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Magnetic physics

Ahee INTERNATIONAL SERIES OF MONOGRAPHS ON PHYSICS

GENERAL EDITORS J. BIRMAN S. F. EDWARDS R. FRIEND C. H. LLEWELLYN SMITH M. REES D. SHERRINGTON G. VENEZIANO

**INTERNATIONAL SERIES OF MONOGRAPHS ON PHYSICS
**

105. Y. Kuramoto, Y. Kitaoka: Dynamics of heavy electrons 104. D. Bardin, G. Passarino: The Standard Model in the making 103. G.C. Branco, L. Lavoura, J.P. Silva: CP Violation 102. T.C. Choy: Effective medium theory 101. H. Araki: Mathematical theory of quantum fields 100. L.M. Pismen: Vortices in nonlinear fields 99. L. Mestel: Stellar magnetism 98. K.H. Bennemann: Nonlinear optics in metals 97. D. Salzmann: Atomic physics in hot plasmas 96. M. Brambilla: Kinetic theory of plasma waves 95. M. Wakatani: Stellarator and heliotron devices 94. S. Chikazumi: Physics offerromagnetism 93. A. Aharoni: Introduction to the theory of ferromagnetism 92. J. Zinn-Justin: Quantum field theory and critical phenomena 91. R.A. Bertlmann: Anomalies in quantum field theory 90. P.K. Gosh: Ion traps 89. E. Simanek: Inhomogeneous superconductors 88. S.L. Adler: Quaternionic quantum mechanics and quantum fields 87. PS. Joshi: Global aspects in gravitation and cosmology 86. E.R. Pike, S. Sarkar: The quantum theory of radiation 84. V.Z. Kresin, H. Morawitz, S.A. Wolf: Mechanisms of conventional and high Tt superconductivity 83. P.O. de Gennes, J. Prost: The physics of liquid crystals 82. B.H. Bransden, M.R.C. McDowell: Charge exchange and the theory of ionatom collision 81. J. Jensen, A.R. Mackintosh: Rare earth magnetism 80. R. Gastmans, T.T. Wu: The ubiquitous photon 79. P. Luchini, H. Motz: Undulators and free-electron lasers 78. P. Weinberger: Electron scattering theory 76. H. Aoki, H. Kamimura: The physics of interacting electrons in disordered systems 75. J.D. Lawson: The physics of charged particle beams 73. M. Doi, S.F. Edwards: The theory of polymer dynamics 71. E.L. Wolf: Principles of electron tunneling spectroscopy 70. H.K. Henisch: Semiconductor contacts 69. S. Chandrasekhar: The mathematical theory of black holes 68. G.R. Satchler: Direct nuclear reactions 51. C. M011er: The theory of relativity 46. H.E. Stanley: Introduction to phase transitions and critical phenomena 32. A. Abragam: Principles of nuclear magnetism 27. P. A.M. Dirac: Principles of quantum mechanics 23. R.E. Peierls: Quantum theory of solids P.P. Bowden, D. Tabor: The friction and lubrication of solids J.M. Ziman: Electrons and phonons M. Born, K. Huang: Dynamical theory of crystal lattices M.E. Lines, A.M. Glass: Principles and applications offerroelectrics and related materials

Physics of Ferromagnetism

SECOND EDITION

SOSHIN CHIKAZUMI

Professor Emeritus, University of Tokyo

English edition prepared with the assistance of C. D. GRAHAM, JR Professor Emeritus, University of Pennsylvania

OXFORD

UNIVERSITY PRESS

OXPORD

UNIVERSITY PRESS

Great Clarendon Street, Oxford 0x2 6DP Oxford University Press is a department of the University of Oxford. It furthers the University's objective of excellence in research, scholarship, and education by publishing worldwide in Oxford New York Auckland Cape Town Dar es Salaam Hong Kong Karachi Kuala Lumpur Madrid Melbourne Mexico City Nairobi New Delhi Shanghai Taipei Toronto With offices in Argentina Austria Brazil Chile Czech Republic France Greece Guatemala Hungary Italy Japan South Korea Poland Portugal Singapore Switzerland Thailand Turkey Ukraine Vietnam Oxford is a registered trade mark of Oxford University Press in the UK and in certain other countries Published in the United States by Oxford University Press Inc., New York © Soshin Chikazumi, 1997 The moral rights of the author have been asserted Database right Oxford University Press (maker) In 1978 and 1984 substantial portions of this book were published in Japanese in two volumes by Syokabo Publishing Company, Tokyo, as a revised edition of the first edition published in 1959 by the same company. The English version of the first edition was published by John Wiley & Sons in 1964 under the title Physics of Magnetism. First published by Oxford University Press, 1997 Reprinted 1999, 2005 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, without the prior permission in writing of Oxford University Press, or as expressly permitted by law, or under terms agreed with the appropriate reprographics rights organization. Enquiries concerning reproduction outside the scope of the above should be sent to the Rights Department, Oxford University Press, at the address above You must not circulate this book in any other binding or cover and you must impose this same condition on any acquirer A catalogue record for this book is available from the British Library Library of Congress Cataloging in Publication Data Chikazumi, Soshin, 1922Physics of ferromagnetism / Soshin Chikazumi; English ed. prepared with the assistance of C. D. Graham, Jr. — 2nd ed. English version of first ed. published under title: Physics of magnetism. New York : Wiley, 1964. Includes bibliographical references and indexes. 1. Ferromagnetism. I. Graham, C. D. (Chad D.) II. Chikazumi, Soshin, 1922- Physical of magnetism. III. Title. QC761.4.C47 1997 538'.44—dc20 96-27148 CIP ISBN 0-19-851776-9 Printed in Great Britain on acid-free paper by Antony Rowe Ltd, Chippenham, Wiltshire

PREFACE

This book is intended as a textbook for students and investigators interested in the physical aspect of ferromagnetism. The level of presentation assumes only a basic knowledge of electromagnetic theory and atomic physics and a general familiarity with rather elementary mathematics. Throughout the book the emphasis is primarily on explanation of physical concepts rather than on rigorous theoretical treatments which require a background in quantum mechanics and high-level mathematics. Ferromagnetism signifies in its wide sense the strong magnetism of attracting pieces of iron and has long been used for motors, generators, transformers, permanent magnets, magnetic tapes and disks. On the other hand, the physics of ferromagnetism is deeply concerned with quantum-mechanical aspects of materials, such as the exchange interaction and band structure of metals. Between these extreme limits, there is an intermediate field treating magnetic anisotropy, magnetostriction, domain structures and technical magnetization. In addition, in order to understand the magnetic behavior of magnetic materials, we need some knowledge of chemistry and crystallography. The purpose of this book is to give a general view of these magnetic phenomena, focusing its main interest at the center of this broad field. The book is divided into eight parts. After an introductory description of magnetic phenomena and magnetic measurements in Part I, the magnetism of atoms including nuclear magnetism and microscopic experiments on magnetism, such as neutron diffraction and nuclear magnetic resonance (NMR), is treated in Part II. The origin and mechanism of para-, ferro- and ferrimagnetism are treated in Part III. Part IV is devoted to more material-oriented aspects of magnetism, such as magnetism of metals, oxides, compounds and amorphous materials. In Part V, we discuss magnetic anisotropy and magnetostriction, to which I have devoted most of my research life. Part VI describes domain structures, their observation technique and domain theory. Part VII is on magnetization processes, analyzed on the basis of domain theory. Part VIII is devoted to phenomena associated with magnetization such as magnetothermal, magnetoelectrical and magneto-optical effects, and to engineering applications of magnetism. Throughout the book, the SI or MKSA system of units using the E-H analogy is used. As is well known, this system is very convenient for describing all electromagnetic phenomena without introducing troublesome coefficients. This system also uses practical units of electricity such as amperes, volts, ohms, coulombs and farads. This system is particularly convenient when we treat phenomena such as eddy currents and electromagnetic induction which relate magnetism to electricity. However, old-timers who are familiar with the old CGS magnetic units such as gauss, oersted, etc., must change their thinking from these old units to new units such as tesla, ampere per meter, etc. Once they become familiar with the new magnetic unit system, however, they may come to appreciate its convenience. To aid in the transition, a conversion table between MKSA and CGS units is given in Appendix 5.

vi

PREFACE

In the previous edition I tried to refer to as many papers as possible. By the time of the revised edition, so many papers had become available that I was obliged to select only a small number of them to keep the text clear and simple. I have no doubt omitted many important papers for this reason, for which I apologize and beg their authors for tolerance and forgiveness. Many authors have kindly permitted me to use their beautiful photographs and unpublished data, for which I want to express my sincere thanks. This book was originally published in Japanese by Shyokabo Publishing Company in Tokyo in 1959. The English version of that edition was published by John Wiley & Sons, Inc. in New York in 1964. The content of the English version was increased by about 55% from the Japanese version. At that time my English was polished by Dr Stanley H. Charap. A revised Japanese edition was published in two volumes in 1978 and 1984, respectively. The content was about 30% larger than the previous English edition. The preparation of the present English version of the revised edition was started in 1985 and took about ten years. This time my English was polished by Professor C. D. Graham, Jr using e-mail communication. The content has not been greatly increased, but has been renewed by introducing recent developments and omitting some old and less useful material. Thanks are due to the staff of Oxford University Press who have helped and encouraged me throughout the period of translation. Tokyo March 1996 S.C.

**CONTENTS Part I Classical Magnetism
**

1 MAGNETOSTATIC PHENOMENA

1.1 1.2 1.3 1.4 1.5 1.6 Magnetic moment Magnetic materials and magnetization Magnetization of ferromagnetic materials and demagnetizing fields Magnetic circuit Magnetostatic energy Magnetic hysteresis Problems References

3

3 7 11 17 22 27 31 32

2 MAGNETIC MEASUREMENTS

2.1 Production of magnetic fields 2.2 Measurement of magnetic fields 2.3 Measurement of magnetization Problems References

33

33 39 42 49 49

**Part II Magnetism of Atoms
**

3 ATOMIC MAGNETIC MOMENTS

3.1 3.2 3.3 3.4 Structure of atoms Vector model Gyromagnetic effect and ferromagnetic resonance Crystalline field and quenching of orbital angular momentum Problems References

53

53 59 68 74 81 83

**4 MICROSCOPIC EXPERIMENTAL TECHNIQUES
**

4.1 Nuclear magnetic moments and related experimental techniques 4.2 Neutron diffraction 4.3 Muon spin rotation (/tSR) Problems References

84

84 93 100 104 104

viii

CONTENTS

**Part III Magnetic Ordering
**

5 MAGNETIC DISORDER

5.1 Diamagnetism 5.2 Paramagnetism Problems References

107

107 110 116 117

6 FERROMAGNETISM

6.1 Weiss theory of ferromagnetism 6.2 Various statistical theories 6.3 Exchange interaction Problems References

118

118 124 129 133 133

**7 ANTIFERROMAGNETISM AND FERRIMAGNETISM
**

7.1 7.2 7.3 7.4 7.5 Antiferromagnetism Ferrimagnetism Helimagnetism Parasitic ferromagnetism Mictomagnetism and spin glasses Problems References

134

134 142 148 151 153 158 159

**Part IV Magnetic Behavior and Structure of Materials
**

8 MAGNETISM OF METALS AND ALLOYS

8.1 8.2 8.3 8.4 Band structure of metals and their magnetic behavior Magnetism of 3d transition metals and alloys Magnetism of rare earth metals Magnetism of intermetallic compounds Problems References

163

163 173 181 188 193 193

**9 MAGNETISM OF FERRIMAGNETIC OXIDES
**

9.1 9.2 9.3 9.4 9.5 Crystal and magnetic structure of oxides Magnetism of spinel-type oxides Magnetism of rare earth iron garnets Magnetism of hexagonal magnetoplumbite-type oxides Magnetism of other magnetic oxides Problems References

197

197 199 207 210 215 220 220

CONTENTS

ix

**10 MAGNETISM OF COMPOUNDS
**

10.1 10.2 10.3 10.4 10.5 10.6 3d Transition versus Illb Group magnetic compounds 3d-lVb Group magnetic compounds 3d-Vb Group magnetic compounds 3d-Vlb Group magnetic compounds 3d-Vllb (halogen) Group magnetic compounds Rare earth compounds Problems References

222

223 226 228 232 234 235 236 236

**11 MAGNETISM OF AMORPHOUS MATERIALS
**

11.1 Magnetism of 3d transition metal-base amorphous materials 11.2 Magnetism of 3d transition plus rare earth amorphous alloys Problem References

239

240 243 244 245

**Part V Magnetic Anisotropy and Magnetostriction
**

12 MAGNETOCRYSTALLINE ANISOTROPY

12.1 12.2 12.3 12.4 Phenomenology of magnetocrystalline anisotropy Methods for measuring magnetic anisotropy Mechanism of magnetic anisotropy Experimental data Problems References

249

249 256 266 274 296 296

**13 INDUCED MAGNETIC ANISOTROPY
**

13.1 Magnetic annealing effect 13.2 Roll magnetic anisotropy 13.3 Induced magnetic anisotropy associated with crystallographic transformations 13.4 Other induced magnetic anisotropies Problems References

299

299 309 318 329 339 339

14 MAGNETOSTRICTION

14.1 14.2 14.3 14.4 14.5 14.6 Phenomenology of magnetostriction Mechanism of magnetostriction Measuring technique Experimental data Volume magnetostriction and anomalous thermal expansion Magnetic anisotropy caused by magnetostriction

343

343 349 357 359 363 376

x

CONTENTS 14.7 Elastic anomaly and magnetostriction Problems References 379 381 381

**Part VI Domain Structures
**

15 OBSERVATION OF DOMAIN STRUCTURES

15.1 15.2 15.3 15.4 15.5 15.6 History of domain observations and powder-pattern method Magneto-optical method Lorentz electron microscopy Scanning electron microscopy X-ray topography Electron holography References

387

387 393 394 396 401 402 405

**16 SPIN DISTRIBUTION AND DOMAIN WALLS
**

16.1 16.2 16.3 16.4 16.5 Micromagnetics Domain walls 180° walls 90° walls Special-type domain walls Problems References

407

407 411 417 422 428 432 432

**17 MAGNETIC DOMAIN STRUCTURES
**

17.1 17.2 17.3 17.4 17.5 17.6 Magnetostatic energy of domain structures Size of magnetic domains Bubble domains Stripe domains Domain structure of fine particles Domain structures in non-ideal ferromagnets Problems References

433

433 439 445 450 453 457 463 464

**Part VII Magnetization Processes
**

18 TECHNICAL MAGNETIZATION

18.1 18.2 18.3 18.4 18.5 Magnetization curve and domain distribution Domain wall displacement Magnetization rotation Rayleigh loop Law of approach to saturation

467

467 480 491 498 503

CONTENTS 18.6 Shape of hysteresis loop Problems References 19 SPIN PHASE TRANSITION 19.1 19.2 19.3 19.4 Metamagnetic magnetization processes Spin flop in ferrimagnetism High-field magnetization process Spin reorientation Problems References

xi 509 516 516 518 518 521 529 533 535 536 537 537 551 556 562 567 574 580 581

20 DYNAMIC MAGNETIZATION PROCESSES 20.1 20.2 20.3 20.4 20.5 20.6 Magnetic after-effect Eddy current loss High-frequency characteristics of magnetization Spin dynamics Ferro-, ferri-, and antiferro-magnetic resonance Equation of motion for domain walls Problems References

**Part VIII Associated Phenomena and Engineering Applications
**

21 VARIOUS PHENOMENA ASSOCIATED WITH MAGNETIZATION 21.1 Magnetothermal effects 21.2 Magnetoelectric effects 21.3 Magneto-optical phenomena References 22 ENGINEERING APPLICATIONS OF MAGNETIC MATERIALS 22.1 Soft magnetic materials 22.2 Hard magnetic materials 22.3 Magnetic memory and memory materials References Solutions to problems Appendix 1. Symbols used in the text 585 585 590 596 598 600 600 605 608 613 615 628

xii

CONTENTS

Appendix 2. Conversion of various units of energy Appendix 3. Important physical constants Appendix 4. Periodic table of elements and magnetic elements Appendix 5. Conversion of magnetic quantities - MKSA and CGS systems Appendix 6. Conversion of various units for magnetic field Material index Subject index

631 632 633 638 639 641 649

Thus they came to be known as 'lode stones' or 'loadstones'. Later in history. This stone was found in Asia Minor. from a word meaning 'direction'. would always align themselves in the same direction relative to the North Star. in the Magnesia district of Macedonia or in the city of Magnesia in Ionia. it was found that these natural magnets. we introduce the phenomena of magnetostatics.Parti CLASSICAL MAGNETISM Magnetism is one of the oldest phenomena in the history of natural science. following the first detailed studies of magnetism by William Gilbert early in the seventeenth century. which were investigated through the eighteenth and nineteenth centuries. In Part I. if properly suspended from a thread or floated on a cork in water. . The word 'magnetism' is believed to originate from these names. It is said that magnetism was first discovered by a shepherd who noticed that the iron tip of his stick was attracted by a stone.

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1.6 A rrT1. see Appendix 6.0 is called the permeability of vacuum.) If a bar magnet of length / (m). Generally a region of space in which a magnetic pole experiences an applied force is called a magnetic field. giving rise to a couple or torque. The force F (N (newton)) exerted on one pole by the other is given by where /u. each pole is acted upon by a force as indicated by the arrows in Fig. This phenomenon can be described by assuming that there are 'free' magnetic poles on the ends on each magnet which exert forces to one another. When a current of i (A) flows in the winding of a solenoid having n turns per meter.) When a magnetic pole of strength m (Wb) is brought into a magnetic field of intensity H (A/m). separated by a distance r (m).0126Oe. thin solenoid carrying an electric current. A magnetic field can be produced by other magnetic poles or by electric currents. whose moment is . the intensity of the field H at the center of the solenoid is defined by The unit of the magnetic field thus defined is the ampere per meter or Am" 1 .1 MAGNETOSTATIC PHENOMENA 1. the force F (N) acting on the magnetic pole is (/AO is defined so as to avoid a coefficient in (1. and has the value It is also found that an electric current exerts a force on a magnetic pole. These are called 'Coulomb forces' by analogy with the Coulomb forces between electrostatically charged bodies. 1 Oe = 79. which has poles m and —m at its ends. is placed in a uniform magnetic field H. Consider two magnetic poles with strengths of ml (Wb (weber)) and m2 (Wb) respectively.1 MAGNETIC MOMENT The most direct manifestation of magnetism is the force of attraction or repulsion between two magnets. A uniform magnetic field exists inside a long.4).1. (1 Am" 1 = 4-n-X 1(T3 Oe = 0.

1. in practice it is rather hard to define the position of magnetic poles . it has the unit of weber meter (Wb m) In terms of M.5) and (1. As seen in (1. the torque exerted on a magnet in a uniform field H is given by irrespective of the shape of the magnet. A translational force acts on the magnet only if there is a gradient of the field dHx/dx. 1.8) and (1. The translational force is given by in the ^-direction (Fig. the work done by the torque (1.eld Fig. The direction from the negative pole to the positive pole is defined as the direction of the magnetic moment.2. A magnet under the action of a translational force in a gradient magnetic gneticc field. We call this product a magnetic moment.6).1. where 6 is the angle between the direction of the magnetic field H and the direction of the magnetization (-mm -» +m) of the magnet.4 MAGNETOSTATIC PHENOMENA Fig. but no translational force.9) can be expressed using the magnetic moment vector M as and Although the magnetic moment is defined here as (magnetic pole) X (distance between poles). 1. so that equations (1. If no frictional forces act on the magnet. Thus a uniform magnetic field exerts a torque on a magnet.2). any kind of force which acts on the magnet involves m and / in the form of the product ml. A magnet under the action of a torque in a uniform magnetic field.8) is reversible. giving rise to a potential energy.

A magnetic moment produced by a closed electric current.4). 6) in polar coordinates. . 1. we assume that the two *Some authors object to the concept of a 'magnetic pole' as unrealistic. 1.3). so that we can use equation (1. we place at P another magnetic dipole M2. Now let us consider how the magnetic moment Ml of a magnet or a current loop placed at the origin O produces magnetic fields in space (Fig. 1. Now in addition to the moment Mj at the origin. accurately. because of the difficulty of realizing a 'point' pole. Figure 1.* However. The magnetic moment produced by a current / (A) which flows in a closed circuit or loop enclosing an area S (m2) is defined as The direction of the magnetic moment is defined as the direction of movement of a right-hand screw which rotates in the same direction as the current in the closed circuit (Fig. A magnetic moment can also be produced by a closed loop carrying an electric current. the moment of force or torque. A source of field meeting this condition is called a magnetic dipole. However. Both concepts are useful to calculate magnetic fields. The components of the field at P are given by The distribution of magnetic fields in a space can be shown by lines of force running parallel to the direction of H at each point of the space. Consider the magnetic field at a point P whose position is given by (r. the same objection can be made to the 'element' of electric current which is used in the Biot-Savart law describing the magnetic field produced by an electric current. which makes an angle 62 with r (for simplicity. is a measurable quantity.MAGNETIC MOMENT 5 Fig. L. For simplicity we assume the size of the magnet / or of the closed current loop v^ is negligibly small compared with r.4 shows a computer drawing of the lines of force calculated from (1.13).8) as the definition of the magnetic moment.3.

4. 1. the potential energy of this system is given by If the two magnetic dipoles are equal in magnitude and parallel to one another.9). so that M1 = M2 = M. Maximum energy occurs at 6 = Tr/2. 1.14) becomes This potential energy is minimum at 6=0. (1. . and 91 = 62 = 6. Computer-drawn diagram of lines of magnetic force produced by a magnetic dipole.5(a) is stable. dipoles lie in the same plane). so that the configuration as shown in Fig. Using (1. 1. so that the configuration as shown in Fig.6 MAGNETOSTATIC PHENOMENA Fig.5(b) is unstable. as in the case of individual atomic dipoles in a ferromagnetic material. This interaction between dipoles is called dipole interaction.

Mnn in a unit volume of a magnetic material. if we rotate M1 by a small angle 0j while keeping the direction of M-. the coefficient in (1. usually denoted by /. In (1. There are strongly magnetic materials that are attracted by a permanent magnet.MAGNETIC MATERIALS AND MAGNETIZATION 7 (a) (b) Fig.19) simplifies to . we have. fixed. 1.5. 1. Taking Ml = M2 = M = 1. In Fig. the coefficient in (1. the intensity of magnetization is given by If these moments have the same magnitude. In the general case.M2. When a magnetic material is magnetized uniformly.. M. we assumed that Afx and M2 are both in the x-y plane. and weakly magnetic materials whose magnetization can only be detected by sensitive instruments. If M2 is antiparallel to MI} as is the case for atomic dipoles in an antiferromagnetic material (see Chapter 7).7)) and r— 1A. from (1.14). (b) unstable..14).6). the potential energy of the dipole interaction is given by 1.16) changes sign. and are aligned parallel to each other (Fig.2 MAGNETIC MATERIALS AND MAGNETIZATION Magnetic materials are materials which are magnetized to some extent by a magnetic field. 1. the magnetic moment per unit volume is called the magnetic polarization or intensity of magnetization.2 X 10 29 (the moment of a single electron spin see (3. Two arrangements of parallel dipoles: (a) stable.5(a). If there are magnetic moments M1..16) is (1. (1..17) (see Appendix 2 for energy conversions).

we find from (1. If we assume that there are n current layers per unit length along the direction of magnetization. so that we have From this expression. only the surface currents remain uncompensated. Using equation (1. Nm signifies the total quantity of magnetic poles existing in a unit volume of material. or the magnetic pole density. Comparing (1. Concept of magnetization as an assembly of magnetic dipoles.7). and accordingly n/S elementary current loops per unit volume of the magnetic material. 1. the concept of magnetization is also interpreted as a displacement of magnetic pole density p relative to — p by the distance / (Fig.12). Since the unit of N is m~ 3 . and also that the cross-section of the elementary closed current is S (m2).22) with (1.20) . Fig.7) for the magnetic dipole.8.20) that the unit of / is Wbm~ 2 .9 X 102 gauss). 1.6. Consequently uncompensated magnetic poles of surface density will appear at the ends of the specimen. How can we connect the concept of elementary magnetic moments consisting of closed current loops with the concept of magnetization? Suppose that the magnetic material is filled with many elementary closed current loops as shown in Fig. p (Wb/m3). 1.7. 1. we have from (1. which has the alternative and simpler name of tesla (T) (1T of I = W4/4ir gauss = 7. Concept of magnetization as a displaced magnetic charge density. we have Thus we can define the magnetization to be the number of magnetic poles displaced across a unit cross-section. we have l/S elementary current loops per unit area of the cross section.8 MAGNETOSTATIC PHENOMENA Fig. where N is the total number of moments M in a unit volume.20) In this expression. we have from (1.23). If we adopt the definition of equation (1. Since neighboring currents cancel one another.

1. 1. we have another method utilizing the electromagnetic induction. Comparing (1.3). the voltage Fig.9. or Thus we have various concepts of 'magnetization': an ensemble of elementary magnetic moments.9(a). we see that the magnetization is given by /JLO times the magnetic field H' produced by the intrinsic current. When we calculate magnetic fields outside a magnetic material. Concept of magnetization as an assembly of small closed electric currents loops. (a) An air-core search coil. The intensity of magnetization can be determined by measuring the magnetic fields produced outside a magnetized specimen. a displacement of magnetic poles. . If we apply a magnetic field H perpendicular to the cross-section of the coil. We will discuss the magnetic field inside magnetic materials in Section 1. Alternatively.3. Suppose that we have a search coil of cross-sectional area 5 (m2) and N turns of wire placed as shown in Fig.8. and an intrinsic current. we obtain the same result no matter which of these concepts we use.25) with (1.MAGNETIC MATERIALS AND MAGNETIZATION 9 Fig. (b) a search coil wound on a magnetic rod. 1.

9(b)). respectively. In this case (1. t Some scientists feel that the magnetization of vacuum is a bad term.29) is written as where ^ is called the magnetic permeability.26) in (1.* n The product of B and the cross-section S is called the magnetic flux: The unit of flux is the weber.29). 7. the voltage is increased to where B is the magnetic flux density or magnetic induction. This quantity B is defined by the relationship The unit of B is also T (1T of B = 104 gauss). We also ignore the effect of the demagnetizing field. we have This relationship tells us that the reason that the voltage of electromagnetic induction is increased by the insertion of a magnetic material is that the magnetic field produced by the intrinsic current is added to the external magnetic field. we have where the proportionality factor x is called the magnetic susceptibility. But we must remember that matter itself is an electromagnetic phenomenon.10 MAGNETOSTATIC PHENOMENA is produced across the coil by the law of electromagnetic induction. (1. because vacuum is not matter.25) in Chapter 2.28). which is the same unit as /i0 (see (1. we must believe that the vacuum is magnetizable! . Therefore we can also measure x an^ M in units of /AO. Using this quantity. For a more detailed discussion of a practical case see Equation (2. From the relationship in (1. so that we cannot specify the nature of vacuum on the basis of a naive concept of matter. H.2)). If we insert a magnetic material in the coil (Fig. 1. If we use (1. we assume that the cross-section of the magnetic material is exactly the same as that of the search coil. Comparing Equations (1. The units of x ar>d P are both Hm" 1 .34). From a different point of view. is proportional to the magnetic field.27) and (1. and denote them x and ~jl.30) to mean that B can be regarded as the sum of the magnetization of a magnetic material and that of vacuum. we can also interpret (1.28) is written as If the magnetization. We call these quantities relative susceptibility and relative permeability. we have * In this case.

^rev has a decreases monotonically. Starting from the value of ^a. but along the minor loop BB'. The slope BB' is called the reversible susceptibility XKV or the incremental susceptibility. / is a complex function of H (see Section 1. which is described by a magnetization curve as shown in Fig. Their magnetization is changed by a magnetic field in a complex way. ranging from 102 to 106. the magnetization returns to zero upon removal of the field. that is. If the field is decreased from its value at point B. it is called the irreversible susceptibility ^irr. The slope of the curve OA is called the initial susceptibility xa. Initial magnetization curve and minor loops. is called the maximum susceptibility Xma*> ^ is a good measure of the average slope of the initial magnetization curve. while in the case of strongly magnetic materials. they have relatively large magnetic permeabilities fL. the slope of the tangent line drawn from the origin O to the initial magnetization curve.3 MAGNETIZATION OF FERROMAGNETIC MATERIALS AND DEMAGNETIZING FIELDS Since ferromagnetic materials can be highly magnetized by a magnetic field. Xditc and Xtot along the initial magnetization curve are shown in Fig.34) holds only approximately in a limited range of fields. Changes in ^rev. x and Jl are normally field-independent.10.3). The slope at any point on the initial magnetization curve OABC is called the differential susceptibility x&ff> an^ the slope of the line which connects the origin O and any point on the initial magnetization curve is called the total susceptibility ^-tot. and ^tot goes to its maximum value ^max and drops off at / = /s. 1. 1. The difference between ^diff and ^-rev represents the susceptibility due to irreversible magnetization. the magnetization increases with increasing field along the curve OABC and finally reaches the saturation magnetization. the magnetization comes back.MAGNETIZATION OF FERROMAGNETIC MATERIALS 11 In the case of weakly magnetic materials. The maximum value of the total susceptibility.36)5 Fig. Starting from a demagnetized state (7 = H = 0).Beyond this region the processes of magnetization are no longer reversible.10. 1. In the region OA the process of magnetization is almost reversible. that is. 1. so that (1. . which is normally denoted by Js. that is.11. not along BAO. while xtm nas a sharp maximum. (1.

The absolute value of the field at this point is called the coercive force or the coercive field Hc (= OE). not along CBAO. If the field is then reversed again to the positive sense. the magnetization / gradually decreases along CD. 1. which is called the residual magnetization or the remanence. Further increase of H in a negative sense results in an increase of the intensity of magnetization in a negative sense and finally to negative saturation magnetization. and at H = 0 it reaches the non-zero value /r (= OD). Fig.12).11.12 MAGNETOSTATIC PHENOMENA Fig. which finally falls to zero. DE. Further increase of the magnetic field in a negative sense results in a continued decrease of the intensity of magnetization. 1. This portion. of the magnetization curve is often referred to as the demagnetizing curve. 1. Various kinds of magnetic susceptibilities as functions of the intensity of magnetization. . The closed loop CDEFGC is called the hysteresis loop.12. If the magnetic field is decreased from the saturated state C (Fig. the magnetization will change along FGC. Hysteresis loop.

MAGNETIZATION OF FERROMAGNETIC MATERIALS 13 The value of the saturation magnetization 7S does not exceed 2. The value of relative maximum susceptibility also varies widely. which states that the surface integral of the normal component of the magnetic field Hn is equal to the magnetic free poles contained in the volume defined by the integral. while it ranges from 50 to 200 kAm" 1 (600 to 2500 Oe) or more for Alnico and Ba ferrites. which are used for motor and transformer core materials. Surface magnetic free poles and resulting demagnetizing field. That is. but also on the shape of the specimen. . Fig. For instance. When a specimen of finite size is magnetized by an external magnetic field. This field is called the demagnetizing field. The apparent magnetization curve of a material depends not only on its magnetic susceptibility. 1. the free poles which appear on its ends will produce a magnetic field directed opposite to the magnetization (Fig.13. so that we have where N is called the demagnetizing factor. 1. divided by /A O . If the intensity of magnetization is 7. which are used as permanent magnets. Fig. but the value of the coercive field can vary over a wide range: it is about 8Am" 1 (= 0. whereas it is large for a thick and short specimen.24)).14). we use Gauss' theorem. then the surface density of free poles on both sides of the plate is +/ (Wb/m2) (see (1. The intensity of the demagnetizing field H& is proportional to the magnetic free pole density and therefore to the magnetization.14.5 T at room temperature for any material. from 10 to 105. 1. 1.13). In order to calculate the demagnetizing field in this case. Demagnetizing field produced by magnetization perpendicular to the surface of a magnetic plate.1 Oe) or less for Permalloy and steel containing a few per cent of silicon. which depends only on the shape of the specimen. N approaches zero for an elongated thin specimen magnetized along its long axis. Let us calculate the demagnetizing factor for a semi-infinite plate magnetized perpendicular to its surface (Fig.

that is the ratio of length to diameter. The calculation of the demagnetizing factor is generally not so simple. If the shape of the specimen is irregular.1 For example. the demagnetizing factor is given by where k is the aspect ratio or the dimensional ratio. Assuming a uniform demagnetizing field in a general ellipsoid. the effect of the free poles is negligible. with the magnetization parallel to the plane of the surface.14 MAGNETOSTATIC PHENOMENA Applying this theorem to the closed surface shown by the broken line in Fig. we cannot define a single demagnetizing factor. we have where k is the ratio of diameter to thickness. In such a case. In the special case of k » 1. provided that the plate is sufficiently wide and thin. The general result is in the form of a complex integral. approaching the shape of a disk.1 gives numerical values of the demagnetizing factor calculated from (1. we can prove that the demagnetizing factors for the three principal axes have a simple relationship .2 Experimental values of N show considerable scatter depending on the method of measurement and the type of material. (1.14.42) reduces to For a flat circular ellipsoid.44) as a function of the dimensional ratio k. we have The demagnetizing factor in this case is given by When we magnetize the plate parallel to its surface.43) and (1. In these calculations. which can be simplified for special cases. the magnetization is assumed to be uniform throughout the material. for an elongated rotational ellipsoid (an ellipsoid with a circular cross-section) magnetized along its long axis. together with experimental values obtained for cylinders of various k. The only shape for which the demagnetizing factor can be calculated exactly is the general ellipsoid. the demagnetizing field is not uniform but varies from place to place in the specimen. Then Thus the demagnetizing factor depends upon the direction of magnetization. Table 1. 1. and assuming that there is no field outside the plate other than the external field.

45) When a long cylinder is magnetized perpendicular to its long axis (which we take as the z-axis).000392 15 From this relationship we can easily obtain the demagnetizing factors for simple ellipsoids with high symmetry. the shape of the curve is sheared as shown by the broken line in Fig. with increased susceptibility and remanence.00675 0. As a result of this correction.0203 0. so that it produces only an internal force which has no effect on the magnetization.1248 0.00129 0. 1. Demagnetizing factors for rods and ellipsoids magnetized parallel to the long axis (after Bozorth2) Dimensional ratio k 1 2 5 10 20 50 100 200 500 1000 2000 Rod 0.26).3333 0.0369 0. Nz = 0.15 as compared with the true magnetization curve shown by the solid line. If we plot a magnetization curve as a function of the external field.00144 0.00617 0.040 0.000125 0.001567 0.0000236 0.2364 0.000430 0. because H' is produced by the magnetization itself. so that we have When a semi-infinite plate is magnetized normal to its surface (which we take as the z-axis).0000036 0. however.01532 0.MAGNETIZATION OF FERROMAGNETIC MATERIALS Table 1.0696 0. The correction for converting the sheared magnetization curve to the true curve is called the demagnetizing correction or the shearing correction. and Nx = Ny. not the case.14 0.000090 0.00390 0.00776 0. Unless otherwise stated.000014 0.000784 0.0000009 Prolate ellipsoid 0.0000019 Oblate ellipsoid 0.0558 0.40). the magnetization curve takes on a more upright form. This is. That is.27 0. . For a sphere in which NX = N =NZ.0172 0. Nx = Ny = 0. published magnetization curves *It may seem that the real effective field should include H' in (1. we have from (1.1735 0. This is because the actual or true field acting in the material (usually called the effective field* // eff ) is smaller than the applied external field //ex.0000066 0.1.3333 0.00036 0. so that 1 in agreement with (1.

025 Oe) to the saturated state. the maximum demagnetizing field is given by In order to saturate this sphere. Suppose that we magnetize a Permalloy sphere with Hc = 2 Am" 1 (= 0.16T (= 920 gauss). This must be true. A high field will be needed to magnetize a sample with a large demagnetizing factor. Finally we consider the field inside a cavity in a material magnetized to an intensity 7 (Fig. because if we superpose the body and the hole.16). 1. the field is given by . In general we cannot ignore the effect of the demagnetizing field.16 MAGNETOSTATIC PHENOMENA / Fig. otherwise the favorable properties of the material become useless. Shearing correction of a magnetization curve. and with the same magnetization as the material surrounding the cavity. we have a uniformly magnetized solid without free poles.15. We must keep this fact in mind when we use magnetic materials with high susceptibility. Since the saturation magnetization of Permalloy is 1. even if it has a high susceptibility. Thus the field produced by the surface free poles of the cavity is given by where N is the demagnetizing factor of a body with the same shape as the cavity. The free pole distribution on the surface of the cavity is the same as that on the surface of a solid body with the same shape as the cavity. In the case of a spherical cavity. therefore. which is 105 times larger than Hc. we must apply an external field which exceeds this value. 1. have been corrected for demagnetizing effects and therefore represent the properties of the material independently of the shape of the sample used for the test. except that the poles are of opposite sign.

1. In the absence of true electric charge. where <f> is the electric potential. . the field inside H^ is the same as Het{.MAGNETIC CIRCUIT 17 Fig.16. The same situation exists when we try to find the distribution of free electric charges in a space containing a dielectric material of irregular shape. The problem of finding a distribution of electric potential is reduced to the problem of solving the Laplace equation under the given boundary condition. as given in (1. If we bore an elongated hole parallel to the magnetization. and its direction is the same as that of the magnetization. Hm is the same as H' + H. On the other hand. This field is called the Lorentz field. this is a fairly complex problem. we must solve (1. so that (1. If we make a thin flat cavity perpendicular to the magnetization.30). 1. there are dielectric materials distributed in an irregular manner.55) for the given spatial distribution of s.53) becomes In a uniform dielectric material we can put s = constant.4 MAGNETIC CIRCUIT As mentioned in the preceding section. and a complicated distribution of magnetization results. Magnetic field inside holes in a magnetic body. however. where D is the electric displacement or electric flux density. If. so that (1.55) becomes or which is Laplace's equation. the demagnetizing field of a specimen of irregular shape is not uniform.

hence the actual situation is quite similar to that of a steady current in a Fig. In magnetism.59). Therefore if conductors of irregular shape with different conductivities are distributed in a medium with finite conductivity. 1. Since the permeability of vacuum is not zero ( /AO = 4ir X 10~7 Hm" 1 ). the conductor is surrounded by insulators. the situation is formally similar to the case of electrostatics. as in the two cases mentioned above. however. .18 MAGNETOSTATIC PHENOMENA In magnetostatics. 1. not true for dielectric materials. Then (1. This is. Current distribution in a conductor of complex shape connecting two electrodes. A similar problem arises in finding the distribution of electric current density in a conducting medium. If. the problem becomes very difficult. however. if a conducting wire is placed in vacuum as shown in Fig. If we assume that the magnetization curve is given by a straight line without hysteresis. we can simply write where <f>m is the magnetic potential. For instance. the relation is always valid. here the D vector leaks more or less into the vacuum.85 X 10~12 FmT1).55) or (1. however. But actually the permeability of ferromagnetic materials is 103-105 times larger than that of vacuum. /x is non-uniformly distributed. the electric current is contained in the wire no matter how complicated the shape of the wire.17. For ferromagnetic materials the situation is intermediate between these two cases. the situation becomes very simple.54). Since where a is the electric conductivity. For a steady current.60) becomes which is also of the same form as (1.57) becomes which has exactly the same form as (1. because the dielectric constant of vacuum is not zero (EO = 8. the situation is quite similar to the case just mentioned. the problem becomes very difficult.17. If. where there are ferromagnetic materials of irregular shape. (1.

Two kinds of magnetic circuit. forms a circuit. The direction of magnetization should always be parallel to the surface of the magnetic material. Figure 1.61) are compared.18. where S is the cross-section of the conducting wire. if a magnetic material.MAGNETIC CIRCUIT 19 Fig.18 shows two typical magnetic circuits. the magnetic permeability /u. especially one of high permeability. corresponding to the resistance of the electric circuit. The flux density B in the circuit corresponds to the electric current density i of an electric circuit. Thus. is found to correspond to the electrical conductivity a-. and ds is an element of length in the circuit. The total flux in the circuit. corresponds to the total electric current. conductor. When (1. we can define the magnetomotive force in the circuit as . and the other by a coil. If B is uniform throughout the cross-section of the magnetic circuit. producing strong demagnetizing fields that act to rotate the magnetization parallel to the surface again. One is magnetized by a permanent magnet. the magnetic flux density B is almost fully confined inside the magnetic material. In other words. because otherwise free poles will appear on the surface. we can define the magnetic resistance or reluctance as Corresponding to the electromotive force. The gray portions of the circuits are made from soft magnetic materials. 1.58) and (1. Thus we can treat the magnetic circuit and electric circuit similarly.

20 MAGNETOSTATIC PHENOMENA where the line integral is taken once around the circuit. If the magnetic field is changed. The product of amperes X turns can thus be considered to have the units of amperes (A). If we translate the origin O to S. (1. we have. of RQ to the abscissa can be regarded as a simple reversible magnetization curve. The reason is that the demagnetizing field of the permanent magnet can be reduced in value by inserting it into a magnetic circuit. that the permanent magnet itself has a considerable reluctance given by * Since the number of turns is not a unit in the SI system. from Ampere's theorem. we can say that a coil of 10 turns carrying a current of 1 ampere is equivalent to a coil of 1 turn carrying a current of 10 amperes. so that where lp is the length of the permanent magnet and Br is the remanent magnetic flux density (OR). the extrapolation.66). . we have This relation corresponds to Kirchhoff s second law of electric circuits. the direction of the magnetic field Hp inside the permanent magnet is always opposite to that of magnetic flux Bp. SR. When the magnetic circuit is magnetized by an electric current i which flows in a coil of TV turns wound around the magnetic circuit. in the second quadrant of the B-H plot (Fig.19). The magnetomotive force is given by integrating HT over the length of the permanent magnet.58). 1. Thus a permanent magnet is equivalent to a magnetic material with permeability /j.64). but can never be changed in direction unless another magnet or coil supplies an additional magnetomotive force.r which can drive magnetic flux against a hypothetical field OS ( = //r). however. and (1.* Using relations (1. the point P will move reversibly on the line RQ whose slope dB/dH is given by the reversible permeability /Ar. Thus the magnetic state of a permanent magnet is represented by a point. It must be remarked. We can proceed as follows: when a magnet supplies the magnetomotive force in a magnetic circuit. so that the magnetomotive force of the coil is given by The unit of magnetomotive force is the ampere turn (AT). say P. that is The calculation of the magnetomotive force for a permanent magnet is fairly complex.

. that a magnetic . however.. Generally /xr of a permanent magnet is very small. just as we can an electric circuit. we have Kirchhoff s first law. we can solve any kind of magnetic circuit..<I> 2 . Demagnetizing curve of a permanent magnet showing the operating point P.19. If a magnetic circuit has a shunt or shunts.. Then where Hp is the field inside the permanent magnet and the integral is taken along the circuit excluding the permanent magnet. so that R'm is fairly large. 1.. 1. By using Kirchhoff s first and second laws. Thus a permanent magnet corresponds to a high-voltage battery with a fairly large internal resistance which supplies a constant current independent of the output impedance. where <!> 1 . Thus This relation corresponds to Kirchhoff s second law. are the fluxes which leave the shunt point through the branches..MAGNETIC CIRCUIT 21 Fig.2. because the electric current is zero. For a magnetic circuit containing a permanent magnet. It must be noted..

.. so that the circuit is practically broken at this point.5 MAGNETOSTATIC ENERGY Let us discuss the energy involved in a magnetostatic system. <£2.. <&. 1. Consider a system consisting of several permanent magnets (Fig. The non-linear relationship between B and H also makes the problem more complex.. . In extreme cases. • • •. • • •. 1. if a part of the circuit is magnetically saturated.'th free poles. it is expressed as where rtj is the distance between the ith and the . The presence of magnetic hysteresis also makes the situation more complicated.m 2 ... If the free poles are Fig.22 MAGNETOSTATIC PHENOMENA circuit has more or less leakage of the magnetic flux. we can neglect the effect of hysteresis.m n (Wb) and the magnetic potential at the position of each pole be $1.20).-. Assembly of permanent magnets. 1. the permeability becomes very small. However.. when the product of the coercive field times the length of the circuit is negligibly small compared to the magnetomotive force.20. <£„ (A). is the potential due to the Coulomb interaction of free poles other than m ( . Let the intensities of the free poles be m 1 .. the leakage is so large than the actual flux is only a small fraction of the calculated value. like an electric circuit dipped in an electrolytic solution.m. In particular. Then the potential energy of the system is Since 0.

85) becomes Fig. at points where there are no magnetic free poles.21. under the given boundary conditions. a2. .21. 1. 1. so that div 7S can be expressed in terms of the direction cosines ( a ^ . «3) of 7S as or where a is a unit vector parallel to 7S. The free pole density pm induced in a ferromagnetic medium is expressed in terms of the magnetization as If the material is homogeneous.MAGNETOSTATIC ENERGY 23 distributed over space with the density pm. the magnitude of 7S should be constant. For example. for a sphere which is radially magnetized as shown in Fig. the energy is expressed by the volume integral where the potential </> is calculated from It can also be calculated by solving the Poisson equation. Ferromagnetic sphere magnetized radially. or the Laplace equation. (1.

944) where N is the total number of magnets. we have (1.88).88) Solving (1.77) becomes (1.24 MAGNETOSTATIC PHENOMENA Solving this equation.95) By using this equation. Let the length of the kih magnet be lk and the magnetic poles at its ends be mk and — mk. Since the intensity of the magnetic field inside the sphere is given by (1. the magnetostatic energy is (1. Then the magnetic moment is (1.89) The magnetostatic energy of the system is then (1.92) where H^ is the component of the magnetic field parallel to the magnetic moment Mk. we obtain (1.96) . Then (1. When the magnetization / is distributed over space.81) becomes (1.90) The magnetostatic energy can be expressed in terms of / and H instead of pm and <f>.21.87) Then (1.91) The difference in the magnetic potential between the positions of the positive and the negative magnetic poles is (1.93) and (1. we can calculate the magnetostatic energy of the sphere shown in Fig. 1.

In this case pm in (1. 1.99)5 where v is the volume of the magnetic body. the field is reduced to H' which is related to pm and p'm by (1. The effect of magnetization induced in the soft magnetic material comes into (1.95) can also be used to calculate the magnetostatic energy even when soft magnetic materials are present with the permanent magnets.97) which agrees exactly with (1. It should be noted that (1. so that additional free poles p'm are induced: (1. In the absence of the soft magnetic material. and / in (1. the magnetostatic energy can be calculated from (1.MAGNETOSTATIC ENERGY 25 Fig. respectively. and is zero outside the sphere.79) and (1.98) the magnetostatic energy is (1.101) As a result. When some soft magnetic materials are present in the system. Since the demagnetizing field is (1.1000) When the soft magnetic material is placed in the space. so that the magnetostatic energy also decreases.79) signifies the pole density produced by the permanent magnetization only.22. 1.22).90). consider that a space in which permanent magnetic free poles are distributed with density pm is filled with a soft magnetic material of relative permeability /Z.95) only through the change in <j> or H. For example. A magnetized ferromagnetic body of finite size. <f> or H always decrease.94) as (1. it produces additional magnetization /'.102) . Consider a magnetic body with demagnetizing factor N magnetized to intensity / (Fig. the divergence of the field due to pm is given by (1. Let us calculate the magnetostatic energy for another example.95) denotes the permanent magnetization.79) and (1.

* When no soft magnetic material is present. (1.97).102) becomes or f1 KVT) Comparing (1.104) The integration is carried out over the space where magnetic field H is present. we cannot ignore this effect in the calculation of the magnetostatic energy. If we include the permanent magnetization in B. according to /' = xH'> so that. The magnetostatic energy can be also expressed in terms of B and H: (1. Accordingly the magnetic potential </> is also reduced to 1//Z times its original value. the magnetic field inside the sphere is given by (1.90) and (1. The energy stored per unit volume is given by (1. so that (1.105) If there is some soft magnetic material. We shall discuss this problem once again in Chapter 17 as what is known as the /j.100). the magnetostatic energy is stored in any space where magnetic fields exist.79) using the relation pm = divB. As seen from (1.104) becomes (1. the magnetostatic energy of the system is also reduced by a factor l/Ji.104) becomes (1. we find that the field H' is reduced by a factor I//A from the field H. using (1.106) Considering again the example shown in Fig. It should be noted that B in the integrand is calculated by excluding the permanent magnetization. . B should equal n0H.108) *The reason is that (1.* correction.105) gives (1. we have always div B = 0. hence (1. 1.107) which is again in agreement with (1.96) and is zero outside the sphere. Therefore. (1. Since this factor is substantially less than unity for most soft magnetic materials.104) is deduced from (1.26 MAGNETOSTATIC PHENOMENA The magnetization /' is magnetized by this resultant field H'.21.103) with (1.101).105).

This heat or energy is called the hysteresis loss and is given by which is equal to the area inside the hysteresis loop. when the line of force expands perpendicular to the force.108) again decreases. the potential energy must return to its original value. The work required for this transportation is H SIS. On the other hand. so that the resultant work must appear as heat. a tension given by acts parallel to the line of force. the work required to magnetize the volume from the demagnetized state to saturation. a pressure expressed by acts perpendicular to the line of force. Consider the work necessary to magnetize a ferromagnetic material. putting 7: = 0 and 72 = 7S. Since the volume of the cylinder is SI. the work necessary to magnetize a unit volume of the magnetic material is given by Then the work required to magnetize a unit volume from 7 = I1 to 72 is given by For example. . is given by (1. The forces calculated by the interaction between magnetic poles and the magnetic field. the line 7 = 7S. must coincide with the result calculated from the Maxwell stresses. 1. is accomplished by transporting a magnetic pole of magnitude 75 through the distance / from the bottom to the top of the cylinder under the action of the force 7S77. the energy density (1. The energy supplied by this work is partially stored as potential energy and partly dissipated as heat which is generated in the material.109) and (1.112). an increase of magnetization. or from the interaction between electric current and the flux density. This is equal to the area enclosed by the ordinate axis.23.108). and the initial magnetization curve. This assumption is. Suppose that the magnetization is increased from / to / + dl under the action of a magnetic field H. If we consider a cylindrical section of magnetic material whose length is / (parallel to 7) and whose cross-section is 5.110) are called Maxwell stresses. however.6 MAGNETIC HYSTERESIS In the preceding discussion. After one full circuit of the hysteresis loop. we assumed that the energy supplied to construct the system is conserved and stored as magnetostatic energy. not necessarily true for actual ferromagnetic materials. parallel to /. as shown in Fig. In other words. 1. 7S. 57.MAGNETIC HYSTERESIS 27 A line of magnetic force therefore tends to shrink so as to decrease the energy in (1. The stresses given by (1. In other words. because a decrease in energy density caused by a decrease in the intensity of the field overcomes an increase in energy density caused by a decrease in the density of the lines of force.

ferromagnetic materials can be classified as 'soft' and 'hard'. for these purposes high permeability. This material has a hysteresis loop which is very wide compared to that of Permalloy. motors. and 72 = / in (1. however. and large hysteresis loss are desirable. Recently developed rare-earth magnets exhibit hysteresis loops about twenty times wider than that of the MK steel. the only stable condition is 7 = 0 and . whose magnetic behavior is described by / = \H. For engineering applications. as shown in Fig. hard magnetic materials are used as permanent magnets for various kinds of electric meters. Similarly. and other apparatus for which high coercivity.112).28 MAGNETOSTATIC PHENOMENA Fig. It should be noted that hysteresis is necessary for the observation of purely magnetostatic phenomena. At the beginning of the twentieth century.24. Magnetic materials have been developed with characteristics ranging from extremely soft to extremely hard. Soft magnetic materials are normally used for the cores of transformers. a modern high-quality soft magnetic material. so that all magnetic materials are soft magnetic materials which can be magnetized only by external magnetic fields. If there are no permanent magnets and no electric current. Work required to saturate a unit volume of ferromagnetic material. hardened carbon steel was the standard permanent magnet material until the beginning of the twentieth century. It has a hysteresis loop fairly narrow compared to a modern permanent magnet material such as MK steel (Fig. low coercive force. It is interesting that the main applications of ferromagnetic materials fall into two groups which require almost opposite properties. There is. 1.25). a large and growing application for magnetic materials in magnetic recording where properties intermediate between the traditional hard and soft materials are needed. and small hysteresis loss are required. 1. On the other hand. For weakly magnetic materials without hysteresis. high remanence.23. 1. loudspeakers. and generators. the potential energy stored in a unit volume is which is obtained by putting 7: = 0. soft iron was almost the only available soft magnetic material.

which. . Magnetic circuit containing a permanent magnet.104)). Comparison of hysteresis loops of hardened carbon steel and MK steel. H = 0.26.104). does not produce a magnetic field in the air gap.115) in the permanent magnet becomes /A 0 // 2 .115) over Fig. Fig. 1. Next we consider the performance of a permanent magnet as an energy source.MAGNETIC HYSTERESIS 29 Fig.24. Thus no magnetostatic phenomena will be observed. Therefore we can stay that permanent magnets are the only source of magnetostatic energy. 1. where P is the permanent magnet and S is soft magnetic material. 1. An energy term that gives the effectiveness of the permanent magnet in producing a field in the air gap is given by the integration of (1. however. the energy stored in this system is given by where B is the flux density of the magnetic circuit excluding the permanent magnetization (see the footnote concerning (1. Comparison of hysteresis loops of soft iron and Permalloy.26. 1. as shown in Fig. Using (1. Let us consider how a permanent magnet produces a magnetic field in the air gap of a magnetic circuit. Therefore the integrand in (1.25.

the actual energy produced by a unit volume of the magnet is one-half of the quantity (BH).116) is non-zero only in the air gap.116) gives a good measure of the effectiveness of the permanent magnet. Since the volume element di> is equal to the cross-section S times the line element ds. but cannot produce a large magnetic flux. The magnet with a small fi. . Since the purpose of this magnetic circuit is to supply a magnetic field in the air gap. because it has a large internal reluctance . to have a large 77C. this contribution should count as a part of the effectiveness of the permanent magnet. and finally to have the demagnetizing curve close to rectangular in shape. The final result (1.119) means that the permanent magnet has greater effectiveness for larger values of the quantity —B-H (note that H < 0). For an ideal soft magnetic material. and also by making the remanence ratio 7r//s as close to unity as possible. 1. Therefore. it follows that so that (1. so that the permanent magnet must supply additional energy to magnetize it. if a permanent magnet material has a demagnetizing curve as shown in Fig. and for larger volume. as shown by (1. (1. Even if the permeability of the soft magnetic material is finite. which is usually denoted by (BH)max. the magnet can be most effectively utilized by setting the working point at A where (577) has its maximum value. This can be done by orienting the crystallites so that the magnetocrystaline anisotropy * In spite of this name.R'm. In order to obtain a large value of (BH)max. ~jl = ».115) becomes Where G means the air gap and S means the magnetic material. Accordingly the quality of a permanent magnetic material can be expressed by the maximum value of (BH). In other words.119). so that H = 0 for a given B.116) becomes where the superscript P means that the integral should be taken only over the permanent magnet. and the integration in (1.27. A large 7r can be achieved by making the value of 7S as large as possible. it is essential to make the value of BT ( = /r) large. results in a large Vm.30 MAGNETOSTATIC PHENOMENA the magnetic circuit excluding the permanent magnet. and is called the maximum BH product or the maximum energy product * If a permanent magnet has a high value of (7?77)max. a small volume of material is needed to produce a given field in a given air gap. The value of (B/f)max does not necessarily correspond to the magnetomotive force Vm. the quantity U in (1. rather than at A' or A" where (BH) is lower. this is quite reasonable. Now considering that for one circuit of the magnetic path.

1 Calculate the magnetic moment of a sphere of radius R made from a magnetic material with magnetic susceptibility x> when it is magnetized by an external magnetic field H. It must be noted here that the important coercivity is not the field at which / = 0. 1.2 Calculate the force needed to separate two semicircular permanent magnets of cross sectional area 5. or superlattice formation). while keeping the air gaps equal. (see Chapter 12) aligns the magnetization parallel to the direction of easy magnetization. Any change in the material that increases the remanence ratio will also tend to produce a rectangular demagnetizing curve. magnetized to intensity I. since where 7C is the value of / at B = 0. or by creating an induced magnetic anisotropy (see Chapter 13). however. Thus BHC is also limited by /s//v We therefore see that high Is is essential for obtaining a high-quality permanent magnet. 1. Discuss this problem in terms of the energy. or BHC.27.27. Demagnetizing curve of a permanent magnet. limited by 7r. as shown in Fig. PROBLEMS 1. These points will be considered in more detail later. so as to align the easy axes parallel to the axis of magnetization. How is the value of the moment changed in the limit of x ~* °°? 1. as shown in the figure. precipitation hardening. The value of BHC is. or by making the size of particles or crystallites less than the critical size for single domain behavior. or jHc. . A high coercive field Hc can be achieved either by increasing internal stresses (caused by a crystallographic transformation. but the field at which B = 0.PROBLEMS 31 Fig.

R. Druck von B. i = 5 A. Use the values N= 200. Theorie der Electrizitaet. G.01 m. New York. 1.5 Calculate the magnetostatic energy per unit length of an infinitely long ferromagnetic rod of radius R which has residual magnetization 7r perpendicular to its long axis. S2 = 5 X 10 ~ 4 m2.3 Calculate the intensity of the magnetic field in the air gap of the magnetic circuit shown in the figure.32 MAGNETOSTATIC PHENOMENA Fig.15T and // = 60kAm~ 1 .4 Using a permanent magnet material with a maximum BH product at B = 0. Prob. Ferromagnetism (Van Nostrand. M.2 1. Bozorth. Prob.5 X 10 ~ 3 m2. assuming that the magnetic circuit has no leakage of magnetic flux and no reluctance. Tuebner. Vol. How is the energy changed when the rod is dipped into a ferromagnetic liquid of relative permeability /I? REFERENCES 1. /2 = 0. fl = 500. 2. Design the size and shape of the magnet. S1 = 2. /j = 1m. 1. . 1933). 1951). we want to produce a magnetic field of 250 kAm"" 1 in an air gap of crosssectional area 12cm2 and width 14mm. R.3 1. Becker. 1 (Verlag u. Fig. 1.

and the uniformity (in space and in time) of the field required. a coil containing no iron or other strongly magnetic material) is proportional to the electric current which flows in the coil. For conversion factors between Am" 1 and Oe or T. A Helmholtz coil is used to produce a highly uniform field in a particular space. A Helmholtz coil. For an infinitely long coil or solenoid.2 MAGNETIC MEASUREMENTS 2.1 PRODUCTION OF MAGNETIC FIELDS There are various methods of producing magnetic fields. The intensity of the magnetic field produced by an air-core coil (that is. see Appendix 6. R is the radius of the solenoid. C is given by where n is the number of turns per unit length (along the axis) of the solenoid. In general. or where C is the coil constant which depends on the shape of the coils and on the number of turns in the windings. the volume. the coil constant is given by where 21 is the length of the solenoid. In this book. and n is the number of turns per unit length along the . The appropriate method depends on the intensity. for fields on the central axis of a single-layer solenoid of finite length. z is the distance from the center O. although for high magnetic fields the tesla (T) is a more convenient unit. magnetic fields are measured in amperes per meter (Am"1). which consists of two identical thin coils located on a common axis and separated by a distance equal to the coil radius. has the coil constant where N is the number of turns in the winding of each separate coil. for instance for cancelling the Earth's magnetic field.

2(b).1.2(c) pancake-type windings are immersed in circulating water or oil. (b) multilayer solenoid. the maximum current density is about 1 Amm~ 2 . 2. 2.2(f) the windings are made of rectangular hollow copper conductors which are cooled by sending purified .34 MAGNETIC MEASUREMENTS Fig. 2.1(b)). 2. In the case of a simple solenoid cooled only by natural convection.2(a).2 shows various methods for cooling the windings. 2.2(d). In Fig. in Fig. 2. thin copper disks provided with internal water-cooling tubes are used instead of the thick . pancake-type windings are insulated by spirally wound filaments instead of continuous films. 2. in Fig. For a multi-layer solenoid of finite length. which in turn is usually limited by the heat generated in the windings. Figure 2. and cooling water or oil is sent through the pancakes. 2. solenoid axis (Fig. (a) Single-layer solenoid.copper disks in (a).2(e). in Fig.1(a)). pancake-type windings of copper tape insulated with paper or polymer film are separated by thick copper disks which are water-cooled at their circumferences. in Fig 2. wide helical copper windings provided with many holes are cooled by sending cooling water through the holes. The maximum field is determined by the maximum current. the coil constant is given by where Rl and R2 are the inner and the outer radii of the solenoid (Fig. in Fig.

2. because it gives an extremely uniform and time-independent magnetic field.8 MA/m (1 T) by using a large iron magnetic circuit with permanent magnets as a source of magnetomotive force. open arrows show electric current. and second to secure magnetic fields that do not vary with time. so that (2. then we have where Hm is the field in the magnetic circuit. Electromagnets are usually used to produce magnetic fields up to 0.3).12T) by using conventional permanent magnets. the electric current i.1-10 T) can be produced.6 MAm" 1 (1-2T).1 It is. and the length of the air gap /a (see Fig. Magnetic fields can also be produced with permanent magnets. 2. current densities of 3-50 A mm"2 can be carried by the coils. The advantages are first to avoid the use of electric power. It is possible to produce fields of 50-100 kAm" 1 (0.PRODUCTION OF MAGNETIC FIELDS 35 Fig. by using a magnetic circuit. and magnetic fields from SOkAm" 1 to SMAm" 1 (0.06-0.8-1. It is also possible to produce a field of about 0. Such a facility is particularly useful for proton resonance experiments. (Thin arrows show water flow. Then the first term can be neglected.6) becomes . 2. Various types of coil windings. Naturally the cost of facilities and of electric power increase rapidly with the magnitude of the required magnetic field.) water through the conductor. By these methods. the length of the magnetic circuit / m . This field is small if the permeability of the circuit is sufficiently large. a serious disadvantage in most cases that the field cannot be changed in magnitude or switched off. If the total number of turns in the windings is N. An electromagnet can be regarded as an apparatus to concentrate the magnetic flux produced by a coil into a small space. however.

as shown in Fig. 2.36 MAGNETIC MEASUREMENTS Fig. In order to make the maximum field as high as possible.4MA. Ni Fig. As the core approaches magnetic saturation. 2. independent of the properties and the shape of the magnetic circuit. For example. 2.6) is no longer negligible. the permeability decreases. the size. Design of an electromagnet. The proportionality factor is given by l// a . 2.S-l^MAm"1 (1-2T) using electromagnets. and electric power consumption increase rapidly as the maximum field is increased beyond these values. cost.3.2 Fields ranging from 3. Magnetic field as a function of magnetomotive force in an electromagnet.7°. The magnetic field produced by the electromagnet then approaches a limiting value.5-3T) by careful design.m~1 (2.0T) in a 5cm air gap. and possible to attain 2-2. the pole pieces can be tapered as shown in Fig. a superconducting magnet provided with hybrid coils of multi-filament Nb-Ti alloy and Nb3Sn compound can produce a maximum field of SMAm" 1 (10T) in a space of 4cm diameter.5 shows a large electromagnet which produces a maximum field of 2. . Theory shows that the maximum field is attained when the tapered surface is a cone whose half-angle is 54. provided the magnetization is everywhere parallel to the cone axis. The advantages of superconducting magnets are that: Magnetomotive force. However.2 It is easy to produce magnetic fields of O.4MAnT1 (3.3.4.4. Figure 2.2 to lOMAm" 1 (4 to 12T) can be produced by means of superconducting magnets. The most important factor in the design of an electromagnet is to avoid magnetic saturation in any portion of the magnetic circuit before the pole pieces begin to saturate. This simple linear relationship holds for any electromagnet up to some value of current or field. so that the first term in (2.

2. because they require enormous electric power and generate tremendous heat. there can be sudden irregular small changes in field intensity caused by 'flux jumps'. Pulsed field methods are therefore usually used to produce fields higher than SMAm"1 (10T). The disadvantages of superconducting coils are: (1) They require cooling with liquid helium. Recently a hybrid magnet in which an air-core copper magnet is installed inside a superconducting magnet has been successfully used to produce about 24MAm" 1 (30T). (2) No Joule heat is generated. Fig.PRODUCTION OF MAGNETIC FIELDS 37 Fig. steady (time-independent) fields are no longer practical. (1) No electric power is needed to excite the magnet.5. Superconducting magnet which produces 12MAm~ 1 (150kOe) in a 32mm diameter bore. the magnet 'quenches' from the superconducting state with the rapid generation of heat which very quickly evaporates the liquid helium. Bitter-type electromagnet (13 tons) which produces 2. 2. (3) It is possible to keep the field completely time-independent by short-circuiting the coil with a superconducting shunt. This is known as persistent current or persistent-mode operation.3 Beyond this limit. (3) The uniformity of the field is perturbed by persistent eddy currents in the superconductors.5 MAm" 1 (SlkOe) in a 5cm air-gap. Magnet at right.6 shows a superconducting coil and the cryostat in which the coil is cooled to liquid helium temperature. (4) When the field is changed. Figure 2.6. cryostat at left. so that no provision is necessary to remove heat from the coil. . (2) If the maximum field is exceeded. except for liquid helium which is used to keep the coil in a superconducting state.

This force results from the Maxwell stresses given by (1.7. This method is limited by the mechanical strength of the coil. First a liner is placed in a one-turn coil which is connected to a condenser bank through a Fig. First a large condenser B is charged from a source A. 2. The so-called Cnare method4 utilizes the kinetic energy of the inward motion of a short metal cylinder called a liner. It is possible to produce magnetic fields of 20-32MAm~ 1 (25-40T) for times of about 1ms by using a condenser bank of 3000 ptF capacitance and a working voltage of 3000 V. the switch E is closed.7. using either explosives or electromagnetic forces. The principle of this method is shown in Fig. Figure 2. the Maxwell stress is calculated to be Since the yield strength of a strong steel is at most 150 kg mm 2. . For instance. Circuit for generating a pulsed high magnetic field. for H = 56MAm" 1 (70T).110). 2. When the current reaches its maximum value. For fields higher than 40MAm~ 1 (SOT).8 illustrates the experimental arrangement for the Cnare method. Conceptual diagram of the Cnare method.38 MAGNETIC MEASUREMENTS Fig. Magnetic fields higher than this limit can be produced by magnetic flux compression. the coil is destroyed by the field even if it is made of high-strength materials.8. then the switch C is closed and a large pulse current is sent to the coil D. 2. in order to make the duration of the current pulse longer and also to prevent charging the capacitor in the opposite polarity. the coil is damaged by the electromagnetic force acting on the lead wires.

The disadvantages are that the maximum field is somewhat lower and the rise time of the field is about ten times faster than in the Cnare method. which was once common but is no longer popular. consists in measuring the torque given by (1. When the switch is closed. Fields as high as 400 MA m"1 (SOOT) have been produced by this method. in which a fast current pulse from a low-impedance capacitor bank is sent through a small coil. Electromagnetic induction produces a current in the opposite sense in the liner. Meanwhile some of the magnetic flux has diffused into the liner. T. so that the specimen is not destroyed. Instead of measuring a torque directly. see Section 3. This stress acts to compress the liner inward toward its axis. about 1 cm in diameter. This trapped flux is squeezed into a narrow diameter by the inertial motion of the liner. reaching a final speed as high as Ikms" 1 after about 10/AS. In this case the coil explodes outward (instead of collapsing inward or imploding as in the Cnare method). producing an increasing magnetic field inside the coil.8) acting on a known magnetic moment M. or where / is the moment of inertia of the magnet. (4) Measurement of a magnetic resonance such as electron spin resonance (ESR). to prevent magnetic flux from penetrating inside the liner.0 MOe) can be produced before the coil fails.5 The major disadvantage of the Cnare method is that the specimen is destroyed by the collapse of the liner. The magnetic flux which passes through the coil is given by . (3) Measurement of an electric signal induced in a galvanomagnetic probe. there appears a high magnetic field which produces a Maxwell stress on the liner. (2) Measurement of the electromotive force induced in a search coil be electromagnetic induction. thus resulting in an ultra high magnetic field. we can measure the period of oscillation.3) or nuclear magnetic resonance (NMR.6 2. see Section 4. of a freely suspended permanent magnet.2 MEASUREMENT OF MAGNETIC FIELDS The methods for measuring magnetic fields can be classified into four categories: (1) Measurement of the torque produced on a known magnetic moment by the magnetic field.MEASUREMENT OF MAGNETIC FIELDS 39 switch.1). The second category includes various methods utilizing the law of electromagnetic induction. the electric current flows in the one-turn coil. Thus in a narrow space between the one-turn coil and the liner. Fields up to 160 MAm"1 (2. An alternative approach is the so-called one-turn coil method. The first method. The liner accelerates inward. ferromagnetic resonance (FMR. Suppose that a search coil of n turns with cross-sectional area S (m2) is placed in a magnetic field H (Am" 1 ) with the coil area perpendicular to the field.

Similarly when the flux change A<& occurs in the search coil. The magnetic fluxmeter is an instrument that integrates this electromotive force with respect to time and produces a signal which is proportional to the change in the magnetic flux.11) results in Thus the total flux change is proportional to the electric charge Q which flows the circuit.10) is reversed. irrespective of the value of the inductance L. Therefore. the deflection 0 is given by Eliminating k from (2. This instrument is a galvanometer having a moving coil with a large moment of inertia. or by reversing the sense of the field. by reducing the intensity of the field to zero. and becomes zero at t = 10 (so that i = 0 again). results in the electromotive force — d<l>/df in the search coil. The resultant deflection of the galvanometer. 2. when the search coil is connected to a ballistic galvanometer. caused by removing the search coil from the magnetic field. or where k is the proportionality factor. by rotating the coil by 180° about an axis perpendicular to the field. &0. we have If the flux given by (2.40 MAGNETIC MEASUREMENTS Any change in the magnetic flux passing through the coil. The proportionality factor can be determined using a standard mutual inductance M whose secondary coil is connected to the circuit (see Fig.9). integration of (2. we have from which we can determine the magnetic field H. An instrument that measures the electric charge Q by integrating the current i is called a fluxmeter. a flux change 2Mi0 occurs in the secondary coil. . When an electric current in the primary coil i0 is reversed. then from Kirchhoff s second law: If the flux has the value <t> (Wb) at t = 0 (so that i = 0).14). is proportional to this flux change. putting A3> = 2$. the change in flux passing through the coil is measured by the deflection of the galvanometer. If the electric circuit containing the search coil has resistance R (H) and inductance L (H). the maximum deflection of the galvanometer is proportional to the electric charge which passes through the coil. One such instrument is the ballistic galvanometer. When a pulse of current flows through this coil in a time interval much less than the natural period of oscillation of the coil.13) and (2.

the DC current / (A) which flows through the plate will produce a DC voltage V (v) across the plate given by . The flux change caused by a rotation of the moving coil is designed to be proportional to its deflection. the Hall effect and the magnetoresistance effect.9.3. or InAs. A fluxmeter is distinguished from a ballistic galvanometer by the fact that a fluxmeter ideally has no stable zero position. InSb. the electromotive force d€>/d? causes a rotation of the moving coil and is balanced by the electromotive force caused by a change in <5m. Magnetic fluxmeter circuit. The suspension system provides a very small restoring torque on the coil. The principle of the Hall effect is illustrated in Fig. A commercially available fluxmeter is provided with a moving coil suspended in the field of a permanent magnet.18). When a magnetic field H (Am" 1 ) is applied perpendicular to a semiconductor plate made from Ge. we have Thus the flux change is measured by the deflection of the moving coil. 2. can be used. is commonly found in portable devices known as gaussmeters or field meters. the pointer will remain at any position on the scale. that is Integrating (2. based on the galvanomagnetic effect. The third category of instrument. Two different physical phenomena. 2.MEASUREMENT OF MAGNETIC FIELDS 41 Fig.10. A more automated recording fluxmeter will be described in Section 2. or When there is a change in the magnetic flux through a search coil connected with this fluxmeter.

and D2O. Direct-reading Hall gaussmeters covering the field range from 8 Am""1 (=0. (3) measurement of the voltage produced in a search coil by electromagnetic induction caused by a change in the position or state of magnetization of a magnetized body. The magnetoresistance effect refers to the change in electrical resistance of a conductor subjected to a magnetic field applied perpendicular to the current. the resonance frequency is proportional to the intensity of the magnetic field. and the two kinds of carriers are combined and annihilated after being driven in the same direction by the magnetic field.OOOOe). For these reasons.0 T) or higher are commercially available. The fourth category.3 MEASUREMENT OF MAGNETIZATION The methods for measuring the intensity of magnetization can be classified into three categories: (1) measurement of the force acting on a magnetized body in a non-uniform field. The standard isotopes used for NMR are H1.4 MAm"1 (= 3. 2.804 ± 0. where d is the thickness of the plate and R is the Hall coefficient. This is because the current carriers consist of equal numbers of electrons and positive holes. magnetic resonance phenomena.001 MHz in a field of 79. LiCl.42 MAGNETIC MEASUREMENTS Fig. is used particularly for accurate calibration of other types of instruments. LiSO4. 2.58Am'1 ( = l.3 for ESR and in Chapter 4.1Oe) to 2. In this case the resistance change is proportional to H2.3] and for magnetically recorded tapes and disks.10. The magnetoresistance effect is particularly large in Bi.1 for NMR. Li1. and D2 contained in H2O. which is inconvenient for a general-purpose instrument. Hall effect element. The standard material used for ESR is DPPH (a-diphenyl-/3-picrylhydrazyl) which resonates at 2. magnetoresistance is rarely used for the direct measurement of magnetic fields. (2) measurement of the magnetic field produced by a magnetized body. In both cases. Magnetoresistive sensors have been used as read-out devices for magnetic bubble memories [see Chapter 22. galvanomagnetic effects are generally temperature dependent and also more or less subject to aging. Furthermore. The principles will be explained in Chapter 3. .

The coil is placed in the radial magnetic field of a loudspeaker magnet. however.11. This force is counterbalanced by an automatic device described later. 2. The magnetic balance1 is the most common example of category 1. a specimen suspended from one arm of a balance is attracted downwards by the inhomogeneous field produced by an electromagnet. x is not not negligible as compared with 1 (say x> 10~2). from which we can determine the magnetic susceptibility x'• If.33).11.21).MEASUREMENT OF MAGNETIZATION 43 Fig. so that a current through the coil produces a vertical force on the coil. x> because of the demagnetizing field. When 7 is proportional to H. the current in the coil is proportional to . and (dH/dz) is the vertical gradient of the field. The downward force is given by where I is the magnetization. Since we have the relationship the true susceptibility is given by The downward force on the sample is balanced by suspending a small coil from the opposite arm of the balance. using (1. When the balance is in equilibrium. 2. we have from (2. Magnetic balance. As illustrated in Fig. v the volume of the specimen. the value of x' in (2.22) is different from the true susceptibility.

It is purely mechanical. which is proportional to the deflection. Magnetic pendulum. 2. absorption of water. the force acting on the specimen is compensated by two attracting coils so as to exert no lateral force on the support. A similar apparatus in which the magnetic force acts horizontally rather than vertically is known as the magnetic pendulum. It has the advantage that changes in the mass of the sample due to oxidation. Figure 2. The system can be made automatic by providing a means to detect electrically the equilibrium position of the balance. without any automatic balancing feature.. The Sucksmith ring balance8 is a once-common apparatus utilizing the same principle.12. Fig.9 . The system is insensitive to magnetic disturbance from outside.44 MAGNETIC MEASUREMENTS the force acting on the specimen and accordingly to the susceptibility. which is a jewelled knife edge. is amplified and sent to the hanging coil as a feedback signal so as to maintain the balance in equilibrium.12 illustrates the construction of a magnetic pendulum with a wide range of sensitivity. The detector signal. etc. do not affect the reading.9 In this pendulum. because only a radial field exerts a vertical force on the coil.

2. In this device. Several manufacturers provide magnetometers of this type. This apparatus is still being used for the measurement of weak residual magnetization of geological specimens. If the sample is driven by a loudspeaker mechanism. and is magnetized to / (T) by an external field //ex. The AC signal induced in the pick-up coil by the magnetic field of the sample is compared with the signal from a standard magnet M and is converted to a number proportional to the magnetic moment. the magnetic flux which passes through this search coil is given by where N is the demagnetizing factor of the specimen and He{{ is the effective field inside the specimen. A mechanical crank drive can also be used. As shown in Fig. 2. and convenience for measurements above and below room temperature. Vibrating sample magnetometer (VSM). perhaps 1-2 mm. The astatic magnetometer also falls into the second category.2 mm. Note that the magnetic field just outside the specimen is the . the frequency is usually near 80 Hz and the amplitude is 0. the magnetic field produced by the magnetization of the specimen is measured by the deflection of a pair of coupled magnetized needles suspended from a fine fiber.2) above. When a rod specimen of cross-sectional area 5' (m2) is inserted into a search coil of n turns with cross-sectional area 5 (m2) (Fig. 2.MEASUREMENT OF MAGNETIZATION 45 Fig. The vibrating sample magnetometer (FSM)10 is a modern version of this type of magnetometer. The principle of the third category (electromagnetic induction) is the same as that described in (2. in which case the frequency is normally somewhat lower and the amplitude larger.13.13. ease of operation. The advantages of this magnetometer are high sensitivity.1-0. the sample S is oscillated vertically in a region of uniform field.14).

46)).14. requires only a small quantity of material (particularly advantageous for noble metals.15. because the tangential component of the field is always continuous. Special combination search coils.15. a spherical specimen has several advantages: it is relatively easy to prepare. it has a well-defined demagnetizing factor (refer to (1. rare earths and single crystals). 2. The only disadvantages are a large demagnetizing factor and a certain difficulty in mounting and holding the sample during the measurement.46 MAGNETIC MEASUREMENTS Fig. but may be inconvenient to prepare. and it is well suited for measurements at high and low temperatures or under pressure. and is also unsuitable for measurements at low and high temperatures or under high pressures. Search coil. especially as a single crystal. while the flux due to H is proportional to r2. When a spherical specimen of radius rs (m) magnetized to intensity / (T) in a magnetic field H (Am" 1 ) is placed at the center of a thin search coil of radius r (m) containing n turns. same as the effective field Hei{ inside the specimen. A long thin specimen is useful for the measurement of the magnetization curve of soft magnetic materials because of its small demagnetizing factor. The construction of the search coil is shown in Fig. permitting measurement along many crystallographic directions in one single crystal sphere. The following is an example of the measurement of a magnetization curve as a function of the effective field He{{ for a spherical specimen. A proper combination of two coils with radii r1 and r2 and number Fig. . On the other hand. the flux which goes through the search coil is given by Then the flux due to / is inversely proportional to r. 2. 2.

Cioffi-type recording fluxmeter. if we make nl:n2 = \/r\ : \/r\. the H term is cancelled. but it can be replaced by any combination of Fig.16. . Figure 2. If we select where and Thus we have a search coil which picks up the effective field.12 In this figure the specimen is shown as a ring. For instance. we can draw a magnetization curve as a function of the effective magnetic field. 2.MEASUREMENT OF MAGNETIZATION 47 of turns «j and «2 can m^ tne ^ a°d ^ terms in any desired ratio.11 By connecting these search coils to recording fluxmeters. so that we have where Thus we have a search coil which picks up a signal proportional to /.16 shows a circuit diagram of a Cioffi-type recording fluxmeter.

the voltages induced in these coils are converted to signals proportional to Hef{ and / by using two recording fluxmeters whose output signals are fed into the x. Since this unbalanced voltage is negligibly small. which are used to generate a feed-back current i' in the primary coil of the mutual inductance L12. First the current i is passed through the primary coil.and y-axes of an x-y recorder to draw an I-Heff curve. In the case of a spherical specimen which is placed in the air gap of an electromagnet together with a set of search coils as described by (2. the signals proportional to / and i' are fed to an x-y recorder so that the magnetization curve is drawn. Figure 2. This deflection is sensitively detected by two photocells.16. In the case of Fig. except for a small uncompensated voltage which keeps a current /' in the primary coil of L12. which induces a voltage in the secondary coil This voltage almost compensates the voltage given by (2.48 MAGNETIC MEASUREMENTS specimen and a search coil.34). . we have the relationship which shows that the flux change is proportional to the current change A/'. we have Integrating (2. so that the specimen S is magnetized. This gives rise to a voltage in the secondary coil This voltage deflects the galvanometer G.17. Hysteresis loops measured for Gd at various temperatures using special combination search coils.11 Fig. 2. Pj and P2.32).31) and (2.28). 2.17 shows hysteresis loops obtained in this way for a Gd sphere at various low temperatures.

T. Japan. If the search coil is removed from the specimen but remains in the magnetic field. Soc. Takeyama. or the specimen itself is removed from a fixed search coil. Sci. The fact that the measuring apparatus must be at liquid helium temperature is clearly a disadvantage in many cases. E. 4. de Phys. 1174. Phys. Muto. which utilizes the Josephson effect. 37 (1966).. Haruyama. and N. . Goto. A. Japan. T. Kakiuchi. Miura. In favorable cases. four to five significant figures can be obtained by this method. 579. (1965). 5. Kido. Katori. C. /. Y. 20. The principle of this method is to move a search coil with respect to a magnetized specimen by a fixed distance. Physica. Sakakibara.1 Calculate the coil constant at the center of a one-layer solenoid of radius r (m).16 A very weak magnetic flux can be measured accurately by a superconducting quantum interference device (SQUID) magnetometer. E. 2... Nakao. K. J. measure the induced voltage with a digital voltmeter as a function of time. Takamasu. the flux change is given by the first term of the final line of (2. and a SQUID magnetometer requires a long time for each magnetization measurement. Instrum.13'15 The same principle has been successfully applied to measure the slowly changing magnetic fields produced by a hybrid air-core and superconducting coil. Appl. Phys. 6. /.17 Counting these flux quanta gives a very sensitive measurement of the flux change and therefore of the magnetization of the sample. B 201 (1994). 3. Hoshi. Phys. Cnare.. Todo. 1018. In this case. Y. S. 2. M. Miura. A. J. 1 (1962). Nojiri. Matsuoka and Y. K. and N. Nakagawa. K. Herlach. F.26). T. 3812. T. 18 (1985). 155. Uchida.2 A magnetomotive force M (A) is applied to an electromagnet made from highpermeability material.25) or the first term of (2. length 2-/J r (m). T. Goto. Appl. Cl-23. especially if the field is changed between readings. K. the flux change is given by (2. and Y. If the air gap is / (m) long. and then integrate these values with respect to time with an analog or digital integrator. provided that the search coil is removed completely from the sample and out of the field. S. what is the magnetic field in the gap? 23 Describe typical methods for measuring magnetic moments and magnetic fields after classifying them according to the principle of measurements. Watanabe. Phys. Ishikawa and S. Chikazumi. PROBLEMS 2.REFERENCES 49 More accurate and stable measurement of magnetic flux is possible using a digital voltmeter. J. Miura. S. and winding density n (turns m"1). 45 (1984). The Josephson effect is the name given to the fact that the flux change in a superconducting circuit interrupted by an insulating layer about 50 A thick is quantized. H. H. REFERENCES 1.25).

170A (1939). Appl. Appl. Rev. Thesis (Grenoble University. (in Japanese) (Kyoritsu Publishing Co. Clarke. 548. S. P. Bartimay. Rebouillat. 15 (1976). Appl. K. Cioffi. Nakagawa and A. R. Phys. 14. Kido and Y. J. Phys. . Japan. 38 (1967). Y. Lecture Series on Experimental Physics. Nakagawa. Ishikawa and S. Sci. Sci. 21 (1950). IEEE Trans. 624. Conf. 17 (12). 13. /. (1985). and S.. 61 (1973). 15. P. 30 (1959). Tokyo. Lecture Series on Experimental Phys. Y. Soc. 17 (10) (in Japanese) (Kyoritsu Publishing Co. Sucksmith. Tasaki. Magnet. 8. M. W. Roy. Mag. 9. Rev. 17. P. Strnat and L.50 MAGNETIC MEASUREMENTS 7. 10. Matsui. T. H. /. 11. 1299... 16. McGuire. 8. Proc. J. Tokyo.. Proc. 299.. 630. Chikazumi. Proc. 551. J. 1968). 1972). Phys. Chikazumi. Foner. Nishio. 38 (1967). Instr.. Tech. 1305. 9th Int.. 12. Instr.. Zurich.. 1968). IEEE. Mag-8 (1972).. G. (London).

Atomic nuclei also have feeble but non-zero magnetic moments. . These have almost no influence on the magnetic properties of matter. Neutron scattering and muon spin rotation are also useful tools for investigating microscopic magnetic structures. In this Part. we discuss the origin of these atomic magnetic moments. but do provide useful information on the microscopic structure of matter through nuclear magnetic resonance (NMR) and Mossbauer spectroscopy.Part II MAGNETISM OF ATOMS In most magnetic materials the carriers of magnetism are the magnetic moments of the atoms.

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3. 3. Therefore the magnetic moment produced by the circular motion of the electron in its orbit is given by Since the angular momentum of this moving electron is given by where m (kg) is the mass of a single electron. where — e is the electric charge of a single electron. (3. The magnetic moment of a closed circuit of electric current i whose included area is S (m2) is known from electromagnetic theory to be n0iS (Wbm). its motion constitutes a current of —ea)/2Tr (A).1). where Z is the atomic number. Fig. Since the electron makes «/27r turns per second.1) may be written as Thus we find that the magnetic moment is proportional to the angular momentum. although their sense is opposite.1 STRUCTURE OF ATOMS In the classical Bohr model of the atom. Z electrons are circulating about the atomic nucleus which carries an electric charge Ze (C). Bohr's atomic model.1. . and e (C) is the elementary electric charge. Suppose that an electron moves in a circular orbit of radius r (m) at an angular velocity to (s"1) (Fig. One of the origins of the atomic magnetic moment is this orbital motion of electrons.3 ATOMIC MAGNETIC MOMENTS 3.

the s component of the angular momentum ps is expressed by the operator* where s is the circular ordinate taken along the circular orbit. so that only discrete orbits can exist. In other words.54 ATOMIC MAGNETIC MOMENTS Now it is well known that the orbital motion of the electron is quantized. is given by The eigenvalue of the angular momentum. which is normal to the orbital plane.3). the angular momentum is quantized. and is related to the azimuthal angle of the electron by The momentum along the orbit is given by Therefore the angular momentum along the z-axis. is obtained by solving the wave equation The general solution of this equation is given by •Although the angular momentum is a physical quantity related to time. and is given by where h is Planck's constant h divided by 2 77. Why the angular momentum of an orbital electron is quantized by h In quantum mechanics. Substituting (3. .4) for P in (3. we have Thus the magnetic moment of an atom is given by an integer multiple of a unit which is called the Bohr magneton. it can be expressed in terms oi only the ordinate s as long as we treat only stationary states. mh. or and / is an integer called the orbital angular momentum quantum number.

The magnitude of the angular momentum associated with spin is ft/2. This concept was first introduced by Uhlenbeck and Goudsmit1 for the purpose of interpreting the hyperfine structure of the atomic spectrum. In 1928.20). we find that the magnetic moment is again given by the Bohr magneton.16).2. 3. Besides the orbital angular momentum. Dirac2 provided a theoretical foundation for this concept by making a relativistic correction to the wave equation. The necessary condition for this solution to be a stationary state is that Otherwise the wave function cannot be a unique function as shown in Fig.2. 3. However.13). Explanation of a stationary state. we find that a factor 2 is missing in the denominator.3). The magnetic moment associated with spin angular momentum P is given by Comparing this equation with that of the orbital magnetic moment or (3. . the electron has a spin angular momentum. so that its angular momentum is given by where s is the spin angular momentum quantum number and takes the values ±^. substituting P in (3. These conditions were proved by Dirac2 using the relativistic quantum theory.STRUCTURE OF ATOMS 55 Fig.14) to (3. Applying (3. we have or Thus the eigenvalue of L2 is an integer multiple of h.19) into (3. we have or In order to satisfy (3.

according to the classical model.g. Using (3. It .21) is calculated to be which is called the gyromagnetic constant.4. As mentioned above. can occupy the orbit defined by n and /. —1. —2 as shown in Fig.2. are called the K.2. n — 1. The orbits which belong to the principal quantum number n can take n angular momenta corresponding to / = 0. The groups of orbits corresponding to n = 1. Figures 3...0. In this case it is meaningless to discuss the azimuthal orientation of the orbit about the magnetic field.4.3.3 only two electrons.. Intuitively this corresponds to discrete tilts of the orbital planes relative to the axis of the magnetic field.4 show such precessions for m = 2. in a neutral atom Z electrons are circulating about a nucleus having an electric charge Ze (C). which takes the numerical values 1.1. .. or the magnetic quantum number can take the values For instance.5). The shape of the orbit is determined by the angular momentum. According to the Pauli exclusion principle.1. and 0.. The component of / parallel to the field. 1. This is called spatial quantization. The total angular momentum of one electron is defined by the sum of the orbital and spin angular momenta...3(a) and 3. with s = + \ and — \...2. we can express (3. Now let us examine the relationship between the electronic structure of atoms and their angular momentum.22). because the orbit precesses about the magnetic field.. N.3. When a magnetic field is applied to an atom. L. The size of the orbit of the electron is defined by the principal quantum number n..2.56 ATOMIC MAGNETIC MOMENTStas Generally the relationship between M and P is given by where the g-factor is 2 for spin and 1 for orbital motion.. or in classical mechanics by the areal velocity. M. The angular momentum is defined by the orbital angular momentum quantum number in (3. are called the s.. in the case of the d electron (/ = 2)..f.4.' is the total angular momentum quantum number. the orbital moment can take five possible orientations corresponding to m — 2.1. 3.d. the angular momentum parallel to the magnetic field is also quantized and can take 21 + 1 discrete states.3.. The coefficient of P in (3. shells.39). respectively.19) in which s can take the values ±|. electrons. The spin angular momentum is defined by (3. m.21) as Thus we find the magnetic moment of an atom is closely related to the angular momentum of the electron motion. The electrons with / = 0.. A more exact definition of the g-factor is given by (3.. so that where .p..3.

3.4. 3.3(b)). 3. and d orbital states. and 2. possible orbital angular momenta are / = 0. I. each orbital states consists of 21 + 1 orbits with different magnetic quantum numbers m. Since the principal quantum number n of the M shell is 3. . When an atom contains many electrons. and 5 for s. and s. p. 3. According to spatial quantization. p.3. Shapes of orbits for various magnetic quantum numbers. is interesting to note that these figures have some similarity with the atomic wave functions shown in Fig. 1.STRUCTURE OF ATOMS 57 Fig. respectively. Figure 3. 3. That is. The spin can take up an orientation either parallel (s = +\) or antiparallel (s = -\) to the magnetic field (Fig. In other words. each electron can occupy one state defined by n. the number of orbits is 1. Therefore the total number of orbits belonging to one atom is given by Fig.5 shows possible states belonging to the M shell. Spatial quantization for orbital (a) and spin (b) angular momenta. and d.18. there are s.

as long as the inner electrons are distributed with spherical symmetry about the nucleus. as shown in Figure 3. It must be noted that the energy defined by n is that of one isolated non-interacting electron. When a number of electrons are circulating around the same nucleus. the 4s orbits are occupied before the 3d orbits are .1 lists the electron configurations of the atoms which are most important in connection with magnetism.1 electrons form a spherical charge distribution about the nucleus. because of a large Coulomb interaction with the unshielded nuclear charge.spins can enter into one orbit. This is the reason why the size of the atom remains almost unchanged from that of hydrogen. up to heavy atoms with many electrons. the ordering of the energy levels remains unchanged. Figure 3. In the case of the M shell with n = 3. if the inner Z . Thus the energy of the 4s electron is lowered. Various electronic states belonging to the M electron shell. Since two electrons with + and . If. 3. the atomic wave function of s electrons is very large in the vicinity of the nucleus. whereas the 3s orbit is elliptical. the charge distribution of the orbit deviates from spherical symmetry. This is the same as the electric field produced by a proton of charge +e. up to argon (Z = 18). the total number of electrons belonging to one neutral atom is equal to In2. Z electrons occupy the possible orbital states starting from the lowest energy state. the electrons occupy the states in the normal order. We see that the 3d orbit is circular. In other words. the outermost electron feels the difference in electric field between the nuclear charge +Ze and the charge of the inner electron cloud — (Z — l)e. As seen in this table. from the lower n states to the higher ones. we must take into consideration the interaction between these electrons. Table 3. irrespective of the number of electrons. the total number is 2n2 = 2 X 32 = 18.5. so that part of the orbit is close to the nucleus. Therefore. For this reason. In an actual atom with atomic number Z. the situation is changed. however. However. because the effect of the inner electrons is simply to shield the electric field from the nucleus.21(c).6 shows the shapes of various Bohr orbits.58 ATOMIC MAGNETIC MOMENTS Fig.

VECTOR MODEL 59 Fig. Similarly. 5p. and lj).. respectively. s. The same thing happens for atoms heavier than hafnium (Z = 72). in which the 6s orbits are filled before the 5d orbits are occupied. the orbitals of each electron are aligned by the strong orbit-orbit interactions. 4d. and 6s orbits are occupied before the 4/ orbits for atoms heavier than lanthanum (Z = 57). In the order mentioned above. As seen in Table 3. thus forming a resultant atomic orbital angular momentum . Let the spin and orbital angular momentum vectors of the j'th and yth electrons be sf. 3.6..1. /. The magnetic elements are found among these transition elements.and /. Various Bohr orbits. rare-earth and 5d transition elements. 5d. respectively. As a result. The elements which have incomplete electron shells exhibit abnormal chemical and magnetic properties. These vectors interact in a local scale. and «•).2 VECTOR MODEL In this section we discuss how the orbital and spin magnetic moments of electrons in an incomplete electron shell form an atomic magnetic moment. thus forming a resultant atomic spin angular momentum Similarly. The most important of these interactions are those between spins (s. they are called the 3d. and those between orbitals (/. 3. the 5s orbits are occupied before the 4d orbits for atoms heavier than rubidium (Z = 37). the 5s. occupied for atoms heavier than potassium (Z = 19). and are called transition elements. the spins of all the electrons are aligned by the strong spin-spin interactions...

Levels and number of states K 2 Z 8 M 18 N 32 3d 10 il4p 2 6 4d 10 4/ 14 5s 2 5p 6 O 50 5d 10 5f 14 5g 18 ITs 2 6p 6 6d 10 P 72 Q 6 / 6 5 6 A 14 18 22 ~ — 7i ••• 2 Ground terms Elements 1 H 2 He 3 Li 10 Ne 11 Na 18 .1. Electronic configuration of elements.Table 3.2 g 2 <*> V Cr Mn Fe Co Ni Cu Zn 1 2 3 5 5 6 7 8 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 1 2 2 2 2 1 2 2 2 2 1 2 2 2 2 2 2 2 2 2 2 2 2 2 2 6 I a 5 0 1 i § § Kr Rb Sr Y Zr Mb Mo 43 Tc Ru 44 45 Rh I 46 Pd v 47 Ag 54 Xe 6 6 6 6 6 6 6 6 6 6 6 6 1 2 4 5 5 7 8 10 10 10 1 2 2 2 1 1 2 1 1 0 1 2 6 .37 38 39 40 41 { 42 Ar K Ca Ti Sc Is 2 1 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2s 2 2p 6 3s 2 3p 6 1 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 1 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 „ 0 1 •3 B .19 20 21 22 23 / 24 \ 25 26 27 28 29 V 30 36 .

10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 :io) :n) 13 14 14 14 14 14 14 14 14 14 14 14 14 14 14 () 3 4 () 5 6 7 7 8 () 9 1 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 1 1 () 0 0 () 0 0 0 (1) (1) (1) 0 0 2 3 4 5 6 7 9 10 10 10 10 10 (13) 1 1 1 1 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 1 1 2 2 2 2 6 6 6 (1) 86 Rn 87 Fr 102 No 2 2 2 10 10 10 1 2 6 6 .1.< 64 Gd 2 £ 65 Tb 2 u 66 Dy 2 " 67 Ho 2 2 c£ 68 Er 69 Tm 2 70 Yb 2 V 71 Lu 2 2 •£12 Hf 2 5 | 73 Ta | 74 W 2 o 75 Re 2 g { 76 Os 2 2 5 j 77 Ir 5 78 Pt 2 g 79 Au 2 ^ ^ 80 Hg 2 >n .) _ la 2 _ ll 8 _ m mm 18 3p 3d 6 10 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 Elements Is 2 2s 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2p 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 3s 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 4s 2 _ nn 32 4p 4d 6 10 Levels and number of states _ 00 4f 14 5s 2 5p 6 50 5d 10 _ p 72 5f 14 5g 18 6s 2 6p 6 6d 10 6f 14 6g 18 6ft 22 __ qw8 — 7s ••• 2 Ground terms 2 55 Cs 56 Ba 2 . 57 La 2 2 58 Ce 59 Pr 2 .„ 60 Nd 2 g 61 Pm 2 £ 62 Sm 2 2 3 63 Eu . (contd.Table 3.

For instance.62 ATOMIC MAGNETIC MOMENTS Fig.8. (3) The third rule is concerned with the coupling between L and S. —2. and also the intra-atomic spin-spin interaction tends to align these spins parallel to each other. of each electron are arranged so as to produce the maximum resultant orbital angular momentum L within the restriction of the Pauli exclusion principle and also of condition (1). while the remaining 2 have negative spin. In the case of 9 electrons.8). When a number of electrons exist in an atom. In the case of the 4/ shell. which would increase the Coulomb energy. thus resulting i n L = 3 + 2 = 5 (Fig. producing no orbital moment. which has the capacity of accepting 14 electrons. the maximum resultant orbit is L = 3 + 2 + 1 + 0 .0. 3. The reason is that the electrons tend to circulate about the nucleus in the same direction so as to avoid approaching one another. the magnetic quantum number m can take the values 3.7). when the 4/ shell has 5 electrons. —1. -3. in the case of the 4/ shell. which is described as follows: (1) The spins s. while the remaining 2 electrons occupy the states with m = 3 and 2. or . 3. thus forming 5 = f. When the number of electrons is 9. 3. the arrangement of these vectors are governed by Hund's rule5. For example. (2) The orbital vectors /. 7 electrons have positive spin.1 = 5.7. are arranged so as to form a resultant spin 5 as large as possible within the restriction of the Pauli exclusion principle. n. In the case of 5 electrons. they occupy the states with a positive spin. the electrons occupy states in the order of the numbers in Fig. When the number of electrons in the 4/ shell.1. Now the senses of these resultant vectors S and L are governed by the so-called spin-orbit interaction energy thus forming the total resultant angular momentum This interaction is called the Russell-Saunders interaction4 (see Fig. is less than half the maximum number. 3. so that the resultant spin becomes 5 = \ — \ = f.2. The reason is that the electrons tend to take different orbits owing to the Coulomb repulsion. the first 7 electrons occupy the half shell with positive spins. Russell-Saunders coupling.

9. / = 5 — f = f. when the Fig. or n > 1. / = 5 + f = ^. Since the orbital angular momentum of this electron points upwards (see Fig. Then its spin points downwards. it follows that / and s of a single electron are always opposite. the electron senses a magnetic field H pointing upwards produced by the circulating nucleus with positive electric charge. n < 1. 3. As a result. 3. 3. .9). Therefore when the number of electrons is less than half the maximum number.VECTOR MODEL Spin angular momentum 63 Fig. So when the number is 5. J = L . Spin and orbital states of electrons in the 4/ electron shell.8.9). / and s are opposite for all the electrons.20)).S. 3. this electron sees the nucleus circulating about itself on the orbit shown by the broken circle in the figure. so that it follows that L and S are also opposite. When the shell is more than half filled. Such an interaction is based on the s — I interaction of the same electron. When an electron is circulating about the nucleus (Fig. because the spin angular momentum is opposite to the spin magnetic moment (see (3. while when the number is 9. However. J = L + S. Explanation of the l-s coupling.

The total angular momentum. n.29). S increases linearly with n from La to Gd. The rare earth elements have an electronic structure expressed by in which the incomplete 4/ shell is well protected from outside disturbance by the outer (5s)2(5p)6 shell. while it is relatively large for n > 1. The outermost electrons (5d)l(6s)2 2 are easily removed from the neutral atom. while / = L + S for n = 1 to 14. . the sign of w is positive when the number of electrons n < 7.10. which has 4/7. 6. so that the only orbital momentum L comes from electrons with negative spin which point opposite to the resultant spin S. which has 4/14. thus resulting in parallelism between L and S. Now let us calculate the values of 5. Fig. 3. because / = L . thus producing trivalent ions in ionic crystals. 3. L and J for rare earth ions.S for n = 0 to 7. As mentioned above. the orbital momentum for the 7 electrons with positive spin is zero. which have incomplete 4/ shells. Further increase in n results in a repetition of the same variation. where a half-shell is just filled. and conduction electrons in metals or alloys.10. changes as shown in Fig. orbital L. So / is relatively small for n < 7. 5. is increased. and then decreases linearly to Lu. The value of L increases from 0 at La to values of 3. Therefore the atomic magnetic moments of rare earth elements are more or less the same in both compounds and in metals. as the number of 4/ electrons. /. In terms of w in (3. and then decreases towards 0 at Gd with 4/7. so that its orbital magnetic moment is well preserved or 'unquenched' by the crystalline field.64 ATOMIC MAGNETIC MOMENTS number of electrons is more than half the maximum number. Spin S. while it is negative when n > 7. This state and also a completely filled 4/14 state are called 'spherical'. and total angular momentum 7 as functions of the number of 4/ electrons of trivalent rare earth ions.

Now let us discuss the magnetic moments associated with these angular momenta.11.VECTOR MODEL 65 Fig. and its magnitude is given by the projection on / or The magnetic moment given by (3. Therefore the average magnetic moment becomes parallel to /.19) and (3. Referring to (3. we have From the relationship between three sides and the angle ^ABO in the triangle A ABO.34) is called the saturation magnetic moment. the vector L + 2S also precesses about /. we have Eliminating cos ZABO. Since. the vector L + 25 takes a direction different from / (Fig.34) and (3. we have from which we obtain an expression for g: . however. 3.33). and also referring to the geometrical relationship shown in Fig.20). we have the spin magnetic moment Therefore.6) and (3. we have the orbital magnetic moment Referring to (3.11). 3.11. Comparing (3. 3.7). L and S precess about /. Composition of atomic magnetic moment M. the total magnetic moment MR is given by When vectors L and S take different orientations.

then / = 5.) Thus it is concluded that the eigenvalue of L2 is L(L + 1). When a magnetic atom is placed in a magnetic field. then J = L. as In quantum mechanics. we must replace S2. The shape of the curve is similar to that of L (see Fi 3. respectively.* Then we have This relationship was first introduced by Lande empirically to explain the hyperfine structure of atomic spectra.65).39) and (3. as will be discussed in Part III. Jz can take the following discrete values as a result of spatial quantization of the vector /: This fact affects the calculation of the statistical average of magnetization. L2 and J2 by 5(5 + 1). L(L + 1) and /(/ + 1). we can write Executing this operator to the atomic wave function given by (3. so that we have In polar coordinates. Experimental values observed for trivalent ions * Let us deduce this relationship for orbital angular momentum L.39) that g=l. except that the magnetic moment is much more enhanced by the g-factor for heavy rare earths than for light ones. the magnitude of the atomic moment deduced from the thermal average of magnetization is given by which is called the effective magnetic moment. Ly and Lz. py and pz.and z-components of L be Lx. As a result. or px. while if L = 0. This is exactly what we find in (3. so that it follows from (3. p must be replaced by —ih(d/dq) (q is the positional variable). we have (Examine this relationship for desired values of / and m in (3. y. Figure 3.40) as a function of the number of 4/ electrons.66 ATOMIC MAGNETIC MOMENTS In quantum mechanics. The calculation will be shown in Chapter 5.1). Then On the other hand. so that g — 2. y. respectively.10). and the position coordinates x. and z.12 shows the effective magnetic moment calculated using (3. these components can be expressed in terms of the components of momentum p. The solid curve represents the calculation based on Hund's rule. . Let the x-.6 If 5 = 0.65).

vector modeldeell.D. and reproduces the experiment well.. This discrepancy was explained by Van Vleck and Frank7 in terms of multiple! terms of these elements.. therefore. in the compounds are also shown as open circles in the figure. Effective magnetic moment as a function of the number of 4/ electrons measured for trivalent rare earth ions in compounds and rare earth metals. whose electronic structure is 4/6. because there is a tendency for atoms or ions to become spherical. whereas Yb 3+ . except for Eu and Yb. The reason is that these ions are divalent in metals. The broken curve in the figure represents this correction. The agreement between theory and experiment is excellent. tends to become Eu2+ or 4/7 by accepting an electron from the conduction band. result in an increase in the magnetic moment. respectively. as seen in the figure. and comparison with the Hund and Van Vleck-Frank theories. S and L almost compensate one another in the ground state. Therefore.G.P. The experimental points for metals. which is 4/13. thus showing the same effective magnetic moments. signify that . while in the excited states. except for Sm and Eu. in which S. or *Fg/2. thus producing a non-zero J. The electronic structures discussed in this section are often expressed in spectroscopic notation such as 2S1/2. Eu3+.. shown as crosses in the figure. 5DQ. S and L make some small angle. are also in excellent agreement with the theory. Fig.F. In these elements. The thermal excitation and the mixture of these excited states. These divalent ions have the same electronic structures as Gd3+ and Lu 3+ . tends to become Yb2+ or 4/14 in the same way. 3.12.

spin and orbital magnetic moments. Since the values of the g-factor determined in this experiment are different from the values determined from a magnetic resonance * The attempts are based on the gyroscopic effect: when a force is applied to change the axis of rotation of a spinning top. The first such experiment was done by Maxwell. so that the gyromagnetic constant in (3. The specimen is suspended by a thin elastic fiber and is magnetized by a vertical field which reverses direction at a frequency corresponding to the natural frequency of mechanical oscillation of the system. the axis always rotates perpendicular to the direction in which the force is applied (see Fig. could be calculated. one rotating about its long axis and the other magnetized by an external magnetic field applied along its long axis. A prefix to the capital letter represents 2S + 1. In 1915. Therefore the crystal lattice must rotate so as to compensate for the change in angular momentum of the magnetic atoms. Then the associated angular momentum must also change. and a suffix represents /.22). the natural period of oscillation was 26 seconds.68 ATOMIC MAGNETIC MOMENTS L = 0.2. respectively. because the effect is extremely small. The most successful measurement technique is known as the Einstein-de Haas effect. 3.13.3 GYROMAGNETIC EFFECT AND FERROMAGNETIC RESONANCE As noted in the preceding section.8 This measurement was based on the simple idea: if a bar magnet supported horizontally at the center on pivots is rotated about the vertical axis. it is expected to tilt from the horizontal plane if it has an angular momentum associated with its magnetization.4. The magnetization was also measured. This relationship between rotation and magnetization is called the gyromagnetic effect.3. the rotation of the bar should drive this momentum towards the axis of rotation. however. there are two possible origins for magnetism in materials. This experiment was. Barnett9 first succeeded in determining the g-factor by comparing the magnetization of two identical magnetic rods.1. unsuccessful. This experiment was based on the idea that if the magnetic atoms in the bar have an angular momentum.14). The mechanism by which the magnetic atoms transfer their angular momentum to the crystal lattice will be discussed later in this section. Since this system is isolated mechanically. 3.11 The principle is illustrated in Fig. The rate of decay of the amplitude of the oscillation was measured with and without an alternating magnetic field applied in synchronism with the mechanical oscillation. Many attempts* have been made to measure the g-factors of various magnetic materials in order to determine the contribution of these possible origins. . and accordingly the g-factor in (3. 3. Consider the moment when the field (and therefore the magnetization) change direction from upward to downward. Electronic configuration and spectroscopic ground terms are given in Table 3.1. the total angular momentum must be conserved. The difference gives the change in angular momentum. In the actual experiment done by Scott.™ which was developed more precisely by Scott.23).

