Complex Metallic Alloys E-Book

• Herausgeber: Wiley-VCH
• Kategorie: Wissenschaft und neue Technologien
• Sprache: Englisch

Seitenzahl: 812

Veröffentlichungsjahr: 2010

Beschreibung

Covering fundamental research as well as real-world applications, this first book on CMAs at an introductory level treats everything from atomistic details to surface processing. Comprehensive, self-contained chapters provide readers with the latest knowledge on the most salient features of the topic, selected in terms of their relevance to potential technological applications. Edited by one of the most distinguished authorities on quasicrystals and this most important of their subclasses, the contributions elucidate aspects of CMAs from a particular viewpoint: physical and chemical characteristics in the sub-nanometer regime, mesoscale phenomena, preparation and processing of thin films, and large-scale engineering properties. The whole is rounded off by a look at the commercial potential of CMA-based applications. For PhD students and lecturers alike.

Leseprobe

Contents

Cover

Related Titles

Title Page

Copyright

Foreword

References

Preface

List of Contributors

Chapter 1: Introduction to the Science of Complex Metallic Alloys

1.1 Introduction

1.2 Complex Metallic Alloy: What Is It?

1.3 Complex Metallic Alloy: Why Is It Complex?

1.4 A Brief Survey of Properties

1.5 Potential Applications

1.6 Conclusion and Introduction of the Following Chapters

Acknowledgments

References

Chapter 2: Properties of CMAs: Theory and Experiments

2.1 Introduction

2.2 Electronic-Structure-Related Properties

2.3 Phonons

2.4 Conclusion

References

Chapter 3: Anisotropic Physical Properties of Complex Metallic Alloys

3.1 Introduction

3.2 Structural Considerations and Sample Preparation

3.3 Anisotropic Magnetic Properties

3.4 Anisotropic Electrical Resistivity

3.5 Anisotropic Thermoelectric Power

3.6 Anisotropic Hall Coefficient

3.7 Anisotropic Thermal Conductivity

3.8 Fermi Surface and the Electronic Density of States

3.9 Theoretical Ab Initio Calculation of the Electronic Transport Coefficients

3.10 Conclusion

Acknowledgement

References

Chapter 4: Surface Science of Complex Metallic Alloys

4.1 Introduction

4.2 Surface-Structure Determination

4.3 Electronic Structure

4.4 Thin-Film Growth on CMA Surfaces

4.5 Adhesion, Friction and Wetting Properties of CMA Surfaces

4.6 Conclusion

Acknowledgments

References

Chapter 5: Metallurgy of Complex Metallic Alloys

5.1 Introduction

5.2 Basic Concepts of Crystal Growth

5.3 Examples of Single-Crystal Growth of CMAs

5.4 Introduction to Chemical Vapor Deposition of Coatings Containing CMAs

5.5 MOCVD Processing of Al-Cu-Fe Thin Films

5.6 Concluding Remarks

Acknowledgements

References

Chapter 6: Surface Chemistry of CMAs

6.1 Introduction

6.2 Surface Chemistry of CMAs Under UHV Environment

6.3 Atmospheric Aging

6.4 Surface Chemistry and Reactions in Aqueous Solutions

6.5 High-Temperature Corrosion

Conclusion

References

Chapter 7: Mechanical Engineering Properties of CMAs

7.1 Introduction

7.2 Structure and Mechanical Properties of CMAs

7.3 Metal Matrix Composites Reinforced with CMAs

7.4 Surface Mechanical Testing and Potential Applications

7.5 Conclusions

Acknowledgments

References

Chapter 8: CMA's as Magnetocaloric Materials

8.1 Introduction

8.2 Materials

8.3 Magnetocaloric Effect and Hysteresis Losses of CMAs

8.4 TEM Investigation of CMAs

8.5 Conclusions

Acknowledgments

References

Chapter 9: Recent Progress in the Development of Thermoelectric Materials with Complex Crystal Structures

