamics

3.3. The Gibbs Phase Rule

3.4. Thermodynamic Origin of Binary Phase Diagrams

3.5. Binary Temperature-Composition Phase Diagrams

3.6. Ternary Temperature-Composition Phase Diagrams

3.7. General Phase Diagram Sections

3.8. Thermodynamic Databases for the Computer Calculation of Phase Diagrams

3.9. Equilibrium and Nonequilibrium Solidification

3.10. Second-Order and Higher-Order Transitions

3.11. Bibliography

Acknowledgments

4. Metallic Glasses

4.1. Introduction

4.2. Compositions, Thermodynamics and Kinetics

4.3. Structure

4.4. Structural Evolution

4.5. Mechanical Properties

4.6. Applications

5. Diffusion in Metals and Alloys

5.1. Introduction

5.2. Atomistic Mechanism and Fundamental Relations of Diffusion

5.3. Interdiffusion in Concentrated Alloys and Thermodynamic Driving Forces

5.4. Experimental Techniques to Study Atomic Transport

5.5. Elementary Diffusion Properties of Metals and Intermetallic Compounds

5.6. Short Circuit Transport

5.7. Diffusion in Nanometric Dimensions

6. Defects in Metals

6.1. Introduction

6.2. Overview

6.3. Experimental Techniques

6.4. Point Defects in Pure Metals

6.5. Statistical Thermodynamics of Point Defects

6.6. Summary and Concluding Remarks

7. Solidification

7.1. Introduction

7.2. Transport Phenomena during Solidification

7.3. Thermodynamics of Solidification

7.4. Nucleation

7.5. Interface Kinetics

7.6. Solidification of Alloys with Planar and Nearly Planar L–S Interfaces

7.7. Cellular and Dendritic Solidification

7.8. Polyphase Solidification

7.9. Cast Structure and Fluid Flow

7.10. Developing and Emerging Processes

8. Diffusional Phase Transformations in the Solid State

8.1. Introduction

8.2. Energetics

8.3. Rate Processes in Solids

8.4. Classical Nucleation

8.5. Diffusional Growth of Phases

8.6. Precipitation from Solid Solution

8.7. Crystallography and Microstructure

8.8. Massive Transformation

8.9. Closure

9. Phase Transformations: Nondiffusive

9.1. Martensitic Transformations

9.2. Crystallographic Theory

9.3. Martensite Morphology and Substructure

9.4. Martensite–Parent Interfaces

9.5. Energetics of Martensitic Transformations

9.6. Crystallographically Similar Transformations

9.7. Omega Phase Formation

9.8. Phase Changes and Charge Density Waves

Volume II

10. Microstructure of Metals and Alloys

10.1. Introduction

10.2. 3D Microstructure and Microstructural Analyses

10.3. Specific Classes of Microstructures and Microstructural Evolution

10.4. Concluding Remarks

11. Orientation Mapping

11.1. Orientation Mapping in the Scanning Electron Microscope

11.2. Applicability of Orientation Mapping

11.3. Orientation Mapping with X-rays

11.4. Diffraction Contrast Microscopy

11.5. X-ray Diffraction Microscopy in Three Dimensions

11.6. Orientation Mapping in the TEM

Summary

12. Transmission Electron Microscopy for Physical Metallurgists

12.1. Introduction

12.2. Electron Diffraction in the (S)TEM

12.3. Imaging in Transmission Electron Microscopy

12.4. Electron Energy-Loss Spectroscopy (EELS)

12.5. X-ray Energy Dispersive Spectroscopy (XEDS) in a (S)TEM

13. X-ray and Neutron Scattering

13.1. Introduction

13.2. Scattering from Real Crystals

13.3. Bragg Peaks and Vicinity

13.4. Between Bragg Peaks

13.5. Near the Incident Beam

13.6. Energy Transfers

14. Structure, Composition and Energy of Solid–Solid Interfaces

14.1. Introduction

14.2. Structure and Composition of Homophase Interfaces

14.3. Structure and Composition of Heterophase Interfaces

15. Atom-Probe Field Ion Microscopy

15.1. Introduction

15.2. Overview of the Atom Probe Technique

15.3. Scope of Atom-Probe Field-Ion Microscopy Technique

15.4. Specific Applications to Materials

15.5. Future Directions

16. Dislocations

16.1. Introduction

16.2. Plastic Deformation and Dislocations

16.3. Elasticity Associated with Dislocations

16.4. Models of Dislocation Cores

16.5. Planar Dislocation Cores: Case of FCC Dislocations

16.6. High-Peierls Stress Dislocations: Case of BCC Screw Dislocations

Appendix 1.