83 1.5 8 4. is associated with the magnetic moment.99 1. experiment. deviates from the direction of the applied magnetic field.5 .84 1. M.91 1.2.85 1. Then a torque will act on M.18 2. P. Values of these two quantities are listed for various magnetic materials in Table 3.13.5 6 9 5 0. 3.01 2.5 from g' 4 7.98 1.91 1.19 g/(g ~ 1) 1. by the angle 6.and g'-values. as will be discussed below.12 2.91 1.85 1. g(%) Material Fe Co Ni FeNi CoNi Supermalloy Cu2MnAl MnSb NiFe2O4 g 2. H. Suppose that the atomic magnetic moment.5 8 4.21 2.5 10. the former is referred to as the g '-factor. the direction of this vector must change by L per unit second or Table 3.10 2. while the latter is called simply the g-factor.2.10 2.84 g' 1.5 5 9.83 1. Since an angular momentum.92 1.5 1 7.85 from g 5 10.10 2. The g-factor can also be determined by a magnetic resonance experiment.5 0. Comparison between g.90 1.21 2. Apparatus for observing the Einstein-de Haas effect.GYROMAGNETIC EFFECT 69 Fig.91 1.84 1.99 1.91 1.

In the actual experiment a specimen is attached to the wall of a microwave cavity. 3. 3. so that P must rotate about H without changing its angle of tilt 6 and its magnitude.44) is independent of the angle 6. Ferromagnetic resonance experiment. 3. precessional motion will be induced for all the magnetic atoms. a>.44). the vector L is perpendicular to P. the magnetic moments of all the magnetic atoms in the material precess with the same angular frequency. Applying this law to a rotational system. so that the radio frequency (r. Processional motion of a magnetic moment. When the intensity H of the magnetic field reaches the value which satisfies the condition (3.15.14.14. Fig. The trace of the point of the vector P is a circle of radius P sin 6. (This relationship is a modification of Newton's second law of motion saying that time derivative of momentum is a force.15). a precession is induced. we have that the time derivative of the angular momentum must be given by a torque.f. Therefore.) As shown in Fig. if an alternating magnetic field of this frequency is applied perpendicular to the static magnetic field. and the intensity of the magnetic field applied perpendicular to the H vector of the microwave is increased gradually (Fig. so that the angular velocity of the precession is given by It is interesting to note that the angular velocity given by (3. no matter how the magnetic moment tilts from the direction of the field. Accordingly. when a magnetic field is applied to a magnetic material. . 3.70 ATOMIC MAGNETIC MOMENTS Fig.) permeability shows a sharp maximum. and also to H.

The precessional motion described above is somewhat idealized. we assumed that the magnetization reverses its sense upon the application of the magnetic field. This phenomenon is known as ferromagnetic resonance (FMR).22). Figure 3. Ferromagnetic resonance curve (Hr: resonance field). A more detailed discussion will be given in Chapter 20. however. From the field at which resonance occurs. . true only if some relaxation process absorbs energy from the precessional motion and allows the Fig. In the preceding discussion of the Einstein-de Haas effect.GYROMAGNETIC EFFECT 71 Fig. 3. we can determine v from (3. This is. The actual precession is associated with various relaxation processes by which the system loses energy.44).16. 3. Ferromagnetic resonance of a cylindrical ferromagnetic specimen.16 shows experimental results for Permalloy. and accordingly the value of g from (3.17.

we have the angular frequency Using equations (3. and the z-axis parallel to the external field.47). let us consider a cylindrical specimen (Fig. a similar calculation shows that Equation (3. 3. For simplicity. The correct g-values were determined by Kittel13 by taking into consideration the demagnetizing field caused by the precessional motion.17). The torque acting on the magnetization is. a demagnetizing field —7s(sin 0)/2/i0 is produced perpendicular to the axis. we can calculate the gyromagnetic constant and accordingly the g-factor.72 ATOMIC MAGNETIC MOMENTS magnetization to relax towards the direction of the field. or Accordingly the resonance frequency (3. we have Solving this equation. therefore.23). The ferromagnetic resonance experiment was first performed by Griffith12 in 1946.47) is obtained as follows: Set the x-axis normal to the sample surface.46) and (3. . The reaction of this relaxation mechanism causes the rotation of the crystal lattice of the specimen. Then we have for the equations of motion Eliminating Py from the above equations by using (3. given by the sum of the torque from the external field and that from the demagnetizing field. When the magnetization tilts from the cylinder axis by the angle 6.44) is modified to If the specimen is a flat plate and the external field is applied parallel to its surface.

and g'-values.13"16 when a magnetic atom is under the strong influence of the crystal lattice. and H2 when the magnetization deviates towards the y-axis. which tells us that the origin of the atomic magnetic moment is not orbital motion but mostly spin. the g-values obtained from magnetic resonance are greater than 2. the g-values determined from magnetic resonance should be equal to the g'-values determined from the gyromagnetic experiment for the same material. and that from orbital motion by (/s)orb.GYROMAGNETIC EFFECT 73 In addition to the demagnetizing field. We also note that the sign of the deviation from a value of 2 is different for g. it orbital angular momentum is not conserved. (3.52) is modified to On the other hand. Let the part of the saturation mangetization due to spin motion be (/s)spin. the values observed for 3d transition elements are close to 2. Then we have Considering that g' = 1 for orbital motion and g' = 2 for spin. Generally speaking. If the magnetic atoms do not interact with the crystal lattice.2. Van Vleck and others. so that only spin angular momentum contributes to the expression for the g-factor: Adding both sides of (3. respectively.2 together with the g '-values determined from gyromagnetic experiments. The deviation of the g'-factor from 2 is apparently caused by a small contribution from the orbital magnetic moment. Then the resonance frequency is given by A high-frequency magnetic material called Ferroxplana takes advantage of this effect to increase the resonance frequency (see Section 20. as seen in Table 3. we have which can be written as . the magnetic anisotropy also influences the resonance frequency.54). As pointed out by Kittel. The corresponding angular momenta will be (Ps)spin and (Ps)orb.3). The restoring force acting on the magnetization can be equated to a hypothetical magnetic field acting parallel to the easy axis.53) and (3. because it produces a restoring torque tending to hold the magnetization parallel to the easy axis (see Chapter 12). Let this field be Hl when the magnetization deviates towards the *-axis. The g-values obtained from ferromagnetic resonance measurements are listed in Table 3.

58) and (3. The mechanism of quenching of the orbital moment must be known more precisely in order to understand the origin of magnetocrystalline anisotropy and magnetostriction. We have learned that the orbital magnetic moment is mostly quenched in materials composed of 3d magnetic atoms. In addition to the ferromagnetic resonance discussed in this section.74 ATOMIC MAGNETIC MOMENTS The g' -values calculated using (3. the potential energy is given by where r (m) is the distance between the electron and the proton.52) and from (3.59) are also listed in Table 3. Since the electron is under the influence of the Coulomb field produced by a proton with electric charge +e (C).5). These resonances are all concerned with electron spins.2. together with the values directly determined from the gyromagnetic experiment. The values calculated from (3. The values are in excellent agreement.56) are listed in Table 3.53) assuming s •« 1. in which a single electron is circulating about a proton. so that they are called electron spin resonance (ESR). while the g'-factor is known as the magnetomechanical factor. Now let us consider the wave function of a hydrogen atom. we can observe paramagnetic spin resonance. The quantity g is often referred to as the spectroscopic splitting factor.2. and s0 is the permittivity of vacuum . which will be discussed in Chapters 12-14. 3.4 CRYSTALLINE FIELD AND QUENCHING OF ORBITAL ANGULAR MOMENTUM We have discussed the magnetism of atoms so far mainly in terms of Bohr's classical quantum theory. These values are all less than about 10%. antiferromagnetic resonance. and ferromagnetic resonance (see Section 20. If we denote the ratio of the orbital contribution to the spin contribution by we can write from (3.

®lm(d) is a function of the polar angle 9 from the axis of quantization.r). The suffixes n.62) is given in all textbooks on quantum mechanics. and m are respectively the principal. as shown for example by Fig.1. as already explained in Section 3. orbital. which must satisfy the Schrodinger equation where %? is the Hamiltonian given by The first term is the operator corresponding to the kinetic energy of the electron. the momentum p is replaced by the operator — \fi(d/ds\ so that the kinetic energy is given by Since the operator A is expressed by we recognize that (3. Here we simply refer to the final solution. I.QUENCHING OF ORBITAL ANGULAR MOMENTUM 75 The state of the orbital electron is described by the wave function fy(. where p is the momentum. the kinetic energy is given by \mv2 = (l/2m)p2. and <&m( <p) is a function of the azimuthal angle <p about the axis of quantization. and magnetic quantum numbers. In classical dynamics.64) is the same as the first term in (3. The solution of the Schrodinger equation (3. 3.2.63). which is where Rn!(r) is a function of the radial distance from the nucleus r. The reason why these functions are characterized by these quantum numbers is that only functions characterized by these numbers express the stationary states. (p are given by and . In quantum mechanics. The specific forms of these functions involving the angles 6.

we recognize that the wave functions for m = 0 in d or / electrons stretch along the z-axis or the axis of quantization. p. however. Note that if the square of wave functions with different m are added. d. In this figure. f electrons The functions (3.69) about the axis of quantization as shown in Fig. meaningless to consider further details of this correspondence.1. while those for m = 1 or the maximum values spread along the z-plane or the plane perpendicular to the axis of quantization. thus producing a circular current. either clockwise or counterclockwise. It is. such wave functions are circulating about the axis of quantization. This is also the case if the square of wave . so that the directional distribution of the wave functions is expressed simply by rotating the functions (3. 3. The reader may recognize a similarity between these pictures and those of the Bohr orbits as shown in Fig.3 or s. When the orbital magnetic moment remains unquenched.2. the azimuthal variations are smeared out.69) express the eigenstates involving the azimuthal angle <p as discussed in Section 3. 3. Accordingly.18.4.76 m| ATOMIC MAGNETIC MOMENTS The term Pj (cos 6) is the /th transposed Legendre polynomial and given for / = 0. the sum becomes isotropic.1.

3. functions with a finite positive m and a half with m = 0 are added. as already mentioned.18. Angular distribution of atomic wave functions with various orbital and magnetic quantum numbers. We call such an electron shell spherical.QUENCHING OF ORBITAL ANGULAR MOMENTUM 77 Fig. .

In the case of 3d electron shells.* Since this wave function spreads to avoid the anions (negatively charged ions) in the environment. 3. *The fact that (3. the resultant wave function is given by Figure 3. as shown in the figure. When such magnetic atoms are assembled into crystals. This figure represents a standing wave constructed by a superposition of the oppositely circulating wave functions. Suppose that two wave functions with m = + 2 and m = — 2 are superposed.70). The magnetocrystalline anisotropy of most rare-earth ions can be interpreted in terms of the atom shapes (Chapter 12). drawn by using ®2+2 m (3. Therefore neither angular momentum nor electric current is produced. . the Coulomb energy will be lowered.69) and (3.68). because the magnetic shells are exposed to the influence of neighboring atoms in the crystal environment. thus cancelling their angular momenta.78 ATOMIC MAGNETIC MOMENTS Fig. Sometimes their orbital angular momentum is totally quenched.70) is real means that the wave function is independent of time. and accordingly no orbital magnetic moment arises.19.19 illustrates the angular distribution of this wave function. Thus the quenched state of orbital moments is stabilized by the crystalline field. The 3d atomic wave functions with m — +2 stabilized by neighboring anions or negatively charged ions. the orbital magnetic moments are strongly influenced by the crystalline field. their magnetic properties are influenced by these shapes. We will elucidate the mechanism of quenching below. Referring to (3.

when d electrons are placed in a crystalline field with cubic symmetry. etc. i/^ extend along the (110> directions. If the state expressed by one of these wave functions is stabilized by a ligand field.3 to discuss the mechanism of magnetocrystalline anisotropy. and L2n'^(t) is the Laguerre polynomial given by * This (/>„ is the same as that shown in Fig. or the same neighbors at different distances. 3. As seen in the figure.20 shows the angular distribution of these wave functions. A better name for this interaction is the ligand field rather than the crystalline field.* The former are called ds. while the functions i[/u.19. we shall elucidate the radial part Rn. if/u extend along the principal axes.(r) in (3. avoiding the principal axes with fourfold symmetry. because . We shall also use the ligand theory in Section 12. the energy of the nearest-neighbor interaction is different for ds and dy. the orbital magnetic moment will be quenched. Finally. The origin of this interaction is not only the Coulomb interaction.QUENCHING OF ORBITAL ANGULAR MOMENTUM 79 In general. along the (110) and <100> directions. Since the 3d magnetic atoms or ions have different neighbors. a0 = 4Tre0h2/me2. but also includes exchange interaction.66). and the latter dy. the wave functions </^. the d wave function can be written in terms of the following orthogonal real functions: Figure 3. covalent bonding. which is given by the general form where x = Zr/a0. i/^.

68) and (3. The magnitude of the wave function is expressed by the density of drawing. the vertical axis is the z-axis or the axis of quantization.21 shows a computer-generated pattern representing the spatial distribution of the atomic wave function (3.67). . and its sign is distinguished by the direction of the lines: radial lines signify positive values and circumferential lines show negative values. as already discussed with the Bohr models shown in Fig.72). In these patterns. It is seen that the s function is large at the nucleus. (3.80 ATOMIC MAGNETIC MOMENTS For a number or orbital electrons the functional form of (3.72) is given by Figure 3.6.66) calculated from (3. The graphs shown below each pattern represent the radial variation of R(r). 3.

2Oe). The d(e) and d ( y ) wave functions of 3d electrons in a cubic ligand field.2 Assuming that a thin Permalloy rod can be magnetized to its saturation magnetization by applying a magnetic field of 100 Am" 1 (= 1. PROBLEMS 3.20. Assume that g = 2. calculate the angular velocity of the rotation of this rod about its long axis necessary to magnetize it to its saturation magnetization without applying any magnetic field. 3. 3.1 Calculate the spectroscopic splitting factor (g-factor) for the neodymium (Nd) atom.3 How strong a magnetic field must be applied parallel to the surface of an iron plate to .PROBLEMS 81 Fig. 3.

while the sign of i/> is distinguished by the direction of drawing. (The magnitude of i/> is expressed by density of lines.82 ATOMIC MAGNETIC MOMENTS Fig.) . Radial lines signify if/ > 0. while the circumferential line signifies i/» < 0. Computer-drawn patterns for spacial distribution of atomic wave functions in a plane including the z-axis or the axis of quantization. 3.21.

Proc. Uhlenbeck and S. J. 18 (1916). Int. 9. 111 (1915). W. Rev. Rev. J. Einstein. S. Russell and F. Phys. J. Van Vleck. Goudsmit. Phys. Physik. Kittel and A. New York. J. p. 4.. E. G. Phys. 6. H. 610. Maxwell. 173. A. and ignore the effect of magnetocrystalline anisotropy. 31 (1925). 3. A. 17 (1915). 372.10 and 7S = 2. Astrophy.. Theory of electric and magnetic susceptibilities (Clarendon Press. J. Deut. 765. 8. Phys. 1. Z. . REFERENCES G. 351. Suppl. 11. 13. 13 (1925). F. Hund.. Deut. Rev.4 Show that the 3d5 electron shell is spherical. Electricity and magnetism (Dover. Physik. Ges.. 1611. Scott. 270. 71 (1947). 73 (1948). C. P. 76 (1949). 1. 6. Verhandl.. 1927). Mag. 3. Verhandl. H. Rev. W. Japan. A. 266.. 575. H. 743. Physik. 423. All? (1928). 15. 78 (1950). 7. Rev. M. Berlin. de Haas. Con/.REFERENCES 83 observe ferromagnetic resonance. 245. -1. Phys. 10. 5. 12. N. 61 (1925). J. and Cryst. B-l) (1962). Soc. Barnett. Dirac.69) for m = 2. Physik. H. by calculating the sum of the square of the wave functions given by (3.. 1932). Z. Ges. 38. 73 (1948). 2. Kittel. Pauli. 15 (1923). Mitchell. C. 18 (1916). G. A. J. E. Nature. de Haas. 14. Physik. Soc. H. Phys. 158 (1946). Einstein and W.. Griffith. 17. A. using microwaves with a wavelength of 3. 82 (1951)..12T.0 cm? Assume that g = 2. J. and — 2. Roy. Oxford. 1954). 239. 0. Saunders. 670. Phys. Ges. 155. Verhandl. 152. Die Naturwissenschaften. A118 (1928). 953. C.. Kyoto (7. 1116. Polder. 542. Proc. D. Lande. p. Linien Spektren und periodisches System der Elemente (Julius Springer. Van Vleck.. 189. 16. Rev. 101 (1956). Deut.

If the charge distribution has spherical symmetry it follows that r2 =x2 +y2 +z2 = 3z2. Accordingly.1.4 MICROSCOPIC EXPERIMENTAL TECHNIQUES 4. atomic magnetic moments originate from orbital or spin magnetic moments of electrons in unclosed electron shells. we see that the electron mass in the denominator is replaced by the proton mass. so that Q = 0 as seen from (4. atomic nuclei possess small but non-zero magnetic moments. One nuclear magneton is given by where mp is the mass of the proton. The nuclear spin and the nuclear magnetic moment for various isotopes are given in Table 4.3). Comparing (4. The quadrupole moment of the nucleus is given by where p is the electric charge density. nuclear magnetic moments make a negligibly small contribution to the magnetization of materials. or 1/1836. so . The nuclear magnetic moment is also accompanied by a quadrupole moment.1 to 5.7). the charge distribution of the nucleus stretches along the z-axis. The spin angular momentum of a nucleus is measured in units of h as in the case of the electron spin. Therefore. from which we see that the magnetic moment is not necessarily proportional to the spin and sometimes even has opposite sign. r the radial vector of the charge. When Q > 0.1) with the Bohr magneton given by (3.1 NUCLEAR MAGNETIC MOMENTS AND RELATED EXPERIMENTAL TECHNIQUES As discussed in Chapter 3. so that the nuclear magneton is smaller than the Bohr magneton by a factor which is the ratio of the electron mass to the proton mass. In addition to these moments. These moments are measured in nuclear magnetons.6. and is denoted by the symbol /. the g-value defined by takes various values ranging from 0. and z the coordinate axis taken parallel to the nuclear spin.

242 -0.827 0 +3.161 -0.49912 ±0.1026 17.75 100 99.6 51.537 49.23 +0.9953 10.14 15.46 +2.8 0 0 -0. Various physical quantities of typical isotopes.678 +2.5758 6.76 100 2.1658 42.86 9.58554 +0.6287 +3.8045 0.3 -1.64140 +1.88 50.90671 Quadrupole moment.3871 +0.0265 0 0.239 0.573 1. 4.14 -0.565 6.312 12.1804 -0.1866 -0.5899 +1.7 100 18.1546 +4.NUCLEAR MAGNETIC MOMENTS Table 4.2522 4.227096 -0.670 11.16 +0.0765 5. .4709 +1. so that the shape of the nucleus is a flat oblate ellipsoid (see Fig.26 +1.857406 +1.8091 -2.317 1.17 +0.82 0.637 +0.304 -0.45656 +2.4485 +4.1 +1.273 0.242 5.09657 +0.52 -0.5356 10.757480 +5.26 -0.47 +0.25 42.5 33.12 30.492 -0.54789 +1.7739 40.13166 +0.386 +0.9114 Element n (neutron) H C N 0 F Al P Cl V Mn Fe Fe*(14.1 15.186 +1.7937 +1.5647 -0.3 +2.422 1.1031 +1.148 +3.323 +1.300 +0.50 2.702381 +0.4keV) Co Ni Ni*(67.40361 -0.78 +0.33 +0.2574 +1.985 0.75 1.7856 9.91314 +2.981 3.5131 -0. the charge distribution of the nucleus spreads along the x-y plane.5 +1.7958 MAm' 1 ) 29.86 0.98 8.231 +0.3094 -0.261076 +1.4037 +1.82183 +5.65 +4.984 -0.29 14.188 +0.1766 -0.3849 +2.4keV) Cu Br Rh Pd Ag Sb 1 La Pr Nd Sm Spin.16 +2.463 100 22.462 +0.14 8.2261 +2.059 -0. If the distribution of atoms surrounding the nucleus deviates from cubic symmetry.8 100 100 1 85 Resonance frequency (MHz) for// = 10kOe (= 0.015 1. M/M N -1.3590 +2.994 -0.22 +0.82 47.88 1.0 -0.7277 +1.89370 +2.911 100 12.0 +1.404 0.87 13.5 0 +0.3436 +0.84 1.80 -0.24 -0.0902 -0.016 -0.547 8.68 +1.0745 11.21204 +0.65 57.465 +1.34 Eu Gd Tb Dy Ho Er Tm Yb Lu Ir Pt Au Bi that the shape of the nucleus is a prolate ellipsoid.88 24.7310 1.113548 -0.16134 -0.53 4.25 — 69.1763 11.06 4.271 +0.404762 +0.529 99.130538 +3.215 +1.35 48.35 0 +0.146 0 -0.050 13.547 +2.060 +1.79277 +0.329 -0.346 1.375 0.1).1056 +2.608 -0.080 -0.107 99.13 1.92 +1.412 38.64 10.12 +1.4841 +1.2696 -0.7 1.1 2.28 0 +0.1 +5.1236 +0.615 -0.43 1.246 -0.0883 -0.74868 ±0.60602 +1.72 -0.212 10.4678 +0.1.2 97.113 +1. I/h 1/2 1/2 1 1/2 1 5/2 1/2 5/2 1/2 3/2 7/2 5/2 1/2 3/2 7/2 3/2 5/2 3/2 3/2 3/2 3/2 1/2 5/2 1/2 1/2 5/2 7/2 5/2 7/2 5/2 7/2 7/2 7/2 7/2 5/2 5/2 3/2 3/2 3/2 5/2 5/2 7/2 7/2 1/2 1/2 5/2 7/2 3/2 3/2 1/2 3/2 9/2 Magnetic moment.5 61.65 +3.86 52.68 -0. Mass number A 1 1 2 13 14 17 19 27 31 35 51 55 57 57 59 61 61 63 65 79 81 103 105 107 109 121 123 127 139 141 143 145 147 149 151 153 155 157 159 161 163 165 167 169 171 173 175 191 193 195 197 209 Abundance % — 99.2300 3.0802 g -3.52 7.94 100 14.91 11.26332 +0.82628 +5.42 10.482 -0.32 +2.23 -0.052 +0.63 1.7781 +4.00282 0 +0.9 +0.134 -0. Q/lO~ucm2 0 0 +0.4 16.58 -0.653 -0.0745 100 100 100 75.7078 3.40361 -1.107 +0.583 -0.7361 6. When Q < 0.534 1.36 +2.21 — 100 1.82 +2.064 -0.21 -0.255 +1.857406 +0.119 10.97 100 22.

e.1. When Q < 0.1 for various isotopes. so that the nuclear spin is forced to rotate towards the z0-axis. This gives rise to a torque in addition to the torque produced by the magnetic field. or Q > 0 and q < 0.86 MICROSCOPIC EXPERIMENTAL TECHNIQUES Fig. If the nucleus is prolate. if q > 0. Quadrupole moment of the nucleus and the field gradient at the nucleus. Since in NMR the size of the magnetic moment is smaller by a factor of 1/1836. The experimental techniques described in the following paragraphs can provide valuable information both about the identity of the nuclei existing in the materials and about the interactions between the nuclei and their environment. The value of Q is given in Table 4. When a nucleus having a nuclear magnetic moment as well as a quadrupole moment is placed in a material. the resonance frequency for NMR is much smaller than that for ESR. 4. the electric field changes from place to place. everything is reversed. this produces a gradient of the electric field 6E/dz0 along some specific crystal axis z0 at the nucleus.1. the nuclear spin precesses about the axis of H. On the contrary. the sign of the torque is opposite.1 Nuclear magnetic resonance (NMR) When the nucleus is placed in a magnetic field H. The sign and magnitude of q are determined by the atomic arrangement in the environment of the nucleus under consideration. The resonance angular frequency for NMR is given by . The magnetude of this interaction is given by the energy e2qQ. while the magnitude of spin angular momentum is more or less the same. 4. there are various interactions with the environment. The resonance phenomenon and the experimental technique are known as nuclear magnetic resonance (NMK). Since the electric field along the z0-axis is given by E = —d<j>/dz0. as in the case of the electron spin. The resonance frequency can be determined by a method analogous to that used in electron spin resonance (ESR). the negative field gradient is given by where q is the field gradient measured in units of . the spin axis z tends to be parallel to the specific crystal axis z0.

from which we can sometimes deduce the value of the atomic magnetic moment (refer to Section 4.4). 4. If nuclei of the same species occupy inequivalent lattice sites such that the direction of the field gradient is different in different sites. therefore.5).1. It is easy. If the nucleus is under the influence of an internal field. we apply another high-frequency pulse for a time interval twice as long as the first pulse.NUCLEAR MAGNETIC MOMENTS 87 which is in the radio-frequency range. Then we observe a sharp high-frequency signal after a further time interval T (s). such as that produced by the polarization of magnetic shells.4 4. and then tilt towards the plane perpendicular to the static field. the resonance frequency is also modified by the field gradient. and surround it with a coil carrying an AC current at a frequency of a few megaherz. Suppose that because of the first high-frequency pulse. we can deduce which lattice sites are occupied by the resonating nuclei. Therefore sometimes it is possible to observe the NMR signal with no external static field. magnetic resonance occurs when the sum of the external field and the internal field satisfies condition (4. some of the spins precess faster than others. absorb energy. The resonance frequency is quite different from isotope to isotope. Moreover.2 Spin echo The spin echo technique5 is one means for detecting NMR signals. say by a factor of 105. the nucleus experiences an extraordinarily large internal field through the polarization of the magnetic shell by the spontaneous magnetization. The mechanism of this phenomenon is illustrated in Fig. Instead of using microwave guide tubes (wave guides). Therefore NMR provides information not only about the chemical species of the nucleus but also on the value of the internal field. therefore. much simpler than that for ESR. From this quadrupole splitting. During the time interval T (s). In the case of ferromagnetic materials. Also the NMR signal is generally greatly enhanced for ferromagnetic materials. because the g-factor varies with isotope. We say that the resonance is 'split' into several lines. to identify a specific nucleus just by observing the resonance frequency. the nuclear spins resonate.1. Because of the spin-spin interaction. In particular. The experimental procedure for NMR is. we can simply place a specimen in a static magnetic field. so that the orientation of spins is spread over some angle. After waiting for a time interval T (s). .2. each site will have a slightly different resonance frequency. which in turn oscillates the nuclear moment through the strong internal fields. The reason is that the radio frequency field may oscillate the spontaneous magnetization. through the quadrupole moment. the spins precess in this plane. so the high frequency field which the nucleus inside the wall feels is greatly enhanced. The procedure is as follows: First we apply a high-frequency magnetic field pulse to the specimen for some time interval. spins located in domain walls rotate through large angles.

The spins with relatively fast precessional speed lag behind the central spin. The relaxation time involved in these processes is known as T! for the spin-lattice relaxation and as T2 for the spin-spin relaxation.7 To observe the Mossbauer effect. while those with relatively slow precessional speed precede the central spin. For the other spins. The spin echo method provides information not only on the internal fields.88 MICROSCOPIC EXPERIMENTAL TECHNIQUES Fig.3 Mossbauer effect The internal field for some isotopes can be measured by means of the Mossbauer effect.5). This y-ray can be absorbed by another nucleus of the same species. 4. so that after a time T (s). only the component parallel to the central spin is reversed. by selective absorption. it is desirable to select an isotope with large mass which emits a low-energy y-ray and to place the isotope in a . because this component has nothing to do with the absorption or the dissipation of the energy (see Section 20. This fact was first pointed out by Lamb6 and was experimentally verified by Mossbauer. In this case the emitted y-ray has an energy equal to the energy separation between the two states of the nucleus before and after the emission. The normal NMR method requires homogeneity of the sample material as well as of the static magnetic field. the central spin tilts by 180° through the z-axis (the axis parallel to the static magnetic field). or in the case of a non-uniform static magnetic field. Then the distribution of the spins is reversed from that before the application of the second pulse. while the component perpendicular to the central spin remains unchanged. but also about the spin-lattice relaxation by which energy is transferred from precessional motion to the lattice. all the spins are precessing in phase with the central spin. 4. The spin echo technique is useful for inhomogeneous materials. This effect utilizes the fact that a y-ray can be emitted from a nucleus without recoil if the nucleus is bound into a solid.2. thus giving rise to a sharp signal in the search coil.1. By the application of the second high-frequency pulse with a double time-duration. The value of 7\ can be obtained by observing the decay of the high-frequency signal associated with the rotation of the spins towards the z-axis. and about the spin-spin relaxation through which the energy is transferred between spins. The value of T2 can be obtained by observing the decay of the echo signal as a function of the time interval T (s). Schematic illustration of spin echo technique.

Co57 (which decays to Fe57) is particularly appropriate for the investigation of magnetism.3. One of the effects is the isomer shift.NUCLEAR MAGNETIC MOMENTS 89 Fig. The energy scheme of the nuclear transition of Co57 to Fe57 is shown in Fig. If a nucleus of Fe57 exists in a magnetic material. which can be made by irradiation of Fe with 4MeV deuterons. d) of the ground and excited states resulting from various interactions. 4.4 keV. which is a shift of the excited level upwards by 5 (Fig. 4. 4. Among various possibilities. One of the reasons for this is the difference in the size of the nucleus in the ground and the excited states. as shown in Fig. solid with a high Debye temperature so that the nucleus is firmly bound. Then it makes a y-transition to the first excited state with / = f and finally transfers with a period of 10"7s to the ground state with 1=\. the energy levels of the ground and the first excited are split by various effects into six levels.3). c. because it allows detailed measurement of the internal field which acts on the nucleus of Fe57 in a magnetic material. The energy separation between the last two levels is 14. Energe level scheme (a) of the nuclear transition of Co57 to Fe57 and energy levels (b. 4. If for some reason the electron .3. decays by electron capture with a half-life of 270 days to a second excited state of Fe57 with spin I=\. which gives rise to a difference in Coulomb interaction between the nucleus and surrounding electrons.3. The isotope Co57.

90 MICROSCOPIC EXPERIMENTAL TECHNIQUES density around the nucleus is different between emitter and absorber.3. as already mentioned in (a).1. On the other hand.3(d)).\ and f as shown in Fig. because the mass of the nucleus is changed during emission or absorption of the y-ray. Between these levels there are six possible allowed transitions which satisfy the exclusion rule A/ z = 0 or ±1. Schematic illustration of the experimental arrangement for measurement of the Mossbauer effect. . which acts on the nucleus. This is called the quadrupole splitting.3(a) by the quadrupole moment of Fe57 in the field gradient q. 4. 4. the ground and the excited states are split into two. The reason why Iz = — \ is lower than 72 = \ is that in most cases the sense of H{ is opposite to the atomic magnetic moment or the external magnetic field. From this shift we can determine the field gradient and deduce the identities of the lattice sites where Fe57 atoms are located. The second effect is the Zeeman splitting by the internal magnetic field //. In this case. The isomer shift can also be caused by a temperature difference or a difference in Debye temperature between the emitter and the absorber. —\. or the rule of conservation of angular momentum. while it is negative for Iz = +\. while the excited levels are split by The sense of the splitting is positive for Iz = ±|. 4. Since / = \ in the ground state of Fe57. No quadrupole moment exists in the ground state. The sense of the splitting is independent of the sign of Iz because the shape of the nucleus is the same for Iz > 0 and for Iz < 0. the energy level is split into two levels with Iz = \ and —^. Fig. The valence of Fe57 can be estimated from the isomer shift. 4. As a result of these three effects. The energy levels are split as shown in Fig.4.and fourfold levels (Fig. the difference in Coulomb interaction should result in a shift of energy levels. the energy is changed by where I2 is the component of the nuclear spin parallel to H^. In the excited state with 7 = f. The mechanism of the internal field is explained in Section 4.4. the energy level of 7Z < 0 is higher than I2 > 0 in the excited state. because the sense of Iz is reversed on excitation. the level is split into four levels with 72 = — f.

In this way we observe the six absorption lines shown in Fig. or opposite to the Lorentz field. and 3s electrons. the energy of the y-ray is modified by hv(v/c). 4.4. The transmitted y-rays are detected by a counter and recorded as a function of the velocity. The most important of these is the internal field.1. produced by Mossbauer effect measurement using a stainless steel source and a natural iron absorber 0. 3.21(c)). 4.4 Internal fields The values of internal fields measured by means of NMR and the Mossbauer effect are listed in Table 4. The oscillation of the speaker modulates the y-ray wavelength through the Doppler effect. Moreover. or in terms of quantum mechanics. 4. the sign of the internal field is usually negative. 3.2 for various nuclei of magnetic atoms and ions. It is therefore possible for the y-rays emitted by Co57 to be absorbed by Fe57 in the magnetic sample material. which is much larger than the Lorentz fields produced by these magnetic atoms or ions. The y-ray source. which is discussed in the following section. containing Co57.025 mm thick.5. The internal field is thought to originate from the polarization of Is. the field gradient and the isomer shift. 2s. the wave functions of these 5 electrons have high values at the nucleus (see Fig.3(d). 4. is attached to a loudspeaker diaphragm. which is of the order of Icms" 1 . we determine the various parameters characterizing the internal fields.6). That is. when the source is moving with velocity v. The hyperfine spectrum of Fe57 in iron metal. By analyzing these absorption lines. these s electrons can approach the nucleus (see Fig. These s electrons are . 4. (After Wertheim8) The six transitions are observed as six absorption lines denoted by 1 to 6 in Fig.NUCLEAR MAGNETIC MOMENTS 91 Fig.10'11 In terms of classical physics. These values are generally tens of MAm" 1 (hundreds of kOe).5. The experimental procedure for observing the absorption lines is illustrated in Fig.

5| |282| +279 ±44 +3500 + 550 +335 ±80 +4200 ±1000 polarized by the polarized d-electrons through the exchange interaction. and 3s electrons are calculated to be —2.1| |339| -24.4 -80 -13.12 -20.3 -280 -17.7 ±1.1 -289 -6.5 -18.1 -540 |43.08 +18.9 -550 -40.9 + 0.1 ±1.5 ±1.2 -215 -36. which has no orbital moment. 2s.4 ±0. —112.7 -460 |37.1 ±1. Internal field Nucleus 57 Temperature (K) 0 0 0 0 78 78 room room room room 78 78 78 78 room 85 room 1. I s and 2s electrons produce negative internal fields.2.51 |22. the contribution of Is. in the case of Mn 2+ .5 ±1.6 -220 -15.3 50 50 169 300 0 0 0 0 0 room 100 100 100 273 283 85 0 Method M NMR M M M M M M M M NMR M NMR M M M ESR M M M M M NMR NMR NMR CB M M M M NMR NMR M M NMR Host Fe Fe Co Ni Fe3Al Fe2Zr Fe2Ti Fe3N (MAnT ) 1 (kOe) Fe 57 Fe3+ 57 Fe2+ 59 Co 61 119 Ni Sn 65 Ci 197 161 Au Dy 159 Tb YIGKtetra) YIG(tetra) YIGKocta) YIG(octa) a-Fe2O3 rFe2O3 NiFe2O4 MgO Fe3O4(tetra) Fe3O4(octa) CoO FeS FeTi03 Co(fcc) Co(hcp) Fe Ni Ni Fe Co Ni Fe Co Fe DylG Tb -27.6 -465 ±20 -16.5 -345 -17.2 ±0.64 ±0. .48 ±0. The internal magnetic fields of several isotopes included in various magnetic materials (after Ishikawa9).01 |212.3| |468| -43.4 -312 ±5 -22.0 117.5 +1.5 -320 -5. and in turn they polarize the nucleus through a mechanism called the Fermi contact.6 -70 -17.8 -200 ±10 -25.1 -515 -41.0 ±0.6 -515 ±20 -40.36 -217.6| 1157. Generally speaking.8 < 10 -27.92 MICROSCOPIC EXPERIMENTAL TECHNIQUES Table 4.6 -510 ±20 -37.3 -342 |27.6 -510 ±20 -43.3 + 0.2 -228 -23.9| |550| -41.4 -280 ±5 -22.8 -190 ±10 < 0. while 3s electrons produce positive fields.3 -81 + 4 -1. For instance.7 ±1.7| |12.4.6 -170 -6.

but not the overall magnetization. the internal field is proportional to the thermal average of the magnetic moment. so that it interacts with and is scattered by the magnetic moments of magnetic atoms.NEUTRON DIFFRACTION 1 93 and +59MAHT (-30. which is smaller than the calculated value for Mn 2+ . The internal field of Fe2+ is much smaller than Fe3+. At the center of the reactor. 4. The orbital magnetic moment is caused by the orbital current.6. Co and Ni exhibits fairly large internal fields in spite of its non-magnetic nature. By making use of this effect. respectively. the neutron carries a nuclear magnetic moment of magnitude —1. which generate neutrons by chain reaction. The internal fields of Fe3+ in Table 4. -1400. so that the internal fields come mainly from the exchange polarization of 5 electrons. 4. to keep it below a critical value. The reason is that the radius of the 3d shell is smaller for Fe3+ than for Mn 2+ . Neutron beams can be obtained from a nuclear reactor. so that the internal field of an ion is caused by the polarization of its own d electrons.7 to -43.913AfN. In magnetic insulators. because the frequency of thermal vibration is higher than that of the nuclear spins.2 range from -40. On the other hand. there are a number of rods containing nuclear fuel such as uranium.2 NEUTRON DIFFRACTION The neutron is an elementary particle which carries no electric charge. A number of neutron-absorbing control rods limit the neutron density.12 In the case of the 3d transition elements. It can be seen in Table 4. On the other hand. in spite of the fact that the electronic structures are the same. the magnetic ions are always separated by anions. in magnetic metals and alloys. However. It is seen in Table 4. but this energy decays in heavy water at the center of the reactor to a value of the . The energy of neutrons produced by nuclear reaction is the order of 10 MeV. At temperatures above absolute zero. because the positive contribution from the partially unquenched orbital moment is added to the contribution of the s electrons. and +740 kOe). These add up to —SSMAm" 1 (-690kOe).3 MAm" 1 (-630kOe). the orbital moment is almost quenched.2 that 119Sn in the ferromagnetic metals Fe. so that it penetrates matter without being influenced by the electric fields produced by electrons and ions.9 MAm" 1 (-510 to -550 kOe). which produces a large internal field at the nucleus. as illustrated schematically in Fig. This is because the internal fields reflect the ionic magnetic moments.2 that 161Dy or 159Tb exhibit fairly large positive internal fields.11 in excellent agreement with the experimentally observed value -52MAH1-1 (-650kOe). in antiferromagnets. the magnetic structure of a crystal or the magnitude of the magnetic moment of an atom can be determined. the internal fields are as large as in ferromagnets. Therefore the internal fields of paramagnets are generally very small. the polarization of the conducting s electrons is affected not only by their own ionic polarization but also by the polarization of their neighbors. Therefore the internal field in this case is a good measure of the ionic magnetic moment. The calculated value on the basis of exchange polarization is -50.

Generally speaking.94 MICROSCOPIC EXPERIMENTAL TECHNIQUES Fig. and T is the absolute temperature of the heavy water (about 300 K). the intensity of the thermal neutrons is 1012-1014 cm~ 2 s"1 in the beam as it comes from the reactor. The scattering amplitudes are different for different atoms. This fact was first pointed out by Elasser13 and experimentally verified by Halban and Preiswerk. either spin or orbital. From this data the crystal structure and the magnetic structure can be analyzed. taking the neutron mass to be 1836 times the electron mass. as shown in Table 4. Neutrons are scattered by magnetic atoms in two ways: scattering by the atomic nucleus and scattering by the magnetic moment. and the angle of diffraction is detected by a counter. This beam is diffracted by a sample crystal. where k is the Boltzmann constant.3.6. in a manner analogous to the interpretation of X-ray diffraction results. The density of thermal neutrons at the center of the reactor is in the order of 1014 cm"2 s"1.14 A neutron beam coming from the reactor through a collimator is reflected by Bragg diffraction from a monochromator crystal to produce a monochromatic beam containing neutrons of a single wavelength. order of kT. Nuclear reactor and double axis goniometer for neutron diffraction. This is reduced to 106-108 after reflection from the monochromator crystal. The first such experiment was done by Shull and Smart15 to detect the antiferromagnetic spin arrangement in an MnO crystal (see Chapter 7). A neutron with energy near kT is called a thermal neutron. The wavelength of the thermal neutron is calculated by the de Broglie wave equation which gives a value of 1-2A. and finally down to 104-106 after diffraction from the specimen. 4. The fact that the wavelength of thermal neutrons is close to the lattice constant of common crystals is quite fortunate for solid-state science. The nuclear o .

(3) By using a polarized neutron beam and switching the direction of polarization. or perpendicular to the scattering plane. while X-rays are scattered by all the electrons.35 0. The effective size of the atom for X-ray scattering is therefore much less than for neutron magnetic scattering.60 1. the form factor for neutron scattering from the nucleus is independent of the scattering angle.08 1. C is negative for the Mn nucleus as a result of resonance scattering.54 0.10 0.51 0.23 Atom or ion Cr 2+ Mn2+ Fe (metal) Fe2+ Fe3+ Co (metal) Co2+ Ni (metal) Ni2+ scattering amplitudes. because neutrons are scattered magnetically principally by the outer electron shell. is given by a quantity called the form factor.3.45 0. For example.21 0. because the nucleus can be regarded as an infinitesimally small point compared with the wavelength of thermal neutrons.47 1.45 0. As seen in the figure. are different not only in magnitude but also in sign. The reason is as follows: When the diameter of the scattering atom is the same order of magnitude as the wavelength of the radiation. The amplitude of the magnetic scattering.35 0. and this value is subtracted from the total intensity to determine the magnetic intensity. On the contrary. There are several methods for separating nuclear and magnetic scattering: (1) The nuclear scattering intensity can be determined at high scattering angles where the magnetic scattering becomes negligibly small.16 0.11)).28 / \ J1'03 Magnetic scattering amplitude D (10 12cm) For 0 = 0 For sin 0/A = 0.27 0. because a phase difference results. When spin . as seen in Fig.57 0. Figure 4.35 0. Nuclear scattering amplitude C.57 0. where 6 is the scattering angle.37 ^ /°-96 jo. (HT12cm) 0. the form factor decreases with increasing scattering angle. D. 4. C. Differential cross sections for nuclear and magnetic scattering (after Bacon16). which varies with the scattering angle due to the size of the scattering body. This phenomenon is quite similar to the diffraction of light after going through a small hole.8.35 -0.25 1.NEUTRON DIFFRACTION 95 Table 4.7 shows the form factors for X-ray and neutron magnetic scattering as a function of sin 0/A. (2) The magnetic scattering can be suppressed by applying an external magnetic field parallel to the scattering vector. First we discuss the nature of magnetic scattering in method (2). The decay of the form factor is faster for neutron magnetic scattering than for X-ray scattering.7. the beams going through the right and left edges of the atom interfere with each other after scattering as shown in Fig. only the magnetic scattering contributes to the change in diffracted intensity.08 1. 4. f (see (4.

as where k and k' are unit vectors parallel to the incident and scattering neutron beams. q. or q = 0. X. The scattering vector given by (4. We define the scattering vector. For instance. 4. respectively. Comparison of atomic form factors for X-ray and for neutron scattering..10) is a factor which includes the unit vector parallel to the magnetic moment of the neutron. is perpendicular to the vector q.96 MICROSCOPIC EXPERIMENTAL TECHNIQUES Fig. magnetic moments are arranged regularly. and the reversed vector parallel to the projection of the unit vector of the atomic magnetic moment. on the scattering plane. A. Illustration of the reason for the decay in form factor with increasing scattering angle. 4.9.12) is a unit vector perpendicular to the scattering plane pointing from the incident side. (After Bacon16) Fig. The scalar product in (4. e. the differential scattering cross-section for neutrons is given by where D is the magnetic scattering amplitude and is given for spin 5 by where y is the magnetic moment of the neutron in units of nuclear magnetons. The magnetic scattering is proportional to the scalar product of q and A. in either a ferromagnetic or antiferromagnetic structure. Also if the magnetic moment of the neutron. no magnetic scattering . The vector q can be expressed as as illustrated in Fig. no magnetic scattering occurs. and / is the form factor amplitude. 4.8. if the atomic magnetic moment is perpendicular to the scattering plane.7.

the magnetic scattering is maximized because q = \. When a magnetic field. and accordingly the scattering vector. e. K and the vector given by (4. . unit vector parallel to the magnetic moment. so the magnetic scattering is completely eliminated.9. (b) field H is applied parallel to the scattering plane. which gives the maximum repulsion when the two dipoles are parallel to each other and perpendicular to the line joining them. H. occurs. 4. This fact can be interpreted in terms of the magnetic dipolar interaction (1. Relationship between various vectors involved in neutron diffraction: incident and scattered wave vectors. If the Fig. e. magnetic scattering is effectively produced by neutrons polarized parallel to the projection of the atomic magnetic moments onto the scattering plane. k.) Now let us consider the method for detecting magnetic scattering in method (2). In conclusion. On the other hand. magnetic scattering will occur from other scattering planes. lie in the horizontal plane (see Fig.10).14). the magnetic scattering vanishes because q = 0. 4. q. One method for separating the magnetic scattering: (a) magnetic field H is applied perpendicular to the scattering plane. so both magnetic and nuclear scattering occur.13). (Note that if the atomic magnetic moments are perpendicular to some particular scattering plane. 4.NEUTRON DIFFRACTION 97 Fig.10. when the magnetic field is applied vertically (see (b)). k'. scattering vector. is applied to magnetize the specimen parallel to the scattering vector (see (a)). Suppose that the incident and scattering beams. The difference between the two cases gives the intensity of magnetic scattering.

we can separate the magnetic from the nuclear scattering. The inverter provides a high-frequency magnetic field perpendicular to the static magnetic field or the precession field.18 They used Bragg scattering from a carefully selected monochromator crystal.15).16) vanishes. while for oppositely polarized neutrons. so that for neutrons whose polarization is parallel to the magnetization of the monochromator crystal. the second term vanishes after averaging over all possible directions of X. so that D in (4.14) leads to Method (2) consists of altering q in (4.98 MICROSCOPIC EXPERIMENTAL TECHNIQUES intensity of the magnetic field is adjusted to allow rotation of the magnetization towards the stable directions. in which D was nearly equal to C. unless D is much smaller than C.11 illustrates the experimental arrangement for generating the polarized neutron beam. we can get information on the magnetic anisotropy (see Chapter 12) or the canting of the spin system (see Section 7. 4. the second term in (4. Accordingly. The polarized neutron beam from the polarizing crystal retains its polarization direction in the collimating magnetic field. q = —1. so that only the neutrons whose polarization is antiparallel to the magnetization of the monochromator can be diffracted. Alternatively. but the polarization can be reversed by the polarization inverter if necessary. we have for the total differential scattering where C is the nuclear scattering amplitude. The precession finally reverses the direction of neutron spins at the end of the apparatus. Possible monochromators for neutron polarization are the (220) reflection from an Fe3O4 crystal and the (111) and (200) reflections from an Fe-Co crystal. Then (4. (4. so that an accurate observation of magnetic scattering is impossible. Figure 4. polarized neutrons can be used to observe magnetic scattering.15) becomes less than 1% of the first term. if there is an appropriate Bragg reflection. When the incident neutrons are unpolarized.) When a vertical magnetic field is applied to the monochromator as in Fig. if C — D. and induces resonance precession of the neutron spins. This method was first proposed by Shull17 and executed by Nathans et a/. Therefore.11) can become equal to C at some scattering angle. Including the nuclear scattering. (The form factor for magnetic scattering decreases with increasing scattering angle. Otherwise (as in the case of Ni metal.10(b).3). (The . where D is about 10% of C).

Schematic diagram of a polarized neutron spectrometer. In other words. For instance. which is large enough to determine the intensity of magnetic scattering.12. (After Nathans et a/. ferrimagnets. Triple axis goniometer for energy analysis in neutron scattering. the velocity and therefore the kinetic energy of the neutrons is conserved. in inelastic scattering a part of the kinetic energy is lost by conversion to some other form of energy. By measuring the change in wavelength as a function of wave vector in inelastic scattering. . The change amounts to 40% of C in the case of Ni metal. and antiferromagnets. The wavelength of neutron beams remains unchanged by Bragg scattering.11. we can elucidate the dispersion relationship of the magnon or the quantized spin wave. from —1 to +1. the neutron can excite spin waves in magnetically ordered systems. the total differential cross-section given in (4. 4. Such scattering is called elastic scattering.) By changing the direction of polarization of the neutron spins. such as ferromagnets.14) is changed by 4CDq.NEUTRON DIFFRACTION 99 Fig. 4. Fig. On the other hand. X.19) intensity of the high-frequency field is adjusted so as to reverse the direction of neutron spins during the transit time of the high-frequency coil.

3 MUON SPIN ROTATION (/tSR) The muon is an artificially produced elementary particle. they lose energy and finally come to rest at some point in the material. which is illustrated in Fig. which disintegrate into neutrinos and muons. . Muons are produced as follows: First high-energy protons collide with nuclei to produce mesons. the velocity of the neutron is determined. The velocity of the neutron is determined by adjusting the rotational speed of a pair of disks. and have their spin axes antiparallel to their velocity. The wavelength of the scattered neutrons is determined by changing the angle of incidence of the analyzer crystal for a known Bragg reflection.13(a)) can pass through the hole in disk B (see Fig. Another method to observe the change in wavelength is the time-of-flight (TOP) method. Principle of the time-of-flight (TOP) method.13.9).96kms"1.100 MICROSCOPIC EXPERIMENTAL TECHNIQUES Fig. the time required to travel the distance. with mass about 207 times larger than the electron mass. 4. 4. This method determines the velocity of the scattered neutrons. 4. between the two disks is 252 ps. 4. a neutron which passes through the hole in a disk A (see Fig. from which the wavelength is found by de Broglie's relationship (4. which can be measured accurately. as shown in Fig.12 shows a schematic illustration of a triple-axis goniometer for the observation of inelastic scattering.13(b)).13. each of which has a single hole. It has a magnetic moment whose magnitude is between that of the Bohr magneton and the nuclear magneton. Knowing this rotational speed. 4. 4. Figure 4. This particle can be used as a microscopic probe for detecting local magnetic fields inside magnetic materials.13. When the rotational speed is correctly set. say 1m. The muons thus produced have high energy (about 100 MeV). After these muons are introduced into a specimen. and the distance between the two disks. Since a neutron of wavelength 1A has a velocity of 3.

The positive muon which stops at an interstitial site has its spin antiparallel to the incident direction. 4. and also reduces the nuclear charge by e as a result of electrostatic shielding. Fig. There are two species of muons: the positive muon. with negative charge -e (C). being repelled by the positively charged nuclei.14. Angular distribution of positrons emmitted from disintegrated ^u.15. The behavior of these muons in the specimen is quite different: The positive muons come to rest at an interstitial site in the crystal. and the negative muon. thus producing a completely new artificial nucleus. p+. This phenomenon is called the pSR.MUON SPIN ROTATION ( M SR) 101 Fig.14 is a schematic illustration of the /tSR apparatus. ^i~. A positive muon travelling from left to right passes through the counter D and stays in the specimen S. The negative muons are attracted to nuclei and take up orbital motion around a nucleus. Figure 4. This orbital muon adds a large magnetic moment to the nuclear magnetic moment of the host nucleus. and then makes a precession motion about the magnetic field at this point. whose radius is very small because of the large muon mass. 4. Finally they stabilize to the Is ground state. with positive electric charge +e (C). Conceptual diagram of the /xSR apparatus. The precession frequency is proportional to the intensity of the magnetic field."1 .

the muon eventually decays with a lifetime of 2. because the velocity of the incident muon is very large.102 MICROSCOPIC EXPERIMENTAL TECHNIQUES A muon which passes through the specimen is detected by the counter X and is ignored. an antimuon neutrino v^. (After Yamazaki et al. and by the reaction turns into a positron e+.20 and Nishida21) . juSR signal for iron observed at various temperatures. The spin of a muon which stays at an interstitial site begins its precession motion at almost the same time as its passage is detected by the counter D. The Fig.16. During the precession motion. and an electron neutrino ve.2 /xs. 4.

16. Figure 4. 4. Fourier transform of Fig. Fig.16 were obtained for metallic iron at various temperatures. 4.20 and Nishida21) . If W(6) is the probability that the positron is emitted along the direction making an angle 6 with the direction of the spin. then where A is a coefficient with a value of about f. but the frequencies obtained after Fourier analysis of the data are quite sharp. as shown in the Fourier spectra of Fig. Then we can observe a precession oscillation as shown in Fig. The number of positrons is counted by the counter E and plotted as a function of the time since the detection at the counter D. 4. The experimental points scatter a great deal. (After Yamazaki et a/.15 shows a polar diagram of W(Q).MUON SPIN ROTATION (/j. The data shown in Fig. In this case the rate of arrival of muons was low enough so that the decay of each muon was complete before the next muon arrived.16. 4.17.SR) 103 positron tends to be emitted parallel to the direction of the spin of the muon.

Phys. E. G. S. 110S. J. W. 17. /. K. Rev. S. 73. Compt. handbook. Z.. what temperature is required for the neutron bath? REFERENCES 1. 2.2 Using the Mossbauer spectrum shown in Fig. Phys. Freeman. 138. M. 4. 4. and the isomer shift (mms"1). 1977). Shull. /. M. Ishikawa. 16 (1961). Phys.. 8. 13. G. Mossbauer. 10 (1959).22 PROBLEMS 4. Letters. 1963). Portis and A. 3. Shirane. Portis. 118S. and K. New York. 1985). Phys. A. 53B (1974). Japan. Shull and J. 12. Hashimoto. Muon spin rotation spectroscopy (Adam Hilger. Rev. Table of isotopes (6th edn. 149 (1959). 4.. Elsasser. Watson and A. Phys. G. 203 (1936). H. Anderson. Rev. E. 3 (1959). 19. Schenck. E. 1690. 1091.3 In order to produce a neutron beam which contains neutrons with an average wave length of 4 A. Phys. C.16. K. Metal Physics. L. J. 21. 117. pp. Amsterdam.. 1967). W. 1968). Soc. calculate the internal field (Am"1). 164. Rev. Hyperfine structure and nuclear radiations (North-Holland. 10. 16.. Shull. Gossard and A. C. A. Phys. 205S. 2nd edn. G. R. K. 18. L. Rev. Compt. Phys. 32 (1961). 123 (1961). 1029. and G. M. 211. G. 6. W. Appl. Phys. 80 (1950). 11. E. Neutron diffraction (Oxford. N.1 Knowing that the nucleus 57Fe has nuclear spin \. M. 9. 202 (1936). A. Appl. (McGraw-Hill. American Inst. A. Nathans. Rend. Smart. Rev. 65. For further details. 8 (1962). C. Shull. C. Nishida. 1256.. 20. Phys. Clarendon Press. 4. 38. M. Mattias and D. Chem.. 4. T. Chem. Shirley. Nathans. Nakai. Halban and P. R. Y. O. Pigott. E. 1955). 81 (1951). Solids. 190. and A. 76 (1949)... Hahn. 55 (1939). Rend. 7. T. K.. Kondo. Phys. Bacon. R. 124. Nagamiya. Bristol & Boston. Naturforsch. Marshall.. /. Letters. 988-1011. the reader may refer to a reference book on this subject. Phys. Thesis (Tokyo University. 31 (1960). 8-6-13. Lederer. Wertheim. calculate the NMR resonance frequency for 57Fe in an internal field of — 27MAm~ 1 . Nagamine. Phys.17. Phys. G. /. as seen in Fig. Rev.. the quadrupole shift (J). C. 626. 32 (1961). Sugimoto. 151 (1958).104 MICROSCOPIC EXPERIMENTAL TECHNIQUES 4. 15. 5.090MN. R. Preiswerk. G. Lamb. Z. 1280. Wiley. 14. Yamazaki. Physik. Gossard. 22. New York. 580.. The relaxation mechanism of ^iSR can also be investigated by observing the decay of the precession. and nuclear magnetic moment 0. Appl. 110 (1958). 6 (1958). Crowe. Hollander and Perlman.5. . Solids. Phys.

in which the atomic magnetic moments are arranged antipaiallel to one another. which we studied in a previous Part. in which the atomic magnetic moments are set parallel. and in Chapter 7 we treat Antiferromagnetism and ferrimagnetism. we shall learn how the atomic magnetic moments. we treat magnetic disorder.Part III MAGNETIC ORDERING In this Part. . are arranged in magnetic materials to produce three-dimensional structures. in Chapter 6 we treat Ferromagnetism. in which the atomic magnetic moments are absent or oriented at random. thus creating spontaneous magnetization. In Chapter 5.

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and the velocity change Ay during the time interval A Ms given by where AH is the change in the magnetic field during A/. According to the law of electromagnetic induction. even when the orbital plane is inclined. According to Lenz's law. The mechanism by which the magnetization is induced opposite to the magnetic field is the acceleration of the orbital electrons by electromagnetic induction caused by the penetration of the external magnetic field to the orbit (Fig. typically x~ 10~5.1 which occurs in a material containing no atomic magnetic moments. the change in the centrifugal force acting on the electron is given by which is just balanced by an increase in the Lorentz force.3). the magnetic flux produced by this acceleration of an orbital electron is always opposite to the change in the external magnetic field.1 DIAMAGNETISM Diamagnetism means a feeble magnetism. an electric field E (VmT 1 ) is produced in such a way that so that The electron is accelerated by this field. and that a magnetic field H (Am" 1 ) is applied perpendicular to the orbital plane. so that the susceptibility is negative. We assume that the radius r remains unchanged. which is in fact the case. This is always true. let us assume that the orbit is a circle of radius r (m). According to (5. the orbit precesses about the applied field without changing its shape.5 MAGNETIC DISORDER 5. with angular velocity . 5. For simplicity. eu&B.1). In other words. The relative susceptibility of such a material is negative and small.

Referring to (1.3). act as closed shells. This relationship holds fairly well for materials containing atoms or ions with closed shells. For instance. Fig. which is influenced by the band structure.3). 5. so that r2 = x2 +y2= la2.1 lists the . where the z-axisjs parallel_to the magnetic field (Fig.2 Diamagnetism is also exhibited by inorganic compounds. 5. Larmor precession of a tilted orbit. Mechanism of atomic diamagnetism.108 MAGNETIC DISORDER Fig. This motion is called the Larmor precession (Fig. the magnetic moment produced by the motion shown in Fig. Therefore (5.6) is replaced by x2 +y2.1.6) becomes When a unit volume of the material contains N atoms.2. conduction electrons play an important role in producing diamagnetism. so that r2 in (5. the magnetic susceptibility is given by where a2 is the average a2 for all the orbital electrons. we have X2 = y2 = z2 = a2/3. but not when the field is parallel to the plane of the ring.12) and (5.3 In the case of diamagnetic metals. electrons are distributed on a spherical surface with radius a (m). Table 5. each of which has Z orbital electrons. 5. Considering spherical symmetry. benzene rings.1 is given by In the case of a closed shell. 5. in which TT electrons are circulating just like orbital electrons.2). 5. They exhibit fairly strong diamagnetism when the field is applied perpendicular to the rings.

values of diamagnetic susceptibility at room temperature for various materials. Superconductivity is also characterized by perfect diamagnetism: that is.05 -16. /. is always zero in the superconducting state. even in the presence of an external field H (Meissner effect).23 6 Reference \ ) 4 5 . diamagnetic susceptibility is not strongly temperature-dependent.3. Materials Cu Ag Au Pb C (graphite) A12O3 H2O SiO2 (quartz) Benzene Ethyl Alcohol x (= ^TTX in cgs) . Table 5.DIAMAGNETISM 109 Fig.9.4 . Relative diamagnetic susceptibility for various materials at room temperature. Superconductivity is the disappearance of the electrical resistivity at some (usually low) temperature called the critical temperature. the magnetic flux density. is given by In other words. Tc.9. Generally speaking.7.7. Since in this case the magnetization.1. B. 5.7 Xl(T -25 -35 -16 -14 -18 . Diamagnetism of spherically distributed electrons.68 .

This table includes oxide superconductors with relatively high critical temperatures as first discovered by Bednorz and Miiller. 1. Magnetization curve of a soft superconductor.4. At absolute temperature T (K). In this case. the magnetization does not drop to zero at the first critical field. increases with decreasing temperature. where k is the Boltzmann constant. Fig. Table 5. and finally vanishes at the second critical field.6.2 lists typical superconductors.6 5. but decreases gradually with increasing field as shown in Fig.5. as shown in Fig.110 MAGNETIC DISORDER Fig. This type of superconductor is classified as a Type I or soft superconductor. At a temperature above absolute zero. 5. Hf. When the external field is increased to a critical field. which we will refer to simply as spin. the superconducting state is destroyed. 5. called a Type II or hard superconductor.38 X 1(T23 JK" 1 . with their critical temperatures and critical fields. 5. 5. so that magnetization. There is another kind of superconductor. the position of each atom undergoes thermal vibration. the thermal energy shared for one degree of freedom is given by kT/2. as does the direction of spin. The critical field.2 PARAMAGNETISM Paramagnetism describes a feeble magnetism which exhibits positive susceptibility of the order of .7. Hc. Let us assume a paramagnetic system containing N magnetic atoms each with magnetic moment M (Wb m). Hc.These critical fields increase with decreasing temperature as shown in Fig. 7. . Hcl.4. The magnetization curve of a superconductor is shown in Fig. 5. vanishes.5. At room temperature. Temperature dependence of the critical field.^=10~ 5 -10~ 2 . 5. This magnetic behavior is found in materials that contain magnetic atoms or ions that are widely separated so that they exhibit no appreciable interaction with one another. Hc2. of a soft superconductor.

Assuming that M= 1MB and H= IMAm" 1 .7 (=260kOe) 8. which is a moderately high field such as that produced by an electromagnet.8 (= llOkOe) — — — .1 10 40 100 110 Hc or Hc2 (0 K) 0. 5. The angular distribution of the ensemble of spins can be expressed by unit vectors drawn from the center of a sphere with a unit radius (Fig.40 9. 5.25 7. H (Am"1).064 (= 803 Oe) 20. the potential energy is given by (1. Superconductors V Mb Pb Nb3Sn Nb-Ti La-Ba-Cu-O Y-Ba-Cu-O Bi-Sr-Ca-Cu-O Type I I I II II II II II Tc (K) 5.6. 5. the potential energy is given by which is about 250 °f the thermal energy at room temperature given by (5. Typical superconductors.9). Fig. To what extent can the spin system be influenced when a fairly high magnetic field is applied? If a magnetic moment is placed in a magnetic field.7.PARAMAGNETISM 111 Fig. In the absence of a magnetic field.113MAm-1(=1420Oe) 0.2. Such a magnetic field barely influences a thermally agitated spin system at ordinary temperatures. the spins are distributed uniformly over all possible Table 5.164 (=2060Oe) 0.12). We can calculate the magnetization of such a system more quantitatively using the Langevin theory.20 18. Magnetization curve of a hard superconductor.8). Temperature dependence of the critical fields Hcl and Hc2 of a hard superconductor.

Angular distribution of paramagnetic spins in a magnetic field. H. so that the probability for a spin to take this direction is proportional to the Boltzmann factor On the other hand. the a priori probability for a spin to make an angle between 6 and 6 + dO with the magnetic field is proportional to the shaded area in Fig. When a magnetic field. the magnetization due to the whole spin system is given by If we put MH/kT= a and cos 0 = x. 5.8. or 27rsin0d0. we get -sin 0 = dx. For a spin which makes an angle 6 with H. the potential energy is given by (1. The physical probability for a spin to make an angle between 6 and 8 + dO is. is applied.8. the points are gathered slightly towards H. given by Since such a spin contributes an amount M cos 0 to the magnetization parallel to the magnetic field. therefore.16) becomes . so that (5. 5. so that the points of the unit vectors cover the sphere uniformly.112 MAGNETIC DISORDER Fig. orientations.9).

5. /. L(a) approaches 1. or Therefore.20) approaches NM. Figure 5. cannot be realized in practice unless we use extra-high fields or cool the sample to extremely low temperatures.13) and (5.PARAMAGNETISM 113 Fig. Langevin function. (5. we have .18) with respect to a.17). referring to (5.17) is reduced to where the function in parentheses is called the Langevin function and denoted by L(a). which corresponds to the complete alignment of all the spins. For a field of the order of 1 MAm"1. and accordingly a.9. given by (5. is increased.9 is a plot of L(a) as a function of a. This means that as H. As a is increased. we have the numerator of (5. the magnetization. This saturation of the paramagnetic system. The integral in the denominator is calculated to be By differentiating both sides of (5. however.12).

The solid curves represent JBj(a) for J=\.25). The functional form of B3(a) is similar to that of the Langevin function and in the limit of / -»°°. All of the theoretical curves reproduce the experimental points quite well. In reality. The susceptibility is. and Gd3+. the z-component of M is given by where Jz can take only 2J + 1 values Therefore. if we set the z-axis parallel to the magnetic field. is given by where the function in parentheses is called the Brillouin function and is denoted by B y (a). For a •« 1. we assumed that the spin can take all possible orientations. so J = S). we have from (5.114 MAGNETIC DISORDER Therefore. only the linear part of L(a) near the origin is observed. This relationship is known as the Curie law. f.20) This means that the magnetization is proportional to the magnetic field. as shown in (3. H. and \ (note that in these ions L = 0. they coincide. therefore. the Langevin function can be expanded as so that retaining only the first term. the average magnetization in a magnetic field. Fe3+. given by Thus we find that the susceptibility is inversely proportional to the absolute temperature. In the above calculation. In particular. B}(a) can be expanded as .10 shows the magnetization curves of three paramagnetic salts containing Cr 3+ . a spin can have only discrete orientations because of spatial quantization. Figure 5. For a <s: 1.

Thus the Brillouin function includes the Langevin function as a special case (/ = <»). 5. E.24). and III gadolinium sulfate octahydrate.28) for the Brillouin function in (5.22).28) becomes equal to (5. we find that if we replace M in (5. if we adopt only the first term in (5. we have Comparing this equation with (5. Considering that a = JMBH/kT.10.27).24) by . we find that (5. Magnetization curves of paramagnetic salts: I potassium chromium alum. Henry7) If we put / = oo in (5. II ferric ammonium alum. (After W.28).PARAMAGNETISM 115 Fig.

5 A. calculate its relative diamagnetic susceptibility. from the saturation magnetization given in (5. atomic mass 63. The quantity MeK is the effective magnetic moment as already given by (3.24) holds. s. Equation (5.94gcm~3.1 Knowing that copper^has atomic number 29. This is called Pauli paramagnetism? The susceptibility in this case is proportional to the density of states at the Fermi level. In addition to Langevin paramagnetism. 5. is known as the Curie law. When the effective magnetic moment is deduced from the temperature dependence of the paramagnetic susceptibility. From the slope of this curve.41). a change in temperature of a few hundred kelvin has only a small effect on the Fermi level. (5. Therefore. as shown in Fig. l/x versus i curve tor Langevm paramagnet.02 X lO^mol"1.27). or we can get the saturation magnetic moment as already given by (3. On the other hand. which gives the linear relationship between l/x and T.116 MAGNETIC DISORDER *ig. For this purpose. and average orbital radius 0. we can calculate the effective magnetic moment. we must measure the temperature dependence over a wide range of temperature. which corresponds to several thousand K (refer to Chapter 8).60 X 10~19 C. so as to separate the Langevin term from the temperature independent one. Orbital paramagnetism produced by orbital magnetic moments9 is also temperature-independent.11. electric charge of electron e = 1.54.11 X 1(T31 kg. paramagnetic metals and alloys exhibit nearly temperature-independent paramagnetic susceptibility. and electron mass m = 9. PROBLEMS 5.29). density 8.34). . Use the following values: Avogadro's number N= 6.li. this temperatureindependent term must be subtracted before applying the Curie law.

Japan. 3. Soc. 1972). Chem. 559. 4 (1936). Avogadro's number is 6. 5. Rev. H. A. J. J. 6. 1969) p. in which each molecule has a magnetic moment with J = 1. Academic Press. 2.2 Calculate the relative paramagnetic susceptibility for an ideal gas.41 at the above-mentioned temperature and pressure. Oxford. J. g = 2. 547. 9. at 1 atmosphere pressure and 0 °C. Rubber Co. 15. . Henry. 81. W. W. Handbook of physics & chemistry (53rd edn. 88 (1952). Rev. Phys. Magnetism and metallurgy I (ed. R. Van Vleck. Phys. Pauling.. Miiller. 252. Bednorz and K. J. Kubo and Y. Cleveland.02 X 1023 mol"1. Z. E. The 1 mol ideal gas takes a volume of 22.. 24 (1952). Myers. E. 7. REFERENCES 1. 189.. Phys. L.. New York. 11 (1956). 41 (1926). Obata. Pauli. Phys. 1932). Physik. B64 (1986). 673. Berkowitz and Kneller. The theory of electric and magnetic susceptibilities (Clarendon Press. W. Phys. R. Vogt.) (Chem. 8. Z. Mod.REFERENCES 117 5. 4.. G.

6 FERROMAGNETISM The term ferromagnetism is used to characterize strongly magnetic behavior. such as the strong attraction of a material to a permanent magnet.3).1 WEISS THEORY OF FERROMAGNETISM The mechanism for the appearance of spontaneous magnetization was first clarified by P. which we call ferrimagnetism. wl. The average magnetization under the action of an external field. It was found (as you will see later) that the molecular field coefficient w in (6. H. the ensemble of non-interacting spins is subject to thermal agitation and can be magnetized only if an extremely high magnetic field is applied. 6. The physical origin of this interaction will be discussed in (6. this term then includes both ferromagnetism and ferrimagnetism. This field was considered to align the neighboring spins parallel to one another. both of which lead to the presence of spontaneous magnetization. Instead of a parallel alignment of all the spins. there can be an anti-parallel alignment of unequal spins.52) acting in a spherical hole in a magnetized body.1) is much larger than the Lorentz field coefficient l/(3p. is given by . He assumed that the intensity of the molecular field is proportional to the magnetization. As discussed in Section 5. In this section we discuss the origin and nature of ferromagnetism in a narrow sense. This also results in a spontaneous magnetization. In this book we describe either of these cases. The origin of this strong magnetism is the presence of a spontaneous magnetization produced by a parallel alignment of spins. so that the molecular field cannot be attributed to a classical magnetostatic interaction. 6.0). He assumed that in a ferromagnetic material there exists an effective field which he called the molecular field. as ferromagnetism in a wide sense. Weiss considered that a molecular field could be produced at the site of one spin by the interaction of the neighboring spins (Fig. and a molecular field. or Note that this is just like the Lorentz field given by (1. Weiss1 in 1907.2.1).

4) becomes a straight line (b) through the origin. The parameter in this case is given by Since (6.2) must satisfy (6. because an external field. where L(a) = l and I = NM.2) represents the Langevin function as shown by curve (a) in the figure.1. (b) function (6. The state of thermal equilibrium represented by curve (a) is above point P' until P' reaches P. Fig. is not necessary to produce a spontaneous magnetization. The intersection points O and P of curves (a) and (b) represent solutions. because if the state changes from P to P". the equilibrium state is always closer to P. H.4) simultaneously with the same value of a. we can solve (6. and obtain The solution of (6. Equation (6.2) and (6. Now let us consider the temperature dependence of spontaneous magnetization on the basis of this graphical solution. However. This state is called absolute saturation magnetization and denoted by I s0 . Let us first assume that H = 0. which requires that the state P' must always stay on the line (b)). point P represents a stable solution.3) with respect to /. Such a solution can be obtained graphically. the relationship (6. say P'. point O represents a completely random orientation of the spins.4) as a function of a. similar to (5.3) includes /. the slope of line (b) is zero. or Is0=NM. Figure 6.5) . the point O represents an unstable solution. Once there is some alignment of spins by random processes.WEISS THEORY OF FERROMAGNETISM 119 Fig. Graphical solution for spontaneous magnetization: (a) Langevin function (6. The molecular field acting at the site from which a spin is removed. On the other hand. because if the magnetization happens to take some non-zero value. Physically. the state P' must rise along the curve b (this follows from the definition of a. 6.2. 6.16). At T = 0.2 shows plots of (6.2). near the origin. In this case. the alignment produces a non-zero molecular field which leads to more complete alignment.4).2) and (6. (6. so that the point P goes far to the right.

and denoted by @ f . must be equal to the gradient of line (b) at T= ® f . (After Becker and Coring2) As the temperature increases.) The curves denoted by / = 1 and / = \ are the solutions using the Brillouin functions B^a) and Bl/2(a). The point P moves down along curve (a) and finally approaches O as the gradient of line (b) approaches the initial gradient of curve (a). The temperature dependence of spontaneous magnetization obtained by this graphical method is plotted as a function of temperature in Fig. 1. In order to determine the Curie point. or .22)). the gradient of the initial slope of curve (a) in Fig. instead of the Langevin function L(a). or (see (5. 6. @ f . meaning that the spontaneous magnetization vanishes. and <». This final temperature is called the Curie point. Temperature dependence of spontaneous magnetization.2. At any temperature higher than the Curie point.3 (see the curve denoted by / = oo. compared with theoretical curves calculated from the Weiss theory using Brillouin functions with / = f.120 FERROMAGNETISM Fig. the slope of line (b) increases. the solution is always 7 = 0. The points are experimental values for Ni and Fe. This means that the spatial quantization of spins is a more realistic picture than the classical view of unlimited spin orientations. respectively. 6. The experimental points for Ni and Fe are in better agreement with the curves J =\ and / = 1 than with the curve J = °°. 6.3.

which causes a shift of line (b) in Fig. In order to measure this susceptibility accurately we must use a high magnetic field. we have where L'(a) is the derivative of L(a) with respect to a. Thus the magnetization I increases slightly. @ f . The susceptibility in this case is given by On the other hand. In this sense. we have 121 If we use the Brillouin function (5. Usually the external field is so weak compared with the exchange field that is has very little effect on the magnitude of the spontaneous magnetization. L'(«) is small enough to give a very small value for the susceptibility (6. When.J= 1. 6. So far we have ignored the effect of the external field.14).12) and (6.13).WEISS THEORY OF FERROMAGNETISM Equating (6.27) for the Langevin function. . we have from which the molecular field is estimated to be This value is very much larger than the Lorentz field which results from the magnetostatic interaction. N = 8.6) with (6. which will be discussed later.4). using the values 0f = 1063K.7). At a temperature T *£. we call it the high field susceptibility. M = 2.54 X 1028 m~3. For iron. we have Eliminating da/dH from (6. The effect of the external field is given by the second term of (6.28)).2 downwards and accordingly a shift of point P upwards. we have (see (5. from the definition of a in (6.3).2MB. Thus the Curie point is a good measure of the molecular field coefficient w. The physical origin of this enormously large molecular field is the exchange interaction.

where L'(a) = |. some effects of technical magnetization may overlap with the high-field susceptibility.4. Let us discuss in more detail the shape of the magnetization curve near the Curie point. the quantity M in (6. 6. 6. Taking into account spatial quantization. The temperature dependence of the susceptibility as predicted from these arguments is shown over the complete temperature range in Fig. the magnetization in this range can be approximated as where the coefficients A and B are given by for the Langevin function and for the Brillouin function.16). Substituting (6. the point P stays near the origin in Fig. L'(«) = 5.3) in (6. T approaches 0 f . Divergence of magnetic susceptibility in the vicinity of the Curie point. At T > @ f .28). According to (5.14) tends to vanish and the susceptibility approaches infinity.122 FERROMAGNETISMm Fig.22) or (5.15) must be replaced by the effective magnetic moment given by (5. so that the denominator of (6. however. so that (6. the susceptibility is inversely proportional to the deviation of T from @ f .30). where the magnetization is relatively small in comparison with the absolute spontaneous magnetization. At T < 0 f .2. Separation of the two phenomena is difficult. which shows a divergence of the susceptibility at the Curie point. 6. we have therefore . and may require the use of extremely high fields.4. and noting that wI»H. This is called the Curie-Weiss law.14) becomes That is.

we get the linear relationship shown in Fig. we obtain the specific heat .4 Kouvel and Rodbell. 6.6. Extrapolating to H/I = 0. For more details the reader may refer to Kouvel and Fisher. Magnetization curve at a tempera- ture near the Curie point. we know that the temperature dependence of spontaneous magnetization is given by Therefore the Curie point can be determined by extrapolating the line representing 7S2 versus T towards I2 -» 0.7 (solid curve). so that the spontaneous magnetization must be determined by extrapolation from the high-field region. Fig. For this purpose. 6. The work necessary to increase the spontaneous magnetization from 7 to 7 + SI in the presence of molecular field (no external field) is given by so that the internal energy of the state associated with spontaneous magnetization 7 is given by This internal energy is plotted as a function of temperature in Fig.5. This relationship between 7 and H is shown graphically in Fig. Arrott plot. By differentiating (6.3 From the first term of (6. such a relationship does not necessarily hold in every case. However.6 The Curie point can also be determined by observing the anomalous specific heat. 6. 6.20).5. 6. we divide both sides of (6.6.19) by / to give Therefore if I2 is plotted against H/I. the magnetization is also affected by rotation against the magnetocrystalline anisotropy (Chapter 12). This plot is called the Arrott plot. In practice.5 and Arrott and Noakes. we can determine the value of 7S.WEISS THEORY OF FERROMAGNETISM 123 Fig.23) with respect to temperature.

6.8. while the dashed curve represents experiment.8. Fig. The solid curve was calculated by the Weiss theory. as shown by the dashed curve in Fig. we know that the internal energy is increasing even above the Curie point. we can also estimate the molecular field coefficient w. By integrating the specific heat with respect to temperature.8. This is due to the presence of clusters of parallel spins above the Curie point. The solid curve was calculated by the Weiss theory. which has a sharp peak as shown by the solid curve in Fig. .124 FERROMAGNETISM Fig. while the dashed curve represents experiment. 6. 6.24).2 VARIOUS STATISTICAL THEORIES Experiment shows that the anomalous specific heat is accompanied by a tail above the Curie point. 6. These clusters exist because the molecular field is due to short-range forces caused by the exchange interaction.7. Anomalous specific heat near the Curie point. 6. Temperature dependence of the magnetic energy. From the relationship (6.

. the energy is lowest when St II S. in which two kinds of atoms. .. and S. He suggested that between atoms with spins St and S. We assume that a particular spin 5. which is 103 times larger than the dipole interaction given by (1. Applying this method to a spin system. The magnitude of / is in the order of 103cm~1 (~103 K). where the parallelism of the spins is considerably disturbed. the molecular field is assumed to be proportional to the average magnetization. This model is called Bethe's first approximation.8 using statistical mechanics in a similar way to the Weiss theory. not just nearest-neighbor pairs. and all the spins 5. thus forming spin clusters. If / > 0. This tendency to align the nearest-neighbor spins parallel (for positive /) causes complete parallel alignment of the entire spin system. except that the exchange interaction from the other spins is replaced by the molecular field. so that a ferromagnetic alignment is stable. which results in ferromagnetism. the exchange interaction is short-range. there is an interaction with energy where / is the exchange integral. and show using the Bethe-Peierls approximation how the spin clusters are created. Since the exchange interaction is short-range.1.17). is stable and antiferromagnetism results.. 5. so that when the temperature is near the Curie point. We will discuss the physical meaning of this interaction in Section 6. The situation is also the same for S. In the Weiss theory of ferromagnetism discussed in Section 6. In reality. near-neighbor spins still tend to remain parallel. so that the z-component of 5. This is equivalent to the assumption that the value of / is the same for all spin pairs. the value of / is largest for nearest-neighbor spins. A similar phenomenon appears in a superlattice. Let us assume the Ising model11* in which 5 = |.VARIOUS STATISTICAL THEORIES 7 125 The exchange interaction was first proposed by Heisenberg in 1928. as treated in Section 6. Sz. Then the exchange energy associated with the spins 5. are arranged in a regular alternating pattern. Peierls10 treated spin clusters in ferromagnetic theory. Therefore this approximation for treating short-range order is referred to as the Bethe-Peierls method. Bethe9 succeeded in calculating the degree of short-range order.1. can have the value of +^ or —\ under the influence of the exchange interaction with the nearest neighbor spins. which is determined by the average value of the spin 5 (see Fig. can take values only of \ or —\.9). A and B.3. an antiferromagnetic alignment of 5. while if / < 0. is given by *The case in which the spins can be oriented in all directions. Considering that the tendency to form a superlattice is equivalent to a short-range force acting to make A atoms tend to attract B atoms as their nearest neighbors. however. This problem was treated by Bragg and Williams. 6. is called the Heisenberg Model.

has the value \ is given by and the probability that 5.9. 6. Model for Bethe's first approximation. while q spins take the value — |. Hm.26) becomes Let us denote U in (6. Similarly the average value of S. remains in pi+ and pt_ as shown in (6. If p spins of the total of the z values of 5. then (6. = \. take the value \.27) as U+ if 5. is given by where the undetermined parameter. .28) and (6. is given by which also includes the undetermined parameter Hm. = -\. and as U~ if 5. has the value — \ is given by Therefore the average value of 5.29). Then the probability that S.126 FERROMAGNETISM Fig.

Approximations Weiss theory Bethe's 1st Bethe's 2nd Exact solution z =4 2 1. and 5. so that MBHm <§: kT. must be equivalent.36).35) and (6. and we have In the case of a two dimensional lattice. Bethe's second approximation rigorously takes into consideration the influence of the second-nearest neighbors. we can calculate the spontaneous magnetization At a temperature near the Curie point. so that In order to compare this result with the Weiss theory. the energy per spin for S = \ is calculated as so that using (6.443 1. and 3 for z = 6. and finally we get 127 From this relationship we obtain Hm as a function of temperature T. both of which are larger than the values given by (6.135 z =6 3 2.466 2. and using (6'. so that In the case of a body-centered cubic lattice. The values of k@f/J for S = \ calculated by various approximations (after Oguchi15).312 1.1. The exact solution is that given by Onsager12 for a Table 6.1. z = 4.> = (Sy). Hm becomes small.30).372 . z = 6.VARIOUS STATISTICAL THEORIES Since 5.9) and taking Meft = 3MB. values of k&f/J are listed for various approximations. In Table 6. (S. we get This gives the values 2 for z = 4.

Experiments also show such a deviation. For instance. as shown by (6.128 FERROMAGNETISM Fig. C. x> near the Curie point are given by and also at the Curie point where the exponents take the values given in Table 6. Let us assume that the temperature dependence of the specific heat. and Gd. which is clearly due to cluster formation above the Curie point. These exponents are called the critical indices According to the Weiss approximation.10 shows the temperature dependence of 7S for Weiss and Bethe's first approximations. The temperature dependences of various physical quantities are altered by the appearance of parallel spin clusters.21). 7S. as shown by the dashed curves in Figs 6. and we can clearly see a difference in the Curie points between the two approximations.7 and 6. The 1/x versus T curve calculated by the Bethe approximation shows a deviation from the linear Curie-Weiss law. and magnetic susceptibility. It can be seen that the value of k@f/J gets smaller as the order of approximation increases. This means that the Curie point is reduced for a given /.10. Ni.8. Thus the linear extrapolation of the high-temperature part of the 1/x versus T curve to the abscissa differs from the real Curie point. and also y = .2 for Fe. fi=\. 6. This fact must be taken into consideration when we estimate the value of / or the value of the molecular field from the value of the Curie point. spontaneous magnetization. two-dimensional lattice. 6. The Bethe approximation also explains the influence of cluster formation on the temperature dependence of energy and specific heat. Fig. Comparison of 7S versus T and \/x versus T curves for the Weiss theory and for Bethe's first approximations. The extrapolated intersection is called the asymptotic Curie point (symbol 0a) to distinguish it from the real Curie point where the spontaneous magnetization vanishes.

Bloch14 treated the thermal disturbance of the spin arrangement at low temperatures using a spin wave model.13 -0. In other words.1 5.and two-dimensional spin lattices.14) and (6. no ferromagnetism appears.6 292.32 ±0. 6.31 1 S 15 129 — 4.1 4. as verified by the numbers for the Weiss and Ising model given in Table 6. 0.0 ± 0.0587 for body-centered cubic. except for the values of the proportionality constant C.050 — 0.34). However.02 0.0294 for face-centered cubic lattices.2 ± 0.0 629.063 — ft 0. in which the spins are connected in a chain. and 0.262 ±0.15). both of which tend to develop a parallel alignment of the spin system. more accurate approximations based on the three-dimensional Ising model with S = \ give better values.04 — 0. Critical indices (after Oguchi ).13 by assuming that the magnitude of the unit moment and the effective temperature depend on the size of the cluster.2. 3 dimens.02 1.2.33 1.2. we find that the right-hand side vanishes.2 3 y' = 1 as shown by (6.51 ± 0. Bloch showed that at low temperature the spontaneous magnetization depends on temperature as where J is the exchange integral and C is a constant which depends on the crystal structure: 0.17 0.313 0. as listed also in Table 6.25 1 y' — — — 1. there exist the following relationships between these critical indices: The first two formulas hold well for various approximations.) Weiss theory 0 t (K) 1043.3 EXCHANGE INTERACTION The exchange interaction was first treated by Heisenberg7 in 1928 to interpret the origin of the enormously large molecular fields acting in ferromagnetic materials. This T 3/2 law holds fairly well experimentally. Other strict statistical treatments also prove that no ferromagnetism appears in a two-dimensional lattice in the Heisenberg model. This .060 — 0. in a one-dimensional ferromagnet. Materials Fe Ni Gd Ising model (S = |.104 ±0.EXCHANGE INTERACTION Table 6. These values are not in very good agreement with the experimental results. This law was deduced by Kadanoff et a/.33 1. He concluded that no ferromagnetism appears for one. According to the scaling law.5 y 1. in which he assumed that the reversed spins propagate just like waves.34 ± 0.5 a <0. If we assume that z = 2 in (6. but that it does appear in the Ising model or in the presence of a uniaxial anisotropy.1174 for simple cubic.125 — a' < 0.

must be invariant for the exchange of the two electrons. <f/(q1. they cannot share a common orbit because of the Pauli exclusion principle. which can explain the magnitude of the molecular field.15 Let us elucidate how this principle is expressed in terms of the atomic wave function. one accepts the Pauli exclusion principle. &2(qi. so that they form separate orbits.17). the exchange interaction may be understood as follows: Suppose that two atoms with unpaired electrons approach each other. The value estimated from (6.42) is 105 times larger that the magnetic dipolar interaction calculated from (1. however. where q1 and q2 are the general coordinates of electrons 1 and 2. the electrons will share a common orbit. Therefore if this Coulomb energy is disturbed by the Pauli exclusion principle by a small factor. The order of magnitude of the Coulomb energy involved in this case is estimated as where r is the average distance between the two electrons. both of which can be expressed by a general coordinate q. The Pauli exclusion principle was first introduced to explain the multiplicity of atomic spectra. . z) and a spin variable a ( = ± |). o or The Pauli principle asserts that condition (6. however. or Since the two electrons are indistinguishable. so that it is rather difficult to explain it in terms of classical physics. the spins of these two electrons are parallel.45) is correct. Now let us consider the wave function of an atom with two electrons. The reasoning is as follows: suppose that electrons 1 and 2 occupy the same state. AJ7e. this wave function becomes i/f1(g2)'/'i(<7iX which is the same as before. If the spins of these two electrons are antiparallel to each other. which can be written as ^-^q^^^q^). In other words. rather than condition (6. The atomic wave function of an atom with a single electron is a function of a spatial coordinate r(x. y. the probability of realizing this state.q2). If. is the order of 1400 K. thus increasing the electrostatic Coulomb energy.By exchange of the two electrons. and fy£q^) of electron 2.44). but it can be approximated by the product of two wave functions i/^^) of electron 1. assumed to be 1A. If. It is difficult to express this function exactly. thus reducing the Coulomb interaction. t/fj. the change in Coulomb energy. respectively.q2). On the other hand. say 1%.130 FERROMAGNETISM m interaction is due to a quantum mechanical effect.

it follows that This is another expression of the Pauli exclusion principle. must be antisymmetric upon the exchange of the two electrons. . let us consider the case in which two electrons occupy the Is state of an He atom.EXCHANGE INTERACTION 131 according to condition (6. Thus the symmetry of the spin variable can affect the symmetry of the part of the wave function containing the spatial coordinates. (l/(q^. The actual forms of these three terms are given by where Z is the atomic number (Z = 2 for He). ^(o-j.) and one containing the spin variables. resulting in a change in electrostatic interaction between the two electrons. while the state which is symmetric for the exchange of spin variables is antisymmetric for the exchange of spatial coordinates. The wave can function $(qi. In order to realize this condition. it must be that or These conditions mean that the state which is antisymmetric for the exchange of spin variables is symmetric for the exchange of spatial coordinates.45). cr2). In order to satisfy these conditions.45).45) asserts that the wave function of the two-electron system. that is According to (6.q2\ .16 The relationship (6. and the third term concerns the interaction between the two electrons. the sign of these wave functions must be different. Example For example. (p(rl. the second term concerns only electron 2. and r12 is the distance between the two electrons.q2) can b£b expressed as a product of two parts. The Hamiltonian in this case is given by where the first term concerns only electron 1. one containing the spatial coordinate.r2).

respectively. A wave function symmetric for the exchange of spatial coordinates is where rl and r 2 are the radial vectors of the electron 1 and 2. respectively.54) and (6. the spatial wave function must be antisymmetric. the wave function must be symmetric for the exchange of spatial coordinates. the energies of the states given by (6.55) are calculated as where . so that The suffixes s and a signify that the function is symmetric and antisymmetric. Since the wave function is antisymmetric for the exchange of spin variables. On the other hand. The energy of the state can be calculated by Assuming that <p1 and tp2 are normalized and also orthogonal.132 FERROMAGNETISM Suppose that the spins of two electrons are antiparallel. if the spins of the two electrons are parallel.

619. Hamblen. Heisenberg.1 Knowing that nickel has the Curie point ®f = 628. E. Ferromagnetismus (Springer. . Lewis. Phys. in (6. Soc. F. 11. Z. 39 (1967).and para-helium. 18 (1967). S. Use the first and second terms in the power series of the Langevin function with respect to a. which correspond to antiparallel and parallel spins. Phys. 31 (1925). Kane. 8. we find that the energies of the parallel and antiparallel spin pairs differ by 2/12. S. 108 (1957). A. E. J. P. Phys. Physik. 1970). Rayl. 19 (1967). 117. Would the accuracy of the value of the molecular field be increased or reduced when more exact statistical treatments were applied? 6. Berlin. 32 (1936). Rev. 12. E. Fisher. J. J=\. 61 (1630). Phys. Ju has no corresponding concept in classical physics. 145 (1934). the sign is + for the symmetric function (6. Phys. Becker and W. Z. Statistical theory of magnetism (in Japanese) (Syokabo Publishing Co. L. A1626. 215. but also the difference between ortho. 136 (6A) (1964). Phys. 65 (1944). 395.. 16.3 K. Roy. 13. 7.7 clarified not only the nature of the molecular field in ferromagnetic materials. Rev. D. Z. W. Rev. Proc. Moreover. 32. 552. and K12 is the Coulomb interaction between these two electrons. Bloch. Letters. which was first given by Heisenberg.. This term signifies the energy produced by the exchange of two electrons between two orbits.. 477. respectively. W. 2. Kouvel and D.57). Proc. 15. 1939). W. Soc. W. Bragg and E. J. a similar treatment was applied to the hydrogen molecule. 6. REFERENCES 1..6AfB. 4. Proc. 206..25). R. 699. L. according to the Weiss theory. Physik. Ray. 6 (1907). Z. 31 (1925). calculate the molecular field at OK according to the Weiss theory. Rev. Mod. Tokyo. S. and is called the exchange integral. Oguchi. A.REFERENCES 133 In equation (6. Weiss. and showed that Ju < 0. Kadanoff. S1 and S2.54) and — for the antisymmetric function (6.. In (6. 661. J. respectively. Aspness. W. p. Gotze. Noakes. Rodbell.57). Rev. and saturation moment Ms = 0. J. and J. H. P. Arrott and J. In (6. L. 9. 3. 253. Phil. Ising. R. 540. Doring.58). so that an antiparallel spin pair is stable and forms a bonding orbit. 786.55).. Physik. D. Hecht. The same situation was expressed in terms of the spins of two electrons. Pauli.] This treatment. Bethe. E.. Soc. A150 (1935). 765. V. Camb. A. Phys. Physik. Palciaukas. Letters. Peierls. 49 (1928). Rev. H 2 . 151 (1935). Kouvel and M. Swift.2 Calculate a magnetization curve at the Curie point. Arrott. 14. R. 5. Onsager. PROBLEMS 6. 10. 1394. Williams. However. T. /! and 72 are the energies of electrons 1 and 2.

Antiferromagnetic spin structure. Since the magnetic scattering of a neutron differs for + spins and . Therefore an antiferromagnet produces no spontaneous magnetization and shows only a feeble magnetism. Such extra lines are called superlattice lines.1. Therefore. The relative magnetic susceptibility of antiferromagnetic materials.spins. a number of extra lines are seen below the Neel point. 7. This is the characteristic feature of an antiferromagnet. As the temperature increases.3). above some critical temperature. so that the temperature dependence of the susceptibility becomes similar to that of an ordinary paramagnet. neighboring spins are aligned antiparallel to one another so that their magnetic moments cancel. Figure 7. Therefore the susceptibility in this case is smaller than for a normal paramagnet. as shown in Fig. x. contrary to the case of the normal paramagnet.4 shows the neutron diffraction lines observed for MnO below and above the Neel point.7 ANTIFERROMAGNETISM AND FERRIMAGNETISM 7. As expected. the spins which are parallel and antiparallel to the field experience almost no torque and so keep their ordered spin arrangement. The crystal structure of MnO is such that Mn ions form a face-centered cubic lattice. the ordered spin structure tends to be destroyed. When an external magnetic field is applied parallel to the spin axis. However. 7. denoted by @ N . This critical temperature is called the Neelpoint. the susceptibility shows a sharp maximum at the critical temperature. 7. as shown in the figure.2. The only difference is the presence of an ordered spin structure. the same as for paramagnets. where the antiferromagnetic structure appears. such spin ordering disappears completely. because they reflect the presence of a structure larger than the basic Fig.1 using neutron diffraction. The spin magnetic moments of the Mn ions are arranged antiferromagnetically. 7. and the susceptibility increases. and O ions are located between each Mn-Mn pair (Fig. as shown in Fig.1. extra diffraction lines appear if magnetic ordering is present. Antiferromagnetic spin ordering was first verified experimentally in MnO by Shull and Smart.1 ANTIFERROMAGNETISM In antiferromagnetism. ranges from 10 ~ 5 to 10 ~ 2 . .

2.5.ANTIFERROMAGNETISM 135 Fig. Fig.3. an idea first introduced by Kramers2 and theoretically interpreted by Anderson. crystallographic unit cell. because it is interrupted by the interstitial O 2 ~ ions. . Crystal and magnetic structures of MnO. 7. However. The antiferromagnetic structure as shown in Fig. 7. 7. as shown in Fig. Temperature dependence of magnetic susceptibility of antiferromagnetic materials. M1 and M 2 . a superexchange interaction acts between Mn ions through the O 2 ~ ion. 7. The />-orbit stretches towards the neighboring Mn ions.3 was deduced by analyzing these superlattice lines.>)6. The direct exchange interaction between Mn ions is very weak.3 The essential point of this mechanism is as follows: The O 2 ~ ion has electronic structure expressed by (ls)2(2s)2(2.

Neutron diffraction lines from MnO powder specimen observed below and above its Neel point. The p-oibit of the O2 on magnetic ions Ml and M2. 7.136 ANTIFERROMAGNETISM AND FERRIMAGNETISM Fig. ion through which exchange interaction acts between the spins . so that its sense will be antiparallel to the total spin of Mn 2+ . (After Shull and Smart1). One of the p-electrons can transfer to the 3d orbit of one of the Mn ions (say the Mj ion). 120 K. because the Mn 2+ has already had five electrons and the vacant orbit must accept an electron with spin antiparallel to that of the five electrons Fig. 7. In this case the electron must retain its spin.5.4.

For more details the reader may refer to the review by Nagamiya et al. 7.5 The first theoretical treatment of antiferromagnetism was made by Van Vleck6 with later advances by Neel7 and Anderson. As a result. the total spin of M t becomes antiparallel to that of M 2 .8 Let us designate as A sites the lattice sites on which + spins are located in a completely ordered arrangement. as in the Weiss theory of ferromagnetism. the interaction tends to become positive. and Br1" ions. The superexchange interaction acts also through S 2 ~.F°r simplicity. The exchange interaction with the other Mn ion (M 2 ) is therefore negative. we put Moreover.5) and (7. When the angle is 90°. It is expected that the spins on the A sites are subject to the superexchange interaction with the spins on the B sites as well as with the other A sites. and becomes weaker as the angle becomes smaller.1. the remaining electron in the p-orbit must have spin antiparallel to that of the transferred electron because of the Pauli exclusion principle. and Se2~. These interactions can be expressed as molecular fields. On the other hand. we can assume that W AA =WBB< and WAB = ^BA. It is experimentally verified4 that positive superexchange interaction at 90° increases in the order O 2 ~. Se 2 ~. and as B sites the locations of the — spins.2) can be written as and The formulas (7. .6) are of the same form as (6.2). the sublattice magnetizations of the A.ANTIFERROMAGNETISM 137 (Hund's rule. must be negative.and B-sublattices are equal in magnitude and opposite in sign.1) and (7. Such a magnetization is called a sublattice magnetization. and 7A and 7B are the magnetizations due to all the spins on the A sites and B sites. The molecular field acting on the A site spins is given by where the inter-site interaction coefficient. Similarly the molecular field acting on the B site is given by Since the antiferromagnetic spin structure in the absence of an external field is symmetric with respect to the A and B sites. WAB . (7. respectively.1) for ferromagnetism. so that Therefore. Cl1". S 2 ~. as shown in Fig. The superexchange interaction is strongest when the angle Mj-O-lV^ is 180°. Section 3.

which is the Neel point.8).138 ANTIFERROMAGNETISM AND FERRIMAGNETISM Therefore. M is the atomic magnetic moment. the sublattice magnetizations are given by Differentiating both sides with respect to H.4) does not hold. we have the magnetic susceptibility . we have Adding the two equations side by side. and vanish at a critical temperature. as in (6. 6. When an external field is applied parallel to the spin axis.7) and (7. 7A and /B are no longer symmetrical. and L(a) is the Langevin function. so that equation (7. The sublattice magnetizations given by (7.3). and solving with respect to (dIA/dH) + (dIE/dH).8) decrease with increasing temperature (see Fig. In this case. the thermal equilibrium values of sublattice magnetizations are given by and where N is the number of magnetic atoms per unit volume. similar to the spontaneous magnetization in ferromagnetism. @ N . The Neel point is given by which is similar to equation (6.2).

15). the asymptotic Curie point. is entirely different from the Neel point @ N .ANTIFERROMAGNETISM 139 If we put and (7.6.22) we have Then (7. If Fig.14) can be expressed in a simple form If the temperature is well above the Neel point. w2. Temperature dependence of reciprocal magnetic susceptibility for antiferromagnetic materials. If we plot \/x as a function of T.15) gives a negative value provided that the intrasite interaction coefficient. 7. 7. (7. the spin arrangement becomes random. so that from (5. Unlike the case of ferromagnetism.6). The reason is that the intersite interaction coefficient. @ a .19) gives a straight line which intersects the abscissa at T = 0a (see Fig. ( x\\ and x± are the magnetic susceptibilities measured by applying magnetic field parallel and perpendicular to the spin axis. so that (7. @ N . .fpoiy is the susceptibility for polycrystalline material calculated by averaging x\\ and x± •) . wlt is relatively small.17) becomes which has the same form as the Curie-Weiss law (6. is always negative.

7. as easily found from (7.19) with T replaced by @ N . As deduced from (7.9) and (7.7.86 5.140 ANTIFERROMAGNETISM AND FERRIMAGNETISM Fig.1. or As the temperature decreases from the Neel point.9 Material MnO NiO Cr2O3 FeS Crystal type Nad NaCl Corundum NiAs (K) 122 520 307 593 ®N ®a (K) -610 -2000 -1070 -917 Meff/MB 5. (Symbols are the same as Fig. If we plot equation (7. Magnetische Eigenshaften Vol II.) Wj = 0.6. so that the point P in Fig. we find that the curve for x\\ diverges as T tends to zero (Fig. Table 7.6 is shown in Fig. The susceptibility at the Neel point reaches a maximum. the sublattice magnetization increases.7. we have This behavior matches well the x~T curve in Fig. as is given by (7. 7. the susceptibility decreases with decreasing temperature.6 3. The %-T curve corresponding to Fig. @a is negative and its magnitude is equal to the Neel point.6). 7. . Various constants for typical antiferromagnetic materials. 7. Typical antiferromagnetic materials and their Neel and asymptotic Curie points are listed in Table 7. 3-148.17). (1962).15). and finally in the limit T -» 0.7.22 * Landolt-Bornstein. 7. 7. Part 9.1.2 rises along the curve L(a) and the value of L'(«) decreases from f.95* 4. Temperature dependence of magnetic susceptibility of antiferromagnetic materials. 6.21) as 1/X-T.

Rotation of antiferromagnetic spins in a magnetic field perpendicular to the spin axis. Suppose an external magnetic field. 7.22) becomes The direction of the sublattice magnetization must coincide with the resultant magnetic field. 7. it follows that Using this relationship.8.and y-components of the molecular field acting on the A-sublattice are given by Since the A.8. we have .ANTIFERROMAGNETISM 141 Fig. composed of the external field and the molecular field. (7. 7.and B-sublattices are symmetrical. is applied parallel to the *-axis. Then the x. which are originally parallel to the y-axis. The sublattice magnetizations. the susceptibility may not vanish even at T = 0. because the rotation magnetization of the sublattice magnetizations occurs even at 0 K (see Fig.8). will rotate toward the x-axis as shown in Fig. Hex.25). Therefore Eliminating /A from (7. When a magnetic field is applied perpendicular to the spin axis.

7. the measured susceptibility is the value averaged over the crystallites of all possible orientations.7. the sublattice magnetizations are given by so that the spontaneous magnetization is At any temperature above absolute zero.20). 7a and 7b. the sublattice magnetizations are thermally disturbed.2 FERRIMAGNETISM In ferrimagnets. or Fig.6 and 7.and B-sublattices are occupied by different magnetic atoms and sometimes by different numbers of atoms.7. let us assume that only one kind of magnetic atom. Such magnetism is called ferrimagnetism and was treated by Neel.142 ANTIFERROMAGNETISM AND FERRIMAGNETISM Therefore the susceptibility in this case is given by which is equal to the maximum susceptibility given by (7. Actually the susceptibility in this case remains constant from the Neel point to 0 K as shown in Figs 7. To describe this disordering. and even at OK. with magnetic moment M. of magnetic atoms is distributed on the A. 2N.7 For simplicity. we introduce the normalized sublattice magnetizations. as shown by the curve labelled 'poly' in Figs 7. where If all the magnetic moments are completely ordered. 7.6 and 7.9). In the case of a polycrystalline material.and B-sites in the ratio A: /A. contributes to ferrimagnetism. Spin structure of a ferrimagnet. so that the antiferromagnetc spin arrangement results in an uncompensated spontaneous magnetization (see Fig. 7. sometimes complete order may not be realized. the A. . The total number.9.

34) with respect to dIJdH. Under the action of these molecular fields. where C is given by The equation (7. the term MH/kT must be added inside the braces { }.and B-sublattices. the sublattice magnetizations are calculated using common statistical procedures as In the presence of an external magnetic field H. or where w is the absolute value of the molecular field coefficient between the A. At temperatures above the Curie point. we have Solving (7.35) can be simplified to where . dl^/dH. using the approximation L'(«) = |. multiplied by 2N. and a and /3 are the intra-site coefficients normalized by w. The molecular field acting on the magnetic atoms is caused by the atoms on the same sublattice as well as the atoms on the other sublattice.FERRIMAGNETISM 143 The quantities 7a and 7b are interpreted as the average magnetic moment at each sublattice site.

so that the remaining terms are approximated by a straight line. the magnitude of the third term in (7. The spontaneous magnetization in this case is given by where 7a and /b can be found by solving (7. the paramagnetic state persists down to 0 K. 7.33) under the assumption that T < 0 f . 1/^ = 0.37) we have Solving this equation with respect to @ f .When the temperature is lowered from well above the Curie point. Temperature dependence of reciprocal susceptibility of a ferrimagnet. 7. which has slope 1/C and intersects the ordinate at TL/XO.37) is graphically shown in Fig. At high temperatures.37) increases as the temperature approaches 0. the susceptibility becomes infinite at 0 f .10.41) therefore . and ferrimagnetism appears. The condition for producing this ferrimagnetism is 0f > 0.10.144 ANTIFERROMAGNETISM AND FERRIMAGNETISM Fig. The relationship between \/\ and T given in (7. The asymptotic Curie point in this case is given by while at the ferrimagnetic Curie point. so that the critical condition 0f = 0 follows from (7. the third term on the right-hand side of (7. while if 0f > 0. we have If 0( < 0.37) becomes negligibly small. so that from (7. 0 f . so that the l/x~T curve departs from the asymptotic line and finally drops to zero at the Curie point.