9.1 Introduction

9.2 Thermoelectric Figure of Merit

9.3 Design Principles

9.4 Thermoelectric Materials

9.5 Concluding Remarks

References

Chapter 10: Complex Metallic Phases in Catalysis

10.1 Introduction

10.2 Why Use Intermetallic Compounds – The General Concept

10.3 The Semihydrogenation of Acetylene

10.4 Complex Metallic Phases as Platform Materials for Heterogeneous Catalysis

Acknowledgments

References

Index

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The Editors

Prof. Jean-Marie Dubois

Ecole des Mines de Nancy

FR2797 CNRS-INPL-UHP

Parc de Saurupt

54042 Nancy Cedex

France

Prof. Esther Belin-Ferré

Lab. Chimie Physique-Matière et Rayonnement

UMR CNRS-UPMC 7614

11, Rue Pierre et Marie Curie

75231 Paris Cedex 05

France

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ISBN: 978-3-527-32523-8

Foreword

The field of Complex Metallic Alloys can, although its roots reach back to the nineteen twenties, be considered one of the most recent research areas in modern materials science. The term Complex Metallic Alloys denotes a broad family of binary or multinary compounds consisting of either metallic elements or mixtures of metals to which metalloids, rare earth elements or chalcogenides are added. Their crystal structure is based on extraordinary large unit cells containing typically some ten to some hundred atoms. Cases with more than a thousand atoms per unit cell are also known. To understand how nature can organise such a high number of atoms into a highly ordered crystalline lattice presents a challenge to science as well as a chance to obtain new insights into the properties of condensed-matter systems. On the other hand the unusual structure gives rise to unusual physical properties with a potential for new technological applications.

In a pioneering paper published in 1923 Linus Pauling described for the first time the structure of an intermetallic compound [1]. He reported on an X-ray diffraction study of NaCd2. In spite of the apparently “harmless” stoichiometry the diffraction patterns of this crystal were so complicated, however, that it was not then possible to assign indices to many of the diffraction spots. Only more than thirty years later, in 1955, Pauling was able to publish a model of the structure [2] based on a cubic space group. Pauling's unit cell has an edge length of about 3 nm and contains 384 sodium and 768 cadmium atoms, making a total of 1152. For metallic materials this is a very large number. Apart from the cases of elementary metals with 2, 2, and, 4 atoms per unit cell for the body-centred cubic, hexagonal close packed and face-centred cubic structure, respectively, we have, for example, 4 atoms for the -phase, Ni3Al, 16 atoms for Fe3Al and the Heusler alloy AlCu2Mn, and 52 atoms per unit cell in the -brass phase, Cu5Zn8. For these new structures the term “giant unit cell crystals” was coined by Sten Samson, another pioneer in the field of intermetallic compounds [3]. Inside the giant unit cells a cluster substructure exists. For example, there is a large group of alloys based on the 55 atom Mackay icosahedron, another group is based on the 105 atom Bergman cluster [4]. Today hundreds of such compounds are known whose structures are based on giant unit cells [5]. However, taking into account that in each new ternary phase diagram studied, more phases based on giant unit cells are found, their number should run into thousands.

Although crystallographers learned to solve these challenging giant unit cell structures the field was essentially abandoned during the nineteen seventies. The primary reason for this was that the tiny single crystals sufficient for structure determination were by far not enough for physical property studies which could have, on the long run, justified the effort. The growth of larger single crystals as a pre-requisite for studies into the intrinsic properties of these compounds was far outside the scope of what metallurgy was able to do at that time. Furthermore, in the pre-computer age, solid-state theory was not developed enough to justify hopes that such systems could ever be understood.

