Amorphous Magnetism Takahito Kaneyoshi, D.Sc. Department of Physics Nagoya University Nagoya, Japan Boca Raton London New York CRC Press, Inc. CRC Press is an imprint of the Taylor &B Foracnaci s RGraotuopn, a, n Finlfoorrmidaa business First published 1984 by CRC Press Taylor & Francis Group 6000 Broken Sound Parkway NW, Suite 300 Boca Raton, FL 33487-2742 Reissued 2018 by CRC Press © 1984 by CRC Press, Inc. CRC Press is an imprint of Taylor & Francis Group, an Informa business No claim to original U.S. Government works This book contains information obtained from authentic and highly regarded sources. Reasonable efforts have been made to publish reliable data and information, but the author and publisher cannot assume responsibility for the validity of all materials or the consequences of their use. 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CCC is a not-for-profit organization that provides licenses and registration for a variety of users. For organizations that have been granted a photocopy license by the CCC, a separate system of payment has been arranged. Trademark Notice: Product or corporate names may be trademarks or registered trademarks, and are used only for identification and explanation without intent to infringe. Library of Congress Cataloging in Publication Data Kaneyoshi, Takahito, 1940- Amorphous magnetism Bibliography: p. Includes index. 1. Amorphous substances—Magnetic properties. I. Title. QC766.A4K36 1984 538 83-3740 ISBN 0-8493-5796-9 A Library of Congress record exists under LC control number: 83003740 Publisher’s Note The publisher has gone to great lengths to ensure the quality of this reprint but points out that some imperfections in the original copies may be apparent. Disclaimer The publisher has made every effort to trace copyright holders and welcomes correspondence from those they have been unable to contact. ISBN 13: 978-1-315-89051-7 (hbk) ISBN 13: 978-1-351-06961-8 (ebk) Visit the Taylor & Francis Web site at http://www.taylorandfrancis.com and the CRC Press Web site at http://www.crcpress.com PREFACE I first started to think about topologically disordered magnetic materials (or amorphous magnets) in 1969, when I read two pioneer papers written by A. I. GubanovandR. Hasegawa. At the time our understanding of the properties of amorphous magnets was distinctly limited. In fact, it was in 1967 that a topologically disordered ferromagnetic alloy was first made by Duwez and Lin directly from a liquid state by means of a rapid-quenched technique. As early as 1960 Gubanov had first developed a theory to treat the question of whether or not ferromagnetism exists in amorphous solids. In recent years there have been many important advances in the understanding of amor- phous magnets. Magnetically ordered solids exhibit a wide range of interesting new phe- nomena involving the nature of magnetic ordering and the dynamical interaction between elementary excitations of the system, in contrast with those of crystalline magnetic systems. The present monograph is addressed to a microscopic treatment of these new phenomena in amorphous magnets with emphasis on the underlying interaction mechanisms and various magnetic effects associated with topologically disordered structure. From this point of view it differs distinctly from the existing texts. This new field is extremely rich in possibilities, both for theorists and experimentalists, and the rapid expansion still continues. In this book, I attempt to present some of the methods used in the theory of amorphous magnetism, from a single standpoint that amorphous magnets have a topologically disordered structure of the type given by the dense random packing of hard spheres. The primary aim is to show systematically the present theoretical apparatus in a form which would allow the reader to use it in investigations of still unsolved problems. Even within these limits, the theory of amorphous magnetism is now a very large subject. It is not designed to review all of the recent developments in this rapidly developing area. This monograph is, however, primarily intended for the novice in this new field, rather than the specialist. I have spe- cifically tried to keep in