In this case. )3. it is evident that ferrimagnetism appears. A.FERRIMAGNETISM 145 For a > 0 and ft > 0. and p. To see how this works. giving rise to spontaneous magnetization. we have The internal energy in this case is given by . If the absolute values of a and /3 are smaller than the values that satisfy (7.43) gives the limiting conditions for realizing ferrimagnetism or paramagnetism: aj8 < 1. By putting and minimizing (7. the internal energy is given by which by using (7. 7a and 7b take their maximum values. negative intrasite interactions may be suppressed.45) with respect to 7b. In this case we must have e internal energy is obtained by inserting (7. If the absolute values of a and /3 become larger than the values that satisfy (7.45) with respect to 7a and 7b in the following four cases: (I) Paramagnetism.45). while for a < 0 and /3 < 0. let us investigate how the values of 7a and 7b vary with the values of these variables.43)..46) in (7. or (II) Saturation in both A and B sites. If there is no external field. so that The internal energy is then given by (III) Saturation in A sites only. The most conspicuous macroscopic feature of ferrimagnetism is the appearance of various forms for the curve of the temperature dependence of spontaneous magnetization. The shape of the 7S-T curve depends on the combination of a. the spin arrangement on the A and B sublattices becomes antiferromagnetic or non-magnetic.43).32) is converted to The stable values of 7a and 7b are calculated by minimizing (7. (7.

where a > -/A/A and /3 > —A/JA. and the line EC for which /3 = -A//A. In order to determine the regions in which the cases (I)-(IV) are realized. and given by Then the A site magnetization takes the equilibrium value so that the internal energy is given by By comparing internal energies in the four cases. Similarly. and IV all give positive values. . and /x. ft.) This is consistent with the condition for the appearance of ferrimagnetism as mentioned just below (7.54) we know that a < -/A/A. A. Case (IV) is realized in the region FCA. we can determine which case is realized for a given set of the parameters a. which is negative unless a > -/i/A and /3 > -A//x. The B site magnetization in this case is fully saturated. and IV in the a-/3 plane (see text).49) is equal to {(«A + /LI)A + (/fyi + A)}/j. because in this case the energies in the cases II. (IV) Saturation in B sites only.43).d < 2NM. because I. Let us discuss the problem on the a-p plane shown in Fig. The paramagnetic case I is realized below the curve ACB. II. First we assume that A < /JL. Equilibrium regions for four stable spin configurations I.. case (III) is realized in the region ECB. we draw the line FC for which a = -/x/A. III. 7. 7.11. (For case II. so that from (7. or a/3 > 1. a < 0 and /3 < 0.146 ANTIFERROMAGNETISM AND FERRIMAGNETISM Fig. Ferrimagnetism appears in the region above and to the right of curve ACB. III.11. consider that the expression in parenthesis in (7. Case (II) appears in region ECF.

11. At T = 6f the Langevin function in (7. In cases (III) and (IV). 7.12). both A and B sublattices are saturated. so that we have where C is given by (7. The possibility of the occurrence of N-type behavior can be examined by investigating the sign of 7A — 7B near the Curie point. This occurs when /3 > — 1 in case (III). this occurs in all of region IV or the area FCA in Fig. At the compensation point. and the spontaneous magnetization decreases as in the case of ferromagnetism.FERRIMAGNETISM 147 Fig.and N-types in Fig. 7.12. 7. @c. 7. In case (II). The most characteristic temperature dependence is the N-type.36). .12. The R-type appears when the sublattice with the larger moment is thermally disturbed more easily. in which the sign of the spontaneous magnetization reverses at the temperature of the compensation point. one sublattice is unsaturated and is easily thermally disturbed. P. resulting in Q-type temperature dependence (see Fig. producing various complicated temperature dependences of the spontaneous magnetization shown as R-.22). The P-type appears when the sublattice with smaller moment is thermally disturbed more easily. Four types of temperature dependence of spontaneous magnetization in ferrimagnets.33) can be approximated by the first term in (5.

The boundary condition (7.148 ANTIFERROMAGNETISM AND FERRIMAGNETISM Fig. 7. or a = /3 = — 1. as seen from (7. all spins in a layered crystal are aligned parallel within each c-plane. and has tangent A//t.12. and is therefore always measured as positive. as shown in Fig. In the experimental determination of the temperature dependence.13. and heated through the compensation point. so that 7S < 0. 7. The magnetization always is aligned parallel to the field. 7. the sample will rotate through 180° as the spontaneous magnetization changes sign. Therefore in the region between the lines SD and SH. In other words.3 HELIMAGNETISM In a helimagnetic structure. however. 7. but the spin direction varies from plane to plane such that the tips of .56) we have or If the left side of (7.3). the various forms of Js vs T curves are illustrated by computer simulation10 for Ga-doped Yttrium-Iron-Garnet (YIG) (see Section 9. N-type temperature dependence results. 7.13. so that using (7. 7S < 0 at T = 0. not only in region (III) but also in region (II). 7S > 0.59) is positive. If.59) gives the line SD which goes through the point S. as shown by the solid N-type curve in Fig. the saturation magnetization is measured in a fairly strong magnetic field. while 7S > 0 near © f . Above the line SH. an N-type ferrimagnet is suspended freely by a thin thread in a weak magnetic field. Demonstration showing a reversal of spontaneous magnetization of a ferrimagnet with a change in temperature.51).14. ft > — 1. In Fig.

45cm-1.36cm-1 were assumed.14.10 the spin vectors of the spins along any line parallel to the c-axis describe a spiral or helix (see Fig. (d) Y3Ga2Fe3O12 (N-type). •^AB = 25. 7^ = 8.15). (c) Y3GaL1Fe39012 (P-type). 7BB = 11. Computer simulation of temperature dependence of spontaneous and sublattice magnetizations in Ga-doped YIG: (a) Y3Fe5O12 (R-type). The resultant . This spin structure is also called a screw structure. 7.HELIMAGNETISM 149 Fig. 7.86 cm-1. (b) Y 3 Ga 5 Fe 45 Oi 2 (Q-type).

Screw spin structure in helimagnet. Then the x-.and z-components of the spin 5 are give by The rotation of the spins is expressed by where /?. helimagnetism can be considered a kind of antiferromagnetism. so that there is no spontaneous magnetization. magnetic moment of such a spin structure is zero over a sufficiently large volume of sample. is the vector drawn from the origin to a particular spin in the ith x-y plane. 7.150 ANTIFERROMAGNETISM AND FERRIMAGNETISM Fig.11 and in MnAu2 by Villan12 and later by Kaplan.13 Let us suppose that all the spins are aligned parallel to one another in an x-y plane.15. In this sense. A screw spin structure was first found in MnO by Yoshimori. and that the spins in the ith x-y plane make an angle </>. with the x-axis. and Q is a vector parallel to the z-axis with magnitude . y. Helimagnetism is found in many magnetic materials.

7. The pitch of a stable helical spin arrangement is given by minimizing (7. n (which is not necessarily an integer) expresses the pitch of the screw spin structure. it appears that ferromagnetism is parasitic on antiferromagnetism. which demonstrates that this material is antiferromagnetic. The mechanism in this case is the oscillatory variation of polarization of the spins of the conduction electrons brought about by the RKKY interaction (see Section 8.4 PARASITIC FERROMAGNETISM Parasitic ferromagnetism is a term used by Neel14 to describe a weak ferromagnetism associated with antiferromagnetism in a-Fe2O3. and a paramagnetic part. If n = 1. 7S. so that the angle (f)i is constant with each x-y plane.25) to the helimagnetic case. Note that the second term of (7. The susceptibility. The helical spin structure appears also in rare earth metals. it is antiferromagnetic.16). which saturates in a sufficiently large field. 7.3). . Observing this phenomenon.61) is constant for all spins in the same x-y plane. ^. the exchange interaction energy stored per unit volume is given by where N is the number of magnetic atoms and S is the spin. @. or °°.PARASITIC FERROMAGNETISM 151 where n is the number of x-y planes required for the spins to rotate by ITT or 360°. The origin of such an unusual spin structure can be deduced by assuming that the exchange interaction between nearest-neighbor planes as well as between spins in a single plane is ferromagnetic. of the latter part shows a maximum at some temperature. Applying the general expression for exchange interaction given by (6. the spin arrangement is ferromagnetic. the second nearest-neighbor interaction must be strong enough to satisfy (7. /s. xH> which is proportional to the field (see Fig.17). while if n = 2. In the general case. and C is the separation between neighboring x-y planes. while that between second nearest-neighbor planes is antiferromagnetic.63) with respect to Q. 7. © (see Fig. The magnetization curve of this material is composed of a ferromagnetic part. or so that we have Therefore the condition for the existence of a helical spin structure is In other words. The saturation magnetization. vanishes at the same temperature.66).

so that D is such a weak interaction that it causes only a small deviation (say a few degrees at most) of the spin angle from 180°. precipitated along its common crystallographic plane with the antiferromagnetic lattice of a-Fe2O3.18). The order of magnitude of Ag/g for 3d ions is 10~2-10~3. 7. the O-vector lies parallel to the c-axis. Table 7. The agreement between the two quantities proves the validity of this mechanism. Fig. Neel suggested that the ferromagnetism in this material is caused by a small amount of Fe3O4. . It is interesting that the material a-Fe2O3 exhibits a phenomenon which demonstrates this mechanism: on cooling through a temperature of 250 K. The Z)-vector lies in a direction which is determined by crystal symmetry. so that the spin-canting occurs in the c-plane. because any tilting of spins from the c-axis makes the vector 5j X S2 parallel to the c-plane. the antiferromagnetic spin axis rotates from the c-plane to the c-axis and the spontaneous magnetization simultaneously disappears. For instance. This idea was deduced phenomenologically by Dzyaloshinsky. Magnetization curve of a parasitic ferromagnet. This is the origin of parasitic ferromagnetism.16. so that WD vanishes.17 This proves the validity of the interaction given by (7. This spin arrangement is almost antiferromagnetic.16 The antisymmetric interaction which causes this spin-canting is expressed by where Sl and S2 are the canting spins and D is a vector coefficient. Magnetic susceptibility in a parasitic ferromagnet exhibits a maximum at the critical temperature at which saturation magnetization disappears. 7. and /super is the superexchange interaction between the two spins. which is called the Morin point.152 ANTIFERROMAGNETISM AND FERRIMAGNETISM Fig. in a-Fe2O3. where A5 is the tilt component of spin which contributes the parasitic ferromagnetism.67).2 lists several materials which exhibit parasitic ferromagnetism and compares the values of AS/5 and Ag/g. but the spin-canting also produces a small spontaneous magnetization in the c-plane. However. The order of magnitude of D is given by where Ag is the deviation of the g-factor from 2.17.15 and theoretically by Moriya. A non-zero value of D arises from an excited state and its perturbation mixed through the intra. If D< 0. 7.and inter-atomic l-s interaction between the two spins. the actual reason was found to be the spontaneous canting of + and — antiferromagnetic spins. the angle between S1 and S2 is not 0 or 180° (see Fig.

20 For further details of this topic. The torque curve in this case contains a component with a period of 360°. . (After Moriya18) Material a-Fe2O3 MnCo3 CoCO3 CrF3 FeF3 * Livinson. 7.20). AS/S and Ag/g. for which we expect that D = 0 from the crystal symmetry. the spin system is frozen with no ordered structure. The distinguishing experimental feature of mictomagnetism is that the magnetization drops abruptly when the material is cooled in the absence of magnetic field.4 X H T 2-6XKT3 2 .19 and 7.5 MICTOMAGNETISM AND SPIN GLASSES 'Mictomagnetism' is a term coined by Beck (Beck21'22. showing the presence of unidirectional magnetic anisotropy (see Section 13.19 and 7. A similar phenomenon was observed for Fe-Al.6 XHT 2 1XHT2 2X1(T 3 * 3 Ag/g ~1X10~3 ~lXl(T3 — -1XHT2 ~1X1(T 3 Parasitic ferromagnetism appears also in NiF2. A better term for parasitic ferromagnetism would be spin-canted magnetism.21. Table 7. Diagram showing the relationship between the coefficient of antisymmetric interaction.4). Beck and Chakrabarti24) to describe a spin system in which various exchange interactions are mixed. the decrease in magnetization disappears (see Figs 7. The prefix micto is a Greek prefix signifying 'mixing'. 7. which suggests the mechanism. This phenomenon is interpreted to mean that the ferromagnetic spins are interacting with the antiferromagnetic spins. Moriya suggested that a strong crystalline field may be responsible for causing the spin canting. If the material is cooled in a magnetic field.2. Typical helimagnetic materials and comparison between tilt of spin. Fe-Al and Ni-Mn alloys.27"29 The reason for this decrease is the reversal of magnetization clusters caused by antiferromagnetic interactions. instead there is a shift of the hysteresis loop along the //-axis30 as shown in Fig. 7. and spins Sj and S2. D. Waber and Beck23.20 Sometimes parasitic ferromagnetism is called weak ferromagnetism. which are fixed with respect to the lattice. as shown in Figs 7. When the temperature is lowered. but this invites confusion with the weak ferromagnetism of metals. see the review article.19 AS/5 1.18.20 for Cu-Mn24 and Ni-Mn25'26 alloys.MICTOMAGNETISM AND SPIN GLASSES 153 Fig. Such magnetism is observed in Cu-Mn.

Temperature dependence of magnetization measured for 24. Sc and SD in the A-. (q) quenched.19.7% Mn-Cu alloys: (a) heat-treated at 100°C.and D-sublattices. Suppose a face-centered cubic lattice contains spins SA. (circles) cooled in a magnetic field. curve be: cooled without magnetic field.22. Temperature dependence of magnetization for 16. If Fig. 7. C.64 MA m"1 (8kOe): curve ac: cooled in a magnetic field. SB.26 . as shown in Fig. 7.20. B-. 7.154 ANTIFERROMAGNETISM AND FERRIMAGNETISM Fig.6 at% Mn-Ni alloys in a magnetic field of 0. (triangles) cooled in absence of magnetic field.23'24 It should be remarked here that the antiferromagnetic arrangement is not strongly fixed in a face-centered cubic lattice.

Left: measured along the axis parallel to the field during cooling. as will be shown below. y.y c ) and (a D .21.70)./3 D . 5C and SD all have magnitude S.8K.and z-components of (7. (a B .2. 0 A . and summing up by considering the relationship a? + fif + y. we have The total exchange energy is then given by . Hysteresis loops measured for disordered 26.MICTOMAGNETISM AND SPIN GLASSES 155 Fig. yB).y A ).30 the antiferromagnetic exchange interactions between all neighboring spins are the same in magnitude.69) are reduced to Squaring the left-hand side of each equation in (7.5 at% Mn-Ni alloys at 1. (a c . Solid curves: cooled in a magnetic field of 0.y D ). then any spin configuration satisfying keeps the total exchange energy constant.4MAm" 1 (5kOe) from 300K to 1.8K. Then the x-. Broken curves: similarly cooled without magnetic field.0 c . SB. and their direction cosines are given by (a A . 7./3 B . Let us assume that spins SA. Right: measured perpendicular to the field during cooling.

7. The relationship between four sublattice spin-vectors under the condition of equation (7. .24. (see (7.22. Illustration of spin vectors in four sublattices in face-centered cubic antiferromagnet. (c) spin axes are parallel to different (110} crystal axes. The condition (7. 7. where N is the number of unit cells in the system.69) is satisfied. Fig.156 ANTIFERROMAGNETISM AND FERRIMAGNETISM Fig.23: (a) and (b) spin axis is parallel to [001]. 7.69). Special cases in Fig. Thus as long as condition (7. 7. Figure 7.71)). Fig.69) is shown as a vector diagram in Fig. 7. (d) spin axes are parallel to different (111) axes. (e) general case. the exchange energy remains constant.24 shows special cases of Fig.23.23.

Therefore. B-.] Figure 7. thus resulting in mictomagnetism.32 7. Figure 7. C. In the spin glass region below 12at% Fe. Solid curves: extrapolated to zero magnetic field.23: (a) and (b) show all spins aligned parallel to the z-axis or [001]. the value and sign of the exchange integral Jtj or the dipole interaction ltj (see Section 12. A spin glass state occurs in dilute alloys in which spins of magnetic atoms are frozen randomly by the oscillatory RKKY exchange interaction (see (8. and the local spin configuration is easily disturbed. Tc. the random spin arrangement is considered to be fixed. A similar phenomenon is also observed in mictomagnetism.38)).MICTOMAGNETISM AND SPIN GLASSES 157 Fig. Tc.3) depends on the chemical identity of the atomic pairs.25 shows an example observed for dilute Fe-Au alloys. a sharp maximum is observed in the temperature dependence of susceptibility measured in a weak field.24(e) shows the case in which none of the spins are parallel to the principal crystal axes.26 shows an example for Fe-Au alloys. Experimentally.32 Below the temperature of this maximum. Thus the antiferromagnetic spin arrangement in a face-centered cubic crystal has freedom to change its spin orientation without changing the exchange energy. Temperature dependence of magnetization measured for 1 and 2 at% Fe-Au alloys in a weak magnetic field. Figure 7. The difference between a spin glass and mictomagnetism is clarified if the critical temperature. [These spin configurations were already suggested by Kouvel and Kasper31 for Fe-Mn alloys.25.and D-sites are different chemical species. while (c) and (d) show all spins parallel to one of the (110) or <111>. if the magnetic atoms in the A-. the . 7. is plotted as a function of the magnetic impurity content.

for Fe-Au dilute alloys. ^-0.1 Consider an antiferromagnetic material which has a susceptibility. where mictomagnetism exists. Tc. 7. at its Neel point 0N. 7.2 Consider a ferrimagnetic material which has the same kind of magnetic ions in A and B sites. it is not certain whether or not the spin glass state is actually realized in real dilute magnetic alloys. Assuming that the exchange interactions within the A and B sites are negligibly small compared to the exchange interaction between A and B sites. @N/2.32 critical temperature.158 ANTIFERROMAGNETISM AND FERRIMAGNETISM Fig. and20 N . so that the interactions are strong. However. But Tc increases rapidly with Fe content above 12 at%. Assuming that the exchange interactions within A and B sites are negligibly small compared to those between A and B sites. PROBLEMS 7. For more details the reference book33 should be consulted. Compositional dependence of the transition temperature. The reason is that ferromagnetic clusters are coupled antiferromagnetically.26. find the nature of the spin arrangement at OK and the ratio of the ferrimagnetic Curie point to the asymptotic Curie point. find the values of the susceptibility which would be measured when a magnetic field is applied perpendicular to the spin axis at T=0. remains low because individual spins are randomly fixed. and the possibility of having a compensation point. . Tc. in the ratio 3:2.

Anderson. 14 (1959). Tech. Physica. 114 (1959). 888. Rev. Letters. Satoh and C. 22. 13. A. P. 1972). J. Nagamiya. 9. S. J. P. New York. Kasper. Soc. G. 8. Phys. Sci. 1427. A. Becker. de Physiq. Phys. Solid State Phys. /. 29 (1958). de Phys. Arrott. Neel: Ann. N. Phys. F. 4 (1960). 9 (1941). 1975). Phys. Livinson. /. Rev. A. Hasegawa (eds). 11 (1959). C. Villain. K. 16. Phys. H.3 In a helimagnetic material. Japan. Adv. Appl. I. Chem. /. 193. Japan. 241. J. J. Kouvel and J. 29 (1958). Arrott and H. Chem. J. 28. 1977).. 4 (1949). 15. S. Less Common Metals. 4 (1958). Chikazumi. 114 (1959). Kubo. 12 (1951). I. and J. P. 303. J. T. Phys. 24. /. H. 2015. Magnetism I (Academic Press. P.. (Kotai Butsuri. S. Rev. W. Oguro. de Graaf). (eds): Handbook on magnetic substances (Asakura Publishing Co. Phys. L. B6 (1972). 32. Arrott. Dzyaloshinsky. A. 1.. Met. . A. 1963. J. P. Appl. Rev. 262. 17. 228. A. Moriya. 28 (1972). 30 (1959). 117 (1960). /. J. T. ed. Mydosh.. T. E. 33. Tokyo). Anderson. 19. Phys. 249. A. 25. Phys. L. 1. by Rado & Suhl). Kouvel. AIME. 19. V. 3. 76 (1949). Phys. Miura. AIP Conf. Solids. New York. Solids. Smart. T. /. p. Morin. Phys. Baltzer.. Rev. Sato and A. 1420. Phys. 79 (1950). in Japanese.. Magnetism in alloys (TMS. W. Physiq. Trans. T.. 11. 1 (1934).. 635. Kaplan. Yosida. H. Phys. M. 2. Phys. Phys. Sato.REFERENCES 159 7. 273. 34 (1976). T. R. Neel. Graham. Beck. /. 6. Chem. Yoshimori. Center.. Solids. 807. Amorphous magnetism (ed. Chikazumi et al. Rev. A. A. 182. Moriya... Rev. 518. 1331. A. 26. Chem. Rev. S. 7. 1256. Hooper and A. Shull and J. Tokyo. Phys. Chem. Moriya. S. D.. 20. Rev. 5. 1534. D. Proc. H. 14. S. Graham. Ann. Solids. 819. /. 23. 539. T. 4. 312S. Beck. 79 (1950).. Amorphous magnetism II (Plenum Press. 350. M. Patton. 45 (1978). 1973)... 78 (1950). Jr. J. Plenum Press. Phys. L. 515. P. 29 (1968). Appl. Cannella and J.. measured in units of the interplanar spacing? REFERENCES C. /. 10. 27. Chakrabarti. Jr. Rev.. 29. 4420. /. 18. Kramers. 24 (1963). 31. K. 21. 2 (1971). p. Phys. 116 (1959). 86. S. 137.. Phys. 705.. Kouvel and C. [12] 3 (1948). 4 (1955). /.. Van Vleck. O. 85. Soc. and R. Rad. Levy and R. Phys. H. 12. Phys. 361.. 2 (1967). Waber and P. Beck and D. 30. Beck. in which J2 is negative and has magnitude ^3/6Jlt what will be the pitch of the screw structure. Sato and A.

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Part IV MAGNETIC BEHAVIOR AND STRUCTURE OF MATERIALS Since magnetism is closely related to the electronic structure of materials. and the structure and magnetic behavior of amorphous materials in Chapter 11. the magnetic behavior of metals. . crystal structures of oxides and their magnetic behavior in Chapter 9. we discuss these phenomena: the band structure of metals and their magnetic behavior is treated in Chapter 8. In this Part. oxides and compounds is not the same. bonding of various compounds and their magnetic behavior in Chapter 10.

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However this model is inadequate to interpret the electronic heat capacity. a particle moving with momentum p is replaced by a plane wave with wavelength where h is Planck's constant.3. so that their magnetic moments are well localized at individual atoms.2). Co. Metals are characterized by free electrons moving or itinerating in the crystal lattice. rather than localized at individual atoms. In other words. Tb. ferromagnetism occurs only in three of the 3d transition metals (Fe. The most naive model of free electrons is to regard them as randomly moving particles. On the other hand. The wave function is expressed as where r is the positional vector. and in heavy rare-earth metals such as Gd. they form a band structure. and Pauli paramagnetism. etc. and Ni). like the molecules of an ideal gas. We shall discuss such cases in Sections 8.8 MAGNETISM OF METALS AND ALLOYS 8. which is commonly observed in metals at low temperatures.1 BAND STRUCTURE OF METALS AND THEIR MAGNETIC BEHAVIOR Of all the metallic elements. Using this model.2 and 8. In wave mechanics. the carriers of magnetism in rare-earth metals are 4/ electrons. and Wiedemann-Franz law (thermal conductivity proportional to electrical conductivity). Dy. The carriers of the magnetism. and are considered to be moving among the atoms (or itinerant). The 3d transition metals have high Curie points and exhibit ferromagnetism with large spontaneous magnetizations at room temperature. are located relatively far from the atomic core. we can explain Ohm's law (electric current proportional to the electric field). which is observed only for metals and alloys (see Section 5. the 3d electrons. so that alloys containing these metals are used as magnetic materials in a wide range of practical applications. and k is the wave number vector given by . which are located deep inside the atoms (see Section 3. These phenomena were explained only after the quantum theory of metals was developed.2).

Each stationary state can be occupied by two electrons with + and — spins.164 MAGNETISM OF METALS AND ALLOYS E Fig. ±1. where nx.nz). (8. to twice the number of states with energy less than E{. The energy of the electron which occupies the highest energy state is called the Fermi level and is denoted by Ef. when N electrons exist in a unit volume. The Fermi level can be calculated by equating the total number of electrons.6). Using (8. ML3. +2. The dependence of E on k is graphically shown in Fig. Since the states can be identified with lattice sites in n-space with positive values of n.. ny. and nz are integers such as 0. The kinetic energy of this particle is given by which is modified. pairs of electrons occupy the states successively from n = 0 (the lowest energy state) up to some non-zero maximum n with finite energy. Now suppose an electron is moving in a cubic box with edge length L. which cannot be expected in a classical picture.. owing to the Pauli exclusion principle. Energy (£) vs wave vector (k) curve for free electrons. 8. using (8. 8. we can write . Thus the ^-vectors of free electrons are quantized.1. Thus in metals the electrons with non-zero kinetic energy are moving even at absolute zero.3). Therefore.ny.5) becomes Thus the kinetic energy of an electron increases with an increase of n.. .1. to where h is equal to h/2ir.1) and (8. The condition for which the wave function forms a stationary wave is given by where n is a vector with components (nx.

3. The Bragg reflection occurs when .11) with respect to E.2): the water level corresponds to the Fermi level.2. Corresponding to this quantity. g(E). The number of states between energy E and E + dE is given by g(E)dE.10) to be 20 000-50 000 K.8).BAND STRUCTURE OF METALS 165 Fig. where nt is the value corresponding to the Fermi level. positively charged metallic atoms forming a crystal lattice. the electron wave tends to be reflected in a Bragg reflection. however. and the total volume of water corresponds to the total number of electrons. 8. the Fermi level is given by Using the relationship (8. If. much larger than the thermal energy kT at room temperature. we have This relationship g(E) is graphically shown in Fig. Referring to (8. Using nf and referring to (8. Consider a one-dimensional crystal lattice with lattice constant a along the %-axis. In order to calculate the total volume of water. (8. we need to know the cross-sectional area of the glass at each level. Slow electrons with long wave length or small k can move without being disturbed by such a crystal lattice. 8. in addition to the free electrons. we define the density of states. Differentiating (8. the total number of electrons is given by This relationship holds for any value of E. Similarity of water in a glass to free electrons in metals. In real metals we have. The situation is analogous to a glass of water (see Fig. 8.7).9) becomes The value of E{ is estimated from (8.10). the wavelength becomes nearly equal to the lattice constant a.

3.6. g(£). Let us consider how such an energy difference modifies the E-k curve in Fig. 8. while the abscissa Fig.3 to Fig. as is usual in resonance phenomena. the effect of the Coulomb interaction with the lattice lowers the energy and so increases the probability of free electrons existing at metal ions. If a wave e'*x propagates in the +. then a wave e~lk* is produced by Bragg reflection. As a result of the appearance of the energy gap. the first wave has its maximum amplitude between the lattice points.4. Next we consider how the situation changes when a magnetic field is applied.4). Two modes of standing waves of wave functions in a crystal lattice. Figure 8. Let this energy difference be AS. the electron wave resonates with the lattice and the energy E increases discontinuously by A £ (Fig.7 illustrates a band structure in which the + spin and — spin bands are shown separately.4. where we find two energy regions are separated by AE. so that the standing wave changes its mode from cos he to sin kx (see (8.14) and Fig. 8. 8. the ordinate represents energy.1. 8. 8. Density of states curve for free electrons. 8.166 MAGNETISM OF METALS AND ALLOYS Fig. As k approaches TT/CI. 8. At k = ir/a. while the second wave has its maximum amplitude at the lattice points. the stationary waves are formed. The modification is negligible for small k. The reason for this discontinuity is that the reflected wave changes its phase angle by 180°. because there is no influence of the Bragg reflection. the density of states curve. As shown in Fig.5). Since t/f 2 signifies the probability of the existence of electrons.t-direction. In this case. the former wave has a higher Coulomb energy than the latter. is changed from Fig. As a result. . 8. We call such a division into limited energy regions the band structure.

8. the + spin band is lowered by an amount Fig. When a magnetic field H is applied parallel to the + spin (here we use the word spin for spin magnetic moment).6.5. The E vs k curve for electrons in a metallic lattice. . 8. Density of states curve for electrons in a metallic lattice.7. Mechanism for the appearance of magnetization by hand polarization.BAND STRUCTURE OF METALS 167 Fig. represents the density of states of the + spin and — spin bands. Fig. 8.

the Fermi level corresponds to a temperature of order ten-thousand K. Fermi-Dime distribution function. so Fig. it produces a special low-temperature heat capacity which is characteristic of metals. as seen in Fig. When the temperature is increased from 0 K. 8. .18) is approximately independent of temperature.8. An.8 for T = 0 (solid line) and for T > 0 (broken curve). bringing their Fermi levels to a common value.8. 8. As mentioned previously. so the susceptibility given by (8. however. so that The resulting increase in magnetization is given by Therefore the susceptibility is given by As will be mentioned later.1 When the temperature is raised from OK. The number of electrons. Such a modification of the electron distribution will be reflected in various physical properties. This is the origin of the Pauli paramagnetism.168 MAGNETISM OF METALS AND ALLOYS Therefore the electrons at the top of the .spin band will be transferred to the + spin band by reversing their spins. the electrons are excited to levels higher than the Fermi level. For instance. 8. so the thermal excitation caused by a temperature of several hundred K will have a very slight effect on the electron distribution. The probability that an electron will occupy a state with energy E which is higher than the Fermi level is given by This /(£) is called the Fermi-Dime distribution function. the electrons in the vicinity of the Fermi level are excited across the Fermi level. and is shown graphically Fig. which will be transferred is given by the area between the old and new Fermi levels. the Fermi level is not strongly temperature-dependent.

we can regard g(E) as constant. so that Putting (E — E{)/kT = x. dE = kTdx.20) is non-zero only in the vicinity of Ef. Let us next calculate this heat capacity.9. so that where x0 = Ef/kT. and dT/T= -dx/x.20) with respect to T. 8.2 . The energy of free electrons at a non-zero temperature is given by The heat capacity per unit volume can be obtained by differentiating (8.BAND STRUCTURE OF METALS 169 that the electronic heat capacity should be a good measure of the density of states at the Fermi level.21). we have the relationships E = E{ + kTx. from (8. Comparison between magnetic susceptibility and the coefficient of low temperature specific heat for Rh-Pd and Pd-Ag alloys. Then. we have Fig. Since the derived function df(E. T)/dTtt in the integrand of (8.

The proportionality factor j in (8. Subtracting (8.27). is a good measure of the density of states at the Fermi level.2 We see a similarity between the two quantities. and is called the electronic heat capacity or the electronic specific heat.23). the Fermi level Ef at T= 0 is defined by At non-zero temperature.22)).18) is equally a measure of the density of states at the Fermi level. At low temperatures it exceeds the heat capacity due to lattice vibration because the latter is zero at OK and increases only slowly with T (proportional to T3).10). g(E). Figure 8. the Fermi level will shift slightly.9 shows a comparison between y and x observed for Rh-Pd and Pd-Ag alloys. has non-zero gradient at Et. As a result of modification of the electron distribution near the Fermi level.25) from (8. g(Ef\ The susceptibility X given by (8. provided the density of states curve.170 MAGNETISM OF METALS AND ALLOYS This heat capacity increases linearly with increasing T. When the density of states is given by g(£). we have . The Fermi level of completely free electrons at T= 0 is given by (8. this condition becomes which is modified by partial integration to (See (8.

30). The increase of the band energy by the transfer of An electrons is given by so that. In general.33). referring to (8.32) and (8. so that the splitting of the bands is much larger than in the case of paramagnetic metals. For this purpose. In the case of ferromagnetic metals. and (8. so that Such a small shift of the Fermi level will cause only a weak temperature dependence of the Pauli paramagnetic susceptibility. the first term in (8. However.28) can be approximated as (Ef(T) — £f(0))g(Ef). we must know the functional form of g(E). the exchange field Hm is stronger than ordinary external fields by a factor of 102 to 103. (8. whether or not ferromagnetism appears can be determined only by g(£f).spin bands is The magnetization induced by this polarization of bands is Since the molecular field Hm is the spontaneous magnetization can be found from a solution which satisfies (8.32).BAND STRUCTURE OF METALS 171 Since g(E) is almost constant between Ef(0) and E{(T). the energy of the system is expressed by Therefore the criterion for the appearance or non-appearance of ferromagnetism is given by .31). the number of electrons in the + spin and .

7 we can treat the band structure by taking into consideration the electronic states of individual atoms. According to this calculation. the energy increases as / appears and ferromagnetism is unstable.11.10. while if the < sign is satisfied.8 Fig.8'9 In A-B alloys.3'4 who treated ferromagnetism in metals in this way. as calculated by the coherent potential approximation. Density of states curves for + and — spins for various Fe-Ni alloys. Such a treatment is called the rigid band model. first the electronic structure of A atoms is calculated by .8 If the > sign is satisfied. Density of states curves for Ni (solid curve) and for Fe (broken curves) as calculated for Ni-Fe alloys by the coherent potential approximation. the energy (8.172 MAGNETISM OF METALS AND ALLOYS Fig. On the other hand. 8. This is the criterion for the appearance of ferromagnetism proposed by Stoner. by means of the coherent potential approximation.5'6 In this case. 8. we can get information on the electronic states and magnetic moments in the vicinity of different kinds of atoms in ferromagnetic alloys. he assumed that the density of states curve remains unchanged even when ferromagnetism appears.34) is lowered as the magnetization / is increased.

2 MAGNETISM OF 3d TRANSITION METALS AND ALLOYS Only the three transition elements Fe.1). with each atom keeping its individual moment.MAGNETISM OF 3d TRANSITION METALS AND ALLOYS 173 assuming an average electronic structure in the neighborhood of an A atom. and Ni are atomic numbers 26. It is possible to interpret this behavior to mean that Co atoms with 1. and 2 vacancies in the 3d shell (see Table 3. and have respectively 4.7. and 28. which means that the 3d electron shell is just filled.6) for Ni.10 The non-integral Bohr magneton numbers of 2. In Chapter 2 we discussed the electronic structure of the elements and learned that the 3d elements (Z = 21-30) have an incomplete 3d electron shell which produces magnetic moments in accordance with Hund's rule.spin bands. This is a famous graph. Looking at this graph. we have a consistent (coherent) solution. 0. respectively (in addition to the orbital magnetic moment).7. Figure 8.6 and 18 (corresponding to the electrons in the filled shells of argon) from 28. Actually. 1. Figure 8. 0) for Cu. Comparison with experiment will be made in the next section. Figure 8. 0).2. then we can subtract 0. However. whereas there are big differences in the .10 shows the density of states curves calculated by this method for Fe^Ni^ alloys. at OK. and also for different alloys constituents. these elements exhibit saturation magnetic moments of only 2.6) for Ni and (29. Most magnetic alloys made for engineering uses contains one or more of these elements. and 2 Bohr magnetons. we expect spin magnetic moments of 4.6 Bohr magnetons. This situation . 0. and Ni are smoothly connected by two straight lines. Co. known as the SlaterPauling curve.6MB are simply mixed in the alloys. According to Hund's rule. 1. If we assume that the number of 4s electrons is 0.6 to obtain 10 electrons. Co. and 0.2. and 0. The vertical lines signify the Fermi levels. Co. Then the average electronic structure is calculated by taking the weighted average of the A and B atom structures. in the case of Ni-Cu alloys.6. 3.7MB and Ni atoms with 0. the experimental points lie not on the straight line connecting the points (28.11 shows the band structure for Ni and Fe separately. Equating this with the structures assumed in the calculation of the electronic structure of the individual atoms. 1. The electronic structure of B atoms is calculated in the same way. This method is somewhat similar to the Bethe approximation in the statistical treatment of ferromagnetism (see Chapter 6). The situation is well described by plotting the saturation magnetic moment at 0 K as a function of number of electrons per atom. but on the straight line connecting (28. we see that the + spin bands of Ni and Fe are not very different. 27. which form band structures together with the 45 electrons. 3.6 for Fe. 0.6 per atom.12 shows such curves plotted for various 3d transition-metal alloys. respectively. The experimental points for Ni-Co alloys fall on the straight line connecting the points (27.7) for Co and (28.8 The important feature of this result is that the shapes of the density of states curves are different for + and spins.6) and (28. The three ferromagnetic elements Fe. however. The carrier of magnetism in this case is the 3d electrons. 8. and Ni exhibit ferromagnetism at room temperature.

Since the density of states at the Fermi level in the + spin band is fairly high.)12 cannot be interpreted in terms of the localized model in which we assume that the 3d electrons contributing to the magnetic moment are well localized on individual atoms. where the + spin band and .174 MAGNETISM OF METALS AND ALLOYS Fig. The situation can be explained by assuming that the 3d electrons are itinerating in the 3d band which is common to all the atoms. In this situation. as seen in Fig. Ni-Cu. In this case the density of states versus energy curve exhibits double peaks and the Fermi level in the — spin band is located in the valley between the two peaks.12. 8.6.14 shows the density of states curve calculated by Wakoh and Yamashita14 for body-centered cubic iron. any decrease in the number of electrons above 1. Ni-Zn and Ni-rich Fe-Ni alloys. The electron vacancies appear only in the — spin band because the density of states has a sharp peak at the top of the 3d band as shown by Fig. As the electron number decreases from 28. the total space in the peak at the top of 3d band is about 1.spin band. Therefore the magnetic moment in Bohr magnetons. any . increases with a decreasing number of electrons at a rate of one Bohr magneton per one electron. Since. NiCo-Cr11 and Fe-Ni(2). 8. This means that the magnetic moment versus number of electrons is given by a straight line with a slope of -45° in the Slater-Pauling curve.spin band are both filled. (After Bozorth10. nature prefers a change to a crystal structure with a different density of states curve to an unnaturally large polarization of bands. electron vacancies appear only in the — spin band. which is given by the difference in the number of electrons in the + spin and the — spin band. Therefore the increase in total kinetic energy of the electrons (band energy) is relatively small. except for NiCo-V. because the electron vacancies can be accommodated in a narrow space at the top of the .13. Slater-Pauling curve. Figure 8.13 The shift of the .5 electrons per atom. 8. This is actually the case for Co-Ni.spin band relative to the + spin band is very small. however.5 must produce vacancies also in the + spin band.12.

resulting in a decrease in magnetic moment. 8.7. irrespective of the chemical Fig. This is the reason why the Slater-Pauling curve has a slope of +45° at the point representing Fe. It is very interesting that the crystal structure changes from face-centered cubic to body-centered cubic at an electron concentration of 26. (After Wakoh and Yamashita14.) . 8. Density of states curve of Ni.MAGNETISM OF 3d TRANSITION METALS AND ALLOYS 175 Fig.) further decrease in the electron number occurs mainly in the + spin band.13.14. Density of states curve of Fe. (After Connoly13.

the intensity of neutron small-angle magnetic scattering should be proportional to (5A — 5B)2. In the case of Fe-Ni. If the spins SA and SB associated with A and B atoms are different in magnitude. Composition dependence of magnetic moments localized on Fe and Ni atoms in Ni-Fe alloys.12 are more recent than those labelled Fe-Ni(l)]. At the peak of this curve.8MB. From this information. This problem is further discussed later.16 The solid curves represent the CPA calculation for magnetic moments of Fe and Ni atoms and their average. 8.176 MAGNETISM OF METALS AND ALLOYS species in the alloy (see Fig. This behavior can be explained neither by a localized electron model nor by a rigid band model.15 shows the magnetic moments of Fe and Ni atoms determined in this way. and its unusual thermal behavior is known as the Invar effect. and also that these values change gradually with alloy composition. Fig. as a function of composition in Ni-Fe alloys. located at 35 at% Ni in Fe. The magnetic moments localized on atoms of different chemical species can be determined by means of small-angle scattering of neutrons from disordered alloys. a very low thermal expansion coefficient is measured at room temperature.6MB. On the other hand. It was shown by Hasegawa and Kanamori8 that this behavior can be explained using the coherent potential approximation (CPA) which was discussed in Section 8. This alloy is called Invar. the saturation magnetization should be proportional to CA5A + CBSB. Experimental points are obtained by means of neutron small-angle scattering.12).8 . while that of Ni is about 0. where CA and CB are the concentration of A and B atoms.1. Figure 8. we can solve for SA and 5B for each alloy composition. The thermal expansion of Invar is apparently related to the instability of its ferromagnetism.15 It is found that the magnetic moment of Fe is about 2.15. 8. the saturation moment drops sharply as the electron concentration is decreased and approaches the phase boundary [the points labelled Fe-Ni(2) in Fig. 8.

2. Fe-Ni. Ga. They showed that the magnetic moments of these impurity atoms are coupled antiferromagnetically with the ferromagnetic matrix moment. Ge. The local magnetic disturbance caused by impurity atoms was investigated experimentally by Low and Collins18'20 by means of magnetic scattering of cold (longwavelength) neutrons (see Problem 4. the magnetic form factor for the scattering of neutrons depends strongly on the size of the 3d shell (see Figs 4. AM.12).spin band (broken curve in Fig. because the addition of these impurities increases the average magnetic moment to some extent.19 A similar situation occurs in Ni-base alloys with non-transition elements such as Al. Figure 8.16 and later explained more quantitatively by Akai et al. The addition of these impurities reduces the average magnetic moment as if the valence electrons of the impurity atoms filled up the vacancies in the 3d band. Cr. Manganese impurities are an exception. 8. The advantage of using long-wavelength neutrons is that we can determine the shape of the form-factor curve over a relatively large range of small scattering angles without interference from elastic scattering (small-angle diffuse scattering). 8. are all inconsistent with the Slater-Pauling curve. Si. between impurity and matrix atoms as a function of the difference in electron number. Therefore by measuring the form factor we can analyze not only the size of magnetic atoms but also the extent of the magnetic disturbance around the atoms. There are many branches from the right-hand straight line of the Slater-Pauling curve (see Fig. The points for Fe-base alloys in the third quadrant. (Note that there is a vacancy accommodating two electron vacancies at the top of the . which results in a sharp decrease in the average magnetic moment.7 and 4. such as Fe-Co. a neutron scattering experiment revealed that the reduction of magnetic moment occurs not at the impurity atom but at Ni atoms surrounding the impurity atom. 8. so that the difference in nuclear charge 2e between Ni and Fe results in a difference in magnetic moment of 2MB. We see that not only the individual moments but also the behavior of the average magnetic moment are well reproduced by the CPA calculation. This behavior was first treated theoretically by Friedel. V.11)).15 represent the CPA calculation for the individual atoms and also the average magnetic moment. or Ti. however.21 The reason is . As explained in Section 4. or Sn.12). The distribution of electrons in the 3d band is not the same in different atom species because the 3d electrons in the — spin band tend to shield the excess nuclear charge. Mn. It was found by neutron scattering experiments that this increase in average magnetic moment in Fe-base alloys occurs not at the impurity atoms but in the Fe atoms surrounding the impurities. i.8). Fe-Pd.MAGNETISM OF 3d TRANSITION METALS AND ALLOYS 177 The solid curves in Fig. Sb.3).16 summarizes the difference in the magnetic moment. since they sometimes couple ferromagnetically. A«. between them. The gradual change in magnetic moment with alloy composition is due to the fact that the density of states changes gradually as a function of the number of electrons. The experimental points scattered along the straight line in the first and fourth quadrants are all consistent with the right-hand and left-hand straight lines of the main Slater-Pauling curve (Fig.e. Each branch describes a sharp decrease in saturation magnetic moment produced by the addition of impurity atoms with fewer positive nuclear charges.11 using a CPA calculation. and Fe-Pt (underline means the main alloy constituent). 8. Actually.

The Invar characteristic (the thermal expansion coefficient becomes negligibly small at room temperature) is one manifestation of a correlation between magnetism and crystal structure. the saturation moment of Fe-Ni alloys disappears at the phase boundary between bcc and fee (see Fig. the cycle is doubled compared with the case of 4d and 5d metals. hep and finally face-centered cubic (fee) structures. the temperature dependence of the thermal expansion coefficient of Invar can be well explained by assuming the thermal . as the Fermi level moves higher. On the other hand. 8. in 3d transition metals. Phenomenologically.19 that the shielding of the nuclear charges of the impurity atoms must be done by the 3d band of the matrix atoms. which has a high density of states. Difference in magnetic moment of impurity atoms and of matrix metals (underlined) as determined by neutron small-angle scattering as a function of difference in number of electrons. the crystal structure changes in the order hexagonal closed packed (hep). this sequence is modified and the crystal structure changes in the order hcp-bcc-aMn-bcc-hcp-fcc. One example of this correlation is Invar behavior. the crystal structure of transition metals depends on the Fermi level in the d-band. Generally speaking. which appears at a composition near a change in crystal structure. because the Fermi level of the non-transition impurity is located in the s-band with a very low density of states.12). Thus the crystal structure and magnetism of 3d transition metals are mutually correlated. In 4d and 5d transition metals. resulting in a repetition of the sequence.178 MAGNETISM OF METALS AND ALLOYS Fig. The reason is that when ferromagnetism appears. the Fermi level splits into different positions in the + spin and — spin bands. 8. body-centered cubic (bcc).16. As mentioned earlier.

**MAGNETISM OF 3d TRANSITION METALS AND ALLOYS
**

22 23

179

excitation of the low spin state of the Fe atom. ' . More physical explanations based on the band theory have been developed by many theoreticians.24"26'17 A complicated phase transition in pure Fe is also caused by a correlation between magnetism and crystal structure. With increasing temperature, pure Fe transforms from bcc to fee at 910°C, and then once again from fee to bcc at 1390°C. Zener27 pointed out that this phenomenon may be explained by assuming an additional 'magnetic' free energy. Since, however, 910°C is above the Curie point, this has nothing to do with magnetic ordering. This phenomenon was also explained theoretically in terms of a disordered local moment theory.28 Manganese metal (Mn) is located next to Fe in the periodic table, and undergoes complicated crystal and magnetic phase transitions. Below 705°C, it has the a-Mn structure with 29 atoms in the unit cell. Below 95 K, Mn develops an antiferromagnetic structure with four different atomic moments, 1.90, 1.78, 0.60, and 0.25MB, each of which takes a different direction.29 With increasing temperature, it transforms at 705°C to the /3-phase with no magnetic ordering, and then to the fee y-phase at 1100°C. The y-phase is paramagnetic in this temperature range. However, this phase can be retained to lower temperatures by alloying with Cu, and is found to exhibit antiferromagnetism with a magnetic moment of 2.25MB per atom below the Neel point of 207°C.30 Chromium (Cr) is located next to Mn in the periodic table. Its crystal structure is bcc at all temperatures, and its magnetism is characterized by a spin density wave, in which the magnitude of the spin forms a spatial wave. This is a kind of antiferromagnetism, with Neel point 312K. The maximum amplitude of the wave is 0.50MB at OK and the spatial propagation of the wave is parallel to {100} with the spin axis perpendicular to the propagation above 122 K and parallel below this temperature. The spin density wave was treated theoretically by Overhauser31 and later by Lomer32 who took an interaction between the Fermi surface of 3d electrons and holes into consideration. Kanamori and Teraoka33 proposed an entirely different interpretation of this phenomenon. In Chapter 6, we learned that the Curie-Weiss law holds in many ferromagnetic metals and alloys. It seems that this fact supports the localized electron model, because this law was deduced from the Weiss theory which assumes a fixed magnetic moment per atom. It is known, however, that there are many ferromagnetic metals and alloys for which the effective magnetic moment, Meff, and saturation moment, Ms, are not consistently described by the same J (see (5.30) and (5.32)). Figure 8.17 shows the variation of PC/PS as a function of Curie point for various magnetic materials, where Ps is gJ, deduced from Ms, and Pc is gJ, calculated by using / deduced from Meff.34'35 It is seen that for ferromagnetic metals with high Curie points, PC/PS is nearly unity, as expected from the Weiss theory, while for metals with low Curie points, this ratio becomes very large. Typical examples of the latter category are ZrZn2 with Ms = 0.12MB and 0f = 22K, and Sc3In with Ms = 0.057MB and 0f = 7.5 K. These are called weak ferromagnets. Even in these weak ferromagnets, the Curie-Weiss law holds. Such behavior has been explained by Moriya35 in terms of spin-fluctuation theory,

180

MAGNETISM OF METALS AND ALLOYS

Fig. 8.17. The ratio PC/PS (see text) of ferromagnetic metals and alloys as a function of their Curie points. (After Rhodes and Wohlfarth34)

which treats the band calculation of metal magnetism at elevated temperatures. The thermally disturbed spin system can be described as an assembly of spin density waves with different wave vectors q. The feature of this theory is to take proper account of the interaction between spin density waves with different modes. In weak ferromagnetism, the spin density waves with large q have much higher energies, so that they Table 8.1. Classification of magnetic materials by the spin fluctuation concept (after Moriya36).

Wave vector q Magnetic moment Amplitude small Localized Non-localized (a) (b) MnSi Cr y-Mn Ni ... ... Non-localized Localized

(c) a-Mn CrB2 MnP Co

saturated

CeFe2 Fe3Pt CoS2 Fe MnPt3

FePd3

(d)

(a) Nearly ferromagnetic metals and alloys such as Pd, HfZn 2 , TiBe2, YRh 6 B 4) CeSn3, Ni-Pt, etc. (b) Weakly ferromagnetic metals and alloys such as Sc3In, ZrZn2, Ni3Al, Fe05Co05Si, LaRh6B4, CrRh3B2, Ni-Pt, etc. (c) Antiferromagnetic metals and alloys such as /3-Mn, V3Se4, V3S4, V5Se8, etc. (d) Localized magnetic moment system such as insulating magnetic compounds, 4/-metals, and Heusler alloys (Pd2MnSn etc.).

MAGNETISM OF RARE EARTH METALS

181

are hardly created by thermal excitation. In other words, spin density waves in weak ferromagnets mostly have small q or long wavelengths. Moriya classified all magnetic materials from the point of view of spin fluctuation as shown by Table 8.1. The columns are arranged from left to right in order of increasing non-localization of q or increasing spatial localization of magnetic moment, while the rows are arranged in order of increasing amplitude of the spin density wave. In the limit of a localized moment system, the spin fluctuation is localized in real space and so is of a short-range nature and its amplitude is large and saturated. On the other hand, in the limit of weak ferromagnetism, the spin fluctuation is localized in ^-space and limited to small q, and its amplitude is small and variable. All magnetic materials can be classified between the two limiting cases as shown in Table 8.1.36 For further details, the review article35'36 should be consulted.

**8.3 MAGNETISM OF RARE EARTH METALS
**

As mentioned in Section 3.2, the carriers of magnetism in the rare earth elements are the 4/ electrons, which are located deep inside the atoms. When these rare earth atoms condense to form metals, three electrons in the outer shells [(5d)l(6s)2] are shared by many atoms and contribute to electrical conductivity and metallic bonding. At the same time, these electrons serve as a medium of exchange interaction which produces ordered arrangements of the 4/ spins. Pure rare earth metals with less than half the maximum number (fourteen) of 4/ electrons, such as La, Ce, Pr, Nd, Sm, and Eu, are known as the light rare earths and exhibit only weak magnetism. The elements with more than half, such as Gd, Tb, Dy, Ho, Er, and Tm, are called the heavy rare earths, and are ferromagnetic at low temperatures. In contrast to the 3d transition metals, most of these heavy rare earth metals exhibit helimagnetism (see Section 7.3) over some temperature range above the Curie point before becoming paramagnetic. Gadolinium has the highest saturation magnetization, with a value at 0 K almost the same as that of Fe. However, the Curie points of the pure rare earth metals are all lower than room temperature, so they cannot be used as practical magnetic materials. Figure 8.18 shows the asymptotic Curie point, Neel point, and ferromagnetic Curie point of the rare earth metals as a function of the number of 4/ electrons. As seen in this graph, the asymptotic Curie point is mostly small and negative for light rare earth metals, indicating that the exchange interaction is weak and negative. In fact, these metals exhibit antiferromagnetic structures with very low Neel points. On the other hand, the heavy rare earth metals have relatively high Curie points, Neel points, and asymptotic Curie points, all of which decrease as the number of 4/ electrons increases. This behavior is quite different from that of the effective magnetic moment shown in Fig. 3.12, but is rather similar to the variation of spin S shown in Fig. 3.10. This is reasonable, because the exchange interaction is related to the spin S and has nothing to do with the orbital momentum L. However, / rather than S is a good quantum number, so that all the vectors precess about /. Therefore the effective spin contributing to the exchange interaction is the spin component parallel to /. As seen

182

MAGNETISM OF METALS AND ALLOYS

Fig. 8.18. Variation of magnetic transition points of rare earth metals with number of 4/ electrons.

in Fig. 3.11, —M is given by gj, which is equal to the component of / + 5 parallel to /. Therefore the spin component parallel to / is given by gJ - 7 or (g - I)/. Since the Curie point is proportional to /(/ + 1), it is appropriate to describe the various transition temperatures in terms of

which is called the de Gennes factor. The Neel points of many rare earth metals and alloys are plotted as a function of £ in Fig. 8.19, which shows that all the Neel points lie on curves of £ 2/3 , indicating the validity of the de Gennes factor. However, no theoretical explanation has been given for this £ 2/3 law. The Curie points of Gd alloys (except for the Gd-La system) deviate from the Neel points for £ less than 11.5 ( W = 0),* indicating the appearance of helimagnetism. Various magnetic constants and the magnetic structures of rare earth metals are summarized in Table 8.2 and Fig. 8.20. The magnetic properties of the individual metals are summarized next, starting with the heavy rare earth metals.

* This means no spin rotation, i.e. ferromagnetic.

MAGNETISM OF RARE EARTH METALS

183

Fig. 8.19. Magnetic transition of rare earth metals and alloys as a function of de Gennes factor (see equation (8.38)).

Gadolinium (Gd) exhibits ferromagnetism below the Curie point 0f = 293 K. It is different from other heavy rare earth metals in that it has no orbital momentum L, so the magnetocrystalline anisotropy is relatively small. It is therefore relatively easy to magnetize. According to older data, the saturation magnetization at OK was 7.12MB,51 which is very close to the theoretical value of 7MB. However, recent measurements on a purified sample (99.99%) gave 7.55MB,52 which is much larger than the theoretical value. The saturation moment of a Gd atom in Gd-Y and Gd-La alloys (calculated from the measured saturation magnetization of the alloys by assuming that only Gd is magnetic), is also found to be much larger than 7MB.52'53 This may be due to some contribution to the saturation magnetization from the 5d electrons. Terbium (Tb) has moments S = 3, L — 3 and J = 6, and is predicted to exhibit a saturation moment gJ = 9.0. The measured saturation magnetic moment at 0 K is 9.34MB,55 which is larger than the theoretical value. Ferromagnetism disappears above the Curie point 0f = 215 K, and helimagnetism is observed above 0f up to 0 N = 230K. The crystal structure is hexagonal closed-packed and the spin rotates about the c-axis with a period of about 18 atomic layers. Note that the distance required for a complete rotation of the spins is not required to be an integral number of atomic layers, and may change with temperature. Dysprosium (Dy) has moments S = f, L = 5 and / = -y, and is predicted to have gJ = 10. The actual saturation magnetization at OK is 10.7MB, slightly larger than the

184

**MAGNETISM OF METALS AND ALLOYS
**

Electronic structure of free ions

**Table 8.2. Various properties of rare earth metals.
**

Crys. type (r.t.) hep hep hep fee fee hex hex — rhomb bee hep hep hep hep hep hep fee hep Tr. pt. (°C) 1335 1459 310 868 725 798 862 Me. pt. No. of 4/ el. S de Genne (g- I)/ factor

R

Density

0f

0N

®a (K)

L

J

(gem- 3 ) Sc 2.992 Y 4.478 La 6.174 6.186 Ce 6.771 Pr 6.782 Nd 7.004 Pm — Sm 7.536 Eu 5.259 Gd 7.895 Tb 8.272 Dy 8.536 Ho 8.803 Er 9.051 Tm 9.332 Yb 6.977 Lu 9.842

(°C) (K) (K) 1539 1509 920

0

0

0 0 00

0

3 5 6 6 5 3 0 3 5 6 6 5 3 0

0

0

0

795 12.5 -46 935 -21 1024 7.5 -16 1035 917 1072 14.8 826 (90) 15 1264 1312 289 310 1317 1356 218 230 236 1407 90 179 151 1461 20 133 87 1497 20 80(53) 41.6 1545 22 53 20 798 824 1652 37 37

6

1 2 3 4 5 6 7 8 9 10 11 12 13 14

1/2 1 3/2 2 5/2 3 7/2 3 5/2 2 3/2 1 1/2 0

2{ 4 4} 4 2} 0 3| 6 7} 8 7{ 6 3j 0

-0.36 -0.80 -1.23 -1.60 -1.78 0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0

3 8

0.182 0.80 1.84 3.20 4.44 — 15.75 10.50 7.08 4.50 2.55 1.17 0.32 0

Ref.

37

theoretical value.55 Ferromagnetism disappears at ©f = 85 K and helimagnetism exists up to 0 N = 178.5 K. The pitch of the helimagnetic structure (the rotational angle per atomic layer) changes from 25°/layer to 43°/layer as the temperature increases. Holmium (Ho) has moments 5 = 2, L = 6 and / = 8, so that gl = 10. The actual saturation magnetization observed at OK is 10.34MB. In the temperature range from 20 to 133K, helimagnetism is observed, pitch varying from 35° to 50°/layer with increasing temperature. Below 20 K, the spins deviate from the c-plane and at the same time develop a screw structure, so that the spin structure is conical, with a net spontaneous magnetization along the c-axis. It was observed by neutron diffraction that the component of spontaneous magnetization is 1.7MB, while the screw component in the c-plane is 9.5MB. Erbium (Er) has a more complicated magnetic structure: between 52 and 80 K the spin oscillates parallel to the c-axis with a half period of seven layers; between 20 and 52 K, a c-plane component is added; and below 20 K a conical screw structure appears. The component parallel to the c-axis is 7.9MB, while the screw component in the c-plane is 4.3MB. The saturation magnetization observed by applying a strong magnetic field is 8.8MB, which is in good agreement with gJ = 9.0. Thulium (Tm) shows spin oscillation parallel to the c-axis with a half-period of seven layers between 40 and 50 K, while below 40 K, four spins point in the +cdirection and three spins point in the —c-direction, thus forming an usual kind of ferrimagnetic structure.

MAGNETISM OF RARE EARTH METALS

185

**Table 8.2. (cont.) Magnetic moments of rare earth metals.
**

Magnetic moment (MB) Meff Theory R

La Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu

**Ms Experiment Theory (g/)
**

2.14 3.20 3.27 2.40 0.72 0.0 7.0 9.0 10.0 10.0 9.0 7.0 4.0 0

Hund

0 2.54 3.58 3.62 2.68 0.85 0.00 7.94 9.72 10.64 10.60 9.58 7.56 4.53 0

V.V.-F.

0 2.56 3.62 3.68 2.83 1.55 3.40 7.94 9.70 10.6 10.6 9.6 7.6 4.5 0

3+ Ion

0 2.52 3.60 3.50 — — — 7.80 9.74 10.5 10.6 9.6 7.1 4.4 0

Metals

0 2.51 2.56 3.3-3.71 — 1.74 8.3 7.98 9.77 10.65 11.2 9.9 7.6 0.0 0

Experiment

Ref.

38 39 40,41 38 42-4 45 46 47 48 49 50

7.55 9.34 10.20 10.34 8.0 3.4

Ytterbium (Yb) has the electronic structure 4/,14 so that it is non-magnetic like lutetium (Lu), as already explained in Chapter 3. The origin of the screw spin structures in heavy rare earth metals is in oscillatory polarization of conduction electrons caused by exchange interaction with the 4/ spins. The polarization of conduction electrons o-(r) at a distance r from the localized spin S is given by where kF is the wave vector at the Fermi surface or the radius of the Fermi sphere in fc-space. The function F(x) is given by

which describes a damped oscillation as shown in Fig. 8.21. The exchange interaction through such oscillatory polarization is called the RKKY interaction, a name originating from initials of the authors Ruderman and Kittel,56 Kasuya,57 and Yosida.58 As discussed in Section 7.3, a screw structure is caused by the coexistence of a positive exchange interaction between nearest neighbor planes and a negative interaction between second nearest neighbor planes. The oscillatory nature of the RKKY interaction is equivalent to such a coexistence of positive and negative interactions. The magnetocrystalline anisotropy and magnetostriction also affect the pitch of the screw structure and may modify the spin structure. Theories on helimagnetism in heavy rare earth metals are discussed in various papers.59"62

186

MAGNETISM OF METALS AND ALLOYS

Fig. 8.20. Spin structures of rare earth metals.53

In contrast to the heavy rare earth metals, light rare earth metals with less than half-filled 4/ shells exhibit only weak magnetism, and the variation of magnetic structure with the number of electrons is not so regular as in the heavy rare earth metals.

Fig. 8.21. Functional form of RKKY interaction.

MAGNETISM OF RARE EARTH METALS

187

Lanthanum (La) has no 4/ electrons and accordingly is non-magnetic. Its outer electron arrangement (5dl(>s2) is similar to those of scandium (Sc) (3d14s2) and yttrium (Y) (4dl5s2\ so that Sc and Y are usually classified as rare earths. Cerium (Ce) has a magnetic moment of about 0.6MB, which is much smaller than g/ = 2.14. The spins are arranged ferrimagnetically in the c-plane and antiferromagnetically along the c-axis below 12.5 K, producing zero spontaneous magnetization. Praseodymium (Pr) has no ordered spin structure. When a magnetic field is applied parallel to [110], the measured magnetization corresponds to a value of 1.6MB per atom, which is much smaller than the theoretical value gJ = 3.20. Neodymium (Nd) has an antiferromagnetic structure below 19 K, with the spins arranged ferromagnetically in the c-planes but antiferromagnetically along the c-axis. This spin structure is changed below 7.5 K. The magnetization in a magnetic field of 4.8 MAm"1 (=60kOe) is 1.6MB per atom, which is substantially less than the theoretical value of 3.27MB. Promethium (Pm) is an unstable element, and no information is available on its metallic state. Samarium (Sm) develops a complicated antiferromagnetic structure below 106 K, which is similar to that of Nd, and undergoes a further change in structure below 14 K.63 Europium (Eu) has a body centered cubic lattice. Below its Neel point of 91 K, it has a screw spin structure with the spins lying in the (100) plane64 with a pitch which varies with temperature from 51.4° to 50.0°/layer. Many investigations have been made on rare earth alloys. When non-magnetic rare earth metals such as La, Y and Sc are added to ferromagnetic heavy rare earth metals, the Neel and Curie points are generally lowered. However, La often stabilizes

Fig. 8.22. Magnetic transition points of rare earth alloys R-La, R-Y and R-Sc.5

188

MAGNETISM OF METALS AND ALLOYS

ferromagnetism. For instance, the Curie points of Dy-La and Er-La alloys increase with La content, as shown in Fig. 8.22. As already shown in Fig. 8.19, the Neel points of rare earth alloys vary as £ 2/3 . On the other hand, the Curie point decreases more rapidly with a decrease in the de Gennes factor, thus increasing the temperature range in which helimagnetism is observed. (The de Gennes factors of alloys are calculated as a weighted average of the factors for the constituent elements.) Considering alloys between heavy rare earth metals, we find that the Neel point of Gd-Dy and Gd-Er alloys changes as £ 2/3 , as shown in Fig. 8.19. This is, however, not a general rule. For instance, the Curie point of Dy-Er alloys undergoes a discontinuous change with composition. The Neel point of Ho-Er alloys changes monotonically, while the Curie point shows a maximum as a function of composition. It was observed that in Ho-Er alloys, the spins of both constituent atoms rotate in the same way about the c-axis. Further topics are considered in several reviews.65'7 8.4 MAGNETISM OF INTERMETALLIC COMPOUNDS Intermetallic compounds are composed of metallic elements in fixed integer ratios, such as Ni3Al or MnBi, which usually exhibit metallic properties such as high electrical conductivity and metallic luster. Generally speaking, they have complicated crystal and magnetic structures. It is rather difficult to explain intermetallic compounds by any unified theory. In this section, we discuss only the intermetallic compounds which show interesting or useful magnetic properties, and we consider only elements which belong to the 3d transition metals, the rare earth metals, and the actinide metals, plus Be. Compounds which contain the elements belonging to the Illb group, such as B, Al, Ga, In, Tl; the IVb group, such as C, Si, Ge, Sn, Pb; and the Vb group such as N, P, As, Sb, Bi, will be treated in Chapter 10. First we discuss the intermetallic compounds which contain only 3d, 4d, and 5d transition metals. They form a-, %-, Laves-, and CsCl-phases, and occur at an electron concentration near that of Mn. As discussed in Section 8.2, this fact is related to the irregularity in the relationship between crystal structure and electron concentration caused by band polarization. The crystal structure of the cr-phase is complex: the unit cell contains 30 atoms, each of which has a high coordination number (number of nearest neighbors), such as 12, 14 and 1568 (see Fig. 8.23). The only ferromagnetic tr-phase compounds are VjFej^ (x = 0.39-0.545) and Cr^Fe^ (* = 0.435-0.50). Other o--phase compounds such as V-Co, V-Ni and Cr-Co exhibit only Pauli paramagnetism. The maximum saturation magnetic moment in the Fe-V system is 0.5MB per atom, and the maximum Curie point is 240 K. The ^-phase has a complicated crystal structure with a unit cell containing 29 atoms, which is the same as that of a-Mn described in Section 8.2. The magnetic structure of this phase has not been investigated in detail except for a-Mn itself. The Laves phase is an AB2-type compound, described by Laves.69 The atomic radius of the A atom is 1.225 times larger than that of the B atom. There are three

MAGNETISM OF INTERMETALLIC COMPOUNDS

189

Fig. 8.23. Crystal structure of cr-phase.54

Fig. 8.24. Crystal structure of Laves-phase MgCu2-type compounds.55

kinds of complicated crystal structures: MgCu2-type cubic (Fig. 8.24), MgZn2-type hexagonal, and MgNi2-type hexagonal. The common feature of these crystals is that A and A atoms, and B and B atoms, are in contact with each other, while A and B atoms are not. All of the ferromagnetic Laves compounds are listed in Table 8.3, from which we see that the B atoms are mostly Fe or Co. The paramagnetic Laves phases have high values of magnetic susceptibility when B is Fe or Co, and they tend to be ferromagnetic for B contents higher than stoichiometric.70 ZrZn2 is a weak ferromagnet containing no ferromagnetic elements, and is a typical itinerant-electron ferromagnet. Even at OK, the magnetization of this compound increases by the application of high magnetic fields, and does not saturate even in a field as strong as S^MAm" 1 (VOkOe).91 It has been found that the saturation moment of the Fe atom in various AFe2 compounds changes linearly with the distance between A atom neighbors.92 There are many ABe2-type compounds, but only FeBe2 is ferromagnetic. The ferromagnetic CsCl-type intermetallic compounds containing only transition metals are listed in Table 8.4. Interesting magnetic behavior is observed in FeRh, as shown in Fig. 8.25: as the temperature is increased through room temperature, a saturation magnetization suddenly appears as the result of a transition from antiferromagnetism to ferromagnetism. Taking into consideration the fact that the electronic configuration of Rh is similar to that of Co, Kanamori and Teraoka100 suggested that Rh atoms become magnetic by transferring some electrons to the Fe atoms, which simultaneously results in ferromagnetic coupling between Fe-Fe pairs. MnZn is known to exhibit a large spin canting.97'98 MnRh seems to be antiferromagnetic below room temperature, but it becomes ferrimagnetic with excess Mn content. In rare earth-transition metal compounds, a negative exchange interaction exists through the conduction electrons. Therefore the light rare earths, where / is opposite

190

MAGNETISM OF METALS AND ALLOYS

**Table 8.3. Magnetic properties of Laves phase intermetallic compounds.
**

Compounds ZrFe2 HfFe2 ZrZn2 FeBe2 ScFe2 YFe2 CeFe2 SmFe2 GdFe2 DyFe2 HoFe2 ErFe2 TmFe2 PrCo2 NdCo2 SmCo2 GdCo2 TbCo2 DyCo2 HoCo2 ErCo2 UFe2 NpFe2 Crystal-type MgCu2 MgCu2 MgCu2 MgCu2 MgNi2 MgCu2 MgCu2 MgCu2 MgCu2 MgCu2 MgCu2 MgCu2 MgCu2 MgCu2 MgCu2 MgCu2 MgCu2 MgCu2 MgCu2 MgCu2 MgCu2 MgCu2 MgCu2 Curie point (K) 588,633 591 35 823 — 550 878 674 813 663 608 473 613 44 116,109 203 412 256,230 146 95,90 36,37 172 600? Mag. moment per formula (MB) (Fe) 1.55 (Fe) 1.46 (ZrZn2)0.13 (Fe) 1.95 — (Fe) 1.455 (CeFe2) 6.97 (DyFe2)5.44 (HoFe2)6.02 (ErFe2)5.02 (TmFe2)2.94 (PrCo2)2.9 (NdCo2) 3.83,3.6 (SmCo2) 1.7 (GdCo2)4.8 (TbCo2) 6.72,6.0 (DyCo2)7.1 (HoCo2) 7.81,7.7 (ErCo2) 7.00,6.6 (Fe) 0.51 Ref. 70-74 75 76 77,78 79 80 80 80 80 80 80 80 80 80 81,82 83 83 82,83 82 82,83 82,83 84-88 89

to 5, tend to align their magnetic moment parallel to that of the transition metal. On the other hand, the heavy rare earths, where / is parallel to S, tend to align their magnetic moment opposite to that of transition metals. Using this pattern, the saturation magnetic moments of the RFe2 and RCo2 compounds (R: rare earth) can be well accounted for, assuming Ms to be 2.2MB for Fe and 1.0MB for Co. Table 8.4. Magnetic properties of ferromagnetic CsCl-type intermetallic compounds.

Compounds FeRh MnZn SmZn GdZn TbZn DyZn HoZn ErZn Composition range 20~53%Rh 50 ~ 56.5% Zn Curie point ®f (K) 673-950 > 550 125 270 206 144 80 50 Saturation mag. moment per formula (MB) Ref.

Fe: 3.2, Rh: 0.6 (in the case of 48% Rh) 83-95 Mn: 1.7 (ferromagnetic component) 97,98 Mn: 2.9 (antiferromagnetic component) (SmZn)0.07 99 (GdZn)6.7 99 (TbZn)6.0 99 (DyZn)4.9 99 (HoZn)4.7 99 (ErZn) 2.3 99

MAGNETISM OF INTERMETALLIC COMPOUNDS

191

Fig. 8.25. Temperature dependence of specific saturation magnetization and reciprocal susceptibility of FeRh.82

Compounds with the CsCl-type structure and the formula RM are found for M = Cu, Ag and Au in the Ib group; Mg (Ha), Zn, Cd, and Hg in the lib group; and Al, Ga, In and Tl in the Illb group. There is a general tendency that RM(Ib) are antiferromagnetic, RM(IIb) are ferromagnetic, and RM(IIIb) are again antiferromagnetic. An attempted explanation of this change in the exchange interaction according to the number of conduction electrons in terms of the RKKY interaction was not successful.101 Ferromagnetic RM(IIb) compounds are listed in Table 8.4. The RCo5-type compounds have a hexagonal crystal structure, as shown by Fig. 8.26. As in the case of RCo2, the light rare earth moments couple ferromagnetically with those of Co, while the heavy rare earth moments couple ferrimagnetically with Co.102 In these crystals the orbital moment L of the rare earth atoms remains

Fig. 8.26. Crystal structure of RCo5-type compounds.92

For this reason some of these compounds show excellent permanent magnet characteristics.37 (Fe) 1.70 (Fe 3.83.76 (Co) 1. Pd 0. The R2Co17-type compounds have even better permanent magnet properties in some ways (see Table 8. Pt 0. and Pu.33.909 0.192 MAGNETISM OF METALS AND ALLOYS Table 8.5.965 1.5 19.04 (Mn 3.06 (Fe 2. so that the magnetocrystalline anisotropy (see Chapter 12) is quite large.30) 4.47) 4. Ni 0.8 44. Ni 0.38 (Fe 2.94 (Fe) 1.5. which require careful handling because of their radioactivity. moment in MB at OK Ref.51) 8.99.4 (Mn 3.64. Compounds YCo5 LaCo5 CeCo5 PrCo5 SmCo5 Sm2Co17 Gd2Co17 Th2Fe17 Th2Co17 ThCo5 Th2Fe7 ThFe3 Crystal type CaCu2 CaCu2 CaCu2 CaCu2 CaCu2 Th2Zn17 Th2Zn17 Th2Zn17 Th2Zn17 CaCu2 Ce2Ni7 PuNi3 Curie point (K) 921 840 647 885 997 920 930 295 1053 415 570 425 Is (T) 1. .5).66 Superlattice FeV Ni 3 Mn FeCo FeNi Ni3Fe UAu4 MnAu4 CrPt3 MnPt3 FePd FePd3 Fe3Pt FePt CoPt CoPt3 Ni3Pt Crystal type CuZn Cu3Au CuZn CuAu Cu3Au Ni4Mo Ni 4 Mo Cu3Au Cu3Au CuAu Cu3Au Cu3Au CuAu CuAu Cu3Au Cu3Au .41 4.4 Ms per formula in MB 0.0.98 (Fe 0. V 0.2 23. Pd 0.95 (Fe 3.73.6. Pt 1.62) 0. 104 104 104 104 104 104 104 105 105 105 105 105 unquenched. Magnetic and crystal properties of ferromagnetic superlattice alloys.52 2. Np.93 Orderdisorder Curie point (°C) 510 730 -320 500 -565 -420 -1000 -700 -800 835 -1300 825 -750 580 6f in ordered state (K) 750 1390 983 53 371 687 370 749 529 430 750 -290 370 / S (OK) emug" 1 (x4irX 10~ 7 Wbmkg" 1 ) 51 105 230 113 2. Pt 0.03) 4.27) 4.42 (Co) 0.9) 4.15 2.18 (Cr 2.8 27. Some Laves Table 8.9.01 1.06 0.1 35. Co 1.2 138 33.5) 1. The actinide elements U.2 0.2 105 65.8 (Fe 2.26) 3. Magnetic properties of RCo5 and similar compounds.2 0.73 (Fe) 1.77 1. form intermetallic compounds with transition metals.72.37 Sat.

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one possibility is shown in (c). * This does not mean that the size of the O atom is much larger than that of M atoms. where the position of atoms in the third layer is different from that in either the first layer or the second layer. 9. which are arranged in an ionic crystal. and finally other oxides in Section 9.1 we note the general features of oxide crystals. There is more than one kind of interstitial site. The size of O 2 ~ is large because it has two extra electrons outside the neutral atom.* The close-packed structure is illustrated in Fig. The metal and oxygen ions are quite different in size. In order to construct oxides.8 A. thus forming close-packed crystals. where x = 1-2.6-0.1 CRYSTAL AND MAGNETIC STRUCTURE OF OXIDES When metallic ions with valence +«. while the M"+ ion is small because it loses n electrons from the neutral atom. molecule. Therefore magnetic oxides such as ferrites exhibit very low losses when magnetized in high-frequency fields.2. Therefore oxides are expressed by the chemical formula MOX. where (a) shows the twodimensional dense packing of spheres in the first layer. Small M"+ ions occupy interstitial sites between them.32A. are chemically combined with divalent oxygen ions O 2 ~. large O 2 ~ ions are in contact with each other. but individual ions M"+ and O 2 ~. the unit of structure is not the MO. where x = n/2. then discuss magnetic and crystalline properties of spinel ferrites in Section 9. the structure becomes hexagonal closed packed. hexagonal ferrites in Section 9.5.2. In most cases.3. but some oxides contain additional metal ions with n = 4 or 1. n = 2 or 3. 9. the oxide MOX is produced. as shown in Fig. This characteristic has been very useful in magnetic materials for communication and information devices. we must insert M" + ions in such a close-packed oxygen lattice.9 MAGNETISM OF FERRIMAGNETIC OXIDES Most oxides are electrically insulating.4. In oxide crystals. When the third layer is placed on the second layer. The cohesive force in this crystal is supplied by an electrostatic Coulomb interaction between the charge +ne of M"+ ions and the charge — 2e of O2~ ions. while the radius of an M" + ion may be small as 0. Such a close-packed structure is face-centered cubic. In Section 9. . The radius of O 2 ~ is 1. 9. while (b) shows a possible placement of the dense packed second layer on the first layer. When the oxides form solids. garnet ferrites in Section 9. or M" + . If the atomic position in the third layer is the same as the first layer.1.

When the angle is nearly 90°. magnetic moments are aligned by the superexchange interaction through the oxygen ions. thus producing a canted magnetic structure (see Section 7. When the angle M-O-M is nearly 180° the magnetic moments on the metal ions tend to be antiparallel. that even when the interstitial metal ion is absent.1. because the surrounding six oxygen ions form an octahedron.2. It should be noted. There are many kinds of oxides. In some cases. in order of increasing x. because the surrounding four oxygen ions form a tetrahedron. .. but aligned at some arbitrary angle.3). with their crystal structures and some additional information.1. thus forming a ferromagnetic structure. oxygen ions are still pushed outward because of their Coulomb repulsion. as described in Section 9. the moments are neither parallel nor antiparallel. 9. The size of these interstitial sites is generally fairly small. This displacement of oxygen ions is expressed in terms of the «-parameter.2. the moments tend to be parallel. 9. however.1 lists many magnetic oxides MO. Site B is surrounded by six oxygen ions and is called the octahedral site.. Table 9. As mentioned in Section 7. Fig.198 MAGNETISM OF FERRIMAGNETIC OXIDES Fig. Site A is surrounding by four oxygen ions and is called the tetrahedral site. but in all cases the metallic ions occupy one of these interstitial sites. as will be discussed later. so that the oxygen ions tend to be pushed outward by the interstitial metal ions. In addition to these two. there is a dodecahedral site. The tetrahedral site A and the octahedral site B in a face-centered cubic lattice. Stacking of atomic layers in close-packed structures. thus giving a ferrimagnetic structure.

Ni (FR) M = Mn.Co 75 Fe 25 (FR) M = Mn.50M3MnO6 2. x Formula 1.La.3.Eu.Zn. Co. Cd (FR) M = Mn. 9..Gd. Fe. which form a face-centered cubic lattice. Fe. Co.Ca 2 Fe(FR) M = CKF) hexagonal Ca-diferrite magnetoplumbite (M) hexagonal ferrite magnetoplumbite(W) magnetoplumbite (Z) magnetoplumbite (Y) ilmenite ilmenite garnet perovskite perovskite perovskite rutile hexagonal ferrite hexagonal ferrite hexagonal ferrite mixed ilumenite RIG orthoferrite (FR) The following sections describe spinel ferrites (section 9. Tm. Cu (FR) M = Cr. Mg.Fe 5 Zn 5 .Pb. Ni 5 La 5 Ag 5 La 5 (FR) M = Mn. Co. Ni. Fe.50MMnO3 1. Fe.Lu(FR) R = Y.42M2BaFe16O27 1. Mg.Ni (FR) M = Co.Ni(FR) R = Y.Ho. Co (FR) (FR) M = Ba. the occupation of A sites by M 2+ ions and B sites by Fe3+ will give a net electrical charge of zero. Since the numbers of nearest-neighbor O 2 ~ ions for A and B sites are in the ratio of 2:3.33MFe2O4 1.40CaFe4O7 1. for a total of 56 ions. Co (FR) M = Mn. many magnetic ferrites are inverse ..MAGNETISM OF SPINEL-TYPE OXIDES 199 Table 9.La 7 Cd 3 (F) M 3 = Gd 2 Co.La 7 Ca 3 . FR: FerriCA: Cant-Magnetism) M = Eu(F) M = Mn. Ni.2). Fe. Cu. Fe.Fe.38 M 2 Ba 2 Fe 12 O 22 1. Crystal and magnetic structure of magnetic oxides MO. Yb. Lu (CA) M = Bi.Sm.33MMn2O4 1.41 M2Ba3Fe24O41 1.Cu. Dy. Co.33 MCr2O4 1.Eu. Ho. These ferrites are typical spinel-type oxides. Sr. Zn.Ni.Tb.50R3Fe5OI2 1. 9.. thus minimizing the electrostatic energy. However.Mn 5 Zn 5 (FR) M = Co.Yb. etc.Ni.Mg.0 MO 1. The open circles in the figure represent O 2 ~ ions. 8 metal ions on A-sites.Dy.50RFeO3 1. Such a configuration is called a normal spinel.3).4).Gd. Fe. Co.Tb.1. with the crystal structure shown in Fig. Er. Fe.Nd. Er.Sm. Co.La 7 Sr 3 . Ni. Mn. and 16 metal ions on B-sites.33 M2TiO4 1.46 MFe12O19 1. Ni. Li 5 Fe 5 (FR) M = Mn. Co (FR) M = Mn. Fe.Mg. The unit cell contains 32 O 2 ~ ions.La 7 Ba 3 La 6 Pb 4 . Fe 25 Zn 75 M = Mn.0 MO2 Crystal-type NaCl spinel spinel spinel spinel spinel Name ferrite cobaltite chromite manganite Examples (F: Ferro. where M represents one or more divalent metal ions such as Mn. and other oxides (Section 9.Tm. Co. There are two kinds of interstitial sites in the oxygen lattice: A or 8a sites which are surrounded by four O 2 ~ and B or 16d sites which are surrounded by six O 2 ~ ions.2 MAGNETISM OF SPINEL-TYPE OXIDES Spinel ferrites have the general formula MO-Fe 2 O 3 .33 MV2O4 1. hexagonal ferrites (Section 9.Ni.33 MCo2 O4 1.Ca.Ba 2 Fe.50 M 8Ti 8Fe 4O3 1.5).50MMnO3 1. Cu. garnet ferrites (Section 9.33 M2VO4 1.

The Mn ferrites are 80% normal. Spinel lattice. spinels. 9.1) gives rA = 0.375.380-0. this means that 80% of the Mn ions occupy A sites.81 A.4. with M = Zn. (9. (9. Therefore when a metallic ion occupies an A site. which are suitable . in which half of the Fe3+ ions occupy the A-sites and the remaining Fe3+ plus the M 2+ ions occupy the B-sites. and R0 is the radius of the O2 ions.50A in most ferrites. while the other 20% occupy B sites. Thus the A sites are much smaller than most metallic ions.200 MAGNETISM OF FERRIMAGNETIC OXIDES Fig. which is defined by the coordinate of the O 2 ~ ion as shown in Fig. Such a deformation of the lattice is expressed by the u-parameter. while in real ferrites u = 0.385.3. and that of both Mn 2+ and The radii of the spheres which fit in the A and B sites are calculated to be where a is the lattice constant of the spinel lattice. is a normal spinel.72 A. Since R0 = 1. Using this w-parameter.52A.32A. and r B = 0.67 A. rB = 0.8 A.1) can be rewritten as If we assume that u = 0. (9. 9. In an undistorted lattice u = f = 0. whose radii range from 0.2) gives rA = 0.385. it pushes the surrounding O 2 ~ ions outward. It is interesting to note that ions occupying the A sites mostly have a spherical configuration: the electronic structure of Zn2+ is 3dw. Zinc ferrite.6 to 0. and a = 8.

34 — 0.33 5.1 2. As mentioned in Section 7.55 4.5 shows the angle and the distance between ions for AB. It is seen that in general the angle A-O-B is closer to 180° than the angles B-O-B or A-O-A. the main negative interaction acts between A and B sites.3 1. Before discussing the magnetism of ferrites. who first developed the theory of ferrimagnetism.3 1.51 8.3 7S r. let us consider what kind of superexchange interactions are expected in this crystal structure.2 for various spinel ferrites.94 2.60 0. so that we expect the AB pair to have a stronger negative interaction than the AA or BB pairs.34 Resistivity (fl cm) 10 104 4XlO~3 107 109 105 — 107 102 — 2 M Zn Mn Fe Co Ni Cu (quenched) Cu (slow cool) Mg Li y-Fe2O3 Mmol at 0 K (MB) — 4.1 3. thus resulting in the magnetic arrangement given by Table 9. a (A) 8.MAGNETISM OF SPINEL-TYPE OXIDES 201 Fig.382 — .381 0.34 8.39 8.385 0.17 ®f (K) — 300 585 520 585 455 — 440 670 575 w-parameter 0.36 8.70 a: 8.52 4.2.38 5.15 0.1.75 — 0. Definition of the w-parameter. Figure 9. (T) — 0. and AA pairs. Values of u are listed in Table 9.3 2.22 8. sizes to accept metal ions.53 0. 9. the sign and magnitude of the superexchange interaction between M t and M 2 ions depend upon the angle of the path Mj-O-Mj. Magnetic and physical properties of spinel ferrites MFe2O4.35 Lattice const.44 8.42 5.24 5.6 2.8 Density (gcm~ 3 ) 5. In the inverse spinel ferrite. The following explanation was given by Neel2.29 5.380 — 4.39 — 0. let us discuss a possible magnetic structure of the inverse spinel.38 8. BB.379 0.33 8. Based on this idea.4.00 5.381 — 0.50 0.t.37 c:8.385 0.

1) in which Fe3+ is 3d5 with a spin magnetic moment of 5MB and M 2+ has a magnetic moment of nME. 32. If the identity of the M ion changes in the order M = Mn. Ni. Co. The real reason is that one electron is transferred from Mn 2+ to Fe3"1". a partly normal spinel. both of which have 4MB.and B-sites cancel one another. and Zn. the molar moment should be given by which agrees with experiment. (Modified from Fig. Cu. or a partial mixture of Mn2+ ions. the molar moment is given by 4 + 4 — 5 = 3MB. such an electron transfer results in a molar moment of 4 + 5 — 4 = 5MB. The tendency for the experimental points to deviate upward from the theoretical line is due to the contribution of some orbital magnetic moment remaining unquenched by a crystalline field. the number of 3d electrons changes in order from 5 to 10. If the ionic arrangement is a normal spinel. 9. Experimental points are very close to this theoretical line. smaller than the theoretical value 5MB. does not result in a change in molar magnetic moment. This occurs in the mixed MZn-ferrites: if x moles of Zn-ferrite (a normal spinel) is . Fe. and the magnetic moment n of the M ion changes from 5 to 0. while if the arrangement is an inverse spinel.6MB. Then we expect that the molar magnetic moment changes linearly from 5MB to zero as shown by the thick solid line in Fig. Various paths for superexchange interactions in the spinel lattice. Therefore the saturation magnetic moment per formula unit (the molar magnetic moment) at 0 K is given by This results in a moment of nMB because the spins of the two Fe3+ ions in A.202 MAGNETISM OF FERRIMAGNETIC OXIDES Fig. An interesting feature of ferrimagnetic oxides is that the addition of a nonmagnetic oxide will sometimes result in an increase in molar magnetic moment. 9.1 in Smit and Wijn. This can be explained as follows: since M 2+ and Fe3+ ions are both 3d5 and have 5MB. The molar magnetic moment of Mn ferrite is 4. thus resulting in Mn 3+ and Fe2+.6.5. Since Mn-ferrite is an 80% normal spinel.

Sometimes the N-type temperature dependence appears. Molar saturation moments of various simple spinel ferrites.6. For small x. however. heading toward a value of 10MB at x = 1. then the ionic arrangement is given by Therefore the molar magnetic moment of the mixed ferrite is given by We see that M increases with increasing x.1) added to 1 — x moles of M-ferrite (an inverse spinel). For large x. Yafet and Kittel5 explained this deviation in terms of a triangular arrangement of spins. Figure 9.7 shows the variation of M with x for various kinds of mixed Zn ferrites.MAGNETISM OF SPINEL-TYPE OXIDES 203 Fig. M falls below the line (9.7). as in Li-Cr ferrites . 9.1).3 (Mark X is from Smit and Wijn. The R-type temperature dependence is commonly observed in spinel-type magnetic oxides.7). On the other hand. M increases along the line given by (9. Ishikawa6 interpreted this phenomenon in terms of superparamagnetic spin clusters produced by the breaking of exchange paths by non-magnetic Zn ions (see Section 20.

A more significant reason for adding Zn is to increase the magnetic permeability by lowering the high permeability temperature range to room temperature (Hopkinson effect. Mn-Zn ferrites are used in relatively lowfrequency applications. as shown in Fig. see Fig. However. The Zn is added partly to increase saturation magnetization at 0 K. the saturation magnetization at room temperature remains almost unchanged. Zn-ferrite is an antiferromagnet with a Neel point near 10 K.2 summarizes the physical and magnetic properties of various spinel ferrites. To end this section we discuss features of some particular ferrites.20). Similar behavior was found in Ni-Al ferrites. 9. 9. 9. Since the resistivity is relatively low. Fe-ferrite or magnetite (Fe3O4) is the oldest magnetic material known by man. see Fig. 18.5Fe2]5_.7. .4 (for x>l in Li0.eCrjeO4. it exhibits weak ferrimagnetism. since the Curie point is decreased by the addition of Zn.8). Variation of molar saturation moment of various spinel ferrites with addition of Zn-ferrite.7 Table 9. Mn-ferrite has the highest saturation magnetization at 0 K of the simple ferrites. When cooled from high temperatures. Mn-Zn and Ni-Zn mixed ferrites are widely used as soft magnetic materials for high-frequency applications because of their high electrical resistivity.204 MAGNETISM OF FERRIMAGNETIC OXIDES Fig.7.

.1). The temperature coefficient of resistivity even becomes positive (like a metal) at high temperatures. This temperature is called the Verwey point. Co-ferrite exhibits an extraordinary large induced anisotropy (see Section 13.4 Since Fe3+ and Fe2+ coexist on B-sites. Because of this contribution. this electron hopping ceases at 125 K. As seen in Table 9.10 The ionic arrangement and crystal symmetry at low temperatures are not yet certain.9 but this has been disproved by recent experiments. electrons 'hop' between these ions.8. This is due to a contribution from the orbital magnetic moment remaining unquenched by the crystalline field.94AfB. so that the resistivity is extraordinarily low for an insulating material. Verwey proposed an ordered arrangement of Fe3+ and Fe2+ ions in the low temperature phase. Co-ferrite has a saturation moment of 3.2 and Fig. 9. below which the resistivity increases abruptly and the crystal structure transforms to a lower symmetry. honoring the name of the discoverer of this transition. which is much higher than the theoretical value of 3MB. Temperature dependence of saturation magnetization of various Li-Cr-ferrites. 9. On cooling.6.MAGNETISM OF SPINEL-TYPE OXIDES 205 Fig.

0. the resulting oxides are called chromltes. but if it is slowly cooled. the lattice becomes tetragonal with a 5-6% distortion from cubic.3892 ± 0.12 Lattice ®a ®f M mol COnSt.14.377 8.n y-(gamma)-Fe2O3 is called maghemite and its crystal structure is an inverse spinel containing vacancies. Fig. whose formula is given by MO-Cr 2 O 3 or MCr2O4. aligns antiparallel to that of 2Cr3+ on the B-site.327 w-parameter 0. The Curie points are low for all the chromites. Fe.15 -570 80 ±10. The ionic distribution and accordingly the saturation magnetization and the Curie point depend on the temperature from which it is quenched. is the most common magnetic recording material. 20. nMB. Ni-Zn ferrites are used as magnetic core materials at high frequencies. Li-ferrite is given by the formula Li 05 Fe 25 O 4 and has an inverse spinel lattice. in which some Mg2+ ions occupy the A-sites.60 0. In most cases. they are normal spinels with Cr3+ ions on the B sites. The frequency limit depends on the Zn content (see Section 20. Cu-ferrite has a cubic structure when quenched from high temperatures.332 8. Magnetic and crystalline constants of various chromites. whose B-sites are occupied by Li1+ and Fe3+ in the ratio of 1:3. It is known that two kinds of ions in the B-sites form an ordered arrangement when it is cooled below about 735°C.248 ("17788 8.51 — .17). The ionic arrangement is given by where V represents a vacancy.2 -400 + 30 90 + 5 0.386 0.3 -600 -380 135 0 N = 10 0.437 8. Table 9. Material MnCr2O4 FeCr2O4 CoCr2O4 NiCr2O4 CuCr204 ZnCr2O4 (K) (K) (MB) (A) 8.00005 -310 55. Co. as will be discussed in Section 14. If we assume according to Neel theory that the magnetic moment of the M 2+ ions. in the form of very small elongated particles. the resistivity is therefore very high. The crystal structures are all cubic spinel.3. so that it exhibits ferrimagnetism. no electron hopping occurs because Ni exists only in the divalent state.8 ± 0. where M represents a divalent metal ion such as Mn. we expect that the molar saturation moment should be given by Table 9. Mg-ferrite is an incomplete inverse spinel. Cu. This is the John-Teller distortion.2 -650 100 0.3 lists various magnetic and crystal constants for several simple chromites.387 ± 0. or Zn.206 MAGNETISM OF FERRIMAGNETIC OXIDES In Ni-ferrite. The Fe3+ ions in ferrites can be replaced by Cr 3+ .43 1.00005 0. For this reason. Ni.7.3. This ferrite.

Sm.15 In these spinel-type oxides. manganese chromite. Tb. where M represents a divalent ion.16 Table 9. Cobaltites are spinel oxides continuing Co3+ with the general formula MO-Co 2 O 3 or MCo2O4. Er.13 Manganites are spinel oxides containing Mn3+ with the general formula MO • Mn 2 O 3 or MMn2O4. Eu.5 4. For M = Mn. etc. respectively.4. Yb. Ni.4 ~ 1. are in poor agreement with (9. Gd.165 -392 80 -450 =200 <4 -450 -164 1. Tm.55 00. The trivalent rare earth ions. The crystal structure is the garnet-type cubic oxide with a unit cell of 160 atoms17 based on a framework consisting of 96 O 2 ~ ions. occupy the 24c sites (or dodecahedral sites) which are surrounded by O 2 ~ ions forming a dodecahedron. 450 and 350 K. and the Cr moments tilt by 94° and 47°.74 4.06 1.0 ~ 1.0.15 1.0 1. . Dy.4. Magnetic and crystalline constants of various manganites. thus distorting the framework of the close-packed oxygen lattice.13-1. and also 16a. where R stands for one or more of the rare earth ions such as Y.08 1. shows a spiral spin structure with the spontaneous magnetization parallel to (110) from which the Mn moment tilts by 68°. sites. probably owing to the formation of canting spin configurations.MAGNETISM OF RARE EARTH IRON GARNETS 207 c/a 1.16 9.5MB. Zn. Fe. while the molar saturation moments are as low as 0. not only divalent M 2+ ions but also trivalent ions can be combined to make mixed spinel oxides. Ni. Mg.27 4. Co. the Curie points are as high as 170. the rare earths push the surrounding O 2 ~ ions outward.14 14 0 N (K) Mmol (MB) Mef£ (MB) 5.3 A.5. Cd.05 1. Fe.1.-590 115 . where M represents a divalent ion such as Cr.105 -550 . or tetrahedral. Since o the radius of the rare earth ions is 1.9). etc. Ho.1 .85 1.20 1.3 MAGNETISM OF RARE EARTH IRON GARNETS Ferrimagnetic rare earth iron garnets (RIG) are oxides with the formula 3R2O3 -5Fe2O3.35 4. Mn. R 3+ .8 1. Various magnetic and crystal data are listed in Table 9.14 1. The Fe3+ ions occupy 24d.9 The experimental values. Cu. or R3Fe5O12. Material CrMn2O4 MnMn2O4 FeMn2O4 CoMn2O4 NiMn2O4 Cu 15 Mn 15 O 4 ZnMn2O4 CdMn204 MgMn2O4 LiMn2O4 0f (K) 0a (K) 65 -300 30-43 42 -564 390-395 85 . Lu.06 . or octahedral.0 and 1.15 3. The reason is that the chromites develop conical spiral spin structures at low temperatures. 1. MnCr2O4. The molar saturation moment is generally small.14-1. sites. which is much larger than that of the transition metal ions. respectively. however. For instance.

and loosely coupled R 3+ on 24c sites which point antiparallel to to the ferrimagnetic component of Fe3+. the R 3+ moments behave paramagnetically under the action of exchange fields produced by the Fe3+ spins. is given by where 7Fe is the total sublattice magnetization of Fe3+ ions on 24d and 16a sites.208 MAGNETISM OF FERRIMAGNETIC OXIDES Fig. and x ls the paramagnetic susceptibility of rare earth ions. H. Therefore. Neel explained this situation by the formulation given below: the sublattice magnetization of the rare earth site under the action of the external field. resulting in an N-type temperature dependence as shown in Fig.9.19 As explained by Neel. while the second . As seen in this graph. the sublattice moment of the R 3+ ions decreases sharply. the magnetic moments of the R 3+ ions are large.9.18 the magnetic structure of rare earth iron garnets consists of strongly coupled Fe3+ on 24d sites and Fe3+ on 16a sites. Generally speaking. so that the resultant saturation magnetization is parallel to the magnetic moment of R 3+ at low temperatures. Then the total magnetization is given by The first term on the right-hand side is the saturation magnetization. since only the exchange interaction between Fe3+ survives at high temperatures. Temperature dependence of molar saturation moment of various rare earth iron garnets. 9. as the temperature increases. Since the intrasite interaction between R 3+ ions is very weak. w is the molecular field coefficient. 9. the Curie point is almost the same for all RIGs.

276 6.28 5.859 6. so that — l/w > 0).533 6.110 0. This is because the spin S decreases. Looking at the first term. we can control the compensation point. This temperature is the compensation point.7 0 0f 0C (K) (K) 560 578 566 564 568 563 567 556 549 548 539 — — — 286 246 226 137 83 — — — 0a (K) — — — -24 -8 -32 -6 -8 — — — Lattice const.082 7. therefore. in the order Gd. the magnetic moment of R 3+ .5.9 and Table 9. it decreases inversely with the absolute temperature and it will satisfy the condition at some temperature (note that w < 0. Dy. This rather sophis- .74 -7.38 12. lattice constant.2 1. MB) 5. (A) Density (gem.653 6. 0C. etc.0 -7. As seen in Fig.14 -0.1 -1.436 6.78 16.235 6. so that ferromagnetic domains can be observed by means of the Faraday effect.110 0.110 0. This fact tells us that most of the orbital magnetic moment is quenched in this type of crystal.078 0.52 12. etc.0 5. g-factor.760 6. giving low magnetic losses even at high frequencies. we find that the saturation magnetization vanishes either when which is realized above the Curie point.2 0 5. It is also possible to introduce Si 4+ or Ge 4+ ions together with the same number of Ca2+ or Mg 2+ ions.0 18. Magnetic and crystalline properties of rare earth iron garnets.005 0.52 12. magnetocrystalline anisotropy.7 -5.169 6. As seen in Table 9. transparent.33 12. Tb.160 0. Thin garnet crystals are.13) is satisfied at a lower temperature.38 12.128 term is the incremental magnetization induced by external fields when the material is nominally saturated. saturation magnetization.5.M B ) 0 0. or to replace Fe3+ on 24d or I6a sites by A13+ or Ga3+.150 12. is rather smaller than the value expected from Hund's rule for most rare earths.5. so that the value of w decreases and the condition given by (9.07 R3+ Y Sm Eu Gd Tb Dy Ho Er Tm Yb Lu 7S (300 K. ' Mmol (OK.019 0. as deduced from the molar saturation moment at 0 K.48 12.7 -7.41 12.040 0.MAGNETISM OF RARE EARTH IRON GARNETS 209 19 20 Table 9.T) M(R3+ ) (OK.21 By such an introduction of non-magnetic ions. the value of ©c decreases monotonically with the increase in the number of 4/ electrons in R.9 15.43 2.170 0.2 16. Therefore no electron hopping occurs and the resistivity is very high.35 12.3 -1.29 12. or when Since x is tne paramagnetic susceptibility.45 12.2 10.3 -6. It is possible to mix several kinds of rare earth ions on 24c sites. The garnet-type oxides contain only trivalent ions. 9.150 0. with no divalent ions.946 7.3 ) 0.

Mg.13). etc.and B-site ions half and half. Sr 2+ or Pb 2+ . Ternary phase diagram of hexagonal ferrites. Fig. The crystal layers containing these large metal ions alternate with spinel layers containing M 2+ and Fe2+ ions with boundaries parallel to {111} planes of the cubic spinel structure. respectively.32A. The hexagonal oxides thus produced are classified as M-. and are therefore comparable to the radius of O 2 ~ (1.10. The result is a hexagonal lattice for the layered structure. Zn. 9. The 1:1 mixture of Fe2O3 and MO. The crystal structure of S shown in Fig. according to the structures and concentrations of the layers containing the large metal ions. denoted by S. Yand Z-types. is a common cubic spinel. 9. The hexagonal oxides are composed of spinel layers (S-type) and hexagonal Rand/or T-type layers. W-. The ionic radii of Ba2+. 1. M 2 + .4 MAGNETISM OF HEXAGONAL MAGNETOPLUMBITE-TYPE OXIDES Magnetoplumbite-type oxides contain 2+ ions such as Ba2+. where M represents Mn. It is seen that an inter-oxygen layer contains either B-site ions exclusively or A. Sr 2+ and Pb 2+ are 1. Fe.210 MAGNETISM OF FERRIMAGNETIC OXIDES ticated materials technology has been utilized in developing bubble domain devices (see Section 17.27 and 1.11 is simply a rotation of Fig.3).3 with the vertical axis perpendicular to (111) or an oxygen layer. Ni. Accordingly. which contain large 3+ metal ions such as Ba3+ on the substitutional sites in the oxygen layers (Figs.32 A). 9. BaO and MO.12 and 9.22 . 9. Figure 9. Cu.10 shows a ternary phase diagram of these hexagonal oxides as a function of composition expressed as a combination of Fe2O3. in addition to Fe3+ and divalent metal ions. 9. Co.43. these large metal ions occupy substitutional sites rather than the usual interstitial sites of the close-packed oxygen lattice.

Crystal structure of cubic spinel drawn taking [111] as the c-axis. The layers denoted S* and R* have the atomic arrangement obtained by rotating the layers S and R by 180° about the c-axis.12. 9.HEXAGONAL MAGNETOPLUMBITE-TYPE OXIDES 211 Fig. 9. The M-type oxide has the formula BaFe12O19 or BaO-6Fe 2 O 3 .10. Fig.11. 9. The small circles with arrows indicate magnetic ions and the directions of . which is indicated as M on the left-hand edge of the phase diagram in Fig. This oxide is a simple mixture of BaO and Fe2O3 and contains no MO. Fig. 9. Atomic arrangement of R-type layers. and R blocks containing Ba2+ and Fe3+. The crystal structure of the M-type oxide is shown in Fig.13. Atomic arrangement of T-type layers.14 as alternate layers of spinel blocks S. containing only Fe3+ metal ions. 9.

212

MAGNETISM OF FERRIMAGNETIC OXIDES

Fig. 9.14. Atomic arrangement of M-type crystal structure. (Modified from Fig. 37.4 in Smit and Wijn22.)

their spin magnetic moments. The numbers of circles are those per two chemical formulas. The magnetic properties of the M-type oxides are listed in Table 9.6. The values of saturation moment per mol formula are very close to the theoretical value, 20MB, for all the M-type oxides. The Curie points are about 450°C, and the saturation magnetizations at room temperature are nearly the same as those of spinel ferrites. The magnetocrystalline anisotropy is fairly large, so that some M-type oxides are used as permanent magnet materials (see Sections 12.4.1(d) and 22.2.2). The W-, Y- and Z-type oxides contain MO in addition to Fe2O3 and BaO (see Figure 9.10). The atomic arrangements of these oxides are shown in Figs 9.15-9.17. These structures contain R and/or T layers in addition to S layers. The W-type oxides are composed of alternate S and R layers as shown in Fig. 9.15. Their magnetic properties are listed in Table 9.7. By replacing some of the M 2+ ions by Zn 2+ , which occupy A sites as in cubic spinels, we can increase the saturation Table 9.6. Magnetic properties of M-type oxides.