The momentum for the rediscovery of giant unit cell compounds was provided by Danny Shechtman's discovery of the quasicrystalline form of solid matter [6]. In fact quasicrystals and giant unit cell compounds share a number of common structural features, the most prominent being the internal cluster substructure. In a sense quasicrystals can be considered giant unit cell structures with an infinitely large unit cell. Indeed considerable progress in the development of models for the structure of quasicrystals was made starting from the known structure of related giant unit cell intermetallics. Nevertheless, giant unit cell intermetallics were for a long time not considered a field of materials science of its own. The term “approximants (to the quasicrystal structure)” indicated that the essentially crystallographic interest was limited to an auxiliary part to be played in the quest for a solution of the structure of quasicrystals. This changed with a programmatic lecture [7] on “Structurally Complex Alloy Phases” given on September 9th, 2002 on the “Eighth International Conference on Quasicrystals” in Bangalore, India, which was meant as an appeal to dedicate intensive research efforts to “one of the last white spots on the map of metal physics”. Today, last but not least, after more than two decades of quasicrystal research, the tools are available to deal with giant unit cell materials. Large single crystals can be grown for many systems allowing intrinsic physical property studies, and the last 30 to 40 years have seen an extraordinary development of solid-state theory allowing today to tackle the difficult consequences of the particular atom arrangement for all kinds of properties.

For purely practical reasons it appeared useful to change, sometime later on, from the term “Structurally Complex Alloy Phases” to “Complex Metallic Alloys” and the acronym “CMA” during the application for a European Network of Excellence in the 6th framework Programme of the European Union. There is no clear division line between the family of Complex Metallic Alloys and more conventional small-unit cell alloys, on the one end, and quasicrystalline alloys, on the other end. The authors of the present volume find it useful to leave the “boarders” open and to benefit from ideas growing on a wide platform accommodating also Zintl-phases, skutterudides, clathrates and Heusler-alloys.

To what extent it is useful to treat quasicrystals as a part of the Complex Metallic Alloy family remains to be seen. From a phenomenological point of view it is useful to define two physical correlation lengths, one related to the lattice parameter, the other referring to correlation effects related to the cluster substructure inside the crystal unit cell. A division criterion between giant unit cell alloys and quasicrystalline phases can then be derived on the basis of the relative importance of the lattice-periodicity related correlation length for a particular feature or property of interest. Although this can help to better understand the properties of either type of atom arrangement, it has to be pointed out that things remain complicated. From an experimental point of view the attempts to construct a correlation between the size of the unit cell volume and the measured electronic density of states at the Fermi level provided valuable insight but they were not entirely successful. On the other hand, an ideal quasicrystal is fully long-range ordered. Its construction rules, although in principle simple in its six-dimensional reference lattice, are complicated in three-dimensional space. Therefore, to build up such a largely defect-free quasicrystal structure as observed experimentally, e.g. in the Al-Mn-Pd system, requires a long-range correlation of an even more stringent nature than that governing conventional crystal formation. In periodic crystals the symmetry of the individual building blocks is compatible with a periodic lattice and therefore both long-range and short-range atomic ordering are driving the system in the same direction. To build up a quasiperiodic lattice requires a long-range structural correlation length exceeding that occurring in conventional crystals.

The use of the term “complex” and the discussion of “complexity” in science is rapidly increasing in recent years. As already pointed out by Warren Weaver in his pioneering paper [8] this can be attributed, on the one hand, to an increasing awareness of the fact that sciences have in the past neglected complexity as a constitutive element of what is happening in nature and in society. On the other hand, sciences have developed to such an extent that phenomena too complex to be dealt with in the past can now be tackled employing the tools and techniques available today.

The field of Complex Metallic Alloys is typical for either group of arguments. Complex Metallic Alloys are characterised by their large crystal unit cells, by a pronounced cluster substructure with a large variety of coordination polyhedra and by inherent disorder both structurally and chemically as well as by partial site occupation, i.e. lattice sites are left vacant as a result of constraints of electronic origin and simple atom size effects. Furthermore, the recent work, in particular on plasticity, has shown that there is another very important feature of this class of materials and this is the existence of a high number of structurally similar phases within a very narrow region (a few atomic percent wide) of the thermodynamic phase diagram. These provide the system with an additional degree of freedom which is, for instance, used by nature in the formation of metadislocations and for plastic deformation. Often these phases differ so little from each other that it is difficult to isolate them and investigate them individually. And, typical for a complex system, the phenomenology of how these materials develop in time, temperature and composition space depends, in a way that is difficult to grasp, on kinetics as well as on the (difficult to define) starting and boundary conditions. A situation not much different from the situation described by Friedrich August von Hayek in his 1974 Nobel Prize Lecture for complexity in Economics [9] applies to such elementary physical phenomena as diffusion in giant unit cell materials. Although mass transport in Complex Metallic Alloys and quasicrystalline phases has been extensively studied experimentally, there is not even an idea how this transport occurs on an atomistic scale and of what nature the decisive variables are or how they can be properly defined maintaining the full complexity of the systems.