17. Plastic Deformation of Metals and Alloys

17.1. Introduction

17.2. Plastic Deformation Processes

17.3. Role of Dislocations in Plastic Deformation

17.4. Experimental Techniques for Characterization

17.5. Development of Deformation Microstructures

17.6. Slip System Dependence

17.7. Microstructure and Local Texture

17.8. Hot Deformation

17.9. Influence of Second-Phase Particles on Structure

17.10. Structure/Mechanical Property Relationships, and Modeling

17.11. Conclusion and Outlook

18. Fatigue of Metals

18.1. Introduction: History, Fatigue Approaches and Nomenclature

18.2. Fatigue Testing

18.3. Performance Parameters of Fatigue

18.4. Cyclic Deformation

18.5. Fatigue Crack Initiation in Ductile Metals

18.6. Fatigue Crack Propagation

18.7. Additional Topics

19. Magnetic Properties of Metals and Alloys

19.1. Magnetic Field Quantities and Properties Survey

19.2. Magnetic Domains and the Magnetization Process

19.3. Alloy Survey

19.4. Current and Emerging Areas

19.5. Further Reading

Volume III

20. Physical Metallurgy of Light Alloys

20.1. Introduction

20.2. Precipitation and Age Hardening

20.3. Aluminum Alloys

20.4. Magnesium Alloys

20.5. Titanium Alloys

21. Physical Metallurgy of Steels

21.1. Introduction

21.2. Martensite in Steels

21.3. Bainite in Steels

21.4. Alloy Design: Strong Bainite

21.5. Widmanstätten Ferrite

21.6. Allotriomorphic Ferrite

21.7. Pearlite

21.8. Overall Transformation Kinetics

21.9. TRIP Steels

21.10. TWIP Steels

21.11. Transformation Plasticity and Mitigation of Residual Stress

21.12. Bulk Nanostructured Steel

22. Physical Metallurgy of the Nickel-Based Superalloys

22.1. Introduction

22.2. Structure and Constitution of the Superalloys

22.3. Planar, Line and Point Defects in the Superalloys

22.4. Strengthening Mechanisms in Nickel-Based Superalloys

22.5. Single-Crystal Superalloys

22.6. Summary and Conclusions

23. Recovery and Recrystallization: Phenomena, Physics, Models, Simulation

23.1. Phenomena, Terminology, and Methods: Recovery and Recrystallization

23.2. Recovery

23.3. Recrystallization

23.4. Driving Forces of Recrystallization and Grain-Growth Phenomena

23.5. Dynamic and Metadynamic Recrystallization

23.6. Grain Growth

23.7. Secondary Recrystallization: Discontinuous Grain Coarsening

23.8. Phenomenological Kinetics of Recrystallization

23.9. Modeling Recrystallization and Grain-Growth Phenomena

24. Porous Metals

24.1. Introduction

24.2. Processing

24.3. Structure

24.4. Physical Properties

24.5. Mechanical Behavior

24.6. Conclusion

25. Hydrogen in Metals

25.1. Introduction

25.2. Fundamentals

25.3. Hydrogen in Defective Metals

25.4. Hydrogen in Nanosized Systems: Thin Films, Multilayers and Clusters

26. Physical Metallurgy of Nanocrystalline Metals

26.1. Introduction

26.2. Basic Concepts

26.3. Synthesis Options

26.4. Microstructure Aspects

26.5. Diffusion Characteristics

26.6. Plastic Deformation of Ultrafine-Grained and Nanocrystalline Metallic Materials

26.7. Phase Transformations in Nanocrystalline Metals

26.8. Selected Examples of Application-Related Microstructure–Property Relations

26.9. Open Issues and Future Perspectives

27. Computational Metallurgy

27.1. Introduction

27.2. Structures and Properties of Single Crystals and Interfaces

27.3. Stability and Evolution of Microstructures

27.4. Responses of a Microstructure under an Applied Field and Effective Properties

27.5. Summary

Index

Copyright of Volume I

Elsevier

Radarweg 29, PO Box 211, 1000 AE Amsterdam, Netherlands

The Boulevard, Langford Lane, Kidlington, Oxford OX5 1GB, UK

225 Wyman Street, Waltham, MA 02451, USA

Fifth edition

© 2014 Elsevier B.V. All rights reserved.

No part of this publication may be reproduced, stored in a retrieval system or transmitted in any form or by any means electronic, mechanical, photocopying, recording or otherwise without the prior written permission of the publisher.

Permissions may be sought directly from Elsevier’s Science & Technology Rights Department in Oxford, UK: phone (+44) (0) 1865 843830; fax (+44) (0) 1865 853333; email: permissions@elsevier.com. Alternatively you can submit your request online by visiting the Elsevier web site at http://elsevier.com/locate/permissions, and selecting Obtaining permission to use Elsevier material.

Notice

No responsibility is assumed by the publisher for any injury and/or damage to persons or property as a matter of products liability, negligence or otherwise, or from any use or operation of any methods, products, instructions or ideas contained in the material herein. Because of rapid advances in the medical sciences, in particular, independent verification of diagnoses and drug dosages should be made.

British Library Cataloguing in Publication Data

A catalogue record for this book is available from the British Library

Library of Congress Cataloging in Publication Data

A catalog record for this book is available from the Library of Congress

Volume I ISBN: 978-0-444-59598-0

SET ISBN: 978-0-444-53770-6

For information on all Elsevier publications visit our website at www.store.elsevier.com

Printed and bound in the UK

Copyright of Volume II

Elsevier

Radarweg 29, PO Box 211, 1000 AE Amsterdam, Netherlands

The Boulevard, Langford Lane, Kidlington, Oxford OX5 1GB, UK

225 Wyman Street, Waltham, MA 02451, USA

Fifth edition

© 2014 Elsevier B.V. All rights reserved.

No part of this publication may be reproduced, stored in a retrieval system or transmitted in any form or by any means electronic, mechanical, photocopying, recording or otherwise without the prior written permission of the publisher.

Permissions may be sought directly from Elsevier’s Science & Technology Rights Department in Oxford, UK: phone (+44) (0) 1865 843830; fax (+44) (0) 1865 853333; email: permissions@elsevier.com. Alternatively you can submit your request online by visiting the Elsevier web site at http://elsevier.com/locate/permissions, and selecting Obtaining permission to use Elsevier material.

Notice

No responsibility is assumed by the publisher for any injury and/or damage to persons or property as a matter of products liability, negligence or otherwise, or from any use or operation of any methods, products, instructions or ideas contained in the material herein. Because of rapid advances in the medical sciences, in particular, independent verification of diagnoses and drug dosages should be made.

British Library Cataloguing in Publication Data

A catalogue record for this book is available from the British Library

Library of Congress Cataloging in Publication Data

A catalog record for this book is available from the Library of Congress

Volume II ISBN: 978-0-444-59597-3

SET ISBN: 978-0-444-53770-6

For information on all Elsevier publications visit our website at www.store.elsevier.com

Printed and bound in the UK

Copyright of Volume III

Elsevier

Radarweg 29, PO Box 211, 1000 AE Amsterdam, Netherlands

The Boulevard, Langford Lane, Kidlington, Oxford OX5 1GB, UK

225 Wyman Street, Waltham, MA 02451, USA

Fifth edition

© 2014 Elsevier B.V. All rights reserved.

No part of this publication may be reproduced, stored in a retrieval system or transmitted in any form or by any means electronic, mechanical, photocopying, recording or otherwise without the prior written permission of the publisher.

Permissions may be sought directly from Elsevier’s Science & Technology Rights Department in Oxford, UK: phone (+44) (0) 1865 843830; fax (+44) (0) 1865 853333; email: permissions@elsevier.com. Alternatively you can submit your request online by visiting the Elsevier web site at http://elsevier.com/locate/permissions, and selecting Obtaining permission to use Elsevier material.

Notice

No responsibility is assumed by the publisher for any injury and/or damage to persons or property as a matter of products liability, negligence or otherwise, or from any use or operation of any methods, products, instructions or ideas contained in the material herein. Because of rapid advances in the medical sciences, in particular, independent verification of diagnoses and drug dosages should be made.

British Library Cataloguing in Publication Data

A catalogue record for this book is available from the British Library

Library of Congress Cataloging in Publication Data

A catalog record for this book is available from the Library of Congress

Volume III ISBN: 978-0-444-59599-7

SET ISBN: 978-0-444-53770-6

For information on all Elsevier publications visit our website at www.store.elsevier.com

Printed and bound in the UK

List of Contributors to Volume I

Zoltan Balogh,     Institute of Materials Physics, University of Münster, Münster, Germany

Dilip K. Banerjee,     Materials Science and Engineering Division, Materials Measurement Laboratory, NIST, Gaithersburg, MD, USA

H.K.D.H. Bhadeshia,     University of Cambridge, UK

William J. Boettinger,     Materials Science and Engineering Division, Materials Measurement Laboratory, NIST, Gaithersburg, MD, USA

A.L. Greer,     Department of Materials Science & Metallurgy, University of Cambridge, Cambridge, UK

NUMAKURA Hiroshi,     Department of Materials Science, Osaka Prefecture University, Naka-ku, Sakai, Japan

M. Inukai,     Toyota Technological Institute, Nagoya, Japan

David E. Laughlin,     Department of Materials Science and Engineering, Carnegie Mellon University, Pittsburgh, PA, USA

U. Mizutani,     Nagoya Industrial Science Research Institute, Nagoya, Japan

Arthur D. Pelton,     Centre de Recherche en Calcul Thermochimique (CRCT), École Polytechnique de Montréal, Montréal, Canada