Saturation magnetization 0K Room temperature Materials BaM PbM SrM CaM Na 5 La 5 M Ag5La'5M (emug" 1 ) (x4irX 1(T7 Wbrnkg' 1 ) 100 80 108 — — — (Memor 1 ) 20 18.6 20.6 — 21.5 — 47r/s (G) 7S X10 4 (T) 4780 4020 4650 — — — Curie point CO 450 452 460 445 440 + 10 435

HEXAGONAL MAGNETOPLUMBITE-TYPE OXIDES

213

Fig. 9.15. Atomic arrangement of W-type crystal structure. (Modified from Fig. 37.7 in Smit and Wijn22.) magnetization. The saturation magnetic moments per mol formula at OK are in fair agreement with the theoretical value calculated by adding the moments for the two S formulas with that of the M-type. The slight differences may be due to the mixing of M 2+ in the R-layers. The Y-type oxides are composed of S and T layers, the latter of which contains equal numbers of divalent ions with opposite spins (Fig. 9.16). It these ions were exclusively Fe 2+ , the spins would cancel, resulting in a molecular saturation moment equal to that of the two spinel formulas. The magnetic properties of various Y-type oxides are listed in Table 9.8, from which we see that the molecular saturation moments are mostly larger than the expected values. This shows that some M 2+ ions intrude into the T-layers. In this type of oxide, the introduction of Zn 2+ ions, which Table 9.7. Magnetic properties of W-type oxides. Saturation magnetization 0K Room temperature (emu g ~ l) 4 777S (G) Curie point ( x A v r X 1(T7 Wbrnkg' 1 ) (Memor 1 ) 7S X 104 (T) (°C) 97 98 79 108 104 27.4 27.4 22.3 30.7 29.5 3900 5220 3450 4800 4550 415 455 520 430 450

Materials Mn2W Fe2W NiFeW ZnFeW Ni 5 Zn 5 FeW

214

MAGNETISM OF FERRIMAGNETIC OXIDES

Fig. 9.16. Atomic arrangement of Y-type crystal structure. (Modified from Fig. 37.6 in Smit and Wijn22)

occupy the A-sites, causes an increase in saturation magnetization as is the case for other ferrimagnetic oxides. The Z-type oxides are composed of S-, R-, and T-layers, as shown in Fig. 9.17. The structure can be regarded as a superposition of M- and Y-types. As a matter of fact, the saturation moment per mol formula is about 30MB, which is approximately equal to the sum of those of the M- and Y-types (Table 9.9). The small difference may be due to the intrusion of M 2 + ions into R-layers, as in the case of W-type oxides. The magnetoplumbite-type oxides discussed in this section exhibit fairly large magnetocrystalline anisotropies, because of their low crystal symmetry (see Section 12.4.1(d)). Because of this characteristic, these oxides are used as permanent magnet materials, and are regarded as possible core materials for extremely high-frequency use (see Section 20.3). Table 9.8. Magnetic properties of Y-type oxides.

Saturation magnetization 0K Materials Mn2Y Co2Y Ni2Y Cu2Y Mg2Y Zn2Y (ernug" ) (x47rX 1(T7 Wbrnkg' 1 ) 42 39 25 28 29 72

1

Room temperature (MBmoP 1 ) 10.6 9.8 6.3 7.1 6.9 18.4 4T7-/S (G) 7S X 104 (T) 2100 2300 1600 — 1500 2850 Curie point (°C) 290 340 390 — 280 130

MAGNETISM OF OTHER MAGNETIC OXIDES

215

Fig. 9.17. Atomic arrangement of Z-type crystal structure. (Modified from Fig. 37.8 in Smit and Wijn22)

**Table 9.9. Magnetic properties of Z-type oxides.
**

Saturation magnetization 0K Room temperature Materials Co2Z Ni 2 Z Cu 2 Z Zn 2 Z Mg 2 Z (emug"1) (x4irX 1(T7 Wbrnkg" 1 ) (MBmorl) 69 54 60 — 55 31.2 24.6 27.2 — 24 4u-/s (G) 7S X 104 (T) 3350 — 3100 3900 — Curie point (°C) 410 — 440 360 —

The descriptions in this section are largely based on Smit and Wijn.22 For further details, this work should be consulted. 9.5 MAGNETISM OF OTHER MAGNETIC OXIDES In this section, we discuss the crystalline and magnetic properties of various oxides not previously described.

9.5.1 Corundum-type magnetic oxides

In addition to magnetite (Fe3O4) and maghemite (y-Fe2O3), (see Section 9.2), there

216

MAGNETISM OF FERRIMAGNETIC OXIDES

Fig. 9.18. Atomic arrangement of metal ions m a unit cell of 50:50 ilmemte-hematite solid solution.

are two well-known iron oxides, hematite (a-Fe2O3) and ilmenite (FeTiO3), both of which have the corundum-type crystal structure. Corundum is the name of the oxide AI2O3. In this crystal, the oxygen ions form a closed-packed hexagonal lattice with two-thirds of the octahedral sites occupied by metal ions. Figure 9.18 shows the positions of the metal ions in a unit cell of a 50-50 mol% mixture of ilmenite and hematite. Each of the metal ions is displaced by about 0.3 A either upward or downward along the c-axis. These small displacements are caused by the presence of vacancies on one-third of the octahedral sites. A combination of electrostatic and mechanical forces causes the metal ions to move towards the vacancies. The atomic arrangement in a-Fe2O3 is given by replacing all the metal ions in Fig. 9.18 by Fe3+. It has an antiferromagnetic spin arrangement, in which all spins on the same c-plane are aligned parallel, while the spins of the alternate planes, the A and B layers are aligned antiparallel to each other. The spin axis is parallel to the c-axis below 250 K, which is called the Morin point,23 while it rotates to the c-plane above this temperature, and at the same time produces a canted spin structure with weak parasitic magnetism through an antisymmetric interaction (Section 7.4). The atomic arrangement of ilmenite is obtained by replacing Fe3+ on the A layers in Fig. 9.18 by Ti4+, and Fe3+ on the B layers by Fe2+, so that all the A layers are occupied by non-magnetic Ti4+ ions (3d0), while all the B layers are occupied by magnetic Fe2+ ions, each with a moment of 4MB. This crystal has also an antiferromagnetic structure, in which spins on alternate B layers are aligned antiparallel. It is interesting to note that ferrimagnetic saturation magnetization appears in ilmenite-hematite solid solutions. The introduction of magnetic Fe3+ ions onto the B layers by mixing a-Fe2O3 into FeTiO3 may induce an antiferromagnetic interaction between A and B layers. At the same time, as seen from Fig. 9.18, the A and B layers are occupied by different numbers and different species of magnetic ions, which gives rise to a ferrimagnetic spin arrangement.24'26 Figure 9.19 shows the variation of saturation magnetic moment per mol formula as a function of the ratio of a-Fe2O3 in M 2+ Ti 4+ O 3 . The straight line represents the theory described above. The experimental values for the oxides with M = Fe are very close to this theoretical line.

MAGNETISM OF OTHER MAGNETIC OXIDES

217

Fig. 9.19. Saturation magnetization as a function of MTiO3 content for various MTiO3-Fe2O3 solid solutions.30

Natural rocks which contain this series of oxides exhibit the so-called self-reversed thermal remanence. When rocks of this kind are cooled in the Earth's magnetic field, the resultant remanent magnetization at room temperature is opposite to the Earth's field.28"29 The mechanism of this phenomenon has not yet been clarified. For more details the reader may refer to the review articles.27"30

9.5.2 Perovskite-type magnetic oxide

Perovskite is the name of a mineral with the composition CaTiO3. Replacing Ti by Fe3+, we have the ferrimagnetic perovskite-type oxide MFeO3, where M represents a large ion such as La 3+ , Ca2+, Ba2+ or Sr 2+ . The basis of the crystal structure is an NaCl-type lattice composed of O 2 ~ and M 3+ , and a small Fe3+ ion goes into an octahedral site surrounded by six O 2 ~ ions (Fig. 9.20). Replacing Fe3+ by Mn 3+ or Co3"1", we also have other perovskite-type oxides MMnO3 and MCoO3. These oxides are antiferromagnetic, but in solid solutions of La 3+ Mn 3+ O 3 and Ca 2+ Mn 4+ O 3 ; La 3+ Mn 3+ O 3 and Sr 2 + Mn 4 + O 3 ; La 3+ Mn 3 + O3 and Ba 2+ Mn 4+ O 3 ; and La 3+ Co 3+ O 3 and Sr 2+ Co 4+ O 3 ; ferromagnetism appears.31 Two examples are shown in Figs. 9.21 and 9.22, in which the broken lines are calculated by assuming that the magnetic moments of Mn 3+ (4MB) and Mn 4+ (3MB) are aligned ferromagnetically. In the composition range 20-40 Mn 4+ , the experimental points are very close to the theoretical lines in both cases. In this range the electrical conductivity becomes very large. Zener32 explained this phenomenon in terms of double exchange interaction: in this composition range, Mn 3+ and Mn 4+ coexist, so that conduction electrons carry

218

MAGNETISM OF FERRIMAGNETIC OXIDES

•"

Fig. 9.20. Crystal structure of Perovskite-type magnetic oxides.

electric charges in the common d band, thus resulting in high conductivity. Since conduction electrons keep their spins during itinerant motion, Mn ions align their spins parallel to those of conduction electrons through the s-d interaction, thus resulting in ferromagnetic alignment. This idea was formulated by Anderson and Hasegawa33 later. Different from the usual exchange or superexchange interaction, this double exchange interaction is proportional to cos(0/2), where 9 is the angle between the spins of two Mn ions. Therefore, if antiferromagnetic superexchange interaction acts in addition to double exchange interaction, spin canting is expected to result.34

Fig. 9.21. Variation of specific saturation magnetization of an LaMnO3-CaMnO3 series with change in Mn 4+ content.31 The broken line is a theoretical curve assuming ferromagnetic alignment of magnetic moments of Mn 3+ and Mn4"1'.

MAGNETISM OF OTHER MAGNETIC OXIDES

219

Fig. 9.22. Variation of specific saturation magnetization of an LaMnO3-SrMnO3 series with change in Mn 4+ content. The broken line is a theoretical curve assuming ferromagnetic alignment of magnetic moments of Mn3+ and Mn4+.31

Orthoferrite of the formula RFeO3 (R: rare earths) is also a kind of Perovskite-type oxide. The crystal structure is deformed slightly from cubic to orthorhombic. The spins of Fe3+ ions are aligned antiferromagnetically through a strong superexchange interaction, because the angle Fe3+-O-Fe3+ is 180°. The Neel point of this oxide is 700 K, which is quite high. Because of the orthorhombic deformation, an antisymmetric exchange interaction (see Section 7.4) acts between Fe3+ pairs, thus resulting in a spin canted magnetism with a feeble saturation moment of 0.05MB per mol formula. This material was used initially for bubble domain devices (see Section 17.3). As a result of the fact that the superexchange interaction through Mn3+-O-Mn3+ or Fe4+-O-Fe4+ is positive, the oxides BiMnO3,35 SrFeO336 and BaFeO337 are all ferromagnetic with Curie points of 103, 160, and 180 K, respectively.

Fig. 9.23. Crystal structure of Rutile-type oxides.

220 9.5.3

MAGNETISM OF FERRIMAGNETIC OXIDES Rutile-type magnetic oxides

Rutile is the name of the oxide TiO2. Its crystal structure is shown in Fig. 9.23. The crystal symmetry is tetragonal, with c < a. Replacing Ti by 3d transition metal ions, we have rutile-type magnetic oxides. A typical example is CrO2, which is ferromagnetic38'39 with Curie point 390-400 K and specific saturation magnetization of 1.23 X 10~4 Wbmkg" 1 (98emug~ 1 ) at 300K. It can be prepared either by heating Cr2O3 in a high-pressure oxygen atmosphere or by hydrothermal synthesis. This oxide is used as a magnetic tape material (see Table 22.4). MnO2 is another example of this type of oxide, but it is antiferromagnetic.

9.5.4 NaCl-type magnetic oxides

A typical example of this type of oxide is MnO, whose crystal and spin structure was shown in Fig. 7.3 as a representative antiferromagnetic oxide. Other similar oxides FeO, CoO, and NiO are all antiferromagnets. The only exception is EuO, which is a ferromagnet40 with a Curie point of 77 K. In this case the electronic structure of Eu is 4f 7 , which has no orbital moment, so that this material is often regarded as an ideal ferromagnet. PROBLEMS

9.1 Describe crystal and magnetic structures of spinel ferrites and discuss the variation of molar saturation moment by the addition of Zn2+ ions. 9.2 Describe the mechanism by which the compensation point appears in rare earth iron garnets. 9.3 Explain why ferrimagnetism appears in ilmenite-hematite solid solutions. 9.4 Explain why ferromagnetism appears in LaMnO3-CaMnO3 solid solutions.

REFERENCES

J. Smit and H. P. J. Wijn, Ferrites (Wiley, New York, 1959), p. 149. L. Neel, Ann. Physique [12] 3 (1948), 137. L. Neel, Proc. Phys. Soc. (London), 65A (1952), 869. E. W. Gorter, Philips Res. Kept., 9 (1954), 295, 321, 403. Y. Yafet and C. Kittel, Phys. Rev., 87 (1952), 290. Y. Ishikawa, /. Phys. Soc. Japan, 17 (1962), 1877. J. Smit and H. P. J. Wijn, Ferrites (Wiley, New York, 1959), p. 159. T. Tsushima, T. Teranishi, and K. Ohta, Handbook on magnetic substances (ed. by S. Chikazumi et al, Asakura Publishing Co., Tokyo, 1975), 9.2, p. 612, Table 9.3. 9. E. J. W. Verwey, P. W. Haayman, and F. C. Romeijn, /. Chem. Phys., 15 (1947), 181. 10. S. Chikazumi, AIP Proceedings, No. 29 (1975), 382. 1. 2. 3. 4. 5. 6. 7. 8.

REFERENCES

221

11. P. B. Braun, Nature, 170 (1952), 1123. 12. T. Tsushima, T. Teranishi, and K. Ohta, Handbook on magnetic substances (ed. by S. Chikazumi et al, Asakura Publishing Co., Tokyo, 1975), 9.2, p. 629, Table 9.16. 13. T. Tsushima, Y. Kino, and S. Funahashi, /. Appl. Phys., 39 (1968), 626. 14. T. Tsushima, T. Teranishi, and K. Ohta, Handbook on magnetic substances (ed. by S. Chikazumi et al. Asakura Publishing Co., Tokyo, 1975) 9.2, p. 630, Table 9.20. 15. G. Blasse, Philips Res. Kept., 18 (1963), 383. 16. T. Tsushima, T. Teranishi, and K. Ohta, Handbook on magnetic substances (ed. by S. Chikazumi et al, Asakura Publishing Co., Tokyo, 1975), 9.2, pp. 607-33. 17. S. Geller and M. A. Gilleo, Acta Cryst., 10 (1957), 787. 18. L. Neel, Comp. Rend., 239 (1954), 8. 19. F. Bertaut and R. Pauthenet, Proc. IEEE Suppl, B104 (1957), 261; R. Pauthenet, /. Appl. Phys., 29 (1958), 253. 20. S. Miyahara and T. Miyadai, Handbook on magnetic substances (ed. by S. Chikazumi et al., Asakura Publishing Co., Tokyo, 1975) 9.4.2., p. 667, Table 9.41. 21. S. Geller, Z. /. Kristgr., 125 (1967), 1. 22. J. Smit and H. P. J. Wijn, Fenites (Wiley, New York, 1959), pp. 177-211. 23. J. Morin, Phys. Rev., 78 (1950), 819. 24. Y. Ishikawa and S. Akimoto, /. Phys. Soc. Japan, 13 (1958), 1298. 25. R. M. Bozorth, D. E. Walsh, and A. J. Williams, Phys. Rev., 108 (1957), 157. 26. Y. Ishikawa, J. Phys. Soc. Japan, 17 (1962), 1835. 27. Y. Ishikawa and Y. Syono, Handbook on magnetic substances (ed. by S. Chikazumi et al., Asakura Publishing Co., Tokyo, 1975) 9.4.1, pp. 645-56. 28. T. Nagata, S. Ueda, and S. Akimoto, /. Geomag. Geoelect., 4 (1952), 22. 29. Y. Ishikawa and Y. Syono, /. Phys. Chem. Solids, 24 (1963), 517. 30. Y. Ishikawa, Metal Phys. (in Japanese), 6 (1960), 19; Progress on Phys. of Mag. (in Japanese) (Chikazumi ed. Agne Pub. Co, Tokyo, 1964), 329. 31. G. H. Jonker and J. H. van Santan, Physica, 16 (1950), 337; 19 (1953), 120; G. H. Jonker, Physica, 22 (1956), 707. 32. C. Zener, Phys. Rev., 82 (1951), 403. 33. P. W. Anderson and H. Hasegawa, Phys. Rev., 100 (1955), 675. 34. P. G. de Gennes, Phys. Rev., 118 (I960), 141. 35. F. Sugawara, S. lida, Y. Syono, and S. Akimoto, /. Phys. Soc. Japan, 25 (1968), 1553. 36. J. B. MacChesney, R. C. Sherwood, and J. P. Potter, J. Chem. Phys., 43 (1965), 1907. 37. S. Mori, J. Phys. Soc. Japan, 28 (1970), 44. 38. C. Guillard, A. Michel, J. Bernard, and M. Fallot, Comp. Rend., 219 (1944), 58. 39. T. J. Swoboda, J. Appl. Phys., 32 (1961), 374S. 40. B. T. Matthias, R. M. Bozorth, and J. H. Van Vleck, Phys. Rev. Lett., 1 (1961), 160.

10 MAGNETISM OF COMPOUNDS

In this chapter, we discuss the magnetism of compounds composed of electropositive 3d transition elements or 4/ rare earth elements combined with electronegative elements which belong to the Illb, IVb, Vb, VIb and Vllb groups. The electronegative elements which belong to these groups are listed in Table 10.1. Some elements such as Al, Ga, In, Tl, Sn and Pb, which belong to Illb and IVb groups, have metallic character, so that they could have been treated as intermetallic compounds in Section 8.4. However, since it is very hard to draw a sharp line between metallic and nonmetallic elements, it is reasonable to treat them in this chapter. We have already treated oxides in Chapter 9, so that oxides are omitted from this chapter. The compounds considered in this chapter include borides, Heusler alloys, MnBi, MnAl and various chalcogenides, all of which have useful engineering applications. We have limited the treatment to compounds with Curie points above room temperature, following a general rule applied throughout this book. In this chapter we discuss compounds in six categories: (1) (2) (3) (4) (5) (6) 3d-lIIb compounds; 3d-lVb compounds; 3d-Vb compounds; 3d-VIb compounds; 3 J-VII (halogen) compounds; rare earth compounds.

As a general rule, with an increase in the group number, the electrical properties of the compounds tend to change from metallic to semimetallic, then to semiconducting and finally to insulating; while with an increase in the period number, the atomic size increases so that the crystal tends to change from interstitial to substitutional. From the point of view of magnetism, the present classification based on the electronegativity of the elements may not be proper, but it has the merit of clarity. When a Table 10.1. Illb-VIIb Group elements with atomic number.

Period

2 3

Illb Group

5 Bk 13 Al 31 Ga 49 In 81 Tl

IVb Group

6 14 32 50 82 C Si Ge Sn Pb

Vb Group

7 15 33 51 83 N P As Sb Bi

VIb Group

8 16 34 52 84 O S Se Te Pb

Vllb Group

9

4 5 6

17 35 53 85

9 F Cl Br

I At

3d TRANSITION VERSUS Illb GROUP MAGNETIC COMPOUNDS 223

Fig. 10.1. Relationship between the atomic magnetic moment on an Mn atom in various magnetic compounds and the Pauling valence.1 compound includes more than one electronegative element, it is classified by the most electronegative element. There is no general guiding principle to interpret the variety of magnetic behavior in these compounds. The only clear feature is that the magnetic behavior is influenced by the covalency. Mori and Mitui1 showed that the magnetic moment of an Mn atom in various Mn compounds is well described as a function of Pauling valence, which is calculated from the atomic distance and coordination numbers, as shown in Fig. 10.1. They interpreted this result to show that electrons which contribute to the covalency have compensated spin pairs and make no contribution to the magnetic moments. This is the reason why the magnetic moment of an atom of one element can be different in different compounds, as seen in the following sections.

10.1 3d TRANSITION VERSUS Illb GROUP MAGNETIC COMPOUNDS 10.1.1 Borides Boron combines with transition elements M to form compounds of formulae M3B, M 2 B, M 3 B 2 , MB, M 3 B 4 , MB2, etc. All these compounds have metallic luster and conductivity, and are stable at high temperatures. The magnetic borides with Curie points above room temperature are listed in Table 10.2. If the saturation moment of

224

MAGNETISM OF COMPOUNDS

**Table 10.2. Crystal structure and magnetic properties of 3d-E compounds.4
**

Material Co3B Co2B Fe2B MnB FeB Co20Al3B6 Co21Ge2B6 Mn5SiB2 Crystal structure Fe3C Fe2B C16 FeB B27 Cr23C6 Cr^Cg Cr5B3 Curie point ©f (K) 747 433 1015 578 598 406 511 398 Magnetic moments per M atom Ms (MB) Meff (MB) 1.12 0.806 1.9 1.92 1.12 0.6 0.56 1.5 — — — 2.71 1.84 2.0 — 2.6

the transition element M in these magnetic borides is plotted as a function of the number of electrons in M, we have the curve as shown in Fig. 10.2,2"4 which is similar to the Slater-Pauling curve (see Fig. 8.12). The difference from the curve for compositions containing only metallic elements is that the curve for M 2 B is shifted to the left by one electron, and that for MB is shifted by two electrons, from the curve for the metallic alloys. This means that boron acts as electron donor which contributes two electrons per atom to the lattice. Other than this, boron has little influence on the magnetic properties of magnetic alloys. This is also the case for amorphous alloys which contain B or P, as will be discussed in Chapter 11. Atomic-scale investigations on borides have been exclusively made by means of NMR or Mossbauer experiments; neutron diffraction experiments are almost impossible because boron strongly absorbs neutrons. It was observed that the internal field of

Fig. 10.2. Saturation atomic magnetic moment of M atom in 3rf-B compounds with the formulas M 2 B and MB at 20K, as a function of the number of electrons in the M atom.3'4

Atomic arrangement of the superlattice Fe3Al and the Heusler alloy Cu2MnAl. 10. but its chemical properties are sometimes electropositive and sometimes electronegative. and is ferromagnetic below its Curie point of 750 K. as shown in Fig.3. 10.3d TRANSITION VERSUS Illb GROUP MAGNETIC COMPOUNDS 225 B in Fe2B has the large value of 2.46MB. Co. and the localized moment at a Cu atom is no more than 0.5MB. and the saturation moment per Mn atom is 3. On the other hand.Fe) are also ferromagnetic14 with Curie points 300-400 K.13 The /c-phase alloys with the general formula M 0 8 Mn 1 2 Al 2 (M = Cu.1MB.20MB at room temperature.1. the magnetic moment is concentrated on the Mn atoms.24 MAm' 1 (28. It was observed that Fe-Al alloys with compositions between the two superlattices have an antiferromagnetic exchange interaction.14MB. Ni. The superlattice Fe3Al has the unit cell shown in Fig. Neutron diffraction shows that Pel. The saturation moment per Mn atom is about 1. is paramagnetic.31MB per Mn atom.2 Al compounds Elemental aluminum is purely metallic. has a moment of 1. while the M atoms are nonmagnetic in all cases.5 This was interpreted6 to mean that the outer electrons of B are polarized through covalent bonds by the magnetized Fe atoms. 10.8"10 The superlattice Ni3Al is ferromagnetic below its Curie point of 75 K. .2). The alloy of composition Cu2MnAl is known as the Heusler alloy. which is surrounded by four Fe and four Al nearest neighbors. has 2. it is notable because it contains no ferromagnetic elements but nevertheless exhibits ferromagnetism12 in the ordered state. MnAl is a metastable compound and is ferromagnetic below its Curie point of 650 K.11 with an effective moment of 2. This material is used as a permanent magnet material (see Section 22. FeAl. Iron-aluminum alloys exhibit ferromagnetism in the Fe-rich composition range. while Fell.3.3. while NiAl and also CoAl are paramagnetic.2kOe). so that it forms various compounds.. The Curie point of this alloy is 610 K. 10. which is surrounded by eight Fe nearest neighbors.15 Fig. According to neutron diffraction measurements.7 Another superlattice.

good electrical conductivity.18 The face-centered tetragonal rj-phase with the CuAu-type ordered structure exists in the composition range 60-54.04 to 7. and have metallic luster.58 to 1.1. This suggests that the binding force is partly metallic and partly covalent.2 3J-IVb GROUP MAGNETIC COMPOUNDS 10.0MB and Meff = 2. It is ferrimagnetic below its Curie point of 690K. thus exhibiting ferrimagnetism.05MB.19 10. some of them have ferromagnetic Curie points.5-70 at% Mn.1 Magnetic carbides All of these carbides are mechanically brittle.78MB per Mn.3 Ga compounds Many ferro.16 There is also an e' -phase having the CuAu-type face-centered tetragonal lattice at low temperature in the composition range 72.1. so that it is rather ferrimagnetic. which are listed in Table 10. 0a.76MB. It is ferromagnetic below its Curie point of 210 K and has the moments Ms = 1. is a typical ferromagnetic carbide. This fact indicates that their spin arrangement is ferrimagnetic. The saturation moment extrapolated to OK is 0.0 at% Mn. and high melting points. fairly different from their asymptotic Curie points.2. while the effective moment is calculated from the linear part of the l/x~T curve is 3. This corresponds to a change in saturation moment of Mn from 1.02MB per Mn. Cementite. 10.0-68.23 the C atoms tend to go into small octahedral sites rather than large tetrahedral sites in the body-centered cubic iron.5 at% Mn.226 MAGNETISM OF COMPOUNDS 10.4 In compounds The compound Mn 3 In has the /3-brass type crystal structure.5MB to account for its ferrimagnetic arrangement. The excess Mn atoms align their magnetic moments antiparallel to those of the other Mn atoms.48 X 10"5 \Vbmkg~ 1 (56.1MB.3 together with their magnetic properties.0 to 59. It is weakly ferrimagnetic below its Curie point at 583 K.20 There are Heusler-type ferromagnetic compounds Cu 2 MnIn 21 (@f = 500K) and Ni 2 MnIn 22 (@f = 323K). but the absolute value of the moment was estimated to be 1. As seen from this table. It is ferromagnetic below its Curie point of 470 K. The l/x~T curve deviates downward from a linear relationship as the temperature is lowered from high temperatures to the Curie point. Fe3C. Therefore the saturation magnetization increases from 7.. There are many other ferromagnetic carbides. 9 f . The saturation magnetic moment extrapolated to 0 K is 0. It was found that the internal field of the Fe atoms that are nearest neighbors of the octahedral C atoms is reduced from .or ferrimagnetic phases have been found in the Mn-Ga series. According to a Mossbauer experiment by Moriya et a/. The ordered hexagonal s-phase exists at high temperature in the composition range 72.5 emug' 1 ) and the Curie point decreases from 640 to 605 K as the excess Mn content decreases.17 The f-phase has a -y-brass type cubic lattice at the composition 62 at% Mn.

0.) Cu2MnAl (Heusler) Curie point (K) 823 373 985 Magnetic moments per magnetic atom Ms (MB) Meff (AfB) 2.54). For further details. to a weak helimagnetism. beyond which it forms a number of silicides.05. and that the amount of reduction is proportional to the number of nearest-neighbor C atoms. 10.4.70 3. magnetic atoms occupy crystallographically different lattice sites and their magnetic moments are different from each other.78 1. this reduction rate is almost the same for all compounds in the Fe-C system.1. Fe.2.0. This result agrees with the prediction by Bernas et a/. and finally to semimetallic. to a peculiar Pauli paramagnetism. Table 10.24 for the compounds Fe 3 C 1 _ x B x (0 <x < 0.1.4.2.0 4. Crystal structure DOn hex.40. monoc. Moreover. The MSi-type compounds retain the same cubic crystal structure (B 20 type) when M is Cr. 3.89 5.4 Materials Fe3Si Fe5Si3 Co2MnSi .2 Magnetic silicides As mentioned in Section 8. and even when these metallic elements are mixed as solid solutions.55 0. the value in pure iron. or Ni. Mn. As the electron concentration of M increases from Cr to Ni.20 1. a recent review25 (mainly on NMR investigations) should be consulted. and finally to diamagnetism.4 Crystal structure Mn3Si Mn5Si3 (hex. 353 K perov.3. the electrical properties change from metallic to semiconducting.75 1. the magnetic properties change from a special diamagnetism.75(Co).ZnC J Co2Mn2C Curie point ®f (K) 483 653 520 368 733 Asymptotic Curie point ®a (K) 233 246 723 Magnetic moments per magnetic atom Ms (MB) Meff (MB) Note 1.57(Mn) — 2. Materials Fe3C Fe2C Fe2C Mn. fperov. The ferromagnetic silicides are listed in Table 10. At the same time. Crystal structure and magnetic properties of ferromagnetic 3 J-Si compounds.72 1.4 1. Co.55 (ferr°~«r^ \ trans.3d-lVb G R O U P MAGNETIC COMPOUNDS 227 4 Table 10. In these compounds. Crystal structures and magnetic properties of 3d-C compounds. the Fe-Si system forms a solid solution in the Si-poor composition range. to a weak ferromagnetism.

4 Sn magnetic compounds Sn forms a number of compounds with 3d transition elements.4.2. 10.30 10.28 By replacing Al by Sn in the Heusler alloy Cu2MnAl (see Section 10.228 MAGNETISM OF COMPOUNDS 10. thus .2. which is ferromagnetic below its Curie point of 612K. It is interesting to note that the introduction of only one N atom in a unit cell changes the weak antiferromagnetism to ferromagnetism. fee iron is antiferromagnetic.79MB per Mn atom. Ni2MnSn has a Curie point of 342 K and Ms = 3.3 Ge magnetic compounds In the Fe-Ge system. MnNiGe. as shown in Fig. We see that one N atom occupies the body-centered site in face-centered cubic iron. Fe167Sn is hexagonal (B 82 type) and ferromagnetic. 360K. we have ferromagnetic Heusler-like alloys. so that it tends to go into the interstitial sites.26"29 10. there are the /3 phase (hexagonal) and the rj phase.3. As is well-known. Pd2MnSn has a Curie point of 189K and MS = 4.31 Another possibility is that the expansion of the lattice caused by the introduction of N atoms may reduce the overlapping of 3d wave functions between Fe atoms. Thus the hexagonal compounds near Fe3Sn are ferromagnetic below the Curie point of 743 K. thus creating electron vacancies in the Fe band.23MB per Mn. respectively.81MB.3 3d-Vb GROUP MAGNETIC COMPOUNDS 10.69MB per Mn. 770K. with a Curie point as high at 761 K. A possible interpretation is that the N atom acts as an acceptor of electrons from Fe. Fe3Sn2 is a monoclinic compound. but the saturation moment decreases abruptly with increasing Ge content. the s^ phase (cubic) has a Curie point of about 760 K.90MB and Meff = 2. Cu2MnSn has a Curie point higher than 500K and Ms = 4.11MB per Mn atom. Most of the nitrides listed in Table 10. Mn 1 4 5 _ 2 0 Sn is ferromagnetic below a Curie point of about 260 K with saturation moment per formula unit of about 2MB. respectively. The compounds FeNiGe.1).1 Magnetic nitrides Ferromagnetic nitrides are listed in Table 10. and have magnetic moments Ms = 1. composed of low-spin-state iron atoms.5 have the face-centered cubic structure of the Fe 4 N type. Its Curie point and the saturation moment are reported by different authors to be 553 or 583 K and 2. both of which are ferromagnetic.2MB per Fe atom. Materials containing even fairly large amounts of nitrogen retain a metallic luster and have magnetic properties qualitatively the same as the nitrogen-free material. For example. and Mn 34 Ge are ferromagnetic below their Curie points. and 870K.27MB per Fe atom.5 with their magnetic properties.10 or 1. Co2MnSn has a Curie point of 811K and Ms = 4. The nitrogen atom is small. there are a number of phases around the composition Fe3Ge: the e phase (hexagonal) compound has a Curie point of 640 K and a saturation moment of 2. NiCoSn is ferromagnetic below a Curie point higher than 830 K. In the vicinity of Fe2Ge. similar to the Ge compounds.

31 Lattice type fee fee bet fee fee fee fee fee hep Curie point (K) 738 761 ca.2 MB for pure iron.8MB as compared to 2. are about 3. 10.88 (mol) 3.0MB per formula unit.4. In fact.2 Magnetic phosphides There are three types of phosphides: MP. It was discovered by Kim and Takahashi32 that metallic Fe films evaporated in a nitrogen atmosphere have much higher saturation magnetic moment than pure Fe: 2. M 2 P and M3P. but still there is a possibility that this effect is caused by a lattice distortion or expansion.5.5 (Fe) suppressing antiferromagnetic interaction.6 A. . Fe-Mn-C and Fe-Mn alloys.15 1. Fe 18 Ni 02 P has ©f = 376K. CoMnP has @f = 583K and Ms = 3.-0.6-2.0MB per formula.90 2. 10. Many M 3 P Fig.02 (mol) 2.52.tC. which exhibit low-spin antiferromagnetism.98 0. For more details on magnetic nitrides a number of reviews31"34 may be consulted.-0. Crystal and magnetic properties of magnetic 3d nitrides. They ascribed this result to the appearance of the compound Fe8N.8 A. while that of Fe4N is much larger.3. FeMnP is ferrimagnetic below @f = 320 K.201 (300 K) 2.14 (mol) 3.6-2.8 0.t Fe3NiN Fe3PtN Fe2N78 Magnetism ferri ferro ferro ferri ferri ferro ferro ferro ferro 1.15 7.479 7. Crystal structure of Fe4N-type compounds.98.3d-Vb GROUP MAGNETIC COMPOUNDS Table 10. MnP has a screw spin structure below 50 K which has been the subject of many investigations. 573 850 899 743-865 1033 640 398 Average Ms (MB) Sublattice Afs (AfB) 229 Compound Mn 4 N Fe4N Fe8N Mn 4 N 75 C 25 Mn 4 N 5 C 5 Fe4N1l.7 (OK) 9. 3.35 Some of the M 2 P type solid solutions containing different metals are ferromagnetic above room temperature. Thus Fcj 2 Co 08 P has the Curie point 0f = 450 K and saturation moment MS = 2.5. the lattice constants of fee Fe-Ni-Cr.

3. 10. 10. MnAs exhibits an interesting magnetic behavior: on cooling.4 120 79 145 Compound Fe 2 4 Mn 6 P Fe3P ' Fe2 25Ni75P Fe 15 Ni 15 P Fe 24 Co 6 P Ms (MB) — 1.35 . (K) 680 716 525 320 670 a (emug" 1 ) x47rX 1(T7 \Vbmkg~ 1 34 155.3 Magnetic arsenides There are many magnetic compounds which have the NiAs-type crystal structure shown in Fig. For further details on magnetic phosphides. This curve is quite similar to the Slater-Pauling curve for 3J alloys (see Fig.6.35 Curie point 0. The saturation moment of M in M 3 P is plotted in Fig. 8. This may be due to a transfer of some electrons from the P atoms to the matrix. but slightly shifted to the left. Magnetic properties of M3P-type compounds. it Fig.84 — — — type compounds are ferromagnetic.6. 10.5.2) and also to the amorphous alloys containing B and P (see Chapter 11).5 as a function of the number of electrons in the M atom. the reviews by Watanabe and Shinohara34 and Hirahara35 should be consulted.230 MAGNETISM OF COMPOUNDS Table 10. This situation is similar to the case of borides (see Fig.6.12). 10. as listed in Table 10. 10. and comparison with the Slater-Pauling curve. Saturation moment of M in M 3 P as a function of the number of electrons in the metal atom M.

In Cr-rich MnSb-CrSb solid solutions. Crystal structure of NiAs-type compounds (unit cell indicated by heavy lines).5 Magnetic bismuthides MnBi has the NiAs-type crystal structure. 10. with saturation magnetization 1.38'41 Crystal type NiAs NiAs CaF2 CaF2 CaF2 CaF2 Cu2MnAl Ni.9 1.3.7).0 4. This phenomenon was explained in terms of the exchange inversion.6 3. ferrimagnetism is realized at low temperatures and antiferromagnetism appears at high temperatures (Fig. undergoes a first-order magnetic transition at 313 K from paramagnetism to ferromagnetism.In Curie point 0f (K) 586 313 490 750 500 470 410 830 Magnetic moments (MB) MsatOK Afeff 3.0/formula Compound MnSb MnAs05Sb05 CoMnSb NiMnSb PdMnSb Ni 16 MnSb Ni 20 MnSb NiCoSb . which is stable below 633 K and exhibits Table 10.5 2.9 1.2 0.3.7. Crystal and magnetic properties of magnetic antimonides.6 1.7. 10.3d-Vb GROUP MAGNETIC COMPOUNDS 231 Fig.23 2.37'8 10.76 X 10~4 Wbmkg" 1 (= 140 emu g"1) at OK.4 Magnetic antimonides Magnetic antimonides are summarized in Table 10.6. which is caused by a combination of a distance-dependent exchange interaction and a spontaneous lattice deformation.0 1. 10.

and an average saturation moment per Fe atom of 0. The Curie point determined by extrapolation is 750 K.^CrSb)^42 ferromagnetism with a saturation moment of 3.6) and its stoichiometric compound has antiferromagnetic spin ordering. or Fe7S8. which is a natural mineral. Magnetic transition points as a function of composition x in (MnStOj. The compound with x = 0.1 is also ferrimagnetic. 10. 10.4. pyrrhotite. but its saturation magnetization disappears once again on cooling to 483 K. from which we see that the saturation magnetization disappears abruptly on cooling to 150 K. has a Curie point @{ = 578K. has the composition Fe^S (x = 0-0. The compound with x .28MB.8 shows the temperature dependence of saturation magnetization for CrS117.93MB.46 A detailed description is given in the review.232 MAGNETISM OF COMPOUNDS Fig. thus producing a ferrimagnetic spin arrangement. For further information on this topic the review article45 should be consulted.4 3d-Vlb GROUP MAGNETIC COMPOUNDS 10.47 .95MB per Mn atom at 0 K.1 Magnetic sulfides The iron sulfide FeS has the NiAs-type crystal structure (see Fig.125. Similar magnetic behavior is observed also for the magnetic sulfides Cr^^S. Figure 10. an effective moment Meff = 5.7. However.0.43 Magnetic writing of patterns was first achieved on evaporated thin films of MnBi.44 10.2) with the vacancies located in alternate c-planes.

NiS2 is semiconducting and highly resistive.9. Temperature dependence of magnetization of CrSj 17. which is used for heating elements. 10. together with the compounds with Se or Te which will be treated later. The crystal structure of this compound is shown in Fig. The solid solution with NiS2 exhibits antiferromagnetism. The magnetic properties also change: FeS2 is paramagnetic but its solid solution with CoS2 becomes ferromagnetic.48 .3d-Vlb GROUP MAGNETIC COMPOUNDS 233 Fig. Some of the sulfide spinels are ferrimagnetic above room Fig. The MS2 compounds are known as pyrites. As M changes from Fe to Co. Crystal structure of pyrite-type compounds MX2. the electrical properties change: FeS2 is metallic but the resistivity is fairly high.9. and CuS2 is again metallic. S forms the spinel-type compounds A 2+ B 2 + S 4 . CoS2 is more metallic and its resistivity is as low as that of Nichrome.8. and their magnetic properties have been extensively investigated. This situation tells us that spin correlations in these compounds affect the electronic structure pronouncedly. These compounds belong to the chalcogenide spinels. 10. Several reviews48'51 are available on this topic. 10. Ni and Cu in increasing order of electron number. Similar to O.

In fact.2MB per mol formula unit.4. provided no evidence for such localized magnetic moments.57 Greigite is ferrimagnetic below the Curie point @f = 606 K. CrI2 and TiNiF3. The reason for this behavior has not yet been clarified. There are ferromagnetic halides such as RbNiF3.375. and Cr2Te3 are all ferromagnetic. K2CuF4. with Mef{ = 5. which are similar to the magnetic sulfides: Fe7Se8 is ferrimagnetic below the Curie point @f = 449 K and has average saturation moment per Fe atom of 0.54'55 The saturation moment per formula unit is 5MB. They have a fairly large magnetoresistance effect (see Section 21.2 Magnetic selenides There are many magnetic selenides. Since this material has a high electrical conductivity. so that they have saturation moment 6MB per mol. Fe3Se4 is ferrimagnetic below 314K. which corresponds to magnetite Fe3O4.1. 9. which may be explained as a difference between the moment of 2Cr3+ or 3MB X 2 = 6MB. CuCr2Se4 (@f = 460 K). The tellurides Cr7Teg.32MB. Neutron diffraction. CuCr2S4 (0f = 420K)52'53 is a normal spinel in which Cu2~ is on the A-site while Cr 3+ is on the B site. which is the ideal value.74A. 10. Fe3S4 remains cubic down to low temperatures without any phase transition. Cr3Te4.5 K) and HgCr2Se4 (@( = 120K) are chalcogenide spinels. so that most of the chalcogenide spinels are semiconducting. CrBr3.2). and its saturation magnetization is 2.5 3d-VIIb (HALOGEN) GROUP MAGNETIC COMPOUNDS Most of the halides with 3d transition elements are antiferromagnetic.234 MAGNETISM OF COMPOUNDS temperature.58MB. Therefore the interstitial sites are large enough to accept metallic ions without any distortion of the lattice. making an angle of 90° (see Fig. CdCr2Se4 (0f = 129.58 This material is also piezoelectric.43 Magnetic tellurides CrTe is ferromagnetic below the Curie point 333 K. which is significantly larger than that of O 2 ". For more details. Cr5Te6. 1. however.60'62 10.32 A. This parallel alignment is caused by a positive exchange interaction through the path Cr-Se-Cr. so that it retains metallic conductivity at all temperatures. and that of Cu2+ or 1MB.60"62 10. as explained in Section 7. The mineral Fe3S4 is called greigite. They are representative magnetic semiconductors and their resistivity changes several orders of magnitude at their Curie points. the w-parameter of Fe3S4 is 0.59 The bonding in chalcogenide spinels has more covalent nature than in oxide spinels. The chalcogenide spinels TiCr2Te4 and CuCr2Te4 are both ferromagnetic below their Curie points of 214K and 365K. The latter two are ferromagnets with parallel alignment of Cr3+ spins (3MB).56 One of the reasons is that the ionic radius of S 2 ~ is 1. its magnetic properties may be interpreted on the basis of band magnetism.5). respectively. but their . a number of reviews60'62 should be consulted. In contrast to Fe3O4.

Yb. A part of the chalcogen X in a chalcogenide spinel CuCr 2 X 4 (X: S. which has attracted much academic interest.RARE EARTH COMPOUNDS 235 Curie points are all below room temperature. Concerning this topic. However. Hirakawa63 and Urya and Hirakawa64 should be consulted. Se) can be replaced by a halogen Y.61 10. in which part of the Cu2+ is changed to Cu1+.66 Fig. many ferromagnetic rare earth compounds have Curie points below room temperature. In the limit of x -> 1.10. which have Curie points of 340 K and 260K. This fact indicates that vacancies in the 3d band.6 RARE EARTH COMPOUNDS All Laves compounds RA12 (R: rare earths) are ferromagnetic. The resultant CuCr 2 X 4 _. Crystal structure of R2Fe14B-type compounds6' and magnetic moments of individual atoms as determined by neutron diffraction. except for those containing only nonmagnetic R = La. many magnetic halides exhibit one. The saturation moments are slightly smaller than Hund's values.65 Generally speaking. and Lu. Therefore they have no engineering applications. t Y c is called a chalcogenide halide spinel. thus reducing vacancies in the conduction band and also decreasing resistivity.or two-dimensional spin ordering. respectively. The maximum Curie point 175 K is realized at R = Gd.69 . 10. which contribute to conductivity. contribute also to the exchange interaction. Exceptional cases are the Th3P-type compounds Gd 4 Bi 3 and Gd4Sb3. and at the same time the Curie point decreases abruptly. resistivity increases abruptly.

Mitsui.82 8. Some of the anisotropy fields.3 Ha (MAirr1) 3. N. 10.73 7. Mori and T. //a (see Section 12.236 MAGNETISM OF COMPOUNDS Table 10.82 8.79 8.75 8. J.8.96 11.3 ) 7.0 18. and these Fe groups are separated by B-Nd layers.98 /8 (T) 1.69 We see that not only Fe atoms but also Nd atoms have fairly large saturation magnetic moments. Crystal and magnetic properties of R2Fe14B compounds. C.02 8.81 7. /. The compound with R = Nd is the main constituent of the Nd-Fe-B permanent magnet (see Section 22.25 12.1 @f (K) 424 564 585 612 661 639 602 576 554 541 565 Other exceptional cases are the R2Fe14B-type compounds.86 0. 3. are also extremely large.80 8. P.77 8. 463.2 Describe the relationship between the period number and the crystal and magnetic structures of magnetic compounds.7 10 12 basal 6.7 12.2.28 Ms (MB mol) 22.8.74 8.6 25.77 8.04 Density (gem. all of which are aligned ferromagnetically. Ark.8 17. J. Rend.33 0. Fys.68 From this table we see that the Curie points of these compounds are all fairly high and the saturation magnetizations are much higher than ferrites.16 1.93 1..24 12.43 1. The Curie point of this compound was raised by introducing such B atoms. .75 8. N. 2.1 Describe the relationship between the electronegativity of electronegative ions and the electromagnetic properties of magnetic compounds. Myers.86 0. Phys. 25 (1968).05 12.09 12. 82. M.15 12. 10. Cadeville and A.93 8.65 0.95 12.24 8.11 12.3 32.10.77 (A) 12.64 0. 20 (1961). 255 (1962).3 12.68 PROBLEMS 10.10 shows also the saturation moments of individual atoms determined by neutron diffraction.2).09 1. The crystal structure is tetragonal (P42/mnm space group)67 as shown in Fig.74 8.99 11.00 11. Soc.05 8. REFERENCES 1. Japan.7 29.68 Lattice constant a c Compound Ce2Fe14B Pr2Fe14B Nd2Fe14B Sm2Fe14B Gd2Fe14B Tb2Fe14B Dy2Fe14B Ho2Fe14B Er2Fe14B Tm2Fe14B Y2Fe14B 8.1 28 25 20 basal basal 3.2).85 7. The atomic arrangement in this lattice is also very interesting. 3391.57 1. Lundqvist and A. Compt.47 7.1 21.55 7.1 26.7 17. There are cr-phase-like Fe groups composed of distorted hexagons. P.13 6. The crystal and magnetic properties of R2Fe14B-type compounds are listed in Table 10. Myers. Figure 10.

Shinohara. Bean and D. p. 1975) 8. 40. Soc. Tokyo. Felcher. Tsuboya and M... Mag. 1. 447. /. /. 28. 410. 385. Tokyo. Soc. Phys. 114 (1959). Ohoyama. T. Fig. 352.. 155. K. I. Fujita. p. p. Chikazumi et al. Wiener and J.4. Lett. /. Japan. 13 (1958). Chikazumi et al. 1975) 8.28. K. R. Phys. 17 (1962). 1427. H. Kanematsu. P. H. 549. 543. Japan Metal Ass. B. R. R. Nagase. Asakura Publishing Co. Table 8. 16 (1961). 1969). Phys. Tables 8. and T. by S. by S. 1975) 7. Japan. Tsuboya and M. 483. by S. Handbook on magnetic substances (ed. 114 (1959). Soc. Chem. New York. Pigott. Japan. Watanabe and T.4. 20 (1972). Moriya. 8. T. Mekata. 16 (1961)... 20 (1965). Hirahara. Soc. Phys. Japan Metal Ass. 33. Arrott. Materials (Wiley. Chikazumi et al. and C. Phys. /. K. 29 (1958). 18 (1963). Handbook on magnetic substances (ed. Solids. Tokyo.. I. and R. Campbell. 1663. H. Colloq. 18 (1963). Sato and K. Sato and A. 6 (1958). Ito. P. P. 125. Phys. Appl. Phys. Rev.) (in Japanese) 7 (1961). Asakura Publishing Co. Handbook on magnetic substances (ed. Aoyagi and M. 24 (1963). Nihon Kinzoku Gakkaiho (Kept. /. /. M. Y . (ed. Japan. 1. 143.. H. Kanematsu. Phys. 25. Nakagawa. Wilkinson.6. R.4. Handbook on magnetic substances (ed. F. T. Subst. Phys. Chikazumi et al.. Adachi. Arrott. 1257. 433. Sugihara. 30. H. 26. 126 (1962). 20. Sugihara. Berger. Soc. Kinzokubutsuri (Metal Phys. 11. /. 1072. Phys.. 1975) p. and K. 8. 5.. 17. K.) (in Japanese) 7 (1972). 10. Asakura Publishing Co. Solids. Rodbell. Lab. H. El. 15 (1960).5. Takahashi. S. 515.40.. Asakura Publishing Co. C. 172. 335.\ 11 (1972).. and H. 24 (1968). Fujita. de Phys. M. Kotaibutsuri (Solid State Phys. Soc. 28 (1967). Watanabe. 13.2. I. Rev. Tebble and D. Kittel. and A. Suppl. Phys..33. J. Takahashi. J. Cable. Tokyo. (1966). Rev. K. /. 8. by S. 20 (1965). Rev. C. Mag. 23. Watanabe. 520. Sugihara. Kotaibutsuri (Solid State Phys. H. S. Shinohara. 6. W.) (in Japanese) 7 (1968). 12 (1977). and M. 16 (1961). Soc. A. 540. and M. Metals. Phys. Hasegawa and I. /. Coles. Phys. 29. 17S B-I (1962). /. Soc. Tokyo. and K. H. Chem. Asakura Publishing Co. T. 120 (1960). 24. /.4. 38. 15. 492. Soc. A196 (1949). 34. Asakura Publishing Co. Japan. Solids. 12. Tsuboya and M. G. Asanuma. Ohoyama. 39. Handb. Sato. Soc..3. Sugihara. S. 60. 571. 152. Adachi. Chikazumi et al. Phys. Tokyo. Japan.REFERENCES 237 4.1. Y. K. CI Suppl. E. . 93. Craik. G. Japan. Phys. Yasuoka. Kimura. Ohoyama. H. G. 525. A. Phys. 1534. Kono. I. Handbook on magnetic substances (ed. 1975) 8. 41. /. Abe. Myers. M. 664. G. Ohoyama and K. 21. H. W. 32. Ann.4. Proc. Soc. Watanabe. 605. Appl. O. by S. 17. 908. Suzuki. 19. 104. Sato and A. Rev. T. Phys. 22. 170. J. T. 21 (1966).) (in Japanese). Endo. 35.. 18. 16 (1968). M. 14. 17 (1962). Japan. A. Nihon Kinzoku Gakkaishi (J. H. Tokyo. Fruchart. Sci. Phys.. 1444. I. H. Tsuboya. Soc. W. Terada. Japan. Chem. 9. 32 (1971). Feb. and Y. RITU. A18. Heusler. 1420. J. Soc. 1096. 19 (1934). 31. Phys. 27. Kanematsu and T. Chem. /. Japan. Shull. Yasukochi. Phys.. Chikazumi et al. Japan. p. Hume-Rothery. 38. Sugihara.31.. by S. K. 37. 236. T. Kept.. Tsuboya and M. /. Bernas.. Shinohara and H. 1875. Japan. 1092. (1955). H. 1975) 8. 77. Maeda. Yasuoka. 36. 3. Nathans. Roy. 18 (1963). 16 (1961). 16. Kim and M. 17 (1962). Phys. 371.. Hirai. 7. p. 34 (1973).. Sato and K. K. Takada. Phys. E. p. /. Katsuraki. Arrott and H. H.

14. . 539. Matsuura. and K. IEEE Trans.. p. Japan. Ogawa. Foster. Chikazumi et al. 607. 43. 11. Handbook on magnetic substances (in Japanese) (ed. 12 (1957). Handbook on magnetic substances (ed. M. Sagawa.2. Y. (Nottingham. 49. C. Chem. Methfessel. M. Tsuya. and W. 688. C. Yamagushi. Rev. Hirakawa. 486. Solid State Phys. 1181. Int. and E. R.. T. 24 (1969). /. Holtzberg. Miyatani. 513. Con/.. S. 47. F. Nagasaki. 251. 5 (1970). Yamamoto. Yelon. Pinkerton. S. Metal Phys. Mag. F. 104 (1956).. Phys. R. Chem. 29 (1974). S. R.. Buturi (in Japanese). Appl. Roberts. Morrish. Phys. and A. Tsubokawa. Suits. F. and B. Harder. 50.. 50 (1972). Maeda. M. M. 66. Res. J. Urya and K. N. 62 (1968). Yuzuri. 60. Adachi. J. 65. Z. Li.. Phys. B.. Tokyo. (in Japanese) 4 (1958). and F. J. Asakura Publishing Co. J. p. Buturi (in Japanese). Hahn. Coey. by S. Kelley. and S. K. Lotgering.. 57. 11 (1976). McGuire. Phys. K. by S. B. 67. H. Rev. 64. 48. /. 44. Wojtowicz. Appl. 441. D.. Mag. H. Solids..6. Buturi (in Japanese). 1033.238 MAGNETISM OF COMPOUNDS 42. T. D. Miyatani. Sekizawa. 3.. 57 (1984) 4100. and J. 25 (1970). 4176. J. by S. 56. Japan. 557. 63. 101. and J. Hiraga. 46. MAG-5 (1969). (in Japanese). K. 62. J. Tsubokawa.. S. K. K. S. H. Sci. Williams. G. Solid State Phys. Can. Watanabe. 59. Tokyo. 54. Colominus.. K. Hirone. 52. E. Asakura Publishing Co. Rev. 69. Soc. H. Inst. T. 518. Croat. 153 (1967). Handbook on magnetic substances (in Japanese) (ed. 55. 10 (1975). p. 140. 12 (1977). /. 45. /.2. 2313. S. White. Phys. Phys. Phys. Asakura Publishing Co. G. 28 (1957). 558. I. Adachi. Solid State Phys. /. H. Givord. Phys. Yuzuri. H. Hirakawa. Maeda. 68. 1964). C. and N. K. 1083. Chem. /. Yuzuri. Phys. Tokyo. M. 42. F. Chikazumi et al. Lehmann. Chikazumi et al. 1975) 8. M. Tasset. Fujimura. 897. Spender. M. Appl. I.. Mag. 28 (1967). 1584. 657. Tsuya. Solid State Phys. S. Hirone. H.. 51 (1980). Uda. 58. (in Japanese). Soc.4.. S. 533. 1975) 10. de Lorent. 283 (1956). Phys. H. 138. Phys. W.. F. MAG-20 (1984).. 707. Ogawa. M. N. 385. Appl. IEEE Trans. Nozaki. J. 28 (1973). Buturi (in Japanese). 840. Herbst. C. P. Sherwood. W. J. 1975) 8. 61. Phys. 35 (1964). Proc. and M. Papers. B29 (1984). 51. 11 (1956). 53. Robbins. (in Japanese). anorg.

There is another group of materials. the amorphous state thus obtained is changed to a crystalline state by heating above a temperature called the crystallization temperature. especially technical magnetization processes. For instance. etc. almost all results on transition-metal amorphous alloys have been obtained from samples made by rapid solidification. C. and may be produced by relatively simple manufacturing processes. by which various properties are changed substantially even though the amorphous structure is retained. When a beam of monochromatic X-rays is scattered by such an amorphous material. These changes are caused by two related but separable processes: diffusion and structural relaxation. there is no well-defined diffraction pattern. and P. rapid quenching. amorphous materials. isotropic (no directional properties). as in the case for crystalline materials. electroless plating. There are several ways for preparing amorphous materials: evaporation onto a cold substrate. we treated metals. it is usually necessary to add 10-20% so-called metalloid elements. In order to stabilize 3d metal-base amorphous materials. the preparation of a perfect single crystal without any imperfections requires extremely high technology. Ordinary glass is a representative example of an amorphous material. However. It is very interesting to note that completely perfect single crystals and completely random amorphous materials both provide us with mesoscopically homogeneous magnetic media.11 MAGNETISM OF AMORPHOUS MATERIALS In Chapters 8-10. an amorphous form of matter might produce a special type of magnetism. Second. amorphous materials are mesoscopically homogeneous.1'2 A similar phenomenon3 was also reported in rare earth-base sputtered amorphous materials. Even below this temperature there are annealing effects. such as B. in which the atoms are distributed in an irregular manner. electroplating. Some amorphous materials have various other useful features: they are mechanically strong. One possible way to avoid this is to eliminate grain boundaries by using a single crystal. The magnetism of amorphous materials is interesting at least concerning the following two points: First. the presence of grain boundaries in polycrystalline materials sometimes interferes with domain wall motion. Si. However. As different crystal structures affect magnetic behavior differently. sputtering. oxides and compounds. how such a random arrangement of atoms affects the magnetic properties. Generally speaking. This fact is very important for engineering applications of amorphous materials. N. . are quite structuresensitive. Instead there are only diffuse halos. all in crystalline form with atoms arranged on regular lattices. from which we can deduce the statistical distribution of atoms. The magnetic properties of materials.

and V to Fe are interpreted by these authors as resulting from the fact that Mn. and V atoms have moments of 3. amorphous alloys as a function of average number of electrons. Co.eM. where M = Ni. These raw materials were mixed. and their magnetic moments are coupled antiferromagnetically with the Fe moment.4 electrons per atom. Cr. and V.12).240 MAGNETISM OF AMORPHOUS MATERIALS We shall discuss magnetism of 3d metal-base amorphous materials in (11. 11. Figure 11.2) and Mn 3 P (see Fig. 4. The steep decreases of the saturation moment caused by the addition of Mn. the Fe-Ni and Fe-Co systems follow an almost straight line parallel to the right-hand line of the Slater-Pauling curve (see Fig. Saturation magnetic moment per (Fe 1 _ jX M.. As seen from this graph.1). This is analogous to the case of borides (see Fig. The behavior of the Curie point is quite different from Fig. c M_ ( . and 5MB. e ) in Bohr magneton for amorphous alloys (Fe1_.1 shows the average saturation magnetic moment of the magnetic atoms of these amorphous alloys as a function of average number of electrons of transition elements. and that of rare earth-base amorphous materials in (11. 8. melted in a plasma-jet furnace.). 11. Mn. shifted to the left by 0. respectively.t:)08B01P0i as a function of average number of electrons in (Fe^^M^. Cr. Cr.4 .) 08 B 0] P 01 .2).1.4 for a series (Fe 1 _.. This shift can be accounted for by considering that B and P act as electron donors.2 shows the Curie point of Fej^M.5 Figure 11.1 MAGNETISM OF 3d TRANSITION AMORPHOUS MATERIALS METAL-BASE Pioneering work on this subject was carried out by Mizoguchi et a/. and then quenched from the melt by rapid compression between cold copper plates. 10. 10.5).

while these are quite different for different crystalline alloys.. 0 f .1 As seen in this graph. The reason may be due to the appearance of . It is interesting to see how the magnetic moment changes when the metalloid element content is reduced. which are plotted by dashed curves in the same figure with respect to the following points: (1) There are no discontinuities as found in crystalline alloys at phase boundaries.4 shows the saturation magnetic moment of an Fe atom in Fe-Si amorphous alloys which were evaporated onto a substrate cooled to liquid H 2 temperature (20K). Figure 11. the Curie temperature is as low as 85°C in an as-quenched sample. It should be noted that the Curie points of amorphous alloys are subject to change by annealing below the crystallization temperature.M. while it increases as high as 112°C after annealing for lOOOOmin at 200°C. (2) The changes in Curie point by the addition of various elements are rather smooth functions of electron concentration for amorphous alloys.MAGNETISM OF 3d TRANSITION METAL-BASE MATERIALS 241 Fig.3 shows the experimental results for the Fe27Ni53P14B6 system. This behavior is quite similar to that of Invar alloys (see Section 8. Curie point.^M.. Figure 11.6'7 It is seen in this graph that the Fe moment drops sharply when the Si content is reduced below 0.2. of amorphous alloys of (Fe 1 _ A . There is a tendency that the effect of annealing is more pronounced by increasing the annealing time at low temperatures. the saturation moment of amorphous alloys is influenced by metalloid elements which act as electron donors to the matrix. as a function of Si content.). t ) 08 B 01 P 0 j as a function of average numbers of electrons in (Fej. As mentioned above. 11.4 the crystalline alloys.2).6 at%. This was suggested to be due to a compositional short-range ordering of different elements.

The annealing times are indicated in the figure.242 MAGNETISM OF AMORPHOUS MATERIALS Fig. The similarity between fee Invar and amorphous alloys seems reasonable. The ordinate is normalized to MFe (= 2.8 which is close to the value of 12 in the fee structure. on Fe atoms in Fe-Si amorphous alloys evaporated on cold substrates. because the number of nearest neighbors in amorphous alloys is 11-13.2MB).3. Change in Curie temperature of amorphous Fe27Ni53P14B6 as a function of annealing temperature. M.4. Saturation magnetic moment. as a function of Si content.1 the low-spin state of Fe atoms caused by an increase in the number of Fe-Fe pairs.6 . 11. 11. Then a question arises why the magnetic moment of Fig.

. ferromagnetism of amorphous materials is not very different from that of crystalline materials. Fukamichi et al? discovered that Fej^B^ (x = 0. 11.MAGNETISM OF RARE EARTH AMORPHOUS ALLOYS 243 Fe in amorphous alloys containing more than 0. The dashed curves in the same figure represent the temperature dependence of the sub-magnetizations of Gd and Co deduced theoretically. refer to various reviews. In R-Fe amorphous alloys.8 MAm" 1 (lOkOe).13 For more details.14'15 11. The spin-wave dispersion relation determined by means of neutron diffraction12 for amorphous materials of composition (Fe 093 Mo 007 ) og B 01 P 01 was also found to be quite normal. similar to that of Invar. Since the first report16 of ferrimagnetic Gd-Co and Gd-Fe films sputtered onto glass plates. we know that the exchange interaction acts over long distances even between atomic moments arranged in an irregular manner. The temperature dependence of spontaneous magnetization of these amorphous alloys was found to be almost linear. we would expect that the amorphous iron-base alloys would also exhibit some Invar anomaly. which is the same as that in fee alloys. which is the same as that of bcc Fe where the number of nearest neighbors is 8. not so simple. . in spite of the irregular atomic arrangement. the magnetic moment of Fe becomes 2.09-0. In fact. Figure 11.2 MAGNETISM OF 3d TRANSITION PLUS RARE EARTH AMORPHOUS ALLOYS The important feature of these amorphous systems is the appearance of antiferromagnetic or ferrimagnetic spin arrangements. Judging from this and other magnetic data.5 shows the temperature dependence of magnetization measured for (Gd 015 Co 085 ) 086 Mo 014 in a magnetic field of 0. the magnetic critical phenomena were investigated in Co01~B02f0^. it was concluded that the atomic magnetic moments and exchange interactions in these amorphous materials have fairly large fluctuations. It is interesting that two kinds of atomic magnetic moments are aligned antiferromagnetically in spite of the irregular spatial arrangement. From these facts. Generally speaking. depends considerably on the composition. many investigations have been reported on this system. as discussed in Section 8. and found to be completely the same as those of the crystalline materials: The Curie point can be determined uniquely and the critical indices are quite normal (Section 6.4).18 The exchange interaction in this system has been interpreted in terms of a 'mean field model'. measured by Mossbauer effect.2). however.21) amorphous alloys exhibit anomalous thermal expansion. when Si is replaced by Au.2). However. thus forming the usual ferromagnetic spin arrangement. This is apparently the temperature dependence of magnetization for an N-type ferrimagnet (see Section 7. the internal fields of Fe075P015C0 x determined by means of the Mossbauer effect were found to be distributed over a fairly wide range. The situation is. the atomic magnetic moment of Fe deduced from the internal field.2MB (see Fig. If the appearance of low spin states in Invar alloys is the origin of their low thermal expansion coefficients.8MB. However.6 at% Si is 2. For instance.17.2.11 etc. and an expansion coefficient as low as that of Invar is found at x = 0.w Fe08P013C007.

19 The number of electrons transferred is smaller in amorphous alloys than in the crystalline state.55MB in both the amorphous and crystalline states.17 It is interesting to compare the amorphous RM 2 alloy prepared by sputtering and the crystalline Laves RM2 phase. which is much higher than the value of 1.244 MAGNETISM OF AMORPHOUS MATERIALS Fig. but still lower than the value 1. in amorphous GdCo2. Temperature dependence of saturation magnetization of the amorphous alloy (Gd 015 Co og5 ) og6 Mo 0 j 4 (circles) and the submagnetizations of Gd and Co (calculated). .4 + 0.15MB.14 However. 11. the Co moment is 1. This situation has been explained in terms of a transfer of electrons from Gd to Co.22 PROBLEM 11.7MB in Co metal. For instance.5. because the separation between Gd-Gd is larger in the former than the latter. GdFe2 has an Fe moment of 1.20 Such a decrease in local moment is suspected to be partly due to a disturbance of the parallel alignment of spins by local anisotropy.02MB in Laves GdCo2.1 State the major differences in magnetism between amorphous and crystalline materials and discuss possible reasons.21 It was observed by inelastic neutron diffraction that the density of magnetic states in amorphous TbFe2 is considerably shifted towards lower energies compared to the crystalline state.

Pickart. Potter. and R. 8. F. Luborsky.. 15. R. f. de Graaf. 563. K. T. and T. Hooper and A. Miyajima.REFERENCES 245 REFERENCES 1. S. Plenum Press. S. 1491. Phys. Appl. Lilienthal. 34 (1976). T. Japan. Z. D. Amorphous magnetism (ed. Prog. 218. Mizoguchi. 10 (1971). Tao. J.. Tsuei and H. Phys. 13B (1976). R. S. Proc. 21. J. Rhyne. R. N. 24 (1974). Japanese J. 18 (1974). T. AIP Conf. 14. R. 1730. 7. Shirane. Endo. T. R. 219 (1969). 23 (1977). and Y. M. Cuomo. 1335. Mizoguchi. 5. Ann. 18. . E. Felsch. AIP Conf.. IEEE Trans.. J. 22. Rev. B. 34 (1973). S. and H. Phys. P. J. Cargill.. 115. N. 1691. K. Hasegawa. /. Koon. 1618. 10. W. J. Heiman. 325. Proc. and H. Yamauchi. Kirkpatrick. 641. Solid State Comm.. Phys. New York. 423. Egami.. J. Solid State Comm.. 955. and N. Lilienthal. 19. 286. Jr. Lee. 18 (1974). and J. J. K. Tao. 4672. Gambino.. J. Rev. MAG-21 (1985). AIP Conf. Appl. Abbundi. Phys. T. O. Sci. Rhyne. Forester. Mizoguchi. 337. R. Sweger. Phys. Wagner... D. and T. Yamauchi. 13 (1973). J. AIP Conf. M. Y. B. Yamauchi.. T. C. Arakawa. Phys. and Y. AIP Conf. 280. E. Ishikawa. 24 (1975). 3. C. 20. AIP Conf. Miyajima. and L. A.. Solid State Phys. Kikuchi. 22 (1973). I. Nakagawa. 2. K. Yamada. 17. G. Cargill. Argyle. 29 (1975). Yamauchi and Y. 138. Proc. J. 2763. 110. Phys. 130. Segnan. 1601. Cuomo. 8 (1978). Lett. G. 29 (1970). 24 (1974). and B. Axe. C. J. 11. W. Z.. 47 (1984).. 227.. Proc. W. Skoda. Schelling. and R. Ueda. 16. D. Mater. Proc. Soc. 16 (1975). 4. Mag. Egami. 1973) p. and H. 4899... BIO (1974). G.. L. J. Alperin. S. K. Mizoguchi. Rep.. J. by H. AIP Conf. and H. B15 (1977). Rev. Felsch. Masumoto.. Proc. T. 9. angew. Solid State Comm. 12. Proc. Gambino. Furey. K. Fukamichi. J. 13. Rev. 6. C. Phys. 30 (1975). Graham. Chaudhari.

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. or several easy axes. if no additional interaction exists. However.or ferrimagnetic materials. and consider some representative data. the spontaneous magnetization has an easy axis. this phenomenon is called magnetostriction. the size or shape of a ferromagnet is more or less changed by magnetization. in actual ferro. Furthermore. This interaction is essentially isotropic. so that the spontaneous magnetization can point in any direction in the crystal without changing the internal energy. This phenomenon is called magnetic anisotropy. along which the magnetization prefers to lie.PartV MAGNETIC ANISOTROPY AND MAGNETOSTRICTION The exchange interaction between spins in ferro. In this Part we discuss the physical origins of these phenomena. Rotation of the magnetization away from the easy axis is possible only by applying an external magnetic field.or ferrimagnetic materials is the main origin of spontaneous magnetization.

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The values of uniaxial anisotropy constants of cobalt at 15°C1 are The higher-order terms are small and their values are not reliably known. the angle between the c-axis and the magnetization vector. We call an energy term of this kind a magnetic anisotropy energy.. and decreases to its original value at 6 = 180°. For example..1 PHENOMENOLOGY OF ANISOTROPY MAGNETOCRYSTALLINE The term magnetic anisotropy is used to describe the dependence of the internal energy on the direction of spontaneous magnetization. If these . parallel to the c-axis of the crystal at room temperature. the anisotropy energy is minimum when the magnetization points in either the + or — direction along the c-axis. hexagonal cobalt exhibits uniaxial anisotropy with the stable direction of spontaneous magnetization. Generally the magnetic anisotropy energy term has the same symmetry as the crystal structure of the material. and we call it a magnetocrystalline anisotropy.4. or easy axis. the anisotropy energy initially increases with 6.) in these equations are called anisotropy constants. The simplest case is uniaxial magnetic anisotropy. We can express this energy by expanding it in a series of powers of sin2 6: where <p is the azimuthal angle of the magnetization in the plane perpendicular to the c-axis.1) is converted to a series in cos nd (n = 2. Using the relationships (12. In other words.6. As the magnetization rotates away from the c-axis.) as The coefficients Kun (n = 1.2.. then reaches a maximum value at 6 = 90°....12 MAGNETOCRYSTALLINE ANISOTROPY 12.

If ^Cul > 0 and Ku2 < 0. In the latter case. afaf by the relationship Thus we have the expression . which is always equal to 1. so that it becomes unstable. In other words. B1. the anisotropy energy. increases with increasing angle 6. therefore. C1. the anisotropy energy is maximum at the c-axis. should bring the magnetization vector to a direction which is equivalent to the original direction. so that E is minimum at 6 = 0.1. B 2 . The first term. Such a plane is called a plane of easy magnetization or an easy plane. A 2 . must vanish.k. the anisotropy energy can be expressed in a fairly simple way: We expand the anisotropy energy in a polynomial series in a l5 a 2 .2may2" must have.1. and «3. Such an axis is called an axis of hard magnetization or simply a hard axis. For cubic crystals such as iron and nickel. the spontaneous magnetization is stable when it is parallel to the c-axis. constants are positive as in the case of cobalt. as shown by the points A1. 12. the stable direction of magnetization forms a cone. 12. for any combination of l. Because of the high symmetry of the cubic crystal. If these constants are negative. Those terms which include the odd powers of a.n.j.250 MAGNETOCRYSTALLINE ANISOTROPY Fig. the anisotropy energy can be expressed in terms of the direction cosines (alt a2. There are many equivalent directions in which the anisotropy energy has the same value. The expression must also be invariant to the interchange of any two a. > . because a change in sign of any of the a. which is called a cone of easy magnetization or an easy cone. the magnetization is stable when it lies in any direction in the c-plane (6 = 90°). Equivalent directions in a cubic crystal. should have the form a 2 + a\ + a\. the same coefficient for any interchange of i. «3) of the magnetization vector with respect to the three cube edges. and C 2 on an octant of the unit sphere in Fig. £a.m. Such an axis is called an axis of easy magnetization or simply an easy axis.s so that the terms of the form a2'a. Next is the fourth-order term which can be reduced to the form E.

Polar diagram of the cubic anisotropy energy for K^ > 0 and K2 = 0. and [001]) directions. For iron at 20°C. If ATj < 0 as in the case of nickel. It is seen that the surface is convex for cube axes . so that [100] becomes the easy axis. a1 = 1. or in other words the energy is minimum. £a for [111] is higher than that for [100]. Figure 12.) Fig. and [111] directions are easy axes. (Radial vector is equal to £a + 2|^j|.3 shows a polar diagram of the anisotropy energy. Figure 12. and ignoring the K2 and K3 terms.PHENOMENOLOGY OF MAGNETOCRYSTALLINE ANISOTROPY 251 Fig. [111]. Polar diagram of the cubic anisotropy energy for K1 < 0 and K2 = 0. so that the value of E& given by (12.5) plus a constant term equal to f ATj. and z.9) (ignoring K2 and K3 terms). in the x-.(or [100].2 shows a polar diagram of the anisotropy energy in this case. Considering the cubic symmetry. £a < 0 for [111] as we see in (12. It is seen that the surface is concave.3 For [100]. 12. (Radial vector is equal to £a + f/Cj. plus a constant term 2\Kl.2 and.2. for nickel at 23°C.5) is If K1 > 0 as in the case of iron. y-. [010]. so that E3 for [111] is lower than that for [100] and [111] and its equivalent [111].) where KI} K2. This diagram is a locus of the vector drawn from the origin in the direction of the spontaneous magnetization with length equal to the anisotropy energy given by (12. [010] and [001] are also easy axes. for Kl < 0 and K2=K3 = 0. a2 = a3 = 0. 123. and K3 are the cubic anisotropy constants.

Figures 12.4 and 12. respectively. y-z. (Radial vector is equal to Ea + ^K2. In these cases.or ferrimagnetic materials Kl > K2.5. (Radial vector is equal to £a + -^K2. however. 12. we have from (12. then we have Using this relationship. 12.252 MAGNETOCRYSTALLINE ANISOTROPY Fig. so that the contribution of the K2 term can be ignored. but Ea for (111) is highest in the case of positive K2 and lowest in the case of negative K2. term.t-axis (see Fig. let us consider the case in which the magnetization rotates in the x-y or (001) plane.6). Before examining the {111} plane.) and concave for the (111) axes. When. .5) Note that there is no contribution from the K-. However. in many ferro. This is the case if the magnetization is confined to the {111} plane. the energy is equal to zero for all directions in the x-y. the K2 term is not necessarily negligible. Polar diagram of the cubic anisotropy energy for Kl — 0 and K2 < 0. 12. the change in a formula for the K2 term is only ^ of that from the K1 term.4. the magnetization rotates in some particular crystallographic plane. and K2 < 0. and z-x planes. Polar diagram of the cubic anisotropy energy for Kt = 0 and K2 > 0. and even if K:=K2. If 9 is the angle between the magnetization and the .5 show the anisotropy energy surfaces for K^ = K3 = 0 and K2 > 0 and for K1 = K3 = 0.) Fig.

and K3) terms. . Rotation of magnetization in the (110) plane out of the z-direction.y'. K2. then we have the relationship Using this relationship..y'. the y'-axis is in the (llO) plane. The direction cosines between coordinate axes of the old (x.1*. Next let us calculate the anisotropy energy in the (111) plane. 12.c'-axis parallel to the [110] axis (see Fig. 12. sa' aan determine other direction cosines.z'\ in which the z'-axis is parallel to the [111] axis. Fig. Rotation of magnetization in the (001) plane out of the x-direction. If 6 is the angle of rotation of the magnetization from the z-axis in the (110) plane (see Fig. The (111) plane in the old coordi* To construct such a table.PHENOMENOLOGY OF MAGNETOCRYSTALLINE ANISOTROPY 253 Fig. 12. For this purpose.z') systems are listed in Table 12. Next we consider the (110) plane. z) and the new (x'. y. 12. and the . we have from (12.7).5) the anisotropy energy which includes contributions from all three (K1. we set up a new coordinate system (x'.7.6.8). first we determine two axes.

1. .15) in (12. z') with x' II [110] and z' II [111]. we have the anisotropy energy in the (111) plane in which only the K2 term has angular dependence and contributes to the anisotropy energy. New cubic coordinate system (x1. then we have Referring to Table 12. nates is the x'y' plane in the new one. 12. y'. Let 6 be the angle between the magnetization and the x'-axis in the x'-y' plane.8.5).254 MAGNETOCRYSTALLINE ANISOTROPY Fig. we have the direction cosines of magnetization in the old coordinates Using (12.

11).1. we have In the case of the (110) plane. by comparison with (12. we have In the case of the (111) plane. we have In the case of the (001) plane in a cubic crystal.2).PHENOMENOLOGY OF MAGNETOCRYSTALLINE ANISOTROPY 255 Table 12. we have Anisotropy energy is also produced by magnetostatic energy due to magnetic free poles appearing on the outside surface or internal surfaces of an inhomogeneous .17) with (12. by comparing (12. the anisotropy energy can be expressed in the general form In the case of uniaxial anisotropy. In summary.

4 Figure 12. and <p be the angle between the *-axis and the projection of the magnetization onto the x-y plane.99). in which elongated precipitates produce the uniaxial anisotropy (see Section 13. Let 6 be the angle between the magnetization and the z-axis. The specimen S is suspended by a thin metal wire in .2 METHODS FOR MEASURING MAGNETIC ANISOTROPY The most accurate means for measuring magnetic anisotropy is the torque magnetometer. the magnetic anisotropy tends to rotate the specimen to bring the easy axis parallel to the magnetization. thus producing a torque on the specimen.22) to the x-. Then applying (12. irrespective of the magnitude of 7S' relative to 7S.1). If precipitate particles of magnetization 7S'. the demagnetizing factor parallel to the x. the magnetostatic energy is given by The easy axis of this anisotropy is the z-axis. Referring to (1. This kind of anisotropy is called shape magnetic anisotropy.' || 7S).256 MAGNETOCRYSTALLINE ANISOTROPY magnetic material.and y-axes is given by NI = Ny = \(l —Nz). The principle of this method is as follows: the ferromagnetic specimen. from which we can deduce the anisotropy constants. the magnetostatic energy due to free poles on the outside surface of a magnetic body of volume v magnetized to intensity 7 along an axis with demagnetizing factor N is given by 0 If the specimen is in the form of an ellipsoid of revolution with the long axis parallel to the z-axis.9 shows a typical automatic torque magnetometer. y. in the form of a disk or a sphere. different from that of the matrix 7S (/. One example of this kind of shape anisotropy is found in Alnico 5..and z-components. If the torque is measured as a function of the angle of rotation of the magnetic field about the vertical axis. There are various types of torque magnetometer. we have the magnetostatic energy which depends on the direction of magnetization. If the easy axis is near the direction of magnetization. 12. we can obtain the torque curve. have demagnetizing factor Nz (Nz < |).3. where Nz is the demagnetizing factor along the z-axis. is placed in a reasonably strong magnetic field which magnetizes the specimen to saturation.

including air-bearings. Automatic recording torque magnetometer.8 Suppose that the anisotropy energy is increased by SE(9). and fed back to the moving coil. Therefore the current in the coil C is always proportional to the torque exerted on the specimen. Various kinds of frictionless bearings are used. the magnetic field between the pole pieces of the electromagnet E.METHODS FOR MEASURING MAGNETIC ANISOTROPY 257 Fig. The amplifier A should have high gain to keep the deflection of the specimen holder as small as possible. which is placed in the field of a permanent magnet P. The torque is recorded by the x-y recorder R as a function of the rotational angle of the magnet. The signal from the phototransistors is amplified by the amplifier A.5 taut-wire suspensions. which can be rotated about the vertical axis.7 etc. and also should have good dynamic properties to prevent unstable oscillations of the specimen.6 multiple elastic plates. which is measured by a helical multi-turn potentiometer resistor H. so as to produce a torque to counterbalance the torque exerted on the specimen by the field. when the magnetization .9. 12. The lateral displacement of the specimen holder is prevented by a frictionless bearing B. The deflection of the specimen holder is detected by the displacement of the light beam from L reflected by the mirror M onto two phototransistors D. The specimen holder is attached to a mirror M and a moving coil C.

27). and (12.••• . . so that or -L(0)50 = 5E(0).26). For example. respectively.10. Then the torque L(0) must act on a unit volume of the specimen in a sense to decrease 6. angle) measured for a single crystal disk of 4% Si-Fe cut parallel to (001).A4. for 0=0-180°. we have the relationship -F(x) Sx = SU(x). the torque is given by (12. The work done by the torque must equal the decrease in the anisotropy energy.20).25) as L ( 0 ) = -2v4 2 sin20-4^ 4 sin40-6^4 6 sin60-8y4 8 sin80. where the coefficients A2. The experimental points are well fitted by (12. are given by (12. where the coefficients are given by (12. of the field measured from the [001] axis. 12. (12.26) If the magnetization is rotated in a plane which includes the c-axis in a uniaxial crystal.17).18). Torque curve measured in (001) plane of 4% Si-Fe single crystal at room temperature (Chikazumi and Iwata). the torque can be calculated from (12. (110). ignoring the K2 term. If the potential energy is increased by 5U(x) when the body is displaced by Sx along the slope. This angle almost coincides with that of the magnetization as long as the field is strong enough. the torque is given by (12. so that we have F(x) = -dU(x)/dx. 6.10 shows a torque curve (a plot of the torque vs.19).26). as a function of the angle of rotation. and (111) planes.258 MAGNETOCRYSTALLINE ANISOTROPY is rotated by the angle 86.. (12. In the case of cubic anisotropy. which oscillates twice in the range Fig.21) for (001). * This relationship is analogous to the force —F(x) which acts on a body placed on a slope. If the anisotropy energy is given by (12.. the torque in the (001) plane is given by Figure 12..

28).METHODS FOR MEASURING MAGNETIC ANISOTROPY 259 Fig. and also the value of 6. 6 curve. ignoring the K3 term. the torque curve is given by Figure 12. 12.11. As the value of K2 increases. are both changed. Torque curve calculated for (110) plane of a cubic crystal (the parameter is K2/Kl). the ratio of the first peak to the second peak is 2. the ratio of the first to the second peak. Using the value of (12.26).3°.5° and 71.67. or if some induced magnetic anisotropy. dangerous to estimate the value of K2 from these changes. however. 6 = 0-180°. Since the amplitude is equal to K^/2. because such changes also occur if the plane of the disk is tilted from a {110} plane. The most reliable method to determine the value of K2 is to measure the torque curve for a (111) plane specimen. or L/Kl vs. In the case of the (110) plane. is present.11 shows the torque curve. where the parameter is the value of K2/Kl. as discussed in Chapter 13. the angle at which peaks appear. we have . the anisotropy constant K^ can be determined from the torque curve. and these peaks appear at 6 = 25. calculated from (12. When K2 = 0.21) in (12. It is.

7S are changed virtually by Saj. 7S.9)). or even if some induced anisotropy is present.32) is as follows: If the direction cosines of the magnetization. H. The Fourier analysis can be performed by the calculation given by Chikazumi. We assume that the uniaxial anisotropy has the anisotropy constant Ku. even if the plane of the sample is tilted from the (111) plane. and the easy axis is parallel to the z-axis. and the angle ip between the magnetic field. Then the anisotropy energy is given by In addition. 12. Let (aj. because the magnetization makes a nonzero angle <p — 6 with the field.32) with respect to the angle 6.32) should be zero when the direction of /s is in an equilibrium state. a 2 . so that we have Therefore. which represents a torque curve oscillating three times in the range 8 = 0 to 180°. we must consider the field energy (see equation (1. the magnetization rotates towards the field by the angle 6. the total energy of this system is given by The direction of magnetization can be found by minimizing (12. a3). respectively. Definition of the angle 0 between spontaneous magnetization. and (/31. which is slightly smaller than <p. The procedure for minimizing the energy (12. As shown in Fig. 8a2. /33) be the direction cosines of /s and H. the associated change in energy (12.10 It must be noted that when the magnetic field is not strong enough to align the internal magnetization in the field direction.29). and the z-axis. and the z-axis (easy axis).260 MAGNETOCRYSTALLINE ANISOTROPY Fig. the uniaxial anisotropy may give rise to an apparent fourth-order anisotropy. Therefore. 12. /32. Sa3.12. the value of K2 can accurately be determined by Fourier analysis of the torque curve to give the term in (12. if the magnetic field H is applied in a direction <p from the easy axis z.9 or by a simple computer program. we have . In this case.12.

and after dividing each side of (12. we have Putting each side of (12.32). we have where p Substituting (a l 5 a2.33).32). 5a2. and Sa3. we put 2Ka/IsH=p (p <s 1). into (12. we have . given by Multiplying (12.38).METHODS FOR MEASURING MAGNETIC ANISOTROPY 261 Since a^ + af + a| = 1. Sa2. a3).36) by ISH.37) equal to 1 + /u. ( /A <K 1). and 8a3.38). there must be a relationship between 5alt Sa2. and Sa3 must be zero. the coefficients of Soj. we have Substituting (12. we have Using (12. Therefore If the field is strong enough to satisfy ISH^>2KU.35) be satisfied for arbitrary changes in Sa1. we have In order that (12. which minimize the total energy (12.39) for (12.34) by an undetermined parameter A and adding (12.

This form is proper to express the torque curve. not 6. the torque curve shows some field dependence.11 In the case of a disk-shaped specimen. the term with twofold symmetry is not affected by the intensity of the applied magnetic field. is determined by the relationship and then the torque curve is corrected by shifting the angle by <p . Thus the torque is deduced from (12. the torque curve exhibits hysteresis.8 Figure 12. which is a function of H. 12. which will have some domains remaining at the edge even in high applied fields.6. Torque curve normalized per one Tb atom in a dilute Tb-Gd alloy. In order to correct for such a higher-order term. which is called rotational hysteresis.262 MAGNETOCRYSTALLINE ANISOTROPY This energy is expressed as a function of the direction of the external magnetic field. the actual rotation of the specimen from the direction of the field is given by <p. because as seen in Fig. If the rotation of magnetization is associated with some loss of energy.13. <p .0.41) as As seen in (12. 12. not the direction of magnetization.12 When the magnetic field is so weak that the magnetization cannot rotate reversibly with the magnetic field. Fig.12.42).11 .13 shows an example of such a correction carried out on the torque curve measured for a Gd alloy containing a small amount of Tb. The dashed curve represents the corrected torque curve as a function of the angle of the Tb moment. the rotation of the magnetization vector from the field direction. The term with fourfold symmetry does include p.

or z-axes in different places. or /32.1. the second term is simply a small correction as in the case of (12. If the easy axis of the uniaxial anisotropy is unique. because the anisotropy gives an additional torque to the spontaneous magnetization to rotate it towards the easy axis. In ferromagnetic resonance. This phenomenon will be treated again in Section 13.41). The fourth-order anisotropy thus produced is field-dependent.16 Magnetic anisotropy can also be measured by ferromagnetic resonance. Therefore if the material has its own inherent Kw. the magnetic anisotropy influences the resonance field. If the applied magnetic field is parallel to the easy axis. But if the easy axes are distributed on the x-. a part of the microwave power is absorbed to excite the precession (see Section 3. the resultant field-dependent Kl will be given by If Kw is small and positive. * In the original paper.41) should be replaced by j31.14 Alnico 515 and Co ferrite. . The second term in (12.13 the coefficient is different. y-.or y-axis. the spontaneous magnetization precesses about the applied magnetic field with a frequency proportional to the magnetic field.44) has the same form as the cubk magnetocrystalline anisotropy (12. so that value of K^ changes its magnitude or sometimes changes its sign with a change in the intensity of applied field. Let us formulate the torque reversal by using (12. because higher order terms were ignored. the uniaxial terms must cancel one other. This phenomenon is called the torque reversal. rotational hysteresis appears even when the field is strong enough to rotate the magnetization reversibly. This effect is equivalent to a presence of the so-called anisotropy field. resulting in the dominant contribution to the anisotropy from the second term.METHODS FOR MEASURING MAGNETIC ANISOTROPY 263 whether internal or external.3). so that the average anisotropy is given by We see that the fourth-order term* in (12. The reason for this phenomenon is that the angle of deviation of the magnetization from the field direction changes sign every time the field passes through the easy or hard axes.42).42) shows the appearance of a higher-order term when the applied magnetic field is not strong enough. If the easy axis is parallel to the x. Kl changes its sign from positive to negative as the field increases.5). If the frequency of the microwave radiation field applied to the specimen coincides with the resonance frequency. Torque reversals have been observed for Fe2NiAl. /33 in (12.

51). Substituting a. 12. In the case of a cubic crystal.46) and (12. we first change the coordinate . the energy is expressed for small 6 by Comparing the terms in 0 2 in (12. when magnetic anisotropy is present. Therefore we conclude that the resonance is expected to occur at a field less than the usual value by an amount Ha. so that the anisotropy field is given by When the magnetization is in a direction near [111]. in (12. Ignoring the higherorder terms in (12.264 MAGNETOCRYSTALLINE ANISOTROPY Let us calculate the anisotropy field for a uniaxial anisotropy. when the magnetization is in a direction near [001].47). we can simplify the anisotropy energy for small 8: On the other hand.5) by (12.1).21) and (3.22)) which is given by The g-factor was defined in (3. we have Then the resonance field should be given by where the coefficient v is the gyromagnetic constant (see (3.47). if an anisotropy field exists.14). we have which has the same form as (12.39). the direction cosines of magnetization are given by where 6 is the polar angle from the z-axis and <p is the azimuthal angle about the z-axis (see Fig.

The polar and azimuthal angles of the magnetization in the vicinity of the z-axis.15 shows the shift of resonance field observed for a single crystal of Fe3O4. and finally substitute using (12. then use polar coordinates. Then we have Using this expression in the first term in (12.14. as in (12.51). 12. we can deduce the anisotropy constant.15).17 From such experiments. .METHODS FOR MEASURING MAGNETIC ANISOTROPY 265 Fig. 12. when the magnetic field is rotated in the (001) or (110) planes. we finally have Comparing this result with (12.47).8. the resonance field should shift by Figure 12. we have the anisotropy field Therefore when the magnetic field is rotated from [001] to [111].5). system as shown in Fig.

2. Moreover.3). so that the anisotropy is different in different places.3. which is composed of parallel spins. is given by . 12.266 MAGNETOCRYSTALLINE ANISOTROPY Fig. (After Bickford17) It should be noted that a torque measurement measures the first derivative of the anisotropy energy with respect to the angle of rotation. We shall discuss this method in Section 18. from one direction (a) to another (b).3 MECHANISM OF MAGNETIC ANISOTROPY Magnetic anisotropy is a change in the internal energy of a magnetic material with a change in the direction of magnetization. Variation^ of the resonance field with a rotation of magnetization in (a) the (001) plane and (b) the (llO) plane. The magnetic anisotropy can also be determined by measuring magnetization curves. The reason that neighboring spins remain parallel is that a strong exchange interaction acts between spins (see Sections 6.16 shows the rotation of ferromagnetic spontaneous magnetization. According to Heisenberg's expression.18 the exchange interaction between spins St and 5. observed for a single crystal of Fe3O4. 12. whereas the magnetic resonance exhibits different absorption peaks corresponding to the local anisotropies. the torque measures only the average of the local anisotropy. Figure 12. if the specimen is inhomogeneous. 6.15. whereas the resonance field measures the second derivative of the anisotropy energy.

Thus the exchange energy is isotropic. Therefore to explain magnetic anisotropy.60). where 5 is the magnitude of the spin and <p is the angle between S. When the magnetization rotates as shown in Fig.MECHANISM OF MAGNETIC ANISOTROPY 267 Fig. we need an additional energy term which includes the crystal axes. 12. Suppose that neighboring spins make the angle <p with the bond axis (see Fig. Then the energy of the spin pair is expressed. 12. 12. Rotation of spins in ferromagnetic spontaneous magnetization. and 5.15)) if the coefficient is given by However. The second term is called the dipole-dipole interaction term.16. as The first term is independent of the angle <p. through a change in the Fig. A pair of spins. because it has the same form as the magnetic dipole-dipole interaction (see (1. 12.. so that if = 0 in (12.17.58) and the exchange energy does not change. so that it corresponds to the exchange interaction. The real mechanism is believed to be as follows: a partially unquenched magnetic orbital moment coupled with the spins lead to a variation in the exchange or electrostatic energy with a rotation of the magnetization. after expanding in Legendre polynomials. .16 from (a) to (b). all the spins remain parallel. we shall find later that the value of / corresponding to the actual measured magnetic anisotropy is 100 to 1000 times larger than the magnetic interaction given by (12.17).

This corresponds to the shape anisotropy given by (12. however. a3) be the direction cosines of parallel spins.18). For spin pairs with bonding . let along the magnitude. If we extend the range of sum to the whole volume of the specimen. so we must calculate the contribution of all the dipoles in a large sphere. In reality. 12. Before going into details of the spin-pair model. because the number of dipoles in a spherical shell with inner and outer radii of r and r + dr increases as r2 dr with increasing r.59) for all the spin-pairs in the crystal. Let us elucidate how magnetic anisotropy is constructed from the spin-pair energy given by (12. The sum of dipole-dipole interactions between all the spin pairs in a ferromagnetic crystal is called the dipole sum. Since the pair energy for distant pairs is small.268 MAGNETOCRYSTALLINE ANISOTROPY overlap of wave functions. and then increase r to infinity. Such a logarithmic function increases only slowly. Therefore the contribution of all the dipoles in the sphere of the radius r increases as In r with increasing r. we first calculate the magnetic field produced at one atom by all the surrounding magnetic dipoles.23). we must calculate the contribution from a spherical shell with radius r. but the result can explain only a part of the experimental value. This model is useful to discuss the effect of crystal symmetry on the magnetic anisotropy and to calculate the induced magnetic anisotropy (see Chapter 13). For simplicity. Such a model is called a spin-pair model. Therefore in order to calculate the dipole sum free from shape anisotropy. This is simply where i identifies the spin pair. the convergence of the dipole sum with distance is not very rapid. first we consider a simple cubic lattice (Fig. let us consider how magnetic anisotropy is produced by the magnetic dipole-dipole interaction. We cannot trust even the sign of such calculated results. The third term in (12.19 Some published papers show the calculation of the dipole sum only in the vicinity of an atomic site.59). The magnetic anisotropy can be calculated by summing up the pair energy given by (12. so that it is not necessary to worry about the range of the sum. we consider only the first nearest neighbors.59) is a higher-order term of the same origin. the convergence is still unsatisfactory. The magnetic anisotropy is calculated by summing up all the spin pairs included in a unit volume of this crystal. In the case of pseudodipolar interaction. and is called the quadrupolar interaction. the range of interaction is truly short range. Such an interaction is called a pseudodipolar interaction. however.94). and then calculate the magnetostatic energy by using (1. so that the dipole sum increases only as (l/r 3 Xr 2 dr) = dr/r. In order to calculate the dipole sum. In the present case. Let (a l9 a 2 . the dipole sum depends on the shape of the specimen. we consider only the interactions between the first or at most the second nearest neighbors. A real calculation of magnetic anisotropy has been made for hexagonal cobalt. Since the dipole field is inversely proportional to the third power of distance. it is tempting to assume that the main contribution comes only from the neighboring dipoles. Although special techniques have been used for such a calculation of the dipole sum.

The Kul term in (12. Generally speaking. such as hexagonal crystals. a? = 1. the dipole term does contribute to the anisotropy. For instance. parallel to the *-axis. in structures with uniaxial symmetry. cos <p is (12. 12. On the other hand.5).or z-pairs it is replaced by a1 and a3. which is much larger than Kl (= 103-104 J m ~ 3 ) for cubic iron or nickel. This is always the case for any cubic crystal.18.MECHANISM OF MAGNETIC ANISOTROPY 269 Fig. so that crystals with low symmetry exhibit relatively large magnetocrystalline anisotropy. since E. / is one or two orders of magnitude larger than q. Comparing this with (12.59) makes no contribution to the anisotropy. the magnitude of Kul for hexagonal cobalt is of the order of 105 Jm~ 3 . Thus we have where N is the total number of atoms in a unit volume.1) is caused by such an interaction. we have Similar calculations for the body-centered cubic lattice lead to and for the face-centered cubic lattice It should be noted here that the second term or the dipole term in (12. Ferromagnetic spins on a simple cubic lattice. Similarly for y. .59) is simply replaced by o-j.

There are two kinds of interstitial sites. Interstitial sites in an oxide lattice: (a) tetrahedral site. In such a case. For example. which are expected to produce a large anisotropy. Fig.20). surrounded by six O 2 ~ ions. the energy levels of d-electrons which are degenerate in the free ion state ((a) in Fig. This is not. 12.20) are split into doubly degenerate dy levels and triply degenerate de levels when they are placed in an octahedral site (see (b) in Fig.6-0. In an oxide crystal. Cobalt-ferrite has the composition Co 2+ Fe2 + O 4 . (b) octahedral sites.19: one is a tetrahedral site. thus forming a close-packed structure. the case for oxides and compounds in which the magnetic atoms are separated by large negative ions. surrounded by four nearest neighbor O 2 ~ ions. they are squeezed into interstitial sites of the oxygen lattice.32A for O 2 ~).19. and the other is an octahedral site. 9. 12. divalent oxygen ions (O 2 ~) are in direct contact to one another. while the other Fe3+ and the Co2"1" occupy two octahedral sites. the theory that treats the behavior of transition metal ions in a crystalline field is called ligand field theory?0 We shall discuss in terms of the one-ion model how the magnetic anisotropy is produced in a cubic crystal.20). plus metal ions which occupy the tetrahedral sites and octahedral sites in a ratio of 1:2. Generally speaking. in which one Fe3+ occupies a tetrahedral site. We shall discuss the behavior of the Co2"1" ions in the octahedral site. In all the oxides. Since the divalent or trivalent metal ions (M 2+ or M 3 + ) are much smaller than the O 2 ~ ions (radius 0. 12. 3.3) consisting of a close-packed oxygen framework with face-centered cubic structure. We have seen in Chapter 3 that the wave functions of d-electrons of transition metal atoms which are placed in a cubic lattice are separated into three ds and two dy functions.8A as compared to 1. In general. . while the dy functions stretch along the cubic axes (100) (see Fig. however. The ds functions stretch along (110) axes. This model is called the one-ion model. metal ions occupy these small interstitial sites. 12. in which atomic spins are close to one another. the magnetic anisotropy results from the behavior of non-spherical magnetic atoms in the crystalline field produced by the surrounding ions. We shall discuss how such wave functions result in a magnetic anisotropy in an oxide crystal.270 MAGNETOCRYSTALLINE ANISOTROPY This spin-pair model is applicable to metals. ferrites have the spinel lattice (see Fig. as shown in Fig.

Splitting of energy levels of 3d electrons by crystalline fields: (a) free ions.19(b)) are arranged symmetrically about the trigonal axis (the [111] axis in the same figure). L points in the + direction of this axis. (b) cubic fields. L is reversed. five electrons out of seven in the Co2+ ion in an octahedral site fill up the + spin levels. so that because of the Coulomb interaction between the negatively charged electron and the O 2 ~ ion. The last electron which occupies the doubly degenerate levels can alternate between the two possible wave functions. L is parallel to 5 (Hund rule (iii)). When S is rotated so that it has a negative component. the triply degenerate de levels are split into an isolated lower single level. while the de wave function stretches between two cubic axes and avoids the O 2 ~~ ions. This orbit produces an orbital magnetic moment ±L parallel to the trigonal axis. S has a positive component parallel to the trigonal axis.29)) is expressed as Since the number of electrons in a Co2+ ion is more than half the number required for a filled shell. This orbital magnetic moment L interacts with the total spin S of the Co2+. (c) trigonal field (arrows represent spins in a Co2+ ion). 12. which corresponds to the wave function stretching along the trigonal axis and the doubly degenerate higher levels which correspond to the wave functions stretching perpendicular to the trigonal axis. while the remaining two electrons occupy the — spin levels (see Fig. thus realizing a circulating orbit. The reason for this behavior is that the dy wave function stretches along a cubic axis on which the nearest neighbor O 2 ~ ion is located. 12.20. the second nearest neighbor metal ions surrounding an octahedral site (hatched circles in Fig. Such spin orbit coupling (see (3.67) becomes . the anisotropy energy produced by (12.MECHANISM OF MAGNETIC ANISOTROPY 271 Fig. Therefore the interaction energy in this case is given by21'22 In cubic crystal there are four (111) axes. If Co2"1" ions are distributed equally on octahedral sites with different (111) axes. In addition to this. and A < 0. When.20(c)). so that they produce a trigonal field which tends to attract the electron along the trigonal axis. 12. the energy level of dy is increased. therefore. In consequence. According to Hund's rule. so that the Coulomb energy is relatively small and the de level is lowered.

the orbital moment L is induced through the LS coupling. the anisotropy constant in (12. For further discussion of various mechanisms of magnetic anisotropy. (/31. «3).27 Consider a ferromagnetic material with spontaneous magnetization produced by parallel spin alignment. In the case of metal ions other than Co2+. a2. In fact.or ferrimagnetic material. the magnetic anisotropy vanishes when the spontaneous magnetization disappears at the Curie point. in any ferro. (04. 0 2 > ^s> and fy are the angles between S and the four (111) axes. The temperature dependence. let us discuss the temperature dependence of magnetic anisotropy. are not the same as those of the total spontaneous magnetization. )83). At temperatures above absolute zero. j32.25 Before closing this section. We shall discuss this problem along the line proposed by Zener26 and developed by Carr. refer to Yosida and Tachiki. This explains the fact that many ferrites have negative Klt but the addition of Co tends to make K^ positive. and the deviations . By Fourier expansion. the direction cosines of a local spin cluster. of the anisotropy is stronger than that of the spontaneous magnetization. so that the pair energy given by (12. We assume that parallel spin clusters survive up to high temperatures because of a strong exchange interaction. so that the temperature dependence of spontaneous magnetization should give rise to a change in magnetic anisotropy.70) is positive.24 and Kanamori. and this induced L gives rise to the magnetic anisotropy through the LS coupling.68) becomes Since A < 0. Generally speaking.23 Slonczewski. cos 6 \ is reduced to Therefore (12.59) is applicable over a wide range of temperature. magnetic anisotropy is produced through the interaction between spontaneous magnetization and the crystal lattice.272 MAGNETOCRYSTALLINE ANISOTROPY where 01.

etc. The cubic anisotropy at temperature T is given by where K(ff) is the anisotropy constant at OK and ( > is the average of the angular function for all the spin clusters. the magnetic anisotropy averaged over all the spin clusters decreases with increasing temperature. such as thermal expansion of the lattice. Fig.21 shows a comparison between the observed temperature dependence of K^ for iron and the function (12. that the mechanism described above gives the general features of the temperature dependence and is not always applicable to particular materials. It should be noted. (After Carr27) . The agreement is satisfactory.MECHANISM OF MAGNETIC ANISOTROPY 273 increase with increasing temperature. Therefore.74). Temperature dependence of observed K1 value for iron in comparison with the 10th power rule. The larger the power of the angular function in ( >.27 thermal excitation of the electronic states of magnetic atoms. temperature dependence of the valence states. even if all the coefficients in (12.21. Therefore we have for n = 2 (uniaxial anisotropy) and for n = 4 (cubic anisotropy) Figure 12. the more rapidly the function < > decreases with increasing temperature. The magnetic anisotropy is also influenced by other factors. 12. According to an accurate calculation for the «th power function. therefore. we have the relationship where K^ is the anisotropy constant for the nth power angular function.59) are independent of temperature.

12.4 EXPERIMENTAL DATA Magnetocrystalline anisotropy constants have been measured for many ferro.0 10. First we consider the case of materials with uniaxial anisotropy. After discussing this topic. the orbital magnetic moments remain unquenched by crystalline fields.68 5 5/2 0. R S c Y L a Ce Pr Nd Pr Sm Eu Gd Tb Dy Ho Er Tm Tb Lu No. Table 12. because generally the anisotropy constants are large.56 3 7/2 4.4. oxides.0 9. and are well protected from the influence of the surrounding atoms. because the magnetic moments are produced by 4/ electrons which are located relatively far inside the atoms. and the origin of the anisotropy is comparatively clear.72 5 15/2 10.34 10.40 0.3).50 — — — 7.60 3.62 6 4 2.and ferrimagnetic materials. of 4/el.34 8.55 9.2).60 6 15/2 9.20 3.0 3.2.80 9. which is composed of the spin angular momentum 5 and the orbital angular momentum L according to Hund's rules (see Section 3.1 4. The magnetic moments in this case originate from the total angular momentum.0 4.74 10.2 lists the angular momenta and magnetic moments for fifteen rare earth ions and Table 12. we proceed to consider uniaxial 3d transition metals. (a) Magnetocrystalline anisotropy of rare-earth metals and alloys In rare-earth metals.85 3 0 0. 3+ Ions 5 L J g\//(/+D Meft/MB gJ 0 0 0 2.0 0 Ref ' on Ms 0 0 0 0 1 1/2 2 1 3 3/2 4 2 5 5/2 6 3 7 7/2 8 3 9 5 / 2 10 2 11 3/2 12 1 13 1/2 14 0 0 00 28 29 30 31 32 33 .58 5 6 7.20 10.00 7. In this section we describe some of these results.52 3.4 0 0 0 2.64 6 8 10.0 7.58 6 9/2 3.5 10.274 MAGNETOCRYSTALLINE ANISOTROPY 12.6 7.54 5 4 3.0 10. because the orbital magnetic moments remain unquenched in these materials (see Section 8.00 0 7/2 7.53 0 0 0 Metals MS/MB 0 0 0 — — — — — — 7. and compounds.14 3. /.72 0.1 Uniaxial anisotropy The magnetocrystalline anisotropies of rare earth metals and alloys are extraordinarily large.4 0 0 0 0 0 0 0 0 0 0 3 5/2 2.94 3 6 9.0 9. Angular momentum and magnetic moment of rare earth ions and metals.27 2.6 9.

23). the sample is magnetized only with great difficulty: only 80% of the saturation magnetization is attained in a field as high as 32MA. thus giving rise to a change in electrostatic interaction between orbits and the lattice. We can say that the spontaneous magnetization is confined in the c-plane by a strong magnetocrystalline anisotropy. let us consider how Tb metals develops its enormous magnetocrystalline anisotropy. In such materials. This proves that the orbital magnetic moments survive almost unchanged in the crystalline solids. The orbital moment of Tb is L = 3. In Table 12. which is the maximum value.59.22). In other words.2.34 metals (see also Table 8. 12. as do many other ferromagnetic rare earth metals. This large anisotropy can be explained in terms of the shape of the 4/ orbit and the crystal symmetry. 12. where the orbital magnetic moment remains unquenched. respectively. whereas when the field is applied parallel to the c-axis. Magnetization curve measured for a Tb metal single crystal at 77 K. The anisotropy constant in this case is approximately /£u = 6 X 10 7 Jm~ 3 (6 X 108ergcm~3).633 for a closed-packed hexagonal lattice. If the c/a ratio were the ideal value . so that the orbital plane spreads perpendicular to / forming pancake-like electron clouds (see Fig 12.2).ni"1 (400 kOe)34 (see Fig. Terbium has hexagonal crystal structure. rotation of the spontaneous magnetization tends to rotate the orbits in the crystal lattice. which is much smaller than the ideal value of 1. On the other hand. the c/a value of the hexagonal lattice of Tb in 1.EXPERIMENTAL DATA 275 Fig.22. When a magnetic field is applied parallel to the c-plane. the lattice is compressed along the c-axis. For example. we see that the observed values of the effective magnetic moments of 3 + ions and the saturation moments of ferromagnetic metals are in good agreement with the theoretical values of g^J(J + 1) and gj. the magnetization is increased rather easily.