Seth Lloyd has compiled a list of about forty different measures of complexity that have been proposed in recent years. Melanie Mitchell, External Professor at the Santa Fe Institute dedicated to complexity research, comments: “…people are going to have to figure out how these diverse notions … are related to one another and how to most usefully refine the overly complex notion of complexity. This is work that largely remains to be done…” [10]. In the present volume, some of the authors directly or indirectly use as a measure for complexity the size of the crystal unit cell. Such type of measures have been discussed before and linked to Shannon Entropy, Algebraic Information Content, Thermodynamic Depth, Degree of Hierarchy and so forth [10]. As it is the case with all attempts to quantify complexity since Murray Gell-Mann's pioneering early paper [11] such definitions, although they may be useful at times, have still to stand the test of practical applicability and usefulness.

Apart from the general scientific insight gained by experimental and theoretical work on Complex Metallic Alloys this field has recently seen a number of surprising discoveries. Among these are particular transport properties, e.g. metallic, semiconducting electronic conductivity and isolating behaviour, the observation of superconductivity [12], the observation of a novel magnetic memory effect [13] and the observation of entirely new mechanisms of plastic deformation [14].

The current volume written by experts in the field of Complex Metallic Alloys gives in separate chapters an overview on the current state of research in this field as well as on first applications which provide excellent examples of the variety of properties. At the same time this book can serve as a comprehensive guide to the literature and as a starting point of further in-depth studies in the future.

References

1. Pauling, L. (1923) J. Am. Chem. Soc., 45, 2777.

2. Pauling, L. (1955) American Scientist, 43, 285.

3. Samson, S. (1969) in Developments in the Structural Chemistry of Alloys Phases (ed B.C. Giessen), Plenum, New York, p. 65.

4. Bergman, G., Waugh, J.L.T., and Pauling, L. (1957) Acta Crystallogr., 10, 254.

5. Villars, P. and Calvert, L.D. (1986) Pearson's Handbook of Crystallographic Data for Intermetallic Phases, American Society of Metals, Metals Park, OH.

6. Shechtman, D., Blech, I., Gratias, D., and Cahn, J. (1984) Phys. Rev. Lett.53, 951.

7. Urban K. and Feuerbacher, M. (2004) J. Non Cryst. Sol., 334–335, 143.

8. Weaver, W. (1948) American Scientist, 36, 536.

9. von Hayek, F.A. (1992) in Nobel Lectures, Economics 1969–1980 (ed A. Lindbeck), World Scientific Publishing Co., Singapore, p. 258.

10. Mitchell, M. (2009) Complexity – a Guided Tour, Oxford University Press, New York.

11. Gell-Mann, M. (1995) Complexity, 1, 16.

12. Bauer, E., Kaldarar, H., Lackner, R., Michor, H., Steiner, W., Scheidt, E.-W., Galatanu, A., Marabelli, F., Wazumi, T., Kumagai, K., and Feuerbacher, M. (2007) Phys. Rev. B, 76, 014528.

13. Dolinsek, J., Feuerbacher, M., Jagodic, M., Jaglicic, Z., Heggen, M., and Urban, K. (2009) J. Appl. Phys., 106, 043917.