H. Sato,     Aichi University of Education, Kariya-shi, Aichi, Japan

Guido Schmitz,     Institute of Materials Physics, University of Münster, Münster, Germany

W.A. Soffa,     Department of Materials Science and Engineering, University of Virginia, USA

Walter Steurer,     Laboratory of Crystallography, ETH Zurich, Zurich, Switzerland

C.M. Wayman,     Deceased but originally from University of Illinois at Urbana-Champaign, USA

E.S. Zijlstra,     Theoretical Physics, University of Kassel, Kassel, Germany

List of Contributors to Volume II

S.S. Babu,     The University of Tennessee, Knoxville, Tennessee, USA

C.Y. Barlow,     Institute for Manufacturing, University of Cambridge, Cambridge, UK

Katayun Barmak,     Columbia University, New York, NY, USA

Joël Bonneville email address: joel.bonneville@univ-poitiers.fr,     Département de Physique et Mécanique des Matériaux, Institut P’, Université de Poitiers, CNRS UPR 3346, France

Hamish L. Fraser,     Center for Electron Microscopy and Analysis (CEMAS), Department of Materials Science and Engineering, The Ohio State University, Columbus, OH, USA

N. Hansen,     Danish–Chinese Center for Nanometals, Section for Materials Science and Advanced Characterization, Technical University of Denmark, Roskilde, Denmark

K. Hono,     National Institute of Materials Science, Tsukuba, Japan

James M. Howe email address: jh9s@virginia.edu,     Department of Materials Science and Engineering, University of Virginia, Charlottesville, VA, USA

Gernot Kostorz email address: kostorz@emeritus.ethz.ch,     ETH Zurich, Department of Physics, Auguste-Piccard-Hof 1, Zurich, Switzerland

Campbell Laird,     Department of Materials Science and Engineering, University of Pennsylvania, Philadelphia, PA, USA

David E. Laughlin,     Department of Materials Science and Engineering, Carnegie Mellon University, Pittsburgh, PA, USA

David W. McComb,     Center for Electron Microscopy and Analysis (CEMAS), Department of Materials Science and Engineering, The Ohio State University, Columbus, OH, USA

Michael E. McHenry,     Department of Materials Science and Engineering, Carnegie Mellon University, Pittsburgh, PA, USA

Pedro Peralta,     School for Engineering of Matter, Transport and Energy, Arizona State University, Tempe, AZ, USA

W.T. Reynolds,     Virginia Tech, Blacksburg, VA, USA

David Rodney email address: david.rodney@grenoble-inp.fr,     Institut Lumière Matière, Université Lyon 1, CNRS UMR 5306, France

Anthony D. Rollett,     Carnegie Mellon University, Pittsburgh, PA, USA

G. Spanos,     The Minerals, Metals, and Materials Society, Warrendale, PA, USA

Robert E.A. Williams,     Center for Electron Microscopy and Analysis (CEMAS), Department of Materials Science and Engineering, The Ohio State University, Columbus, OH, USA

List of Contributors to Volume III

H.K.D.H. Bhadeshia,     University of Cambridge, UK

Long-Qing Chen,     Department of Materials Science and Engineering, The Pennsylvania State University, University Park, PA, USA

Russell Goodall,     Department of Materials Science and Engineering, University of Sheffield, Sheffield, United Kingdom

Yijia Gu,     Department of Materials Science and Engineering, The Pennsylvania State University, University Park, PA, USA

R. Kirchheim,     Institut für Materialphysik, Georg-August-Universität Göttingen, Göttingen, Germany

Andreas Mortensen,     Laboratory for Mechanical Metallurgy, Ecole Polytechnique Fédérale de Lausanne (EPFL), EPFL–STI–IMX–LMM, MXD 140 (Bâtiment MX), Lausanne, Switzerland

Jian-Feng Nie,     Department of Materials Engineering, Monash University, Clayton, VIC, Australia

A. Pundt,     Institut für Materialphysik, Georg-August-Universität Göttingen, Göttingen, Germany

Dierk Raabe email address: d.raabe@mpie.de,     Max-Planck-Institut für Eisenforschung, Düsseldorf, Germany

C.M.F. Rae,     Department of Materials Science and Metallurgy, University of Cambridge, Cambridge, UK

R.C. Reed,     Department of Materials, University of Oxford, Oxford, UK

Gerhard Wilde,     Institute of Materials Physics, University of Münster, Münster, Germany

Preface to the Fifth Edition

These three volumes represent the fifth edition of Physical Metallurgy, a prestigious and famous family formerly edited by Robert Cahn (University of Cambridge) and Peter Haasen (Universität Göttingen). Physical Metallurgy was first published as a single volume in 1965. See the preface to the fourth edition for a history of this series. It is an authoritative reference tool, providing a complete knowledge set in Physical Metallurgy, the largest discipline in the fields of Materials Science and Engineering. This series describes and explains most aspects of physical metallurgy across the full breadth and in considerable depth. Each article has been either rewritten by new authors, or thoroughly revised and expanded, either by the 4th edition authors alone or jointly with new co-authors.

In the preface to the first edition of Physical Metallurgy, the founding editor of this series stated that Physical metallurgy is the root from which the modern science of materials has principally sprung. (R. W. Cahn (1965), Physical Metallurgy North Holland Publishing Company, Amsterdam-London). Over the next five decades this has continued to ring true. While both of the editors of this edition were educated as physical metallurgists, nowadays it is more common to call ourselves Materials Scientists, and indeed our respective departments do not utilize the word metallurgy. But the core concept (or sometimes called its paradigm) of Materials Science, that the properties and performance of materials have their origin in their processing and resulting microstructure, is derived directly from Physical and Process Metallurgy. For an exhaustive history of Materials Science see The Coming of Materials Science by R. W. Cahn and compare this to A Brief History of the Science of Metals, by R. F. Mehl.

In the article The Historical Development of Physical Metallurgy by R. F. Mehl, which appeared in the first two editions of this series, Mehl wrote: "Physical Metallurgy has been … interwoven with Extractive Metallurgy, and for a long time, historically, these two branches constituted a common art, practiced by the same artisans…" Early in 2014 there appeared the three volume Treatise on Process Metallurgy, edited by Seshadri Seetharaman and also published by ELSEVIER, which may be said to be the companion to this set. These six volumes certainly cover Metallurgy comprehensively.

This fifth edition of Physical Metallurgy is published some eighteen years after the 4th edition of this series, which was published in 1996. The lamented death of the founding editor in 2007 slowed down the appearance of this 5th edition. Finally we are ready to present the 5th edition.

This edition has a more international flavor to the listing of authors. Indeed in this 21st Century the ease with which correspondence can be sent makes the task of editing easier. It does not seem to speed up the writing and response of all authors however!

Several new subjects were added in this edition to update the progress in physical metallurgy in the last 18 years. Several of the chapters are written by the same authors as those in the fourth edition; but they have all been updated to include new topics and approaches.

We do thank the 45 authors for their hard work and diligence to get their chapters and proofs in. It is of course to authors, more than the current editors, that a series such as this gets its reputation. In a day when bean counters in our institutions do not always appreciate the work that goes into writing a chapter in a series such as this, we are grateful that each of the authors put that aside and wrote up work about which they are experts, whether or not it gets indexed in the Web of Science!