mind the needs of the graduate student and of the experienced physicist and metallurgist who are looking into the field of amorphous magnetism for the first time. I have tried to keep the discussions at such a level that they are at least familiar with elementary quantum theory of magnetism. For the general reader who wants no more than a quick bird's-eye view of this subject, suggested reading is Chapter 2 which I con- tributed to Glassy Metals: Magnetic, Chemical, and Structural Properties (CRC Press, 1983). The first part of Amorphous Magnetism begins with a brief introduction in which the basic topics and definitions of the physics of amorphous magnetism are presented. In Chapter 2 the atomic structure of amorphous magnets is described. This is useful in understanding the magnetic properties in amorphous magnets, which is the main theme of this book. In Chapters 2 to 5 the emphasis is on the magnetic properties of amorphous transition metal-metalloid alloys, and Chapter 6 is concerned with those of amorphous rare earth alloys. However, each of the six chapters is written as a more or less continuous narrative. This book is an outcome of two lectures given at Bussei Wakate Summer School in 1977 and at Universidade Federal de Pernambuco in 1979. I am very grateful to Professor I. P. Fittipaldi and his colleagues in Departamento de Fisica of Universidade Federal de Pernam- buco for their contributions in making my visits beneficial and pleasurable. I owe a deep debt of gratitude to Professor T. Matsubara, who first directed my attention to disordered systems. I am indebted to Mr. B. J. Starkoff, President of CRC Press, for his interest in the present book and also to the staff for their assistance in so many ways. T. Kaneyoshi THE AUTHOR Takahito Kaneyoshi, M.Sc., D.Sc. has been Research Associate in Department of Phys- ics, Nagoya University since 1968. He received his B.S. degree from Waseda University in 1963, his M.Sc. in 1965 and his D. Sc. in 1969 from Kyoto University. He was also twice a visiting professor at Universidade Federal de Pernambuco, and a guest scientist at Universitat Duisburg Gesamthochschule. He is author of over 60 papers and has contributed a chapter to the book, Glassy Metals: Magnetic, Chemical, and Structural Properties. His areas of research interest include physics of disordered condensed matters, especially for amorphous magnetism, amorphous semi- conductors, and liquid metals, and statistical mechanics. Dr. Kaneyoshi is a member of Physical Society of Japan, and of Applied Magnetic Society of Japan. To my parents, Chukichi and Ine TABLE OF CONTENTS Chapter 1 Introduction 1.1 General Information and Definitions 1 Ferromagnets 1 Ferrimagnets 3 Canted (Noncollinear Ferrimagnets) 4 1.2 Spin Hamiltonians and Exchange Interactions 5 Exchange Interactions 6 Chapter 2 The Structure 2.1 Statistical Description of the Structure 11 Mixtures 18 2.2 The Structure of Amorphous Magnets 19 2.3 Structural Model 22 Chapter 3 Effective Field Theories 3.1 The Weiss Molecular Field 27 Random Configuration Average 29 3.2 Effective Field Theories of Amorphous Magnets 30 Amorphous Ferromagnets 30 A Unified Effective Field Theory 35 Handrich-Kaneyoshi Approximation 36 Gauss Approximation 36 3.3 Quasiclassical Method and Critical Concentration 38 Critical Concentration 43 3.4 Spin-Glass Phase 44 Replica Method 46 3.5 Effective Field Theory of Amorphous Antiferromagnets 50 3.6 Inelastic Scattering of Neutrons in the Spin-Glass Phase 54 3.7 Analyses of Experimental Results 59 Saturation Magnetization 59 Curie Temperature 61 Mixtures 62 Reduced Magnetization Curves 68 Critical Concentration 69 Spin-Glass Phase 71 Paramagnetic Curie Temperature 73 Amorphous Ferrimagnets 74 Chapter 4 Elementary Excitations 4.1 Green Function Method 79 4.2 Spin Waves at Low Temperatures 83 Diluted Ferromagnets 91 4.3 Spin Waves at Finite Temperatures 95 4.4 Computer Experiments 100 Krey's Method 100 Alben's Method 103 4.5 Inelastic Scattering of Neutrons 105 Chapter 5 Nonuniform Distribution of Local Fields 5.1 Mbssbauer Experiments Ill 5.2 Theoretical Attempts 120 5.3 Discussion on the Existence of Amorphous Antiferromagnets 126 5.4 Critical Phenomena 131 