14. Heggen, M., Houben, L., and Feuerbacher, M. (2010) Nature Materials, 9, 332.

Germany

September 2010

Knut W. Urban

JARA Senior Professor

RWTH Aachen

University & Research Centre Jülich

Preface

The European Network of Excellence CMA, for Complex Metallic Alloys, was active during the five years from July 2005 until the end of June 2010. It has assembled in a joint effort twenty research institutions based in twelve different European countries, with more than 500 individuals on board. The areas of focus were metallurgy and crystal growth, crystallography and defects, electronic, phononic and mechanical properties, surface physics and chemistry, surface treatment and coating technologies, as well as a number of applied topics such as composites, thermoelectricity, magnetocaloric materials, and catalysts.

The present book is an attempt to summarize the knowledge gained by the network over this short period of time. Addressing specifically beginners in the field, it complements the more detailed Series of Books on Complex Metallic Alloys,1 which was edited by one of us (EBF) in combination with the annual sessions of the so-called EuroSchool of the network. It is organised in ten self-contained chapters, with the view to begin with the more general notions, explain how complex metallic alloys may be grown using standard metallurgical routes, see how specific their properties are, either in bulk or at the surface, and finish with application-driven issues: coatings, magnetocalorics, thermoelectrics and catalysts.

The editors are deeply indebted to the authors of the chapters, who have accepted – within a tight schedule – to describe in a pedagogical way the many facets of the science and engineering of complex metallic alloys. They are grateful to the many colleagues, throughout Europe, who have contributed, in one way or another, to the life of the network, especially as task leader or as responsible of the Virtual Integrated Laboratories of CMA-NoE, and who took care to achieve a very high degree of integration of our research teams in order to counterbalance the fragmentation of research within the European Research Area.

Special thanks go to Annemarie Gemperli, the secretary general of CMA-NoE, to Mr Karl Hoehener and Prof. Louis Schlapbach, who acted with one of us (JMD) as executive officers to lead the CMA-NoE. In this respect, the inspiration and dedication gained from Prof. Knut Urban during the early period of the network was instrumental in the success of the whole process. As a pioneer in the field of complex metallic alloys, Prof. Urban has kindly accepted to write the foreword of the present book. Last, but not least, we acknowledge the financial support offered by the European Commission under contract N° NMP3 – CT – 2005 – 500140.

1. Book Series on ComplexMetallic Alloys, Vols. I, II, III & IV, World Scientific, Singapore, 2008–2010.

Nancy, July 14, 2010

Jean-Marie Dubois

Esther Belin-Ferré

Directors of Research at CNRS

List of Contributors

Marc Armbrüster

Max-Planck-Institute for Chemical

Physics of Solids

Nöthnitzer Str. 40

01187 Dresden

Germany

Wolf Assmus

University of Frankfurt

Physikalisches Institut

Max-von-Laue-Str. 1

60438 Frankfurt

Germany

Marie-Geneviève Barthés-Labrousse

Institut de Chimie Moléculaire et des

Matériaux d'Orsay

Laboratoire d'Etude des Matériaux Hors

Equilibre (UMR CNRS-UPS 8182)

Bâtiment 410, Université Paris Sud

91405 Orsay Cedex

France

Esther Belin-Ferré

Université Pierre et Marie Curie

Laboratoire de Chimie Physique-

Matière et Rayonnement (UMR 7614 CNRS-UPMC)

11 rue Pierre et Marie Curie

75231 Paris Cedex 05

France

Alessandra Beni

Swiss Federal Laboratories for Materials

Testing and Research (EMPA)

Laboratory for Corrosion and Materials

Integrity

Abt. 136, Ueberlandstrasse 129

8600 Dübendorf

Switzerland

Marc de Boissieu

Grenoble INP/CNRS

Sciences de l'Ingéniérie des Matériaux

et des Procédés (SIMaP)

UJF 1130 rue de la piscine, BP 75

38402 Saint Martin d'Hères Cedex

France

Janez Dolinšek

Jožef Stefan Institute

Solid State Physics Department

Jamova 39

1000 Ljubljana

Slovenia

University of Ljubljana

Faculty of Mathematics and Physics

Jadranska 19

1000 Ljubljana

Slovenia

Jean-Marie Dubois

Nancy-Université UPV-Metz

Institut Jean Lamour (UMR 7198 CNRS)