In 1970 one of the editors of these volumes (DEL) studied for his qualifying examinations for entrance into the Ph.D. program from the first edition of the series of Physical Metallurgy. Little did he suspect that nearly five decades later he would be editing the 5th edition to this well received series on Physical Metallurgy.

We wish to dedicate these volumes to our predecessor editors: Prof. Robert W. Cahn and Prof. Peter Haasen. We trust that our efforts in the continuation of this series will be up to the high standards which they have set.

David E. Laughlin,     ALCOA Professor of Physical, Metallurgy, Department of Materials Science and Engineering, Carnegie Mellon University, Pittsburgh, PA USA

Kazuhiro Hono,     ZNIMS Fellow, Naitonal Institute for Materials Science, Tsukuba, 305-0047, Japan

Preface to the Fourth Edition

The first, single-volume edition of this Work was published in 1965 and the second in 1970; continued demand prompted a third edition in two volumes which appeared in 1983. The first two editions were edited by myself alone, but in preparing the third, which was much longer and more complex, I had the crucial help of Peter Haasen as co-editor. The third edition came out in 1983, and sold steadily, so that the publishers were motivated to propose the preparation of yet another version of the Work; we began the joint planning for this in early 1992. We agreed on the changes and additions we wished to make: the responsibility for commissioning chapters was divided equally between us, but the many policy decisions, made during a series of face-to-face discussions, were very much a joint enterprise. Peter Haasen was able to commission all the chapters which he had agreed to handle, and this task (which involved detailed discussions with a number of authors) was completed in early 1993. Thereupon, in May 1993, my friend of many years was suddenly taken ill; the illness worsened rapidly, and in October of the same year he died, at the early age of 66. When he was already suffering the ravages of his fatal illness, he yet found the resolve and energy to revise his own chapter and to send it to me for comments, and to modify it further in the light of those comments. He was also able to examine, edit and approve the revised chapter on dislocations, which came in early. These were the very last professional tasks he performed. Peter Haasen was in every sense co-editor of this new edition, even though fate decreed that I had to complete the editing and approval of most of the Chapter I am proud to share the title-page with such an eminent physicist.

The first edition had 22 chapters and the second, 23. There were 31 chapters in the third edition and the present edition has 32. The first two editions were single volumes, the third had to be divided into two volumes, and now the further expansion of the text has made it necessary to go to three volumes. This fourth edition is nearly three times the size of the first edition 30 years ago; this is due not only to the addition of new topics, but also to the fact that the treatment of existing topics has become much more substantial than it was in 1965. There are those who express the conviction that physical metallurgy has passed its apogee and is in steady decline; the experience of editing this edition, and the problems I have encountered in holding enthusiastic authors back from even more lengthy treatments (to avoid exceeding the agreed page limits by a wholly unacceptable margin), have shown me how mistaken this pessimistic assessment is! Physical metallurgy, the parent discipline of materials science, has maintained its central status undiminished.

The first three editions each opened with a historical overview. We decided to omit this in the fourth edition, for two main reasons: the original author had died and it would have fallen to others to revise his work, never an entirely satisfactory proceeding; it had also become plain (especially from the reaction of the translators of the earlier editions into Russian) that the overview was not well balanced between different parts of the world. I am engaged in writing a history of materials science, as a separate venture, and this will incorporate proper attention to the history of physical metallurgy as a principal constituent. — It also proved necessary to leave out the chapter on superconducting alloys: the ceramic superconductor revolution has virtually removed this whole field from the purview of physical metallurgy. — Three entirely new topics are treated in this edition: one is oxidation, hot (dry) corrosion and protection of metallic materials, another is the dislocation theory of the mechanical behavior of intermetallic compounds. The third new topic is a leap into very unfamiliar territory: it is entitled A Metallurgist's Guide to Polymers. Many metallurgists — including Alan Windle, the author of this chapter — have converted in the course of their careers to the study of the more physical aspects of polymers (regarded by many materials scientists as the materials of the future), and have had to come to terms with novel concepts (such as semicrystallinity) which they had not encountered in metals: Windle's chapter is devoted to analysing in some depth the conceptual differences between metallurgy and polymer science, for instance, the quite different principles which govern alloy formation in the two classes of materials. I believe that this is the first treatment of this kind.

Six of the existing chapters (now numbered 1, 4, 21, 22, 27, 30) have been entrusted to new authors, while another five chapters have been revised by the previous authors with the collaboration of additional authors (8,13,16, 17, 19). Chapter 19, originally entitled Alloys rapidly quenched from the melt has been broadened and retitled Metastable states of alloys. A treatment of quasicrystals has been introduced in the form of an appendix to Chapter 4, which is devoted to the solid-state chemistry of intermetallic compounds; this seemed appropriate since quasicrystallinity is generally found in such compounds. — Only three chapters still have the same authors they had in the first edition, written some 32 years ago.

27 of the 29 new versions of existing chapters have been substantially revised, and many have been entirely recast. Two Chapters (11 and 25) have been reprinted as they were in the third edition, except for corrected cross-references to other chapters, but revision has been incorporated in the form of an Addendum to each of these chapters; this procedure was necessary on grounds of timing.

This edition has been written by a total of 44 authors, working in nine countries. It is a truly international effort.

I have prepared the subject index and am thus responsible for any inadequacies that may be found in it. I have also inserted some cross-references between chapters (internal cross- references within chapters are the responsibility of the various authors), but the function of such cross-references is better achieved by liberal use of the subject index.

As always, the editors have been well served by the exceedingly competent staff of North–Holland Physics Publishing (which is now an imprint of Elsevier Science B.V. in Amsterdam; at the time of the first two editions, North–Holland was still an independent company). My particular thanks go to Nanning van der Hoop and Michiel Bom on the administrative side, to Ruud de Boer who is responsible for production and to Chris Ryan and Maurine Alma who are charged with marketing. Mr. de Boer's care and devotion in getting the proofs just right have been extremely impressive. My special thanks also go to Professor Colin Humphreys, head of the department of materials science and metallurgy in Cambridge University, whose warm welcome and support for me in my retirement made the creation of this edition feasible. Finally, my thanks go to all the authors, who put up with good grace with the numerous forceful, sometimes impatient, messages which I was obliged to send in order to get the show on the road, and produced such outstanding chapters under pressure of time.

I am grateful to Dr. W.J. Boettinger, one of the authors, and his colleague Dr. James A. Warren, for kindly providing the computer-generated dendrite microstructure that features on the dust-cover.

The third edition was dedicated to the memory of Robert Franklin Mehl, the author of the historical chapter and a famed innovator in the early days of physical metallurgy in America. I would like to dedicate this fourth edition to the memory of two people: my late father-in- law, Daniel Hanson (1892–1953), professor of metallurgy at Birmingham University for many years, who did more than any other academic in Britain to foster the development and teaching of modern physical metallurgy; and the physical metallurgist and scientific publisher — and effective founder of Pergamon Press — Paul Rosbaud (1896–1963), who was retained by the then proprietor of the North–Holland Publishing Company as an adviser and in 1960, in the presence of the proprietor, eloquently urged upon me the need for a new, advanced, multiauthor text on physical metallurgy.