It is interesting to note that the magnetization does not retrace back along the initial magnetization curve after the maximum magnetic field is applied parallel to the c-axis (see Fig. 12. 12. 12. the neighboring 3+ ions approach the electron clouds of the reference ion from above and below. if the lattice is compressed along the c-axis. and was attributed to the formation of mechanical twins which have the easy axis parallel to the applied field. which just half fill the 4/ shell. the lattice is plastically deformed: elongated by 7% along the c-axis and compressed by 6% parallel to the c-plane.23. it has no orbital moment (L = 0). in spite of the fact that the magnetization process is expected to occur exclusively by reversible rotation magnetization.23). The same phenomenon was observed for Dy metal. The situation remains unchanged with respect to the uniaxial crystalline field about the c-axis even if the triangular atom group is rotated back to its original position. . thus attracting the clouds as shown in Fig.35 Since Gd has seven 4/ electrons. so that no uniaxial anisotropy should be produced. At the same time.22). 12. Therefore J is forced to point parallel to the c-plane. Electron cloud of the 4/ electron of a Tb atom in a hexagonal lattice. the reference ion and its neighbors would have face-centered cubic symmetry. and accordingly exhibits no large magnetocrystalline anisotropy. However.23.276 MAGNETOCRYSTALLINE ANISOTROPY Fig. and also if three nearest neighbor ions underneath a reference ion were rotated 60° about the c-axis (from the solid triangle to the broken one in Fig.

when a small amount of another rare earth element. Therefore.25. is alloyed with Gd. —1. 12.2 K for a 1.26. 12. According to Hund's rule (Section 3.24. 12. —2. so that the two rotate together when a field is applied. The shapes of the electron clouds are independent of the sign of m. thus making the c-axis an easy axis (D < 0).2). the electron cloud for m — 0 extends along the c-axis. the amplitude of the torque curve is increased by a factor of five. By adding only 1.36 The general form of this curve can be interpreted intuitively in terms of the electron clouds of 4/ electrons. The result is that Gd tends to exhibit an anisotropy characteristic of R.26). as shown in Fig. 12. Gd has the maximum spin (S = f ).8% Tb. showing that a large anisotropy is produced by Tb.24 shows the torque curve measured for an alloy of 1. as shown in Fig. On the other hand. When all the states less than half are occupied with seven electrons. the 4/ electron successively takes states with magnetic quantum numbers m = 3. the resultant electron clouds become . The solid curve is from a theory based on a rigorous calculation of 4/ orbits and their interaction with the crystalline field of Gd. is deduced and plotted as a function of the number of 4/ electrons of R in Fig.633. Torque curve measured at 4.11 Figure 12. D. Since the c/a value of Gd metal is less than the ideal value of 1. From the uniaxial anisotropy measured in this case. a pancake-like electron cloud for m = 3 results in an easy plane parallel to the c-plane as in the case of Tb (D> 0).26.0. R.11 Moreover. The dashed curve is that for pure Gd. -3 as the number of 4/ electrons per atom increases (see Fig. 12.2.EXPERIMENTAL DATA 277 Fig. the anisotropy constant per one R atom.8% Tb-Gd alloy single crystal in a plane containing the c-axis. the magnetic moment of R is strongly coupled by the exchange interaction with the moment of Gd.8% Tb in Gd.1. so that its exchange interaction is quite large. The broken curve is for pure Gd.

In fact.26.11 spherical. a hypothetical group composed of one electron in each of the states m = 3. Configurations of 4/ electron clouds for various magnetic quantum numbers.11 . the Fig. because L = 0. and 1 and a half in m = 0 will also result in a spherical electron cloud. Uniaxial anisotropy constant D per one rare earth ion dissolved in Gd metal. as a function of the number of 4/ electrons in the dissolved rare earth. 12.278 MAGNETOCRYSTALLINE ANISOTROPY Fig. 2. 12. Since the shape of the electron clouds is independent of the sign of m.25.

respectively (see Fig. and Sm. Cr and Ni. and are plotted against the atomic percentage of added element M in Fig.27.5 = 7 + 3. because they are divalent in the metallic state. or Cu.12).5) and between Ho and Er (n4f = 10. Although it is difficult or impossible to produce hexagonal ferromagnetic iron or nickel. The experimental points shown by crosses are in good agreement with the theory. (b) Magnetocrystalline anisotropy of Co-alloys Metallic cobalt is a 3d transition metal with hexagonal closed-packed structure which exhibits a fairly large magnetocrystalline anisotropy. This is because the nuclear charge is relatively smaller for n4f < 7.EXPERIMENTAL DATA 279 theoretical curve in Fig. Pm. Kul. Kul. 12. The values of D are generally larger for « 4 y < 7 than for n4f > 1. of cobalt alloys containing a small amount of Cr. and accordingly are identical to Gd and La. we can see the anisotropy of iron or nickel in a hexagonal crystal by alloying these elements in hexagonal cobalt and measuring the change in the anisotropy constant. measured for pure Co and for Co-alloys containing small amounts of Mn.5). In this connection. so that the average radius of the 4/ orbits is relatively larger and the interaction with the crystalline field is larger. Fe. The Z)-value is zero for Eu and Yb. the values of Kul at T = 0 were determined. Temperature dependences of the uniaxial anisotropy constants. the replacement of Co atoms by nonmagnetic atoms. One of the reasons for this large anisotropy may be the low crystal symmetry. except for Ce.25 intersects the abscissa between Nd and Pm (« 4 y= 3. The dot-dash line shows the calculated effect of simple dilution. The lines for all the other added elements except Fe have slopes steeper than that for Fig. The line for M = Cu is very close to that for simple dilution.37 Figure 12. Extrapolating these curves to zero absolute temperature.37 . that is. this is expected. Ni. Mn.28. because Cu is nonmagnetic.27 shows the temperature dependences of the uniaxial anisotropy constants. 3. it is of interest to investigate how large an anisotropy would be found in hypothetical hexagonal iron or nickel. The reason for this disagreement may be that the effect of crystalline fields is more influential than the exchange interaction on the orbital states in these elements. 12. 12.

280 MAGNETOCRYSTALLINE ANISOTROPY Fig.2 X 105 Jm~ 3 . in which the crystalline field effect results in the following level scheme: m = +1 are the lowest. and finally reaches a large negative value of —10. This means that these elements make negative contributions to Kul.. The origin of this phenomenon must be due to atomic interactions of longer range than the second-nearest neighbors. In the case of the Co-Fe system. However. in close-packed hexagonal.and C-layers have the same nearest neighbors as in the face-centered cubic lattice (see Fig. and m = 0 is the highest. 9. as a function of the number of 3d holes in M. 12.39 (c) Magnetocrystalline anisotropy of rare earth-3d metal compounds The rare earth-cobalt compounds of the compositions RCo5 and R2Co17 have .28. this change in crystal structure does not explain the dramatic change in Kal. changes sign to negative. At the same time the crystal structure changes from closed-packed hexagonal to double hexagonal. The atoms in an A-layer between B. at 0 K for various Co-alloys as a function of the 3d metal alloys content. and in the sequence ABACABAC. m = ±2 the next. Kul. however. at which point Kul decreases discontinuously. This behavior has been interpreted quantitatively in terms of the pseudo-localized model.. the value of Kul first increases and then decreases slowly with the addition of Fe up to 1. deduced from the slope in Fig.29 shows a plot of the anisotropy constant per M atom. The difference between the two is that the stacking sequence of close-packed planes along the c-axis is in the sequence ABAB. The actual origin. 12.28. has not yet been clarified.1). in double hexagonal.05at% Fe... Figure 12. Uniaxial anisotropy constants.38 which contributes a positive Kul.37 simple dilution. It is interesting to note that Fe and Mn exhibit an anisotropy larger than Co. since Kl for face-centered cubic Co is negative.

but it changes sign at 126 K.4 7. and exhibits a very strong magnetocrystalline anisotropy. and Pb 2+ are 1. 12.29.42 (d) Magnetocrystalline anisotropy of hexagonal ferrites The crystal structures and magnetic properties of hexagonal ferrites were described in detail in Section 9. the anisotropy constants amount to 106-107Jm~3 (107-108 ergcm"3).7 X 106 Jm~ 3 at 275 K. which contains Fe3+.37 hexagonal crystal structure.43 1.3. and 1.7 1. The ionic radii of Ba2+. The value of Kul is — 6 . 5 x l 0 6 J m ~ 3 at OK. Table 12. which is the main constituent of NdFeB magnets. M 2+ and Ba2+. so that they exhibit strong magnetocrystalline anisotropies.6 10. which are very large as compared with Table 12. The crystal structure is the magnetoplumbite-type hexagonal.5 -7 -40 10.57 1.40 Compounds YCos CeCo5 PrCo5 NdCo5 SmCo5 Curie point (K) 978 673 921 913 984 M s /M B atOK per RCo5 per Co 7.4. This is due to a very strong crystalline field acting in a crystal of a very uniaxial nature (see Fig. respectively.3 list various magnetic data40 for the compounds of the RCo5-type. The compounds of the R2Co17-type exhibit comparable values of magnetocrystalline anisotropy. Sr 2+ . Saturation moment and anisotropy constants of RCo5.32 1. 1.43.5 Ku2atOK (MJm~ 3 ) ~0 ~0 18 19 ~0 . has the tetragonal structure (see Section 10.41 The rare earth compound Nd2Fe14B.32 A. or Pb 2+ . As seen in this table.44 1.4 10. 8. and reaches +3.EXPERIMENTAL DATA 281 Fig.40 KulatOK (MJm~ 3 ) 6.27.26). Uniaxial anisotropy constant per added 3d alloy atom in Co as a function of vacancies in the 3d band.6).5 5.9 6. Sr 2+ .

282 MAGNETOCRYSTALLINE ANISOTROPY Table 12. the anisotropy constants were determined by means of a magnetic torsion pendulum45 from the frequency of the torsional vibration of a specimen with the c-axis perpendicular to the torsional axis. Magnetocrystalline anisotropy of hexagonal ferrites at 20°C.32 A)..339 430 280 390 130 340 410 the radii of Fe3+ and M 2+ . thus forming hexagonal crystal structures.1 KU1 + 2KU2 (10 5 Jm~ 3 ) /. (10s J m ~ 3 ) 3. and Z-types. which has the same electronic .478 0. The frequency is related to the second derivative of the anisotropy energy (12.415 0. etc. Ku. because in spite of the presence of a cubic spinel phase the overall symmetry of the crystal is uniaxial.478 0. In this case.1).6 -1.285 0.150 0.56 Ku2 = 0.21 -1. the compounds are classified into M-. Depending on the structures of the layers containing Ba2+.0 0. The actual origin of this anisotropy is considered to be an Fe3+ ion surrounded by five O 2 ~ ions.8 ("O (Ref.4. (0.2 to 0.4 2. and their ratios to the spinel phase. the anisotropy constant for a Y-type compound was expected to be Kul = -5 to —7 X 10 5 Jm~ 3 (Xl0 6 ergcm~~ 3 ) at OK. Therefore these large metal ions cannot enter the interstitial sites in the closed-packed oxygen lattice. so that it is proportional to Kul for a positive Kul and to Kul + 2Ku2 for a negative Kal. 43 43 44 44 43 43 43 43 43 43 43 6 9 8 0.9 -1.46 However.5 T. while for negative Kul the c-plane is the easy plane.232 0. together with other magnetic properties.86 2. but occupy substitutional sites in the layer parallel to (111) of the spinel phase. Table 12. W-. The magnetocrystalline anisotropy of these hexagonal ferrites is expressed by (12.395 Ku2 = 0. From the calculation of a dipole sum. In the case of positive Kul. It is interesting that such a large anisotropy is observed in spite of the fact that the main magnetic constituent of these ferrites is Fe3+ with no orbital magnetic moment. the c-axis is the easy axis.4. and are comparable with that of O 2+ (1.5 X 105 J m~ 3 .1) with respect to the polar angle.8 A). These compounds are all ferrimagnetic with Curie points about 400°C and with saturation magnetizations at room temperature from 0. As seen in Table 12. Y-.6-0.160 0.6 -0. which has the opposite sign of the observed value. the anisotropy constants for these hexagonal ferrites are all of the order of 105 J m ~ 3 (106 ergcm"3).0 -2.3 3. a similar calculation for the M-type compound led to Kul = —1. (T) 0.75 -0.4 lists magnetocrystalline anisotropy constants measured at room temperature for various hexagonal ferrites.46 Kondo47 showed that an Mn 2+ ion. 44) 450 455 ©f Symbols M Fe2W FeCoW Co2W FeZnW Ni2W Mg2Y Ni2Y Zn2Y Co2Y Co2Z Composition BaFe12O19 BaFe18O27 BaCoFe17O27 BaCo2Fe16O27 BaZnFe17O27 BaNi2Fe16O27 Ba2Mg2Fe12O22 Ba2Ni2Fe12O22 Ba2Zn2Fe12O22 Ba2Co2Fe12O22 Ba3Co2Fe24O41 Ref. 6.

the c-axis is oriented perpendicular to the substrate surface. he considered a distortion of the ion. The compound Fe7Seg has a similar spin structure and also exhibits ferrimagnetism. overlapping of the electron clouds with the surrounding O 2 + .4. which has an easy plane parallel to the c-plane. exhibits a very strong uniaxial anisotropy with the easy axis parallel to the c-axis.49 The compound MnBi. The anisotropy constants measured for a polycrystalline material with the c-axes aligned parallel are X nl = 9.50 When this compound is evaporated onto a glass substrate and annealed. It has been demonstrated that 'magnetic writing' can be performed by using a magnetic needle to locally magnetize such a grain-oriented MnBi film.51 . The spin axis of the ferrimagnetic Fe7S8 tilts by 20° at OK. The magnetocrystalline anisotropy of typical uniaxial compounds will be described here.1 X 106 ergcnT 3 ) and Ku2 = 2. which have the easy axis parallel to the c-axis. and also the relationship 2|Xul| > \Ku2\ holds. can produce the expected anisotropy. and the shape of the curve of easy axis angle vs temperature. depend on the ordering scheme of the lattice vacancies. These phenomena were interpreted by the one-ion model of the Fe2+ ion surrounded by lattice vacancies. The feature of the magnetocrystalline anisotropy of these compounds is that the easy axis is parallel to or near the c-axis at low temperatures. In the case of FeS. (e) Uniaxial anisotropy of magnetic compounds Magnetism of ferro.EXPERIMENTAL DATA 283 configuration as an Fe3+ ion.4).1 X 105 J m ~ 3 (9.46 The mechanism of the easy cone in Co2Y and Co2Z has been explained in terms of the Co2+ anisotropy48 discussed in Section 12. which is a NiAs-type ferromagnetic compound (Section 10. the anisotropy results in an easy cone of magnetization with polar half-angle sin"1 ^ —Kul/2Ku2. which has antiferromagnetic spin structure (see Section 10.2). Ferroxplana. are used as permanent magnet materials (see Section 22.3). The uniaxial anisotropy observed in the low-temperature phase of magnetite (Fe3O4) will be discussed in relation to the cubic anisotropy of this material (see Section 12.3.2(b)). and then rotates discontinuously to the c-plane at 400 K. These useful properties are based on the strong magnetocrystalline anisotropy of these materials. and gradually approaches the c-plane with increasing temperature. It was observed for Fe7Seg that the temperature range for the rotation of the easy axis.6 X 106ergcm~3).6 X 105 JnT 3 (2. Pyrrhotite (Fe^^S) has the NiAs-type crystal structure and exhibits ferrimagnetism as a result of the ordering of vacancies in the stoichiometric compound FeS. the spin axis is parallel to the c-axis in the temperature range from 0 to 400 K.and ferrimagnetic compounds other than oxides was described in Chapter 10.3). When the anisotropy constants Kul and Ku2 have opposite signs. has excellent high-frequency characteristics (see Section 20. rotates gradually towards the c-plane with increasing temperature. which is antiferromagnetic. and reaches the c-plane at about 80 K. Barium and strontium ferrites. and mixing of the excited states.

12. Figure 12.4.32 shows the composition dependence of K^ of Fe alloys with the . (After Hall52) 12. The exact form of the decrease also depends on the annealing treatment.52 The exact nature of the variation depends on the annealing of the alloy.284 MAGNETOCRYSTALLINE ANISOTROPY Fig. Therefore most soft magnetic materials. Some of the experimental results will be summarized below. have cubic crystal structures with low cubic anisotropy (see Section 22. 10. The value of Kl becomes more negative as the degree of order increases. (a) Magnetocrystalline anisotropy of 3d transition metals and alloys First we will discuss the anisotropy of iron alloys with body-centered cubic structure. The origin of the cubic anisotropy is not as clear as the uniaxial anisotropy.2 Cubic anisotropy Generally speaking. which produces a superlattice as already explained in Chapter 10 (see Fig. which exhibit high permeability and low coercive force.30. Variation of Xt with composition in Fe-Al alloys (room temperature). cubic anisotropy is smaller than uniaxial anisotropy. because many higher-order terms caused by various mechanisms can contribute to this anisotropy. suggesting the formation of the superlattices Fe3Co and FeCo (Fig. The anisotropy constant K1 of Fe-Al alloys decreases monotonically with the addition of nonmagnetic Al as shown in Fig. 12.31). because of its higher crystal symmetry. 1230.1).3). The K-t value of Fe-Co alloys also decreases with an increase of Co content.

. in Fig. The Ni-Fe alloys with face-centered cubic structures form the Cu3Au-type superlattice Ni3Fe. is much more steep. 12. as shown in Fig. 12. Variation (After Hall52) of K^ with composition in Fe-Co alloys (room temperature) nonmagnetic elements Ti53 and Si. Variation of K^ with composition in Fe-Ti and Fe-Si alloys (room temperature). as already discussed in Chapter 8.EXPERIMENTAL DATA 285 Fig. below which the ordering develops. the value of K^ increases with the addition of nonmagnetic Ti.33.55 When the alloy with composition Ni3Fe is quenched from about 600°C.54 The saturation magnetization of Fe-Si alloys decreases with the addition of Si as if Si simply dilutes the magnetization with the atomic magnetic moment of Fe remaining constant.32. The ordering temperature of this superlattice is about 600°C. The variation of Klt however. 12. It is interesting to note that in the case of Fe-Ti alloys. it retains the disordered state.31.

and then once again from positive to negative at 20at% Co52'58'59 (Fig.12).34 shows the variation of K-^ as a function of logarithm of the cooling rate in the temperature range from 600°C to 300°C.286 MAGNETOCRYSTALLINE ANISOTROPY Fig. Similar behavior can be seen for Ni-Cr and Ni-V60 in Fig.1). Fig. 8. with the probability of 3:1. In Ni-Co alloys.36). K^ changes sign from negative to positive at 4at% Co.36. (After Bozorth56) .2). 18.35 shows the composition dependence of K^ for the ordered and disordered states. which exhibits extraordinarily large permeability (see Fig. which the lattice sites are occupied by Ni and Fe at random. 12.33.56 The alloy corresponding to K1 = 0 is called Permalloy. 12.56 Figure 12. 12.34. Figure 12.27 and Section 22. The anisotropy constant Kl in this state is very small or almost zero. Variation of A^ in Ni3Fe as a function of logarithm of cooling rate in the range 600-300°C (room temperature). 12. during which the superlattice is formed. The Kl values of the Fe-rich alloys containing more than 65% Fe decrease once again with increasing Fe content. The superlattice Ni3Fe. but it increases with increased ordering. This complicated compositional dependence of Kl is quite different from the monotonic change in the saturation magnetization as seen in the Slater-Pauling curve (see Fig. reflecting the instability of ferromagnetism due to the Invar characteristic57 (see Section 8.

3). whose unit cell is composed of 32 close-packed O 2 ~ ions and 24 interstitial metallic ions. Cd and Mg). 12. (After Bozorth56 and Kagawa and Chikazumi57) (b) Magnetocrystalline anisotropy of spinel-type ferrites The crystal and magnetic structures of spinel-type ferrites were discussed in detail in Section 9. 9. The essential features may be summarized as follows. Fe. such as M 2+ and Fe3+. Ni.35. Zn.36. The composition of these oxides is represented by the chemical formula M 2 + O-Fe^ + O 3 (M = Mn. Co.2. 8 M 2+ ions occupy A sites. Composition dependence of K^ at room temperature for ordered and disordered Ni-Fe alloys. The crystal structure is the spinel-type. 12. while the Fig. while the other 16 Fe3+ ions occupy B sites. located on two sites called the A and B sites (see Fig.EXPERIMENTAL DATA 287 Fig. In an inverse spinel. . Composition dependence of K1 at room temperature for various Ni alloys. In a normal spinel. 8 Fe3+ ions occupy A sites. Cu.

3. Temperature dependence of K1 for various spinel ferrites containing Co2+.37 shows the contributions of Co2+ ions to Kl for Fe3O4. Figure 12. the Co2"1" ions on B sites produce a positive Kv Most ferrites have negative Klt so that the addition of Co tends to decrease the magnitude of K\. the shape of the ions which occupy A sites. As explained there. so that only the magnetic moments of M 2+ ions contribute to the net spontaneous magnetization. It is seen that the contribution of Co2+ ions to K^ is positive for all the ferrites. are spherical (see Section 3.2). so that these ions do not make a large contribution to the magnetic anisotropy. begins to increase at 230 K and changes sign to positive at 130K. Below about 125 K. etc. as as shown in Fig. Mn 07 Fe 2i3 O 4 . 12. when Co is added. Generally speaking. The magnetocrystalline anisotropy of ferrites is interpreted by the one-ion model as explained in Section 12.37.38. The Fe2+ ions also make a large contribution to the magnetic anisotropy. The value of Kl is negative at room temperature. or the Verwey point. such as Zn 2+ . Tv. MnFe2O4. Most ferrimagnetic ferrites have the inverse spinel structure. (After Slonczewski24) remaining 8 Fe3+ ions and 8 M 2+ ions occupy B sites. the crystal transforms to a structure of lower . One example is the anomalous behavior of K^ of magnetite or Fe3O4. in which magnetic moments of Fe3+ ions on A sites couple antiparallel to those of Fe3+ and M 2+ on B sites. 12. Mn 2+ and Fe3+.288 MAGNETOCRYSTALLINE ANISOTROPY Fig. decreases with decreasing temperature.

77). Then the magnetocrystalline anisotropy energy is expressed as where a m is the direction cosine referred to the longest body-diagonal or [111]. The a-. was found to be expressed by the Arrhenius equation. the magnitude of these constants should be in the ratio 3:3:10. Temperature dependence of K1 for magnetite (Fe3O4). If the K1 term is converted to the coordinate system for the low temperature phase.2).61 as shown in Fig. with the same activation energy. b-. The activation energy Q was found to be 0. The actual . so that the magnetocrystalline anisotropy becomes uniaxial.23 eV for Ka. Therefore the origin of the magnetic anisotropy of the low-temperature phase is considered to also be related to Fe2+ ions on B-sites. and c-axes. 12. and ac be the direction cosines of spontaneous magnetization referred to the a-. The higher order constants Kaa. b-. The electrical conductivity has a similar temperature dependence. and Kab correspond to K^ of the cubic phase. It seems clear that this phenomenon is caused by a hopping motion of electrons between Fe2+ and Fe3+ on the B-sites. Kb. symmetry (see Section 9. Kbb.20-0. The temperature dependence of these anisotropy constants. 12. Ku. [110] and [001] axes of the original cubic structure.61 The Kl values below Tv were calculated by (12.38. and c-axes of the low temperature phase are almost parallel to the [110]. ab.39.EXPERIMENTAL DATA 289 Fig. Let aa.

62 The low-temperature transition of magnetite was first found by Verwey. .4:10. disproved by later experiments. Then the Kl value can be calculated by the relationship which is plotted in Fig.2 K was 2.65 Miyata66 measured the temperature dependence of Kl for various mixed ferrites. T curve above 350 K. 12. 1239. and finally condensed to a low-temperature phase. In the same figure.6:3.61 It is to be noted that these points fit well with the extrapolation of the K^ vs. various physical quantities are condensed towards 81 K. Temperature dependence of magnetic anisotropy constants for low-temperature phase of magnetite (Fe3O4). from the broken curve connecting the points at high and low temperatures as caused by some clustering related to the Verwey transition.64 This transition may be a sort of structural transition.63 who assumed an ordered arrangement of Fe2+ and Fe3+ ions on B-sites as a result of a cessation of the electron hopping between these ions. which is very close to the prediction. which extrapolates to the abscissa at 81 K.61 ratio observed at 4.62 The variation of K1 is regarded as one of the critical phenomena associated with this transition. in which some phonons accompanying a charge ordering are softened with decreasing temperature. This model was. We can regard the deviation of Klt A/Cj. As a matter of fact.38 in the temperature range T < Tv. the reciprocal of hKl is plotted against temperature as a solid line.290 MAGNETOCRYSTALLINE ANISOTROPY Fig. however.

40-12. we see that the anomalous increase of AjSTj observed in Fe3O4 is Fig. (After Miyata66) Figures 12. 12.EXPERIMENTAL DATA 291 Fig. Temperature dependence of K1 for MnFe2O4-Fe3O4 mixed ferrites. 12.41. Ni. and Zn.42 show the results for Fe3O4 with added Mn. (After Miyata66) . Temperature dependence of K1 for NiFe2O4-Fe3O4 mixed ferrites.40. Comparing these graphs.

the composition is MnFe2O4. If should be noted that mechanisms (2) and (3) are not realized for magnetic ions . When Ti4+ ions are added to Fe3O4. A large positive shift of Kl was observed by this addition. because they have ionic sizes larger than Fe+3.292 MAGNETOCRYSTALLINE ANISOTROPY Fig. thus increasing the number of Fe24" ions. while this anomaly is completely suppressed by the addition of Mn or Zn.O4. 12. (2) Deformation of the 3d shells of magnetic ions produces a magnetic anisotropy through a dipole interaction in the shell (a kind of shape anisotropy (see Section 12. as shown in Fig. (3) An excited state with an orbital magnetic moment is mixed through the spin-orbit interaction and this orbital magnetic moment produces magnetic anisotropy through the interaction with spins. Yosida and Tachiki23 summarized the origin of magnetic anisotropy as follows: (1) The contribution from magnetic dipole interaction is small.68 These facts tell us that the Fe2+ ions on B-sites contribute to a positive K^. while Fe2+ ions appear as soon as x is reduced from 1.67 For x= 1. The Ni 2+ ions go into B-sites and do not disturb Fe3+ ions on A-sites. they go into B-sites.Fe3_J. This fact suggests that the AJ£j anomaly may possibly be caused by Fe2+ ions coupled with the lattice instability related to the low temperature transition. 12. the K1 value becomes more positive as soon as x is reduced from 1. whereas the Mn 2+ or Zn2+ ions go into narrow A-sites and change the instability of the lattice. Magnetic ions other than Co2+ and Fe2+ do not contribute strongly to the magnetic anisotropy. in which no Fe2+ ion exists.43. (After Miyata66) not very much influenced by the addition of Ni.1)). Temperature dependence of Kl for ZnFe2O4-Fe3O4 mixed ferrites.42. In the mixed ferrites MnJ.

Temperature dependence of Kl/Is for MnFe2O4 and the comparison with theory (solid curve). because these magnetic shells do not deform. For instance. Fig.44 shows the temperature dependence of Kl/Is observed for Mn-ferrite or MnFe2O4 and the comparison with the theoretical curve calculated on this basis. (After Yosida and Tachiki23) .cO4 (0 <x < 2) with x measured at various temperature.23 We see that the agreement is excellent. Ni 2+ with 3d8 (S = 1) and Co2+ with 3d1 (S = f ) do not develop magnetic anisotropy from these mechanisms. (After Penoyer and Shafer67) with S = \.44. In the case of Mn 2+ and Fe3+ with 3d5 (S = f). 12.EXPERIMENTAL DATA 293 Fig. Figure 12. the 3d shell is deformable.43. 12.3_. Variation of Kl for MnxFe. 1 and f.

so that there is no electron hopping. The essential points are as follows: The garnet-type ferrites are oxides containing rare earth (R) and iron (Fe) ions with a complicated crystal structure represented by a chemical formula 3R2O3 • Fe2O3 or R3Fe5O12.294 MAGNETOCRYSTALLINE ANISOTROPY Fig.46. The Curie point is 540-580 K. with their spins antiparallel.45. All the metal ions are trivalent and no divalent ions exist. Five Fe3+ ions in a formula unit of R3Fe5O12 occupy 24d and 16 a lattice sites in the ratio 3:2.70 . Temperature dependence of K^ and K2 for YIG (Y3Fe5Oi2). thus exhibiting ferrimagnetism. 12. Since the Fe3+ ion has 5MB (Bohr Fig. 12. Temperature dependence of Kl for Sm 3 Fe 5 Oj 2 . Dy3Fe5O12 and Ho3Fe5O12. (After Hansen69) (c) Magnetocrystalline anisotropy of garnet-type ferrites The details of this class of oxide have been described in Chapter 9.

9.06 K2 (104 JnT 3 ).56 -0.023 -0.14 -2. since the interaction between R3+ and Fe34" moments is weak.3 ) -0.45 shows Table 12.2 77 295 4. The former contribution can be found experimentally by measuring the anisotropy of yttrium-iron-garnet or YIG.0005 21 Sm -400 -14.082 -9.06 .6 -0.05 +90 +0.035 -0.70 R Y T(K) 4. R3Fe5O12. thus producing a large spontaneous magnetization at OK. and a contribution from R3+ ions. However.2 77 295 4.06 2. these five Fe ions contribute 5MB to the resultant magnetic moment per formula unit at OK.9).021 -0.041 Tb Dy Ho -7.010 -76 Gd 4.2 293 K1 (10 4 Jnr 3 ). Magnetocrystalline anisotropy constants of garnet-type ferrites.7 +500 Er 4. and is compensated by the Fe3+ moment at a particular temperature called the compensation point.22 -0.38 Eu -1.05 -120 -8 < -0.06 -67 -0.17 -4 -0. the spontaneous magnetization of most garnet-type ferrites exhibits the N-type temperature dependence (see Fig.30 -0.25 -0. (10 5 ergcm.06 -0.3 ) -0. Figure 12.2 78 300 -2. The magnetocrystalline anisotropy of the garnet-type ferrites is composed of two parts: a contribution from Fe3+ ions. In other words. the contribution of the R 3+ moment decreases rapidly with increasing temperature.2 80 300 Tm Yb ~0 +80 +0.2 80 320 80 300 80 300 4.(10 5 ergcm.39 -0.7 < -0. measured at various temperatures.5.037 -0.EXPERIMENTAL DATA 3+ 295 magnetons). In addition.2 77 300 77 293 4.3 -0.41 -0.44 -0. because Y has no magnetic moment. the magnetic moment of three R3+ ions on the 24c sites couple with this resultant Fe moment ferrimagnetically.36 -0.

S. R.. 4 above. 29 (1968). Series in experimental physics (in Japanese). 12. Barnier. 4.44. Japan. 321 in volume quoted in Ref. Radium. Kouvel and C. and K. Stat. 293-325. Proc.71 and affect these anisotropy constants to a great extent (see Section 14. Tajima. 3. The reason for this large contribution of R3+ is that the orbital moment becomes aligned with decreasing temperature. Graham. S. 718. Rev. 8. Phys. 623. Appl. 13.6). J. Penoyer. 340.1 X 105 Jm~ 3 . Chikazumi. 5. Soc. (1974). thus giving rise to a large interaction with the crystalline field. 495.296 MAGNETOCRYSTALLINE ANISOTROPY the temperature dependence of K1 and K2 of YIG. 1964). 12. 10. what functional form should be expected for angular dependence of the anisotropy energy? Use the Zener-Carr formulation. H. Appl. J. which has an orbital angular momentum L. Yamada and S. Phys. 477. C-I. Phys. Franse and G. J. is quite large and has a strong temperature dependence. 7.) (in Japanese). 9. the magnetostriction constants (see Chapter 14) are also very large. J.. 1975. 9 (9). Y. New York. in volume quoted in Ref. R. Pauthenet. 15 (1960). 711. /. 1968).79T and Kul = 4. calculate the anisotropy field in the c-axis for cobalt. Toyama. Chikazumi. above. Hofmann. Rimet. Jr. Phys. 132-3. K. 39 (1968). 309. 306 in volume quoted in Ref. 409. J. 11.46. and G. PROBLEMS 12. Chikazumi. Gengnagel and U.. Phys. 6. B-I (1962). calculate the magnetocrystalline anisotropy constant Kl for a ferromagnetic metal with body-centered cubic structure (a = 3 A). de Vries. Kotai Buturi (Solid State Phys. 91. Phys. Pearson. 17 (Kyoritsu Publishing Co. Japan. so that they exhibit a monotonic temperature dependence similar to that in Fig. Japan. the contribution of R 3+ . D. The origin of this anisotropy is the same as that of Fe3+ ions in the spinel-type ferrites. M. J. p. Chikazumi. REFERENCES 1. 4. Sci. express the anisotropy energy as a function of the angle 9 between the magnetization and the [001] axis. 30 (1959). 12. 28 (1957). T. /. (1970).3 Assuming q = 3 X 10 ~ 25 J. Wakiyama and S. 179. Grenoble Con/. Chikazumi. Sol. . S.4 If the temperature dependence of an anisotropy constant were the same as that of spontaneous magnetization.2 Knowing the values for 7S = 1. pp. Chikazumi. 15 (1976). Table 12. Instr. 13. K.1 When the magnetization is rotated in the (210) plane in a cubic crystal. 12. F.. 20 (1959). 2. /. Physics of Magnetism (1st edn) (Wiley. Chikazumi. In some cases. Physica.5 lists the values of K^ and K2 at a number of temperatures for various garnet-type ferrites. 17 Suppl. 4 above. T. Soc. F. 12. S. as shown in Fig. Abe and S. 12. S. Ignore terms higher than K2. Phys. Soc. In contrast to this. pp.. No. using the spin-pair model. R. Japan. 11 (1956). p.

Legvold. H. Phys. 35. J. Soc.. 619. D. R. 1. Otani. Phys. W. Phys. and F. S. 31. J. New York. 26 (1955). /. Stevens. CI-551. 38. 756. A. Phys. Phys. L. S. Bozorth. Jr. J. R. H. Chikazumi. Appl.. F. P. and F. Sci. Rhodes. S. 53. Dryvesteyn. Berlin. 118. R. 39. 2046. 436. 23 (1960). Wijn. A. 45. 18. 197. 449. Okamoto. Legvold. Soc. Liebermann and C. (Grenoble.. Prog. Miyajima. Ferromagnetismus (Springer-Verlag. /. H. S. 1092.. E. Ono. and O. Kelley.. Perkins and S. J. Vol. L. 297 E. MAG-5 (1965). and F. 1055. 15. E. H. Wakiyama. and C. T. H. Legvold. H. 348. Bickford. S. S. Proc. p. C. 31 (1960). Gorter. Phys. Phys. Physik der Fertile (Academic Press. G. Fac. Ferrites (Wiley. Enz. D. 54. 110 (1958). H. 24. 1964). 23. Phys. Phys. F. and E. 55. (1928). Conf. London. Okiji. Rodbell. Int. K. 253S. H. H. Graham. R. 20.. Legvold. Phys. 28. S.. 313. M. S. Wiley. and Y. R. Behrendt. Appl. Proc. 816. L. 17. Fast. 56. Spedding. J. Foster. Boothby. Chikazumi. 22.. 1181.. R. S. B15 (1977). K. Chikazumi. 259S. E. 17B-1 (1962).. L. Phys. Fujii. 32 (1961). 29 (1975). /. Rev.. 32. J. W.. Theor. I. 96 (1954). 36. Phys. 33. Yosida. Tanabe.. H. /. S. 822. S.. Rev. 50. J. A65 (1962). 27. A. Tokyo. Chikazumi. 119 (1960). 52. Nesbitt. 48. 43 (1933). Rev.. Rev. Phys. C. U. 1959). Phys. 2 (1938). Conf. 127 (1962). Phys. de Phys. Kaya. 1217. AIP Conf. 106. H. No. 22. Slonczewski. Bozorth. Rev. /. H.Y. Phys. Tachiki.REFERENCES 14. L. Int. Tachiki. Appl. Tajima. 331. H. 1547.. 827. Heidenrich. Phys.. Tatsumoto.. 28 (1957). 39. Mod. et Rod. Y. For instance. W. Japan. Mag. K. Theor. J. J. P. J. Williams. McKeehan. P. /. Oguro. 49. 30. 2058. 445. 1963). and S. D. J. 1970). L. 17 (1957). R. 27 (1956). and F. and R. E. Japan. E. K. and S. 132 (1963).. 19. Heisenberg. Phys. Phys. Inoue. W. D. J. and K. J. H. 1025. G. Nesbitt and H. Phys. Wijn. B. S. Phys. 42. H. J. de Jong. J. Spedding. Appl. N. 48 (1980). and F. D. 30 (1959). 16. D. E. p. Spedding. Legvold.. Ferrites (J. D. 51.. 25 (1953). J. Kamimura. 49. 3436. Spedding. H. Phys. 47. Phys. 21.. 34. Appl. J. 25. Theor. 1973). 26. 127. Sherwood. /... 109 (1958). 448. . /. R. Chan. Phys. Ligand field theory and its applications (in Japanese) (Syokabo Publishing Co. Proc. Sugano. Rev. Smit and H. C. Williams. 23 (1960). Z. Rev. Appl. 37. 122 (1961). Rev. Magnetism (ed. Phys. Bickford. Appl. Kanamori. Wijn. 1544. 78 (1950). J. Williams. M.. Kneller. Hegland. Rev.. 20 (1959). Adachi. Hall. 477. 598. IEEE Trans. C. 42. Mag. Rev. 43. (Nottingham. 204.. C. W. Tanuma. Nigh. Krupicka. Yosida and M. Conf. J. Casimir. (Kyoto). 29 (1958). 1964). Yosida. H. J. p.. Rev. B. W. Phys. /. Prog. (Nottingham. Chikazumi. Jr. 44. Univ. W. Hokkaido Imp. Phys. T. Legvold. 109 (1958). W. Mag. 29 (1958). 265. 1959). S. J. 29. 40. and K. and F. 85. Proc. New York. K. J. Williams. J. 61 (1987).. Fast. 158. Soc. and J. Williams. Spedding. Phys. 1335.. Sherwood. Slonczewski. Phys. S. A. Appl. 46.. Strassler. H. /. H. Appl.. R. Miyajima. Kondo. F. M. Strandburg. Rev. Phys. and S. M. 131 (1963). C. Spedding.. Prog. Zener. H. Nesbitt. 28 (1957). Appl. 360.. 24 (1963). Rev. 41. Smit.. Proc. /. 1970). 25 (1954). 1962). Mag. 1341. 725. Int. Mitsuoka. Phys. by Rado and Suhl) (Academic Press. de Phys. R. and E. Appl. 1014. Smit and H.. J. 1000. J. Carr. S. Green. A.

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13. no field was applied during annealing.5% Fe-Ni alloy.7 . We shall discuss various types of induced anisotropy in this section. to the direction along which the magnetization curve is measured.1 shows the effect of magnetic annealing on the shape of the magnetization curve of a 21. Curves A and C are measured after annealing in a magnetic field applied parallel and perpendicular. Magnetization curves of 21. and was investigated by Dillinger and Bozorth2 in detail. Not only the magnitude but also the easy axis of the anisotropy can be altered by appropriate treatments.13 INDUCED MAGNETIC ANISOTROPY The induced magnetic anisotropy differs from the ordinary magnetic anisotropy discussed in Chapter 12. This behavior can be attributed to an induced anisotropy whose easy axis is parallel to the direction of the annealing field. The effect was first observed by Kelsall1 in Fe-Ni alloys.1. in that the induced anisotropy is produced by a treatment (often an annealing treatment) that has directional characteristics.1 MAGNETIC ANNEALING EFFECT The magnetic annealing effect is obtained by heating or annealing a magnetic material in an applied field. In the case of curve B. respectively. and (C) with perpendicular (or circular) magnetic field.5 Permalloy which was cooled from 600°C (A) in a longitudinal magnetic field. (B) in the absence of magnetic field. but local easy axes were produced parallel to Fig. Figure 13. 13.

as a function of Ni content in Fe. 14. or an anisotropic distribution of different atomic pairs such as Ni-Ni. Both models explained the fact that the induced anisotropy disappears when complete ordering is developed. This result conflicts with both the models. On the other hand.9"11 We discuss the problem using the formulation first given by Neel. This alloy. called Permalloy.300 INDUCED MAGNETIC ANISOTROPY the direction of spontaneous magnetization in each magnetic domain during annealing. or Ni-Fe. Then the anisotropy . and AB pairs. AA. and /AB. Before going into details of this phenomenon. BB. We assume that the coefficients of the dipole-dipole interactions (see (12. and nearly quadratic with respect to the Fe composition. 12. This puzzle. where the ordering process starts. The structure of this superlattice is shown in Fig. Later Dahl4 proved the presence of a superlattice in Ni-Fe alloys. and AB.59)) of AA. and a long annealing time (about one week) at this temperature is required to attain the equilibrium state. let us describe the history of this alloy. From the average susceptibility of curve C.5wt% Fe-Ni. Fe-Fe. was investigated by many researchers with inconclusive results. he assumed that the length of an Ni-Fe pair is smaller than the length of other possible atomic pairs. which can produce an induced anisotropy through the magnetoelastic energy. Chikazumi7 found that the induced anisotropy tends to disappear as the alloy approaches the fully ordered state.11). the uniaxial anisotropy constant of the induced anisotropy is estimated to be 1 X 102 JnT 3 . are different from one another. BB. and Kaya5 investigated the process of formation of the superlattice in relation to changes in magnetic properties. where the degree of order is maximum. and explained the induced anisotropy as the result of shape anisotropy of the second phase (see (12. because the strain model predicts a minimum at about 80% Ni where the magnetostriction constants go through zero (see Fig.33. while the ordered phase model predicts a maximum at the Ni3Fe composition.24)). given by l^. In a binary A-B alloy there are three kinds of atomic pairs. Based on the fact that complete ordering decreases the specific volume of the alloy by 5 X 10"4. It was found that the order-disorder transformation takes place at about 490°C. reaching a maximum at a composition of 21. It was discovered by Arnold and Elmen3 in 1923 that Ni-rich Ni-Fe alloys exhibit very high permeability. The open circles in Fig. Slow cooling or annealing at intermediate temperatures greatly lowers the permeability.2 represent the maximum values of induced anisotropy constant observed after field cooling from 600°C at various cooling rates. Tomono6 discovered that magnetic annealing is effective at 500°C.9 The curve form is quite monotonic. has unusual annealing behavior: high permeability is attained only when the alloy is quenched from high temperatures. known as the 'Permalloy problem'. We ignore pair interaction terms higher than the quadrupole interaction. He tried to explain this phenomenon in terms of 'directional order'. Kaya8 assumed that ordering occurred by the growth of distinct volumes of the ordered phase. The directional order model was then reinterpreted in terms of atomic pair interactions whose magnitudes are different for different pairs. 1BB. 13. most of which show improved soft magnetic properties after slow cooling or annealing. This behavior is different from other magnetic alloys. Then directional ordering causes lattice distortion.

1) where i denotes the pair directions. an AA pair has two A sectors. and attach each of these sectors to one nearest-neighbor bond. Thus the total number of A sectors attached to the atomic pairs with the ith bond direction is where z is replaced by 2. and <pf is the angle between the magnetization and the ith bond direction. where NA is the total number of A atoms. Similarly the number of B sectors attached to atomic pairs with the ith bond direction is . Induced anisotropy of Fe-Ni alloys due to magnetic annealing and cold-rolling. NBBi. BB and AB pairs directed parallel to the ith direction.9 energy due to an unbalanced distribution of three kinds of atomic pairs over differently oriented pair directions is (13.. Note that A^. because each A atom has just two sectors attached to bonds in a single direction. whereas an AB pair has one A sector. Nmi.. and NABi are the number of AA. for the following reasons (see Fig. Thus the total number of A sectors is given by 2NAA + NAE.3): if we divide each atom into z sectors. 13.2. A^. where z is the number of nearest neighbors.MAGNETIC ANNEALING EFFECT 301 Fig. and A^Bi are not independent variables. 13. The total number of A sectors is also given by zA^. where A^ and A^B are the total number of AA and BB pairs.

provided /0 < 0. where the migration of atoms takes place easily. a3) and (ju. Now suppose that this alloy is annealed at T K. BB and AB atom pairs. /32. y3i) are the direction cosines of the magnetization and of the ith bond directions respectively. and we have . where l'Q is the value of /0 at T K. The energy change for one BB pair is given by /Q cos2 <p\. 133. The number of BB pairs found in the /th bond direction at thermal equilibrium is proportional to the Boltzmann factor exp( .302 INDUCED MAGNETIC ANISOTROPY Fig. Then the BB pairs tend to align themselves parallel to the direction of magnetization.2) and (13.3). y2i. we can express the anisotropy energy (13. Using (13. Counting the number of A and B sectors in terms of the number of A and B atoms.a 2 . and also in terms of the number of AA. and at the same time a saturating field is applied parallel to the direction (jSj./Q cos2 <p't/kT).3) can be expressed in terms of the direction cosines of the pair directions as where (aj. /33).1) in terms of the number of BB pairs as where The anisotropy energy (13. where JVB is the total number of B atoms.

(13. when we expand the exponential function. and they give rise to magnetic anisotropy which is calculated by putting (13.1. which depend on the crystal structure. these atom pairs are locked in place.6).8) into (13.MAGNETIC ANNEALING EFFECT 303 where AfBB is the total number of BB pairs.7) becomes After the alloy has been quenched. If 1'0 •« kT. as in which Putting we have the constants kl and k2. their numerical values are listed in Table 13. Using these constants.9) is expressed as . (13.

we can express the anisotropy constant as The composition dependence of this expression explains the experimental result shown in Fig. As a matter of fact. the average value of / is As we discuss in Chapter 14.10)).2.11) becomes where <p is the angle between the magnetization and the direction of the annealing field. Crystal type Isotropic Simple cubic Body-centered cubic Face-centered cubic kr ^y | 0 -^ k2 3j 0 f -^ For an isotropic material. hence where N is the total number of atoms per unit volume. so that these magnetostriction constants of A-B alloys are also expected to change in a way similar to (13.304 INDUCED MAGNETIC ANISOTROPY Table 13. Values of k1 and k2 for various crystal types (cf. 13. the . For a dilute and disordered solution of B atoms in a matrix of A.15). the anisotropy constant becomes negative. and the easy axis develops parallel to the annealing field. On using (13. where CB is the concentration of B atoms. BB. Neel estimated the values of Ij^.1. (13. / BB and 1AB from the composition dependence of magnetostriction constants. (13. which will be treated in Chapter 14. If /„ has the same sign as /'0. the magnetostriction constants A100 and Am are related to the dipole interaction. respectively.13). C| and 2CACB. the probability of finding BB pairs is proportional to CB. Since the numbers of AA. and AB pairs in disordered alloys are proportional to C\.

is estimated from the value at room temperature given by (13. It is seen from these curves that magnetic annealing is most effective for (111) annealing. and Fe as B. the value l'Q at 700 K. where Is is 1. we express the anisotropy energy as where 6 is the angle of magnetization as measured in the (110) plane from the [001] direction (so that we have a1 = a2 = (l/\/2)sin 6 and a3 = cos 6) and 60 represents . Figure 13.17). whereas it tends to deviate toward (111) for intermediate directions of the annealing field.2 is expressed as the coefficient given by (13. is much smaller than the value at room temperature. /FeFe and / NiFe . or 1'0.7 X 106 JnT 3 . shown in Fig.11) shows that the magnitude of the induced anisotropy depends on the crystallographic direction of the annealing field. 13.18) is large enough to explain the experimental result.38 X 10~23 JKT 1 .MAGNETIC ANNEALING EFFECT 305 composition dependence of these constants.4 shows the anisotropy energy curve observed for a (110) oblate single crystal of Ni3Fe after cooling from 600°C at a rate of WKmin" 1 in a magnetic field whose direction could be rotated in the (110) plane.12 These energy curves are obtained by integrating torque curves with respect to the angle.73)).50/1. we get the expression Using (14. The relationship (13. so that we have This formula will be described in detail in Section 14. The reasons why quantitative agreement is not obtained may lie in the approximate estimates of various quantities and in failure to attain complete thermal equilibrium. Using z = 12.0 X 107 X (0.13 T. 14.2. The arrows in the figure indicate the direction of the annealing field and the dots show for each curve the minimum value of the uniaxial anisotropy energy. k = 1. as Nl'0 = 3.14) as Since the experimental curve shown in Fig. can be fitted with parabolic curves.11. To compare experiment with theory. Af=9. Ku is calculated by (13. where /s is 0. This figure also shows that the minimum point coincides with the direction of the annealing field for the three principal axes. and are then separated by Fourier analysis into the cubic crystal anisotropy and the induced uniaxial anisotropy energy curves. we can estimate the values of / NiNi . and least effective for (100>. less effective for (110>.50).50 T. Denoting Ni as A. Using the 7S3 law (see (12. At the temperature at which the alloy is normally annealed.17Xl0 2 8 m" 3 .13)3 = 2. the value of 10.

13. On comparing (13. A0. however. In order to fit the theoretical curve to the experiment quantitatively. Curve A is the theoretical curve deduced from (13.5. as shown in Fig.306 INDUCED MAGNETIC ANISOTROPY Fig.5 . from the direction of the annealing field. the experiment shows a larger directional dependence. however. Magnetic anisotropy energy induced by magnetic annealing of a (110) disk of Ni3Fe. we find that the ratio of the Ku should be 2:3:4 for the three principal axes. 13. 13. The solid curves B in Figs. not satisfactory. 13. we find that k ^ : k2 = 1:8.11) we have. The deviation of the minimum point of the energy curve.20) and (13.12 the minimum point.4 and 13. Curve A is the theoretical curve deduced from (13. in Fig.1.5. Quantitatively. is plotted as a function of 8.11) with the parameters deduced from the best fit to the experimental curve B.11) and qualitatively explains the experimental curve B.. for three principal directions of the annealing field. 6.4. This agrees qualitatively with the experimental results.6. On putting into these formula the theoretical values of k1 and k2 listed in Table 13. The agreement is.

5. or k1 and k2 times the proportionality factor outside the parentheses in (13.8.6. Single crystal experiments were made for the same system by Penoyer and Bickford. even for face-centered cubic alloys. The induced anisotropy was measured for Fe-Co ferrites by lida et al.9 to 9. The values of the ratio k1: k2 have been measured by several investigators12'16 for a number of alloys. 13. The values for body-centered cubic Fe-Al alloys are also quite different from the theoretical ratio of 0:1.20 who discovered that the effect is sensitive to the partial pressure of oxygen during cooling (Fig.MAGNETIC ANNEALING EFFECT 307 Fig.19 This annealing has been used to improve the (5//)max or energy product. 13. such as Co ferrites.7).. 13. the magnetic annealing of ferrites is effective only in the presence of lattice vacancies.21 who found that the coefficients of the first and second terms. That is. For further details refer to Ferguson17 and Iwata.18 Magnetic annealing has been found to be effective also for some ferrites.P. their results are listed in Table 13. which measures the quality of a permanent magnet material. which have been used as oxide permanent (O.) magnets.12 are drawn using this ratio. Induced anisotropy constant as a function of crystallographic orientation of the annealing field. have different composition dependences. as shown in Fig. They found that the material responds to magnetic annealing only when it is more or less oxidized. One of the reasons for this discrepancy may be a contribution from the interaction of second nearest neighbor atoms. The values range from 1.11). F increases as the square of .2. In other words. F and G.

Theoretical and experimental values of the ratio kl:k2. 13. Slonczewski22 explained this behavior in terms of the one-ion anisotropy of the Co2+ ion on the octahedral sites. whose energy levels are split as shown in Fig.308 INDUCED MAGNETIC ANISOTROPY Fig. Since the axis of the uniaxial anisotropy of Co2+ ions is parallel to (111).6 1:1. If all the Co2"1" ions are distributed equally along the four equivalent (lll)s. the uniaxial anisotropies cancel out because of the cubic symmetry.3-9.u Aoyagi etal.12 the Co content.69)). the Co2"1" ions tend to occupy the octahedral sites whose (111) axis is nearest to the magnetic field.u Suzuki15 Chikazumi and Wakiyama16 . When this ferrite is cooled in a magnetic field.14 Aoyagi etal. so as to lower the anisotropy energy.5 1:3. the F or kl Table 13.6. 12. between the direction of annealing field and the easy axis of the induced anisotropy as a function of crystallographic orientation of the annealing field.20(c).6 1:3.4 1:8.4 1:1 Investigator Chikazumi12 Aoyagi eta/. The doublet thus produced gives rise to a uniaxial anisotropy with its axis parallel to (111) (see (12. while G increases linearly with the Co content. After cooling.3-2.5%Co-Fe 54%Ni-Fe 83%Ni-Fe Fe335Al Fe4 7A1 Theory 1:2 1:4 1:4 1:4 1:4 1:4 0:1 0:1 Experiment 1:2 1:8. A0. *i:*2 Material Polycrystal Ni3Fe 20%Co-Fe 12.9-2. Angle of difference.13 Aoyagi et a/. this unbalanced distribution of Co2"1" ions results in an induced anisotropy.0 1:2.2.

This alloy. whose composition is 50% Fe-50% Ni. which has constant permeability over a wide range of applied fields. they produced a new magnetic material called Isoperm.23"25 Oxidation was also found to be necessary for the magnetic cooling of Ni-ferrites. This one-ion induced anisotropy should be proportional to the available number of Co2+ ions. Actually the F term is very small compared with the G or k2 term. 13. Magnetization . Utilizing this effect. The presence of lattice vacancies is assumed to speed the diffusion of ions.7. The sheet thus manufactured exhibits a large uniaxial magnetic anisotropy with its easy axis in the plane of the sheet but perpendicular to the rolling direction. Effect of magnetic annealing of Co-Fe ferrites under various partial pressures of oxygen.8.2 ROLL MAGNETIC ANISOTROPY It was discovered by Six et al. as seen in Fig. and finally cold-rolled again to about 50% reduction in thickness. The quadratic composition dependence of the F term was ascribed to directional ordering of the Co2+-Co2+ pairs.26 13. then recrystallized to give a (001)[100j crystallographic texture.20 term should vanish just like the directional order in the body-centered cubic lattice. This explains the linear dependence of the G term on the composition. is first strongly cold-rolled.ROLL MAGNETIC ANISOTROPY 309 Fig. 13.27 in 1934 that a large magnetic anisotropy is created during the process of cold-rolling iron-nickel alloys.

giving rise to a linear magnetization curve (Fig. Variation of coefficients F and G (which are proportional to kl and fc2. Magnetization curve and domain structure of Isoperm. and by Rathenau and Snoek29 in 1941. 13. .8. Fig.310 INDUCED MAGNETIC ANISOTROPY Fig.9.28 in 1940. 13.9). They concluded that this anisotropy cannot be explained in terms of the coupling between magnetostriction and internal stresses. 13. respectively) with change in Co content in Co-Fe ferrite. Detailed investigations of this phenomenon were made by Conradt et a/.21 parallel to the rolling direction takes place exclusively through domain rotation.

These phenomena were interpreted in terms of 'slip-induced anisotropy' by Chikazumi et a/. along the slip plane. In this crystal structure.ROLL MAGNETIC ANISOTROPY 30 10 11 311 Neel ' and Taniguchi and Yamamoto extended their interpretation of magnetic annealing to this phenomenon.31 . a kind of line lattice defect. because single crystal measurements revealed that both the magnitude and the easy axis of the induced anisotropy are quite dependent on the crystallographic plane and direction of rolling.10 shows a slip deformation in a face-centered cubic crystal. about 50 times larger than that induced by magnetic annealing. However.10). and in a specific crystallographic direction. called the slip plane. when a crystal is deformed plastically. Such a slip deformation usually takes place through the motion of a dislocation.2). as is directional order anisotropy (shown by the dashed curve in Fig. many BB Fig. Figure 13. There is no doubt that directional order is the main origin of this anisotropy. and suggested that A and B atoms migrate to produce a stable directional order during the process of cold-rolling.10. called the slip direction. 13. 13. however. roll magnetic anisotropy is not so simple as magnetic annealing. the slip plane is parallel to {111} and the slip direction is parallel to (110). one part of the crystal slips relative to another part along a specific crystal plane. If such a slip deformation takes place in a perfectly ordered crystal. because its magnitude is proportional to Cg. such as a A3B-type superlattice. Diagram jndicating the appearance of BB pairs due to a single step slip along the (111) plane in the [Oil] direction in an A3B-type superlattice. The passage of one dislocation results in a displacement of one part of the crystal by one atomic distance (see Fig.31 as will be explained below. 13. The magnitude of the anisotropy induced by rolling is. Generally speaking. They considered that the plastic deformation played a role in bringing atoms into stable positions.

10. so as to avoid the creation of disordered atomic pairs. The factor \ in (13. Putting (13. thus producing directional order. The number of BB pairs depends also on the number of slipped planes. Since there are n = \/3 /a atomic planes in a unit length perpendicular to the slip plane.6). As a matter of fact. We call such directional order produced by slip deformation the slip-induced directional order.26) results from the fact that even if all the dislocations are isolated from one another. where a is the lattice constant. Then the number of atomic planes upon which BB pairs are created in the ith slip system is given by If we denote by a those lattice sites that are occupied by A atoms in the ordered state. the number of /3/3 pairs which are created in a unit area of the slipped plane is given by l/Cv^fl 2 ). Now we consider that ns dislocations run through the crystal per n atomic layers (s is called the slip density hereafter). and by /3 those occupied by B atoms. the probability of having a disordered plane is still \. the distribution of BB pairs becomes anisotropic. Since there are no BB pairs in the unslipped part of the crystal. . We define the quantity p' as the probability with which dislocations are created on new atomic planes. because the motion of a pair of dislocations produces no BB pairs.26) into (13. there is a tendency for dislocations to exist and move in pairs in an ordered crystal. as indicated by double lines in Fig. we have the anisotropy energy where The possible slip systems in a face-centered cubic lattice consist of four slip planes parallel to {111} and three slip directions parallel to {110} in each slip plane. the number of BB pairs created in a unit volume is given by where N is the number of atoms in a unit volume and is equal to 4/a3 and Many dislocations tend to be created from a single source. such as a Frank-Read source. and the number of BB pairs created in a unit area of the slipped plane is given by S 2 /(\/3~fl 2 ). The number of BB pairs thus produced depends on the degree of order S and on the probability p0 of creating an isolated dislocation. with long-range order parameter 5. Suppose that the alloy is partially ordered. 13. The probability of finding B atoms in a j8-site is S times larger than in other sites.312 INDUCED MAGNETIC ANISOTROPY pairs appear across the slipped plane.

in which one of the three kinds of a-sites is replaced by a /3-site. type).F.(«!.a 3 ) a i a2 a3 a2a3 a3ai aia2 2 1 0 0 0 1 0 0 0 1 (111) [101] [Oil] [110] 0 -1 1 0 0 0 --1 1 0 0 1 00 0 (111) [110] [101] [Oil] 0 .F. We can expect the appearance of another type of anisotropy. The direction cosines of the induced BB pairs.10 continues to travel over an out-of-step boundary to bring itself onto the neighboring order domain. BB pairs are expected to be distributed equally among the [Oil]. rt . The same thing is expected when the size of ordered domains is small. and the coefficients of the terms in /. and [101] directions.3. Coefficients in/(a 1 . « 2 > as) m tne expression for long-range order-fine slip type (L. 313 No.1 Therefore the total number of slip systems is 4 X 3 = 12. y2.(<*!> « 2 . a3) are listed in Table 13. (y1. 13. [110]. type) ofF anisotropy for each slip system (see (13.3. of slip system 1 2 3 4 5 6 7 8 9 Slip plane (111) Slip direction [Oil] [101] [110] y^ y2 73 . Suppose that the upper part of the crystal in Fig. Thus when coarse slip takes place. This type is calledL long-range order (fine slip) type (L.29)). Then the direction of BB pairs created on the slipped plane is changed from [Oil] to [110] or [101].1 1 0 -11 1 1 00 0 0 0 10 11 12 (111) [Oil] [101] [110] 0 0 - 1 0 0 .ROLL MAGNETIC ANISOTROPY Table 13. Direction cosines of BB pairs and the coefficients of each term in 0 inthe /.a 2 . or .J?).

The average anisotropy of these three BB pairs is given by where (nl. Assuming these two kinds of anisotropy. The comprehensive explanation for this is that. In the case of rolling on the (110) plane in the [001] direction.30) is a uniaxial anisotropy with the axis normal to the slipped plane. the atomic relation between the two sides of the slipped plane becomes disordered.C. which is Using (13. The anisotropy given by (13. when only short-range order prevails in the crystal. We call this type of anisotropy short-range order (fine-slip) type (S.34). we can explain all the experimental facts for rolled single crystals. a3) for all the slip systems.n2. 5 contribute to the roll deformation (see Fig. The number of BB pairs produced in a unit area of the slipped plane is where a. a 2 . By a simple calculation.n2i. 2.n3i) and the coefficients in each term of &(«!. we observe slip bands as shown in Fig.314 INDUCED MAGNETIC ANISOTROPY PY in other words. 4. we can deduce the relationship between rolling reduction r and the slip densities st. the roll magnetic anisotropy in this case is calculated as and . 13. if slip takes place in a crystal with short-range order. The anisotropy energy is expressed as Table 13.n3) are the direction cosines of the normal to slip plane of the z'th system.is the short-range order parameter.4 lists the values of (nlt.11(b)). 13. type). provided that /0 > 0. which proves that the slip systems 1. signifying an abundance of BB pairs and thus rendering the hard axis normal to the slip plane.11(a).

the plane perpendicular to the rolling direction becomes an easy plane.C.a 2 . In other words. a^) in the expression for short-range order-coarse slip type (S. (13. type has the hard axis parallel to the z-axis. Equation (13.35) shows that the L. a3 ) nj n2 n3 a a 2 3 a 3ai a a \ 2 10 11 12 In the case of Fe-Ni alloys. but at high reductions it tends to decrease again.ROLL MAGNETIC ANISOTROPY 315 Table 13. which have a positive /0 as given by (13. or (110). As expected.( a i> a2.F. type has the easy axis parallel to [110]. . Figure 13. With increasing reduction in thickness by rolling. Of siip system 1 2 3 4 5 6 7 8 9 Coefficients in g(a 1 . This is probably due to the destruction of ordering by severe rolling. the observed Ku is negative.12 shows the variation of Ku produced by (110)[001] rolling.C.17).33)). type) of anisotropy for each slip system (see (13. Direction cosines of the normal to the slip plane and the coefficients of each term in g. If we measure the anisotropy in the rolling plane. No.36) shows that the S.4. The effects of heat treatment will be explained later. both types result in an easy axis perpendicular to the rolling direction. the anisotropy grows monotonically.

13(a)). however. in the case of (110)[001] rolling. so that the slip deformation along this slip plane causes a rotation of the crystal which encourages slip on the different slip plane (see Fig.11. operate.316 INDUCED MAGNETIC ANISOTROPY Fig. the slip plane rotates and its tilt angle approaches 45°. 13. The slip plane in this case makes an angle greater than 45° from the rolling plane (see Fig. In contrast. the slip plane makes an angle of 35. (a) Slip bands and (b) slip systems for (110)[001] rolling. or 4 and 5 (see Fig. This kind of slip is called easy glide. as verified by the observation of slip bands on the side surface of the rolled slab (see Fig. only two of the slip systems. Then the maximum shear stress acts on a slip plane tilted 45° from the rolling plane. it is possible that four slip systems contribute to the deformation.5° with the rolling plane.13(a)). 13.12.11(a)). 13. 1 and 2. Actually. the same as for (110)[001] rolling. Fig. which encourages continued slip on the active slip system. The reason is as follows: The rolling process is equivalent to a tension in the rolling direction and a compression of the same strength perpendicular to the rolling plane. 13. 13. In the case of (001)[110] rolling. As a result of the rolling deformation. Variation of the uniaxial anisotropy constant of roll magnetic anisotropy with the progress of (110)[001] rolling Ni3Fe crystal.13(b)). This kind of slip is called cross slip.31 . 13.

the crystal rotates by easy glide so as to tilt the slip plane. Finally we shall discuss the influence of heat treatment of the alloy in advance of the rolling. type does not contribute to the anisotropy in the rolling plane (001).14 shows the variation of the anisotropy constant. As explained before.ROLL MAGNETIC ANISOTROPY 317 Fig. a perfectly ordered specimen develops the anisotropy rather slowly as compared to a less-ordered specimen. Therefore.12 that a quenched specimen develops almost the same roll magnetic anisotropy as a slowly cooled or annealed specimen. (111). We see in Fig. As expected from the theory. as in Isoperm.F. the easy axis in the rolling plane is perpendicular to the rolling direction. also tilts towards the rolling plane. Figure 13. type produces an easy axis perpendicular to the rolling direction in the rolling plane.C. 13. measured in the rolling plane for (001)[110j rolling. thus producing an easy axis in the rolling plane parallel to the rolling direction. 4 and 5 contribute in a complex manner. These facts can be interpreted in terms of the pair-creation of dislocations in an ordered crystal. whereas the S. type. which is the intersection of the two easy planes (Oil) and (101). the slip densities are given by from which the anisotropy energy leads to and This L. In the case of (001)[110] rolling. In the case of (001)[100j rolling.F. which assumes the presence of some ordering in the alloy when rolling takes place. 13. as a function of the roll reduction. but changes sign and increases in a positive sense in the later stage of rolling. Ku. [111]. therefore. The reader may note that this behavior appears to be contradictory to the theory. Ku increases in a negative sense in the initial stage of rolling. 2. closer to the rolling plane. because «3 = 0 so that Ea = 0. r. (a) Slip bands and (b) slip systems for (001)[110] rolling. The easy axis perpendicular to the rolling direction seems to be produced by crystal rotation. in the initial stage of rolling.13. Then the real easy axis of the L. all four slip systems 1. As the rolling progresses. however. the disordering created after one dislocation passes can be cancelled to recover the original state of order by the passage of a . Moreover.

318 INDUCED MAGNETIC ANISOTROPY Fig.27) decreases as S increases.33 Takahashi34 used electron microscopy to observe dislocations produced by compression.32 This kind of investigation has been extended to other kinds of cold-working. The roll magnetic anisotropy was measured also for body-centered cubic alloys. In other words. crystal growth or a phase transformation takes place at a temperature below the Curie temperature. the easy axes of the resulting grains may be aligned to some extent parallel to the magnetic field. This results in a net macroscopic induced anisotropy in the material. Therefore dislocations tend to occur in pairs in an ordered alloy. so as to make the stacking disorder between the pairs as short as possible. and investigated their relationship to the created magnetic anisotropy. in which elongated precipitate particles are aligned by a magnetic field during the precipitation process. 13.14. p0 and therefore p in (13. keeping Sp0 nearly constant.31 second following dislocation. such as wire-drawing. Variation of the uniaxial anisotropy constant due to roll magnetic anisotropy with the progress of (001)[110] rolling Ni3Fe crystal. If. This treatment can be applied to Alnico to improve its permanent magnet . by Chin.3 INDUCED MAGNETIC ANISOTROPY ASSOCIATED WITH CRYSTALLOGRAPHIC TRANSFORMATIONS Materials with uniaxial magnetocrystalline anisotropy will exhibit no net magnetic anisotropy if they are in the form of polycrystalline samples with the easy axes of the crystals (grains) distributed randomly. 13. however. First we treat the induced magnetic anisotropy of precipitation alloys.

and Co. Both the precipitates and the matrix have bcc structures. Jones and Emden37 applied this procedure to Alnico and obtained a rectangular hysteresis loop with a large value of (5//)max. in addition to Fe. This alloy transforms to a superlattice with tetragonal crystal structure during neutron irradiation. As suggested by its name. if v is very small. at least over small distances. The electron micrographs of Fig. Therefore the spontaneous magnetization is different in the two phases. this alloy consists of Al. and a shape anisotropy as given by (12. When the precipitate particles are densely packed as in Fig.1 Induced magnetic anisotropy in precipitation alloys In 1932 Mishima35 invented a very strong magnet called MK steel. changing the ionization state of both ions. when the surface is a {111} plane. the anisotropy should be proportional to the precipitate volume. Ni.CRYSTALLOGRAPHIC TRANSFORMATIONS 319 characteristics. while the matrix contains more Ni and Al. and is weakly magnetic or nonmagnetic. or Fe3O4.24) should be replaced by a function which has the general behavior of v(l . while the magnetite transformation takes place purely by the transfer of electrons from one ion to another (electron hopping).3. The anisotropy constant in this case is given by (13. Above 1300°C it consists of a homogeneous solid solution with bcc crystal structure. 13. an induced anisotropy is observed when polycrystalline cobalt is cooled through the transformation temperature in a magnetic field. whose crystal structure changes from cubic to a lower symmetry at about 125 K.v). The difference between the last two cases is that the cobalt transformation requires the physical displacement of atoms. but the precipitates contain more Fe and Co. This is apparently due to the appearance of an induced magnetic anisotropy with its easy axis parallel to the direction of the magnetic field applied during cooling. It is observed that the precipitates are always elongated parallel to the (100) direction which is nearest to the field applied during cooling. Then if v becomes 1. and a uniaxial anisotropy is induced if a magnetic field is present during irradiation. Therefore v in (12. Let v be the volume fraction of precipitates. 13. At the opposite extreme. A similar phenomenon is observed for magnetite. These phenomena will be discussed below. Another example is the neutron irradiation of a 50% Fe-50% Ni alloy in the presence of a field. and are ferromagnetic.40) . which is known as Alnico 5 in Europe and the United States.24) is produced. but it separates into two phases by precipitation below 900°C.15 show elongated precipitates in field-cooled Alnico. Photograph (a) shows a cross-sectional view and (b) a side view of the elongated precipitates. A third case is the phase transformation in cobalt metal from fee to hep (with uniaxial anisotropy) at about 400°C. meaning that the entire sample consists of the precipitate phase.15. the shape anisotropy should disappear. In 1938 Oliver and Shedden36 discovered for a similar alloy that the magnetic properties could be greatly improved by cooling it in a magnetic field. It is also observed that ferrimagnetic garnets exhibit growth-induced anisotropy with the easy axis normal to the surface. 13. we cannot ignore the magnetic interaction between particles.

In the commercial heat treatment of Alnico 5. The wavelength of the fluctuation in concentration is determined by a balance between the chemical energy difference of the two phases and the elastic strain energy produced by the composition change. the second derivative of free energy with respect to concentration must be negative. and if the Curie point depends strongly on the composition. quenched to 950°C to prevent the precipitation of the fee gamma phase. 0. The mechanism of growth of the precipitate particles was explained by Cahn38 as spinodal decomposition.320 INDUCED MAGNETIC ANISOTROPY Fig. (b) side view of the elongated precipitate particles.6 wt% Al. For this reason the precipitate particles are elongated only along the direction of magnetization. balance Fe) annealed at 810°C for lOmin in a magnetic field of 0. precipitation occurs if the free energy of the system decreases when an atom is transferred from the matrix phase to the precipitate phase. in which the composition changes continuously from a homogeneous single phase to a two-phase structure by the gradual build-up of a sinusoidal composition variation. however. This precipitation process is called spinodal decomposition. If. This can result in a special kind of precipitation. and then cooled slowly from 900 to . the alloy is first annealed for 30 min at 1250°C to produce a homogeneous single phase structure.39 where 7S and 7S' are the saturation magnetization of the matrix and the precipitate phases. and results in a very regular. a fluctuation in composition perpendicular to the direction of magnetization will not affect the magnetostatic energy. the local saturation magnetization will vary strongly with the local composition and therefore with position. 3wt% Cu. 13. However. and Nz is the demagnetization factor (along the long axis) of an isolated precipitate particle. If spinodal decomposition occurs near the Curie point of an alloy. Therefore in order to initiate precipitation. 6.13 MAm" 1 (1600Oe): (a) cross-sectional view. 14wt% Ni. In general.1 wt% Si. small-scale precipitate structure. In this case the magnetostatic energy is increased by the fluctuation in composition if the fluctuation occurs along the direction of magnetization. Electron micrographs of Alnico 8 (36wt% Co. respectively. 5wt% Ti. an increase in elastic energy will oppose the process of precipitation.15. the precipitation results in a change in lattice constant.

This means that neutron irradiation in a magnetic field applied parallel to [100] resulted in a larger value of the product Sv for the region with its c-axis parallel to [100]. 5. The values of u. and also requires an increase in elastic energy. Further heat treatment between 580 and 600°C for an appropriate time causes the elongated precipitates to grow to a size at which it is reasonable to regard them as single domain particles. 0. y and z. and each occupying a different volume fraction vt. The degree of order. Ku = (1. For Alnico with higher Co content. During these magnetic heat treatments many small precipitate nuclei are produced.1.01. A single crystal disk cut parallel to (Oil) was irradiated at 295°C by 1.CRYSTALLOGRAPHIC TRANSFORMATIONS 1 321 700°C at a rate of 0. This is partly due to the development of an irregular geometry of the precipitate particles. determined by X-ray diffraction. The long axis of these precipitates is parallel to the (100) direction which is nearest to the direction of the applied magnetic field. Iwama et al.3. were 0. for i =x. the magnetic heat treatment is performed at 800-820°C. d = 200-600A.7. The reason for this is that the elastic modulus is smaller along (100) than along (111). the easy axis of the induced anisotropy deviates by an angle a which is always less than /3 as shown in Fig. This results from the fact that the long axis of the precipitates approaches the nearest (100).32 + 0.05 and 0. because any change in particle shape requires diffusion of atoms over long distances corresponding to the particle size. or [001] axes.12MAm'1 (1500 Oe). 13.21 ± 0. The final size of the particles is somewhat less than about 1000 A long and 100 A in width.6) X 105 Jin" 3 for v = volume fraction of precipitate = 0.40 observed that a slower cooling rate gave larger induced anisotropy and also large dimensional ratio (length //diameter d) of the precipitate particles. [010].2 Induced anisotropy produced by neutron irradiation It was discovered by Pauleve et al.05. the precipitates continue to grow in an anisotropic way even without the presence of a magnetic field. y or z.3 Ks' in a magnetic field stronger than 0. The magnitude of ^u decreases as /3 increases from 0 to 45°. where i represents x.1-0. This heat treatment is called aging.5 X 1020 neutrons (14% of which had energy higher than IMeV) in a magnetic field of 200 kAm" 1 (=2500Oe) applied parallel to [100]. Once the precipitate nuclei have formed. 13.41 that neutron irradiation of 50 at% Fe-Ni alloy results in the formation of a tetragonal CuAu-type superlattice. each with its tetragonal c-axis parallel to one of the original cubic [100]. It was discovered by X-ray diffraction that the crystal had divided into three regions.5. In one case.2 . so that the increase in elastic energy is smaller when the precipitates elongate parallel to (100).39 The magnetic anisotropy thus produced is hardly changed by further aging with a magnetic field applied perpendicular to the easy axis.21 + 0. This formation of precipitate nuclei is most effective at a temperature just below the Curie point of the precipitate phase. also may vary between the three regions. l/d = 3-5. The magnetocrystalline anisotropy of this material determined by magnetization . In this work it was also observed that when the magnetic field is applied in a direction which deviates by the angle fi (/3 < 45°) from [100] towards [010] in a (001) disk. respectively.16..

Ku. all the spins are also aligned parallel to [100].40 curves was found to have the easy axis parallel to [100]. ^ul[010] and ATul[001]. [010]. it was concluded that the size of the ordered regions is about fifty lattice constants. and the angle. and finally annealed for 16h at 600°C. a.3 X 105 JnT 3 (= 2. and 20%. The anisotropy was determined from torque measurements on a (100) disk of Alnico 5 which was homogenized for lOmin at 900°C. and the hard axes parallel to [110]. Kul[ of the ordered region with its c-axis parallel to [100] is larger than those of other regions. As a result of this analysis. The reason why the magnitude of Ku2 is comparable with that of Kul was explained as follows:42'43 The size of the ordered regions is much smaller than that of the magnetic domains. are slightly different from those deduced from torque curves. The anisotropy constants were determined to be Kul = 3.2 X 105 J m ~ 3 (= 3. but when the magnetic field is in some other direction. This reasoning is similar to that of the torque reversal discussed in Section 12. which are deduced from magnetization curves.16. cooled in a magnetic field of 0. The uniaxial anisotropy constant. of the easy axis from [100] as functions of the angle ft between the magnetic field applied during cooling and [100]. The anisotropy constant. the spins will take a transitional distribution.64 MA m"1 (8kOe) at a rate of 0. and [001] regions are 60%. which makes [110] a hard axis. respectively.322 INDUCED MAGNETIC ANISOTROPY Fig.5Ks"1 in a direction ft from [100].3 X 106ergcm"3). When the external field is parallel to [100]. so that the spin distribution is determined by a balance of the local magnetocrystalline anisotropy. 20%. and that the volume fractions of the [100]. The values from magnetization curves are . the external field energy.2. 13.2 X 106ergcnT3) and K^ = 2. and the magnetostatic energy. These values. the exchange energy.

The maximum value of the induced anisotropy constant is 2. The sign of Ku is negative from 100 to 95% Co.3.17 shows the dependence of Ku determined in this way. as a function of Co content in Ni. of the single crystal magnetocrystalline anisotropy of the alloy with the same composition. Since.CRYSTALLOGRAPHIC TRANSFORMATIONSO 3 while those from torque curves are In conclusion. the induced anisotropy continues to increase with irradiation. Figure 13. A large induced anisotropy constant.44"47 The ordering may have been produced by annealing over astronomical time periods. however. because in this composition range Ku of the hep phase keeps the same sign at all temperatures above room temperature. he proposed the following mechanism: fee Co transforms to hep Co in such a way that the c-axis of an hep grain is parallel to a (111) axis of fee Co. Based on this experiment. the major effect of irradiation in a magnetic field is to alter the volume fractions of the three kinds of ordered regions. The anisotropy constant was determined by the difference in magnetization curves between the two cooling processes: cooling with and without a magnetic field through 400°C. at which the phase transformation takes place.24 MAm" 1 (= 3000 Oe) through the phase transformation point. . For compositions below 80% Co. because Ku of the hep phase changes sign between the phase transformation temperature and room temperature. which is interpreted in terms of the induced anisotropy due to directional order in the binary alloy.3 Induced anisotropy associated with crystallographic transformation of Co and Co-Ni alloys It was found by Takahashi and Kono48 that polycrystalline Co and Co-Ni alloys exhibit induced magnetic anisotropy after they are cooled in a magnetic field through the phase transformation from fee to hep. In either case it is an interesting story. Since there are four (111) axes in an fee grain. 3. so that Ku is extremely small.3X 10 5 ergcm~ 3 ). Thus the c-axis of hep Co should be distributed equally among the four possible directions if the transformation takes place in the absence of a magnetic field. there are four possible orientations for the c-axis of the transformed hep Co. rather than to alter the anisotropy constants or the directional order in each region. The sign of Ku is positive from 95 to 70% Co. It was also observed that the temperature dependence of the induced anisotropy is proportional to that of the magnetocrystalline anisotropy of pure Co.3 X 10 4 Jm~ 3 (=2.3 X 10 5 Jm~ 3 (=3. was observed by Graham49 for polycrystalline pure Co after it was cooled in a magnetic field of 0.42 Recently it was reported that the ordered phase of 50%Fe-Ni is found in iron meteorites. or by a strong irradiation in space. 13. the observed induced anisotropy may be far from the final value. and depends on composition as C(Co)2C(Ni)2. — 2 X 104 Jm~ 3 .3x 10 5 ergcm~ 3 ). which is only 7% of the estimated value. the phase transformation occurs below room temperature.

324 INDUCED MAGNETIC ANISOTROPY Fig. No induced anisotropy due to magnetic cooling was observed for a specimen melted in an argon atmosphere. as a function of Co content.48 However. induced by cooling Ni-Co alloys in a magnetic field from 1000°C at a rate of S. the anisotropy energy will cause an unbalanced volume distribution of these grains. Ku. and annealed. 13. and that the induced anisotropy cannot be removed by annealing below 700°C. the more effective the magnetic cooling. Thus a preferred orientation of the c-axes results.17.SKmin"1. if a magnetic field strong enough to rotate the magnetization out of the easy axis of each fee grain is applied during transformation. producing an induced anisotropy. Sambongi and Mitui50 observed that the magnitude of Ku thus induced for Co is considerably influenced by cold working in advance of the heat treatment. These facts suggest that the presence of some lattice defects may play a role in the mechanism of this induced anisotropy. The anisotropy constant. hot-worked. The numerical values give the intensity of the magnetic field applied during cooling (1 Oe = 80 Am"1). It was found that the higher the annealing temperature. shaped. .

However. The resulting mixture of two kinds of twinned regions will result in a uniaxial anisotropy with the easy axis parallel to the c-axis.3 X 10s J m ~ 3 (= 1. the magnetic field during cooling should be parallel to the direction in which the magnetocrystalline anisotropy of one twin is considerably lower than that of the others.75).6at% Fe. If the magnetic field applied during cooling is accurately parallel to one of the (100) directions. this proposed ordering scheme has been disproved by later experiments. 12. there is another class of twins.CRYSTALLOGRAPHIC TRANSFORMATIONS 51 325 Wakiyama et al. are given by where the symbol * indicates values at 4.53 The crystal axis can be established at such a low temperature because the transition is caused by quenching of the electron hopping between Fe2+ and Fe3+ on the octahedral or B sites of the spinel lattice. The crystal axes or a-. 13. Fe2+ and Fe3+ ions form an ordered arrangement on the B sites. or sub-twins. The magnetocrystalline anisotropy energies in the (110) plane are plotted in Fig. in which .2 K. The anisotropy constants observed52 at 120 K. so that no atomic migration is required. It was found that when a magnetic field is applied parallel to one of the (100) axes during cooling through the transition point.3 X 106 erg cm'3) for an alloy of Co-1. The magnetocrystalline anisotropy of this low temperature phase is given by (12. but the b-axis becomes parallel to one of the two possible (110) directions.28) and obtained the record value of Ku = 1. b-. the c-axis of the low temperature phase is established parallel to this <100>.18 for all the possible twins. Since Ka > Kb > 0. 13.4(b)). observed the same effect for Fe-Co alloys with the double hep structure (ABAC stacking sequence. both of which are perpendicular to the c-axis. and c-axes of each twin with respect to the cubic axes are listed underneath the graph. the c-axis is established parallel to this (100) as mentioned above. Verwey et al. In addition to the twins with different a-. respectively.54 considered that as a result of this quenching of the electron hopping. b.3. which is just below the transition point. we find that the a-. and easy axes.and c-axes are the hard. intermediate. b-.4 Induced anisotropy associated with the low temperature transition of magnetite (Fe3O4) The crystal structure of magnetite or Fe3O4 transforms from cubic to lower symmetry at about 125 K (see Section 12. and c-axes. see Fig.55 No final conclusion has been reached on this point. In order to establish a unique b-axis.

where all the indices are referred to the cubic axes. The dashed curves with dashed numbers refer to sub-twins which have uniaxial anisotropy with different easy axis. The twins thus developed have the c-axis parallel to the (100) which is nearest to the magnetic field during cooling. the anisotropy energies of the twins with dashed numbers (shown by dashed curves) differ slightly from the solid curves for the non-dashed numbers. If a magnetic field is applied in the direction 9 = 40° out of the (100> during cooling through the Verwey point. Because of a small difference due to the Ku term.18.326 l.75)) with a different axis and are indicated by a dashed number under the graph.Or INDUCED MAGNETIC ANISOTROPY Fig.55 These twins have a Ku term (see (12.23° out of the z-axis in the z-a plane. and the fe-axis at 0=90° in the {110} plane . the anisotropy energy for twins 1 and 1' is considerably lower than for the other twins. Variation of magnetocrystalline anisotropy in (110) of all possible twins of the low-temperature phase of magnetite as a function of the angle of magnetization measured from [001]. the c-axis tilts by 0. The numbers on the curves refer to twins whose axes are shown in the table underneath the graph. 13. so that we expect the twins 1 and 1' will develop uniquely. This is actually the case.23° or -0.

43) were determined for such a squeezed specimen. and was found to be negligible. corresponding to the . He observed a shift of the resonance line of lower fields by applying a magnetic field parallel to a new (100). so that the resonance occurs at a higher field.19. so that the generation of more than one twin was impossible. If a cylindrical specimen with its long axis parallel to (111) is inserted (at room temperature) into tightly fitting aluminum rings and cooled through the Verwey point with a magnetic field applied as described above. 13. while heating the specimen from -195°C to -181°C (Fig. Bickford56 observed this switching phenomenon by means of ferromagnetic resonance. In order to remove the twin 1'. it is possible to switch a once-established c-axis to another (100) by applying a magnetic field parallel to a new <100> at a temperature below the Verwey point.4% parallel to [111].19). In a freely supported specimen. The peaks at the higher field are due to the original twin. we can utilize _the difference in deformation of the two twins: twin 1 elongates by 0. while twin 1' elongates parallel to [111]. which has its easy axis perpendicular to the field and contributes a negative anisotropy field. and twin 1 is uniquely selected. The anisotropy constants given by (13.56 containing the c-axis and the magnetic field during cooling. 13.4%). the difference in thermal expansion coefficient between aluminum and the specimen exerts a uniform compressive stress in the plane perpendicular to the [Til] axis of the cylinder. the space between the specimen and the aluminum rings is very small (less than 0.52 Even if the stress is negligible.CRYSTALLOGRAPHIC TRANSFORMATIONS 327 Fig. Ferromagnetic resonance absorption curves observed for magnetite at temperatures below the Verwey transition point. The effect of a compressive stress on Ku was estimated by changing the magnitude of the stress.

so that the resonance occurs at a lower field. This means that the change is not caused by changing the magnitude of the anisotropy in each twin. Yamada showed that the switching occurs at the angle where the anisotropy energies of the two twins become equal. as shown in Fig.20. Switching of the c-axis of the low-temperature phase caused by rotation of magnetization in the (001) plane of magnetite. The numerical values on the torque curves give the magnetic field in which the torque was measured.58 and is therefore called the growth-induced magnetic anisotropy.5 resonance field plus the anisotropy field. 13.3) containing more than two kinds of rare earth ions sometimes exhibit a uniaxial anisotropy in addition to cubic magnetocrystalline anisotropy.20.328 INDUCED MAGNETIC ANISOTROPY (001) Fig.59'60 .5 Growth-induced anisotropy The rare earth iron garnets (see Section 9. corresponding to the resonance field minus the anisotropy field. This uniaxial anisotropy has its axis parallel to the direction of the crystal growth. as observed through a change in torque curves. It should be noted that the resonance peaks change not by shifting position along the abscissa but by a decrease in the height of the higher field peak and an increase in the height of the lower field peak. Two possible interpretations have been proposed: one considers that the anisotropy is caused by directional order of rare earth ions on dodecahedral sites of garnets. but by the growth of a new twin at the expense of the old twin. He explained this phenomenon in terms of the displacement of twin boundaries. The peaks at the lower field are due to a new twin. The torque changes abruptly when the switching occurs. Yamada57 observed the switching phenomenon by means of a torque magnetometer. 13.3. which has its easy axis parallel to the applied field and contributes a positive anisotropy field. 13. He also found that switching occurs between 77 and 120 K if the nucleus of a new twin is present.

For instance.64 In general. 13. photo-induced anisotropy. rotatable anisotropy.4. it was observed by torque measurement that when a thin film of Sm 0 4Y 26 Gaj 2 Fe 3g O 12 (Sm-YIGG).1 Exchange anisotropy Meiklejohn and Bean65 discovered that when a slightly oxidized Co powder with particles of 100-1000A diameter is cooled from room temperature to 77K in a magnetic field. the larger the difference in size between the two kinds of rare earth ions.63 If was also observed that in the case of growth plane parallel to {111}. induced anisotropy in amorphous magnetic alloys. so that the magnetization of the particle is forced to align parallel to the direction of the field applied during cooling. These are: (1) (2) (3) (4) (5) exchange or unidirectional anisotropy. 6-7/Lim thick. while the growth direction becomes the hard axis if the film plane is parallel to {100}. the larger the growth-induced anisotropy. 13. it exhibits a unidirectional (as opposed to a uniaxial) anisotropy.21(a)). the Co2+ spin at the surface must be aligned parallel to the Co spin in the particle when the antiferromagnetic spin structure is established in CoO at the Neel point during cooling (see Fig. the growth direction becomes the easy axis if the plane of the thin film is parallel to {111}. a fairly large uniaxial anisotropy is induced by stresses through magnetostriction. is antiferromagnetic with a Neel point at about 300 K. When an external magnetic field is applied out of the easy direction as . which covers the surface of Co particles. If a positive exchange interaction acts between a Co spin in the particle and a neighboring Co2+ spin in the CoO layer at the particle surface.OTHER INDUCED MAGNETIC ANISOTROPIES 329 while the other invokes a one-ion anisotropy caused by some anisotropic rare earth ions which select particular octahedral sites during crystal growth. After cooling in a magnetic field down to a temperature well below the Neel point. 13.1-13.3. the spin structure of CoO is firmly fixed to the lattice through a strong anisotropy of the order of 5 X 10 5 Jm~ 3 .61'62 This anisotropy is rather complex: the direction of crystal growth becomes the easy or hard axis depending on the crystallographic plane of the crystal growth. but the cobalt monoxide CoO. when there is a large misfit of lattice parameters between the substrate and the garnet film. which tends to hold the magnetization in the direction of the field applied during cooling. is grown epitaxially onto gadolinium-gallium-garnet (GGG). mictomagnetic anisotropy.4 OTHER INDUCED MAGNETIC ANISOTROPIES Here we shall discuss induced magnetic anisotropies other than the categories already described in Sections 13. Cobalt metal undergoes no crystal transformation in this temperature range.

22. This curve was observed at 77 K after cooling through the Neel point with a magnetic field of 10 6 Am~ 1 (= 104 Oe) applied in the + direction. Solid curve: cooled in magnetic field.65 . thus increasing the exchange energy at the surface. Hysteresis loop observed at 77 K for a slightly oxidized Co powder. shown in Fig. the hysteresis curve shifts to the left along the abscissa as shown by the solid curve in Fig. The dashed curve was observed for the same specimen cooled without magnetic field. dashed curve: cooled in absence of magnetic field. The reason for this shift is that the magnetization of Fig. 13.22. the magnetization of the particle rotates and makes an angle 8 with the spin axis of CoO. 13.330 INDUCED MAGNETIC ANISOTROPY Fig. As a result of this anisotropy. depending on the total surface area of the particles and therefore on the average particle size. Spin arrangement in a Co particle coated with CoO.21.21(b). The magnetic anisotropy thus produced is called the exchange anisotropy. 13. The anisotropy energy thus produced has the form The value of Kd is of order 1 X 105 Jm 3. 13.

16a and 24d sites.6) is associated with the torque curve of this material. in which the spontaneous magnetization is stabilized by new ion distributions produced by illuminating an appropriate magnetic material with non-polarized light. This phenomenon was first observed in yttrium-iron-garnet (YIG) by means of ferromagnetic resonance by Teale and Temple. Equating this energy with kT. As described in Section 9. When Si ions are introduced into YIG.69 in all of which some antiferromagnetic interactions exist.65 Exchange anisotropy was also observed in an Fe-FeO system66 and for many ferromagnetic alloys such as Ni-Mn. independent of the direction of the magnetizing field. we find the corresponding temperature to be 24 000 K.2 and 18.67 Fe-Al. so that an excess field must be applied in the . It was also observed that a rotational hysteresis (see Sections 12.70 The energy quantum of light of frequency v is given by h v. 13. and their spins are aligned antiparallel. a magnetic anisotropy can be induced.4. so that the ion distribution is changed to where x is the number of Si atoms per formula unit. . If such a shifted hysteresis curve can be obtained at room temperature. One of the photomagnetic effects is photomagnetic annealing.70"72 Another effect is the polarization-dependent photoinduced effect. so that h v for visible light with a wavelength of 600 nm is calculated to be 3.2 Photoinduced magnetic anisotropy By illuminating some transparent ferromagnets in a magnetic field. This phenomenon may be useful for some magnetic logic system. The reason is thought to be that some of the antiferromagnetic spins in CoO are irreversibly flipped over when the magnetization in the Co particles is rotated. the magnetic Fe3+ ions in YIG occupy 24d and 16a lattice sites in the ratio 3:2. This distribution can be described by the following formula: where { }.OTHER INDUCED MAGNETIC ANISOTROPIES 331 the Co particle tends to point in the + direction due to the exchange anisotropy.direction in order to reverse the magnetization into the . and that the hysteresis does not disappear even in a high magnetic field. thus exhibiting ferrimagnetism.3.3 X 10~19 J or 2.direction. respectively. it has more than enough energy to overcome the normal binding energy that holds the electron in the atom. they occupy 24 d sites selectively. [ ] and ( ) signify the 24c. it becomes possible to have a material in which the remanent magnetization always points in one specific direction.1 eV. Therefore if an electron absorbs this light. This induced anisotropy is called the photolnduced magnetic anisotropy. Nonmagnetic Y 3+ ions occupy 24c sites.68 and Fe^CNij^Mnj). in which polarized light can selectively excite electrons from the ions on some lattice sites.

The lattice site from which the electrons are excited is called the photomagnetic center. 13. thus increasing the number of Fe2+ ions which have their easy axis parallel to the magnetization.68 A. In other words. The specimen can be irradiated by polarized infra-red light in a magnetic field applied by .99 A. the 16a site which has its special axis parallel to [111] is the most stable site for an Fe2+ ion. In photomagnetic annealing. Figure 13. so that if the magnetization is parallel to. There are four equivalent 16a sites. the distribution of Fe2+ and Fe3+ ions on 16 a sites is random. A spherical specimen of YIG with added Si is mounted on a torque magnetometer and cooled to 4.2 K in liquid helium. It is clear from experiments that this special (111) is the easy axis of the Fe2+ ion on this site.73 As explained in Chapter 12. The Fe2+ ion tends to occupy the 16 a site which is the nearest to Si4+ and located on the other side of the O 2 ~ ion.23.73 Suppose that an Si4+ ion occupies the 24d site at the center of the cube. [111]. while the length of the other edges is 2. Position of each sublattice site in the garnet structure.73 The four 16a sites which are the nearest to the Si4+ ion have their special axis parallel to different (111) directions. At high temperatures.23 shows the positions of all the lattice sites in a garnet crystal.332 INDUCED MAGNETIC ANISOTROPY Fig. anisotropy is induced in the direction of the magnetization during illumination. but as the temperature is lowered. Fe2+ ions tend to be attracted by electrostatic forces to Si4+ ions on the 24 d sites. say. a 16a site is surrounded by six O 2 ~ ions octahedrally. the Fe2+ ion is anisotropic. Therefore the [111] axis is a special axis for this particular 16o site. the electrons excited from Fe2+ ions surrounding Si4+ will collect in the most stable site. The shape of this octahedron is considerably distorted: the length of the edge of the face parallel to (111) is 2. As seen in the figure. Figure 13.24 shows an experimental arrangement for observing the polarizationdependent photomagnetic effect.

034 was irradiated for four minutes with nonpolarized infra-red light in a magnetic field of 1.45).72 an electromagnet. When a specimen of YIG with Si content x = 0. The torque curve measured in the (110) plane is given by the general expression where 9 is the angle between the magnetization and the [001] axis.2MAm"1 (= 15kOe) parallel to [001] or [110]. of polarization-dependent photomagnetic induced anisotropy as a function of the direction of magnetization during illumination. 13. <t>. In other words. the torque curve was given by only the first term in (13.72 . Fig.45).24. Anisotropy constant. measured from [001]. Experimental arrangement for observing polarization-dependent pbotomagnetic effect.OTHER INDUCED MAGNETIC ANISOTROPIES 333 Fig. Lc = 0.25. Lc in equation (13. 13.

resulting in a decrease in the number of Fe2+ ions on this site. the curve is shifted upwards. The mechanism of the excitation of electrons from the photomagnetic center is discussed from a more microscopic point of view by Alben et a/. Lc was nonzero. the metal vapor impinges onto the substrate in a direction tilted from the normal to the surface. which are symmetrical with respect to [001] or [110]. The resulting Lc vs. . 13. The sinusoidal curve shown with solid circles in Fig.AT A. 13. The same experiment was repeated with plane of polarization of the infra-red light perpendicular to [111]. as shown by the crosses in the figure. 13. This is due to a decrease in Fe2+ on the site whose special axis is parallel to [111]. various magnetic anisotropies can be produced by varying the preparation procedures.74 Tucciarone75 calculated the distribution of electrons on the basis of the symmetry of octahedral and tetrahedral sites and also discussed the associated dichroism together with the photomagnetic effect. Columnar structure produced by incident-angle evaporation. The interpretation is that electrons are excited from the photomagnetic centers with the special axis parallel to [111] more effectively. The uniaxial anisotropy of a film produced in this way 78 Fig.. On the other hand.25 is a plot of Lc as a function of <t>.26. One of these is the anisotropy produced by control of the angle of incidence during evaporation.76 that is. When the magnetic field was applied in a direction making the angle $ with [001]. because there are two (111) axes in the (110) plane. when the light is polarized with the polarization perpendicular to [111]. <l> curve is shifted downwards.43 Rotatable magnetic anisotropy in anomalous magnetic thin films In magnetic thin films. because the two (111) axes in the (110) plane are no longer symmetrical with respect to the applied field. as shown by the open circles in the figure.334 INDUCED MAGNETIC ANISOTROPY This is reasonable.

The dependence of this anisotropy on alloy composition is different from that of directional order. 13.1 (= 250Oe). Induced anisotropy constant. A Evaporated onto the substrate kept at 300°C and annealed at 450°C in a magnetic field. 13. of this anisotropy is plotted in Fig.2779 as a function of Ni content in Fe-Ni alloy films for various evaporation conditions. in several ways: the magnitude is much greater and there is a non-zero value in pure Ni.60 It was found that the rotatable anisotropy is caused by stripe domains. Ku. X Evaporated onto the substrate kept at 300°C in a magnetic field.28. if the film is magnetized parallel to its surface during the evaporation an in-plane anisotropy is produced.78 Even when the direction of evaporation is accurately normal to the substrate surface.27. The anisotropy constant. as a function of Ni content (dashed curves show the anisotropy produced by directional order (see Fig. This anisotropy is called the rotatable magnetic anisotropy. In all cases the field strength is 20kA m .2)). 13.81'82 The structure of this domain will be described in detail in Section 17. The anisotropy is apparently caused by the shape anisotropy of a tilted columnar structure.OTHER INDUCED MAGNETIC ANISOTROPIES 335 Fig. Moreover. 13. 13. The magnetization in each . O Evaporated onto the substrate kept at 20°C in a magnetic field. of anomalous Fe-Ni magnetic thin films evaporated under various conditions. the easy axis can be rotated by applying a strong magnetic field. which is shown by dashed curves.4.77 which is clearly observed by electron-microscopy as shown in Fig..79 has its easy axis parallel to the direction of inclination of the incident vapor.26. so that now we simply glance at a conceptual view as shown in Fig. Ku.

13. Powder patterns of stripe domains in a 10Fe-90Ni alloy thin film: (a) observed after removal of a magnetic field applied in the horizontal direction. Spin structure of stripe domains.82 .28. (c) observed after removal of a very strong magnetic field perpendicular to the original stripes. (b) observed after removal of a relatively strong magnetic field perpendicular to the original stripes. which is produced by the columnar structure. and the exchange Fig. 13.82 domain deviates from the plane of the film.336 INDUCED MAGNETIC ANISOTROPY Fig. the magnetostatic energy due to surface free poles. alternatively upwards and downwards. The spin structure of the stripe domain is determined by a balance of the perpendicular anisotropy energy. This deviation is caused by presence of an anisotropy with its easy axis perpendicular to the film surface.29.

When a magnetic field that is strong enough to decrease the deviation angle of the magnetization out of the film plane is applied perpendicular to the stripes. This is the origin of the anisotropy caused by stripe domains.82 When a weak magnetic field is rotated in the film plane. which are prepared by evaporation in relatively poor vacuum (less than 10 ~ 4 Torr) and onto a cold substrate (between -120°C and 100°C). the stripes are disturbed (see the photo (b)). while the coupling of the Mn-Mn pairs is negative.33. 12. so that their spins tend to align ferromagnetically.84 The appearance of this anisotropy has interfered considerably with the development of magnetic thin film computer memories. so that their spins tend to align antiferromagnetically. The rotatable anisotropy is observed only for anomalous magnetic films. This fact also suggests that the phenomenon depends strongly on the antiferromagnetic interaction of . Ku. and smallest for (111). as well as uniaxial anisotropy. In this alloy. a weak uniaxial anisotropy of the order of 103 J m ~ 3 is induced. the exchange coupling of the Mn-Ni and the Ni-Ni pairs is positive. the magnetization rotates with the field without changing the direction of the stripes. and the alloy is ferromagnetic. and their negative interaction disturbs the ferromagnetic spin arrangement and produces mictomagnetism (see Section 7. and magnetocrystalline anisotropy. K^. Kd. in which no Mn-Mn nearest neighbor pairs exist. if the alloy is partially ordered. This explains the mechanism of rotation of the easy axis.87 Since no atomic migration can occur below room temperature.OTHER INDUCED MAGNETIC ANISOTROPIES 83 337 energy. Figure 13. The value of K1 depends strongly on the intensity of the magnetic field used in the measurement of the anisotropy.4 Induced anisotropy associated with mictomagnetism It was found by Satoh et a/. and finally rotate perpendicular to the original direction after removal of a very strong magnetic field (see (c)). A neutron scattering experiment showed directly that some of the Mn spins are antiparallel to the spontaneous magnetization. 13.6 MA m^ 1 (20kOe). On the other hand. Measurements on a single crystal show that this induced anisotropy is largest when the cooling field is applied in the (100) direction.85'86 that when a partially ordered Ni 3 Mn is cooled from room temperature to 77 K in a magnetic field.5). thus changing the total energy. Ni and Mn atoms form a Cu3Au-type superlattice as shown in Fig. Such a rotation of magnetization relative to the stripes changes the spin structure. This anisotropy also depends on the pre-annealing treatment that determines the degree of ordering. When the alloy is perfectly ordered. According to the experiment by Satoh et a/.29(a) shows a photograph of stripe domains as observed by the powder-pattern technique. Mn-Mn pairs exist. and continues to increase up to a field of 1. The appearance of the unidirectional anisotropy suggests the presence of some antiferromagnetic interaction. Therefore all the interactions between spins are positive.88 this induced anisotropy contains unidirectional anisotropy.4. intermediate for (110). and tends to vanish as the degree of order approaches unity. the origin of this induced anisotropy is to be attributed to a spin rearrangement rather than to an atomic rearrangement.

338 INDUCED MAGNETIC ANISOTROPY Fig. we assumed that the pseudodipolar interactions of A-A. Polycrystalline samples were also measured over a wider temperature range down to 4.1. Ku. Figure 13. some mechanism specific to the amorphous structure can also be considered. a uniaxial anisotropy can be induced during preparation or by magnetic annealing. Uniaxial anisotropy constant.)78Si10Bi2 9 as a function of x.cNi1_. suggesting that a major part of this induced anisotropy is caused by directional order. However.cCo1_. no detailed theoretical treatment has been published. This may be attributed to directional ordering of the nonmagnetic metalloid atoms. increases as x decreases from x = l. induced by magnetic annealing of the alloys with compositions (Fe.89 This induced anisotropy is considered to be caused by rearrangement of the mictomagnetic spin system.92 as a function of x. and A-B pairs are constants.l. The only difference is that a nonzero anisotropy is found even at x=l.5 Induced anisotropy of amorphous alloys In amorphous alloys. which are treated in Chapter 11. Mn-Mn pairs. Ku. In the concept of directional order discussed in Section 13. This is the . Numbers in the figure are the temperatures in °C at which the magnetic annealing was performed. induced in amorphous materials of composition (Fe^Nij^ggBjo and (Fe. As in the case of magnetic annealing of crystalline alloys. However.2 K.30 shows the uniaxial anisotropy constant. B-B. in which ferromagnetic clusters are coupled antiferromagnetically with one another to minimize the pseudodipolar interaction between clusters during cooling in a magnetic field. 13JO. 13. Ku.)78Si10B12. the anisotropy constant. Si or P.)goB2091 and (Fe. First we discuss the anisotropy induced in amorphous alloys composed of 3d transition metals containing 10-20 at% of metalloid elements such as B.tCo1_J. N.1.4. prepared by quenching from the melt.

This phenomenon has been interpreted in terms of a columnar structure as well as by directional order. however.REFERENCES 339 case for crystals. J. 621. Evaporated or sputtered Gd-Co or Gd-Fe films exhibit a uniaxial anisotropy with the easy axis perpendicular to the film surface. so that the pseudodipolar interaction is not the same for every A-A pair (similarly for every A-B and B-B pair). a body-centered cubic and a face-centered cubic lattice. [110] or [111].1 After a single crystal of a body-centered cubic alloy is cooled in a magnetic field applied parallel to [001]. assuming only nearest neighbor interactions. W. Calculate the ratio between the two values for a simple cubic. Physics. Calculate the induced anisotropy energy expressed in terms of the angle of rotation of magnetization in the (111) plane. D. 285. For x=l.3 A partially ordered single crystal of a binary alloy with the face-centered cubic lattice is deformed by slip deformation only on a single slip system. only one kind of magnetic atom pair exists. Bozorth.93 It was pointed out that not only compositional short-range ordering but also topological short-range ordering may be responsible for the anisotropy induced in amorphous materials. in amorphous materials the distances between nearest neighbors are variable. However. because the sign of Ku depends on the presence of a DC bias voltage during sputtering. A. it was found that even below this crystallization temperature a long annealing causes a change in the average atomic volume (structural relaxation). Franklin Inst. PROBLEMS 13. 3. Kelsall. 195 (1923).2 After a binary alloy with a cubic lattice was annealed in a magnetic field applied parallel to [110]. Amorphous materials prepared by quenching will crystallize if heated above some critical temperature. However. H. Calculate the ratio of the induced anisotropy constants for the three cases. Arnold and G. 6 (1935). 13. the induced anisotropy was measured in the (001) and (110) planes. 5 (1934). 2.94 The relationship between this microscopic structure and the macroscopic magnetic properties has also been discussed. The anisotropy constants determined for two planes are generally not the same. 279. .95 Stress-induced anisotropy96 and exchange anisotropy97 have also been found in amorphous materials. 169. F. REFERENCES 1. The reader may refer to the review by Eschenfelder" on these topics. the induced anisotropy is measured by rotating the magnetization in the (110) plane. G.. (111)[110]. not so simple. but a slight change in the length of the pairs to decrease the total pseudodipolar interactions can cause the induced anisotropy. Physics. J. However. M. not only the magnitude but also the sign of Ku is different for different preparation conditions. 13. as do all A-B and B-B pairs. because every A-A pair has identical length and symmetry.98 The mechanism is. Dillinger and R. Elmen.