Ecole des Mines, Parc de Saurupt

CS 14234 54042 Nancy Cedex

France

Jürgen Eckert

IFW Dresden

Institut für Komplexe Materialien

Postfach 270116

01171 Dresden

Germany

Michael Feuerbacher

Forschungszentrum Juelich GmbH

Institut fuer Festkoerperforschung

52425 Juelich

Germany

Vincent Fournée

Nancy Université-UPV Metz

Institut Jean Lamour (UMR 7198 CNRS)

Ecole des Mines, Parc de Saurupt

54042 Nancy Cedex

France

Claude Godart

ICMPE – CMTR

CNRS UMR 7182

2–8 Rue H. Dunant

94320 Thiais

France

Saskia Gottlieb-Schoenmeyer

University of Frankfurt

Physikalisches Institut

Max-von-Laue-Str. 1

60438 Frankfurt

Germany

Yuri Grin

Max-Planck-Institute for Chemical

Physics of Solids

Nöthnitzer Str. 40

01187 Dresden

Germany

Samuel Kenzari

Nancy-Université UPV-Metz

Institut Jean Lamour (UMR 7198 CNRS)

Ecole des Mines de Nancy, Parc de

Saurupt

CS 14234 54042 Nancy Cedex

France

Spomenka Kobe

Jozef Stefan Institute

Department for Nanostructured

Materials

Jamova 39

1000 Ljubljana

Slovenia

Matej Komelj

Jozef Stefan Institute

Department for Nanostructured

Materials

Jamova 39

1000 Ljubljana

Slovenia

Kirill Kovnir

Fritz-Haber-Institute of the Max-Planck-Society

Faradayweg 4-6

14195 Berlin

Germany

Julian Ledieu

Nancy Université-UPV Metz

Institut Jean Lamour (UMR 7198 CNRS)

Ecole des Mines, Parc de Saurupt

54042 Nancy Cedex

France

Enrique Maciá

Universidad Complutense de Madrid

Fac. CC. Físicas

Dpto. Física de Materiales

28040 Madrid

Spain

Paul John McGuiness

Jozef Stefan Institute

Department for Nanostructured

Materials

Jamova 39

1000 Ljubljana

Slovenia

Jeong Y. Park

Korean Advanced Institute of Science

and Technology (KAIST)

Graduate School of EEWS

Daejaon, 305-701

Republic of Korea

Silke Paschen

Vienna University of Technology

Institute of Solid State Physics

Wiedner Hauptstr. 8–10

1040 Vienna

Austria

Benjamin Podmiljšak

Jozef Stefan Institute

Department for Nanostructured

Materials

Jamova 39

1000 Ljubljana

Slovenia

Nathalie Prud'homme

CIRIMAT

ENSIACET

118 Route de Narbonne

31077 Toulouse Cedex 4

France

Muriel Sales

Austrian Institute of Technology

Aerospace and Advanced Composites

2444 Seibersdorf

Austria

Robert Schlögl

Fritz-Haber-Institute of the Max-Planck-Society

Faradayweg 4-6

14195 Berlin

Germany

Patrik Schmutz

Swiss Federal Laboratories for Materials

Testing and Research (EMPA)

Laboratory for Corrosion and Materials

Integrity

Abt. 136, Ueberlandstrasse 129

8600 Dübendorf

Switzerland

Sergio Scudino

IFW Dresden

Institut für Komplexe Materialien

Postfach 270116

01171 Dresden

Germany

Ana Smontara

Institute of Physics

Laboratory for the Study of Transport

Problems

Bijenika 46, POB 304

10001 Zagreb

Croatia

Mihai Stoica

IFW Dresden

Institut für Komplexe Materialien

Postfach 270116

01171 Dresden

Germany

Constantin Vahlas

CIRIMAT

ENSIACET

118 Route de Narbonne

31077 Toulouse Cedex 4

France