Robert W. Cahn,     Cambridge November 1995.

Preface to the Third Edition

The first edition of this book was published in 1965 and the second in 1970. The book continued to sell well during the 1970s and, once it was out of print, pressure developed for a new edition to be prepared. The subject had grown greatly during the 1970s and R. W. C. hesitated to undertake the task alone. He is immensely grateful to P. H. for converting into a pleasure what would otherwise have been an intolerable burden!

The second edition contained 22 chapters. In the present edition, 8 of these 22 have been thoroughly revised by the same authors as before, while the others have been entrusted to new contributors, some being divided into pairs of chapters. In addition, seven chapters have been commissioned on new themes. The difficult decision was taken to leave out the chapter on superpure metals and to replace it by one focused on solute segregation to interfaces and surfaces—a topic that has made major strides during the past decade and which is of great practical significance. A name index has also been added.

Research in physical metallurgy has become worldwide and this is reflected in the fact that the contributors to this edition live in no fewer than seven countries. We are proud to have been able to edit a truly international text, both of us having worked in several countries ourselves. We would like here to express our thanks to all our contributors for their hard and effective work, their promptness and their angelic patience with editorial pressures!

The length of the book has inevitably increased, by 50% over the second edition, which was itself 20% longer than the first edition. Even to contain the increase within these numbers has entailed draconian limitations and difficult choices; these were unavoidable if the book was not to be priced out of its market. Everything possible has been done by the editors and the publisher to keep the price to a minimum (to enable readers to take the advice of G. Chr. Lichtenberg (1775): He who has two pairs of trousers should pawn one and buy this book.).

Two kinds of chapters have been allowed priority in allocating space: those covering very active fields and those concerned with the most basic topics such as phase transformations, including solidification (a central theme of physical metallurgy), defects, and diffusion. Also, this time we have devoted more space to experimental methods and their underlying principles, microscopy in particular. Since there is a plethora of texts available on the standard aspects of X-ray diffraction, the chapter on X-ray and neutron scattering has been designed to emphasize less familiar aspects. Because of space limitations, we regretfully decided that we could not include a chapter on corrosion.

This revised and enlarged edition can properly be regarded as to all intents and purposes a new book.

Sometimes it was difficult to draw a sharp dividing line between physical metallurgy and process metallurgy, but we have done our best to observe the distinction and to restrict the book to its intended theme. Again, reference is inevitably made occasionally to nonmetallics, especially when they serve as model materials for metallic systems.

As before, the book is designed primarily for graduate students beginning research or undertaking advanced courses, and as a basis for more experienced research workers who require an overview of fields comparatively new to them, or with which they wish to renew contact after a gap of some years.

We should like to thank Ir J. Soutberg and Dr A. P. de Ruiter of the North-Holland Publishing Company for their major editorial and administrative contributions to the production of this edition, and in particular we acknowledge the good-humored resolve of Dr W. H. Wimmers, former managing director of the Company, to bring this third edition to fruition. We are grateful to Dr Bormann for preparing the subject index. We thank the hundreds of research workers who kindly gave permission for reproduction of their published illustrations: all are acknowledged in the figure captions.

Of the authors who contributed to the first edition, one is no longer alive: Robert Franklin Mehl, who wrote the introductory historical chapter. What he wrote has been left untouched in the present edition, but one of us has written a short supplement to bring the treatment up to date, and has updated the bibliography. Robert Mehl was one of the founders of the modern science of physical metallurgy, both through his direct scientific contributions and through his leadership and encouragement of many eminent metallurgists who at one time worked with him. We dedicate this third edition to his memory.

Robert W. Cahn,     Paris

Peter Haasen,     Göttingen. April 1983.

Preface to the First and Second Editions

This book sets forth in detail the present state of physical metallurgy, which is the root from which the modern science of materials has principally sprung. That science has burgeoned to such a degree that no author can do justice to it at an advanced level; accordingly, a number of well-known specialists have consented to write on the various principal branches, and the editor has been responsible for preserving a basic unity among the expert contributions. This book is the first general text, as distinct from research symposium, which has been conceived in this manner. While principally directed at senior undergraduates at universities and colleges of technology, the book is therefore also appropriate for postgraduates and particularly as a base for experienced research workers entering fields of physical metallurgy new to them.

Certain topics have been left to one side or treated at modest length, so as to limit the size of the book, but special stress has been placed on others, which have rarely been accorded much space. For instance, a good deal of space is devoted to the history of physical metallurgy, and to point defects, structure and mechanical properties of solid solutions, theory of phase transformations, recrystallization, superpure metals, ferromagnetic properties, and mechanical properties of two-phase alloys. These are all active fields of research. Experimental techniques, in particular diffraction methods, have been omitted for lack of space; these have been ably surveyed in a number of recent texts. An exception has however been made in favor of metallographic techniques since, electron microscopy apart, recent innovations have not been sufficiently treated in texts.

Each chapter is provided with a select list of books and reviews, which will enable readers to delve further into a particular subject. Internal cross-references and the general index will help to tie the various contributions together.

I should like here to acknowledge the sustained helpfulness and courtesy of the publisher's staff, and in particular of Mr A. T. G. van der Leij, and also the help provided by Prof P. Haasen and Dr T. B. Massalski in harmonizing several contributions.

Brighton, June 1965 (and again 1970)

R.W. Cahn

About the Editors

David E. Laughlin is the ALCOA Professor of Physical Metallurgy in the Department of Materials Science and Engineering at Carnegie Mellon University, Pittsburgh, PA. He obtained his B.S. in Metallurgical Engineering from Drexel University in 1969 and his Ph.D. in Metallurgy and Materials Science from MIT in 1973. He has taught at CMU since 1974. He is Principal Editor of Metallurgical and Materials Transactions and has co-edited eight books. His research has centered on the structure of materials as observed by electron microscopy, phase transformations and magnetic materials. He has published more than 450 peer reviewed research papers and is co-inventor on eleven US patents. Laughlin is a Fellow of TMS and ASM International.

Kazuhiro Hono is NIMS Fellow and Director of Magnetic Materials Unit at National Institute for Materials Science and Professor of Materials Science at the University of Tsukuba. He obtained his B.S. from Tohoku University in 1982, and Ph.D. in Materials Science and Engineering from the Pennsylvania State University in 1988. His research interests are mirostructure-property relationships of metallic materials, in particular of magnetic materials.