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1. magnetostriction is an important factor in controlling domain structure and the process of technical magnetization. thus resulting in a deformation of the specimen as a whole (Fig. so that the elongation of the radius PP" in the direction AB is given by Fig.3).14 MAGNETOSTRICTION 14. Although the deformation is small.1. 14.2). in the range 10~5 to 10"6. In order to calculate the dependence of the strain on the direction of magnetization. and finally reaches a saturation value A. or along the x-axis. The magnetostrictive strain changes with increasing magnetic field as shown in Fig. 14. 14. Magnetostrictive elongation as a function of applied field. .1 PHENOMENOLOGY OF MAGNETOSTRICTION Magnetostriction is the phenomenon whereby the shape of a ferromagnetic specimen changes during the process of magnetization. 14. Suppose that the elongation of the radius OP is measured along the direction AB that makes an angle (p with the direction of magnetization. The deformation SI /I due to magnetostriction is usually very small. The point P is displaced in the ^-direction by PP' = e cos <p. when it is magnetized to saturation (Fig. we consider a ferromagnetic sphere. which is an exact sphere with radius 1 when it is nonmagnetic but is elongated by SI/I = e in the direction of magnetization. The reason for this behavior is that the crystal lattice inside each domain is spontaneously deformed in the direction of domain magnetization and its strain axis rotates with the rotation of the domain magnetization. A deformation of this magnitude can be conveniently measured by means of a strain-gauge technique. the details of which are described later.

14. . 14.344 MAGNETOSTRICTION Fig.1). When the domain magnetization is distributed at random in a demagnetized state as shown in Fig. the average deformation is given by the average of (14. 14. thus Fig. Elongation of the radius of a sphere with unit radius in the direction making angle <p with the axis of spontaneous strain.3. Rotation of domain magnetization and accompanying rotation of the axis of spontaneous strain.2.2(a).

. 14. We have assumed here that the spontaneous strain f A is constant. If the magnetic field H makes an angle \\i with the easy axis (Fig.4). 14. let us consider how the magnetostrictive elongation changes as a function of intensity of magnetization. in other Fig. irrespective of the crystallographic direction of the spontaneous magnetization. First we consider a ferromagnetic material with uniaxial anisotropy.2(b). 14.PHENOMENOLOGY OF MAGNETOSTRICTION 345 Since in the saturated state. We call this quantity the isotropic magnetostriction. (14. that is. if i// = 0. that is. the domain magnetization rotates towards the direction of the applied field.6) gives A(S///) = 0. During this process no magnetostrictive elongation occurs. until the magnetization reaches the value 7S cos i/f. because the magnetization is everywhere (except within the domain walls) parallel to the easy axis. the magnetization takes place by the displacement of 180° walls. the saturation magnetostriction is given by Thus the spontaneous strain in the domain can be expressed in terms of A as The factor f which appears frequently in the following equations thus results from the definition of A as a deformation from the demagnetized state.4. the domain walls separating anti-parallel domain magnetizations. At higher fields. such as cobalt. Rotation of the spontaneous magnetization 7S by an applied field H in a uniaxial crystal. Assuming isotropic magnetostriction. during this process the elongation changes by If H is parallel to the easy axis. as shown in Fig.

Magnetostriction of a uniaxial crystal as a function of the intensity of magnetization. are given by The changes in 81/1 are shown graphically in Fig. 14.1). and the corresponding elongation changes. \li=TT/2. the magnetization is parallel to one of the (100) directions in each domain in the demagnetized state. the magnetizations at which the displacement of 180° walls is complete. we have. assuming that all wall displacements are finished before the onset of rotation magnetization. that is. Since. (14.6) gives A(S///) = §A. 14. The 81/1 vs / relation for this crystal is shown by the dashed curve in Fig. so that the average elongation is Fig. .5. 14. in this case magnetization takes place entirely by rotation. For a cubic crystal with Kl > 0.5. simply by averaging the above values.346 MAGNETOSTRICTION words. thus If i// has some value between 0 and Tr/2. On the other hand. we put / = 7S cos <p in (14.5 as a function of magnetization for various values of i/f. if H is perpendicular to the easy axis. For a polycrystal. there is no change in the length of the specimen from the demagnetized state to saturation.

If this crystal is magnetized to saturation parallel to [100] (5///)sat = f A. after which elongation due to 90° wall motion begins. If 180° walls are very easily displaced. which represents (14.6. the entire magnetization takes place by the displacement of domain walls. 14. Magnetostriction of an iron single crystal as a function of the intensity of magnetization in the [100] direction. and the 90° wall. only 90° wall motion contributes to the elongation.13). The lines are drawn by assuming (1) preferential motion of 180° walls before 90° wall motion. regardless of the direction of observation. / should increase to /s/3 without changing the length of the specimen.6. the elongation should be given by Both cases are shown in Fig. Thus On the other hand. if the displacement of 90° and 180° walls takes place at the same time. 14. (2) simultaneous displacement of 180° and 90° walls. separating domains magnetized in perpendicular directions. There are two kinds of walls: the 180° wall separating domains magnetized in opposite directions.PHENOMENOLOGY OF MAGNETOSTRICTION 347 given by (S///) demag = A/2. The experiment points observed by Webster1 for iron agree fairly well with line 1. When magnetization changes by displacement of these domain walls. A famous textbook on Fig. Experimental points according to Webster.1 . so that In this example. Thus the 81/1 vs I/IS curve depends on the ease of displacement of 90° walls relative to that of 180° walls.

assuming the displacement of domain walls. When the crystal is magnetized parallel to [111]. . [010] and [001] domains. and fitted the experimental points to a theoretically deduced parabolic curve. 14. [010] and [001] domains by the displacement of 180° walls at a sacrifice of [100].8).348 MAGNETOSTRICTION ferromagnetism written by Becker and Doring2 describes the story of the interpretation of this phenomenon: Heisenberg3 tried to explain this observation by statistical treatment of domain distribution using an old concept of magnetic domains. For [100] magnetization the effect of anisotropic magnetostriction is not observed.9 shows the experimental result for [110] magnetization. so that This relationship is shown graphically in Fig. just opposite to the case of [100] magnetization. during this process / = /„ cos 6 and also 81/1 = f A(cos2 9 — f). Magnetostriction expected for (111) magnetization under the assumption of isotropic magnetostriction. 14. 14. while Akulov4 fitted the points to a straight line. we must understand the physical origin of the magnetostriction.577/s. Thus the sign of A as well as its magnitude depends on the crystallographic direction of magnetization.7. We call this anisotropic magnetostriction. the domains are first reduced to [100]. A slight positive elongation due to 90° wall displacement occurs in the early stage of magnetization. Then domain magnetization will rotate towards the direction of H. In order to discover the origin of the anisotropic magnetostriction. because /s is always parallel to one of the (100) directions throughout the entire magnetization process. At the end of this stage I = Is/i/3= 0. while a fairly large contraction is observed later during the rotation process. Figure 14. The experiment for iron reveals similar behavior.7. Fig. but the sign of the elongation is negative (see Fig. where 9 is the angle between 7S and H.

6 which was developed in his paper on magnetic annealing and . We discuss the origin of magnetostriction following the treatment of Neel.2 Experimental points according to Kaya and Takaki5) 14.2 MECHANISM OF MAGNETOSTRICTION Magnetostriction originates in the interaction between the atomic magnetic moments. Experimental magnetostriction data for (111) magnetization of iron.MECHANISM OF MAGNETOSTRICTION 349 Fig.9. (Figure after Becker and Doring. 14. (Figure after Becker and Doring.2 Experimental points according to Kaya and Takaki5) Fig. Experimental magnetostriction data for <110> magnetization of iron. as in magnetic anisotropy. 14.8.

/33) those of the bond direction. = 0. surface anisotropy. exy. The following terms also contribute to the usual magnetostriction. if. Neglecting these higher-order terms. but normally their contributions are small compared to those of the second term. eyy. The second term represents the dipole-dipole interaction. we express the pair energy as Let (<*!.10. Then (14. is the exchange interaction term. and angle. 14.17) becomes Now let us consider a deformed simple cubic lattice whose strain tensor components are given by exx. its bond length r0 will be changed to r0(l + exx) and . Thus the crystal deformation caused by the first term does not contribute to the usual magnetostriction.5. which is discussed in Section 14. y32. The first term.18) with 8. r. eyz. and can be regarded as the principal origin of the usual magnetostriction. For instance.10). each pair changes its bond direction as well as its bond length. ezz. = 1. A spin pair with a variable bond length. the crystal lattice will be deformed when a ferromagnetic moment arises. When the distance between the atomic magnetic moments is variable. which depends on the direction of magnetization. but it does play an important role in the volume magnetostriction. between parallel spins and the bond. the interaction energy (12. If the interaction energy is a function of r. and ezx.59) may be expressed as where r is the interatomic distance (Fig. if the crystal is strained. a2. because such an interaction tends to change the bond length in a different way depending on the bond direction. When the crystal is strained. it is independent of the direction of magnetization. /39 = R. 14. that is whereas. a spin pair with its bond direction parallel to the *-axis has an energy in the unstrained state given by (14.350 MAGNETOSTRICTION Fig. «3) denote the direction cosines of domain magnetization and (/3j. g(r).

(32 ~ \ex.y j83 = \ezx). for the y and z pairs.18) will be changed by an amount Similarly. is given by where c n .. ezx.. we have where The energy thus expressed in terms of lattice strain and the direction of domain magnetization is called the magnetoelastic energy.23) is a linear function with respect to exx. Since the magnetoelastic energy (14. it increases rapidly with increasing strain and equilibrium is . Since the elastic energy is a quadratic function of the strain. Similar calculations for the bodycentered cubic and face-centered cubic lattice yield the same expression (14. and c12 are the elastic moduli.. c 44 . eyy. for a cubic crystal.23) with for the body-centered cubic lattice and for the face-centered cubic lattice.MECHANISM OF MAGNETOSTRICTION 351 the direction cosines of the bond direction will be changed to (/3 t = 1. the crystal will be deformed without limit unless it is counterbalanced by the elastic energy which.. Then the pair energy (14. Adding these for all nearest neighbor pairs in a unit volume of a simple cubic lattice.

The condition for equilibrium is obtained by minimizing the total energy. we have the equilibrium strain The elongation observed in the direction (/3j. /33).352 MAGNETOSTRICTION attained at some finite strain. which is given by . /32. That is. Solving these equations.

33) and (14. By using A100 and A m . the elongation in the same direction is obtained by putting a Similarly. 2. and 3) in (14. but is related to them by as will be found by putting a1 = ftl = a2 = /32 = 1/^2. Putting (14. (14.32) can be expressed as 4 Thus the magnetostriction of a cubic crystal may be expressed in terms of A100 and A m .34). (14.24).26) into (14. we can express A100 and Am in term of the coefficients of the pair energy: . when the magnetization is along [111]. = ft =l/i/3~ (i = 1.35).32). the elongation is calculated to be by putting a.32) into (14. a3 = y33 = 0 in (14.MECHANISM OF MAGNETOSTRICTION becomes 353 If the domain magnetization is along [100].25) and (14. The elongation in [110] is not independent of A100 and AU1.

Composition dependence of the magnetostriction constants A100. The condition for isotropic magnetostriction is thus expressed by equating the expressions for A100 given by (14.354 MAGNETOSTRICTION If (14. and (14.1). A110.2 K for less than 44% Ni.11 shows the dependence of magnetostriction constants on the alloy composition for iron-nickel alloys. where the magnetostriction is isotropic at 15% and at 40% Fe-Ni. For isotropic magnetostriction. Fig.) . and A nl for Ni-Fe alloys.Figure 14.35) becomes where 6 is the angle between the direction of domain magnetization and that of the measured strain. (14. it can be seen by putting (14.8 for dashed curves measured at room temperature and dot and dashed curves measured at 4. it is hard to attribute any significant physical meaning to the isotropic magnetostriction.40) into (14.38). The final form is the same as that of the isotropic magnetostriction given by (14. 14.37).11. Since the coefficients of the pair energy and the elastic moduli included in these expressions are entirely independent of each other.39) to those for Am.36) that ^ = ^100 = ^111 = ^110. (After Lichtenberger7 for solid curves and Kim et al.

by setting the z-axis parallel to the c-axis. assuming a. The average longitudinal magnetostriction is calculated by averaging (14. even if A100 =£ A m . from the composition dependence of A100 and Ain observed for binary alloys. the expression for the magnetostriction of a cubic crystal becomes more complicated than (14. = 6. respectively. it is possible to deduce its coefficient.MECHANISM OF MAGNETOSTRICTION 355 For polycrystalline materials. thus In the preceding discussion we considered only the dipole-dipole interaction term in (14. /.16). If we take into account the third term of (14.35): where and h1 and h2 are related to A100 and Am by hl = (3/2)A100 and h2 = (3/2)Am. the magnetostriction is isotropic. 14. the composition dependences of A100 and Am can be .16). and 3). (i — 1. because the deformation in each grain is averaged to produce the overall magnetostriction.35) for different crystal orientations. 2.11. As seen in Fig. In a hexagonal crystal. the deformation from the state with the magnetization parallel to the c-axis is given by9 A more precise expression10 is given by Since the magnetostriction constants are related to the dipole-dipole interaction.

39) for an fee lattice. the composition dependences in the fee region are expressed by where CNi and CFe are the fractions of Ni and Fe. where CA and CB are the fractions of A and B atoms.52) with (14. the probabilities of finding AA. we have Comparing (14. the origin of magnetostriction is the magnetoelastic energy. .48).356 MAGNETOSTRICTION Z approximated by quadratic functions. respectively. for all three possible kinds of atomic pairs. Neel6 deduced the coefficients.3 in Section 14. AB and BB pairs are proportional to CA. If the atomic distribution of A and B atoms is completely random. 2CACB. the Is. respectively. This value was used for estimating the induced anisotropy due to directional order in Ni-Fe alloys in Chapter 13.4. we have If we assume that the elastic moduli of Ni-Fe alloys are the same as those of Ni. In Ni-Fe alloys. As discussed above. Therefore the average / is given by Similarly the average dl/dr is given by Solving (14. and C\. Using these relationships. as given in Table 14. we can determine from which we have for Ni-Fe alloys.

on which a thin serpentine resistance wire or foil is cemented as shown in Fig.MEASURING TECHNIQUE 357 which is the magnetocrystalline anisotropy of the deformed crystal. we cut a disk parallel to (110) from a single crystal and cement a strain gauge parallel to [100] or [111]. For more details the reader may refer to the review by Kanamori. so that the elongation given by (14. is made of a small piece of paper or polymer sheet.13 14. S. the agreement with experiment was not satisfactory. 12.35) is reduced to Fig. 14. the direction cosines of the magnetization are given by (12.12. thus changing its resistance. and a decrease in cross-sectional area. sometimes called a resistance strain gauge. where R is the resistance of the strain gauge. If we assume that Poisson's ratio is 0. The calculated A100 agreed with experiment. Paper strain gauge.5.2. as shown in Fig. should result in a gauge factor of 2.3. but the value for A U1 and its temperature dependence were not satisfactory. Jn order to determine A100 and A U1 in a cubic material. an elongation of A///.14-15 A strain gauge. A calculation of magnetostriction was made by Tsuya11 for ferrites using a one-ion model. by AS/S = A///. which means that the volume of the gauge material does not change during elongation. the resistance wire in the strain gauge is also elongated. The proportionality factor between A/// and AR/R. 14. then rotate a magnetic field in the plane of the disk. Therefore the microscopic origin of magnetostriction is the same as that of magnetocrystalline anisotropy.3 MEASURING TECHNIQUE A convenient means for measuring magnetostriction is the strain gauge technique.12. Usually the value of the gauge factor ranges from 1. However.7.12). is called the gauge factor. and measure the strain parallel to [100] or [111]. Slonczewski12 calculated magnetostriction in Co ferrites using the one-ion model discussed in Section 12. and also that the effect of strain is only geometrical. If we denote the angle between [001] and the magnetization by 6. When a specimen to which this strain gauge is cemented is elongated.14 .8 to 2.

the volume magnetostriction is increased. For the strain gauge parallel to [111]. The data in this case is shown as curve B in Fig. so as to experience the same magnetic field and the same .5). so that the sensitivity of the strain gauge is reduced. in agreement with (14. the demagnetizing factor becomes so large that it may be difficult to reach magnetic saturation. which has a minimum at 54. Changes in gauge resistance are measured in a bridge circuit. Equating the amplitude of this curve to f A m .93% V-Ni (110) disk: (A) elongation parallel to [001]. Magnetostriction measured as a function of the angle of magnetization from [001] for 3.13 shows the experimental result of magnetostriction measured for 3. 14.56). so that (14. we can determine A100. It should be noted that if the cement applied to attach the strain gauge to the specimen is too thick or the specimen is too thin. (B) parallel to [111]. so that we have where 90 = 54.57).7°. The functional form of curve A is well fitted by cos26. 14.55) gives Figure 14. three dummy gauges completing the bridge may be cemented onto a nonmagnetic disk placed near and parallel to the specimen. and /33 = 1. On the other hand.7° in agreement with (14. Moreover. Curve A shows the elongation parallel to [001] as a function of the angle 6.13. Equating the amplitude of this term to f A100.93 at% V-Ni alloy.a N Fig. we can determine A1U. To compensate for resistance changes due to temperature and to magnetic field.13.55). This curve has the functional form cos26. we put /3j = /32 = 0. which makes the determination of saturation magnetostriction difficult (see Section 14. we put ^ = )32 = ft = l/i/3~ in (14. if the specimen is too thick. the rigidity of the specimen is altered by the presence of the strain gauge.14 When the strain gauge is parallel to [001].

AB. Magnetostriction measurements can also be made by a capacitance technique.1 Magnetostriction of uniaxial crystals (a) Magnetostriction of rare earth metals Heavy rare-earth metals with more than seven 4/ electrons such as Gd. these metals have unquenched orbital magnetic moments which give rise to large magnetocrystalline anisotropies.EXPERIMENTAL DATA 359 temperature as the specimen.(a)). Cy. and Tm exhibit ferromagnetism at low temperatures (Section 8.3). and AD observed for gadolinium single crystal. Temperature dependences of magnetostriction constants AA. the gauge factor is influenced by the magnetic field and by temperature. Gadolinium is an exceptional case. which may be too small to mount a strain gauge.4. a sensitive length-measuring device called a linear variable differential transformer (LVDT) may be useful. 14. so that they can be magnetized to saturation only in very high fields (see Section 12.1. so that a calibration is needed. However.16 . Tb.4. Except for Gd. Details are given by Wakiyama and Chikazumi. some strain gauges are made with the gauge factor quite insensitive to both magnetic field and temperature. Er.14.14 Strain gauges made of semiconductor materials are also available. Ho. Ac. they have very high sensitivity (gauge factor over 100).4 EXPERIMENTAL DATA 14. but correspondingly high values of magnetoresistance and temperature coefficient of resistivity. For wire and ribbon samples. Even in this case. because it Fig. in which the magnetostrictive strain changes the gap between two conducting plates and hence changes the capacitance. 14.

03.15. some thousands times 1(T6 for Dy. Figure 14.3) are listed in Table 14.5X10~ 6 5 -32. However.360 MAGNETOSTRICTION Fig. c12=1.5 -1099 -1233 -70. even though there is no orbital magnetic moment.58.20 The magnetostriction constants and elastic moduli measured for single crystals are listed in Table 14. extrapolations to 0 K from the small values near the Neel points give very large values. Magnetostriction constants and elastic moduli of hexagonal cobalt.76 X 10 u Nnr 2 (Xl0 12 dyncm.65.1. and is easily magnetized to saturation in any crystallographic direction.17'19 (b) Magnetostriction of cobalt Cobalt transforms from fee to hep at about 420°C on cooling.5 -52 -66 5 -88.4) and MnBi.5 X KT 6 105xlO~ 6 120 126 126 -82 -108 -128 -52XMT6 -200 cn = 3.21 t\ Oj A^ Ag A£ Aj) 200 0 -200 400 -16. has no orbital moment (L = 0).1. The Table 14. Therefore magnetostriction can be measured without any difficulty. (c) Magnetostriction of hexagonal oxides and compounds Magnetostriction constants of a hexagonal ferrite BaFe18O27 (see Section 9.16'17 Note that the magnitudes of some of these constants are as large as 100 to 200 X 10~6. c13 = 1. For other rare earth metals (with nonzero orbital magnetic moments) it is hard to determine accurate values of magnetostriction constants. a NiAs-type compound. 14. c44 = 0. Er. c33 = 3.45)) of Gd.17 Ho18.2. The magnetostriction constant of polycrystalline cobalt changes its sign at this transformation point as shown in Fig.2 ) . 14. Temperature dependence of magnetostriction constant observed for polycrystalline cobalt in various magnetic fields20 (numerical values of H are in Oe (= W3/4irAm~1J). (see Section 10.14 shows the temperature dependences of magnetostriction constants (see (14.07.15.

although the magnetocrystalline anisotropy constants of these materials are almost the same (see Sections 12.60 1.17.12 \ 2.2 Magnetostriction of cubic crystals (a) Magnetostriction of 3d transition metals and alloys AS A A The magnetostriction constants and elastic moduli observed for iron at room temperature are listed in Table 14.2 ) 6 n 2 12 Ref. The magnetostriction constants and elastic moduli observed for nickel at room temperature are listed in Table 14. together with those of nickel. respectively. the magnitude of the magnetostriction decreases monotonically with dilution. 14. reflecting a monotonic decrease of the saturation magnetization.16 for Fe.19).24. Since the Fe-Al alloy develops the superlattice Fe3Al. In all these cases. 6 3xlO~ 22 23 constants of MnBi are two orders of magnitude larger than those of BaFelgO27.50 1.3.9 -21. The effect of dilution with nonmagnetic elements such as Si. Al.2. in spite of the fact that the saturation magnetization of both the alloys decreases as if the magnetic moments of Fe atoms are diluted by nonmagnetic atoms (see Section 8. 14. 14.3 2.29 The magnetostriction constants of Fe-Ti alloys exhibit fairly complicated composition dependences (Fig. Magnetostriction constants for Fe-Ni alloy are already shown as a function of Table 14.4.3. Temperature dependences of five constants (see (14. both the constants A100 and Am are negative. Magnetostriction constants and elastic moduli of iron and nickel (room temperature). the magnetostriction constants are also influenced by heat treatments. while the Curie point increases. Contrary to iron. and 14.21-14.18 / .2). Compounds BaFe18O27 MnBi AA 13XlO~ -800 6 AB 3 X 1(T -210 6 Ac -23X10" 640 Ref. C ll ^12 C 44 Metal A100 Am 6 X 10 Nnr (x!0 dyncm. It is interesting that the values of A100 for Fe-Si and Fe-Al increase with a dilution with these nonmagnetic elements.41 1.43)) are shown in Fig.46 1. with addition of Ti. 14.2X10' -24. Magnetostriction constants of hexagonal compounds.18. and Ti on A100 and Am of Fe are shown in Figs 14. the saturation magnetization stays almost constant.7 X l O ~ -45.3. The temperature dependences of five constants are shown in Fig.20.19. 24 Fe Ni 20. In the case of Fe-Ti alloys. Effects of dilution with nonmagnetic elements such as Cu.1(d) and 12.4. and Ti are shown in Figs 14.EXPERIMENTAL DATA 361 AD 6 Table 14. V.4.1(e)). 14. respectively. Cr.

Most of the constants are of the order of magnitude of 10~5. . In the case of Co. 14. a fraction of Fe3+ ions on the A sites change to Fe2+ ions. Particularly in those ferrites containing more than 50% Ti.0. Despite the formation of the superlattice FeCo37 (see Section 8.25 (The constants in the figure are related to those in (14.43) by A^ = hlt A2 = 2h2. This is also due to the appearance of Fe2+ ions. Temperature dependences of five magnetostriction constants observed for iron in a magnetic field of 0. Most ferrites have negative A100.27 shows the composition dependence for MnA. Similar to the composition dependence of K1 of the same system. 14.4). and isotropic magnetostriction occurs.3 may contribute to these large values.25 and 14. The isotropic magnetostrictions are realized at 60 and 85% Ni. Figure 14.48 Also the Fe2+ ions on the A sites tend to produce the Jahn-Teller effect (see Section 14. In the case of Ti.16. which is an anisotropic ion and can be responsible for the large magnetostriction. (b) Magnetostriction of spinel-type ferrites The magnetostriction constants A100 and Am are listed for various spinel-type ferrites in Table 14. A3 = h3.33'34 Magnetostriction constants of Ni-Co and Fe-Co alloys are shown as a function of composition in Figs 14.26.4.64MAm"1 (= 8kOe). and A5 = 2hs. the introduction of Ti4+ may give rise to a change in valence from Fe3+ to Fe2+. the magnetostriction constants are insensitive to heat treatments. which contribute to large values of magnetocrystalline anisotropy and magnetostriction. A4 = H4.7) and the accompanying lattice softening may also contribute to the large magnetostriction. the one-ion anisotropy of the Co2+ ion discussed in Section 12. respectively. both constants change abruptly as x becomes smaller than 1.Fe3_J.) composition in Fig. except for very large values for ferrites containing Co or Ti. except for some ferrites containing Fe2+ ions.11. A100 decreases and A ni increases with the formation of the superlattice Ni3Fe.362 MAGNETOSTRICTION Fig.O4. In the vicinity of 75% Ni.

O12 was also measured. 14.5 VOLUME MAGNETOSTRICTION THERMAL EXPANSION AND ANOMALOUS In the preceding sections we assumed that the volume of a ferromagnet remains . This is due to the fact that the paramagnetic rare earth ions are strongly magnetized by the exchange field at low temperatures.VOLUME MAGNETOSTRICTION 363 Fig. A change in magnetostriction by replacing Fe3+ with Ga3+ in YIG or by an increase in x for Y3Fe5_jGa_. 14.26 (Data after Tatsumoto and Kamoto26 and Carr and Smoluchowski27) (c) Magnetostriction of garnet-type ferrites The magnetostriction constants measured at various temperatures for pure iron garnets are listed in Table 14. the values at low temperatures become very large as seen in Fig. The values at room temperature are of the order of magnitude of 10~6-1CT5.59 14. Composition dependence of magnetostriction constants of Fe-Si alloys. With the addition of anisotropic Tb..5.17.29 which shows the temperature dependences of magnetostriction constants. but for those garnets containing rare earth ions with nonzero L the values are very large at low temperatures. Figure 14.28 shows the temperature dependence of magnetostriction constants of YIG containing only nonmagnetic yttrium.

this term depends on the length of the bond. First we discuss the effect of the first term.16). or the distance between the paired spins. we have ignored the first term and all terms higher than the second term in (14. g(r). the fractional volume change is given by Using the spontaneous strain tensors given by (14. For the spin pair whose bond direction is given by the direction cosines (/31. This term describes the exchange interaction between spins. In terms of strain tensors.30).18.28 constant during the process of technical magnetization. r.364 MAGNETOSTRICTION Fig. Composition dependence of magnetostriction constants of Fe-Al alloys (room temperature).58) that However. However. a change in the pair energy is given in terms of the lattice strain by .16). 14. We call this phenomenon the volume magnetostriction. and is independent of the direction of the spins relative to the bond direction. )33). we find from (14. These terms can produce a small but nonzero change in volume with magnetization. j32. in (14.

14.20.VOLUME MAGNETOSTRICTION 365 Fig. (The constants in the figure are related to those in (14. A^lhi.29 Fig.19. and A5 = 2hs. A3=h3.43) by A1=h1. A4 — h4. 14. Temperature dependence of five magnetostriction constants observed for nickel.) . Composition dependence of magnetostriction constants of Fe-Ti alloys at 77 K and 300 K.

32 .22.31 Summing up the pair energies for all the nearest neighbor pairs in a simple cubic lattice. Composition dependence of magnetostriction constants of Ni-Cu alloys (room temperature). 14. Composition dependence of magnetostriction constants of Ni-Cr alloys.21.366 MAGNETOSTRICTION Fig. Fig. Minimizing the total energy. or the sum of the magneto-volume and elastic energies. we have which is called the magneto-volume energy. 14.

Composition dependence of magnetostriction constants of Ni-Ti alloys.32 we*. Composition dependence of magnetostriction constants of Ni-V alloys.24. the. re. have. 14.latinnshins Fig.29 .23.VOLUME MAGNETOSTRICTION 367 Fig. 14.

14.25.26.368 MAGNETOSTRICTION Fig.36 . Composition dependence of magnetostriction constants of Ni-Co alloys (room temperature). we have the volume change This is the volume magnetostriction produced by the appearance of spontaneous Fig.35 Adding up these terms. Composition dependence of magnetostriction constants of Fe-Co alloys (room temperature). 14.

g. 20°C 20°C Ref.43Zn0.5Al0. Using this relationship.63FeL26Mnj.5 -10.14Fe2.1 -19.5 -26 -5 -0.3 2.5 -22 49.9 109 86 92 (330) Temp. 38 39 40 41 42 41 38 43 44 44 45 40 46 41 47 47 47 48 48 48 48 369 5 20°C 9 6 6 3 290 K 80K 290 K 80 K magnetization in a simple cubic lattice.5 Xl(T 6 78 120 -14 4. is independent of at.0 -12.ioFe2. Composition MnFe2O4 Fe3O4 Co08Fe22O4 NiFe2O4 CuFe2O4 MgFe2O4 Li05Fe25O4 Mn 06 Fe 24 O 4 Mn028Zn016Fe237O4 Mn104Zn022Fe182O4 Mgo.53) is replaced . Then the internal energy associated with the spontaneous magnetization is given by where z is the number of nearest neighbors.0704 Li0.6 110 -38. is regarded as the average exchange interaction energy.7 1. g. Magnetostriction constants of spinel-type ferrites (mainly after Tsuya49).3 47 142 170 990 Am 6. the coefficient. in (14.2 4. Similarly we have and These are the volume changes produced by the appearance of ferromagnetism.56Ti0. g.7 37 -3. the coefficient. Co 032 Zn 022 Fe 22 O 4 Co01Ni09Fe2O4 Li0. In other words.2 0.VOLUME MAGNETOSTRICTION Table 14.1504 Lio.nO.1 -16.35Fe2. (14.8 45 36 3 -2.5 -210 -109 -27.52).4. but is nonzero when the material is ferromagnetic.51).3504 Li05Ga14FeL1O4 Ti018Fe282O4 Tio56Fe244O4 A100 -31Xl(T 6 -20 -590 -42 -57. The coefficient. and (14.6 3.

c. and the elastic moduli. which is a 34 at% Ni-Fe alloy used as a low thermal expansion material (see Section 8. 14. the anomalous thermal expansion coefficient of Ni shown in the inset of Fig. c n and c12.. This relationship can also be deduced from thermodynamic considerations. 14.27..69) results in an anomalous thermal expansion coefficient. Since the magnetic internal energy depends on temperature through a change in spontaneous magnetization. In fact. Dependence of magnetostriction constants on the composition x in Mn^Fcj^O. 14. The main graph in Fig. the volume change given by (14.370 MAGNETOSTRICTION X Fig. (Data after Miyata and Funatogawa43) by E. The anomalous region shown by the hatched area in Fig. Also.2). 14. covers a wider temperature range.30 shows the temperature dependence of thermal expansion coefficient for Invar. This behavior can be interpreted in terms . and has no sharp peak at the Curie point.30 is much larger than that of Ni. or where Cp is the anomalous heat capacity per unit volume due to the appearance of ferromagnetism. using the relationship between the bulk modulus.30 is quite similar to its anomalous heat capacity. we have for all crystal types where (a = 8 v/v.

61"3 A theory based on the spinfluctuation model can also explain this phenomenon.2 51 GdIG 7.5 -3.5 20 4 5 1 78 196 300 50 50 50 78 196 300 50 50 50 4.9 5 4.3 5. Magnetostriction constants of garnet-type ferrites (after Tsuya57.8 -4. and a high-spin state with a large magnetic moment and large atomic volume.5 -4.8 78 196 300 4.1 -4.VOLUME MAGNETOSTRICTION Table 14.64 .0 1. YIG SmlG EuIG -1.4 3 -550 560 65 12 -145 -21.4 -4.2 56 50 50 50 50 50 18.9 -11. Temp.2 -31.5.0 9 0 9 2A 78 196 300 0 55 78 196 300 0 50 50 50 50 50 50 55 TmlG YbIG 25 10.3 -7.4 -8.1 -8.2 -10.1 -5.0 -19.1 -4.6 -12.4 -7.2 78 196 300 78 50 97 -31 196 300 4.2 54 DylG -1400 67 -10.3 -5.0 1.4 159 110 86 51 21 49 21 4 -3.4 9 5 4 4.0XHT -1.1 9.3 1.9 1.7 4.6XKT -3.5 5 78 196 300 of a model which assumes two spin states for Fe atoms: a low-spin state with a small magnetic moment and small atomic volume.1 2.4 -183 -28. RIG 371 A100 Am 6 (K) 6 Ref.2 52 50 50 53 50 50 50 TbIG 1200 4.3 HoIG -1400 -169 -46.4 -14.6 -5.7 5.5 -82. Hansen58).3 -3.6 -3.7 0 2420 78 196 300 78 196 300 4.9 -2.1 -1.2 55 50 50 50 50 50 50 -330 ErIG 630 -450 -56.

Fe5O12 U-values are from up to down: 3. 0.26 and O. 1.50.60) . 14. 0.OO)58 (Data after Belov et al. 14.12. 1. H. 2. Temperature dependence of magnetostriction constants of TbxY3_.00. g.17. which causes an increase in spontaneous magnetization. the energy of spontaneous magnetization is given by Fig.372 MAGNETOSTRICTION Fig.58 (Data after Hansen59) The exchange energy. Temperature dependence of magnetostriction constants of YIG.28. In the presence of a high magnetic field.29. 2.65.t. can also be changed by the application of an external field.54.

referring to (14. we see that this effect is caused by a rotation of the spontaneous magnetization against the magnetocrystalline anisotropy.16).61 (see (6. because (14. This effect is isotropic: in other words. The h3 term in (14. Temperature dependence of the anomalous thermal expansion coefficient for Ni and Invar.VOLUME MAGNETOSTRICTION 373 Fig.73) (other than the constant term) is Comparing with (14. 14. Consider a ferromagnetic specimen of nearly unit volume. where w is much smaller ... which does not contain any /3. the volume change is spherical. so that. Let us proceed to the volume magnetostriction that arises from the quadrupole interaction q(r) in (14. The anomalous thermal expansion and the forced magnetostriction are essentially isotropic. For the simple cubic lattice. we have a volume change produced by the application of a field We call this volume magnetostriction caused by the forced alignment of spins by high magnetic field the forced magnetostriction. it is called the crystal effect.69).74) does not contain any /3. which are the direction cosines of the observation direction. (1 + «).68). this term produces a volume magnetostriction given by Using the relationships (12.69).62) and (14. because they are caused by the isotropic exchange interaction.30. The volume magnetostriction depends also on the shape of the specimen.23)).43). the main term in (14. corresponds to this effect.

31. the volume magnetostriction of a specimen with a finite size is expected to change as a function of external field as shown in Fig. depending on the sign of q (or of Kj) and that of dq/'dr. the volume change decreases and then increases linearly due to the forced magnetostriction. and with demagnetizing factor.72)). Generally speaking.75) for E in (14. Substituting U in (14. The sign is negative for iron and nickel. the magnetostatic energy is given by where M is the magnetic moment of the specimen as a whole. N. 14. For a specimen in the form of a rotational Fig. this volume change also reaches a saturation value The feature of this effect is that the volume change is proportional to I2. and considering M ~ I. but it becomes comparable to the linear magnetostriction when the magnetic field is stronger than 1 MAm"1 (about 104 Oe). or to H2 if the magnetization curve is linear. When this sample is magnetized to an intensity of magnetization.31.69). In this case. 14. It should be noted that the form effect produces not only volume magnetostriction but also normal linear magnetostriction.65 . Fig. because the forced magnetostriction is linear with H (see (14. The sign of the crystal effect can be either positive or negative.32 shows the volume magnetostriction observed for two iron samples with different demagnetizing factors. and then the crystal effect appears in the region of rotation magnetization. Schematic variation of the volume magnetostriction with increasing magnetic field. In summary. When the specimen is magnetized to saturation. /. First the volume increases proportionally to H2 as a result of the form effect. we have We call this effect the form effect. the volume magnetostriction is small when the magnetic field is reasonably weak.374 MAGNETOSTRICTION than 1. 14.

(Data after Kornetzki66) ellipsoid with the long axis parallel to the x-axis.43). (14.78) becomes where a is given by .32.9. Experimental data on the field dependence of the volume magnetostriction for two iron specimens with different dimensional ratios.VOLUME MAGNETOSTRICTION 375 Fig. (b) k = 41. (a) k = 16. 14.6. the demagnetizing factor depends on the strain as where k is the dimensional ratio or aspect ratio (length/diameter). we have Using (14. Let the length of the specimen be / and the diameter d.78) and (14. Then we have Since the demagnetizing factor of the elongated ellipsoid is given by (1.79).

Let the direction cosines of this tension be (y^ y2.85). we must use a specimen with a small demagnetizing factor. In order to avoid this effect in measuring the ordinary linear magnetostriction. Suppose that a stress.376 r MAGNETOSTRICTION (N = dN/dk\ Ignoring the volume magnetostriction. and eyy and ezz should become more negative.6 MAGNETIC ANISOTROPY CAUSED BY MAGNETOSTRICTION Since a magnetostrictive elongation is caused by magnetization. y3). Such an effect is called the inverse effect of magnetostriction. we have where exx is the longitudinal magnetostriction. cr (Nm~ 2 ). exx should become more positive. Then the tensor components are given by a-fj = crjijj.23) we have the magnetoelastic energy . is acting on a ferromagnetic body. and eyy or ezz is the transverse magnetostriction. Using these relationships in (14. Magnetostriction plays an important role in determining domain structures through this effect. The resultant strain can be found by minimizing the total energy or Solving (14. The measurement of the anisotropic form effect is discussed by Gersdorf.67 14. which results in a strain with components where su. the magnetostatic energy is expressed in terms of strain tensors as Therefore in order to decrease the magnetostatic energy. sn. a mechanical stress is expected to have some effect on magnetization. 544 are the elastic constants.

For simplicity.93) becomes This relationship holds always if we define <p as the angle between the magnetization and a. and c44 and sn. In other words. Magnetostriction can also influence the cubic anisotropy. cu. the energy changes as the magnetization rotates.89) leads to Let <p be the angle between [111] and a.MAGNETIC ANISOTROPY CAUSED BY MAGNETOSTRICTION 377 The coefficients B1 and B2 are related to A100 and Am by (14.89). because as the magnetization rotates. Using this relationship between cn. Hereafter we use (14. When the easy axis is parallel to [111].88) can be rewritten as For a ferromagnet with K^ > 0 such as Fe. a magnetic anisotropy is produced. If instead of fixing the direction of magnetization. <r. the lattice distorts. This is a kind of uniaxial magnetic anisotropy. This difference in energy between domains results in a force acting on the 90° domain walls between them. a domain with magnetization parallel to [100] has energy Similarly. we fix the axis of stress. for the [010] and [001] domains we have and respectively. s12.33) and (14. Then we have the relationship so that (14. Then. thus producing changes in magnetoelastic and elastic . (14. (14.34). according to (14. we assume isotropic magnetostriction. A100 = Am = A. and su* (14.96) when we discuss the effect of stress on magnetization.89) becomes where <p is the angle of the magnetization measured from the axis of stress.

Using the values of Table 14.30). Therefore the observed magnetocrystalline anisotropy constant must be compared with the theoretical value using the correction given by (14.28) becomes A£ = A^Ufcf + a\a\ + a ^ a f ) .378 MAGNETOSTRICTION energies. Substituting the strain tensor in the magnetoelastic energy (14. (14.7)).27): Thus a change in the total energy (14.100).33) and (14. 3 (see (12.3 for Ni. where AKl is given by from the relationships (14. we have We have also a change in elastic energy from (14.100) gives This value is small compared with the observed value of -5. .34).23) using the strain tensor components in (14.7 X 103 J m but is not negligible.

while the other dy function has the form 2z2-x2-y2 and stretches along the z-axis (see Fig. Therefore if the elastic moduli are decreased for some reason. the 3d ions under consideration are more separated from the O 2 ~ ions on the same z-axis than from those on the same x.t 2 — y2 has a lower electrostatic energy than the other. 14. the magnetostriction is produced by a balance between a decrease in the magnetoelastic energy and an increase in the elastic energy.68 Intuitively this phenomenon is interpreted as a deformation of the lattice by anisotropic electron clouds of 3d electrons.or _y-axis. One of the mechanisms that can cause a decrease in the elastic moduli is a structural phase transition. Therefore the ninth electron occupies this level.4. as shown in Section 3.33. the magnetostriction must increase. This is the Jahn-Teller distortion. because Fig.2) observed at room temperature is due to this effect. One of the dy functions has the form x2 — y2 and stretches along the x. At high temperatures this material is cubic. so that the total energy of the occupied levels is lowered as the lattice is elongated along the z-axis. For example. occupies an octahedral site in a cubic crystal.20). As discussed in Chapter 12.and y-axes. suppose that the Cu2+ ion. the balance of the two energies results in a nonzero distortion of the crystal. A typical example is the John-Teller distortion. which has nine 3d electrons.ELASTIC ANOMALY AND MAGNETOSTRICTION 379 14. If the cubic crystal is elongated along the z-axis (c > a). When a cubic phase at high temperatures transforms to phase with lower symmetry at some transition temperature. 14. As noted in Section 14.7 ELASTIC ANOMALY AND MAGNETOSTRICTION In this section.33. Splitting of the dy levels of the Cu2+ ion on the octahedral site. The tetragonal distortion of copper ferrite (see Section 9.2. . we discuss several topics on the relationship between elasticity and magnetostriction of magnetic materials. 3. the elastic modulus corresponding to this deformation decreases with a decrease of temperature towards this transition point. Since such a deformation of the crystal increases the elastic energy. Then nine electrons distribute on five energy levels according to Hund's rule as shown in Fig. Then the dy function with 2z 2 -. three d levels are lowered and two d levels are raised by cubic crystalline fields.

Schematic diagram of stress-strain relationships for ferro and nonferromagnetic materials.4. so that the elastic modulus cn is reduced.380 MAGNETOSTRICTION Fig. 14.2(b)) is considered to be due to lattice softening caused by Fe2+ ions on the A sites. there is still a tendency for the lattice to deform to a tetragonal structure. 14. Figure 14.34 shows the stress-strain curves for ferromagnetic and Fig. However. the thermal excitation to the excited dj level lowers the total energy levels by reducing the separation of the two levels.34. The elastic moduli of ferromagnetic materials are reduced to some extent due to magnetostriction.69 (Data of AE effect from Koster70) . A value of magnetostriction observed for Ti-ferrite (see Section 14.35. This phenomenon is called the lattice softening. Comparison between the AE effect and A for Fe-Ni alloys.

2. 274. 78. J.71'72 PROBLEMS 14. Rev.. Mason. Chikazumi. Webster. 10. thus resulting in a decrease of the Young's modulus. (London). Phys. 4.4 When a tensile stress cr is applied parallel to [123] in a ferromagnetic crystal with positive Klt how much energy can be stored in the x. Phys. In ferromagnetic metals. R. Japan. Berlin. D. Soc. Ann. L. L. Proc. Lichtenberger. W. the magnetostriction contributes an additional strain irrespective to the sign of A. S. J. 7. N. Calculate the elongation measured in the [010] direction as a function of the intensity of magnetization in that direction. Matsui.. where magnetization can rotate freely. Phys. 2 (1935). 143 When a single crystal sphere with magnetostriction constants hlt h2. Berlin.5 Calculate the value of AX^ for iron at room temperature.1 Consider a cubic ferromagnetic crystal with a large positive magnetocrystalline anisotropy constant (K1 > 0) which contains only [100] and [100] domains in the demagnetized state and is magnetized parallel to [010]. 1939). 5. Radium. and S. Hokkaido Univ. E.35. 14. Carr. 9. 96 (1954). 45.. Neel. estimate the order of magnitude of the dipole-dipole interaction. Roy. which demonstrates the proportionality between LE/E and A in Fe-Ni alloys. Phys. Takaki. Boring. Ferromagnetismus (Springer. . 1959) Chap.K1. Z. Turbine blades are usually made from magnetic 13% Cr stainless steel. 6. S284. 10 (1932). Becker and W. Phys. 44 (1978). 15 (1954). 69 (1931). Physik. and h3 is magnetized to its saturation by a constant magnetic field which makes an angle 6 with [100] in the (001) plane. Kim. W. Kaya and H. 8.. Handbuch der Physik (Springer-Verlag.REFERENCES 381 nonferromagnetic materials. 3. 570. /. W. Cleveland. Sci. a mechanical vibration produces eddy currents through the rotational vibration of magnetization. Akulov. Fac. It is naturally proportional to the magnitude of A as shown in Fig. Magnetic properties of metals and alloys (American Society of Metals. y. 225. W.. 302. Heisenberg.2 Knowing that the saturation value of magnetostriction is in the order of 10 ~ 5 and also that the elastic modulus is in the order of 1011 Nm~ 2 . and z domains? Assume \100<r*K. because vibrational energy is more strongly absorbed in a magnetic material because of this effect. how do the elongations parallel to [100] and [010] change as a function of 07 14. C. 1152. 287. A109 (1925). 14. Nl. REFERENCES 1. 69 (1931). At moderate stresses. Soc. 10. 14. J. P. which exhibit the A£ effect. Z. This phenomenon is called the AE effect. M. instead of nonmagnetic 18-8 stainless steel. which results in an additional internal friction. 1966). XIII/2. F. 227.

Conf. Phys. 228. Proc. Solids. /. N. Soc. Phys. Vol. /. /.. Phys. Phys. J. Petrakovski. Japan. 30 (1959). 2 (Wiley-Interscience. E. 24. Tatsumoto and T. N. Jones. 509. Phys. 2544. 21.. Handbook on magnetic materials. 392. R. G. Mitsuoka. J. 50. Donne. J. 328 (in Japanese). K. S. Appl. Rev. Rev. Rept. 39 (1968). Chap. A.. 28 (1957). Hall. Phys.. 279.. C. H. Slonczewski. 168. Jr. 23. Stull. 46. 52. H. L. 35. S. 165. K. Rept. G. Soviet Phys.. Nilsen. M. /. Appl. 14. R. DeSavage. E. 301. p. S. Phys. 616. 45. 1283. Rev. 13 (1958). Japan. 9 (1967). Y.. Arai and N. 33. C. Callen. T. F. /. Williams and A.. 624. New York. Williams. L. 15 (1960). Appl. Boothby. Experimental Physics Series (Kyoritsu Publishing • Co. Appl. 1236. 71. and S. Rev. Soviet Phys. 571. 47. C. Phys. 3 (1964). Nakamichi... Japanese!. 51. Borzorth. B. 431. Tokyo. /. 1. 14. Appl. Phys. Phys. 18. J. Benninger and A. p. and O. 42. Phys. 335.9 (in Japanese). Ferrites (1970). Appl. and N. Phys.. 89 (1953). p. Appl. Table 13. /. 27. A. Solid State. 10 (1968). M. Legvold. Soc.. Phys. Nakamichi. 707. J. M. 31. Chan. Soc. G. 41. B8 (1957).. E. Phys. Phys. Lett. Phys. M. 1967).. Hall. Tilden. 184. H. J. Goldman. 99 (1955). Appl. 310S. Legvold. JETP. Clark. Appl. C. Spring Meeting of Phys. Chikazumi. Ishizumi. Rev.. J. Phys. Phys. 15. Lett.. H.. Honda and S. S. 48. Phil. Japan (1973). L. Tsuya. 445. 17. Soc.. Experimental methods in magnetism. 8. (Asakura Publishing Co. 37. Pavlovic. J. J. 816. Phys. Appl. 1303. 19. Japan. Magnetism (Academic Press. Arai. B. Alstad. Carr and R.. Japan.. M. Yamamoto and T. 30. 4 (1965). N. 138 (1965). Phys.. 1963). Funatogawa. R. 30 (1959). V. Miyata and Z.. E. V. C. Soc.. Phys.. Inc. F. Phys. Fonton and A. Smoluchowski. 6 (1903). Wakiyama and S. Walker. 1001. and E. Comstock. Tohoku Univ. 18 (1955). J. 38. 80 (1950). 576.382 11. 11 (1959). G. Clark. Rev. N. McSkimin.. J. 12. Res. 51. Appl. Sci. Wakiyama and S. R. A216. R. Phys. Wakiyama. 15 (1960). Tsuya. and A. Appl. Soviet Phys. . S.. 11 (1972). Phys. M. S. 48 (1980). Int. 153 (1967). Phys. R. 1975).. 29. A1243. 36. Japanese J. Chem. Williams. 1788. N. J. 25. 449: Sci. MAGNETOSTRICTION N. Pappis. Bozorth and J. 40. T. 573. Chikazumi et al. J. 42. J. Rhyne. Rev. G. Chem. Phys. 1210. Pavlovic. 1968). L. Phys. 99 (1955). 34 (1963).. Chikazumi. 4.. Solid State.. /. Chap. Phys. R. F. 53. Okamoto. Y. M. Tohoku Univ. 4486. 20 (1965). /. Repts. J. Lee. Bozorth. 10 (1963). Syono. and R. 44.. W. 40 (1969). K. Rev. 42 (1971). 29 (1958). J. Phys. and R. T. Kanamori. W. G. Res. Zalesskii. 25 (1953). 17 (1962).. J. /. 34 (1973). /. Mag. 406. Walker. 32. Tsuya. 37 (1966). 43. 6 (1963). Phillips and R. W. G. White. lida. 16. Kotyukov. Mod.. K. 39 (1968). 852. 83 (1951). 1588. 26. Rev. 1325. 1673. Miyajima. 14 (1959). R. 26 (1955). R. S. Geophys. Prog. 127. J. I. 49. Phys. Bozorth. E. Inst. 822. Zijlstra. A. Japan. Vol. Rhyne. Phys. Rev. Inst. A. Smith and R. K. 899. Phys. Kainuma. by S. Rev. 39. Ohta. Yamamoto and T. Vol. 140 (1965). 22. 1975. A472. J. W. 28 (1957). Appl. 161. 28. 34. Soc. and J. 38 (1957). I. Phys. L. ed. Solids. Bozorth and T. K. Tsuya.. Sherwood. E.. Rhyne and S. 13. Phys. 18 (1963). 139 (1965). 1138. Magnetism. Chikazumi. /. /. Appl. and J. Shimizu. L. M. 17. Japan. R.Y. 97. Soc. Bickford. 20. Phys.

(London). P. Weiss. School Phys. Phys. L. Sokolov and T. Hien. Rathenau. Appl. /. 59. A. 986. Int. ed. Chikazumi.. F. Phys. 157. Chikazumi. K. 72. Physik. /. A. Proc. A161 (1937). A. Soc. J. C14 (1981). 458. ASTM. 131. Appl. 27 (1961). 37 (1966). P. B. 65. 63. F. 15-18 (1980).REFERENCES 54... W. 281. p. /. and Yu. Soc. Kornetzki. 58.12 (in Japanese). R. A. 20 (1953). Berlin. Table 13. Bozorth.. Phys. W. N. 45 (1978). Lazan and L. Phys. Cochardt. 117. A. Hansen. W. DeSavage. L. 66. 55. R. H. 67. Japan. by S. Berlin. . 220. Mech. p. Appl. 1975). LXX (1978). 1978). 41 (1975). 381. 383 V. JETP. 64. Tsuya. 70. R. Gersdorf. 196. Sou. 1324. K. JETP. H. Markosyan. Clark. J. 1130. S. Hansen. (Asakura Publishing Co. J. Levitin. R.. 560. 69. 35 (1943). Teller.J.. 45 (1974). Raymond. Physica. M. 60. 611. Belov. D. 194. M. Gapeev. Proc. 1951). S. Ferromagnetismus (Springer-Verlag. Chikazumi et al. N. Comstock and J. Phys. Phys. Tsuya. Doring. M. Proc. 855. 71. Stoelinga. H. Z... Z. p. 61. 38 (1967). Mag. Appl. Handbook on magnetic materials. 3638. Ferromagnetism (Van Nostrand. 1939). /. Mat. Koster. I. Part a. Sou. Proc. M. 56. 25 (1967). /. 87 (1933). Popov. E. N. Landolt-Bornstein (Springer-Verlag. Becker and W. /. R. Matsui and S. Kawakami. and G. Hasegawa. III/12a. J. Demer. Enrico Fermi. 57. (London). 82 (1963). Soc. Mag. Phys. 51 (1951). Mag. 68. Roy. and S. Z. 56. Jahn and E. P. Phys. Princeton. R.. 62. 3737. Oxides & Related Comp. Metalk. 2793. J.

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.Part VI DOMAIN STRUCTURES Ferro. In this Part we shall discuss various aspects of domain structure.or ferrimagnetic materials have domain structures in which the spontaneous magnetization takes different directions in different domains.

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15. it was thought that each step in magnetization corresponds to the flip of a complete domain.5% Fe-Ni alloy with a very small magnetocrystalline anisotropy and a positive magnetostriction.15 OBSERVATION OF DOMAIN STRUCTURES 15. so that the axis of tension becomes an easy axis. It means that the magnetization of a ferromagnetization specimen takes place in many small discontinuous steps. He connected a loud speaker to the circuit and heard a roaring noise like the sound of waves on the sea shore.1. Barkhausen effect. because the spontaneous magnetization takes different directions in different domains. This is called the Barkhausen noise. the volume of a single domain was estimated to be about 10 ~ 8 cm3. they reduced the field to zero and applied a small reverse field. Barkhausen was a famous vacuum tube engineer. In 1919 Barkhausen2 discovered that the magnetization process in ferromagnetic materials takes place in many small discontinuous steps.1 HISTORY OF DOMAIN OBSERVATIONS AND POWDER-PATTERN METHOD Weiss pointed out in his famous paper1 on spontaneous magnetization in 1907 that ferromagnetic materials are not necessarily magnetized to saturation. Cj (see Fig. 15. From the magnitude of a single step. . who used his skill to amplify the noise signals which are produced in a search coil wound on a ferromagnetic specimen when the magnetization of the specimen is changed (see Fig. Later this volume was found to be simply the volume traversed by a domain wall released from some constraint. This effect is called the Barkhausen effect. Then they applied a strong local field Fig. After removing the domain structure by magnetizing the whole wire to saturation in a long solenoid.1).2). but people at that time tended to believe that ferromagnetic domains were small enough to be regarded as a mesoscopic feature. 15. In 1931 Sixtus and Tonks3 succeeded in producing a large domain in an elastically stretched Permalloy wire. At the time. Permalloy is a 21.

15. The experiment consisted of placing colloidal ferromagnetic particles onto the polished surface of a ferromagnetic crystal and observing the image of domains outlined by the magnetic particles using a reflecting (metallurgical) optical microscope. The main reason may be that the surfaces of the single crystals used were not oriented so that they contained a magnetic easy axis. he hesitated to conclude that these were real images of domain walls. in this case a complicated layer of surface domains prevents the observation of the underlying simple domain structure. one thing that was confusing the investigators was the appearance of the maze domain pattern as shown in Fig.3(a). so that the volume of a single block was estimated to be about 10~8 cm3. This phenomenon can be considered as a large Barkhausen effect. One block of the maze pattern is about 10~2 to 10~ 3 mm in width. The first attempt to observe ferromagnetic domains directly under a microscope was made by Bitter4 in 1931 and independently by Hamos and Thiessen5 in 1932. and a single domain wall travelled along the wire. This experiment was the first measurement of the speed of domain wall motion. This is because the magnetization reversal toward the center of the wire is damped or retarded by local eddy currents. During this period. 15. Large Barkhausen effect.2. this is in good agreement with the domain volume estimated from the Barkhausen . as shown in the inset of Fig. This technique of observing domain structure is called the powder-pattern method. The reason may be that the sizes of the observed domains were too large according to the then-current concept of domain structures. Although some micrographs in Bitter's paper revealed domain walls. with a small coil.6 both in the techniques for preparing the collidal ferromagnetic suspension and for electropolishing the crystal surface. Sa and S2. 15. to reverse the magnetization. Sixtus and Tonks also observed that the shape of the domain wall is concave. They observed that a reverse domain nucleated at C 2 .2. but no definite conclusion was drawn for about seventeen years. The speed of the wall displacement was determined by measuring the time interval between the signals arising in two separate search coils. Some improvements were made by Elmore. The idea is similar to the observation of the magnetic lines of force around a permanent magnet by scattering iron filings on a sheet of paper above the magnet. Many investigations were made thereafter using the same technique.388 OBSERVATION OF DOMAIN STRUCTURES Fig. C2.

Black magnetite precipitate is deposited as a result of the reactions The precipitate particles are removed by filtration. called ferro-fluids. with a solution of sodium hydroxide. NaOH (Fig.3% solution of a high-quality soap which is free of Cl1" ions. However Kaya8 showed in 1934 that the maze pattern is caused by stresses introduced during polishing the surface. and hydrated ferric chloride. they took into consideration the effect of magnetostatic energy. A high-quality colloidal suspension is reddish-brown and transparent.3(b). (b) true domain observed after removal of 28 /xm of material from the surface. Colloidal particles of Fe3O4 are prepared by mixing a solution containing ferrous chloride. A theoretical prediction of domain structures was made by Landau and Lifshitz9 in 1935. (After Chikazumi and Suzuki7) effect.3.4. Quite unlike the maze domain shown in Fig.4). and more geometrical. . Similar suspensions. as predicted by Neel and others. The structure of the maze domain will be described in Section 16. In 1949 Williams et al. Nevertheless. the true domain size remained unclarified. bounded by planar domain walls. and rinsed repeatedly with distilled water until the wash water shows no trace of Cl1" ions. 15. and mixed using a mechanical stirrer or an ultrasonic blender. stress-free surface of an Si-Fe single crystal. 15. 15. Ferromagnetic domain pattern observed on (001) surface of 4% Si-Fe single crystal: (a) maze surface domain.3(a). are commercially available. This agreement seemed to support the 'small block concept' of ferromagnetic domains.n succeeded in observing well-defined domain structures by an improved powder-pattern method on a precisely cut. as shown in Fig. 15. In the following we describe some details of the powder-pattern method. FeCl2. In 1944 Neel10 made a detailed calculation of a particular type of domain structure. FeQ3.HISTORY OF DOMAIN OBSERVATIONSs 389 Fig. The particles are then added to a 0. the true domains are much larger in size.

15.390 OBSERVATION OF DOMAIN STRUCTURES Fig. many small surface domains appear. An electrolytic solution is made by mixing phosphoric acid (85%) and solid chromic acid in the ratio 9 to 1 (by weight). The area of the cathode should be fairly large compared to that of the specimen. Before observation of domain patterns. Preparation of Fe3O4 precipitate. 15. 15. so as to produce a large potential drop near the specimen. which is held in the electrolyte by tweezers or a clamp connected to the anode of the power supply.4.5.5 shows an example of a complicated domain pattern observed on a tilted crystal plane.6). It is also necessary to remove residual stresses introduced during the process of cutting. Fairly heavy currents in the range 10-20Acm~2 are used to polish the specimen. we must cut a crystal along a crystallographic plane that contains at least one of the easy axes. Figure 15. the electrolyte should be completely removed from the specimen by washing with distilled water. For this purpose. Complicated domain pattern observed on a crystal surface which makes a fairly large angle with an easy axis (4% Si-Fe). . with a large copper plate serving as the cathode of the electrolytic cell (Fig. In order to observe a well-defined domain pattern. Fig. the best means is electrolytic polishing using high current density. The solution is contained in a beaker of 100-600 ml capacity.

then a drop of colloidal suspension is applied to the electropolished surface and a thin microscope cover glass is placed on the liquid drop to spread the colloidal suspension uniformly on the crystal surface (Fig. we use a reflecting or metallurgical microscope. in which the light strikes the sample surface at a small angle.8). First the specimen is placed on the magnet. increases the optical contrast and makes the domain walls more easily visible. 15. at a magnification of 70-150 times.6. 15. Figure 15. or light lines under dark-field illumination. .7 is convenient for applying a horizontal or a vertical magnetic field to the specimen. 15. which is set under the microscope. 15. thus the domain walls are visible as black lines under normal illumination.HISTORY OF DOMAIN OBSERVATIONS 391 Fig. Method of electrolytic polishing.9 shows an example of the domain pattern observed on a (001) surface of a 4% Si-Fe crystal. Small electromagnet for the observation of domain patterns.7. The black straight lines are the domain walls and the arrows show the direction of spontaneous magnetization in each domain. Sometimes a dark-field illumination system. A small electromagnet as shown in Fig. The most convenient means to determine the axis of magnetization is to observe the striations which appear perpendicular to Fig. To observe the domain structure. The ferromagnetic colloidal particles are attracted to the domain walls where the gradient of the stray field is maximum.

15. thus collecting the colloidal particles.392 OBSERVATION OF DOMAIN STRUCTURES Fig. In order to find the sense of the local magnetization. Williams et al. does not attract colloid.9. If the groove is perpendicular to the domain magnetization.8. 15.10(a).9. the magnetic flux emerges from the groove as shown in Fig. 15. if the scratch is parallel to the domain magnetization. The black line at the center is drawn as a schematic illustration of the appearance of a mechanical scratch. and is not visible (Fig. the domain magnetization. Powder-pattern method. it induces no free poles. The irregularities which cause the striations are thought to be non-flatness of the electropolished surface and inhomogeneity in alloy composition. . Domain pattern on (001) surface of 4% Si-Fe crystal (retouched). This behavior of a scratch is shown schematically in Fig.10(b)). The same thing happens at a groove made deliberately by scratching the electropolished surface with a fine glass fiber. 15.n devised a Fig. The reason is that magnetic free poles appear at irregularities which are perpendicular to the local magnetization. 15.

Figure 15. 15. the field produced by this S pole induces a spike-like reverse domain which points in the direction of domain magnetization (Fig.MAGNETO-OPTICAL METHOD 393 Fig.2 MAGNETO-OPTICAL METHOD Magneto-optical effects such as the magnetic Kerr effect and the Faraday effect can be used for observing magnetic domain structures.11). 15. indicating the sense of domain magnetization. Magnetic flux line around a mechanical scratch: (a) scratch perpendicular to the domain magnetization.12(b) . so that they can be used at any temperature.12 High-temperature observation using a dry ferromagnetic powder13'14 and low-temperature observation using solid oxygen powder15 (oxygen is strongly paramagnetic) have also been reported. Figure 15. The light from the lamp is polarized by a polarizer. analyzer.11. These effects do not make use of a colloidal magnetic suspension. The light reflected by the specimen reaches the observer after going through the half-silvered mirror. 15. reflected by a half-silvered mirror. (b) scratch parallel to the domain magnetization. Small spike domain induced by a thin magnet wire. and eyepiece. The magnetic Kerr effect is the rotation of the plane of polarization of light on reflection from the surface of a magnetized material. Fig.12 illustrates a domain observation system using the Kerr effect. Figure 15. and projected onto the surface of the specimen. 15.10. The powder pattern technique was adopted for electron microscopy by making a replica of the surface after the powder dried. clever technique using a thin permanent magnet needle: if the S pole at the end of the needle approaches a domain surface.12(a) shows a polarizing microscope as used for the observation of magnetic domain structures.

and for stronger contrast. The Faraday effect is the phenomenon by which the polarization axis rotates during the propagation of light through the material. in spite of a large demagnetizing field. 15. Alternatively. for the case of magnetization perpendicular to the surface.13(a)-(c) show the domains observed for specimens of different thickness. We shall see the reason in Chapter 17.13 shows the domain structures observed by this device on the c-plane of MnBi. shows rotation of the polarization axis in opposite senses on reflection from domains magnetized in opposite directions. except that the incident polarized light passes through the specimen as in a biological microscope. Figures 15. Figure 15.12(a) will not reveal the domain structure. In this apparatus the polarizer and the analyzer must be arranged so as to satisfy the law of reflection.3 LORENTZ ELECTRON MICROSCOPY In magnetic thin films which are thin enough to allow the transmission of an electron . so that the magnetization can lie perpendicular to the c-plane. The construction of the apparatus is the same as that for the Kerr effect.4. If the magnetization lies parallel to the surface.1(e) MnBi has its easy axis parallel to the c-axis.12.394 OBSERVATION OF DOMAIN STRUCTURES Fig. As explained in Section 12. so that the magnetization has a nonzero component parallel to the beam. Domain structures in transparent ferromagnetic materials such as iron garnets can be observed by this method. the size and shape of domains vary with sample thickness. (a) Optical microscope for the observation of domain structures by means of the magnetic Kerr effect and (b) rotation of polarization axis upon reflection of polarized light from the surface of domains with magnetizations perpendicular to the surface. 15. If the analyzer is adjusted for maximum transmission of light reflected from domains of one sign. the analyzer can be adjusted for minimum transmission from one set of domains. 15. domains of the other sign will appear darker. and its magnetocrystalline anisotropy is enormously large. so that the other set appears relatively light. In this case we must use a polarized incident beam making a small incident angle with the surface. the arrangement shown in Fig.

(b) intermediate. (c) the thinnest.LORENTZ ELECTRON MICROSCOPY 395 Fig. 15. the domain structure can be observed using the electron microscope. the domain walls appear as . (Due to Roberts and Bean16) beam. Domain structures observed by the magnetic Kerr effect on the c-plane of MnBi plates: (a) the thickest plate. The principle is to use the deflection of the electron beam by the Lorentz force which acts on the moving electrons because of the spontaneous magnetization.17 If the objective electron lens is defocused slightly from the specimen film.13.

18 The spin structures of the cross-ties perpendicular to the main domain walls will be explained in Section 16. Figure 15. as illustrated in Fig.16 shows a Lorentz micrograph observed for a single crystal film of iron parallel to the (001) plane. as will be described in Section 15. from which we know that the magnetization lies in four equivalent crystallographic directions. back or white lines. Principle of Lorenz microscopy. The inset shows the diffraction pattern.15 shows an example of domain structures observed in a Permalloy thin film of thickness 600 A. but because of the defocusing it is not possible to observe well-defined crystalline and magnetic structures at the same time. a parallel electron beam focuses to a spot (a diffraction spot).19 We see many domain walls appearing as black and white lines. Figure 15. 15.14. This method is called Lorentz microscopy. 15.14. If the objective lens is focused at infinity. the method known as transmission Lorentz scanning electron microscopy (SEM) overcomes this difficulty.396 OBSERVATION OF DOMAIN STRUCTURES Electron beam Fig.5. The strong point of this method is its high magnification. from which we can deduce the direction of magnetization.4.4 SCANNING ELECTRON MICROSCOPY Scanning electron microscopy (SEM) enables the observation of domain structures in . 15. However.

15. while other domains deflect the electrons more deeply into the specimen.18 thick specimens by using the deflection of electron beams.19 . Some of the domains deflect the electrons towards the surface of the specimen. and its intensity is modulated by the number of collected electrons. The electron beam is scanned over the specimen surface and the deflected electrons are collected by the electron detector. and its diffraction pattern (inset). Then the domain structure is reproduced as a black and white pattern as shown in Fig. Domain pattern observed in a Permalloy film of thickness 600 A. 15.16. when electrons penetrate into a tilted ferromagnetic specimen.15. Fig.SCANNING ELECTRON MICROSCOPY 397 Fig. 15. they are deflected by the Lorentz force in directions which are different in different domains. Domain pattern observed in a (001) iron single crystal film of thickness 2500 A. This method is called reflection Lorentz SEM. As shown in Fig.17. The electron beam in the display tube is synchronized with the scanning electron beam in the electron microscope. 15.18.

By a refinement of this method it is possible to observe the dynamic behavior of domain walls.398 OBSERVATION OF DOMAIN STRUCTURES Fig.17. 15. Domain pattern observed on a Si-Fe plate. From such a wave form we can. if the wall motion is sufficiently repeatable. an electron Fig.19. see the nucleation and motion of the domain walls. and the domain walls appear as sinusoidal waves as shown in Fig. we can utilize the Lorentz deflection22 from a magnetic thin film (see Section 15. 15. 15. In this method.3).20 . An AC magnetic field is applied to the sample at a frequency which is a small multiple of the scanning electron beam sweep frequency. The principle of the observation of domain walls in a thick specimen using scanning electron microscopy.18. Instead of reflecting electrons from a bulk specimen.

As a result of interference scattering. In this method the electron beam is scanned over the surface of a ferromagnetic specimen and the polarization of the scattered secondary electrons from domains. Another method for observing domain patterns on bulk specimens is spin-polarized SEM.24 Figure 15. the sense of which is different for different domains.20. D .23 We call this method transmission Lorentz SEM.SCANNING ELECTRON MICROSCOPY 399 A Fig. The secondary electrons are collected and accelerated towards a thin-film target made of gold. in which the electron beam is slightly defocused from the film. Thus well-defined structural and micro-magnetic structures can be observed on the same pattern.19. the strong point of this method is that the electron beam can be sharply focused on the film. As compared with the usual Lorentz microscopy. under a potential gradient that produces an electron wave with a wavelength of the order of the atomic radius of gold. 15. is detected by a Mott detector.20 illustrates the principle of the Mott detector. Dynamical behavior of the domain wall observed by the application of an AC magnetic field to a Si-Fe plate. 15. The principle of the Mott detector.21 beam is scanned over the specimen film. the brightness of the electron beam in the display tube is modulated according to the diffraction angle to make the domain pattern visible. the cross-section of the scattering beam depends strongly on the scattering angle at some specific W Fig.

Suppose that the spin angular moment. Therefore the unbalanced signal between Dj and D2 becomes proportional to the spin polarization. as observed by spin-polarized SEM. For electrons with opposite spin. Two electron detectors. Picture (b) was taken with the detector adjusted to detect the vertical spin directions: not only are spin directions in the closure domains distinguishable.21. but .25 scattering angle. s. the sign of the unbalanced signal is opposite. of the electron points upwards perpendicular to the paper (denoted as s+ in the figure). Its magnetic moment tends to depress the clockwise orbital motion about the nucleus because of the spin-orbit interaction (see Section 3. respectively.21 shows the domain structure of a Permalloy thin-film head used for high-density magnetic recording. Domain structure of a thin Permalloy head as observed by spin-polarized SEM. Dj and D2. so that the orbital radius becomes smaller than that of the anticlockwise orbital motion of the electron with the same spin.2).400 OBSERVATION OF DOMAIN STRUCTURES Fig. Figure 15. are set at this angle symmetrically on both sides of the direction of acceleration. 15. Picture (a) was taken with the Mott detector adjusted to detect the horizontal spin directions: the black and white zones indicate that the spin directions point right and left.

As shown in Fig.27'28 . 15. Figure (c) illustrates the spin map as deduced from these experiments. Domain pattern observed by means of X-ray topography on a Si-Fe (001) plate 120/Am thick. 15. the X-rays Fig. Principle of X-ray topography. 15.23.22.X-RAY TOPOGRAPHY 401 Fig.22.5 X-RAY TOPOGRAPHY X-ray topography was invented by Lang26 to investigate the distribution of internal strains in a crystal. The principle is to utilize the change in the diffraction angle of the diffracted X-rays due to a strain in the crystal. 15. also we can see the spins inside the 180 degree walls.

29 . but a strain image caused by magnetostriction. the diffraction angle is changed. The actual construction of the electron biprism consists of two earthed parallel electrodes with a positively charged thin gold wire inserted between them. Schematic diagram of electron-hologram formation.30 The electrons tend to be attracted towards the gold wire from both the electrodes. thus being deflected in the same way as a beam of light passing through an optical biprism. 120 yum thick.29 The electron microscope used for this purpose is provided with an electron biprism which overlaps a reference beam with the electron beam going through the specimen to produce an electron hologram. If the crystal is distorted.6 ELECTRON HOLOGRAPHY Electron holography enables the direct observation of lines of magnetic flux not only in a magnetic thin film but also outside the film.24. this electron Fig. This is not a magnetic image. so that the diffracted X-rays are blocked by the slit S and cannot reach the film B. The strong point of this method is that it allows the observation of the interior domain structure.402 OBSERVATION OF DOMAIN STRUCTURES diffracted from the specimen A go through the slit S and strike the film B unless the crystal lattice is distorted. Figure 15. the distribution of the internal strain in the specimen appears as a black and white pattern in the film B. 15. 15.24. 15.23 shows the domain pattern observed by this method for a (001) single crystal plate of Si-Fe. as shown in Fig. In order to produce a good coherent electron beam. If the specimen A and the film B are displaced at the same velocity.

25(a) shows a Lorentz micrograph produced in this way from an amorphous film of composition (Co094Fe006)79Si10B11. The reason for this will be explained below. the electron wave undergoes a phase shift given by where h is Planck's constant divided by 2ir. when an electron passes through a space where the vector potential A exists. and after overlapping with the reference optical beam reproduces a real image of the specimen. Figure 15.26. Therefore when the reference optical beam is directed almost parallel to the beam passed through the hologram. 15.25. 15. These fringes run parallel to the magnetization in the film. which have the same phase . The magnetic structure in these photographs will be discussed in Chapter 16. Several domain walls can be observed. interference fringes as seen in (b) are formed. and the integration is along the electron path. A laser beam with the same wavelength as that of the electron beam used to produce the hologram is passed through the hologram plate. (a) Lorentz image and (b) electron interference fringes as observed by electron holography for an amorphous film of (Co094Fe006)7QSilnB11.32 Suppose that the electron waves P and Q in Fig. The holograph contains information not only of the real image but also of the phase difference of the electron waves. According to quantum mechanics.ELECTRON HOLOGRAPHY 403 Fig.31 microscope uses field emission from a sharp cold tungsten cathode. The hologram exposed on the photographic plate is developed and transferred to an optical system to reproduce a real image of the specimen.

If the saturation flux density Bs in the film is the only magnetic flux penetrating the area PP'Q'Q. 15. the phase difference between the two electron beams at z = z0 is given by where $ is the magnetic flux penetrating the area PP'Q'Q.1).27 two electron waves PP' and QQ' passing through a magnetic thin film of thickness d form two neighboring interference fringes. which is just twice the flux quantum h/le. In other words. From (15. the integration in (15.404 OBSERVATION OF DOMAIN STRUCTURES Fig.. A dS = fj Bn AS = AO. we see by putting the final term in (15. If this phase difference were ITT. Illustration of phase difference between two electron waves. at z = 0. if neighboring interference fringes correspond to P' and Q'. travel through the magnetic field and reach P' and Q' at z = z0. we have * Since B = curl A. Suppose that in Fig.1) along ABCD is given by <j)A • ds = fl curl. we have where / is the separation between the two fringes. where AO is the magnetic flux penetrating the area ABCD. 15. From (15. $ in (15.2) equal tO 27T.4).26. .3) must be twice the flux quantum.

Williams. However. Mag. 11.. 10 (1955). Bozorth.. 39 (1932). J. 8. 51 (1937). Chikazumi and K. if there is leakage flux in the area PP'Q'Q. 20 (1919). 90 (1934). V. F. 96 (1935). 43 (1933). Kaya and J. 5. Soc. Phys. Bitter. f. 982. 661. 410 (1932). S. Therefore it the thickness of the film. This method is useful for finding the location of free magnetic poles. J. and the separation of the fringes is inversely proportional to Bs.. Z. S... 279. For instance. IEEE Trans.5). Sowjet U. Barkhausen. the interference fringes run along the lines of flux density. 6 (1907).. which exist where the lines of flux emerge. when we observe the flux in space. Craik and P. 337. 37 (1931).. 42 (1932). Lifshitz. 12. Phys. Appl. 54 (1938). /. 4. 89 (1934). S. <E> in (15.. Weiss. /. 419. 7. 15. 62 (1942). L. 442. Z. Phys. 930. 1291. D. Phys. Sekiya. 8 (1935). 757. Lifshitz. J. J. Phys. J.. and W. Rev.4) decreases. MAG-15 (1979). K. R. 931. 153. if the flux caused by the magnetization in the film leaks into space and comes back through the area PP'Q'Q. Elmore. M. Hamos and P. Griffiths. Rev. Phys. 38 (1931).27. 507. A. 265.. so that the separation / becomes larger than (15. 9 (1958). Phys. 523. Rev. 796.5) does not hold. Z. d. 9. Phys. 551. 53 (1938). 5 (1944). Rev. H. Phys. 357. Landau and E.. 71 (1932). 3. 155. C. Phys. is uniform. 10. USSR. the fringes run parallel to the magnetization. 6. M. 8 (1944). REFERENCES 1. L. Kaya. Magnetic flux in a magnetic thin film. Z. 401. 53. 70. /. Suzuki. Tonks. P. Neel. (15. Phys. Phys. 309. On the other hand. 1903. Thiessen.REFERENCES 405 Fig. Rad. Phys. E. 486. 2. 75 (1949). . Z. H.. L. 241. Phys. Japan. British J. Shockley. W. Sixtus and L..

K. 252.. B25 (1982). Matsuyama.. Shiroishi. Nozawa. 28. 24. 5811.. A. 25. and Y. 145 (1956). /. and H. Mag. and K. and Szymczak. S. Matsuo. Yamamoto. Hanazono.. Mag. Phys. 789. 30. Mollenstedt and H. A.. W. Phys. Lang. 1985). N. A. Y. Rev. Osakabe. Polcarova and A. Sugita. N. (St. S. 979.. MAG-15 (1979). Piotrowski. For instance. 334. 55. A. J. Takeshita. Chapman. Bohm. 21. Y. Aharonov and D. Phys. 13. Part II (1983). 3 (1978). H. Mag. MAG-23 (1987). 16. T. H. Waddel. Physik. W. Roberts and C. Andra and E. 31-34. Kessler. Ichikawa. Acta Cryst. Y. J. Ultramicroscopy. A. /. Appl. Z. Mag. T. Batson. E. K. and R. E.). H. Phys. Sudo. 536. Rev. Mat. Y. Tanabe. Kobayashi.. Polcarova. M. 17. MAG-S (1969). 22. Kawakatsu. Y.. 20. B. Waseda Univ. Shinagawa. Ann. Lett. 972. 12 (1959). M. 25 (1961). Sci. IEEE Trans. 15. T. T. Yajima. E. Takayama. 249. J. Hosoe. Ohya. 115 (1959). T. Tonomura. Phys. Fukahara. Bean. Phys. and H. Mag. Polarized electrons (2nd edn.406 OBSERVATION OF DOMAIN STRUCTURES 13. Takahashi. Soc. Fujiwara. Fujiwara. 27. T. S. Tonomura. 80. Osakabe. Rev. A. M. Phys. Louis) (1982).. and H. and Y. 14. K. N. T. and Y.. 29. IEEE Trans. Szewczyk. 30 (1959).. 96 (1954). Rubinstein. 203. Phys. Mem. 31. 377. MAG-14 (1978). P. 32 (1972). Japan. 485. . M. Endo. 1494. 17 (1955). Mag. 18. Matsuda. IEEE Trans. Lang. T. 26. Ducker. Mitsuoka. Ann. (Springer-Verlag. Ohya. Hale. 72. Sugita. J. R. M. Ichinokawa. 66. 73 (1993). Narishige. K. Andra. Y. Tsukahara and H. 2155. Y. P. Phys. 1 (1962). N. Koike. Schwabe. M. IEEE Trans. W. W. Fuller. R. 23. Matsuda. 32. 19. I. M. 1982 TMS-AIME Fall Meeting Abs. P.. Nozawa. Ferrier. Eng.. Appl. 6799.. G. Matsuo. Yamamoto. Hayakawa. [7] 3 (1959).

16 SPIN DISTRIBUTION AND DOMAIN WALLS 16. such a single domain produces surface free poles which give rise to magnetostatic energy. Ua. as shown in Fig. 16. exchange energy. are increased. Uniformly magnetized disk (single domain structure). As a result. thin ferromagnet.1 MICROMAGNETICS Micromagnetics is the name coined by Brown1'2 for the procedure by which the distribution of spins in a ferromagnet of finite size is solved from first principles. which modifies the complete parallel spin alignment. In a ferromagnet of finite size. If this disk is uniformly magnetized to saturation along a diameter.0 appears opposite to the spontaneous magnetization 7S. and the demagnetizing field Af/s/ju. the spontaneous magnetization is aligned parallel to the long axis. 16. so that there is a magnetostatic energy (1. i/mag. the spin distribution must be altered. magnetocrystalline energy. free magnetic poles N and S appear at the edges.1.1. or magnetoelastic energy. In order to reduce t/mag.99) given by where v is the volume of the disk given by Fig. Circularly magnetized disk (no free poles). thus forming a single domain. Fig. Ux. The stable spin distribution is determined by minimizing the total energy Consider a ferromagnetic disk of radius r and thickness d.2. . 16. U3. In an infinitely long.

This is analogous to the elastic energy.408 SPIN DISTRIBUTION AND DOMAIN WALLS The demagnetizing factor N can be approximated by that of a thin oblate spheroid. In a ferromagnet.2.. Umag = 0.5. at P be a. One possible spin configuration that eliminates magnetostatic energy is the circular configuration shown in Fig. which is separated from S. Instead. by the distance r-t. This formula shows that the exchange increases as the square of the angle (p. Since cos <p in (16.2. According to a detailed calculation by Weiss. and its z nearest neighbor SyS.. the exchange pair energy (16.4) reduces to where S is the magnitude of the spin. Let us calculate the sum of the exchange pair energies between 5. the exchange pair energy given by (16.1 for various statistical approximations. we find another spin at Q' which is located —r .27). y-. Similarly the exchange energy density can be expressed in terms of the spin distribution in the lattice. neighboring spins make some non-zero angle. In a cubic lattice. be a'.1. in addition to the spin S. The value of / is related to the Curie point as listed in Table 6. and can be calculated using equation (1. and that of Sj at Q. which increases as the square of the strain in the lattice. z •) are the components of the distance r. In other words. As discussed in Section 6.7) can be expressed in terms of a and a' as cos <p = a • a'. if we assume S = 1 for iron. and Sj is small. at Q. using the relationship (16. There is no divergence of magnetization and therefore no free poles. A general discussion of magnetostatic energy is given in Section 1. the exchange energy stored in a pair of spins 5.44) or found from Table 1. it follows that When the angle tp between spins S.8). and S.3 the relationship between / and the Curie point is given by For instance. / > 0. 16. a' can be expanded as where (x. The elastic energy density can be expressed in terms of the strain tensor as shown in (14. is given by where / is the exchange integral. so that some exchange energy is stored.7) can be expressed in terms of a. If we assume the variation of a is smooth and continuous.4 Let a unit vector parallel to the spin S.

is given by n = 1 for a simple cubic lattice \ = 2 for a body-centered cubic lattice > .12) becomes where A is given by .8) over Q and Q' vanish. where a is the lattice constant or the length of the edge of a unit cell.9) over all the atomic pairs in a unit volume.13). = 4 for a face-centered cubic lattice j Summing (16. The number of atoms in a unit cell. and the facecentered cubic lattices. 16.3.3). we have Using (16. the exchange energy density becomes On the other hand. Therefore the summation of the exchange pair energy over the nearest z neighbors is given by In a cubic lattice which gives the value 2 a 2 for the simple cubic. differentiating (a • a) = 1 twice with respect to x. n. Calculation of exchange energy in a given spin distribution. from P (see Fig. 16.MICROMAGNETICSs 409 Fig. (16. body-centered cubic. so that the summations of the second terms in (16.

25(b) shows such a circular spin configuration at the center./'dr = 0.15) is called the exchange stiffness constant.20) is large where r is small. da.25(a). so as to reduce the magnetostatic energy.14) is similar to that for the elastic energy density which is expressed as a quadratic function of strain tensors. The spin configuration in the intermediate region is not circular but rather rectangular. 15. As a result. In this sense the coefficient A in (16. In such regions there appear black or white lines in a Lorentz image. we have Since where i and j are unit vectors parallel to the x. as shown in Fig.2.and y-axes. At the edge of the film. This is because the exchange energy density £ex given by (16.410 SPIN DISTRIBUTION AND DOMAIN WALLS The terms such as da/dx correspond to the strain in an elastic body. and the expression (16. the spin direction is parallel to the edge. the domain structure in a disk with cubic . If we rewrite (16. with areas where the spin direction changes sharply. respectively. z) with the origin at the center of the disk and the z-axis perpendicular to the plane of the disk.16) we have Therefore the exchange energy of a disk with radius r and thickness d is given by We see from (16. so that from (16.21) that the average exchange energy density t/ex/i> increases as the radius r decreases. 15.3). The actual domain structure in an amorphous film as seen in Fig. depending on whether the sense of spin rotation is clockwise or anticlockwise (see Section 15. the spins are forced to align parallel to one of the easy axes.14) using cylindrical coordinates (r. da/dz = 0. 16. however. we have so that In addition to this. When the magnetocrystalline anisotropy is large. Let us calculate the exchange energy of the spin configuration shown in Fig. 6.

16.7). Fig. 16. Sometimes they are referred to as Block walls. Real domain structures will be determined by minimizing the total energies given by (16. We have discussed here various domain structures and the various kinds of associated energies. the magnetostrictive strain does not actually cause gaps to appear.2 DOMAIN WALLS At domain boundaries there are transition layers where spins gradually change their direction from one domain to the other. Domain structures of a disk with uniaxial magnetocrystalline anisotropy. the domain walls which separate the neighboring domains store energy which is called domain wall energy. We shall treat this problem in Chapter 17.1). crystal structure and large crystal anisotropy becomes as shown in Fig. some magnetostatic energy is stored. and the elastic energy will be concentrated into the small flux-closure domains. however. We shall discuss this problem in Section 16. Since the magnitude of A is generally small. after Bloch5 who first investigated the spin structure of these transition layers in detail.5. One possible way to avoid or reduce this energy is to increase the volume of the main domains with magnetization parallel to one of the easy axes and reduce the volume of domains magnetized along the other axes. These transition layers are called domain walls. 16.4.6. a considerable amount of elastic energy must be stored in the crystal. Domain structures of a disk with cubic magnetocrystalline anisotropy. while that of a uniaxial crystal becomes as shown in Fig. However. In the equilibrium state. this term is also .5. which are forced to strain so as to fit the deformation of the main domains (Fig. the crystal will separate at the domain boundaries as shown in Fig.2. 16. (Domains with antiparallel magnetization have the same strain. In addition to this. the total energy is distributed among these associated energies in appropriate ratios. Consider next the case of a ferromagnet with a large magnetostriction (A > 0).DOMAIN WALLS 411 Fig. Because of the free magnetic poles appearing at the edges of the disk.) In this case the deformation of the bulk sample will be determined by the magnetostriction of the main domains. 16. 16. 16. In order to keep the domains in contact with each other.4. If each domain elongates as required by the magnetostrictive strain.

the thicker the wall. so that an abrupt change in the angle <p increases exchange energy to a great extent. the smaller the exchange energy. Fig. .5). Postulated domain structures of a disk with a large positive magnetostriction (unrestrained magnetostrictive deformation leads to the formation of gaps at the domain boundaries). 16.6. Let us consider a simple cubic lattice with lattice constant a.. 16. Since the number of atoms in a unit area of one layer is given by I/a2. to distinguish it from another type called a Neel wall (see Section 16. Rotation of spins in the domain wall. the spins change their direction in steps of equal angle from (p = 0 to 180° over N atomic layers.7)). sometimes used to describe one particular type of domain wall.412 SPIN DISTRIBUTION AND DOMAIN WALLS Fig. the number of nearest neighbor spin pairs in a unit area of the wall is given by N/a2.8. In other words. between spins on the neighboring two layers is given by ir/N. so that the exchange energy stored in a unit area of the domain wall is This formula shows that the exchange energy is inversely proportional to the thickness of the wall. 16. Therefore the angle (p. Fig.7. 16. Expected domain structure of a disk with normal magnetostriction (elastic energy is concentrated in the small fluxclosure domains). Let us calculate the domain wall energy using a simplified model: as shown in Fig.8. The reason why spins change their direction gradually is that the exchange energy of spin pairs increases as the square of the angle <p between neighboring spins (see (16.

the anisotropy energy density is increased by the anisotropy constant K when a spin rotates from the easy axis to the hard axis (see Chapter 12).26) into (16. the direction of each spin in the wall deviates from the easy axis. In this simple model. so that the anisotropy energy stored in a unit area of the domain wall is This formula shows that the anisotropy energy is proportional to the thickness of the wall.25).23). The actual thickness of the wall is determined by a balance of these competing energies. so that = 150 lattice constants.DOMAIN WALLS 413 On the other hand. Roughly speaking. the larger the anisotropy energy. The total energy of the wall per unit area in this equilibrium state is obtained by substituting the values of N given by (16. the thicker the wall.22) and (16. In other words. The equilibrium thickness is obtained by minimizing the total energy Solving (16. giving . so that anisotropy energy is stored in the wall. we have Therefore the thickness S of the wall is given by For iron. the volume of the wall per unit area is given by (TV/a2) X a 3 = Na.

Actually. Set the z-axis perpendicular to the wall surface. is denoted by g(<p). the orientation of each spin in a wall is determined so as to minimize the total energy. . however. so that the exchange energy is expressed as JS2a2(d<p/dz)2. the energy of the wall per unit area is calculated as In the above model. Let us solve this problem using the variational method.9. The azimuthal angle <p of the spin about the z-axis is measured from the direction of the spin at z = 0 (the center of the wall) (Fig. the total anisotropy energy stored in a unit area of the wall is given by * When the energy is given by a term proportional to x plus a term inversely proportional to x. <p(z). if the anisotropy energy measured as a function of the angle of spin.* For iron. 16.414 SPIN DISTRIBUTION AND DOMAIN WALLS Fig. It is interesting to note that yex and ja are equal in the equilibrium state. The angle of spins between two neighboring layers is given by (d<p/dz)a.9). we assumed that the rotation of spin occurs at a constant rate. the two terms are numerically equal in the equilibrium state with respect to changes in x. Azimuthal angle of spin rotation in the wall. 16. Accordingly the total exchange energy stored in a unit area of the wall is given by On the other hand.

15). 5 = 1.9 X 1(T10 and n = 2. so that Next the stable spin configuration can be obtained by minimizing the total energy (16.DOMAIN WALLS Therefore the total energy becomes 415 where A is the exchange stiffness constant given by (16. For iron. we have .35) requires that In order that this condition be satisfied for any selection of S<p(z). the total energy of the wall is changed by which should vanish for the stable spin arrangement. regardless of its orientation in the lattice. that is This equation is usually called the Euler equation of the variational problem. the value of A is the same for any wall.6)). Since the exchange interaction is isotropic. Multiplying by (d(p/dz) and integrating from z = —<*> to z = z. a = 2.16 X 10~21 (see (16. Then the vanishing of (16.33) for a small variation of the spin arrangement inside the wall. When the angle tf> of the spin at z is varied by 8<p. The second term of the integrand is treated by integrating by parts: where the first term vanishes because 8<p = 0 at z = °° or —°o. / = 2. the integrand must always be zero.

Modifying (16. Then (16. Let us treat the domain wall of a ferromagnet which has uniaxial anisotropy.39) tells us that the anisotropy energy density is equal to the exchange energy density at any part of the wall.40).416 SPIN DISTRIBUTION AND DOMAIN WALLS Here the origin of g(<p) is defined to be the value at <p = + ir/2. where the anisotropy energy is the highest. From this fact we can see that the spin rotation is more rapid at any position where the spin has a higher anisotropy energy. we obtain. so that g = 0 inside the domains at z = +°°. 16.1). as indicated by the dashed line in Fig. An effective wall thickness is conventionally defined as that of a wall in which the spin rotation at the center remains constant throughout the wall. and tends to vanish far from the center of the wall. and vice versa. The relationship (16. Referring to (16. the spin rotation is most rapid at the center of the wall.10. for the total surface energy of the wall given by (16. so that g must be zero for <p = 90°. this becomes We shall calculate this function for several examples later. The thickness of the wall is strictly speaking infinite. where the anisotropy energy approaches zero. The rate of spin rotation at z = 0 is given by so that the thickness of the wall is given by . 16.33).44) is graphically shown in Fig.41) becomes The relationship between <p and z given by (16. we have On integrating.10. The anisotropy energy in this case is expressed as This expression differs from the usual one such as the first term in (12. As discussed above.39). because the origin of <p is defined to be the hard axis.

12(b).11).29).43) in (16.8. Commonly. and [001]. they share the property of being sensitive to mechanical stresses.27). as seen in the domain pattern observed on the (110) surface of Permalloy (Fig. 16. 16. There are six possible directions of domain magnetization: [100]. If we observe such a wall on the (001) surface. In this section we treat 180° walls. as in iron.10.3(b).3 180° WALLS Magnetic domain walls are classified into two categories: 180° walls separating two oppositely magnetized domains. A domain wall between [100] and [100] domains is a 180° wall.42): which is also nearly equal to (16. Let us consider the geometry of a 180° wall separating [100] and [100] domains in a cubic ferromagnet with K1 > 0. magnetic free poles would appear along the curved portion. 109°.180° WALLS 417 Fig. 16. [010]. Consider a cubic ferromagnet having its easy axes parallel to <100>. In the case of a ferromagnet having its easy axes parallel to (111). giving rise to a demagnetizing field opposite to the magnetization . there are three kinds of domain walls: 180°. such as nickel. as seen in Fig.3). This expression is the same as (16. 16. [001]. [010]. and 90° walls separating two domains whose magnetizations make a 90° angle. [100]. The energy of the wall can be calculated by using (16. all domain walls other than 180° walls are classified as 90° walls. Variation of spin direction within a 180° wall in a ferromagnetic crystal with uniaxial anisotropy. it appears as a straight line. and 71°. The reason is that if the wall were curved as shown in Fig. Similar results are obtained for domain walls in materials with cubic anisotropy (see Problems 16. which was deduced from the simplified model shown in Fig. while a wall between [100] and [010] is a 90° wall. 15.2 and 16. 16.

when the wall is observed in a direction parallel to the domain magnetization. 16. Therefore the wall is straightened as shown in Fig.11.12. 16. 16. 16. .6 in the swollen part of the domain. because this curvature does not result in the appearance of any magnetic free poles Fig. However. Diagrams showing how domain walls are flattened to decrease magnetostatic energy.12(a). Domain pattern observed on the (110) surface of ordered Permalloy. the cross-sectional view of the wall can be curved as shown in Fig.13.418 SPIN DISTRIBUTION AND DOMAIN WALLS Fig.

9 to avoid the appearance of magnetic free poles in the wall. on the wall. Imagine a cylindrical 180° wall between [100] and [100] domains as shown in Fig. 16. Possible mechanisms for sustaining curvature in the wall result from the presence of inclusions or voids. The magnetocrystalline anisotropy energy is given by as shown in (12. the normal n must lie in the y-z plane.13. in which the *'-axis is parallel Fig. and the dependence of the wall energy on its crystallographic orientation. Let the angle between n and y-axis be i/>. n. and consider how the wall energy depends on the crystallographic direction of the wall normal.5). This curvature does increase the total area of the domain wall. so the wall tends to decrease its surface area unless there is some reason to sustain the curvature. We set new coordinates (x'. 16. and accordingly the total wall energy. z'). . The spins in the wall rotate about n as shown in Fig. 16.14. 16.14. The angle i/< indicates the direction of the normal to the wall surface.yr. A cylindrical domain wall. with the *-axis parallel to the magnetization. As explained above.419 Fig. Possible curvature of a domain wall. irregular distribution of internal stresses or alloy composition.

the wall energy (16. the anisotropy energy (16. a'3) with respect to the new coordinates. it follows that s = 0.42) becomes Putting sin i/> cos if> = s.54) and is shown by the solid line in Fig. in terms of new direction cosines as Using the angle. a'2. we have so that the anisotropy energy in the wall is expressed as Using this expression. we have from (16.9. sin q> = t. 16. The maximum value is . or parallel to the x-z plane (i/f = 0). so that The change in j during the rotation of the wall from tj/ = 0 to 90° can be calculated using (16.420 SPIN DISTRIBUTION AND DOMAIN WALLS to the jc-axis. through the use of (16. <p. Using direction cosines ( a ( . 16.53 If the plane of the wall is parallel to the x-y plane (i/> = Tr/2). As seen in this graph. the wall energy is maximum at if/ = 45°. where the wall is parallel to (Oil).48) is expressed. z) are expressed as Considering that 0:3 = 0 in the wall. or cos <p d<p = dt. as indicated in Fig.49). y. the direction cosines with respect to (x.15.

.16. Fig. in the case of a single crystal plate cut parallel to (Oil). For iron. Configuration of 180° walls in a (Oil) single crystal plate. 16. 16. The total energy is given by Fig^ 16. 16.180° WALLS 421 Fig. Orientation of a 180° wall in a (Oil) single crystal plate. wall energy per unit area. However. Dependence of 180° wall energy on the orientation of the normal to the wall surface. dashed line. total wall energy (energy per unit area X total area) for a wall in a (Oil) single crystal plate.34) and K\ given by (12.17. using values of A given by (16.15. Solid line.16.6). we have and Therefore the 180° wall tends to become parallel to {100}. the 180° wall tends to tilt so as to minimize the total energy (= wall energy X total area) as shown in Fig.

In the case of t/j = 0. the spin rotation is separated into two stages. Such a double wall behaves in the same way as a single 180° wall in fields parallel to the direction of magnetization on either side of the double wall. because of the appearance of strong magnetic free poles on a plane perpendicular to the direction of magnetization.4 90° WALLS A 90° domain wall separates domains whose magnetizations make an angle of 90° . of course. However. It is almost impossible to observe such an end-on or cross-sectional view of the zig-zag wall. the field is applied parallel to the magnetization of the intermediate domain.422 SPIN DISTRIBUTION AND DOMAIN WALLS where d is the thickness of the crystal and / is the length measured along the direction of domain magnetization. Accordingly the wall has two stable orientations. however. the spin rotates smoothly. the wall tends to separate into two 90° walls. thus generating a new domain which is magnetized perpendicular to the original domains.7 The geometry of spin rotation in a 180° wall is solved by using (16. on the magnitude of the magnetostriction constants of the material. In order to reduce this energy.52) in (16. When. which has two minima at t// — 13° and <{/— IT. the presence of a tilt was confirmed by observing the position of 180° walls on the top and bottom surfaces of a thin crystal. For a material with small magnetostriction. so that the spin direction approaches another easy axis. In Fig. [001].17. In an actual ferromagnet with nonzero magnetostriction. In the case of i/f = 45°. 16. 16. In this case the wall is nearly parallel to (010).18 shows the angle of spin rotation <p as a function of z (normalized) for t/f = 45° and if = 2.87°.4 The magnitude of this effect depends. so that it must store a magnetoelastic energy density |{(f)A100}2 X (cn — c12). the two 90° walls cannot move very far apart. This is one possible mechanism for nucleation of 90° walls in the process of demagnetization.87°. the domain between the two 90° walls is highly strained. thus making possible the zig-zag shapes shown in Fig. the double wall may be separated into two independent 90° walls. whereas in the case of i/> = 2. a 180° wall is expected to split into two 90° walls.15 the function U/Qd) is shown as a dashed curve.41) to give Figure 16. 16. where the rotation rate should be very small.

so that cos 0=(l/v^)sin i/». This condition does not uniquely specify the orientation of the wall. a 2 = sin i//. Let the two magnetizations on both sides of the 90° wall by ll and 72. We shall discuss these matters in this section. /33 = 0. The 90° wall is oriented so as to make the normal component of magnetization the same on both sides of the wall.z') (see Fig. 16. n. with respect to (x'. a3). where a^ = 0.y'. 16. from which we have (16. Let the angle between the normal to the wall. It is easily verified that the plane of the wall which satisfies this condition must contain the bisector of the angle between /j and —I2. The two angles are related by* Now let us investigate how the wall energy changes as the orientation of the wall varies by changing the angle i/f. a3 = cos i/». a2. Then we have cos 8= al/3l + a2f}2 + a 3 /3 3 . But the 90° wall has the freedom to change its orientation about this bisector (Fig. and the domain magnetizations be 6. However. n. to avoid the appearance of magnetic free poles on the wall surface. and those of the magnetization of one domain be ( f t l t /32. 16. /3j = /32 = 1/V^. /33).19) be (<*!. and the normal to the plane which contains the two magnetizations be i/f.18. . the details are somewhat different. n.90° WALLS 423 Fig. and the angle between the normal. Geometry of spin rotation in a 180° wall making angles i/» = 45° and i/» = 2. The fundamental properties of 90° walls are similar to those of 180° walls.87° with the (001) plane (K1 > 0).61). In order to see the rotation of spins in the wall more *Let the direction cosines of the normal to the wall. (or near 90°).19).

16. the magnetization makes the angle 6 with the normal to the plane wall.62). z.19. a^ + /^i ft + 7iT2 = 1> where al = a2 = sin 8 cos <t>lt fa = .72).20) be (a1.20. .424 SPIN DISTRIBUTION AND DOMAIN WALLS Fig. Directions of magnetization on both sides of a 90° domain wall. from which we have (16. /32. 16. 16. easily.^2 = cos "> so that sin2 0(cos2 (j>1 — sin2 $[) + cos2 8 = 0. 16. yj) and (a2. * Let the direction cosines of the two magnetizations with respect to (x. From a consideration of the geometry. y. Diagram showing possible orientation of a 90° wall which has no magnetic free poles.* we have The angle between the spins in neighboring atomic layers in the 90° wall is given by Fig.Since the two magnetizations are perpendicular. let us choose new coordinate axes so that the x-y plane is parallel to the plane of the wall as shown in Fig.ft2 = sin 6 sin 4>i. As defined above. Let us assume that the azimuthal angle of the magnetization about the z-axis changes from <f»l to <£2 (<j)l = — $2). fa. z) (see Fig. and 7i .20.

64). y. U.21. The energy per unit area parallel to the average zigzag wall. minimizing the sum of the energies (16. as a function of orientation of the wall.42) for the 180° wall]. by By the numerical calculation of (16. for \\i = 90°. </>). is minimum for i// = 0. is minimum at fy = 62°. As seen in this graph.5). the total energy of the wall is given [similar to (16. so that the larger range of integration makes the wall energy larger in spite of the smaller value of sin2 6. g(6. By using this result. 16. the wall energy per unit area. the total change in the azimuthal angle is 180°.65). 16. . Fig. using the first term of the magnetocrystalline anisotropy given by (12. On the contrary. On the other hand. where a is the spacing of the atomic layers.90° WALLS 425 sin 9(d<f)/dz)a. where the plane of the wall is parallel to the magnetization of the domains on either side. The 90° wall energy. Therefore the exchange energy stored in a unit area of the wall is given by where sin2 8 can be taken outside the integral because the angle must be the same for all the spins to avoid the appearance of magnetic free poles in the wall. then the anisotropy energy per unit area is given by The spin rotation in the wall can be found by the variational method.63) and (16. we get the wall energy as a function of the angle ^ as shown in Fig. y.21. The reason for this is that the rotation of the spin in the wall is only 90°. if the anisotropy energy density is expressed as a function of the two angles 6 and (j).

each segment must be out of the (001) plane. 16. As seen in this graph the energy. When we observe these zigzag walls on the (100) crystal surface (the y-z plane in Fig. Domain structure induced by the application of a mechanical scratch on a (100) surface of 4% Si-Fe crystal. It is observed that the zigzag angle is nearly 106° at places far from the scratch. The energy of the zigzag wall per unit area of the average wall plane containing the z-axis is given by which is graphically shown in Fig. These domains are connected by closure domains at the crystal surface to avoid the appearance of magnetic free poles. thus resulting in zigzag-shaped walls. 16. It is concluded. the angle CD between the zigzag line segments. 16.22). .22) in order to attain the minimum total wall energy. Let us consider the actual shape of 90° walls which are produced by a mechanical scratch on the (100) surface of a silicon iron single crystal.24. It was discovered that the mechanical stresses induced by the scratch result in the appearance of many fine domains which have their magnetizations perpendicular to the crystal surface (Fig. that the stable configuration of the 90° wall is a zigzag shape.426 SPIN DISTRIBUTION AND DOMAIN WALLS Fig. 16. The thick groove seen on the right-hand edge of the photograph was made by a weighted ball point pen drawn parallel to [010] (the y-axis). 16. U. but becomes smaller at places nearer to the scratch. The reason for the variation of the zigzag angle. composed of alternate segments each making an angle i/f = +62° with the x-y plane. Since in this case 90° walls must stretch along the z-axis. which we call the zigzag angle.22. Many zigzag lines run perpendicular to the scratch.23 shows zigzag walls observed on the scratched (100) surface of a 4% Si-Fe single crystal. is 106°. may be understood as follows: a tension stress is produced in the region around the scratch. CD. is minimum at if/ = 62°. therefore. The 90° walls between the fundamental domains and the closure domains tend to rotate their segments toward an orientation parallel to (001) (the x-y plane in Fig.21 as a function of if/.22). 16. The observed zigzag angle is plotted as a function of the distance from the scratch in Fig. Figure 16.

90° WALLS 427 Fig.8 . because their magnetizations are perpendicular to the tension. discourages the closure domains.24. This tension is the main origin of the underlying domains parallel to the x-axis. however. Txx. 16. Variation of zigzag angle and calculated internal stress as a function of a distance from the scratch. thus Fig.23. This tension. Therefore the closure domains tend to become shallower. Zigzag domain walls produced by a mechanical scratch on a (100) surface of 4% Si-Fe crystal (Chikazumi and Suzuki8). so that the normal components of magnetization across the zigzag walls are no longer continuous. because the magnetostriction constant parallel to <100> is positive. which has only the component Txx underneath the maze domain. 16.