Landau Theory 133 Analyses of Critical Exponents 136 Inverse Paramagnetic Susceptibility and Arrott Plots 138 5.5 Ferromagnetism and Resistivity Minimum 146 Kondo-Type Effect 147 Structural Effect 148 Chapter 6 Random Magnetic Anisotropy 6.1 Origin of Random Magnetic Anisotropy 153 Crystal Field in the R.C.P. of Atomic Spheres 155 6.2 Coercivity and the Ground State 157 6.3 Molecular Field Theories 159 The Classical Calculation 160 Coercivity 162 Quantum Mechanical Calculations 164 Analysis of a Sperimagnet 167 6.4 Spin Waves 164 References 175 Index 183 1 Chapter 1 INTRODUCTION There is now a rich variety of amorphous magnetic materials that exhibit spontaneous long-range ordering of localized magnetic moments below a critical temperature which is characteristic for each substance. Although crystalline magnetic systems are in general classified in four categories according to the nature of its long-range order (or ferromagnetic, antiferromagnetic, ferrimagnetic, and helimagnetic systems), a number of amorphous mag- nets with new-type spin ordering not classified by those of crystalline systems have been found, because of its topologically disordered nature. The topological disorder is at the heart of the special aspects of amorphous magnets. The key to the difference between crystalline and noncrystalline solids is that no two atomic sites are equivalent in amorphous substances, whereas all macroscopic directions may be equivalent in the bulk. In this monograph, the theoretical aspects of amorphous magnetism are discussed from a view point that amorphous magnets have a topologically disordered structure of the type given by the dense random packing of hard spheres (D.R.P.H.S.) The D.R.P.H.S. state can be studied on the mac- roscopic scale; namely by pouring a lot of rigid ball bearings into a container and shaking them together until they can not be compressed further. The structural aspects will be discussed in next chapter. At first we should note that*'amorphous" and "disordered" do not mean the same thing. "Amorphous" refers to the lack of a crystalline lattice, which implies that amorphous magnets are disordered. But not all disordered magnets are amorphous. There are also disordered crystalline alloys. For example, in a random solid solution of magnetic elements, the atomic positions are fixed by the crystal structure but the magnitude of the localized magnetic moment varies in an aperiodic random fashion. A spin glass is a dilute solution of a magnetic element in a nonmagnetic host crystal, in which the atomic positions are fixed but the spin distribution is random. The spin system of solid solution compounds is periodic in magnitude and spacing, but may be aperiodic in the strength of the exchange interaction. For comparison, a classification of disorder in magnetic systems is shown in Table 1.1. Thus, amorphous magnets constitute a class of systems with the highest level of disorder. The main concern of this monograph is to clarify the physical properties of this most disordered case. In amorphous magnetic materials, although the long-range order for the distribution of magnetic atoms does not exist, a magnetic long-range order is possible, since its magnetism is determined by exchange interactions between neighboring atoms and also randomly dis- tributed local magnetic anisotropies. Accordingly, these magnetic systems have been mainly classified into three categories according to the nature of long-range order.1 In this chapter, we present general information and definitions about the natures of these three categories. 1.1 GENERAL INFORMATION AND DEFINITIONS In this section, we shall adumbrate some important physical properties of the three cat- egories given by Figure 1.1. Ferromagnets In an amorphous ferromagnet the spins are all oriented in the same direction but the topological arrangement of spins is not regular. Some typical examples of amorphous fer- romagnetic materials are transition metal-metalloid alloys, Fe _ B _, (Fe^i^JgoB^P^, 80 x 20 x etc. Below the critical (Curie) temperature Tc, all the spins are, on the average, oriented parallel to one another, giving rise t€> a large spontaneous magnetization of the sample in