Volume I

Outline

1. Crystal Structures of Metallic Elements and Compounds

2. Electron Theory of Complex Metallic Alloys

3. Thermodynamics and Phase Diagrams

4. Metallic Glasses

5. Diffusion in Metals and Alloys

6. Defects in Metals

7. Solidification

8. Diffusional Phase Transformations in the Solid State

9. Phase Transformations: Nondiffusive

1

Crystal Structures of Metallic Elements and Compounds

Walter Steurer     Laboratory of Crystallography, ETH Zurich, Zurich, Switzerland

Abstract

Besides reviewing the most frequent structure types as well as those of technologically and commercially important materials, we will illustrate the major structural building principles on typical examples and underline interesting structural interrelationships wherever existing. We will exclusively discuss ideal structures of macroscopic single-crystalline elements and compounds in thermodynamic equilibrium and, consequently, will not deal with any size- or processing-related topics. First, some factors governing the formation of crystal structures, in general, are introduced. This is followed by a comprehensive discussion of the structures of the metallic elements and, subsequently, by a presentation of the most relevant (frequency, properties, didactical content) structure types of intermetallic phases. Finally, a few representative examples of the structures of quasicrystals will be given.

Keywords

Crystal structures; Metallic elements; Intermetallic phases

1.1 Introduction 2

1.2 Factors Governing Formation and Stability of Crystal Structures 5

1.3 Crystal Structures of the Metallic Elements 24

1.4 Crystal Structures of Intermetallic Phases 47

1.5 Crystal Structures of Quasicrystals 78

References 94

Further Reading List 100

Glossary

Allotrope

    Modification of an element at a given temperature and pressure range.

Alloy

    A homogenous mixture of two or more (inter)metallic phases that may form a solid solution or remain phase separated.

Aperiodic crystal

    The signature of ideal aperiodic crystals is that they show a pure-point Fourier spectrum (Bragg diffraction pattern) as periodic crystals do but have no translationally periodic structures. Examples are incommensurately modulated structures, composite (host/guest) structures and quasicrystals.

Atomic environment type (AET)

    Local coordination of an atom by the surrounding atoms (first coordination polyhedron).

Cluster

    Polyhedral arrangement of atoms in several cluster shells.

Crystal structure

    It is defined by its chemical composition, metrics (lattice parameters), space group symmetry, equipoint (Wyckoff) positions occupied by the different types of atoms (crystallographic orbits) and their specific coordinates in one asymmetric unit. The metrics may differ for all chemical compounds or phases adopting one particular structure type.

Intermetallic compound

    Special case of an intermetallic phase with sharply defined composition ("line compound").

Intermetallic phase

    A phase, constituted by two or more metallic elements, which may have a narrow or an extended compositional stability range.

Intermetallics

    Short form for intermetallic phase.

Pearson notation

    Symbol for the shorthand characterization of crystal structures in combination with the structure type. It consists of a lower-case letter denoting the crystal system, an upper-case letter giving Bravais lattice type and the number of atoms per unit cell.

Quasicrystal

    Intermetallic phase with noncrystallographic symmetry and quasiperiodic structure. The Fourier module of a quasiperiodic structure is of rank n  >  d, with d, the dimension of the quasiperiodic structure in physical space, and n, the number of basis vectors spanning the Fourier module.

Solid solution

    Solution of one or more elements in the structure of another element or of an intermetallic phase by substituting atoms without changing the structure type.

Sphere packing

    Infinite set of noninterpenetrating hard spheres with the property that any pair of spheres is connected by a chain of spheres with mutual contact. A sphere packing is called homogenous for all spheres being symmetrically equivalent, otherwise it is called heterogenous.

Structure type

    Crystal structure representing a whole set of similar crystal structures, i.e. structures with the same space group symmetry and atomic environment types (AET).

Superspace group

    The symmetry of modulated structures can be described by superspace groups. The symbol describing a (3  +  1)-dimensional superspace group, for instance, consists of the space group of the basic structure and the components of the modulation wave vector. For instance, the superspace group I4/mcm(00γ) refers to a tetragonal basic structure that is periodically distorted by a modulation wave along the [001] direction, i.e. along the fourfold axis.

Tiling

    A tessellation of the plane or the space where the unit tiles (copies of prototiles) fill the plane or space without gaps or overlaps.

-module

    A vector module of rank n is an infinite set of vectors resulting from all possible linear combinations of its n -module to emphasize that the coefficients of all linear vector combinations are integers.

1.1. Introduction

Intelligent materials design depends on a deep understanding of the relationships between chemical composition, crystal structure and physical properties. Particularly, in case of multiphase materials, the microstructure, which strongly depends on processing parameters, can drastically modify physical properties provided by individual components. One also has to keep in mind that structure and properties of materials on the nanoscale can strongly differ from those on the macroscale due to size effects. However, in the present chapter, we will exclusively discuss ideal structures of macroscopic single-crystalline elements and compounds in thermodynamic equilibrium and, consequently, will not have to deal with any size- or processing-related topics.

Although only a very few technologically and commercially important materials consist of metallic elements in their (almost) pure form such as Cu, Au, Ag, Pd, Pt, etc., their crystal structures are of more than academic interest. Just to give an example, the crystal structure of a pure metal remains unchanged if it forms a solid solution (single-phase alloy) when one or several other elements are added for tuning or modifying its properties. This technique has been used since time immemorial by alloying gold with copper or silver, for instance, to make jewelry or coins more mechanically resistant. Especially, closest packed structures and their derivatives, typical for many metallic elements, are also characteristic for numerous materials consisting of multicomponent solid solutions.

Even though elements are chemically simpler model systems than intermetallic phases, their structures can be quite complex, mainly originating from intricate electronic interactions. Most elements are polymorphous, i.e. they adopt several different crystal structures as a function of ambient conditions (temperature, pressure, …). The understanding of the phase transformations in these homoatomic cases is not only of interest on its own but also very helpful for understanding in general why a phase with given chemical composition is adopting a particular crystal structure under given conditions.

The structural chemistry and crystallography of intermetallic phases is incredibly rich. More than 2000 different structure types are known, with the number of atoms per unit cell ranging between one and more than 20,000; in the case of aperiodic crystals such as incommensurate structures, composite crystals or quasicrystals (QCs), three-dimensional (3D) unit cells even do not exist at all. However, only a comparably small number of intermetallics have found so far important applications since their physical properties have rarely been studied in the past. Well known is the usage of some intermetallics as strengthening phases in precipitation hardening systems such as LiAl3 in Al–Li alloys or Ni3Al in superalloys (both of the cP4-AuCu3 type). There are also several intermetallic phases known that have important applications as functional materials such as cP8-Cr3Si (A15)-type structures as superconductors (Nb3Sn), cF24-Cu2Mg-type Laves phases as magnetostrictive materials (Terfenol D) or hP6-CaCu5-type structures as powerful permanent magnets (SmCo5).

Neither is it possible nor would it make sense to discuss all structure types of intermetallic phases in a similar way as we do for the metallic elements; their crystallographic data can be found in Pearson’s Handbook of Crystallographic Data for Intermetallic Phases (Villars and Calvert, 1991) or in the database Pearson’s Crystal Data (Villars and Cenzual, 2011), anyway. Besides reviewing the most frequent structure types as well as those of technologically and commercially important materials, we will illustrate the major structural building principles on typical examples and underline interesting structural interrelationships wherever existing.

The visualization of a crystal structure usually aims at elucidating the structural building principles in as general as possible way. In case of intermetallic phases, contrary to ionic or molecular crystals, the chosen visualization is not always reflecting the sometimes very complex underlying crystal-chemical reality. However, it provides a very useful construction kit that can make clear complex packing principles or structural relationships, particularly, if different visualization tools are applied to one and the same structure:

• Ball-and-stick model for highlighting atomic connectivity.