Neel pointed out that in the case of very thin films. 15.27). 16.5 SPECIAL-TYPE DOMAIN WALLS We have assumed in the preceding discussion that the normal component of magnetization is continuous across a domain wall so that no magnetic free poles exist in the wall.25. which normally appear to be poorly defined and thick. Let us calculate the energy of the Neel wall for a uniaxial ferromagnet.3(a)) observed on mechanically polished crystal surfaces.9 producing magnetic free poles on the zigzag walls. a rotation of the spins in a plane parallel to the thin film surface has less magnetostatic energy than rotation in a plane parallel to the wall. 16.10 We call the former type of wall a Neel wall. so that a decrease in the angle results in the same number of free poles spread over a larger wall area. 16. are in fact composed of fine zigzag lines.24.25. these surface free poles have little effect. in good agreement with the calculation.& The value of Txx deduced from the observed value of the zigzag angle is also plotted in Fig. such a spin rotation must produce free poles on the sample surface where the domain wall terminates.26). It was found by a careful observation of the powder pattern using a dilute colloidal suspension that the walls of maze domains. In contrast to the spin rotation in the Bloch wall (Fig. This experiment was performed for the purpose of clarifying the nature of maze domains (see Fig.9 The crystal is a few millimeters in length and has a rectangular cross-section. which is close to the yield strength of the material.31). by .9). The total magnetic free pole on a zigzag segment is independent of the angle t/>. The domain patterns observed on each surface of the crystal revealed that the 90° wall tilts as shown in Fig. similarly to (16. The exchange energy stored in a unit area of this wall is given. The zigzag angle was theoretically calculated as a function of TXJC. Since Txx increases nearer to the scratch. 16. but in thin samples their contribution to the total energy of the system may not be negligible. However.428 SPIN DISTRIBUTION AND DOMAIN WALLS Fig. The tilt of 90° walls was also observed on iron whisker crystals. 16. In thick samples. A tilted 90° wall as observed for an iron whisker. The result shows that the maximum value of the internal tension is 90kgmm~ 2 . the zigzag angle is expected to decrease close to the scratch. grown by the reduction of ferrous bromide by hydrogen gas at about 700°C. 16. thus reducing the magnetostatic energy. 16. and the latter a Block wall (see Fig. the spin rotation in the Neel wall occurs in a plane containing the normal to the wall (Fig.

32). for uniaxial anisotropy: (a) Bloch wall. The anisotropy energy per unit area of the wall is given.43). similarly to (16.27. 16. similarly to (16. . by where g(0) is given. the Neel wall stores magnetostatic energy due to the demagnetizing field Fig. 16.26. (b) Neel wall (Chikazumi). Two types of spin rotation across a magnetic domain wall.SPECIAL-TYPE DOMAIN WALLS 429 Fig. Spin rotation across a Neel wall (the rotation occurs in the plane of the page). by In addition.

11 . 16. Spin configurations inside and outside the cross-tie wall.68) and (16.72) with (16. the wall energy of the Neel wall is given by Comparing (16.430 SPIN DISTRIBUTION AND DOMAIN WALLS Fig. we find that the Neel wall always has higher energy than the Bloch wall.47).28.10 This term has the same functional form as (16. N. 16. 16.33) to (16.47) hold in this case by using the substitution Therefore.28. because the demagnetizing factor. Dependence of the wall energy on film thickness (a) Bloch wall. which was assumed to be 1 in (16. which increases with a decrease of film thickness as shown by the curve a in Fig.69).29. In the case of magnetic thin films. the Bloch wall has an additional magnetostatic energy due to free poles at the film surfaces.47). On the other hand.70). decreases with a Fig. (b) Neel wall. so that all the equations from (16. the magnetostatic energy of the Neel wall decreases with a decrease of film thickness. referring to (16.

where the direction of spin changes discontinuously.13 .12 decrease of film thickness as shown by the curve b in Fig. while the Neel wall is stable for relatively thin films. Figure 16. 16. Leakage field-free spin configuration of a Bloch wall. For films of intermediate thickness. Electron interference micrographs of a cross-tie wall as observed for a Permalloy film: (a) Lorentz image. The spin arrangement on both sides of the wall is modified and results in cross-ties. The value of y is the direction cosine of spins with respect to the normal to the page. 16. 16.31. a cross-tie wall as shown in Fig.28.SPECIAL-TYPE DOMAIN WALLS 431 Fig.30(a) shows a Lorentz image of a cross-tie wall observed for a Permalloy film. Bloch-type and Neel-type spin configurations appear alternatively along the wall. where the energies of both types of domain wall are comparable. (b) interference fringes. 1630.29 appears. Therefore the Bloch wall is stable for relatively thick films. while (b) shows interference fringes Fig.11 In this wall.

10 (1955). D. Phys. Huber. W. Mod.. Brown. Phys.. It is a line boundary in a domain wall. F. which is described in a later paper: S. This paper ignored the H* -correction. 295.. Suzuki. IEEE Trans.. 17 (1978). Neel. 6. Kittel.. a (lattice constant) = 3 A. Appl. 736. 28 (1957). 29 (1958). 11. 3. Hubert13 theoretically predicted a leakage field-free spin configuration of a Bloch wall. Jr. B. Brown. S. S. Phys. f. Tonumura. Rev.. Rev. 32 (1962). 21 (1949).4 In a single crystal plate parallel to the (001) plane. 1291. MAG-15 (1979). Stat. /. Neurath. Micromagnetics (Wiley-Interscience. Phys.. Bloch lines appear as bright spots or dark spots from which cross-ties emerge. and the magnetocrystalline anisotropy is expressed only by the first term. 6799. 699. Solidi. Suzuki. H. 1.432 SPIN DISTRIBUTION AND DOMAIN WALLS as observed by electron interference microscopy which show the same spin configuration as the postulated structure in Fig. 74 (1932). and P. Phys. 11 (1940).. Graham. Rend. is called a Bloch line. The line in either a Bloch or a Neel wall where the spin rotation changes from right-handed to left-handed. Assume that the effect of magnetostriction can be ignored.. 16. Endo. /.. D.. Fujiwara. Phys. Fukuhara. Matsuda. 1493. A. 918. 2. 16. 10.Y. and H.. 16. 5. 29 (1958). Chikazumi. 523. F. 58 (1940). Chikazumi and K. 888. E. Jr. 9. Jr. 160. Osakabe. O. Such an asymmetric spin configuration was experimentally'verified by electron microscopy. N. Shinagawa. 16.31. Rev. Appl. Smith. . Chikazumi and K. In Fig. A. formulate the energy of a 180° wall which is present in this crystal. /. F.2 Calculate the energy of 180° walls which are parallel to the (100) and (110) planes in a cubic crystal with K1 = 0 and K2 > 0. K. Jap. 0f (Curie point) = 527°C. Phys. I. Goodenough. 241 (1955).3 . R.30(a). Phys. 533. and Kl = 6xl0 4 Jm. Graham. Soc. and J. Z. 541. Weiss. 14. 12.. B25 (1982). Appl. Appl. 4. W. /. A. D.. Appl. 294. 74 (1948)..29. Phys. Phys. 525. T.14 PROBLEMS 16. there is an infinitely long x-domain touching both crystal surfaces with a quadrilateral cross-section surrounded by y-domains. N. W. Japan. Compt. Mag. Hubert. as shown in Fig. or vice versa. Phys. Bloch. E. REFERENCES W. Phys. 141. Calculate the inner angles of the cross-section of the ^-domain perpendicular to its length. 85 (1952). J. 16. Rev. L. 8. DeBlois and C. 163 Calculate the energy of a 180° wall which is parallel to (100) of a bcc ferromagnetic crystal with 5 (spin) = \. 38 (1970). C. Tanabe. P. 7. Phys. Jr. T. Suzuki. 1963). /.. R. C. 13.1 Assuming that a ferromagnetic crystal with isotropic magnetostriction constant and with negligibly small magnetocrystalline anisotropy energy is subjected to a uniform tension cr. Rev.

As shown by (1.and ferrimagnetic materials are divided into multiple domains. In this section we discuss how the magnetostatic energy is reduced by the appearance of domains.77). Let the thickness of each domain be d. 17. . 17. First we calculate the magnetostatic energy of the domain structure as shown in Fig.1 MAGNETOSTATIC ENERGY OF DOMAIN STRUCTURES Ferro.1. Free poles on the crystal surface produced by the plate-like or laminated domains.17 MAGNETIC DOMAIN STRUCTURES 17.1. We assume a crystal with a surface parallel to the x-y plane at z = 0. is given by where m is an index that numbers the domains. The magnetic potential must satisfy the Laplace equation Fig. CD. The domains are separated by 180° walls lying parallel to the y-z plane. The reason for the existence of domains is that the magnetostatic energy is greatly reduced. in which there are many plate-like domains with magnetization 7S along the +z or — z direction. the magnetostatic energy is given by where <p is the magnetic potential. in which the spontaneous magnetization takes different orientations. For simplicity we assume that the crystal extends indefinitely in the —z and also in the ±x. Then the surface density of magnetic free poles.and +y-directions.

6). the potential must be symmetrical with respect to the plane z = 0.7) for <p in (17.7) is a solution of (17. we have The solution of the Laplace equation (17. The coefficients An are determined to satisfy the boundary condition (17. The value of 9 at z = 0 is obtained from (17. Using (17. where magnetic free poles exist.1) in (17. It must satisfy the boundary condition at z = 0. because the free poles are confined to this plane.4). so that Using this relationship in (17.3) must have the form where n is an odd number. In the present case.7) and (17. we may use (17. In order to prove that (17.6). we have The coefficients An are obtained by integrating the above formula from 2md to 2(m + l)d after multiplying by sin n(iT/d)x to give where n is an odd integer.3) and find that (17.3).434 MAGNETIC DOMAIN STRUCTURES in all space other than at the crystal surface.3) holds.8) as .

A decrease in d. 17.1. as shown in Fig. Such wavy domains were observed in MnBi.2 and the circular pattern as shown in Fig.12) show that the magnetostatic energy is proportional to the size of the domains. because the N and S poles are mixed more densely. Using (17.1 who also extended the treatment to the checkerboard pattern shown in Fig. the spontaneous magnetization lies perpendicular to the crystal surface. we can calculate the magnetostatic energy per unit area of the crystal surface as Thus we find that the magnetostatic energy is proportional to the width of the domains. Comparing (17.11) and (17. All three formulas (17. In all the cases considered above. we see that the magnetostatic energy is greatly reduced by mixing N and S poles more closely.13(c). Checkerboard domain pattern. therefore. results in a decrease in the magnetostatic energy. d. 17.11) and (17. In these cases.12) with (17.2).10). (17. 17.10). 15. d.MAGNETOSTATIC ENERGY OF DOMAIN STRUCTURES 435 Fig. 17.4 has a much lower magnetostatic energy than the plate-like or laminated domain structure of Fig. The energy is rather closer to that of the checkerboard pattern (17.11).3. 17.2. obtaining for the checkerboard pattern and for the circular pattern. magnetic free poles are confined in the crystal . The above calculation was carried out by Kittel. Goodenough2 showed that a wavy pattern as shown in Fig.

5. where there is a discontinuous change in magnetization. Laminated domains with magnetizations making a small angle 6 with the surface. Circular domain pattern. the surface density of magnetic free poles is obtained by the substitution 7S -»7S sin 6 in (17. surface. 17. 17. as shown in Fig. This results in a reduction of magnetostatic energy. Then the surface density of free poles is given by If the magnetization is fixed in the easy axis (Fig.4. Fig.436 MAGNETIC DOMAIN STRUCTURES Fig. if the easy axis makes an angle other than a right angle with the crystal surface. as shown in Fig. giving the magnetostatic energy per unit area However.5. the demagnetizing field in each domain will rotate the magnetization out of the easy axis. 173. Wavy domain pattern. 17. 17. Let the angle of inclination of the easy axis from the crystal surface be 6. However. .6(a)). thus producing a volume distribution of free poles. in the crystal each domain magnetization is rotated non-uniformly by the demagnetizing field resulting from the free poles at the crystal surface.10).

It must be noted that there is some increase in anisotropy energy in case (b). 17.6(b). One way to solve this problem is to replace the ferromagnetic crystal by a homogeneous magnetic material with a modified permeability n* and to assume the same free pole distribution as in (a) (Fig.6.MAGNETOSTATIC ENERGY OF DOMAIN STRUCTURES 437 + + + + + Fig. This produces a volume distribution of magnetic free poles instead of a planar distribution. Fig. 17. Fig. but a special permeability resulting from rotation of the magnetization. . because free poles with the same sign tend to repel one another.7.6(b). 17.5: (a) The direction of magnetization is fixed. The permeability p* is not the real permeability. which results from domain wall motion.* correction.6(a) and (b).5. As mentioned in Section 1.4) must be replaced by This means that the permanent free poles give a divergence of B which does not include the permanent magnetization. Distribution of magnetization vectors in a domain in Fig. 17. It is easy to see that the magnetostatic energy is much lower for (b) than for (a).7). Then the boundary condition (17. because the magnetization is rotated away from the easy axis. It is easily shown that the total number of free poles is the same in Figs. (b) the local magnetization is rotated out of the easy axis by the demagnetizing field. Model for /a. 17. 17. 17. the magnetostatic energy in such a system is calculated in terms of magnetic potential at the permanent free poles: the polarization free charge in the soft magnetic material is automatically taken into consideration. equivalent to Fig.

5). we have On the other hand. is no longer symmetrical with respect to the plane z = 0. Let the solution for ^t* = /AO be The solution for /u.22) and (17. we have Since (17. Using these relationships in (17. we have and where fz signifies df(x. we have Therefore (17. <p.9).21) becomes The potential at z = 0 is obtained by multiplying A by (17. thus .16) must satisfy the conditions (17. we have Comparing (17.* = (JL* is no longer symmetrical for z > 0 and z < 0.23).15).18). we find Similarly from the Laplace equation for z < 0.5) does not hold. so that Similarly in the case /A* = /A O .438 MAGNETIC DOMAIN STRUCTURES In this case the magnetic potential. so that we can assume the form Using this formula in (17.4) and (17. z)/<?z. so that the relationship (17. the potential must satisfy the Laplace equation for z > 0.

Therefore such a correction can never be ignored when the fields produced by free poles cause a rotation of the magnetization.26) is 0. On the other hand.2 X 104 Jm~ 3 and spontaneous magnetization 7S = 2.1 17.1-17. a very small value.22.4. Therefore the magnetostatic energy is reduced by reducing the width of the domains.2 SIZE OF MAGNETIC DOMAINS As mentioned previously. the crystal on both sides of the wall has /x*. Let us calculate the value of JL* for iron. d. This correction is called the mu-star correction. so that When the magnetization makes 45° with the crystal surface.0435.14) must also be multiplied by A. of the domains. a ferromagnetic body is divided into many domains in order to reduce the magnetostatic energy. 16.SIZE OF MAGNETIC DOMAINS 439 Therefore the magnetostatic energy (17. Using these values. However. which has magnetocrystalline anisotropy K1 = 4. the magnetostatic energy is always proportional to the width. 17. . when the magnetization is perpendicular to the crystal surface as in Figs. by putting 00 » 7r/4 in (18.103)).26) becomes This situation can be understood by considering that the magnetic field is reduced by a factor 1/71 due to the presence of the soft magnetic material (see (1. and (17. so that the factor A given by (17.15 (T). such as the zigzag 90° domain walls in Fig.82) we have In the case of the 90° wall on which magnetic free poles appear. and (17. The equilibrium size of the domains is determined by minimizing the sum of the magnetostatic energy and the total wall energy.26) gives A = 1 and there is no such correction.29) gives JL* = 45. so that we have The value of /A* is determined by the rotation of the magnetization out of the easy axis (see (18. As seen from the preceding calculations. the total domain wall area per unit volume is increased by reducing the width of the domains.82) in which 60 ~ Tr/2). /I* = 1. irrespective of the geometry of the domain structure. its importance was first pointed out by Kittel. (17.

(a) Single domain structure. N poles appear on the top and S poles appear on the bottom surfaces.8(a). so that the magnetostatic energy per unit area of the plate is given by two times the results of (17. or On the other hand. 17. The equilibrium domain width.8. If the entire plate consists of a single domain as shown in Fig. The magnetostatic energy of such a free pole distribution is given by (17. d. so that the total wall energy per unit area of the plate is given by where y is the wall energy. as shown in Fig. 17. the total domain wall area is l/d. Consider a ferromagnetic plate with thickness / having an easy axis perpendicular to the plate. is given by minimizing the total energy or Solving (17.440 MAGNETIC DOMAIN STRUCTURES Fig.10). we can ignore the interaction between free poles on the two surfaces. (b) multi-domain structure. In the present case. both of which produce demagnetizing fields -/S//AO m tne plate.36). we have . If / » d.8(b). The magnetostatic energy stored per unit area is given by The magnetostatic energy is lowered if the plate is divided into many laminated domains of thickness d. free poles exist on the top as well as on the bottom surfaces. 17.10).

33). This contradiction between theory and experiment can be understood by observing the domain pattern on the surface parallel to the c-axis of the same crystal (Fig. we find that (17. We therefore conclude that the checkerboard domain structure will never exist. to give The magnetostatic energy of the single domain given by (17.01 mm. y100 = 1. y.39) for any value of /s. of the order of 0. /s = 2. The total energy of this domain structure is evaluated by using (17. Actually.15. On the other hand. 17. the magnetostatic energy of the free poles on the top and bottom surfaces is given by which is smaller that that of the laminated pattern.01 (m) is calculated to be Thus the magnetic domain width is small.39). or Minimizing the total energy leads to an equilibrium domain width so that the total energy becomes Comparing (17. we observe a checkerboard-like domain pattern on the c-plane of a cobalt single crystal. however.SIZE OF MAGNETIC DOMAINS 3 441 In the case of iron.37) in (17.35).45) with (17.9(a). or /. 17. the total domain wall area is twice as large as that of the laminated domains. In the case of the checkerboard pattern shown in Fig. but increases . 17. so that the domain width in a plate with / = 1 cm = 0. We see that the width of the domains is small at the surface perpendicular to the c-axis. as shown in Fig.45) is larger than (17.2.6 X 10~ . given by (17.9(b)).32) is evaluated as Therefore the energy of the equilibrium domain structure is about 1/10000 of that of a single domain.

17.11. ferromagnetic materials exhibit magnetostriction.10. the closure domains tend to elongate parallel to the crystal surface. the formation of magnetic free poles can be avoided by generating closure domains with magnetizations parallel to the crystal surface. 17.12. In a cubic crystal such an iron or nickel where the number of easy axes is more than one. In general. Schematic illustration of the surface domain structure below the crystal surface perpendicular to the uniaxial easy axis. (After Y. In this case no free poles appear. Domain pattern observed on cobalt crystals with the crystal surface (a) perpendicular to the c-plane and (b) parallel to the c-axis. In this case.9. so that if the magnetostriction constant is positive. Figure 17. The strain in the closure domain is given by exx = 3A100/2. The surface domains exist only to a limited depth. as shown in Fig.10 is a sketch of the domain structure at the crystal surface. Since the closure domain must be compressed into a triangular form which matches the major domains. 17.442 MAGNETIC DOMAIN STRUCTURES Fig. which means that work amounting to c e n £r/2 Per unit volume must be done in order to squeeze the closure domain to fit Fig. as shown in Fig. the width of the domains will be determined by a balance between the magnetoelastic energy and the wall energy. and no magnetostatic energy is stored. some magnetoelastic energy is stored. however. so that the total domain wall area is not as large as that assumed in the above calculation. . Takata) gradually with increasing the distance from this surface. 17.

6 X 10 3. . Here c u is the elastic modulus of the crystal. 17.07 X 10 5.SIZE OF MAGNETIC DOMAINS 443 Fig.11. Hypothetical magnetostrictive elongation of a closure domain. with the neighboring major domains. Closure domain structure of a cubic single crystal. The magnetoelastic energy stored per unit area of crystal surface is given by The total energy is given by The condition for minimizing the total energy is from which we have For an iron single crystal with thickness / = 1 cm. A100 = 2. y = 1. 17. cn = 2.12.41 X 1011. so that Fig.

1). 17. The total energy is given by which is much lower than (17. and is much larger than the case of (17.38). When the easy axis tilts from the normal to the crystal surface. The anisotropy energy stored per unit area of the crystal surface is given by For cobalt Ku = 6.79 in (17.13. the magnetostatic energy of the domain structure without closure domains is calculated by putting /s = 1.54).14 shows a fir-tree pattern. Such closure domains are actually observed. The closure domain in this case stores magnetic anisotropy energy. as shown in Fig. In a uniaxial crystal such as cobalt.13. thus where Kul and Ku2 are the anisotropy constants defined by (12.5 mm.33). This value is of the order of 0.3)).0 X 105 (see (12. so that On the other hand. we find that the structure with closure domains has lower energy.444 MAGNETIC DOMAIN STRUCTURES Fig. 17. for the (001) surface of an iron single crystal containing a small amount of silicon. 17. it is also possible to produce closure domains which are magnetized in hard directions. Powder pattern of closure domains observed on the (100) surface of an Fe + 4% Si crystal (Chikazumi and Suzuki). giving Comparing (17. the shape of the closure domains is greatly modified. .39).55) with (17. Fig. For instance.

16.14. Powder pattern of fir-tree domains (a kind of closure domain structure) observed on a tilted (001) surface of an Fe + 4% Si crystal (Chikazumi and Suzuki). 17. suggested the possibility of utilizing it as .15.BUBBLE DOMAINS 445 Fig. The structure is illustrated in Fig. The observation of well-defined domain patterns and the interpretation mentioned in this section were developed by Williams et al? 17. Bobeck.3 BUBBLE D O M A I N S A bubble domain is a cylindrical domain created in a ferromagnetic plate with an easy axis perpendicular to the plate in the presence of a magnetic field normal to the plate. The tree-like domain serves to transport a part of the free poles appearing on the crystal surface from one domain to the neighboring domain.15. Schematic illustration of fir-tree domains. which is determined by the condition that the normal component of magnetization is continuous across the 90° boundary underneath the crystal surface (see Fig. The domain boundaries of the fir-tree pattern tilt from the main domain wall by some angle.19). which is the closure domain structure observed on a tilted (001) surface of an Fe or Fe + Si crystal.4 who discovered the bubble domain. 7. Fig. 17.

The reason is as follows.446 MAGNETIC DOMAIN STRUCTURES Fig. the magnetization and free pole distribution of the bubble domain (a) can be regarded as a superposition of those of the magnetic plate magnetized downwards without any bubble domain (b) and those of a single bubble domain with a double magnetization (c). A superposition of (b) and (c) is equivalent to (a). . The demagnetizing field in (b) is given by /S//AO. The latter effect is due to the fact that the internal magnetic field in the bubble domain is parallel to its magnetization. Surface free poles and the demagnetizing field of a bubble domain: (a) a bubble domain.16 shows the structure of the bubble domain. while the magnetostatic energy of the magnetic free poles tends to increase the radius. (b) a magnetic field without bubbles. where r is the radius of the bubble and h is the thickness of the plate. (c) a hypothetical bubble domain with double magnetization.16. the shape of the bubble may be regarded as a sphere. whereas that in (c) is given by -2NIs/ju.0. so that N is approximately f. As shown in Fig. The resultant demagnetizing field is given by If r = h/2. Fig.17. 17.17. a digital memory device. The surface tension of the domain wall tends to reduce the bubble radius. Structure of a bubble domain. Figure 17. 17. 17. where N is the demagnetizing factor of the bubble domain.

which tends to decrease the radius of the bubble.0.59) is /. the domain wall energy y (Jm~ 2 ) gives rise to a surface tension. so that the left-hand side of (17.59) is 7s/3ju.4)). r/h. (17. 17. These three fields must be balanced. On the other hand. .57). and surface tension field.BUBBLE DOMAINS 447 Therefore we find that the demagnetizing field given by (17. Fig.//*„. These points represent equilibrium states. Therefore the demagnetizing field in the bubble tends to increase its radius. being 0 for r = 0. In order to stabilize the bubble.so that the left-hand side of (17. is a function of the radius of the bubble. HA. 17. which is 2IsHy (see (18.18.0. P and Q. Comparing this with the pressure on the wall produced by a hypothetical field Hy. which favors the magnetization in the bubble.18 shows the left-hand and right-hand side values of (17. the inner pressure of the magnetic bubble is given by y/r (Nm~ 2 ).59) as functions of the reduced radius.56) and (17.56) is positive. For r = h/2.58) becomes The demagnetizing factor. For r -»oo. where (17. r/h. giving Using (17. so that this value approaches -/s/ju. N. we must apply a bias field -Hb. Hb. N=^.59) is satisfied. Fig. as functions of the reduced radius. y/2/sr + bias field. The two values are equal at two cross-over points. #-» 1. Demagnetizing field. we have where the negative sign means that the effect of the field is to reduce the radius of the bubble. As in the case of a soap bubble.

2r.21 shows a Lorentz electron micrograph of the bubble domains observed . which acts to increase r. which corresponds to the physical situation described in this paragraph.19. There is a special class of bubbles whose radius is rather insensitive to Hb. the term that decreases r becomes larger.5 However. 17. This behavior is illustrated by the experimental curve denoted by N = 0 in Fig. r. for a number of bubbles with different values of N. y. Hb. 17.& Therefore a normal bubble as shown in Fig. Hd.59) becomes steeper. For a hard bubble with large N. for a number of hard bubbles with different values of N. because any deviations of r tend to return r to its original value. as shown in Fig. if r decreases. thus increasing the exchange energy and accordingly the wall energy. On the other hand.18 representing the right-hand side of (17.19 shows the dependence of the bubble radius on the bias field. so that the decrease in r caused by increasing Hb should become more gentle. a decrease in the bubble radius. Variation of the bubble diameter. 17.20(b). Figure 17. When the bias field. the point Q shifts to the left. 17. is increased. Hb. These bubbles contain many Bloch lines. and are called hard bubbles.19. because if r increases. the point P represents an unstable equilibrium. Figure 17. results in an increase in the density of Bloch lines. We see a beautiful agreement between theory and experiment. the point Q represents a stable equilibrium. 17. with increasing bias field.448 MAGNETIC DOMAIN STRUCTURES Fig.20(a) has N = 0. Hb. becomes even larger. so that the bubble shrinks. Therefore the curve in Fig.5'1 Let the number of revolutions of the spin in the midplane of the bubble wall along the full circumference of the wall be N.

Three kinds of bubbles are seen in the photograph.20. corresponding to N = 1. However. Bubble domains can be utilized as memory or logic devices in which the bubbles are transferred along a circuit patterned on a single-crystal plate (see Section 22. or One crystal that meets this condition is orthoferrite (see Section 9. and 0. Specifically.5) is used to create the bubble domains.3). and (c) can be interpreted assuming the spin structure as shown in (a)'. In this case a growth-induced anisotropy (see Section 13. The contrasts of these bubbles illustrated in (a).10 The soft magnetic layer is effective in removing the complicated spin structure of the hard bubbles. (a) a normal bubble (N = 0). (b)'. respectively.2kOe). 17. because some normal wall nuclei are created in the soft layer and propagate downwards through the wall to destroy the unstable spin structure. (b) a hard bubble (N = 3). under the application of a bias field of 0. which exhibits a feeble spontaneous magnetization by spin-canted magnetism. because their movement is abnormal. —1. Variation of orientation of spins in the midlayer of the bubble domain. in a Co thin film with the c-axis perpendicular to the film surface.9 or a thin Permalloy film is evaporated on top of the crystal. The necessary condition to create a bubble domain is that a large perpendicular anisotropy exists in the crystal. the anisotropy field 2KU/IS must be larger than the demagnetizing field Is/fj. . (b). and (c)'.74MAm"1 (=9.3.BUBBLE DOMAINS 449 Fig. Bubble domains can also be produced in rare-earth iron garnets with a small spontaneous magnetization made by replacing some of Fe ions on the 24 d lattice sites by nonmagnetic Ga ions. hard bubbles are undesirable for such devices.5).0. In order to suppress the appearance of hard bubbles. the perpendicular anisotropy of a surface layer of the crystal is erased by ion bombardment.

21.4. 17.60). (b) and (c) are interpreted by assuming the spin structure (a)'.11 Figure 17. This spin .2 kOe). Stripe domains appear when the perpendicular anisotropy is not greater than the value that satisfies (17.3).74 MAm" 1 (= 9. Watanabe). The broken arrow indicates a Bloch line.4 STRIPE DOMAINS Stripe domains are associated with a rotatable magnetic anisotropy discovered in anomalous magnetic thin films (see Section 13. 17. respectively. Three kinds of bubbles (a).22 shows a schematic illustration of the spin distribution in stripe domains. (b)' and (c)'. (Courtesy of D.450 MAGNETIC DOMAIN STRUCTURES Fig. Lorentz electron micrograph of bubble domains observed in a Co film with the c-axis perpendicular to the film surface in the presence of the bias field of 0.

17. structure is nature's clever solution to the problem of simultaneously minimizing the perpendicular anisotropy and the magnetostatic energy. where x is the coordinate axis perpendicular to the average spin axis and A is the wavelength of the spin variation or the width of a stripe domain.10): where the value is doubled by considering the effect of free poles on both sides of the thin film. as in (17. The magnetic anisotropy energy is expressed in terms of the angle.STRIPE DOMAINS 451 Fig. When 6 <s: 77/2. as . 9. Schematic illustration of the spin structure of stripe domains. We assume that the angle of deviation of the spins from the surface of the thin film can be approximated by a sinusoidal function.22. the surface density of magnetic free poles is given by The magnetostatic energy of such a free pole distribution is easily calculated by adopting the first term (n = 1) in (17.7) and averaging over one wavelength.

w represents the function in parentheses.452 MAGNETIC DOMAIN STRUCTURES Using (17. is obtained by minimizing w with respect to A. the condition w > 0 reduces to When a rotating field of moderate intensity is applied to the stripe domains. to be The total energy is given by where .61) and averaging over one wavelength of the spin oscillation.14). whereas the spontaneous magnetization rotates with the external field. we have the anisotropy energy per unit area as where h is the thickness of the film. giving Using this value. The wavelength. using (17. the stripe domain appears. If w > 0. A. the configuration of stripe domains remains unchanged. In this process some magnetostatic energy is .61) in (16. The exchange energy per unit area stored in this spin system is calculated.

Stripe domains observed by the powder pattern method were shown in Fig. Consider a spherical ferromagnetic particle with radius r.23. This is the rotatable anisotropy discussed in Section 13.5 DOMAIN STRUCTURE OF FINE PARTICLES As discussed in Section 17. If this sphere is divided . 17.29.49). Murayama12 calculated this spin configuration more precisely by using a variational method.23 shows a Lorentz electron micrograph of stripe domains as observed on an Fe-Ni thin film. I. In other words. Lorentz electron micrograph of stripe domains as observed on a 95Fe-5Ni alloy thin film. which means that the easy axis of this anisotropy is changed. We have assumed that the variation of the spin-canting angle is sinusoidal. the domain width is related to the thickness of the crystal. 1200A thick. 17. and (17.13 added to the energy given by (17. Figure 17. the domain width decreases more gradually than the size of the particle. an additional magnetic anisotropy energy is created. thus finally resulting in a single domain structure. 13. If the field exceeds some critical value. the stripes rotate. keeping its shape unchanged. For instance.DOMAIN STRUCTURE OF FINE PARTICLES 453 Fig.67).2.3. (17. because some magnetic free poles appear at the domain boundaries.4. the domain width is always proportional to i//.37).44). Therefore when the size of the particle is decreased. as seen in (17.

each of width d (see Fig. the magnetostatic energy is roughly estimated to be d/2r times the value for a single domain particle. 17. Relationship between the size of ferromagnetic particles and the width of magnetic domains. 17. into multiple domains. giving The total energy of the particle is minimized by the condition giving . the total wall energy is roughly estimated as On the other hand.454 MAGNETIC DOMAIN STRUCTURES Fig.24.24).

17. the width of the domains is decreased proportional to Vr. so that from (17. and more than ten years later.15 Neel.16 and Stoner and Wohlfarth. d = 2rc. Electron micrographs of powder patterns (Colloid SEM) of Ba-ferrite: (a) for relatively large particles showing a multi-domain structure.DOMAIN STRUCTURE OF FINE PARTICLES 455 As the radius r of the particle is decreased. At this critical radius. Figure 17.25. 17. attaining finally the single domain structure below a critical radius. (b) for relatively small particles showing a single domain structure.25 shows an experimental verification of single domain structure as observed for Ba-ferrite fine particles by means of a powder pattern method using a Fig.19 (Courtesy of K. so the number of domains in the sphere decreases as shown in Fig.24. rc.74) we have The presence of a single domain structure was first predicted by Frenkel and Dorfman14 in 1930. further detailed calculations were made by Kittel.17 It was pointed out by Kittel15 that single domain structures are also expected for ferromagnetic fine wires and thin films. Goto) .

showing a multi-domain structure (see photo (a)). Tonomura) scanning electron microscope (Colloid SEM). showing that this platelet tends to have a single domain structure. the magnetostatic energy is reduced by the magnetostatic interaction between particles. while in photo (b) a flux line emerges outside a thin platelet. In photo (a) we see that the lines of magnetic flux are confined inside a relatively thick platelet. but only a cluster of magnetic powder on a small particle. the .456 MAGNETIC DOMAIN STRUCTURES Fig. if the direction of the easy axis changes from grain to grain.26 shows electron interference micrographs of Co platelets with different thicknesses. In an assembly of single domain particles. separated by a nonmagnetic matrix.20-21 (Courtesy of A. showing a single domain structure (see photo (b)).20'21 In the preceding discussion we treated an isolated particle. showing the magnetic flux lines inside and outside of the platelet.18 We see many domain walls on a relatively large particle. The situation is also the same for a ferromagnet that contains many nonmagnetic inclusions or voids. 17.26. The thickness of the platelet in (b) is about one quarter of that of (a). Even in a purely magnetic material. so that the critical size for a single domain structure is more or less increased.19 Figure 17. Electron interference fringes observed for Co platelets showing lines of magnetic flux inside and outside the platelets.

27. If Ql is in the range —Tr/2 < dl< Tr/2. This would lead to a large magnetic free pole density that could be lowered if one of the magnetizations reversed its direction. hence we only need to calculate the average value of ca2 over all possible combinations of 0j and 02. The domain magnetization is more or less continuous across grain boundaries. Thus . 62 must be also in the range — Tr/2 < 62< Tr/2. First we treat a uniaxial crystal with positive Ku. as shown in Fig. The domain structure of such a non-uniform magnetic material will be discussed in Section 17. internal stresses. we learned that ideal ferromagnets have quite regular domain structures. such as cobalt. the domain structures of ordinary ferromagnetic materials are influenced by irregularities such as voids. to decrease the magnetostatic energy.6 DOMAIN STRUCTURES IN NON-IDEAL FERROMAGNETS In the preceding section. the magnetostatic energy is always proportional to a2. This continuity is. First we discuss the domain structure of polycrystals. The surface density of magnetic free poles is given by As seen in previous calculations. In contrast. 17. Let us calculate the magnetostatic energy of the free poles which appear at an average grain boundary. In magnetically hard materials such as permanent magnets. and grain boundaries. Suppose that the domain magnetizations on the two sides of the grain boundary make angles 91 and 62 with the normal to the boundary.22 except in the special case where the grain boundary has a particular orientation with respect to the directions of the axes of easy magnetization on both sides of the boundary. nonmagnetic inclusions.DOMAIN STRUCTURE IN NON-IDEAL FERROMAGNETS 457 individual grains will have a single domain structure if the grains are sufficiently small. such irregularities are the main factors which govern the size and distribution of the ferromagnetic domains. because otherwise the two magnetizations have components in opposite directions. however. not perfect. 17. that has only one easy axis. Such a regular domain structure can be actually attained for carefully prepared single crystals.6.

or z-direction (/ or . 72. The free pole density on the grain boundary is then given by . hence the magnetization in either grain can lie along the x-. For crystals with positive K^ such as iron.80).458 MAGNETIC DOMAIN STRUCTURES Fig. the axes of easy magnetization are (100). which has three or four axes of easy magnetization (depending on the sign of the anisotropy). /32. = 1.28. and that the total domain energy is lower by a factor l/\/2 . 17. y-. because this is the easy axis closest to II. in the right-hand grain should be parallel to the z-axis. or 3). If the individual grains are separated from one another. it follows that Thus we find that the magnetostatic energy of a uniaxial polycrystal is about one-half that of the isolated grains. z) of the right-hand grain.29 shows the three crystal axes (x. the direction of magnetization.27. 2. the normal n to the grain boundary. Crystal orientations on both sides of a grain boundary. Fig. Let the direction cosines of the normal to the grain boundary be (/31.y-i.28). /33) with respect to the cubic axes of the left-hand grain.y^) with respect to the right-hand grain (Fig. we find that the domain width in a polycrystal is about /2 times larger than the domain width in isolated grains. the probability of having a good continuity of magnetization across the grain boundary is much greater. For a cubic crystal. and the direction of magnetization 7j in the left-hand grain. Angles of magnetizations of the neighboring grains as measured from the normal to the grain boundary. y.y\. Figure 17. and (. 17. If y3 > y2 > y\ and /3. 17. When the magnetization is in the r'th easy axis in the left-hand grain and the . Therefore from the calculation in (b) above. > y3. the surface density of magnetic free pole is given by Now let us find the magnetization directions in the two grains that minimize the surface density of magnetic free poles given by (17.'th easy axis in the right-hand grain.

72. If the domain magnetization 7j in the first grain is in the region indicated by 1. respectively. and JC-direction. f» becomes smaller when the magnetization in the right-hand grain. and 3. the domain magnetization 72 in the second grain must be parallel to the z-. 2. If /3. y-. is further decreased and it happens that ft < (y2 + Ti)/2.84) over all possible orientations of the right-hand . < (y3 + y2)/2.I D E A L FERROMAGNETS 459 Fig. to minimize the surface density of free poles appearing on the grain boundary.29. then &> changes its sign. is parallel to the y-axis. the Ac-direction becomes the most favorable for /2. If ft is less than y3. we have On averaging each term in (17. 17. thus On averaging a>2 with respect to /?. Then If /3..DOMAIN STRUCTURE IN N O N .

460

MAGNETIC DOMAIN STRUCTURES

Fig. 1730. Illustration indicating the range of integration to calculate the average values in (17.85).

grain in the range y3 > y2 > yj, which is shown as a shaded area in Fig. 17.30, we have

Then (17.84) becomes

On comparing (17.86) with the average value (17.79) for an isolated grain, we see that the magnetostatic energy of a cubic polycrystal is about 0.20 that of the separated grains, so that its domain width will be I/ \/0.20 = 2.2 times larger, and the total energy will be v/0.20 = 0.45 that of the separated grains. Thus the magnetostatic energy of the magnetic free poles appearing on the grain boundaries is small but still nonzero, so that the domain structures of polycrystalline materials are essentially determined by the size of the grains. Next let us discuss the domain structure of a strongly stressed crystal. When a tension stress cr exists in crystal, there will be an induced magnetic anisotropy, given by (14.96), which rotates the local magnetization towards the axis of tension if A > 0. Figure 17.31 shows the domain pattern observed on the (001) surface of an Fe3Al crystal containing a mechanical indentation. Since this alloy has a large magnetostriction (A = 3.7XlO~ 5 ) and a small magnetocrystalline anisotropy, the direction of domain magnetization is mainly determined by the distribution of residual stresses in the crystal. If we assume that cr= lOOkgmm" 2 = 109 Nm~ 2 , the anisotropy constant becomes

DOMAIN STRUCTURE IN NON-IDEAL FERROMAGNETS

461

Fig. 1731. Magnetic domains induced by strong stresses produced by an indentation on (001) surface of Fe3Al (Chikazumi, Suzuki, and Shimizu).

which is almost of the same order of magnitude as the magnetocrystalline anisotropy constant of iron. The domain structure of such a strongly stressed crystal is similar to the uniaxial polycrystal, except that the easy axis changes its orientation from place to place. Domain structures of extremely soft materials such as Permalloy and Supermalloy, which have a small magnetocrystalline anisotropy, are considered to belong to this category.20 Next we discuss the domain structure of a material which includes voids, inclusions, and precipitates. Figure 17.32(a) shows a spherical void or nonmagnetic inclusion existing in a magnetic domain. Since the surface free poles on a sphere are equivalent to a dipole, the magnetostatic energy associated with the void is given by

where r is the radius of the sphere. If a domain wall bisects this void as shown in (b), the free pole areas are divided into regions of opposite polarity, thus reducing the magnetostatic energy to about half the value given by (17.87). Therefore the magnetostatic energy is reduced by

Suppose that N spherical voids are distributed in a unit volume of the crystal. We assume that the crystal is composed of ±y domains separated by 180° walls which are almost parallel to the y-z plane (Fig. 17.33). The total wall energy per unit volume of the crystal is given by y/d, where d is the average separation of the neighboring walls. On the other hand, an individual wall tends to pass through a void to decrease the

462

MAGNETIC DOMAIN STRUCTURES

Fig. 1722. Free magnetic poles appearing on a surface of a spherical void or a nonmagnetic inclusion: (a) a void isolated in a magnetic domain; (b) a void bisected by a domain wall. magnetostatic energy by At/, given by (17.88). The number of voids which are intersected by a single wall is roughly estimated to be N2/3, so that there are N2/3/d voids in a unit volume, leading to a decrease in the magnetostatic energy. Therefore the decrease in total magnetostatic energy is given by N2/3&U/d. If

a wall is generated, irrespective of the outside shape of the crystal. In the case of iron,

Fig. 17.33. Domain walls stabilized by a high density of distributed voids in a crystal.

PROBLEMS

463

which contains voids of radius r = 0.01 mm, we can estimate At/ taking 7S = 2.15, obtaining From condition (17.89) and using y= 1.6 X 10 3, we find that

In other words, if the separation of the voids is less than TV 1/3 = 10 3 (m) or 1 mm, these voids can create a domain wall. Since even carefully prepared single crystals can contain such a number of voids or nonmagnetic particles, the domain structures in these crystals are determined by the distribution of voids, rather than by the external shape of the crystal.

PROBLEMS

17.1 Assume an array of ferromagnetic domains with their magnetizations parallel to the +*-axis and also parallel to the ±y-axis separated by a 90° wall and many 180° walls parallel to the x-y plane at an interval d (see the figure). When the angle between the surface of the 90° wall and the x-z plane, <f>, is varied, how does the magnetostatic energy per unit area of the 90° wall change? Let the intensity of domain magnetization be /s, the magnetocrystalline anisotropy constant be Klt and assume that the crystal is infinitely large.

17.2 Consider a single crystal plate of a ferromagnet with uniaxial anisotropy described by an anisotropy constant Ku. How does the width of parallelepiped domains change with a change in Ku in the following cases: (i) the easy axis is perpendicular to the crystal surface, and (ii) the easy axis makes a small angle 6 with the crystal surface. Assume that /s2/Ai0 » Ku.

464

MAGNETIC DOMAIN STRUCTURES

173 Calculate the width of parallelepiped domains for a 1 cm thick cobalt crystal with the c-axis (easy axis) making the angle 6 = 0.1 radian with the crystal surface. Assume that Ku = 4.1 X 10s Jm~ 3 , /s = 1.8T, and y = 1.5 X 10~2 Jm~ 2 . 17.4 Estimate the critical size of a grain of polycrystalline Fe in which the individual grain is composed of a single domain. Assume that the shape of the grain is a sphere.

REFERENCES

C. Kittel, Rev. Mod. Phys., 21 (1949), 541. J. B. Goodenough, Phys. Rev., 102 (1956), 356. H. J. Williams, R. M. Bozorth, and W. Shockley, Phys. Rev., 75 (1949), 155. A. H. Bobeck, IEEE Trans. Mag., MAG-5 (1969), 554. T. Kobayashi, H. Nishida, and Y. Sugita, /. Phys. Soc. Japan, 34 (1973), 555. W. J. Tabor, A. H. Bobeck, G. P. Vella-Coleiro, and A. Rosencweig, Bell. Sys. Tech. J., 51 (1972), 1427. 7. A. P. Malozemoff, Appl. Phys. Lett., 21 (1972), 142. 8. J. C. Slonczewski, A. P. Malozemoff, and O. Voegili, AIP Con/. Proc., 10 (1973), 458. 9. R. Wolfe and J. C. North, Bell Sys. Tech. J., 51 (1972), 1436. 10. M. Takahashi, N. Nishida, T. Kobayashi, and Y. Sugita, J. Phys. Soc. Japan, 34 (1973), 1416. 11. N. Saito, H. Fujiwara, and Y. Sugita, /. Phys. Soc. Japan, 19 (1964), 421, 1116. 12. Y. Murayama, /. Phys. Soc. Japan, 21 (1966), 2253; 23 (1967), 510. 13. T. Koikeda, K. Suzuki, and S. Chikazumi, Appl. Phys. Lett., 4 (1964), 160. 14. J. Frenkel and J. Dorfman, Nature, 126 (1930), 274. 15. C. Kittel, Phys. Rev., 70 (1946), 965. 16. L. Neel, Comp. Rend., 224 (1947), 1488. 17. E. C. Stoner and E. P. Wohlfarth, Nature, 160 (1947), 650; Phil. Trans., A240 (1948), 599. 18. K. Goto and T. Sakurai, Appl. Phys. Letter, 30 (1977), 355. 19. K. Goto, M. Ito, and T. Sakurai, Japan J. Appl. Phys., 19 (1980), 1339. 20. A. Tonomura, T. Matsuda, J. Endo, T. Arii, and K. Mihama, Phys. Rev. Lett., 44 (1980), 1430. 21. T. Matsuda, A. Tonomura, K. Suzuki, J. Endo, N. Osakabe, H. Umezaki, H. Tanabe, Y. Sugita, and H. Fujiwara, /. Appl. Phys., 53 (1982), 5444. 22. W. S. Paxton and T. G. Nilan, J. Appl. Phys., 26 (1955), 65. 23. S. Chikazumi, Phys. Rev., 85 (1952), 918. 1. 2. 3. 4. 5. 6.

**Part VII MAGNETIZATION PROCESS
**

In this Part, we discuss how a ferromagnet increases its magnetization upon the application of an external magnetic field. In Chapter 18 we consider technical magnetization, in which the net magnetization is changed by domain wall displacement and by rotation of domain magnetization. In Chapter 19, we see how the intrinsic magnetization responds to very high magnetic fields, where the phenomena are described in terms of a spin phase diagram. Finally, dynamical magnetization processes or time-dependent magnetization will be discussed in Chapter 20.

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18 TECHNICAL MAGNETIZATION

18.1 MAGNETIZATION CURVE AND DOMAIN DISTRIBUTION

When a magnetic material is subjected to an increasing magnetic field, its magnetization is increased and finally reaches a limiting value called the saturation magnetization. This process is called technical magnetization, because it is essentially achieved by a change in the direction of domain magnetization and can be distinguished from a change in the intensity of spontaneous magnetization. The technical magnetization process is composed of domain wall displacements and rotation of the domain magnetization. Suppose that a magnetic field, H, is applied parallel to the magnetization of one of two domains separated by a domain wall (Fig. 18.1). When the domain wall is displaced as shown in (b), there is an increase in the volume of the domain magnetized parallel to H, and an equal decrease in the volume of the domain magnetized opposite to H. The net or resultant magnetization is therefore increased. This process is called domain wall displacement.

Fig. 18.1. Schematic illustration of the domain wall displacement.

468

TECHNICAL MAGNETIZATION

Fig. 18.2. Hypothetical pressure acting on a domain wall.

The effect of the magnetic field H on the domain wall can be replaced by a hypothetical pressure, p. Suppose that a 180° domain wall of area 5 is displaced by a distance s by the application of a magnetic field H parallel to the magnetization of one of the domains (see Fig. 18.2). Since the magnetization in a volume of magnitude Ss is reversed, the magnetic moment M is increased by where /s is the spontaneous magnetization. Therefore the work W done by the field is given by The hypothetical pressure p acting perpendicular to the domain wall gives a force pS on the wall, and the work done by this force in moving the domain wall a distance s is given by Comparing (18.3) with (18.2), we have Thus the effect of the magnetic field acting on a domain wall is equivalent to the hypothetical pressure p given by (18.4). When the field makes an angle 6 with 7S, only the component of the field H cos 6 is effective in moving the wall, so that In the case of a 90° wall, in which the domain magnetizations on either side of the wall make the angles 6l and 02 with the magnetic field, the hypothetical pressure is given by

MAGNETIZATION CURVE AND DOMAIN DISTRIBUTION

469

Fig. 18.3. Domain pattern observed on the (001) surface of Si-Fe crystal.

Figure 18.3 shows a typical domain structure that includes several 90° walls in addition to 180° walls, as observed on the (001) surface of a Si-Fe crystal with positive KI. Suppose that an external magnetic field is applied parallel to one of the easy axes as shown in Fig. 18.4(a). Then a pressure is exerted on every domain wall as the domains magnetized parallel to the field (shown as shaded areas) try to expand into the neighboring domains. This results in an increase in the volume of the shaded domains, until finally the shaded area expands to cover the entire sample. This state corresponds to saturation magnetization. If there is no hindrance to domain wall displacement, this process is achieved in a weak magnetic field, so that the magnetization curve rises parallel to the ordinate until it reaches the saturation magnetization (see the curve labelled [100] in Fig. 18.5). When a magnetic field is applied parallel to the [110] axis as shown in Fig. 18.4(b), the domain walls enclosing the domains which have their direction of magnetization nearest to the field (shown by the shaded areas) expand so as to increase the shaded area. Finally there remain two kinds of domains, with magnetizations parallel to [100] or [010]. Further increase in the external field causes rotation of the domain magnetizations away from the easy axes. This process is called magnetization rotation. The intensity of magnetization, 7r, at which the magnetization rotation starts is given in this case by 7S cos 45°, so that

The value of Jr is called the residual magnetization. When the field is applied parallel to [111], all the domain magnetizations lie along [100], [010], or [001] after the wall displacement is completed, so the residual magnetization becomes

470

TECHNICAL MAGNETIZATION

Fig. 18.4. Domain wall displacement and magnetization rotation: (a) HII [100]; (b) H \\ [110].

Fig. 18.5. Magnetization curves measured for a cubic ferromagnet with positive K1 along three principal crystal axes.

MAGNETIZATION CURVE AND DOMAIN DISTRIBUTION

471

Fig. 18.6. Polar diagrams showing the magnetization distribution at various points on the magnetization curve.

In fact, the magnetization curves measured for a single crystal of iron (Fig. 18.5) break away from the y-axis at the magnetization levels given by (18.7) and (18.8) when the field is applied parallel to [110] or [111]. In polycrystalline uniaxial ferromagnets, the situation is not so simple. Figure 18.6 shows the changes in the polar distribution of domain magnetizations on the magnetization curve. Starting from the demagnetized state at O where the distribution is isotropic, the magnetizations pointing in the negative direction are reversed and increase the population in the positive hemisphere as the field increases in the positive direction, as shown by the distribution at B. In this case the magnetization in the negative direction is reversed first, because the strongest pressure acts on the walls which contribute to this domain reversal. At a sufficiently strong field, all magnetizations are lined up nearly parallel to the field direction, as shown at C. This is the saturated state. As the field is reduced from point C, each domain magnetization rotates back to the nearest positive easy direction and thus covers a hemisphere at the residual magnetization point D. When the field is then increased in the negative direction, the most unstable magnetization, which is the magnetization in the positive direction, is reversed first. This results in the distribution shown at point E, where the net magnetization is zero. The intensity of the field at point E is called the coercive force or coercive field, and is a measure of the stability of the residual magnetization. Further increase in the field in the negative direction results in negative saturation. Figure 18.6 shows the equivalent magnetization process towards positive saturation from E' to C. Such a change in the distribution of domain magnetizations is different in different materials. Figure 18.6 shows the case of a uniaxial material such as polycrystalline cobalt or randomly stressed nickel. In this case, the local magnetization in zero or small fields lies parallel to the easy axis, in either the positive or negative direction. At the point of residual magnetization, the domain magnetization lies everywhere in the

472

TECHNICAL MAGNETIZATION

Fig. 18.7. Domain magnetizations at the residual magnetization of polycrystalline ferromagnet with positive Kv

positive direction of the local easy axis and the distribution covers the positive hemisphere. The value of the residual magnetization is given by

where 6 is the angle between the magnetization and the previously applied field. In fact, severely stressed ferromagnets exhibit an 7r//s value of about 50%. For cubic ferromagnets, the situation is different. If Kv > 0, the easy axes are <100>. Therefore at residual magnetization each domain magnetization lies parallel to the <100> which is the nearest to the previously applied field direction, as shown in Fig. 18.7. The largest deviation of the magnetization from the direction of the previously applied field occurs when the field was applied parallel to <111>. The deviation angle in this case is cos'1 (1/1/3) = 55°. The polar distribution of domain magnetization in this case is shown in Fig. 18.8. In order to calculate the value of the residual magnetization for any direction of the applied field, we fix the coordinate axes and vary the direction of the applied magnetic field, as shown in Fig. 18.9. When the previously applied field direction is in the area marked with concentric circles, the magnetization should remain parallel to

Fig. 18.8. Polar diagram of magnetization distribution at the residual magnetization for a cubic ferromagnet with positive K^.

the z-axis. The range of integration in (18.10.10. the magnetization remains parallel to [111] when the applied field was in the first quadrant (the area marked with circles) in Fig. is given by where <p is the azimuthal angle of the field measured from the (110) plane.MAGNETIZATION CURVE AND DOMAIN DISTRIBUTION 473 Fig. which is the residual magnetization. 18. Fig.10). and <p0 is given by . 18. Let the angle between the z-axis and the direction of the applied field be 6. and <p0 is given by Similarly. we find the residual magnetization to be where tp is the azimuthal angle about [111] measured from the (Oil) plane. and average over the circled area. If we let the angle between [111] and the applied field be 0. The average z-component of magnetization. The range of integration in (18. 18.9. in the case of K^ < 0 (easy axes parallel to <111».12).

and z-magnetizations at the residual point is parallel to the long axis of the cylinder (Fig.6. The probability of selecting the nearest easy axis is larger when there are more easy axes. 18. and /. thus increasing the magnetostatic energy. the magnetostatic energy of the free poles which appear on grain boundaries is 20-50% of that of an isolated particle. has . As we discussed in Section 17. so that the magnetization is easily reversed. In real polycrystals. while in the former case it is three. Kaya2 measured the residual magnetizations of variously oriented cylindrical single crystals of iron. y-. which is made by rolling a grain-oriented Ni-Fe alloy (see Section 13. In the above treatment. The value of the residual magnetization is influenced by the shape of the specimen. and z-axis be Ix. is given by the formula where 7S is the saturation magnetization. Isoperm. the residual magnetization is reduced by this effect. In ferromagnets with a special anisotropy.14). however. thus reducing the magnetostatic energy.12). m. Figure 18. sometimes the free poles which appear at residual magnetization reverse a part of the magnetization to reduce the magnetostatic energy. in spite of the fact that the largest deviation angle is 55° in both cases. Iy. and discovered a rule called the Imn rule or Kaya's rule: The residual magnetization. 7r. It is reported1 that Permalloy has residual magnetization as small as 7% of the saturation magnetization. the reduction of the residual magnetization is incomplete. if the cubic anisotropy is predominant.2). and n are the direction cosines of the long axis of the cylinder with respect to the cubic axes. The reason is that in the latter case the number of easy axes is four. because of the difficulty of nucleating reverse domains. and 72. Kaya explained this rule by assuming that the vector sum of the x-. domain walls will be generated to create domains of reverse magnetization. In any case. Then we have the relationships from which we can deduce (18.10).474 TECHNICAL MAGNETIZATION This value is larger than that given by (18. unless the grain size is smaller than the critical size for a single domain. respectively. where we see that the experiment is well expressed by (18. Actually. Thus the value of 7r/7s is in the range 70-90% for cubic ferromagnets. Accordingly the shape of the hysteresis loop is more rectangular than in materials with uniaxial anisotropy.11 shows the experimental plot 7r as a function of !/(/ + m + n). v-.14). Otherwise nonzero free poles appear on the side surface of the cylinder. The reason is that this alloy is magnetically very soft. unusual values of 7r/7s may be obtained. or the lack of mobility of the domain walls. Let the magnetization components parallel to the x-. we ignored the influence of free poles which may appear on the grain boundaries. Therefore.

. grain-oriented Si-steel (see Section 22.11.1. and n are the direction cosines of the cylinder axis with respect to the cubic crystal axes. so that the residual magnetization (measured after magnetizing parallel to the rolling direction) is almost zero. Fig. The orientation is expressed by !/(/ + m + n). However. Bozorth3 explained this phenomenon as follows: This alloy exhibits an induced uniaxial anisotropy as a result of the annealing (see Section 13. Permalloy annealed at 490°C exhibits an /r//s value of about 30%. where /. The relationship between residual magnetization and crystal orientation of cylindrical single crystals of iron. if the easy axis of the induced anisotropy is parallel to one of the other cubic easy axes. the domain magnetization rotates back to the nearest cubic easy axis and stays in this direction. m.1) has its easy axis parallel to the rolling direction. in addition to some cubic anisotropy with positive K^ As the field is reduced from a high value. On the other hand. 18. so that the value of 7r//s is almost 100%.1).MAGNETIZATION CURVE AND DOMAIN DISTRIBUTION 475 Fig. Distribution of magnetizations in an elongated cylindrical specimen with positive K^ (Kaya's rule). if the easy axis of the induced anisotropy coincides with this cubic easy axis. 18. (After Kaya2) its easy axis perpendicular to the rolling direction.12.

thus giving no contribution to the residual magnetization. Since the probability that the easy axis of the induced uniaxial anisotropy coincides with one of the cubic axes is f. Let the half-polar angle of the cone of the reversed magnetization be 00. the most unstable magnetization is reversed first. As seen in Fig. Then the distribution of magnetization is shown at point E in Fig. the domain magnetization which points in the positive direction is most unstable. Figure 18.476 TECHNICAL MAGNETIZATION Fig. when the field is increased in the negative direction from the residual magnetization. 18.13. Values of Ir/Is for various categories of ferromagnetic materials.6. the magnetization will split into plus or minus directions along this preferred easy axis.13 summarizes the predicted values of 7r//s for various magnetic materials. If the easy axis of the uniaxial anisotropy is distributed at random and the magnetization reversal occurs by wall displacement. 18. Since the reversed magnetization is equal to the unreversed magnetization at the coercive field. the 7r//s value becomes We expect the same situation for a sample of iron under elastic stress.6. we have the relationship so that therefore . 18. Next we shall discuss the polar distribution of domain magnetizations at the coercive field point.

4 It should be noted that this process of remagnetizing permanent magnets is effective. once it has been brought to the coercive field point. Finally the sample reaches point H.14.MAGNETIZATION CURVE AND DOMAIN DISTRIBUTION 477 Fig. But if the magnet is first magnetized and then brought to the coercive field point by applying an appropriate reverse field. except for a grain-oriented uniaxial magnet. and the coercive field is the field needed to move a 180° wall making 45° with the positive direction. are reversed first by . As shown in Fig.12MAm""1( = 1500Oe) larger than Hc. whose distribution is almost the same as that of the residual magnetization. irrespective of magnetization mechanism. Thus the half-polar angle of the cone is 45°. we need a fairly strong field to reverse the directions of domain magnetizations which are almost perpendicular to the field direction. only reversible magnetization rotation occurs from the point E to F (where H = 0). This field is about 0. 18. which is the magnetization pointing in the negative direction (point G in the diagram). Let us consider the magnetization process which may occur when the field is increased in the positive direction from the coercive field point E. which requires the application of a large field.lZMAmT 1 (=1500Oe) requires about O. it can be easily remagnetized by a relatively weak field. Next we discuss the case of a ferromagnet in which a cubic magnetocrystalline anisotropy is predominant. a Ba-ferrite magnet with coercive field Hc = O. However. When the field is increased in the negative direction from the residual magnetization to the coercive field.24MAm~ 1 (= 3000Oe) is required to magnetize to residual magnetization. For example.SOMAirT1 ( = 10 000 Oe) to magnetize to saturation from the demagnetized state. assuming uniaxial anisotropy and magnetization occurring by domain wall displacement. the most unstable domain magnetizations. which make small angles with the positive field direction. If we try to attain the same domain distribution from the demagnetized state. 18. because the field must overcome the demagnetizating field. starting from the coercive field. Further increase in H in the positive direction causes a reversal of the most unstable magnetization. Change in domain distribution during the magnetization process. only 0. A permanent magnet is often magnetized after it is assembled into a device.14.

Similarly. the magnetization reversal is exclusively performed by magnetization rotation. In the case of an assembly of single domain particles. or 0.832/s.416/s. we have the relationship from which we have Therefore the domain magnetizations in the angular range 81 = 30° to 02 ~ 60° are reversed to reach the coercive field point.478 TECHNICAL MAGNETIZATION 180° wall displacement. magnetization at an angle of 45° to H is most unstable. 18.10).15 summarizes polar diagrams of magnetization distribution at residual magnetization and at the coercive field for various categories of magnetic materials. or 0.9). and is reversed first. As will be discussed in Section 18. and its physical meaning. If we assume that domain magnetizations in the range 0j = ir/4 — s to 02 = 7J/4 + s are reversed until the net magnetization goes to zero. Thus we have the relationship from which we have Equation (18. so that half of this value. if Kl < 0.10). because 00 is less than 45° (see Fig. the coercive field state is attained when half of the residual magnetization 0.21) includes no complicated integration with respect to the azimuthal angle. the residual magnetization is 0. There are two methods of demagnetization: thermal demagnetization and AC demagnetization. must be reversed to get to the coercive field point. because 00 < 35° (see Fig. in the case of uniaxial crystal anisotropy.866/s. If /C: > 0. is reversed.3. Figure 18. 18. Finally we discuss the process of demagnetization or of obtaining zero net magnetization. Therefore we have the relationship from which we have Again the equation (18.19) does not include a complicated integration with respect to the azimuthal angle as in (18.433/s. or an elongated particle with uniaxial shape anisotropy. The former method consists in heating the .

in which the magnetization reversal takes place by wall displacement.16 shows the changes in domain distribution during AC demagnetization for a material with uniaxial anisotropy. the domain magnetizations that make large angles with the field direction are settled first. specimen above its Curie point and cooling it to room temperature in the absence of a magnetic field. The latter method consists in magnetizing the specimen with an AC (alternating current) field with a sufficiently large amplitude and then decreasing the amplitude of the AC field to zero in the absence of a DC field. Since the thermal demagnetization requires a heat treatment and accordingly is time-consuming. It should be noted that in the case of a cubic ferromagnet. The final state is an isotropic distribution as shown by the diagram at the origin. 18. Magnetization distributions at residual magnetization and at the coercive field for various categories of ferromagnetic materials.15. In order to realize a completely isotropic angular distribution. Let us consider what happens during AC demagnetization. usually AC demagnetization is used. the rate of decrease in the amplitude of the AC field should be small. In order to realize an isotropic domain distribution in . Figure 18. As the amplitude of the AC field is decreased.MAGNETIZATION CURVE AND DOMAIN DISTRIBUTION 479 Fig. AC demagnetization results in a domain distribution in which the local magnetizations are confined to a cone with a half angle of 55°.

Variation of angular distribution of magnetization during AC demagnetization.480 TECHNICAL MAGNETIZATION Fig. Similarly the displacement of the wall becomes reversible only when the wall energy varies from place to place. The wall therefore does not return to its original position after the field is removed. This situation corresponds to a sphere placed on a level surface. which has no stable position. 18. this case.2 DOMAIN WALL DISPLACEMENT When a domain wall moves in a large plate of a homogeneous magnetic material. the wall is in neutral equilibrium. then the sphere will settle in a concave depression. the surface of the plate must be uneven. AC demagnetization must be performed by using a rotating field of decreasing magnitude instead of an AC field along a fixed axis. assuming random uniaxial anisotropy and magnetization occurring by domain wall displacement. Suppose that a plane wall moves. about which position its displacement becomes reversible for small displacements. as shown in Fig. Let us assume that the wall energy per unit area. sw.17.16. 18. In order that the sphere have a position of stable equilibrium. s. keeping its shape unchanged. In other words. 18. When there is no external magnetic field. the wall must settle at the position . the wall energy is independent of its position. changes as a function of position.

and the field is applied parallel to the direction [a1. a3]. a 2 . Variation of domain wall energy with position (schematic). the magnetization component parallel to H is increased by 2/s cos 9 s. 7S.5) on the wall.DOMAIN WALL DISPLACEMENT 481 Fig. so that the magnetization of the specimen is increased by where 5 is the total area of the domain wall in a unit volume. Therefore the initial susceptibility is given by If the easy axes are {100} as in the case of iron. 18. where dew/ds = 0. this field gives a pressure p given by (18. so that the energy supplied by the field is given by The total energy is given by and we find its minimum from giving As a result of displacement. The wall energy can be expressed approximately by s If a magnetic field H is applied in the direction which makes an angle 6 with the domain magnetization.17. or the wall energy is minimum. the value of cos2 9 averaged over all the 180° walls is given by .

however. provided the total domain wall area S is the same. using picture-frame single crystal specimens cut out of a bulk single crystal of Si-Fe as shown in Fig. so that Thus we have the relationship (18. because the domain structure is not the same for the three picture-frame specimens.18. 18. 18. {110} or (111) from a bulk single crystal. (110) and (111). so that In the (111) crystal. He discovered that the initial susceptibility was not constant.33) as follows: in the case of the (100) crystal. Becker and Doring6 explained the ratio given by (18.482 TECHNICAL MAGNETIZATION Fig.31). irrespective of direction of the applied field. . domain walls are parallel to either one of the two easy axes which are closest to (110) edges. so that cos2 6= 1.33) from (18. Williams5 measured initial permeability parallel to (100).18. but varied as This result. In order to check this. domain walls are parallel to either one of the three easy axes. a 180° wall runs parallel to the edge. Therefore we expect that the initial susceptibility is constant. In the (110) crystal. the last assumption is quite doubtful. Method of cutting picture-frame single crystals with sides parallel to (100). However. is not necessarily in disagreement with the theoretical treatment given above.

we can regard the anisotropy given by (18. irrespective of the field direction.38) as remaining constant throughout the wall. so that Thus the initial susceptibility is again constant. (18.39) can be expanded near 5 = 0 as . (18. we have Thus in all the cases. s.7 This idea was developed by Kersten. although the functional form is generally different between anisotropy energy and the magnetoelastic energy.17 is the presence of randomly distributed internal stresses. easy axes are parallel to (111).31) becomes One mechanism for generating variations in wall energy as shown in Fig. 18. as The anisotropy constant therefore varies as This form is assumed for simplicity. as first pointed out by Kondorsky. When the easy axes are randomly distributed.8 whose treatment may be described as follows: he assumed that the internal stress varies as a function of displacement. Then the wall energy is deduced from (16.DOMAIN WALL DISPLACEMENT 483 In the case that K1 < 0.55) as Assuming that K1^> \a. If the wavelength of the stress variation is sufficiently larger than the wall thickness.

if we assume that a domain wall exists at every energy minimum. it follows that Using (18. the susceptibility is large when the wavelength of stress variation. Therefore the minimum susceptibility is realized when / ~ 8. /.36) According to this expression. 16. /. a~ 50kgmm~ 2 = 5 X 108 Nm~ 2 .18.41) is expressed in terms of 8 as Moreover.44). so we cannot have great faith in the calculation. 8. our assumptions of internal stress and total domain wall area are fairly arbitrary. we can estimate that JL&« 200. This is because the wall is easily displaced when the wall energy changes slowly with position.25). the effect of the stress will be smoothed over by the effect of the exchange interaction. so that the wall becomes easily movable again. giving Since there are contributions from other mechanisms such as 90° domain wall displacement and magnetization rotation. However. we can express the thickness of the domain wall approximately as so that (18.43) and (18. and z-directions. so that We can estimate the value of the initial susceptibility for iron from (18.16. If / < 8. is large.484 TECHNICAL MAGNETIZATION Comparing (18. Ordinary soft steel or iron exhibits /Za ~ 100 ~ 200.46) or Fig. When the wavelength.07 X 10~5. 7S = 2.40) with (18. and also that the wall energy varies similarly in the x-. so that this estimate seems reasonable.46) by assuming that A100 = 2. is smaller than the thickness of the wall. . we have from (18. we have Based on (16. the above calculation is not applicable. y-.

a pressure given by (18. Since s is approximately related to r and / by (18.13. Actually.9 aand Kersten10 proposed a new mechanism of reversible wall displacement as shown in Fig. 18. (18. 18. so that the wall bulges in a cylindrical form as shown in Fig.51) to give In many cases we have cos2 0= f (see (18.19. the relationship between the pressure and r leads to the formula The volume increase of the upward-magnetized domain is given by where 5 is the displacement of the wall at the center. Let us assume a domain wall pinned from place to place as shown in Fig.50) is modified using (18. however. The increase in magnetization produced by this wall bulging is where S is the total domain wall area per unit volume. The wall shown in Fig. 18. When a field H is applied in a direction which makes the angle 6 with the magnetization /s.52) leads to the susceptibility .19.48) and (18.33. 17.19.19 is pinned at the side edges but is free to bulge under the action of the field pressure. so that (18. as shown in Fig.5) acts on the wall.34) and (18. This was first pointed out by Neel. the wall is deformable.10 We assumed above that the wall is rigid and undeformable. If the radius of curvature is r. 18. 16. A 180° wall bulging under the action of a magnetic field.35)).32).DOMAIN WALL DISPLACEMENT 485 Fig.

Ni. we have the relationship Figure 18.47) for a 180° wall. Th£ mechanism described here is considered to contribute to this high initial susceptibility.486 TECHNICAL MAGNETIZATION If we assume that voids or nonmagnetic inclusions (pinning sites) are distributed in a simple cubic array with spacing /. which is given by (16. varies with the displacement s as shown in Fig. When a field is applied. In order to describe the temperature dependence of the wall energy.5)). further increase in . Suppose that the wall energy.15)). Kersten10 treated this phenomenon. he assumed that the exchange stiffness constant. Therefore the wall energy changes with temperature as Using this expression in (18.21.20 shows the temperature dependence of x* for Fe. the initial susceptibility increases with increasing temperature and exhibits a sharp maximum just below the Curie temperature. A. or because A is proportional to S2 (see (16. let us treat a rigid plane wall. the wall displaces irreversibly and does not return to its original position even after the field is removed.53) leads to In the case of iron. is proportional to 7S2. a pressure acts on the wall (see (18. ew. y = 1. When the field becomes strong enough to drive the domain wall out of the stable pinned region. and we can assume from the observation of domain patterns that / = 10 ~ 4 (m). so that we have Well-annealed pure iron exhibits xa ~ 10 000. which displaces without any deformation.6 X 10 3. which displaces until the restoring force becomes equal to the pressure.15 (Wbm 2).59). This phenomenon is called the Hopkinson effect. 7S = 2. 18. For simplicity. and Co fitted to formula (18. Excellent agreement is seen. or If the wall reaches the point sl where the gradient is maximum. we have Then (18.53). Generally speaking.

60) is satisfied for a new field. 18. at which the wall is swept out of the crystal is determined by the maximum gradient of the curve in Fig. Positional variation of the wall energy and the irreversible displacement of the wall. so that we have If we assume that the variation of the wall energy is caused by variations in the Fig. where K = Kl +K2 for cobalt.20.10 field intensity causes an irreversible displacement of the wall to the next equilibrium position.59)). 18.21. Solid curves represent the theory (see (18. . 18. s2. but not to the original position. s3. where the condition (18. Thus the critical field. s0.21. the wall comes back to the nearest stable point.DOMAIN WALL DISPLACEMENT 487 Fig. H0. cobalt and nickel. Further increase of the field will bring the wall to the next equilibrium position. If the field is reduced to zero. Temperature dependence of the relative initial susceptibility for iron.

and also we adopt a maximum internal stress cr0 = lOOkgmrcT 2 = 109 NnT 2 . Figure 18. The radius of curvature of the cylindrical wall. Next we shall discuss the critical field for a pinned domain wall. so that the radius of the wall decreases as H is increased.23 shows the cross-sectional view of a domain wall with both ends pinned. the maximum gradient of the wall energy is given by where S is the wall thickness (see (18. the wall bulges under the action of the pressure (18. For H = 0. Therefore the critical field is obtained by putting r = 1/2 in (18.64). so that the numerical value of (18. the wall is plane (curve a). Further increase in H causes an increase in r.61). which. the wall energy is maximum when / ~ 8.39).48). we have As already mentioned. Therefore we have For ordinary ferromagnets. is inversely proportional to H as shown in (18. Kersten11 measured the coercive field of Ni as a function of the internal stress (see Fig.63) also becomes maximum. Both curves agree well with (18. we assume that A = 10 5. does not satisfy the equilibrium condition (18.5) as shown by curves b and c. cos0~l.22). Curve a shows the result for a Ni wire which was stretched plastically by various amounts. where sw = j. is increased. however. H. up to curve c where the radius r is equal to half the distance between the two pinned points.48). Using this expression in (18. so that H0 (18.48) to give . r. while curve b is for a cold-rolled Ni plate that was annealed for various lengths of time to release the internal stress.42)).488 TECHNICAL MAGNETIZATION internal stress as shown by (18.64) becomes which is about the average coercive field of alloy permanent magnets. so that the wall must expand irreversibly to the next pinned points. 18. As the field. 7S = 1T.

In this model. 18. Assuming that / = 10~ 5 (= 10~3 cm). Kersten10 explained the composition dependence of the coercive field in Fe-Ni alloys and also the temperature dependence of Hc of Fe. 18. as shown in Fig. and is independent on the pinning strength. 18. Suppose that the pinning points are arranged in a simple cubic array with spacing /.32. Reversible and irreversible expansion of a wall with both ends pinned by voids. However. . (b) cold-rolled Ni plate annealed for various lengths of time.23. if the pinning is not so strong.22. Under the action of the Fig. the critical field is exclusively determined by the distance between neighboring pinning points. Kersten assumed in this paper that a dislocation may be a possible pinning site.DOMAIN WALL DISPLACEMENT 489 Fig. if the pinning is strong enough. and a wall is trapped in a (100) plane. In any case. Relationship between coercive field and internal stress for nickel:11 (a) Ni wire plastically elongated by various amounts.23 and expanding irreversibly. the wall will pull free of the pinning site before reaching position c in Fig. the pinning mechanism is considered to be voids or nonmagnetic inclusions. 17.

88) for At/. H0 on the angle. if the interval between Fig. Dependence of the critical field.490 TECHNICAL MAGNETIZATION field. The critical field in this case is given by the condition or If we use (17. H. Let the energy of pinning be At/ at each pinning site.24. 00. Therefore the irreversible expansion of the wall will occur before the wall leaves the pinning points. (18. . However. the wall bulges in a cylindrical form. the wall will leave the pinning point. and if this value exceeds At/. 18. Then the energy of the field is reduced by 2/s/f cos 912r. between the field and easy axis of the uniaxial anisotropy (see (18. Suppose that the wall is displaced by the radius r of the pinning point under the action of the field H.67) becomes which is much smaller than (18.69).71)).

Magnetization rotation away from an easy axis. the critical field is proportional to I/cos 6.3 MAGNETIZATION ROTATION If a ferromagnetic medium contains no domain walls or only immobile domain walls. Generally speaking. 18. the critical field is given by which is shown graphically in Fig. the domain magnetization 7S rotates from the easy axis by the application of a magnetic field H. roll magnetic anisotropy. As shown in Fig. First we discuss reversible magnetization rotation. the wall leaves the pinning points before the irreversible expansion point is reached. the domain magnetization 7S rotates from the easy axis to a direction which makes the angle 9 with the field (Fig. and rotates back to the easy axis reversibly upon removal of the magnetic field. This is equal to Kul for uniaxial magnetocrystalline anisotropy. This mechanism is called magnetization rotation. and shape magnetic anisotropy of elongated precipitates. 18.25.25. Let this value be H0 y . and equal to f ACT for magnetoelastic energy due to stress a. for uniaxial anisotropy. H0 is smallest when the field is applied parallel to the easy axis. 18. a uniaxial anisotropy can arise from various induced anisotropies such as magnetic annealing. for domain wall displacement.24. and the applied magnetic field H makes an angle 90 with the easy axis. 18.25). . The equilibrium direction of magnetization can be found by minimizing the energy (18. it can be magnetized only by rotation of the domain magnetization. Moreover. The energy density in this case is given by where Ku is the uniaxial anisotropy constant. giving Fig. Thus the critical field is larger for larger 00.72) with respect to 0.MAGNETIZATION ROTATION 491 the pinning points is smaller by two orders of magnitude. 18. For instance. If the magnetic anisotropy is uniaxial. then when the field makes an angle 00 with the easy axis.

26. It is interesting that for 00 = 30° and 60°. with almost no residual magnetization.492 TECHNICAL MAGNETIZATION Fig.74).26). for Isoperm.26. Numerical values are the angles between the field and the easy axis. we have from (18. decreases as seen in the magnetization curves calculated from (18. the residual magnetization increases.75).26. . we have which is a linear magnetization curve (see Fig.1).73) where p=IsH/Ku. Such linear magnetization curves are observed for a stretched nickel wire (A < 0). the magnetization decreases along the same linear curve. for which the magnetization saturates completely at H = 2KU/IS.9). and for a Co single crystal with the c-axis perpendicular to the magnetic field. or the susceptibility. which is a cold-rolled grain-orientated Fe-Ni alloy (see Fig.73) Putting this in (18. 13. in contrast to the case of 00 = 90°. As 00 is reduced. Putting cos 6 = x.74) in Fig. 18. 13. for a Permalloy wire annealed with an electric current flowing through itself (see curve c in Fig. For the case in which 00 = 90°. Magnetization curves due to magnetization rotation against the uniaxial anisotropy. the magnetization does not saturate. Solving for x in (18. 18. 18. 18. we have The magnetization curve can be obtained by plotting x as a function of p as shown in Fig. while the slope of the magnetization curve. we have from (18. When the magnetic field is removed.

there is no doubt that domain wall displacement contributes to the mechanism of magnetization at low fields.85).MAGNETIZATION ROTATION In very weak magnetic fields (H <.73) becomes or The initial susceptibility is obtained from (18. KU/IS\ 8 ~ 60. much larger than the value given by (18. so that the initial susceptibility is given by In the case of negative Kl the anisotropy energy is expressed as — (2.72) is expressed as Ku&62. (18. If we put 493 the anisotropy energy in (18.79) we have In the case of cubic anisotropy with positive KI} the anisotropy energy is expressed as .K\A0 2 as shown in (12. the susceptibility due to wall displacement is quite structure- .2 X 104 / m~ 3 .55).82) becomes For iron in which 7S = 2. As mentioned in the previous section. so that the initial susceptibility is given by In the case of a random distribution of the easy axes.52). so that (18.K\/3)A02 as shown in (12.84) gives Since iron usually exhibits relative initial permeability of 100-200.75) as so that from (18.15 T and Kv = 4. so that condition (18. sin2 0 0 = f.

the relative permeability of Fe-Ni alloys depends upon the heat treatment: The maximum value of about 10 000 is observed at 22% Fe. At 19% Fe the magnetoelastic anisotropy is zero irrespective of stress.1. while K1 = 420 Jm~ 3 (see the curve for the disordered state in Fig. Furnace cooling means cooling from 1000°C in the furnace. Thus the high permeability is not due to magnetization rotation.27. so that it can increase indefinitely by improving the homogeneity of the material. Annealing means prolonged annealing below 500°C after annealing at 1000°C. Initial permeability of Fe-Ni alloys (After Bozorth12).494 TECHNICAL MAGNETIZATION Fig. 18. Double heat treatment means that the specimen was annealed for 30 min at 1000°C. 12. This value is too large to permit such a high permeability. we can calculate the value of K using (18. and then quenched on a copper plate kept at room temperature. as follows: In Fe-Ni alloys K^ is zero at 24% Fe. and 7S = 1. At 24% Fe. Therefore we must consider wall displacement. Assuming that this value is due to magnetization rotation. This value of stress is about 1% of ordinary working stresses. On the other hand. and A is zero at 19% Fe. 14.84) with JLa = 10000. the susceptibility due to magnetization rotation depends only on the magnitude of magnetic anisotropy and is insensitive to the homogeneity of the material.35).27. as discussed previously. .11) which means a stress cr less than 3 X 106 Nm~ 2 = 310gmm~ 2 is needed in order to produce a magnetoelastic anisotropy less than 32Jm~ 3 . Thus we can say that the susceptibility due to magnetization rotation is the lower limit of the initial susceptibility. where K^ is almost zero. 18. while A = 7 X 10~6 (see Fig. Kl = 0. As shown in Fig. cooled slowly to 600°C. sensitive.

Next we discuss irreversible magnetization rotation. the alloy must be annealed at 1000°C for 30min. thus resulting in easy rotation of magnetization locally.28 shows an elongated single domain particle whose long axis makes an angle 6Q with the Ac-axis.27. an induced anisotropy Ka{ with the easy axis randomly oriented is produced. while in single domain particles.28. Therefore the high permeability is reduced. By this treatment. irreversible magnetization occurs by magnetization rotation. there is another possibility involving magnetization rotation: As explained in Chapter 13. with the easy axis in the direction of the long axis of Fig. In order to obtain high permeability.MAGNETIZATION ROTATION 495 However. and then quenched at a moderate rate to room temperature (double heat treatment). In ordinary ferromagnetic materials. 18. with the magnetic field. irreversible magnetization takes place by domain wall displacement. For uniaxial anisotropies other than shape anisotropy. Irreversible magnetization rotation in an elongated single domain particle. 18. This local anisotropy cancels the cubic anisotropy from place to place in a composition range where K! « Kuf. the treatment is the same. P . First we treat the case of uniaxial anisotropy. The energy density of this system is given by The equilibrium direction of the magnetization is obtained by minimizing this energy. as seen in the dashed curves in Fig. 6. is applied in the -x-direction. directional order develops in this alloy system. Further annealing or slow cooling results in the development of directional order. thus creating a uniaxial anisotropy much larger than the cubic anisotropy. creating an induced magnetic anisotropy Kuf which stabilizes the magnetization parallel to its direction during annealing. 18. the spontaneous magnetization rotates to the direction which makes the angle. Figure 18. giving E Fig.28. H. cooled slowly down to 600°C. When a magnetic field. This picture can explain why such a high permeability is obtained reproducibly in a definite composition range.

and it is unstable when With increasing field H.496 TECHNICAL MAGNETIZATION When this is a stable equilibrium.89) can be expressed as Squaring both sides of the two equation in (18. or the critical field.88). which is given by . In other words. We see that p.29.92) we can solve for sin20 0 from (18. the magnetization rotates. we have an equation for sin2 6 from which we have Using (19. the magnetization changes from a stable to unstable equilibrium. increasing the angle 6. At this instant. so it must be that Differentiating (18. and adding them together.90). this condition gives Equations (18.88) and (18. when the field makes the angle 45° the magnetization reversal occurs at the smallest critical field.90). to get This relationship between p and 00 is shown graphically in Fig. and then suddenly rotates towards the —^-direction. H0. 18. is minimum when 00 = 45°.

Since the functional form of the anisotropy is more complex. H0. so that the total energy is given by . the total energy of the system is given by O Therefore the critical field can be solved by the conditioi O and Solving these two equations. the situation is not so simple. we have Next we shall consider the case of cubic anisotropy. Dependence of the critical field. we have the critical field In the case of negative K^.93)). The critical field becomes larger as 60 deviates from 45°. Since the anisotropy energy with positive Kl is approximately expressed by (12.MAGNETIZATION ROTATION 497 Fig. on the orientation of the applied field (refer to (18.29.55) when /s is close to an easy axis. We discuss only the case in which the field is applied opposite to the magnetization pointing parallel to one of the easy axes.52). the anisotropy energy is given by (12. At 00 = 0° or 90°. 18.

so that the magnetization is described by where /j and Hl are the amplitudes of / and H. we expect a reasonably good permanent magnet material. In the common ferromagnets 7S = 1~2T. the magnetization is well approximated by the first term. and K^ = 104 ~ 10s JnT 3 . The upper half of the loop can be described by The value of 7: can be obtained by putting / = Jj at H = Hlt to give . respectively. When H is decreased. the second term changes its sign. Thus if such an irreversible rotation magnetization is realized. the second term becomes significant because of the appearance of irreversible magnetization.4 RAYLEIGH LOOP In or near the demagnetized state the magnetization caused by the application of a weak magnetic field can be described by where xa 's ^he initial susceptibility and 17 is the Rayleigh constant. 18. the magnetization changes along a loop as shown in Fig.498 TECHNICAL MAGNETIZATION From the conditions for neutral equilibrium and we have the critical field Thus the magnitude of the critical field for irreversible magnetization rotation is the order of K/IS. so that H0 = 104 ~ 105 Am" 1 (= 102 ~ 103 Oe). In the lower half of the loop. Therefore if H is oscillated about the origin. which starts at point B. In the reversible magnetization region where H is small. 18. the magnetization changes approximately as given by (18. This phenomenon was investigated by Lord Rayleigh13 a long time ago.104). With increasing amplitude of H. These values are in the range for permanent magnet materials.30.

Rayleigh loop.105) and (18. we find that the phase of the fundamental waveform of / is shifted by the angle 8. it is a . Figure 18.30. because it causes not only power losses but also a distortion of the waveform.RAYLEIGH LOOP 499 Fig. and also there appears a third harmonic wave sm3a)t.112) is called the Klirr factor. The hysteresis loss is calculated to be which shows that the loss increases rapidly with an increase of the amplitude //j. The quantity k given by (18. and has a nonzero value when there is hysteresis loss.106) as ascending pa: desebnding pa These curves are called the Rayleigh loop. Using (18. By analyzing this waveform. The appearance of this hysteresis loop is undesirable for magnetic cores. we can rewrite (18. Thus the flux density B is expressed by Calculation shows that and The quantity tan 8 is called the loss factor. 18.31 shows how the waveform of / is distorted by the Rayleigh loop when a pure sine wave of H is applied.107).

Distortion of the wave form of magnetization by the Rayleigh loop when a pure sinusoidal field is applied. measure of the third harmonic relative to the fundamental frequency. Let us consider the mechanism in terms of wall displacement. and displaces discontinuously from the maximum to the next positive slope. so that we can postulate that f(H0)) is a constant. The critical field to get over a maximum. As discussed in Section 18.500 TECHNICAL MAGNETIZATION Fig. On the other . the longer the jump in each discontinuous displacement. If the field is increased from H to H+dH. the number of walls which are released should be proportional to /„ dH. In Fig. At H= 0 the wall stays at a point. similar to the Gaussian distribution function centered at HQ = 0. The only difference is that the amplitude of the field is very small in the case of the Rayleigh loop. where /(//„) is a function of H0. The reason is that the maxima which are lower than those that have already been surmounted by the wall are no longer effective in stopping the wall. In the present case. HQ is limited to a small range. for then the voltage induced by the third harmonics is shorted in the delta circuit. where dew/ds = 0.61). the wall is held at the place where condition (18. Let the number of maxima that have critical fields between H0 and H0 + dH0 be /(//0)d//0. Now we can derive the second term in Rayleigh's equation from this model. The presence of the third harmonic is harmful because it not only distorts the waveform but also gives rise to a loss if three-phase AC lines are delta-connected. say to B. With an increase of the field. the point rises along the slope. H0. ds^/ds is plotted as a function of the displacement s. 18. say A. It should be noted that the stronger the field.60) is satisfied. 1831.2. The origin of the Rayleigh loop is the same as that of the ordinary hysteresis. With further increase of H.32. the point displaces from B to C -» D -> E. say /0. is given by (18.

Irreversible displacement of domain wall along the Rayleigh loop. The shape of the loop AEFK closely resembles the shape of a Rayleigh loop. all the magnetizations are . When the field is decreased from the point E in Fig. Preisach14 explained the Rayleigh loop by regarding the magnetic material as an assembly of units. Figure 18. I. each of which exhibits a shifted hysteresis loop with different values of half-width a and shift b. The irreversible magnetization caused by the change from 0 to H is thus given by which is Rayleigh's second term. while the ordinate corresponds to the magnetic field. Therefore the minor loop LMNO in Fig.32 is the displacement of the wall. . 18. The abscissa of the graph in Fig. and K.32. 18.RAYLEIGH LOOP 501 Fig. where in the region b > a above the line OA.32 corresponds to the shifted rectangular hysteresis loop as shown in Fig.(see Fig. Here + means that the magnetization of the unit points the + direction. so that it corresponds to the magnetization. 18. Figure (a) shows the demagnetized state.33). each displacement jump is proportional to the number of maxima with H0 less than the applied field H.34 shows the states of magnetization of these different units. hand. 18. H. the point displaces reversibly along the curve to F and then jumps to G.33. all the magnetizations are +. or The irreversible magnetization should then be proportional to (number of displaced walls) X (one jump of irreversible displacement) or where c is a proportionality factor. 18. J. while in the region b < a below the line OB. 18. while — means the magnetization points in the — direction.32.

34 (b)). A shifted rectangular hysteresis loop. 18. .33. Changes in magnetization with field according to the Preisach model.34.502 TECHNICAL MAGNETIZATION Fig. Now we apply the field Hl in the + direction. reversing the — magnetization below the Fig. 18. 18. so that the boundary lines AOB are shifted by H^ to A'O'B' (see Fig.

32. 18.5 LAW OF APPROACH TO SATURATION Under a moderately strong field. ferromagnetic materials are generally magnetized to their saturated state. It is the rate of increase of jua by an increase in the amplitude of H.104).13 3. Then the component of magnetization in the direction of the field is given by . In this case.014 0.6 0.32 0. It is also possible to regard the Preisach model as an assembly of small magnetic particles with various rectangular hysteresis loops. or to H2 (see Fig.1. 18.1 200 4300 150000 0.0005 0. Let the angle between magnetization and the magnetic field be 6.41 0.0013 Wh f o r A / = l ( r 4 T = 1/477 gauss /uJm 3( X10/xerg cm 3) 2.34 (c)). The magnetization reversal occurs from one end of the triangular area. line O'B' to +. 18. where all possible wall displacements have taken place and the magnetization is pointed almost parallel to the applied field.00002 Iron Fe powder Cobalt Nickel 45 Permalloy 4-79 Mo Permalloy Supermalloy 45-25 Perminvar 200 30 70 220 2300 20000 100000 400 * The value of 17 measured in units of f i a .34 (c). the shift b is caused by the magnetic interaction from the neighboring particles. This corresponds to the Rayleigh relationship given by the second term in (18.34 (f)).013 0. and the magnetization change is proportional to the area of AO'C'O"". thus resulting in an increase in the number of — magnetized units.25 0. In this section we examine the rotation of the magnetization under such circumstances. If the field is decreased to —H^ the boundary lines are shifted to A"O"B" (see Fig. The parameters of Rayleigh loops measured in various magnetic materials are listed in Table 18. The Preisach model is essentially the same as the explanation given above with respect to Fig.1. If the field is changed back and forth between H^ and — H^ magnetization changes only in the shaded triangular area O'C'O" shown in Fig.LAW OF APPROACH TO SATURATION 503 Table 18. 18. 18.0001 0. Parameters of Rayleigh loops Material /Za 15 TJ* 103 per Am Hper —— Oe) 4ir 25 0.

118) in (18. where (6. Rotation of magnetization against the magnetic anisotropy.116). it can be found from (18.504 TECHNICAL MAGNETIZATION Fig. Since the magnetization rotates along the maximum gradient of the anisotropy energy in the vicinity of H. Since £a is normally . we have where Now we solve for the actual form of C for cubic anisotropy. The torque exerted by the magnetic field is counterbalanced by the torque resulting from the magnetic anisotropy (see Fig.117) to be where On substituting (18. tp) are the polar coordinates of the magnetization. Since 6 is very small. 18.35): where E& is the anisotropy energy.35. 18.

. a3 = cos 6. a2 = sin 8 sin q>. a 2 > as) °f magnetization.5).LAW OF APPROACH TO SATURATION 505 expressed as a function of the direction cosines («1. <p) by a1 = sin 6 cos <p. and Then (18.122) becomes If we adopt the first term of (12. which are related to (6.

The experimental points are well fitted by straight lines. instead of measuring / itself. Czerlinsky17 measured dl/dH in the high-field region. because in the latter method a small error in the measurement of / may have a fatal influence on the determination of a and b in (18.129).128) the values of Kv We obtain (at room temperature) These values are in fair agreement with the values given in (12.506 TECHNICAL MAGNETIZATION Then (18. 18.36 and 18.129). we have Figures 18. \oH. averaging over the all possible orientations of the individual On putting this in (18.36 and 18.7).124) becomes For a polycrystal. is caused by an increase of the spontaneous magnetization itself. a/H. obtained by experiment. From (18. A close inspection of the graphs in Figs.121). Using the values of b thus determined we can calculate from (18. This means the presence of the a/H term. has been discussed by many investigators.6) and (12.37 show dl/dH as a function of 1/H3 for iron and nickel. The first term.37 reveals that the experimental points deviate from the linear relationship near the origin.129). This means that the experiments are well described by the b/H2 term in (18. This term cannot be explained in terms of a uniform . as we shall see later. is The last term. The law of approach to saturation. we obtain This result coincides with that obtained by Becker and Doring16 by an entirely different method.

4. small spike domains. For instance. The same thing is also expected for the magnetization surrounding a special precipitated particle producing an exchange anisotropy (see Section 13.LAW OF APPROACH TO SATURATION 507 Fig. because this leads to the b/H2 term. which remain around voids at high fields. as shown by Thus we must conclude that the term a/H is valid only within some finite range of field strength.36. Law of approach to saturation for iron (Czerlinsky17).120). As pointed out by Neel. while Neel19 interpreted it in terms of nonmagnetic inclusions and voids. if the expression including the a/H term is valid to infinitely strong magnetic fields. as already discussed in (18. so that here we show only the basic ideas of the two interpretations. we must assume the presence of a restoring force which increases as the magnetization approaches saturation. Both calculations are very complicated. If local internal stresses caused by dislocations or lattice vacancies fix the direction of the local magnetization firmly. the work necessary to magnetize the specimen to complete saturation diverges. . 18.1). Since a constant restoring force or torque leads to the b/H2 term. will diminish in volume with increasing field strength up to a demagnetizing field of the order of /s/ju. the magnetization surrounding these points will form transition layers which are similar to an ordinary domain wall. magnetization rotation. Brown18 explained the a/H term as the result of the stress field about dislocations.0.

508

TECHNICAL MAGNETIZATION

Fig. 18.37. Law of approach to saturation for nickel (Czerlinsky17).

The thickness of such a transition layer decreases with increasing field strength. In both cases, the change in magnetization is first proportional to 1/H1/2 and finally to 1/H2. It is naturally expected, therefore, that the change becomes proportional to l/H in an intermediate field range. In any event, the magnitude of the term a/H is expected to be a good measure of the inhomogeneity of the magnetic material. Fahnle and Kronmuller20 treated such a problem for amorphous ferromagnets where spatially random magnetostatic, magnetocrystalline, magnetostrictive and exchange fluctuations all are present. Finally we discuss the last term, ^0//, in (18.129). This term arises from an increase in spontaneous magnetization produced by the external magnetic field. According to the Weiss theory, the change in spontaneous magnetization by the external field is given by (6.14), so that the high-field susceptibility ^0 is given by

where L(a) is the Langevin function (see (5.20)). Experimentally, the value of %o can be obtained from the extrapolation of the curve to the ordinate in Figs 18.36 and 18.37. The experimental values thus obtained are normally about ten times larger than the value calculated by (18.133). These values were found to be dependent on the impurity level of the materials. When the specimen is purified, the value is considerably reduced. Becker and Doring21 considered the reason to be that the spins in the impurities or the spins of the matrix separated by impurities will be thermally agitated more than the spins in a pure material, giving rise to the large value of Xo-

SHAPE OF HYSTERESIS LOOP 18.6 SHAPE OF HYSTERESIS LOOP

509

As discussed above, there are various mechanisms by which materials may be technically magnetized. The shape of the hysteresis loop depends on the predominant mechanism. The simplest case may be an assembly of randomly oriented single-domain uniaxial ferromagnets, such as a random aggregate of elongated single-domain particles. Since there are no domain walls in the single-domain particles, all the technical magnetization must take place by magnetization rotation. Reversible magnetization rotation was discussed in Section 18.3, and the resulting magnetization curve is given in Fig. 18.26. When the magnetic field is reversed, an irreversible rotation of the magnetization occurs at a critical field given by Fig. 18.29. By combining the two magnetization processes, the hysteresis loop for a single-domain particle whose easy axis makes an angle 00 with the external field can be constructed, as shown by the curves in Fig. 18.38 for different values of 60. In these curves, the curved portions correspond to reversible magnetization and the vertical jumps correspond to irreversible magnetization rotation. It is interesting that for 00 > 45° the reversible magnetization is predominant, so that even after a fairly strong negative field brings the magnetization to a negative value, the magnetization returns to a positive value when the field is removed (see the curve denoted by 70° in Fig. 18.38). If an array of such single-domain particles are oriented randomly, the hysteresis loop of the assembly is obtained by averaging the individual hysteresis loops in Fig. 18.38 to give Fig. 18.39. In this graph the solid curves represent reversible magnetization rotation, while the dashed curves represent irreversible magnetization rotation.

Fig. 18.38. Hysteresis loops due to magnetization rotation of variously oriented single domain particles with uniaxial anisotropy.

510

TECHNICAL MAGNETIZATION

Fig. 18.39. Hysteresis loop of an assembly of randomly oriented single domain particles with uniaxial anisotropy, calculated by averaging the loops in Fig. 18.38.

In the field range H> —KU/IS, magnetization takes place exclusively by reversible magnetization rotation. Therefore, if the magnetic field is reduced from the coercive field to zero, the magnetization returns reversibly to the residual magnetization (/r = 0.5/s). In this model, the critical field H0 is a unique function of the direction 00 of the elongated particles. In real materials, the critical field depends more or less on the nature of the particles; the hysteresis loop for real magnetic materials can be obtained by averaging many loops with different scale factors of the abscissa of Fig. 18.39. Thus some irreversible magnetization occurs in the second quadrant, and the ideal reversible rotation as mentioned above may not be observed. A difference in behavior between particles of different sizes may be the main reason why H0 depends on the nature of the particles. Moreover if the size is too small, H0 can be reduced by thermal fluctuations (see Section 20.1). Various parameters for the hysteresis loop in Fig. 18.39 are listed below: Residual magnetization Coercive field Maximum susceptibility Hysteresis loss Next we discuss the hysteresis loops of uniaxial materials in which the magnetization reversal takes place exclusively by the displacement of domain walls. This magnetization mechanism was discussed in Section 18.2. When the magnetic field is applied exactly antiparallel to the direction of magnetization, we assume that the

SHAPE OF HYSTERESIS LOOP

511

Fig. 18.40. Hysteresis loops due to reversible magnetization rotation and irreversible displacement of domain walls for variously oriented multi-domain particles with uniaxial anisotropy.

magnetization reversal takes place at the critical field H0 „ . The critical field when the easy axis makes an angle 00 with the magnetic field is given by (18.71), and the hysteresis loops for various 00 are shown in Fig. 18.40. The small irreversible displacements of domain walls prior to the main magnetization reversal appear as small vertical steps in the curves. Assuming that the directions of the easy axes are randomly oriented, the resultant hysteresis loop is calculated to be as shown in Fig. 18.41. In this figure, the solid curves correspond to reversible rotation of the magnetization; the dashed curves correspond to irreversible magnetization; and the dotted curves correspond to small irreversible displacements of the domain walls. The unit of the scale of the abscissa is H0]]. The coercive field of this average hysteresis loop is 1.3HQll. The reversible magnetization rotation is determined by the value of KU/IS, irrespective of the value of //0||. The hysteresis loop in Fig. 18.41 is drawn by assuming H0]l = 0.2KU/IS. In this graph, the curve in the second quadrant is due to irreversible displacement of the wall. Various parameters of this hysteresis loop are as follows: Residual magnetization Coercive field Maximum susceptibility Hysteresis loss

512

TECHNICAL MAGNETIZATION

Fig. 18.41. Hysteresis loop of an assembly of randomly oriented multi-domain particles with uniaxial anisotropy, calculated by averaging the loops in Fig. 18.40.

Let us consider the magnitude of the residual magnetization after applying a magnetic field, H, to an assembly of elongated particles and reducing the field to zero. If the magnetization reversal occurs by domain wall displacement, the magnetization reversal occurs first in particles with 00 = 0. But if the magnetization reversal occurs by rotation of the magnetization, the magnetization reversal occurs first in particles with 00 = 45°. Figure 18.42 shows the dependence of residual magnetization (normalized to the saturation magnetization) on the previously applied field (normalized to the minimum critical field // min ) for two mechanisms of magnetization reversal. It is seen that the initial rise is steeper for magnetization rotation than for domain wall displacement. The reason is that the population of particles with 00 = 45°

Fig. 18.42. Residual magnetization (normalized to saturation magnetization) as a function of the previously applied magnetic field (normalized to the minimum critical field), calculated for two magnetization mechanisms.

SHAPE OF HYSTERESIS LOOP

513

Fig. 18.43. Hysteresis loop calculated for cubic magnetic materials (K1 > 0). is much larger than that with 60 = 0. Such a sharp rise in residual magnetization is desirable to increase the sensitivity in magnetic recording. Next we consider the case in which the cubic anisotropy is predominant. As shown in Fig. 18.15, in the condition of residual magnetization the spins lie within an angular range 6 ^ 55°. The critical field for domain wall displacement must be Therefore the magnetization reversal will take place more easily than in the case of uniaxial anisotropy. Accordingly the shape of the hysteresis loop is expected to be more rectangular. Assuming that the cubic crystallites are randomly oriented, and that all the magnetization reversals are performed by 180° wall displacement, we have the average hysteresis loop as shown in Fig. 18.43. This is the case where K1 > 0, but the shape of the loop is not very different for K1 < 0. We assume that H0 is the same for all the crystallites, and also that none of the 90° walls contribute to the magnetization reversal. Even so, Fig. 18.43 well reproduces the common hysteresis loop of cubic metallic magnetic materials. Various parameters of this hysteresis loop are listed below: Residual magnetization Coercive field Maximum susceptibility Hysteresis loss

514

TECHNICAL

MAGNETIZATION

Fig. 18.44. A snake-shaped or constricted hysteresis loop. (After Taniguchi22)

If the coercive field is determined by the internal stress, we have from (18.64)

Using this relationship, we find the hysteresis loss in (18.137) is expressed as In spite of the assumption that the cubic anisotropy is predominant, the expression in (18.139) does not include K^ This is because the coercive field in this case is determined by internal stresses and not by cubic anisotropy. On the other hand, the expression for Wh in (18.134) does include Ku, because the magnetization reversal in this case occurs by irreversible rotation magnetization against the uniaxial anisotropy. Comparing Fig. 18.43 with Fig. 18.41, we see that the hysteresis loop for cubic materials is more rectangular than that for uniaxial materials. This results from the fact that the residual magnetization is larger for cubic materials than for uniaxial materials (see Fig. 18.13). From the 7r//s values, we can deduce the shape of the hysteresis loop. In some special materials, the snake-shaped or constricted hysteresis loop shown in Fig. 18.44 appears. This phenomenon is often observed for alloys or mixed ferrites which are strongly affected by magnetic annealing (see Section 13.1). The real mechanism is as follows: when these materials are cooled in the absence of a magnetic field, a magnetic anisotropy with its easy axis parallel to the local magnetization is induced. This is also the case even inside the domain walls, where the direction of magnetization changes gradually. As a result of stabilizing the direction of the spins by the local induced anisotropy, the wall is stabilized in the position it occupied during the anneal. When the magnetic field is strong enough to drive the wall from its pinned position, the magnetization is driven irreversibly to saturation22 (see Fig. 18.44). In order to avoid this effect, the material must be cooled in a strong magnetic

SHAPE OF HYSTERESIS LOOP

515

Fig. 18.45. Schematic illustration of the experimental determination of rotational hysteresis loss. The torque must be measured over an angular range of more than 180°, and the loss is determined from the area between two torque curves in the interval between 0 and 180° (see the shaded area).

field that removes all the domain walls, or in a rotating magnetic field that does not allow atoms or vacancies to occupy permanent preferential positions. Hysteresis loss is caused by irreversible displacement of domain walls and/or by irreversible magnetization rotation. In order to separate these two effects, the measurement of rotational hysteresis loss is useful. When torque is measured as a function of angle of rotation by means of a torque magnetometer (see Fig. 12.9) for polycrystalline or powder specimens, the energy loss resulting from irreversible magnetization rotation appears as a torque opposing the rotation of the sample. That is, energy loss produces a negative torque for positive direction of rotation, and vice versa. Therefore, the integral of torque with respect to angle of rotation over one revolution,

becomes nonzero. This value is equal to the energy loss per unit volume of the specimen during one rotation and is called the rotational hysteresis loss. In practice, the value of WT can be measured by rotating the field back and forth between the angles of —40° or less and 220° or more, and measuring the area between the two torque curves between 0 and 180° (see the shaded area in Fig. 18.45). There is no contribution to this hysteresis loss from the irreversible displacement of domain walls, because no domain walls exit at the relatively high fields used in this experiment. Rotational hysteresis appears only when the field intensity is moderately strong: in a weak field magnetization cannot follow the rotation of field, while in a field stronger than the anisotropy field (see Section 12.2) magnetization rotation occurs reversibly. The form of the Wr vs. H curve depends on the model of magnetization reversal, which is characterized by a quantity called the rotational hysteresis integral

516

TECHNICAL MAGNETIZATION

The experimental value of this integral indicates that in the case of electrodeposited elongated single-domain particles the magnetization occurs by a non-uniform rotation rather than a uniform rotation of magnetization.23

PROBLEMS

18.1 Calculate the value of 7r//s for an assembly of elongated single domain particles randomly oriented in a plane. 18.2 In a ferromagnet with cubic crystal structure and K1 > 0, many voids are distributed in a face-centered cubic array with the cube edge length a. Find the critical field in [110] for a 180° wall separating x and x domains. Assume that the pinning by the voids is sufficiently large that the wall will expand irreversibly before it leaves the pinning points. Denote the wall energy by y180o, and the spontaneous magnetization by /s. 183 The initial susceptibility measured parallel to the c-axis of a cobalt single crystal is Xa = 20, and that measured perpendicular to the c-axis is xa = 5. What values can we expect for the directions 30°, 45°, and 60° away from the c-axis? What value can we expect for a polycrystalline sample made from the same material? 18.4 Suppose that elongated single domain particles are randomly distributed in the x-y plane (assume that all the particles are held parallel to this plane). A magnetic field slightly stronger than H = /s/4/j,0(= TT!S in CGS) is applied parallel to the -t-x-direction, then rotated towards y-, —x-, —y-, and finally back to the +*-direction, where its intensity is decreased to zero. How much residual magnetization is left and in which direction? 18.5 When a magnetic material is magnetized by a small AC magnetic field, how does the average susceptibility change with an increase in the amplitude of the AC field?