• Space-filling atomic representation for illustrating the packing density.

• Polyhedra model for depicting atomic environment types (AET) and their connectivity.

• Cluster model for visualizing the packing of larger structural subunits.

• Layer decomposition for demonstrating the modularity.

• Framework representation to emphasize the role of substructures.

Some comments to our terminology: by intermetallic compound, we mean a phase, constituted by two or more metallic elements, with sharply defined composition ("line compound"), while the compositional stability range of an intermetallic phase in general may be extended; a solid solution is formed if an element or an intermetallic phase can dissolve one or more elements that are not constituents of the base element or intermetallic phase; by alloy, we denote a mixture of two or more (inter)metallic phases that remain phase separated; the short form "intermetallics" will be used for both intermetallic compounds and intermetallic phases. The arrangement of elements in the chemical formula of a compound, AxByCz…, follows increasing Mendeleev numbers (Table 1) MA  <  MB  <  MC <… These numbers are related to a chemical scale χ introduced by Pettifor (1988 and references therein) mainly for the derivation of structure maps.

For the shorthand characterization of crystal structures, the Pearson notation in combination with the prototype formula defining the structure type is used throughout this chapter. In accordance with the IUPAC recommendations (Leigh, 1990), the old Strukturbericht designation (A3 for hP2-Mg, for instance) should not be used any longer. A comparison of the Pearson notation, prototype formula, space group and Strukturbericht designation for a large number of crystal structure types is given in Massalski (1990), for instance.

The Pearson symbol consists of two italic letters and a number. The first (lower case) letter denotes the crystal family and the second (upper case) letter, the Bravais lattice type (Table 2). The symbol is completed by the number of atoms in the unit cell. The symbol cF4, for instance, classifies a structure type to be cubic (c), all-face centered (F) with four atoms per unit cell. In the case of rhombohedral structures such as the hR3-Sm type, for instance, the number of atoms per unit cell in the rhombohedral setting (a  =  b  =  c, α  =  β  =  γ  ≠  90°) is given. This notation is used by Villars and Calvert (1991), Villars and Cenzual (2011) and Daams et al. (1991) in all their large databases. The number of atoms in the corresponding hexagonal setting (a  =  b  ≠  c, α  =  β  =  90°, γ  =  120°) would be three times as large and hR3-Sm would be given as hR9-Sm. Unfortunately, in the literature, both notations are used without further explanation.

Table 1

Periodic table of the elements. The structures of the elements below the thick line and with Z  ≤  103 are discussed in this chapter. Ge, Sb and Po are included, although usually considered as metalloids or semimetals, because they can form compounds with metallic character. Above each element the atomic number Z is given, below the Mendeleev number M (Pettifor, 1988) is listed

Table 2

Meaning of the letters included in the Pearson Symbol. In case of symbols of the type hRn, we use the symbol in the same way as it is done by Villars and Calvert (1991): n means the number of atoms in the rhombohedral unit cell, i.e., 1/3 of that in the hexagonal setting

We will use the Pearson symbol for characterizing a structure type, for instance, cI2-W. We use it as well if we want to denote a particular modification of an element such as cI2-Li, for example, which has the cI2-W structure type. If several different structure types have the same Pearson symbol, then we explicitly name the structure type in addition. To give an example, tI2-Hg has the tI2-Pa structure and not that of tI2-In.

This chapter contains four main sections. First, some factors governing the formation of crystal structures, in general, are introduced. This is followed by a comprehensive discussion of the structures of the metallic elements and, subsequently, by a presentation of the most relevant (frequency, properties, didactical content) structure types of intermetallic phases. Finally, a few representative examples of the structures of QCs will be given.

1.2. Factors Governing Formation and Stability of Crystal Structures

Crystalline order is the outstanding characteristics of condensed matter in thermodynamic equilibrium. It is usually realized in the form of a 3D translationally periodic repetition of a particular atomic configuration (recurrent structural subunit). However, crystalline order is also present in aperiodic crystals with incommensurately modulated structures, composite or host/guest structures as well as in quasiperiodic structures. The term aperiodic crystals refers to the fact that these structures can be described as irrational 3D sections of virtual nD (n  >  3) periodic hypercrystals. The signature of ideal aperiodic crystals is that they show a pure-point Fourier spectrum (Bragg diffraction pattern) as periodic crystals do.

The kind of atomic interactions (chemical bonding), the electronic band structure and geometrical factors, such as atomic size ratios and packing density, determine which kind of crystal structure has the lowest Gibbs free energy, G  =  H  −  TS, for a given chemical composition and temperature/pressure. At finite temperature, entropical contributions from atomic vibrations or intrinsic structural disorder can also be crucial for the stability of a structure. This particularly applies to the so-called high-entropy alloys (HEA), which are equiatomic solid solutions of four or more elements. Their usually simple body centered cubic (bcc) or face centered cubic (fcc) structures are stabilized by mixing entropy, preventing the formation of intermetallic phases at sufficiently high temperatures. There have been many attempts to predict the stability of crystal structures based on either first-principles calculations (Oganov et al., 2011; and references therein) or (semi)empirical parameters. Quite successful has been the prediction of stability fields of binary and some groups of ternary phases based on the Mendeleev numbers (Pettifor, 1986, 1988) and, additionally, some other empirical parameters (Villars et al., 2001).

For the study of chemical bonding and the electronic structure, first-principles calculations are indispensable. Since it is not possible to solve analytically the Schrödinger equation for a crystal, numerous approximations have been developed. In most approximations, the many electron problem is reduced to a one electron problem by the assumption that the electrons, surrounded by a mutual exclusion zone, are moving independently from each other in the average field of all other ones (local-density-functional approximation, LDA). This works quite well for modeling known structures up to a few hundred atoms per unit cell, depending on the kind of atoms involved. On the contrary, structure prediction based on first-principles calculations is much more computer time-consuming and still limited to a few tens of atoms per unit cell. Beside this powerful quantum-mechanical approach for understanding and predicting crystal structures, there are a number of useful methods and rules in use that cannot be considered here.

In the following, we want to discuss just a few aspects of two important factors crucial for structure formation: the chemical bond factor, which is particularly taking into account the directionality of chemical bonds, and the geometrical factor, which is considering optimum space filling, symmetry and connectivity. Under these aspects, a crystal structure is considered to result from packing optimization under the constraints imposed by chemical bonding. In case of metallic bonding, the stability of particular structures can be greatly enhanced by nonlocal interactions such as Fermi-surface/Brillouin-zone nesting, which can lead to the opening of (pseudo)gaps in the electronic density of states at the Fermi-energy (Hume-Rothery-type stabilization). Such structure-stabilizing pseudogaps can also be caused by hybridization effects in particular atomic configurations (clusters).

1.2.1. Chemical Bonding

The concept of chemical bonding interprets and explains formation and stability of molecules and/or crystals based on local interactions. These atomic interactions are usually described in terms of idealized limiting types of chemical bonding:

Ionic (heteropolar): isotropic electrostatic interaction between ions that can also consist of larger structural units (complexions, polyions).

Covalent (homeopolar): directed bonds based on electrons localized between the bonding partners, which have contributed all of them.

Metallic (delocalized): isotropic interactions based on delocalized electrons in which the ionized bonding partners, which have contributed all of them, are embedded.

van der Waals: (in case of atoms isotropic) dipole–dipole interactions, where the dipoles may be permanent or induced.

Hydrogen bonds: directed bonds based on a kind of resonance state of the H+ proton between two strongly electronegative atoms.

In the first approximation, the collective interaction of all atoms in a crystal may be replaced by the sum of nearest neighbor interactions. A further simplification comes in by the fact that only electrons of the outer electron shells (valence electrons) contribute to chemical bonding.

The types of bonding in crystals of the metallic elements at ambient conditions range from typical metallic in alkali metals to increasingly covalent for zinc or cadmium, for instance. The structural implications of these two bond types, which are just two contrary limiting manifestations of electronic interactions with a continuously changing degree of electron localization, shall be characterized in the following a bit more detailed.

The covalent bond may be described and illustrated in terms of the valence bond (VB) theory by overlapping atomic orbitals occupied by unpaired valence electrons. Its strength depends on the degree of overlapping and is given by the exchange integral. In terms of the linear combination of atomic orbitals–molecular orbitals (LCAO–MO) theory, molecular orbitals are constructed by linear combination of atomic orbitals. The resulting bonding, nonbonding and antibonding molecular orbitals, filled up with all valence electrons of the bonding partners according to the Pauli principle, are localized between the bonding atoms with well-defined geometry. Generally, covalent bonds can be characterized as strong, directed bonds.

Increasing the number of atoms contributing to the bonds increases the number of molecular orbitals and their energy differences become smaller and smaller. Finally, the discrete energy levels of the molecular orbitals condense to quasicontinuous bands separated by energy gaps. Since, in a covalent bond, each atom reaches its particular stable noble gas configuration (filled shell), the energy bands are either completely filled or empty. Due to the localization of the electrons, it needs much energy (several electron volt) to lift them from the last filled valence band into the empty conduction band. The classic example of a crystal built from only covalently bonded atoms is diamond: all carbon atoms are bonded via tetrahedrally directed sp³ hybrid orbitals. Thus, the crystal structure of diamond results as a framework of tetrahedrally coordinated carbon atoms.

The metallic bond can be described in a similar way as the covalent bond. The main difference between these two bonding types is that the ionization energy for electrons occupying the outer orbitals of the metallic elements is much smaller. In typical metals, such as the alkali metals, these outer orbitals are spherical s orbitals, allowing overlaps with up to 12 further s orbitals of the surrounding atoms. Thus, the well-defined electron localization in bonds, connecting pairs of atoms with each other, loses its meaning. Quantum mechanical calculations show that in large aggregates of metal atoms, the delocalized bonding electrons occupy lower energy levels than in the free atoms; this would not be true for isolated metal molecules. Thus, contrary to the other bond types that also can occur in isolated small molecules, metallic bonding can take place in larger arrays of atoms, only. The metallic bond in typical metals is nondirected, favoring structures based on closest sphere packings. With increasing localization of valence electrons, covalent interactions cause deviations from spherically symmetric bonding leading to more complex structures.

Since the interaction of electron orbitals of different atoms depends on their distance and mutual orientation, the bond type may change with the structure during phase transformations. An example is the transition from metallic white tin to nonmetallic gray tin (tin pest) that takes place at 286 K deteriorating organ pipes in churches that are not heated properly during winter time; another example is the transformation from molecular to metallic hydrogen under very high pressure.

1.2.2. Geometrical Factors

A crystal structure is fully defined by its chemical composition, metrics (lattice parameters), space-group symmetry, equipoint (Wyckoff) positions occupied by the different types of atoms (crystallographic orbits) and their specific coordinates in one asymmetric unit (Figure 1). The metrics may differ for all chemical compounds or phases adopting one particular structure type. Also, for general Wyckoff positions, the numerical values of the coordinates may vary in a range not destroying the characteristics of this crystal structure such as coordination polyhedra (AET) or clusters and their connectivity. In our crystallographic notation, we will use Miller indices in parentheses (h k l) and in braces {h k l} to denote lattice planes or sets of lattice planes symmetrically equivalent under the action of a point group, respectively; vector components in brackets [u v w] indicate lattice directions; lattice basis vectors are denoted by a, b, c in case of 3D periodic structures, and quasilattice vectors ai, i  =  1…n in case of quasiperiodic structures.

Figure 1   (a) Information given in the International Tables for Crystallography (. Left side, top line: space group symbol in short Hermann–Mauguin and in Schoenflies notation, point group (crystal class), crystal system. Second line: consecutive space group number, full Hermann–Mauguin space group symbol, Patterson symmetry and its short Hermann–Mauguin space group symbol. Upper drawing: projection along [001] of the framework of symmetry elements in a unique part of one unit cell (upper left quadrant in this case). Inclined reflection and glide planes around high-symmetry points are shown in their orthographic projection. Lower drawings: point complexes generated by the action of symmetry operations in stereoscopic projection along [001] and rotated by 6° and 12°, respectively. Below: unit-cell origin and its site symmetry, definition of the asymmetric unit. (b) Sets of symmetry operators and their orientation as well as generating symmetry operators. Below: information about the different equipoint positions. The Wyckoff letters a, b, c, …, i denote the equipoint positions with multiplicities 4, 4, 96, and their respective site symmetries. The reflection conditions in the right column refer to systematically extinct Bragg reflections in diffraction experiments.

For the comparison of different crystal structure types, clear definitions of some terms are necessary (Lima-de-Faria et al., 1990):

Isopointal: two structures are isopointal if they have the same space-group type, and the atomic (Wyckoff) positions, occupied either fully or partially at random, are the same in both structures; as there are no limitations on the values of the adjustable parameters of the Wyckoff positions or on the cell parameters, isopointal structures may have locally different geometric arrangements and atomic coordinations (AET) and may belong to different structure types.

    An example for isopointal structure types are tI2-In and tI2-Pa (Figure 2).

Figure 2   Comparison between the isopointal structures of (b) tI2-In and (d) tI2-Pa and their AET, (b) a cuboctahedron (coordination number CN12) and (d) a rhombdodecahedron (CN14). Due to the strongly differing axial ratios c/a of 1.522 for tI2-In, one for cF4-Cu and 0.824 for tI2-Pa, their AET differ significantly as well. As their AET show, the structure of tI2-In is closer to the cF4-Cu type (a), and that of tI2-Pa is closer to the cI2-W type (c). The distances histograms for (e) tI2-In and (f) tI2-Pa differ significantly from each other: the first big gap appears after 12 atoms in (e) and after 14 atoms in (f). Since the first 10 atoms in (f) have almost the same distances from the center, the first big gap opens after 14 atoms.

Isoconfigurational: two structures are configurationally isotypic if they are isopointal and both the crystallographic point configurations (crystallographic orbits) and their geometrical interrelationships are