REFERENCES

1. R. M. Bozorth, Ferromagnetism (Van Nostrand, 1951), p. 502. 2. S. Kaya, Z. Phys., 84 (1933), 705. 3. R. M. Bozorth, Z. Phys., 84 (1933), 519. 4. Gerald, Hugs and Weber (N. B. Philips Fab.), Japan Patent S32-2125 (1957). 5. H. J. Williams, Phys. Rev, 52 (1937), 747, 1004. 6. R. Becker and W. Doring, Ferromagnetismus (Springer, Berlin, 1939), p. 153. 7. E. Kondorsky, Phys. Z. Sowjet., 11 (1937), 597. 8. M. Kersten, Phys. Z., 39 (1938), 860. 9. L. Neel, Annal. Univ. Grenoble, 22 (1946), 299. 10. M. Kersten, Z. f. angew. Phys., 7 (1956), 313; 8 (1956), 382, 496. 11. M. Kersten, Probleme der tech. Magn. Kurve (Berlin, 1938); R. Becker and W. Doring, Ferromagnetismus (Springer, Berlin, 1939), p. 215. 12. R. M. Bozorth, Ferromagnetism (Van Nostrand, Princeton, N.J., 1951), p. 114.

REFERENCES 13. 14. 15. 16. 17. 18. 19. 20. 21. 22. 23. Lord Rayleigh, Phil. Mag., 23 (1887), 225. F. Preisach, Z. Physik, 94 (1935), 277. R. M. Bozorth, Ferromagnetism (Van Nostrand, Princeton, N.J., 1951), p. 494. R. Becker and W. Doring, Ferromagnetismus (Springer, Berlin, 1939), p. 168. E. Czerlinsky, Ann. Physik, V13 (1932), 80. W. F. Brown, Phys. Rev., 60 (1941), 139. L. Neel. /. Phys. Rad., 9 (1948), 184. M. Fahnle and M. Kronmiiller, J. Mag. Mag. Mat., 8 (1978), 149. R. Becker and W. Doring, Ferromagnetismus (Springer, Berlin, 1939), p. 176. S. Taniguchi, Sci. Rept. Res. Inst. Tohoku Univ., A8 (1956), 173. I. S. Jacobs and F. E. Luborsky, /. Appl. Phys., 28 (1957), 467.

517

**19 SPIN PHASE TRANSITION
**

19.1 METAMAGNETIC MAGNETIZATION PROCESSES

Metamagnetism is defined as a transition from an antiferromagnetic to a ferromagnetic spin arrangement by applying a magnetic field or by changing temperature.1 When a magnetic field is applied to an antiferromagnetic material with a small anisotropy, the spin axis flops to the direction perpendicular to the magnetic field, because susceptibility in this case, x± > is larger than that, x\\ > in the case with the spin axis parallel to the magnetic field (see Section 7.1). This phenomenon is called spin-axis flopping. Further increase in the magnetic field results in the magnetization increasing with a constant susceptibility given by

where w2 is the molecular field coefficient acting between the A and B sublattices (see (7.27)). The magnetization curve in this case is shown in Fig. 19.1. Along the linear magnetization curve, the two sublattice magnetizations rotate towards the direction of the field and reach a saturation magnetization, 7S, at a field given by When the spin axis is held in the easy axis (z-axis) by a strong anisotropy, an increasing magnetic field applied parallel to the easy axis (z-axis) increases the sublattice moment parallel to the field gradually, with the susceptibility, x \\ > unlil the spin axis flops at a critical field Hc. The critical field Hc can be found as follows: The anisotropy energy density is assumed to be uniaxial, thus given by

Fig. 19.1. Magnetization curve of antiferromagnetic material with magnetic field applied perpendicular to the spin-axis.

METAMAGNETIC MAGNETIZATION PROCESSES

519

Fig. 19.2. Magnetic field applied at angle 6 to the spin axis.

where Ku is the anisotropy constant, and 6 is the angle between the spin axis and the z-axis. When the spin axis makes an angle, 0, with the z-axis (Fig. 19.2), the susceptibility is given by Therefore the field energy density is given by Spin-axis flopping occurs when the total energy reaches an unstable equilibrium, that is

and

From (19.7) we have 6 = 0° or 90°. The condition (19.8) gives

depending on the coefficient within braces in (19.8) ^ 0, where Hc is the critical field for the spin-axis flopping. When the field is increased beyond Hc, 6 is changed from 0° to 90°, and the susceptibility is changed discontinuously from x\\ to X ± • If ^c < ^s (see (19.2)), the magnetization curve should be as shown in Fig. 19.3. If Hc > Hs, the magnetization curve is as shown in Fig. 19.4. Such a discontinuous change in spin orientation is called spin flopping. Figure 19.5 shows metamagnetic magnetization curves observed for MnF2 at 4.2 K. This antiferromagnetic crystal has a body-centered tetragonal structure with the spin

520

**SPIN PHASE TRANSITION
**

/!

Fig. 19.3. Metamagnetic magnetization curve of antiferromagnetic materials with magnetic field applied parallel to the easy axis(# c <H s ).

Fig. 19.4. Metamagnetic magnetization curve of antiferromagnetic materials with the magnetic field applied parallel to the easy axis (Hc > Hs).

axis parallel to the c-axis. The number for each curve denotes the angle between the direction of applied magnetic field and the c-axis. For 0°, we expect a sharp transition as indicated by a solid line. In the actual experiment, 9 is nonzero, so that a spin-axis rotation takes place, before the spin flopping occurs. For the powder specimen, in which the spin axes are distributed at random, the average magnetization curve is expected to be as shown by the dashed curve.2 A two-stage spin flopping was observed for CoCl2'2H2O.3 This phenomenon was interpreted by assuming the presence of an

Fig. 19.5. Magnetization curves for MnF2 measured at 4.2K (6 is the angle between the c-axis and the applied magnetic field).2

7A is aligned parallel to the magnetic field. as long as the field is moderately weak. At the same time 7A tilts from the +77-direction under the action of the molecular field from the B sublattice. the effective fields which 7A and 7B feel are given by Taking the difference on each side in (19. resulting in a ferromagnetic arrangement (see Fig.1).SPIN FLOP IN FERRIMAGNETISM 521 exchange energy. and tilts from the -77-direction. If 1/A| > |7B|. 7B becomes unstable.2 SPIN FLOP IN FERRIMAGNETISM Ferrimagnetism is the result of two uncompensated sublattice magnetizations. while 7B is aligned antiparallel.6 19. 19.4 A theoretical treatment of metamagnetic magnetization processes in antiferromagnetic materials is given in a detailed review. we have therefore . 7A and 7B. in addition to the first neighbor exchange.2). Further increase in 7:7 causes a rotation of 7A and 7B towards the field. This interaction is equivalent to a magnetic field of several hundred MAm" 1 (several MOe). The two sublattice magnetizations are aligned antiparallel by the superexchange interaction (see Section 7. In an external field 77. Let us consider a ferrimagnet consisting of two sublattice magnetizations. Therefore the technical magnetization for ferrimagnetic materials behaves in the same way as that for ferromagnetic materials. Jj. acting between second nearest neighbor spins.11). As the field is increased.5 Experimental data on metamagnetic magnetization processes for various antiferromagnetic materials are given by Jacobs.7 but experimental studies have been started only recently when ultra-high magnetic fields become available. a ferrimagnet responds to a high magnetic field quite differently from a normal ferromagnet. A theoretical investigation of this behavior was made in 1968. The spontaneous magnetization is the difference between the two sublattice magnetizations (7S = 7A |7B|) (see Section 7. 7A and 7B.6). while — w is the inter-sublattice molecular field coefficient (w > 0). aligned antiparallel and having different magnitudes (/A > |/B|). /2. Thus 7A and 7B form a canted spin arrangement. so that a ferrimagnet behaves like a normal ferromagnet in magnetic fields of moderate strength. The molecular fields acting on these sublattices are expressed as where WA and W B are the intra-sublattice molecular field coefficients. However.

However. 19. 77c2. independent of the intensity of the external field.12) is satisfied only when both sides of the equation are zero. Since 7A and 7B must be parallel to 77Aeff and HBeK respectively. Canted spin arrangement. do depend on temperature. independent of temperature. 19. The magnetization composed of 7A and 7B is given by which is proportional to H. by putting 7 = |7A| + |7B|. Thus the magnetization curve of a ferrimagnet must be the same straight line with susceptibility. we have This relationship is shown in a vector diagram in Fig. This means that |/A| and |/B| are determined by their own magnitudes. I/TV.7. We can find 77cl. at any temperature. to give . 7B and H. the field. |/A| and |/B| have constant magnitudes independent of the angles between /A. the left-hand side of (19. 77cl. at which it ends. whereas the right-hand side must be parallel to 7B. these sublattice magnetizations have different directions.7.13) in (19. In the canted-spin arrangement. 19.12) must be parallel to 7A. by putting 7 = |7A| — |7B| to give In the same way. we can find 77c2. so (19. Thus in the canted-spin arrangement. at which the linear magnetization curve begins and the field. as long as the canted-spin arrangement exists. Ferrimagnetic spin-flopping: (a) Fig. In other words.6.522 SPIN PHASE TRANSITION Fig. Using the relationship (19.11).

21) and . where Y is nonmagnetic while Fe is magnetic. Yttrium iron garnet (YIG) is a ferrimagnet with the chemical formula Y3Fe5O12. Three Fe ions on the 24 d sites and two Fe ions on the 16a sites are coupled antiferromagnetically.10) by converting the sublattice names from A and B to d and a. we have Similarly we have for a-d interaction and for d-d interaction We can express these energy densities in terms of the molecular field in (19. resulting in a spontaneous magnetization of 5 Bohr magnetons per formula unit associated with one Fe ion (see Section 9. z.18) and this 5-value. respectively. we can express the exchange energy density for a-a interaction as where N is the number of Fe ions per unit volume. Since we have where AfB is the Bohr magneton. site spin 5. these critical fields are also dependent of temperature.20). (19.SPIN FLOP IN FERRIMAGNETISM 523 Since |/A| and |/B| depend on temperature.. 5 is the spin of an Fe ion (5 = f). The number of nearest neighbor /-sites of an /-site. Using this formula.3). Using (19.. where Jtj is the exchange integral. is given by -2JijSiSj. A computer simulation of such spin-flop behavior is shown below. Comparing this expression with (19. for the 16a and 24 d sites are given by The exchange energy between the /-site spin St and the .

19. Anderson8 assumed the following two sets of values for the exchange integrals for YIG: and The results are plotted in Fig. The spontaneous magnetization of a ferrimagnetic garnet is given by where According to (19.8. we have the molecular field coefficients in terms of the exchange integrals as These exchange integrals can be determined from the temperature dependence of spontaneous magnetization.22).26) and (19.27).524 SPIN PHASE TRANSITION (19. which shows the temperature dependence of Id . or the temperature dependence of Id and Ia can be found by successive integrations of (19. Ido and Ia0 for YIG. Hmd and Hma are given by Starting from the initial values at 0 K.10).

9 The solid curves assume the values of /(j. the solid curves are calculated by using set A (see (19. Nevertheless the temperature dependence of 7S thus obtained is not so different from the solid curve. the magnitude of the sublattice magnetizations.27). and temperature dependence of the spontaneous magnetization.8. respectively. where the spin canting takes place. the values of //cl and Hc2 . 19. cannot be accurately determined by such a procedure.29)) and the dashed curves are drawn using set B (see (19. together with (19. The temperature dependence of 7S thus obtained is in good agreement with the experimental values of Anderson.11). and the inclination of the magnetization curve.9 and Ia as well as the spontaneous magnetization 7S. These graphs show field dependences of normalized values of sublattice magnetizations.15) or (19.29)). Temperature dependence of normalized sublattice magnetization calculated by using two sets of exchange integrals. Another method for determining the value for w or Jad is to observe spin flopping in a high magnetic field (see (19.16)). stay constant as mentioned before.SPIN FLOP IN FERRIMAGNETISM 525 Fig. and a different value for Jad. The magnetization curve in high magnetic fields can be simulated by using (19. their z-components and the resultant magnetization. which ignores Jaa and Jdd. This means that values of the three /i. calculated by using the values Jtj for set A (see (19.30)).26).8 The dashed curves assume the values of set B. in which the molecular fields Hm are replaced by the effective fields /feff in (19.for set A.9(a) and (b) show the results for YIG at 100 K and 200 K. Figures 19. In the field range Hcl <H<Hc2. However.

Magnetization process during spin flopping calculated by using the exchange integrals (set A) in (19. (b) T= 200 K.9 are different at different temperatures. .10 shows a spin-phase diagram in which the traces of //cl and Hc2 are drawn in the H-T plane.9.29) for YIG: (a) at T= 100 K. 19.526 SPIN PHASE TRANSITION Fig. Figure 19.

SPIN FLOP IN FERRIMAGNETISM 527 Fig.11. Spin phase diagram constructed for YIG by using the exchange integrals (set A) in (19. because it requires very high magnetic fields. 0 f . This means that above the Curie point the material is paramagnetic in zero field.29). 19. but becomes ferrimagnetic in an applied field up to the phase boundary (dashed curve).10 is the phase boundary at which the ferrimagnetic spin arrangement changes to ferromagnetic. 19.9 This spin-phase diagram is difficult to verify experimentally.10. The dashed curve in Fig. Conceptual spin phase diagram for an N-type ferrimagnet. 19. . and Fig. It is interesting to note that this boundary continues above the Curie point.

19. go to zero at the compensation point.12. In this case spin-flopping can be observed in a relatively weak magnetic field such as 80MAm.and a-sites.2).11 The unit of the exchange integrals is cm ferromagnetic in higher fields.1 (= 1 MOe).12 shows a part of the spin phase diagram observed for DylG. |/A| . The solid circles . The dashed critical curves are calculated on the basis of this two sublattice model. ©c. When nonmagnetic Ga ions are added to YIG. which is an N-type ferrimagnet. so that the exchange interaction between a. Therefore spinflopping can be observed in a relatively weak field near the compensation point. Figure 19.9'10 In an N-type ferrimagnet (see Section 7.16). they dilute the Fe ions on d. The critical fields. and a comparison with experiments.and d-sites is weakened. shown by solid and open circles. Above TQ. and Hcl = 0 as found by (19. it is always ferromagnetic in a nonzero field. They are in poor agreement with experiments.528 SPIN PHASE TRANSITION Fig. In this ferrimagnet a Dy3+ spin on the 24c site and an Fe3+ spin on the strongly coupled 16a and 24d sites are loosely coupled antiferromagnetically.11 is a conceptual spin phase diagram of an N-type ferrimagnet. Hcl and Hc2. A part of the spin phase diagram for DylG constructed by using two sets of exchange integrals. Figure 19.|/B| = 0 at the compensation point.

the atomic rf-wave functions are split into de and dy states under the influence of the cubic crystalline field (see Section 3. In some real magnetic materials. so that / = 0. which shows XQ ~* 0 as T -> 0. According to Hund's rule.HIGH-FIELD MAGNETIZATION PROCESS 11 529 were measured by means of Faraday rotation (see Section 21. the ground state for Eu 3+ has \L\ = \S\ = 3. In Sm3+ and Eu 3+ ions. the number of parameters is increased. For instance. the high-field susceptibility is given by (18.29) and (19.5. the atomic magnetic moment of rare earth atoms is generally well described by Hund's rule (see Section 3.6cm"1 and Jaa = —6. If.133).2). because the sublattice magnetization on the d-site. while the latter is called the low-spin state.or z-axis. This has been done by applying ultra-high magnetic fields12 up to 350 T (see Section 2. Moreover. because interactions between Dy and other spins are introduced. thus resulting in a non-magnetic ion. while the first excited state with / = 1 is higher than the ground state by 600 K or about 700 MAm"1 (= 9MOe). because L'(d) decreases as T2.30). The situation is the same for the Co3+ ion. When such an ion is located on an octahedral site in an oxide. In 3d transition metals. . If we assume the three sublattice model in which not only the Dy spin on 24 c site but also Fe spins on 16a and 24d sites form a canted-spin arrangement. 19. the energy difference is rather small between the ground state with J = \L\ — \S\ and the first excited state with / + 1. the exchange integrals Jad — — 25. The former state is called the high-spin state. is saturated during the spin flopping at low temperatures. For example. it may find a nearest neighbor O 2 ~ ion on the x-. The reason for this is that we assumed the atomic magnetic moment to be independent of the field.3 HIGH-FIELD MAGNETIZATION PROCESS As discussed in Section 18. the two + spins which occupied dy levels fall into the lowest ds levels (see Fig.4).2cm" 1 were determined.1). however. however. in which L and 5 make some angle.20). By fitting a calculated Hcl versus temperature curve to the experiment. it is necessary to observe spin-flopping in pure YIG. we obtain the solid curves in the Figure. which fit the experimental points reasonably well. Therefore by selecting 6 parameters (sets A and B) in the figure we can easily fit the experiment with the calculation. 12. This results in a magnetic moment of 4MB. This means that such an experiment is not very satisfactory for measuring exchange integrals. all the + spin levels are filled first and then the lowest — spin level is occupied. L is generally quenched by the crystalline field. 19. y.13(a).13(b)). 19. as shown in Fig. Unlike sets A and B in (19.13 Therefore at temperatures above 600 K or in an ultra-high magnetic field above 700 MA m"1 we expect that the excited state with / = 1 will be mixed with the ground state. In order to determine exchange parameters. The value of Jdd cannot be determined. the level splitting due to the crystalline field is too large. Suppose we place an Fe2+ ion that has six 3d electrons on the octahedral site. Therefore the de orbits whose orbital wave functions are stretched between these cubic axes are more stable than the dy orbits whose orbital wave functions are stretched along the cubic axes (see Fig. Md.3). this is not necessarily true.

the probability of obtaining the state with energy U is proportional to the Boltzmann factor exp( . Assuming the energy of the low-spin state to be zero. whose separations increase with increasing field H. Generally speaking.0. the high-spin states are split into three levels with Jz = 1..530 SPIN PHASE TRANSITION Fig. let us assume that the magnetic moment of the low-spin state is zero. 19.. -1.-J.14 shows the variation of the energy levels of the two-spin states for /=!. For simplicity. (b) low-spin state. The energy separation between the two states is denoted by At/..U/kT\ so that the probability of Fig.. while that of the high-spin state is gJME. the high-spin states are split into 2J + 1 levels in a magnetic field H with J2=J.J~1. Level splitting and electronic states of Fe2+ or Co3 + (d6) ions on octahedral site: (a) high-spin state. . Saturation magnetization of these two-spin-state compounds changes considerably with temperature and applied magnetic field.14. Variation of level splitting between low-spin and high-spin (/ = 1) states with increasing magnetic field. Figure 19. the energy levels of these states are given by low-spin state high spin state with high spin state with high spin state with where the subscripts on the Us number the states in order of increasing energy levels.13. According to statistical mechanics. 19.

19.15. Temperature dependence of saturation magnetic moment with / = 1 calculated by assuming A U= 0. However.75 MOe).15 up to 300MAnT1 (=3. the transition from low-spin state to high-spin state due to a crossover of the high-spin level with Jz — ~ 1 and the low-spin level is clearly seen. 40. 100 and 200K are plotted in Fig.0086 eV (100 K). the field dependences of the saturation magnetic moment Ms calculated from (19. Assuming that t±U = 0.HIGH-FIELD MAGNETIZATION PROCESS finding each of these states is given by 531 Therefore the average atomic magnetic moment Ms is given by since the levels for states 0 and 2 are nonmagnetic. at high temperatures such as Fig.33) for T = 4. 19.0086 eV (corresponding to 100 K). At 4K. .

2K are18 This phenomenon is interpreted as an enhancement of the band-polarization by the external field. as seen for the curves for x > 0. When Se is added. with the Co ion having an atomic magnetic moment of 0. 0. Invar is an alloy of 35at% Ni-Fe whose thermal expansion coefficient at room temperature is almost zero. 19. it has a number of practical uses. Co ions with many Se neighbors tend to take the low-spin state14 with zero magnetic moment.14 100 and 200 K the transitions are spread out and the curves resemble the Brillouin function. 0. 0.28. 0.35. The values measured for Fe. Magnetization curves measured for CoS2_^Sex at 4.375. Co.45). which is a pyrite-type compound. The composition dependence of the high field susceptibility could be . measured at 4K. The small thermal expansion has been interpreted in terms of a high-spin to low-spin-state transition by assuming that the high-spin state has a larger atomic volume than the low-spin state.16. If the magnetic material containing such two-spin-state ions is ferromagnetic.17 The high field susceptibility. we must consider the effect of the molecular field and use H + wI for H.1. 0.40 and 0. (from top to bottom x = 0. 0. Figure 19.2. 0.15'16 Recently this characteristic was alternately interpreted in terms of the temperature dependence of local magnetic moment in spin fluctuation theory. and Ni at 4.532 SPIN PHASE TRANSITION Fig.9MB. Xo> °f 3d transition metals exhibits non-zero values even at OK. Therefore a transition from the low-spin state to high-spin state occurs. The nonzero atomic magnetic moment remains in low fields. because there are still some high-spin Co ions with a small number of Se neighbors.2K.28.30. The compound CoS2 is ferromagnetic..25.16 shows the magnetization curves for CoS2__tSeA.

temperature and magnetic field are two major parameters: Temperature ranges from 0 to 1000 K. If the paraprocess were described by a unique function of H/T. which is called the paraprocess. In the usual statistical theory of ferromagnetism. Since. As seen in the figure. while magnetic field ranges from 0 to IMAnT 1 (= 13kOe). Paraprocess calculated for a ferromagnet by the Weiss approximation. an ultra-high magnetic field of 800 MAm" 1 (= 10 MOe) corresponds to 680K. depends independently on H and T. This additional experimental parameter may be useful for checking various statistical theories (see Section 6.SPIN REORIENTATION 533 Fig.2).4 SPIN REORIENTATION Spin reorientation is defined as a transition of the state of magnetic ordering between .17. all the curves would be identical. In the statistical mechanics of spin systems. Therefore one is tempted to consider that the field H and temperature T are not independent parameters to describe the magnetic state. the populations of the spin states in a magnetic field H are described in terms of the parameter a = MH/kT. 19. the shape of the curve changes with temperature. a high magnetic field influences the magnetic structure as the temperature does. 19. Figure 19. the magnetization curve of a ferromagnet above its Curie point. this is not the case. the energy of a magnetic moment of 1MB in a magnetic field of SOMAnT1 ( = 1 MOe) corresponds to 68K.17 shows the paraprocess of a ferromagnet calculated by the Weiss approximation. However. The parameter on each curve is the value of T/@f. well accounted for in this way. The abscissa is MH/kT. however. however. For example.19 As discussed above. Therefore all magnetic phase transitions can be caused by applying an ultra-high magnetic field as well as by temperature.

Because this crystal structure is a distortion of the cubic structure. we must assume that the Dy spins have taken a conical spin arrangement above rSR1. Figure 19. Ia. ferrimagnetic or ferromagnetic).21 This is a spin reorientation corresponding to a second-order phase transition. Rare earth orthoferrites are magnetic oxides with composition given by RFeO3 (R: rare earth).20 In these phenomena. an antisymmetric exchange interaction (see Section 7.3).18.22 Many RCo5-type intermetallic compounds (see Section 12.19 shows the temperature dependence of spontaneous magnetization measured for a spherical specimen of DyCo5 hung by a thin thread perpendicular to Fig. they have orthorhombic crystal structure (see Section 9. the spontaneous magnetization.23 Figure 19.4) acts on the antiferromagnetically arranged Fe34" spins. In the case R = Dy. In the case R = Sm. In order to explain all the phenomena reasonably. Similar phenomena are observed for other magnetic orthoferrites.20 This spin reorientation is interpreted as occurring because the sublattice magnetization comprising the Re3+ moment changes dramatically with temperature and this affects the spontaneous magnetization of the Fe3+ moment through the R-Fe exchange interaction. Spin reorientation of DyCo5 caused by temperature change.and Dy-spins are coupled ferrimagnetically on the a-axis below 325 K (rSRj). or a change in the orientation of the spin axis.534 SPIN PHASE TRANSITION two of the possible magnetic structures (antiferromagnetic. and then the spontaneous magnetization rotates gradually until it reaches the c-axis at 367K (rSR2). thus resulting in a canted-spin arrangement with a small spontaneous magnetization. Co. the a-component of 7S. and 7C.23 .4) undergo second-order type spin reorientations. not only the exchange interaction but also the magnetic anisotropy plays an important role. but their transitions occur at low temperatures. canted. the spontaneous magnetization points parallel to the a-axis at 450 K and rotates gradually with increasing temperature until it reaches the c-axis at 500 K.18 shows the temperature dependences of 7S. the c-component (7S = y 72 + 72 ). 19.

and rotates with increasing temperature until it reaches the c-axis at TSR2 = 285 K.to the c-axis with increasing temperature from TSR1 to rSR2. 19. Assume that the magnetic anisotropy is negligible. . It was observed that the specimen rotates from the a. CrSj 17 (see Section 10. 7. Temperature dependence of /s measured for a spherical specimen of DyCo5 freely rotatable about an axis perpendicular to the a-c plane. The numbers identifying the various curves are the angle 6 measured from the c-axis. In the case R = Nd. It is also interesting that |/s| depends on the intensity of the field in this temperature range. etc.1 Draw the spin-phase diagram for an antiferromagnet containing N magnetic ions each with magnetic moment M.3) undergo a first-order type spin reorientation. When 7B is perpendicular to H. change in sign of the anisotropy constant. how many degrees does 7A tilt from 77? Find the magnitude of 77 in this case. the spontaneous magnetization is parallel to the fe-axis below TSR1 = 245 K. and the temperature dependence of /A = —7B is the Q-type (see Fig. including reorientation of the easy axis.4).19. The sublattice magnetizations of the A. draw a high field magnetization curve at 0 K. Assuming the molecular field constant to be —w.PROBLEMS 535 Fig.23 the a-c plane. However. PROBLEMS 19.12).4) and MnAs (see Section 10.and B-sublattices are given by 7A = \ NM and 7B = — \NM at T= 0 and 77 = 0. There are a variety of spin reorientations. we shall not go further into the details of such behavior. 19.2 Suppose a ferrimagnet contains N magnetic ions with a magnetic moment M in a unit volume. 193 Consider a possible engineering application of spin reorientation.24 Some magnetic materials such as FeRh (see Section 8.

Phys. American Institute of Physics Handbook. A1581. Neel. Soc. Miura. and M. S. 16. Kobayashi and T. Kawauchi. J. Haseda. Rev. and F. 7. and R. Oguro. Mag. Callen. Appl. /. H. MAG13 (1977). 281. 9. Jacobs.. Kido. 5. 1. 195. and S. Phys. 22. 4269. 86-88B (1977). Phys.. 6. Nakao. Tsushima. Rebouillat. 86-8 (1977). and L. F. Van Vleck. Jacobs. Washimiya and C. E. J. 1369. Miura. Becquerel and J. Hirano. Katayama. 773. S. L. Japan. New York. 19 (1964). C: Solid State Phys. 8. N. 10. Lahrichi. 37 (1974). Tsushima. /. Japan. Phys. /. 61S. Ohkoshi. G. Dillon. Weiss. No. Chikazumi. N. 4 (1955). Phys. T. Nuovo Cimento. Satoko. Kobayashi. 3rd edn (McGraw-Hill. Oguro. 19. 1. T. R. 285. ICM. Katayama. Appl. Chikazumi. Appl. 45 (1978). 12 (1979). J. G. 24. H. Kido. Kobayashi. R. 5-242. Hagedorn. 134 (1964). I. Nagamiya. Phys. M. Hirano. E. 3. /. 1932). J. Japan. P. 942. . Soc. Mag. Phys. 246. p. and T.. J.. P. T. GE Report No. S. Chikazumi.. Phys. E. Mag. M. Uitert.536 SPIN PHASE TRANSITION REFERENCES 1. M. M. Japan. Physica B. 40 (1969). Moriya. Miura. Miura. 45 (1978). Radium 10 (1939) 10. F. M. 17. L. 1534. Proc. N. 1204. M. 18. Phys. P. 35 (1966). Japan. White. IEEE Trans. Soc. T. p. Goto. 765. Phys. I. /. G.. Proc. Ono and S. Tanaka. K. 23. Kanamori. /. 39 (1968). 2.. MAG-8 (1972). Remeika.. Physica. J. 458. 21. /. K. Adv. 630. 5f-16. Theor. Lapierre-Revet. 82 (JMMM 31-34) (1983). 14 (1979). /. /.... 32 (1961). F. H. Appl. J. Gyorgy. /. and T. 15. Physica. T. IEEE Trans. B. 11. Matsui and S. Magnetics. 1972). Prog. Nakao. A. Mat. E. 39 (1968). 631. Chikazumi. Kubo. 155 (1989). Soc. 1158. I. Phys. Panissod. /. Theory of electric and magnetic susceptibilities (Oxford University Press. Clark and E. Krill. Ohkoshi. 6S (1957). 12. van den Handel. and S. M. 14. K. 13. 5972. Chikazumi. 1219. Phys. 16. 4. Phys. H. 20. 82 (1963). 69-C-112 (1969). J. Soc. G. 45 (1978). Yosida. Soc. 1061. Jr. I. Anderson. Phys. S. Phys. and N. K. T.

Suppose that a magnetic field H = H1 is applied to a magnetic material. . /n. For example. occurring over time as shown in Fig. this kind of magnetization change is also excluded from the definition of magnetic after-effect. to give where 7n0 is the total change in magnetization from t — 0 to °°. are usually known as aging. In the simplest case. not including /. The difference between magnetic after-effect and magnetization changes due to aging is that changes resulting from magnetic after-effect can be erased by applying an appropriate magnetic field.20 DYNAMIC MAGNETIZATION PROCESSES In this section we treat time-dependent magnetization processes. diffusion.1 MAGNETIC AFTER-EFFECT Magnetic after-effect is defined as the phenomenon in which a change in magnetization is partly delayed after the application of a magnetic field.. Magnetization may also be affected by purely metallurgical phenomena such as precipitation. Structural changes like those in the previous sentence. but this kind of purely electrical phenomenon is regarded here as distinct from magnetic after-effect.1. In(t) can be expressed by a single relaxation time T. and also depends on the final magnetic state at H2. The time-varying part /„ can be written generally as The magnitude of /„ is a function of /. if the final state is in the field range for magnetization rotation. while if the final state is in a field range for irreversible magnetization. This phenomenon is sometimes referred to as magnetic viscosity. as in high-frequency or pulsed fields. but there is an additional change. 20. such as near the residual magnetization or the coercive field. There is an immediate change in magnetization. These processes become particularly important when the magnetization must change rapidly.2) may cause a delay in magnetization. and is suddenly changed to H = H2 at t = 0. Eddy currents (see Section 20. the value of /„ is very small. or crystal phase transition. if they occur slowly at or near room temperature. /„ may be fairly large. 20. while changes due to aging are not recoverable by purely magnetic means. 7j.

1 .2) describes the experiment well.104)) is Fig.2. 20. Magnetic after-effect observed for a low-carbon iron. The applied field in this experiment is in the initial permeability range. Figure 20.538 DYNAMIC MAGNETIZATION PROCESSES Fig.2 shows a semi-log plot of /„(/) vs time measured for pure iron containing a small amount of carbon.1 The curves measured at various temperatures can all be fitted with straight lines corresponding to a (log In)-t relationship. This means that (20.1. where the Rayleigh term (the second term in (18. 20. Time change in a magnetic field and the associated change in magnetization.

the magnetization can be expressed as The magnetic after-effect also causes a delay in magnetization in a material subjected to an AC magnetic field.3. In order to express this phenomenon mathematically.1 . tan 5. we use (20. Figure 20. we call this angle 8 the loss angle and tan d the loss factor. If we denote this ratio as £.MAGNETIC AFTER-EFFECT 539 negligibly small. we consider a differential equation which leads to (20. 20. Then we find and Since the appearance of a nonzero angle S results in a power loss.4) and (20.5) in (20.6). The numerical values are the frequencies of the AC field in hertz. Temperature dependence of the loss factor. observed for a low carbon iron. Then changes in magnetization are delayed so that where S is the delay expressed as a phase angle. to give Suppose that an AC magnetic field expressed as is applied to a magnetic material.3) for DC magnetization. The value / n0 //j was 30%.3 shows the temperature dependence of the loss factor measured at Fig. In order to find the angle S and the amplitude /„.

For small T. Snoek's model of magnetic after-effect. 20. If we consider (20. Logr vs 1/T curve obtained from semistatic (open circles) and high-frequency measurements (center-dot circles). Each curve shows a maximum at some temperature. while the numerator increases only as T.1 various frequencies for low-carbon iron. tan 8 becomes very small for large T. while the denominator stays almost constant. because the numerator becomes small. The maximum occurs for Therefore we can determine the relaxation time from the angular frequency of the maximum at a particular temperature. because the relaxation time T varies with temperature. which means that both phenomena have the same origin. because the denominator increases as r 2 . 20. In order to understand the nature of this phenomenon. tan d becomes also small. Figure 20. a model proposed by Snoek2 is helpful.7) to be a function of T. 20.4 shows the logarithm of relaxation time.5.540 DYNAMIC MAGNETIZATION PROCESSES Fig.4. As shown in Fig.5. as determined from AC measurements as well as from semistatic measurements. . We see that both groups of experimental points fall on the same straight line. as a function of reciprocal temperature.1 the same material used in the semistatic measurement shown in Fig. suppose a heavy ball is placed on a concave Fig. 20.2.

This corresponds to the semistatic magnetic after-effect. and a very large loss results. for TJ < T< T2. If the relaxation times are distributed over a wide range. again resulting in very low loss.13) can be expressed as .MAGNETIC AFTER-EFFECT 541 surface covered with a layer of thick mud.11) becomes If we set (20. we have. the ball will move through a low-viscosity mud layer. This is the reason why the loss factor has a maximum at an intermediate temperature. At an intermediate temperature. In general the relaxation times are distributed over some finite range. the ball will move on the hard mud surface with very low loss. we can conveniently use In r as a parameter instead of r. On the other hand. Since g(T)d(lnr) = (g(r)/T)dT. the motion of the ball is most severely damped. resting on the concave surface. the second term of (20. it will sink gradually into the layer of mud. from (20. the distribution function g(r) can be normalized by 0 Then the time change of magnetization can be described by If we assume for simplicity that the distribution function is a constant g from TJ to T2 and zero outside this range. If the ball is displaced by a lateral force H. As the viscosity of mud increases at low temperatures. Let the volume in which the logarithm of the relaxation time is in the range Inr to I n T + d Q n r ) be g(r)d(lnT). when the viscosity decreases at high temperatures. The magnetic after-effect is not necessarily described by a single relaxation time.10). If we put t/T=y. AC magnetization corresponds to the case when the ball is oscillating back and forth around the minimum position of the concave surface under the action of an alternating force. changing its equilibrium position.

F Fig. log £ measured at 55°C for well-annealed carbonyl iron.6 shows the time decrease of magnetization vs. If this material is magnetized by an AC magnetic field. we see that A/ n decreases linearly with time t. we expect that the loss factor tan 8 will be zero when T becomes very large at low temperatures. T2 = 0.7).14s. We see in Fig. then A/ n varies proportionally to In t. This loss is referred to as the Jordan-type magnetic after-effect. According to (20.4 so that it is referred to as the Richter-type magnetic after-effect. This type of magnetic after-effect was investigated by Richter. or for t <sc TJ < T2.15) drawn by assuming TI = 0. E . the loss factor will be maximum at a frequency where 1/ca lies between TI and T2. and finally tends towards to zero according to for T! < r2 <K f. r2. 20.542 DYNAMIC MAGNETIZATION PROCESSES The function N(a) is expressed approximately by Using these formulas. Figure 20.0048s. Richter-type magnetic after-effect. and it reproduces the experiment very well. 20. however. The solid curve represents the function (20. or for TJ •« t <. that some non-zero value remains even at OK.3. This magnetic loss is also independent of the angular frequency ca.6.

Then the anisotropy energy is given by where (o^. In such a case.5 The origin of this magnetic after-effect is that the distribution of relaxation times is very large: TJ. 20. in a unit volume of the iron lattice. the pseudodipolar interaction of the Fe-Fe pairs in the ^-direction is changed. verifying (20. and z-sites be Nx.7. identified as x-. occupy interstitial sites in the body-centered lattice of iron. In this case (20. 20.E MAGNETIC AFTER-EFFECT 543 0 Fig. while T2 is sufficiently large. Let the number of carbon atoms on the x-. Figure 20. y-.8. y-. Ny. the volume in which T is equal to \/u> is constant independent of a>. The physical mechanism of the magnetic after-effect was proposed by Snoek2 and later corrected by Neel. and z-sites in Fig. thus inducing a uniaxial magnetic anisotropy (see Section 13. Magnetic after-effect for Alnico V. and for rl •« t «: T 2 .6 The carbon or nitrogen atoms.1). The experimental points lie very well on straight lines. This type of magnetic after-effect is often observed for permanent magnet materials.18) holds. is very small. which are very small compared with an iron atom.20). respectively. and Nz. so that tan 8 becomes independent of (a.7 shows the time variation of magnetization as a function of log t observed for Alnico V. «3) are the direction cosines of the spontaneous magnetization and /c is the change in dipolar interaction coefficient due to the insertion of the carbon . we have where S is called the magnetic viscosity parameter. «2. If many carbon atoms occupy x-sites preferentially. There are three kinds of interstitial sites.

20. 20. We postulate that a carbon atom must get over a potential barrier of height Q when transferring from one site to a neighboring site (Fig.22). It is given by Q + (f . Q + (| .8. This height is also influenced by the orientation of the domain magnetization. At thermal equilibrium at a temperature satisfying the condition lc <zz kT.a32)/c for the three kinds of lattice sites.al)lc. 20. the distribution of carbon atoms is given by where the subscript °° indicates an equilibrium value after a sufficiently long time.a|)/c and Q + (f . The potential barrier between x. Ny.9.9). and Nz at t = 0 to thermal equilibrium at t = °° given by (20. Fig. atom.544 DYNAMIC MAGNETIZATION PROCESSES Fig. Now we consider the process by which carbon atoms change their position from the given distribution Nx. Three kinds of interstitial lattice sites for carbon atoms in body-centered cubic iron. .and y-sites.

MAGNETIC AFTER-EFFECT 545 The numbers of carbon atoms which transfer from one kind of site to another kind should be proportional to (the numbers of carbon atoms present in the same kind of sites) X exp( . This value agrees well with the activation energy for diffusion of carbon atoms in body-centered cubic iron. we have Assuming that lc «. Then (20. Since the rate of increase in Nx is given by one-half of the carbon atoms which escape from _y-sites and from z-sites less the number of atoms which escape from the *-sites. the carbon . From the slope of the log T vs l/T curve. When a field drives a domain wall to a new place. we expand the exponential functions in (20. or K^s>Nlc. and gradually approaches the final direction.25) can be regarded as constant. This equation explains the relationship between log T and l/T shown in Fig. If the magnetocrystalline anisotropy is much greater than anisotropy resulting from the carbon atoms.4. kT. 20. we obtain the activation energy Q. and.height of barrier). we have Since Ny and Nz change with time in a similar way. The effect of diffusion of carbon atoms on the displacement of domain walls is more complicated. Since the angle of the final rotation is small. the domain magnetization rotates instantaneously to the equilibrium direction upon the application of a magnetic field. £acc in (20. described by a single relaxation time. which is equal to 0.22) in power series of lc/kT.21) changes with time as where c is a coefficient that includes the relaxation time. in this case. the anisotropy energy given by (20.99 eV in this experiment. First we discuss the effect of such diffusion of carbon atoms on magnetization rotation.25) is readily solved as where Ea0 is the anisotropy energy at t = 0 and Thus the time variation in the anisotropy is. neglecting the higher order terms and using the relation Nx + Ny+Nz = Nc.

If the magnetization is reversed to the negative direction. respectively. the height of the potential barrier as measured from U+ and U_ is changed to v(2Ku — IsH)2/4Ka and v(2Ku + ISH)2/4KU. Neel6 made a detailed calculation for such a gradual displacement of the wall.2). If the length of such a gradual displacement is larger than the wall thickness. Since usually the height of the potential barrier is much larger than kT/2. such coherent rotation is not able to overcome the potential barrier. At room temperature T=273K. Let us consider an elongated single domain particle which is magnetized first in the positive direction and then is subjected to a field applied in the negative direction. in which state the energy of the system is given by where v is the volume of the particle. and oscillating.546 DYNAMIC MAGNETIZATION PROCESSES atoms in the wall rearrange their lattice sites so as to stabilize the local orientation of spins inside the wall.87) and (18. and the wall starts to move gradually.25) must be regarded as a function of time. If the intensity of the field is less than the critical field H0. so that £aoo in (20. the energy becomes The potential barrier between the two states can be easily calculated from (18. however. This phenomenon is similar to Langevin paramagnetism (see Section 5. At temperature T each spin is subject to thermal agitation whose energy is kT/2 per degree of freedom of motion. the volume of the particle is so small that the height of the potential barrier vKu at H = 0 is the same order of magnitude as kT/2. Such a rearrangement of carbon atoms changes the wall energy through a change in the anisotropy energy. so that for Ku = 105 J/m3. Neel7 proposed another type of magnetic after-effect called the thermal fluctuation after-effect. We refer to the magnetic after-effect caused by diffusion of carbon or nitrogen atoms as the diffusion naf after-effect.77 X 10~21 J. This phenomenon is caused by thermal fluctuation of the magnetization of an isolated single domain. so that it is called superparamagnetism? When a magnetic field of intensity H is applied in the negative direction. The coherent rotation of all spins included in this particle is also thermally activated and has energy kT/2. If. its radius is In such particles the domain magnetization is always thermally activated.88). Since the former is less than the . thermal activation will allow the domain magnetization to rotate over the potential barrier. the magnetization will stay in the positive direction. to give [7max = vI2H2/4Ku at cos 0 = ISH/2KU. the directions of spins in the wall are changed by an angle comparable to IT. the critical volume becomes If we assume that the particle is spherical in shape. kT= 3. by letting 00 = 0.

2KU/IS. or the values of Ku.MAGNETIC AFTER-EFFECT 547 latter. Thus the condition TJ •« t <c T2 is always valid for a practical duration of measurement. Thus the rate of increase in the number of particles magnetized in the plus direction is given by where N_ is the number of particles magnetized in the minus direction.33) is quite similar to (20. If the particles volumes v.34) . and we have where Thus thermal activation of the flux reversal can occur even for particles having a volume larger than the critical volume v0. and the time change in magnetization in this case is expected to be proportional to log t as shown by (20. If the field is increased to just below the critical field. if H is close enough to the critical field.24). the important difference between the two is that the activation energy in (20. If we let Kum3X and t>max denote the maximum values of Ku and v.32) becomes sufficiently large compared to the second term to permit us to neglect the second term. Although the form of time change of N+ given by (20. Neel7 estimated that a particle of volume 1 X 10 ~ 24 m3 exhibits a relaxation time T~ 10"l s at room temperature. H0 .34) includes H. whereas a particle of volume 2 X 10~24 m3 exhibits T ~ 109 s (several tens of years) under the same conditions. Neel considered c' to be determined by the precessional speed of coherent rotation of the spin system caused by a thermal distortion of the crystal lattice through the change in magnetostrictive anisotropy or in demagnetizing field. are scattered around average values. the value of r given by (20. the first term of (20. the number of particles whose magnetization is activated from the plus direction towards the minus direction is greater than the number which activated in the opposite direction.18).34) is expected to cover a very wide range. it follows from (20.

the wall can be released by a thermal disturbance. the slope of the A/ n — log t curve. Snoek used the model shown in Fig. in a Pt-Co alloy the parameter S decreases rapidly with increasing temperature. 20. When the ball is displaced to a new place. The important difference between the diffusion after-effect and the thermal fluctuation after-effect is as follows: In the former type. This phenomenon is called the superposition principle. Therefore in the former type. For instance. the history of the previous magnetization distribution is retained by a non-magnetic mechanism. Neel10 considered that the thermal agitation of the local spin system gives rise to a fluctuation in local magnetic fields which may cause irreversible displacement of weakly pinned domain walls. some materials exhibit a quite different temperature dependence of the parameter S.20). In this sense Snoek13 named the phenomenon disaccommodation. Neel12 called the former type the reversible after-effect.11 Under a fixed magnetic field of 0. However.ct and the latter the irreversible after-effect. We can regard the ball in this model as representing a domain magnetization driven by an external field against the .4 MAm"1 (5 kOe) a domain of 10 /j. This is actually the case for permanent magnets such as Alnico V (see Fig. it can be moved fairly easily on the surface of the mud layer by an external force.18). m in diameter was observed to increase to about 100 pt m in a time of about 3 min. Such a slow displacement of domain walls was actually observed by means of the polar Kerr magneto-optical effect for sputter-deposited Tb-Fe thin films. if the magnetization is changed from state A to state B. 20. the magnetic after-effect corresponding to the change from A to C continues to occur in addition to that of the change from B to C. In contrast. This phenomenon was discovered from the fact that the resonance frequency of an L-C circuit used in a commercial radio receiver shifts with time from the designed frequency. is expected to be proportional to the absolute temperature T. S in (20. After some period of time the ball will sink into the mud layer and will lose its mobility.5 to explain this phenomenon. and then later from B to C. In this case the viscosity parameter S decreases with increasing temperature.9 This phenomenon was interpreted in terms of Neel's disperse theory. Figure 20. or the magnetic viscosity parameter.10'12 A thermal fluctuation after-effect can also be considered for domain wall displacement.ct It is commonly observed that the permeability of a magnetic material changes with time after application of a magnetic field or a mechanical stress. The result was interpreted in terms of temperature dependence of the "activation volume". hence the superposition principle is not valid for the latter type.7). we have According to this conclusion. while in the latter type the history is retained only by magnetic means.10 shows the time decrease of permeability measured for Mn-Zn ferrite. such as the distribution of carbon atoms. When a domain wall is pinned by a small obstacle. in the latter type any memory of the previous state would be destroyed by changing the magnetic state.548 DYNAMIC MAGNETIZATION PROCESSES On putting these two expressions into (20. We see that the permeability changes significantly for a long period of time.

Let us consider this phenomenon in terms of diffusion of carbon atoms. Disaccommodation observed for Mn-Zn ferrite. 20. The final distribution of the carbon atoms is calculated by putting al = 1.10. carbon atoms will diffuse into energetically favorable sites. a2 = «3 = 0 in (20.22) to give Expanding these exponential functions and putting the results into (20.13 magnetic anisotropy.21).MAGNETIC AFTER-EFFECT 549 Fig. the susceptibility due to magnetization rotation is given by . Therefore. After some period of time.82). similarly to (18. Suppose that the magnetization lies parallel to [100] in a material with K1 > 0. we have the anisotropy energy where A 6 is the angle of deviation of magnetization from [100]. a part of which can be changed by diffusion of C or some other structural change. stabilizing the domain magnetization as it exists.

as shown by (18.10 by this magnetization rotation model.53)). Since the susceptibility is inversely proportional to a. When the wall is displaced by a distance A s. which is smaller than the thickness of the wall 8.25). the spin in the wall rotates by the angle if we postulate uniform rotation of the spins across the wall. its value is given by (18. we find the second derivative of the wall energy with respect to the displacement s to be where «0 is due to potential fluctuation of y.43) with (18. Let us consider next the displacement of domain walls.43). 20. After the wall has remained for a prolonged time in the same place.550 DYNAMIC MAGNETIZATION PROCESSES If we assume that the concentration of carbon atoms is 0. Therefore we cannot explain a large disaccommodation as shown in Fig. The local anisotropy energy is changed by so that the wall energy is changed by Comparing (20.38). and also Mc « 107 (see (14.01 at%. each spin in the wall is stabilized by a local anisotropy given by (20. where N is the total number of iron atoms in a unit volume = 8. we can estimate the induced anisotropy at 300 K as which is lower than the magnetocrystalline anisotropy K1 by a factor 10 3. then NC/N = 1 X 10~4.5 X 1028 m~ 3 . the susceptibility change is provided . If «0 is caused by internal stress.31). This time we regard the ball as representing a domain wall.

20. it was confirmed that the cooling of ferrites from high temperatures in a nitrogen atmosphere. He suggested that electron hopping between the octahedral sites of the spinel lattice could be the cause of this phenomenon. considering that the activation energy for the electron hopping is O. and assuming uniform magnetization I. we have Thus we can explain the experimental values by this model. magnetized parallel to its long axis (see Fig.2 EDDY CURRENT LOSS Eddy current loss is defined as the power loss resulting from the eddy currents induced by changing magnetization in magnetic metals and alloys.8 eV. or Then the current density is given by . They interpreted this result as due to the selective distribution of vacancies among four kinds of B sites which have different trigonal axes. Applying the integral form of the law of electromagnetic induction to a circuit with radius r drawn about the center axis of the cylinder. However. which avoids oxidation and the resulting generation of lattice vacancies. Ohta and Yamadaya15 observed an induced anisotropy of 102 Jm3 after cooling Mn-Zn ferrite in a magnetic field. 20. we have. is effective in suppressing disaccommodation. Disaccommodation in ferrites was first observed by Snoek13 for Mn-Zn ferrite.01 for annealed iron. and also that disaccommodation is larger for a specimen containing more lattice vacancies. while that for disaccommodation is 0. for r < r0. Ohta14 concluded that the selective distribution of lattice vacancies on B sites could be the real origin of this phenomenon. In order to prove this consideration. In fact.5-0.leV. Let us consider first a long cylinder of radius r0 made from ferromagnetic or ferrimagnetic material. Yanase16 explained this phenomenon in terms of magnetic dipole interaction affected by lattice vacancies. In contrast.11(a)).EDDY CURRENT LOSS 4 3 551 If we tentatively assume that Aer0 ~ 10 /m~ and S/l = 0.

In real ferromagnets. In Fig. as long as the skin depth is sufficiently small compared to the diameter or thickness of the specimen. the skin depth is calculated to be The magnetic cores of AC machines are usually made of laminated thin sheets of magnetic metal. That is. and electrically isolated from its neighbors.17 The depth 5 is called the skin depth. therefore. where R is the radius of the wall. If dl/dt is sufficiently large. treated as a constant. so that the magnetization is damped away inside the cylinder. there is no flux change. this means that the loss can be decreased by subdivision of the material into electrically isolated regions. hence . each sheet thinner than the skin depth. so that the magnetic flux penetrates completely through each lamination. Its value is independent of the size or shape of the specimen. In Fig. given by Thus the eddy current loss is proportional to the square of the rate of the magnetization change. the integrated magnetic field produced by the total eddy current is strongest at the center and decreases to zero at the surface of the cylindrical specimen. we considered a homogeneous change in magnetization. the eddy currents become strong enough to give rise to a magnetic field that is comparable to the applied field.11(b) a ferromagnetic cylinder is separated into two domains by a cylindrical 180° domain wall.11(a). It is also seen in (20. The magnetic field produced by the eddy current always opposes the change in magnetization. Since the eddy current that flows around a cylinder of radius r produces a magnetic field only inside this cylinder. 20. the power loss increases proportional to the square of the frequency as long as the flux penetration is complete. for r < R. 20. This is also true for an alternating magnetization. magnetization mostly occurs by domain wall displacement. The power loss per unit volume is.552 DYNAMIC MAGNETIZATION PROCESSES where p is the resistivity. This is the reason that ferrites are more useful at high frequencies than ferromagnetic metals and alloys. When a magnetic metal with p = l X l O ~ 7 n m and JL = 500 is magnetized by a 50Hz AC magnetic field.51) that the power loss is proportional to r\. The amplitude of magnetization change is decreased to 1/e of that at the specimen surface at a depth where a> is the angular frequency of the alternating magnetic field and ft is the permeability. Inside the wall. It is natural that the loss is inversely proportional to the resistivity.

A single crystal of Si-Fe cut into a picture-frame shape with (100) legs. Fig. 20.12. 20.EDDY CURRENT LOSS 553 Fig. and its domain structure. and (b) by wall displacement.18 Outside the wall. Eddy current in a cylindrical specimen with magnetization changing (a) homogeneously. we have .56). for r > R.11.48) that or Thus the average power loss per unit volume is given by If we use the rate of magnetization change. for (20. it follows from (20.

Thus on equating (20. When a cylindrical wall with radius R is expanding with the velocity dR/dt. Before the success of this experiment. the calculation of eddy current losses made under the assumption of a homogeneous magnetization gave only one-half to one-third of the observed value.13(a). and they showed that the calculated power loss is in good agreement with the observed one. so that Comparing this with (20.12). The cylindrical wall vanishes very rapidly. we have which shows the proportionality between v and H. . 20. 20. The reason is that the eddy currents are localized at the wall and such localization gives rise to a larger power loss. 20.51). since the surface tension of the wall helps to diminish its area. The proportionality between v and H can easily be inferred from the model shown in Fig.13(b) when a strong magnetic field is applied.554 DYNAMIC MAGNETIZATION PROCESSES Thus we find that the power loss depends on R. It is now known from this experiment that the anomaly results from ignoring the localization of eddy currents at the domain walls. This fact was first experimentally verified by Williams et a/.18 They used a picture-frame single crystal specimen of 3% silicon iron which contains a 180° wall running parallel to each leg of the specimen (Fig. They also found that the wall shrinks into a cylinder as shown in Fig. we find that the power loss is four times larger than that for a homogeneous magnetization change. 20. On average. The velocity of the domain wall was measured as a function of the applied field and found to be expressed by where c is a proportionality factor and H0 is the critical field for displacement of the wall. Williams et al. because the displacement of the wall is strongly damped in the interior of the specimen.ls calculated the distribution of eddy currents for a rectangular cross section in which a plane domain wall is moving as shown in Fig. There was very good agreement between the calculated and observed behavior of the wall in this cylindrical case also. because the power loss is proportional to i2.62) with (20. which was known as the eddy current anomaly. the position of the wall.56). this energy must appear as heat produced by the eddy current.11(b). the power supplied by the magnetic field per unit volume is Since there is no change in the potential energy.

20. The calculation of the distribution of eddy currents is very difficult for an actual material which contains many walls. Let us now assume Fig. 20. Cross-sectional view of a domain wall moving (a) at low speed and (b) at high speed.14 shows a comparison of the eddy current distribution in the two cases shown in Fig.55): This relation is generally valid for a 180° wall moving at velocity v.11. This discontinuity. . since it depends not only on the shape and the distribution of domain walls.14. Ai. but also on the dimensions and external shape of the specimen.EDDY CURRENT LOSS 555 (b) Fig.13. It is seen that the eddy current changes discontinuously at the location of the domain wall. is easily found by letting r = R in (20. Figure 20. 20. Distribution of eddy current in a cylindrical specimen for homogeneous magnetization and for wall displacement.

Spatial distribution of macroscopic and microscopic eddy currents. We call the eddy current due to homogeneous magnetization the macroscopic eddy current.556 DYNAMIC MAGNETIZATION PROCESSES Fig. and accordingly the velocity of an individual wall is small. z ma . 20. This is a natural conclusion because this presence of a large number of domain walls means that the magnetization is quite homogeneous. however. as it is in Fig.3 HIGH-FREQUENCY CHARACTERISTICS OF MAGNETIZATION In this section we summarize various losses and resonances that appear in high- .65). The power loss is then given by where the integration should be made over a unit volume of the specimen. If the spatial variation of the macroscopic eddy current is gentle compared to that of the microscopic eddy current. that the distribution of eddy currents is shown by curve a in Fig. as seen in (20. and the deviation from macroscopic eddy current due to wall displacement the microscopic eddy current. and also cannot distinguish the two categories of macroscopic and microscopic eddy currents. / mi . the paths of eddy currents are complicated because of the presence of many non-conducting inclusions. 20.15. 20. If. 20.15. the third term should vanish. For this case we can approximate the power loss by a macroscopic eddy current. Apparently the actual eddy current is expected to exhibit sharp changes at the locations of domain walls as shown by curve b in the figure. or if the separation of domain walls is comparable to the size of the specimen. the individual microscopic eddy currents become small. since plus and minus values of imi cancel each other.64).15 for homogeneous magnetization. If there are a large number of domain walls. For such a case we can calculate the power loss as the sum of those of the macroscopic and microscopic eddy currents. we cannot ignore the third term in (20.

Desirable properties for soft magnetic materials are high permeability and low loss. Since a power loss of this type increases in proportion to the square of the frequency. the loss factor due to the hysteresis loss depends on the amplitude of magnetic field. The quality of soft magnetic materials is often measured by the factor p/tan 8.66) becomes In these expressions /// expresses the component of B which is in phase with H. regardless of the origin of the delay. because the wall displacement. If a magnetic material is magnetized by an AC magnetic field H = H0eltat. as distinguished from the other types by reducing the amplitude of H towards zero. is mostly damped in this range and is replaced by magnetization rotation. the magnetic flux density B is generally delayed by the phase angle 8 because of the presence of loss. The ratio AI" to /*' is. The presence of such a component requires a supply of energy to maintain the alternating magnetization. the most important loss is the hysteresis loss. and is thus expressed as B = B0e*ia'~s\ The permeability is then If we put (20. In the low-frequency region.67). so it corresponds to the normal permeability: if there are no losses. very thin Permalloy sheets (approaching 10 ^tm) are . If the amplitude of magnetization is very small. and so tan 8 is also called the loss factor.'. The permeability /A" expresses the component of B which is delayed by the phase angle 90° from H. For instance. Let us consider what kinds of losses appear as the angular frequency « is increased. it plays an important role in the high-frequency range.HIGH-FREQUENCY CHARACTERISTICS OF MAGNETIZATION 557 frequency magnetization. The hysteresis loss becomes less important in the high-frequency range. which is the main origin of the hysteresis. from (20. as discussed in the preceding section. as will be discussed later. The next important loss for ferromagnetic metals and alloys is the eddy current loss. we should have /A = /j. and accordingly in the Rayleigh region. One means to reduce eddy current loss is to reduce the dimension of the material in one or both directions perpendicular to the axis of magnetization.

so that it does not contribute to the high-frequency loss at room temperature. the rare earth iron garnets (see Section 9. It is estimated that this temperature maximum would be shifted to room temperature at a frequency of several hundred megaherz. 20. the presence of excess Fe2+ ions in various mixed ferrites results in a decrease in resistivity and accordingly in an increase in eddy current loss at very high frequencies.558 DYNAMIC MAGNETIZATION PROCESSES produced by rolling to reduce eddy currents. However. is to use electrically insulating ferromagnetic materials such as ferrites and garnets. tan 8 exhibits a temperature maximum when measured at a fixed frequency. so that they can be and are used extensively at high frequencies (see Fig. respectively. Mn-ferrites with excess Fe content are used to attain increased permeability. The most effective means of avoiding eddy currents. Since the relaxation time decreases with increasing temperature. The velocity of an electromagnetic wave is reduced by a factor (ejl)'1 as compared with that in vacuum. but the resistivity is of the order of 1 ft m ( = 102 ft cm). if ferrite cores are used for a large-scale machine. Figure 20. which shows a maximum at a certain value of to. The Ni-ferrites have resistivities as high as 107 ft m (= 109 ft cm).3) contain no divalent metal ions. Some of the garnet crystals are transparent to visible light.5 cm2. 20. In this case the eddy current loss is not negligible at frequencies over 100 kHz. eddy current losses are observed. and therefore no electron hopping occurs. Thus metallic cores tend to be replaced by ferrite cores for high-frequency applications.16 shows a drop of permeability between 1 and 2 MHz for an Mn-Zn ferrite core with cross-section dimensions of 1. For instance. In contrast. where e and /I are the relative permittivity and relative permeability.17). however. Since. so that even bulk material can be used as a magnetic core. Even in this case. sometimes their permeability drops at a certain frequency. the resistivity of magnetite (Fe3O4) is fairly low (10~4 £1 m = 10~2 ft cm). Vacuum evaporation. however. However. Magnetic cores composed of fine metallic particles ('dust cores') are also made for the purpose of reducing eddy currents. so that they exhibit extraordinary low magnetic losses. Hence the wavelength in the material is given by . as discussed in Section 20. Magnetic after-effect also gives rise to a magnetic loss. The resistivity of a typical ferrite is about 104 ft m (=10 6 ftcm).20 This drop in permeability is shifted to a higher frequency when the size of the cross-section is reduced.19 The origin of this phenomenon in ferrites is considered to be the diffusion or 'hopping' of electrons between Fe2+ and Fe3+.1. as will be discussed later. The loss factor due to ionic diffusion exhibits a maximum at room temperature only for very low frequencies (as low as a few herz). as shown in Fig.3 for a low-carbon iron.7). electroplating and sputtering are also effective in preparing very thin metal films which are used in high-speed and high-density memory devices. A similar phenomenon is also observed for Ni-Zn and Mn-Zn ferrites at — 150°C at a frequency of several kHz. The relation between tan 8 and the relaxation time r is given by (20. if the material contains excess Fe2+ ions. The origin of this phenomenon is considered to be the building up of an electromagnetic standing wave inside the core.25 X 2. this phenomenon cannot be distinguished from the natural resonance which occurs in this frequency range.

20. Dimensional resonance observed for Mn-Zn ferrite cores with different crosssections.HIGH-FREQUENCY CHARACTERISTICS OF MAGNETIZATION 559 Fig. if some kind of resonance is induced at frequency fr (Hz is replaced by /. e~ 5 X 104. and Hr by /r).16 is recognized as the resonance type. The resonance frequency can be obtained by setting H = 0 in (12. the electromagnetic wave will resonate within the core.21 The curve forms are also of the resonance type.20 where c is the velocity of light in vacuum and / is the frequency. giving rise to a standing wave.5 MHz. permeability drops off and magnetic loss increases at very high frequencies because of the occurrence of a magnetic resonance. /x'j. Generally.49). This phenomenon is called dimensional resonance. For Mn-Zn ferrite. Figure 20. It is commonly known that yu. If. The form of the experimental curves in Fig.6 cm.17 shows the frequency dependence of /J. to give where v is the gyromagnetic constant given by . the dimension of the core is an integer multiple of the wavelength A. if we assume /= 1.23.' and //' (or \' and ^") vary with frequency as shown later in Fig. therefore.16. Ji ~ 103. the wavelength A is found to be 2. 20.' and /A" observed for Ni-Zn ferrites with various compositions. The ordinate is normalized to the value at 1kHz. It is seen in this graph that a ferrite with high permeability tends to have its permeability decrease at a relatively low frequency. 20. Snoek22 explained this fact in terms of the resonance of magnetization rotation under the action of the anisotropy field.

5 (C). This can be explained as follows: If we assume that KI > 0.17 that the higher the permeability. 39. 48.9:24. or This value is in the range of frequency where resonance occurs. 24.17. as seen in Fig.2 (A). We see in Fig.7:16. therefore.21 If.71). we have from (20. This phenomenon is called natural resonance.3T for Ni-Zn ferrite. If we take K1= — 5 X 102 Jm~ 3 . 20.71) is applied. Natural resonance observed for Ni-Zn ferrites with different compositions: Mole ratio of NiO: ZnO = 17. we can calculate the anisotropy field from (12.560 DYNAMIC MAGNETIZATION PROCESSES Fig. the anisotropy field is given by (12. the lower the frequency where natural resonance occurs. resulting in abrupt changes in yj and /A". 20. a high-frequency magnetic field with angular frequency given by (20.4 (D). remainder Fe2O3.17.53) or . the magnetization rotation about the easy axis will resonate with the field. 7S = 0.56) as Using this value and assuming that g = 2. 31.7 (E).2:0.5:33. 20.0:9.9 (B).

If the anisotropy in the c-plane is small. for random distribution of in-plane easy axes in a polycrystalline material.23 Table 20. Then the resonance frequency is given. H&2 > Hal.HIGH-FREQUENCY CHARACTERISTICS OF MAGNETIZATION 561 so that the resonance frequency increases with an increase of K1 as On the other hand. therefore. One of the materials that satisfies this condition is a magnetoplumbite-type hexagonal crystal (see Section 9.79).82). similar to (3. 20. and using a = 2irf.4) called Ferroxplana.' drops to one-half its maximum value.17 is drawn by connecting the points where /u. while that for rotation out of this plane be Ha2. so that the permeability may be high. by On the other hand. we have The dashed line in Fig.3 T. to give In order to eliminate KI} we multiply (20.78) together. It was confirmed experimentally that the natural . It is therefore predicted that no ferrite can have a permeability higher than the Snoek limit.1 lists various magnetic parameters for two Ferroxplanas. It was discovered that this limit can be overcome by using a special magnetocrystalline anisotropy.80) coincides approximately with this line: this line is called the Snoek limit. The condition expressed by (20. we have the relationship If.77) and (20. this limit is higher than the Snoek limit given by (20. as long as a cubic magnetocrystalline anisotropy is present. the permeability due to rotation in the plane is given. by From (20. to obtain The same relation holds for K^ < 0. which exhibits an easy plane perpendicular to the c-axis.23 This anisotropy is a uniaxial anisotropy with ^u < 0.51).84). Let the anisotropy field for this magnetization rotation be H3l. assuming the occurrence of magnetization rotation. the permeability decreases with an increase of Klt as we know from relation (18. magnetization rotation in this plane can occur easily. Assuming that 7S = 0.81) and (20. and fjb = 4ir X 10~7 /I.

and is called the relaxation frequency. we discuss the dynamic character and switching mechanism of a spin system.3 X 102 Oe) 1.09 T (=72G) 0.43).4xl0 4 0e) 3700MHz 2500MHz Mg2Ba2Fe12O22 0. As discussed in Section 3. The factor A.25 Since the second term in braces in (20.1 X 10s Am' 1 (=1. 20.3.32 X 102 Oe) l^XlO'Am. This situation is described by the Landau-Lifshitz24 equation where / is the magnetization vector and H is the magnetic field vector.85) represents the component of H parallel to 7. The — sign comes from the fact that the angular momenta of electron spins are opposite to their magnetic moments. The first term represents the precession motion of the magnetization (see (3.27 T (=2150) l.562 DYNAMIC MAGNETIZATION PROCESSES Table 20. but tends to rotate toward the external torque if its free precession is restricted by some boundary condition.OxWAnr1 (= 1. however.1 (=1. which has dimension s"1. Practically. The second term describes the damping of the precession motion in the direction (/ X H). a gyroscope performs a precession motion under the action of an external torque. Various constants and resonance frequency of two types of ferroxplana Co2Ba3Fe24O41 Saturation magnetization/s Anisotropy fields Hal tfa2 Resonance frequency /r Theory Experiment 0. defines the degree of damping action. the magnetization moves towards — (7 X (/ X 77)). thus approaching the axis about which the precession occurs. the magnetization moves in a direction perpendicular to both / and H.5xl0 4 0e) 2100MHz 1000 MHz resonance occurs at frequencies higher than the Snoek limit.1. or in the direction — (7X77). so that they cannot be used at very high frequencies.1 (= 0. The equation of motion may also be written as as shown by Kittel. The factor v is the gyromagnetic constant given by (20. it has been difficult to reduce the resistivity and accordingly the loss factor of these materials. which are the origin of magnetization. the resultant vector given by both terms in braces represents the component of 77 perpendicular to 7.25xl0 4 Am.72). This component of 77 exerts a .4 SPIN DYNAMICS In this section.

First we consider the precession motion.84) and (20. the damping should act on the resultant motion of the magnetization d//df. however. so that the exact equation of motion should be This equation was first derived by Gilbert and Kelley. Thus the magnetization performs a precession motion under the action of the external force and the damping. the damping should act not only on the precession motion. but also the motion induced by the second term in (20.85) can be derived from this equation by neglecting the higher-order terms in a 2 .85) is mathematically equivalent to (20. Strictly speaking.SPIN DYNAMICS 563 torque on the magnetization and causes a rotation of 7 towards the direction of H as a result of damping action on the precession motion.84) or (20. Suppose that a static magnetic field H is applied parallel to the —z-direction. neglecting the damping action.84) and (20. If we put this assumption is equivalent to a 2 < s l . The equation of motion is given by which can be written for each component of Cartesian coordinates: On solving this equation. In other words.84).85).25 Equations (20. In equations (20. it is implicitly assumed that the first term (called the intertial term) is much larger than the second term (called the damping term).85). we have where This solution represents the precession motion of magnetization keeping a fixed angle . It is easily verified that (20.

We rewrite (20. we obtain If we start from (20.84) or (20.18.18). we obtain a similar set of equations. It should be noted that without damping.564 DYNAMIC MAGNETIZATION PROCESSES Fig. the precession motion will decay unless there is a source of external energy to maintain it. 20. The two sets of solutions are the same when a 2 « 1. 20. an external field cannot rotate the magnetization towards the field direction. with (1 + a 2 ) everywhere replaced by 1. In the . Precession motion of magnetization in the absence of damping.87) for each component of the Cartesian coordinates as On solving these equations with respect to dlx/dt.85). If a non-zero damping acts on this precession motion. dl /dt and dI2/dt. with respect to the z-axis (Fig.

Fig. The motion of magnetization for small damping. The motion of magnetization for large damping.19). The switching time also . The angular frequency &> and time constant r in this equation are where o>0 is the resonance frequency given by (20. so that !/&>«: T. 20.93).19. general case including a 2 » 1.98) that 1/w = ar. 20.91) and TO is If a 2 « 1. 20. (20.SPIN DYNAMICS 565 H Fig.20. we obtain where Q is a function of time and is given by and 00 is the initial inclination of magnetization. This switching motion of magnetization becomes more viscous as the relaxation frequency becomes large. it turns out that \/u>» T.93) with respect to Ix(t\ Iy(t) and Iz(t). If a2 » 1. we know from (20. hence the magnetization performs a number of precession rotations before it finally points to the -z-direction (Fig.96). however. 20. Solving the differential equations (20.97) and (20. and the magnetization rotates more directly towards the —z-direction without making many precession rotations (Fig.20). we must use (20.

566 DYNAMIC MAGNETIZATION PROCESSES Fig. taking a strong magnetic field Hz — 1. becomes very large if the relaxation frequency is too small. 20. The fastest switching is therefore attained for an intermediate value of the relaxation frequency. as 1 ( = 20 000 Oe) The condition for critical damping (16. which includes the relaxation frequency A (see (20.6 MAm and g = 2. The minimum value of T is given by which can be estimated. The graph shows that the relaxation time T is minimum when or This condition is called critical damping. . the relaxation time T is plotted as a function of TO.51) is. for 7S = 1 T.21. because the magnetization performs too many precession rotations. The relaxation time for switching of magnetization as a function of the relaxation frequency. In Fig.21.98)). 20.

5 FERRO-.91).FERRO-. it is easily seen in (20.105). In order to produce a . FERRI-. One of the reasons was to take advantage of their eddy currents to obtain critical damping.90) with the angular frequency at resonance given by (20. AND ANTIFERROMAGNETIC RESONANCE The fundamental concept of spin resonance has already been described in Section 3. Let H0 be the amplitude of the rotating field. On comparing (20.3. Consider a thin metal wire. we obtain In order to attain critical damping. which is insufficient for the critical damping. the relaxation frequency as determined for nickel ferrite from the width of the resonance line is 107-108 Hz. AND ANTIFERROMAGNETIC RESONANCE 567 For instance.50) as On the other hand. There we assumed that all the spins forming the spontaneous magnetization maintain perfect parallelism during precession. 20. we see that the relaxation frequency due to eddy currents given by Using the values 10 ~ 7 H m. and w its angular frequency about the z-axis.87) that the damping action is equivalent to the presence of the demagnetizing field. FERRI-. must be In the past. We call this the uniform mode or Kittel mode. magnetic thin films and thin wires were investigated as possible fast switching devices.104) and (20. we have the uniform mode of precession expressed by (20.103).107) must be equal to the value given by (20. the relaxation frequency (20. If a damping force acts on the precession motion. The demagnetizing field due to the total eddy currents is calculated from (20.88). thus the radius of the metal wire. One method to obtain critical damping is to use eddy current damping. r0. the motion can be maintained only if energy is supplied to the system by an oscillating or rotating magnetic field. Starting from (20.

568 DYNAMIC MAGNETIZATION PROCESSES Fig. the Landau-Lifshitz equation (20. .22. In the stationary state. Torque components exerted on magnetization /s by the rotational field H0. the rotating field vector H0 must make a non-zero azimuthal angle $ with the component of the magnetisation vector 7S normal to the z-axis (Fig. 20.22). in cylindrical coordinates.84) becomes. non-zero torque on the magnetization vector. The components of the torque acting on the magnetization vector are then expressed. 20. as If we apply a static magnetic field parallel to the z-axis. for each component.

23 for various values of a. Then tan 0 = 1 in (20. while x" nas a maximum at Hz = Hl. so that </> becomes -90°.117).111) with (20. tan </> becomes infinity.FERRO-. 20. As soon as Hz becomes larger than HT. where Hr is the resonance field. Therefore x' m (20.114).114). because at this value sin2 <f> becomes half its maximum value 1. so that (f> becomes 90°. 20. as shown in Fig. the width of the absorption peak increases. The width of the absorption peak at half the height of the maximum value is called the half-value width. As the parameter a or the relaxation frequency T increases.113). These susceptibilities are plotted against the DC magnetic field Hz in Fig. FERRI-. As Hz increases and becomes equal to HT in (20.110). The real and imaginary parts of the susceptibility are expressed as or from (20. AND ANTIFERROMAGNETIC RESONANCE 569 Comparing (20.23. we have from which we obtain and for 6 •« TT. so that the half-value width is given by . tan (j> changes to minus infinity. This value is calculated by putting </> = 45° in the equation for x" m (20.117) changes sign at Hz = Hr.

55 X 105 Am' 1 .59 X 103 Am" 1 . Hz. electron hopping between Fe2+ and Fe3+ ions. 20. generation of spin waves caused by inhomogeneity of the material.25T. A# = 5. The reason why the line width is not zero is that the precession motion of the spin system is damped by various mechanisms such as eddy currents. In the vibration of a string.23. near the resonance field HT (numbers on the curves are values of or). 7S = 0.570 DYNAMIC MAGNETIZATION PROCESSES Fig. generation of lattice vibrations caused by magnetoelastic coupling. x' and x". on the intensity of the DC field. various higher-order harmonic standing waves are . For Mn-Zn ferrite. A. Hr = 2. Dependence of the real and imaginary parts of the rotational susceptibility. and we have Thus we can determine the relaxation frequency. etc. from the half-value width. and g = 2.

Dillon27 observed many absorption peaks for a DC field less than the main resonance field HT. a possible higher precession mode is shown for each cross-section. shown in Fig. 20.FERRO-. Since the wavelength of such a spin wave is fairly short. Multiple absorption peaks in a (100) disk of Mn ferrite. Many absorption lines were also observed for magnetic thin films to which a DC magnetic field is applied perpendicular to the surface. which produces magnetic free poles on the side surface as shown in Fig. 20. as shown in .32 Suppose that the sublattice magnetizations 7A and 7B make different angles 0A and 0B with the easy axis (the z-axis). Walker28 attributed this phenomenon to the excitation of non-uniform modes of precession. this mode produces distributed free poles. in ferromagnetic resonance.24. AND ANTIFERROMAGNETIC RESONANCE 571 Fig.24. it stores a considerable exchange energy. Therefore this mode is often referred to as the exchange mode. various higher-order harmonic modes can be generated in addition to the uniform mode. thus storing a considerable magnetostatic energy.30 Thus we call this resonance spin-wave resonance.29 The origin of these higher modes is the excitation of standing waves formed as a result of interference of spin waves propagating perpendicular to the surface. The RF field variation across the disk is indicated. Therefore this mode is referred to as a magnetostatic mode or Walker mode. for a (100) disk of Mn ferrite placed in a static magnetic field parallel to [100] with an inhomogeneous RF field parallel to the disk as shown at the top of the figure. after Walker28) generated in addition to the fundamental standing wave. 3. 20. thus reducing the magnetostatic energy. which was first treated theoretically by Nagamiya31 and independently by Kittel. Arrows in the figure represent the in-plane component of spins which rotate with the same rotational speed.25. In contrast to the uniform mode. (Experiment by Dillon27.17. Assuming that the shape of the specimen is spherical. FERRI-. Similarly. Next we discuss antiferromagnetic resonance. as shown in Fig.

and a magnetic field H is applied parallel to the z-axis. The negative exchange interaction acting between 7A and 7B tends to align the two magnetization vectors antiparallel. 3. 20. and H^ and 7fmB the molecular fields. respectively.84). 20. which are as shown in (7. 0) mode.26. The configuration of inplane component of magnetization in each cross section of a spherical specimen corresponding to the (4. (After Walker28) Fig. the magnetic amsotropy. so that the anisotropy field is given by . can combine to cause the same precessional speed of 7A and 7B about the z-axis keeping the angle between the two magnetizations constant. These three effects. i.25.1) and (7. we assume uniaxial anisotropy with its easy axis parallel to the z-axis. and the exchange interaction. the external field.e.572 DYNAMIC MAGNETIZATION PROCESSES Fig.2). For simplicity.. Neglecting damping terms in (20. H^ and #aB the anisotropy fields acting on the A and B sublattices. we have the equations of motion for two sublattice magnetizations: where H is the applied field.

Let Hm be the absolute value of the exchange field acting between the two sublattices. FERRI-. where //a is the absolute value of the anisotropy field. AND ANTIFERROMAGNETIC RESONANCE 573 Fig.120) become . Antiferromagnetic resonance. or We assume that the external field H is applied in the + z-direction.26.FERRO-. Then the components of (20. 20.

so that such a resonance mode cannot be excited by an external RF field. another resonance is observed at higher frequency in the infrared region. The theory was extended by Yosida33 to a more general type of anisotropy. Since this mode stores exchange energy. However.128). He treated the resonance of CuCl 2 -2H 2 O. in this case we find that 0A = 0B from (20.6 EQUATION OF MOTION FOR DOMAIN WALLS It was first pointed out by Doring39 in 1948 that a moving domain wall exhibits . in the sense that the spontaneous magnetization precesses as a whole about the external field.127). as is known from (20. we have the relations from which we have and for Hm » Hz we obtain It is interesting to note that the solution for « can exist even when Ha = 0. Ferrimagnetic resonance34'35 is essentially the same as ferromagnetic resonance. The latter mode is caused by division of the spin axis between the two sublattice magnetizations. we call it the exchange mode. and obtained beautiful agreement with experiment.38 20.36'37 Observation of this phenomenon in GdIG was in good agreement with theory. however. which has a fairly small exchange interaction that allows the observation of resonance in the microwave region. On putting these equations into (20. In addition to this mode. the angular momenta of the two sublattice magnetizations are almost compensated near the compensation point. In the case of the N-type ferrimagnet. as is the case for antiferromagnetic resonance.124). In such a case the resonance frequency of the exchange mode drops down into the microwave region.574 DYNAMIC MAGNETIZATION PROCESSES The components of the two sublattice magnetizations are given by where / is the absolute value of spontaneous magnetization.

41)).to the +*-axis). and a is the restoring coefficient as expressed by the second derivative of the wall energy (see (18. which results in a rotation of spins out of the x-y plane. /3 is the damping coefficient. The term on the right side of the equation represents the pressure acting on the 180° wall and should be replaced by ^ISH for a 90° wall. The demagnetizing field produced by these free poles is given by . The mass of a domain wall has its origin in the angular momenta of the spins forming the wall. In view of this property. induces a precession motion of each spin. this field exerts a pressure on the wall in the z-direction and forces the spins in the wall to rotate clockwise (from the +v. Spin structure of standing and moving domain walls. This force. the equation of motion for a 180° wall is where m is the mass of the wall per unit area. and causes the appearance of magnetic free poles. despite the absence of any mass displacement. if the wall is not moving.EQUATION OF MOTION FOR DOMAIN WALLS 575 Fig. In a Bloch wall. 20. spins are confined in the plane (the x-y plane) perpendicular to the normal to the wall (the z-axis) (Fig. If a magnetic field is applied parallel to the x-direction. 20. however. inertia.27).27.

576 DYNAMIC MAGNETIZATION PROCESSES where Iz is the z-component of magnetization induced in the wall.39).42)). Furthermore. we find This means that the wall must have a z-component of magnetization in order to move with nonzero velocity. The rotational velocity of this precession is.136) and (20. In this case the wall has an additional energy Since as shown in (16. This energy is proportional to v2 and corresponds to the kinetic energy of the wall. This field acts on each spin so as to induce precession motion in the x-y plane.134) becomes where y is the wall energy per unit area (see (16. we have . v = 2. and fj. from (20. through comparison of (20. We can express it as where m is the virtual mass of the wall per unit area and is given.0 = 4irX 10~7.6 X 10~3. This phenomenon is described as the inertia of the domain wall. v. if the wall has a z-component of magnetization. by For a 180° wall in iron. by Comparing these equations. the wall continues to move even without any external magnetic field. which results in a displacement of the wall in the z-direction. This angular velocity can be related to the translational velocity of the wall. with y = 1.91).137). A = 1.21 X 105.49 X 10~n. (20.

63). and assuming ln(r 0 /R) ~ 1. For highly insulating materials such as ferrites. If we neglect the first and third terms.129).EQUATION OF MOTION FOR DOMAIN WALLS 577 Next we consider the damping term /3(ds/df) in the equation of motion (20. p = 1 X 10~7. and we have For iron.84). with /s = 2.8X102. we have )3 = 1.140).84) gives Thus the internal magnetic field does. we have For Ni-ferrite with . Formally it can be expressed in terms of the relaxation frequency A which appears in the Landau-Lifshitz equation (20. The power loss per unit area of the wall is then calculated to be The external field supplies the power to the travelling wall which is given. using (20.146). The z-component of (20. (20. a quantity of work given by which is dissipated as heat.15 (T). in one second.129) becomes For eddy current damping we can compare (20. the origin of the wall damping is the same as the damping acting on the precession motion of the magnetization. we have Even if we assume that the radius is as small as R = 1X10 6 (=1 /im). by On comparing (20.140) with (20.145) and (20.

The latter value is of the same order of magnitude as the value of (20. Therefore. 7S.148). This value is much smaller than the value obtained for the eddy currents in a very thin iron wire. The origin . The value of j8 for magnetite is as large as 4. the wall velocity is expected to saturate and then decrease with an increase in the external magnetic field.29 shows the wall velocity as observed in the shrinking of bubble domains (Section 17. reaches the saturation magnetization.140). In the preceding discussion. The reason for this large value of j8 is considered to be the hopping motion of electrons between Fe2+ and Fe3+ ions in the 16d sites associated with the wall displacement.3). observed for a normal bubble.578 DYNAMIC MAGNETIZATION PROCESSES Fig. Figure 20.26 for Ni-ferrite.24m2 s-'A" 1 (=1900 cms" 1 Oe~ 1 ) for magnetite and 2.84 for magnetite and £ = 0. we have Using this relationship. shows a monotonic increase in velocity with increasing field. Gait40 measured the velocity of a domain wall in single crystals of magnetite and Ni-ferrite.28. On the other hand. 20. He found the values of c at room temperature to be 0. 20. Curve (a). the wall velocity is determined by the demagnetizing field inside the wall which is produced by the z-component of magnetization. The third term in (20.61) and (20. when the z-component of magnetization.61). which was deduced from the relaxation frequency. curve (b). observed for a hard bubble in which spin rotation is not so easy as in a normal bubble.5m2 s^A'1 (= 20000cms -1 Oe"1) for Ni-ferrite. cut in a picture-frame shape as shown in Fig. shows that the velocity exhibits a maximum and then decreases with increasing external magnetic field. On comparing (20.41'43 Actually this characteristic was observed for a garnet crystal film with very low magnetic losses.06 even after the effect of eddy currents is subtracted from the observed value. Ferrite single crystal in picture-frame shape. we can determine )3 = 4. and confirmed the validity of (20. Iz.129) signifies the restoring force acting on the wall.28.

where y is expressed. the equation of motion (20. 20. » ^-a) to give The mass m is given by (20.2 for several examples. we have here This means that the wall will oscillate about an equilibrium position.EQUATION OF MOTION FOR DOMAIN WALLS 579 Fig.29. as observed for a garnet crystal film with very low magnetic losses: (a) normal bubble. as so that the mass becomes .138). (b) hard bubble. Domain wall velocity of a shrinking bubble as a function of magnetic field.44 of this force is given in Section 18.36) ( /JL. The factor a is related to the permeability /A by (18. If we neglect the second term and the right-hand term. from the comparison of (16.129) becomes On solving this differential equation.47).46) and (16.

as compared to the case when the field is maintained at 90% of the critical field? Assume the occurrence of the thermal fluctuation after-effect. while wall displacement requires 7r/(255)rads~ 1 . magnetization rotation requires an angular velocity (ir/2)rads"1. wall displacement is more rapidly damped than is magnetization rotation. fine magnetic particles with distributed sizes is magnetized parallel to the aligned axis and is then subjected to a field which points in the negative direction.155) into (20.1 After magnetizing a single crystal of carbon-iron parallel to [010] for a long time to its saturation. assuming diffusion after-effect and also lc <s kT.153) and (20.3 Suppose that a plane 180° wall is travelling with velocity v from the top surface to the bottom surface of an infinitely wide plate of thickness d which is made from a ferromagnetic . except for the factor \/5S.2 Suppose that an aggregate of aligned.580 DYNAMIC MAGNETIZATION PROCESSES On putting (20. we obtain ( (2001 ft>0v/7l = 0. the angular velocity is 104 times larger for wall displacement than for magnetization rotation. long. therefore. note that these differences between wall displacement and rotation depend on the value of 55. the difference between the two mechanisms would be large. so that the specimen would be filled with domain walls and the wall displacement would become practically equivalent to incoherent magnetization rotation. it turns out that SS~ 10~4 for 8= 10~5 mm. 20. the total loss is expected to be proportional to (SS)"1. If this value could be increased to approach 1. the magnetization is switched to [100]. On the other hand. For the example mentioned above. Since S is the total area and S is the thickness. the quantity SS is the fractional volume of wall per unit volume of the specimen.156) This relationship is similar to formula (20.//40. (20. The reason is that for a given amplitude of magnetization. hence the wall resonance frequency is expected to be lower by a factor 102 than in the case of natural resonance. Since the power loss in the wall is proportional to w 2 or (SS)~ 2 .46VSS v/. It was observed by Gait40 that the relative permeability of a frame-shaped single crystal of magnetite drops from 5000 to 1000 between 1 kHz and 10 kHz. since the specimen contains only one domain wall.152). One of the reasons for this is the high original value of permeability. the power loss should also be larger for wall displacement than for magnetization rotation. For a given amplitude of magnetic field. 20.79) for the natural resonance derived on the basis of magnetization rotation. wall displacement could survive to high frequencies. PROBLEMS 20.1 mm. Solve for the time change in the anisotropy energy. In order that the magnetization changes by 7S per second. if the spacing of the walls is 0. but also it is partly because 58 is very small (10~6). How fast is the magnetization change if the intensity of the field is maintained at 89% of the critical field. This would require that the wall spacing be very small. However. By the same reasoning. the angular velocity of spins in a wall is much larger than that for magnetization rotation. Thus magnetization rotation becomes more important at high frequencies. if S8 is very small. For instance.

17. Dillon. Rev. J. 1005. 80 (1950). 100 (955). Phys. 174. W. 25 (1953). p. L. Phys. Snoek. 345. Rev. L. Landau and E. Proc. 5 (1949). Tomono. Phys. C. Phys. /. Neel. Tsuji. Physica. 245. 14 (1948). 1 (1956). C. 27. F. H. Z. Ann. /.. Japan. Phys. H. Street and J. 337. 1949). Japan. B-I (1962). Appl. Ohashi. 228 (1949). L. Uchiyama. Brawn.. E. Assume g = 2. 125.. 1381. L. Proc. Compt. Phys. Yamadaya. 21. p. Wooley. 43 (1955). K. Amsterdam. Rev. Shockley and C. 7. Williams. R. Lifshitz. 8 (1935). 24. 10. 25. H. 1951) Chap. 25 (1953). Phys. 249.. 29 (1937). Snoek. Japan. p. Kittel. II. 1st 3M Conf. 1 (1952).. B68 (1955). 16 (1961). Becker and W. Lifshitz. J. Find the time required to rotate the magnetization from 9 = 60° to 9 = 120°. J. S. Suppl. 49. Ferromagnetismus (Springer. Ohta and T. Gilbert. 2. 12. Phys. 6. Street. Physik. Soc. 26 (1955). Mod. and S. Brockman. J. G. Rev. R. Berlin. Steneck. §17. Phys. Phys. Rev. 293. 46. Neel. Rend. 15. Dowling. Yanase. Ser. New developments in ferromagnetic materials (Elsevier. J. P. 20. Radium. 339. G. 918. and R. B. REFERENCES 1. 254. §16. Soc. and P. USSR. Amsterdam. Phys.. Ferromagnetism (Van Nostrand. J. C. 80 (1950) 1090. 3. Jap. Soc. 1949). 153. Neel. Japan. 605. 98. Mod. P. L. 18 (1956-57). van der Heide. Kittel. H. 9. Jr. 17 (1962). Kelley.REFERENCES 581 metal with resistivity p and saturation magnetization /s. (1955). Ohta. Philips Tech. Proc. 14. Gilbert and J. E. Doring. Ann. 1939).. 20. J. 5 (1938). 22. Neel.. J. Phys. 253. 77 (1950). Bull Am. 663. Geophys. Bozorth. J. G. Sowjetunion. Bean. 18.Y. 54. Soc.. T. Calculate the eddy current loss per unit area of the plate as a function of the distance. Tsunashima. K. initially travelling at 10ms""1 move after the magnetic field is switched off? Assume the relaxation frequency is 1 X 108 Hz. Soc. H. Phys. 11 (1950). 17. L. L. Phys. 19. IRE. and W. J. /. .. 562. Phys. Rev. A. Y. Phys. 8 (1944). 12 (1951). Appl.5 How far does a 180° wall. Gorter. J. /. Proc. 23. 664. J. A62 (1949). 16. 250. 145. M. Physica. J. R. W.4 A spherical sample with saturation magnetization 7S = 1T and relaxation frequency A= 1 X 108Hz is magnetized along the z-axis (0 = 0). G. Phillips. and the number of precession rotations that occur in this time interval. 11.. Wijn and H. 207. K. 180. Rev. Radium. 1333. H. of the wall from the top surface of the plate. 26. Soc. Phys. T.. 17. New development in ferromagnetic materials (Elsevier. 85. 19 (1980). 291. 5. C.. L. L. 13. Jonker. Soc. Phys. H. F.. 99. 8. 1243. Phys. 20. 13 (1952). Wooley. 4. Wijn. z. Snoek. P. N. Radium. P. M.. Phys. A uniform magnetic field H= — 1 X 102Am"1 is applied in the —z-direction. /. Richter. L. /.

S. Z. 263. 2 (1972). J. Phys. 29. K. 7 (1952). 6 (1951). 1023. 7 (1953). Phys. 85 (1952). Phys. Walker. F. C. R. 33. Phys. 3a (1948). Appl. 318. C. Tannenwald. J. 163S. 45 (1974). Bell Sys. R.. 36. (Kyoto). Doring. 1 (1958). Narita. 5406. S. Rev. 831.. H. Yosida.. Phys. Theoret. K. (Kyoto). Phys. Sugano. J. 101. AIP Conf. 831. Progr. R.. 373. 45 (1974). . 227S. 29 (1958). Konoshi. 110 (1958).. W... and K.. Gschwind and L. Tsuya. Rev. /.. 35.. K. and P. 68. 97 (1955).. 41. 145.. Okabe. Phys. Mag. Y. Nagamiya.582 DYNAMIC MAGNETIZATION PROCESSES 28. 38. Walker.. 37. J. Phys. 425. McGuire. Appl. Wangsness. Phys. R. N. R. Progr. J. 43. Takigawa. Phys. Rev. Phys. 25. 85. Gait. Phys. and T. 2705. M. C. N. E. Slonczewski. 32. 664. T. Appl. Tech. Toyooka. M. Schryer and L. 30. Rev. Proc. Phys. Rev. J. /. 34. Theoret. Naturforsch. 44. 93 (1954). T. 40. 25 (1953). Rev. 82 (1951). Progr. Phys. Mod. Phys.. 1295. Appl. L. Int. 31. Jr. 565. Seavy. K. Phys. Walker.. Kittel. 39. Phys... 42. Wangsness.. Phys. 105 (1957). 30 (1959).. 390. 15 Suppl (1976). Watanabe. /. Theoret. Mizuno. Kittel. 30 (1959). Rev. 33 (1954).. 97 (1955). 342. Appl. No. 168. Rev. T. Appl. 34 (1976). Lett. Rev. 93. L. /. K. Jap. R..

thermal.Part VIII ASSOCIATED PHENOMENA AND ENGINEERING APPLICATIONS In this part. we discuss various phenomena . The engineering applications of magnetic materials are also summarized. . electrical and optical .associated with magnetization.

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In this model. The entropy 5 is generally given by k In W. magnetic materials have additional entropy due to the presence of spins. For simplicity. while the number of — spins. Consider a paramagnetic material composed of a number of spins.1 MAGNETOTHERMAL EFFECTS In magnetic materials.21 VARIOUS PHENOMENA ASSOCIATED WITH MAGNETIZATION 21. we have the entropy S for a given I. decreases. so that the entropy becomes Thus the entropy is reduced by the application of a magnetic field.2) containing N spins in a unit volume. 7 = 0. the spins can undergo thermal motion. Adiabatic demagnetization is a method to create a low temperature by manipulation of this extra entropy. or N+ = N_ = N/2. we assume an Ising model (see Section 6. N_. N_ = 0 and 7V+ = N. increases. When H = 0. where M is the magnetic moment of one spin and N+ + N_ = N. This entropy is controllable by an external magnetic field. When a magnetic field H is applied in the + direction. each spin magnetic moment (simply called 'spin' hereafter) can take either a + or — direction. In other words.1). the number of ways of realizing this combination is expressed by Using Stirling's formula ln(«!) = n In n — n. When N+ and N_ are given. when H increases and the magnetization saturates at 7S. so that the entropy becomes On the other hand. N+. thus the magnetization increases. . where k is the Boltzmann factor and W is the number of different ways of realizing the state (in this case. the number of + spins. magnetization). Therefore magnetic materials exhibit an additional or 'anomalous' specific heat in addition to the normal specific heat caused by the thermal motion of the crystal lattice (see Section 6.

^0. the spin entropy contributes to the magnetocaloric effect. In order to keep the same entropy. must be held constant (see (21.u. using nuclear magnetic moments with very small interactions.3)). so that H cannot be neglected. In this temperature range the Curie-Weiss law (6. a temperature as low as 0. Therefore the heat generated in a unit volume is given by At T «: @ f . the high field susceptibility. The work done by the field must be converted to heat.9 or Fig. Using a paramagnetic material containing a dilute concentration of magnetic ions.K (= 10~6 K) have been obtained by means of nuclear adiabatic demagnetization. so that neglecting H in (21. wl and H are comparable in magnitude. the temperature T decreases as the field H is reduced. the heat change is zero. /. Since the magnetization of a paramagnet is a unique function of H/T (see Fig. H.133). so where dS is the entropy change. which magnetizes to the intensity. At magnetization levels approaching saturation.22)). Then the paramagnet is thermally isolated from the heat reservoir.10) we have At T > ®f. 5. keeping the temperature constant at T (isothermal process). Q: which is transferred to the heat reservoir to keep the temperature constant. This is the principle of adiabatic demagnetization. The work d W done by the field (per unit volume) is given by On the other hand.586 VARIOUS PHENOMENA ASSOCIATED WITH MAGNETIZATION First a strong magnetic field. so that we have . 5.01 K can be attained by adiabatic demagnetization.15) holds. Super-low temperatures in the range of . In the case of a ferromagnet. In an adiabatic process. the molecular field wl is much larger than H.10). is given by (18. /. and the field is reduced (adiabatic process). such as CrK alum. Suppose that the magnetization is increased by SI under the application of a magnetic field H. the magnetization. Therefore the entropy must be kept constant during adiabatic demagnetization. the internal energy is changed by (see (6. is applied to a paramagnet. The approach to low temperatures is limited by the interaction between magnetic ions.

14). (21. It is predicted from (21.MAGNETOTHERMAL EFFECTS 587 Fig. It is seen that the proportionality factor between 8T and 5(/2) is constant below 360°C. we obtain The temperature change is given by where C.8).10).11) and (21. If we express (21.1 shows the magnetocaloric effect observed for Ni below and above its Curie point of 360°C. as expected from (21. 21.1 after Becker and Doring2) Using the expression for the Curie point (6. (Experiment by Weiss and Forrer. Figure 21.11) and (21.1. Temperature change caused by magnetization in Ni at temperatures near the Curie point as a function of the square of magnetization/density ( p : density).11) in terms of H. it becomes .12) is converted to the form Using this in (21.14) that the temperature change is proportional to 72 below and above the Curie point. while it increases with increasing T. is the specific heat for constant /.

7 In addition to the reversible change in temperature (magnetocaloric effect) occurring at high fields. (21.3 shows the temperature changes observed for Ni as it is cycled around the hysteresis loop. The prediction is thus that 8Q has a maximum at the Curie point and decreases with either decreasing or increasing temperature.85 K for Ni and 2K for Fe at // = 0. (Experiment by Weiss and Forrer. Co. Detailed investigations were made by Bates and his collaborators7 for Fe. and Ni. Figure 21.2. 21. Temperature dependence of magnetocaloric effect in Ni. 6.6 MAm"1 (= SOOOOe). Investigations were also extended to ferrites8 and permanent magnets. nickel and pure iron. Numerical values in the figure are fields in Oe or (103/4ir) (Am"1).4). Since L'(«) approaches zero more rapidly than T does as T-»0. so that SQ becomes very small again. so that the temperature will increase continuously if the material is cycled around the hysteresis loop. The curves are quite similar to the temperature dependence of the high field susceptibility (see Fig. The temperature change due to this magnetothermal effect is partly irreversible. 8Q given by (21.001 K. The temperature change at the Curie point is 0. an irreversible increase in temperature is . The temperature change due to this magnetothermal effect is the order of 0. The temperature of a ferromagnet is also changed by the generation of heat associated with technical magnetization processes.15)). This phenomenon has been investigated by a number of workers4"6 for carbon steel. much smaller than the magnetocaloric effect. at T > @ f .2 shows the temperature dependence of the magnetocaloric effect as measured for Ni. This corresponds to the heat generated by the hysteresis loss. the denominator becomes larger more rapidly than the numerator as the temperature increases.16) becomes very small at low temperatures. showing the expected behavior. On the other hand.14) becomes At very high temperatures.1 after Bozorth3) (see (6.588 VARIOUS PHENOMENA ASSOCIATED WITH MAGNETIZATION Fig.9 Figure 21.

during the magnetization rotation from Fig. Magnetothermal effect in Fe as a function of the applied field. This heat change is caused by magnetization rotation against the magnetocrystalline anisotropy.3. like a decrease in molecular field. opens up the angular distribution of spins. 21. Since the anisotropy field is changed by \H= -WK^/3^ (see (12. Reversible changes in temperature are observed not only at high fields but also in very low-field regions near the origin. which. (After Okamura6) .57)). Figure 21. (After Townsend5) observed at the coercive field.4 shows the magnetothermal effect observed for Fe. Magnetothermal effect in Ni as a function of the applied field. 21. The work done by the magnetic field is mainly used to raise the anisotropy energy.4. increasing the entropy of the spin system and resulting in an absorption of heat.MAGNETOTHERMAL EFFECTS 589 Fig. and the rotation of magnetization results in a decrease in anisotropy field.

4. This scattering is.0025 and C = 3.12 It is seen that irrespective of the direction of the applied field with respect to the current.5 the ordinate scales are adjusted so that the resistivities are equal at the Curie point of Ni. ME effect. L'(a) ~ 0. Mott explained the temperature variation of resistivity fairly well by this picture. the resistivity always decreases with an increase in spontaneous magnetization. permitted in a nonmagnetic metal. and the other is the dependence of resistivity on the orientation of the magnetization (anisotropic magnetoresistance effect). T= 300 K. the magnetization rotates from <111> to <100>.590 VARIOUS PHENOMENA ASSOCIATED WITH MAGNETIZATION (100) to (111).5 compares the temperature dependence of the reduced resistivity of Ni and Pd. the heat generated during this process is calculated from (21. The same effect is also observed in the forced increase of spontaneous magnetization by the application of high magnetic fields.6 shows the field dependence of resistivity of Ni parallel and perpendicular to the magnetic field.10 21. If the material is ferromagnetic. half of the 3d shell is filled.2 MAGNETOELECTRIC EFFECTS There are various magnetoelectric effects. There are two kinds of magnetoresistance effect: One is the dependence of resistivity on the magnitude of spontaneous magnetization. In Fig. and in this sense is quite similar to Ni which has ten electrons outside the argon shell. Mott13 interpreted these phenomena in terms of the scattering probability of the conduction electrons into 3d holes. 21. magnetic tunneling. the magnetothermoelectric effect. however. so that SQ is still negative. in which both the plus and minus spin states of the upper 3d levels are vacant. as measured by Englert. including magnetoresistance. so that the temperature change is calculated to be which is in good agreement with the heat absorption seen in Fig. The first case causes a temperature dependence of resistivity in ferromagnetic metals resulting from the temperature change in spontaneous magnetization. Kasuya14 interpreted these phenomena by a picture quite different from the Mott theory. For iron. Kv = 4.16) to be When K^ < 0. so that the scattering of 4s electrons into the plus (magnetic) spin state is forbidden. Hall effect. ®f= 1043 K. Experimental separation of the reversible and irreversible temperature changes was attempted by Bates and Sherry. Figure 21.2 X 104. He considered that d electrons are localized at the lattice sites and interact . 21. etc. Pd has ten electrons outside the krypton shell. Figure 21.5 X 106 Jdeg"1 m~ 3 . It is seen that the resistivity of Ni is considerably reduced by the appearance of spontaneous magnetization below its Curie point.

6.12 . because the spins of 3d electrons on all the lattice sites point in the same direction. The 4s electrons are scattered by this irregularity of the periodic potential. the conducting 6s Fig.5.MAGNETOELECTRIC EFFECTS 591 Fig. resulting in an additional resistivity. 21. At nonzero temperatures. At 0 K. (After Becker and Doring11) with conduction electrons through the exchange interaction. the magnitude of the latter being explained by his theory. in which the 4/ electrons are responsible for the atomic magnetic moment. Kasuya postulated that the temperature dependence of resistivity of ferromagnetic metals is composed of a monotonically increasing part due to lattice vibration and an anomalous part due to magnetic scattering. 21. the potential for conduction electrons is periodic. Variation of resistivity of Ni as a function of magnetic field. the spins of the 3d electrons are thermally agitated and the thermal motion breaks the periodicity of the potential. In rare earth metals. Comparison of reduced resistivity of Ni and Pd.

7 shows the temperature dependence of Ap m as measured for Fe and Fe-Al alloys by Tatsumoto et a/. The numerical values are in the range 0.592 VARIOUS PHENOMENA ASSOCIATED WITH MAGNETIZATION Fig. Actually the anomalous part of the resistivity measured for a number of rare earth metals is proportional to the square of the magnitude of the spin magnetic moment. 21.a3) and (/3j. can be described in a similar way to magnetostriction. The change in resistivity is described as where (alt a2. because both quantities depend not on the sense but only on the direction of spontaneous magnetization. These coefficients have been measured in Fe and Ni single crystals by a number of investigators. the anisotropic magnetoresistance effect. respectively. The second case of magnetoresistance.1-4%. Temperature dependence of 3Apnl for Fe and Fe-Al alloys. /32. /33) are the direction cosines of spontaneous magnetization and electric current. the Mott theory is considered to be invalid.7. Figure 21.16 electrons are considered to be scattered by the irregularity in the polarization of 4/ elections. Since the 4/ electrons are completely localized.15 in accordance with the Kasuya theory.16 The anisotropic magnetoresistance effect was explained by Kondo17 in terms of the scattering of s electrons by a small unquenched orbital moment induced by 3d spin . at least for rare earth metals.

Magnetoresistance effect as a function of the mean number of Bohr magnetons per atom observed for various magnetic 3d transition alloys. The magnetoresistance effect is particularly large for magnetic semiconductors such as chalcogenide spinels (see Chapter 10). and the spin-dependent magnetic scattering of conduction electrons is reduced by the application of a magnetic field which causes parallel alignment of the magnetization in the Fe layers. (Smit18.23"26 Recently a giant magnetoresistance effect has been found in multilayer magnetic thin films. the origin of which has been discussed by a number of investigators. In fact.20 Since the deviation of the gyromagnetic ratio from 2 is a good measure of the remaining orbital moment.8. Kondo explained the magnitude and the temperature dependence of this effect satisfactorily.^Gd^Se. Similar phenomena have been observed for various combinations of ferromagnetic and antiferromagnetic metal multilayers. exhibits very large temperature dependence of resistivity and also a very large magnetoresistance. They found that the resistance of the film drops to about half of its original value upon the application of a magnetic field. Figure 21. after Jan19) magnetic moment. in In-doped CdCr2Se421 or HgCr2Se4. This phenomenon was first discovered by French scientists27 in 1988 in multilayer Fe-Cr films. which are composed of alternating thin layers of Fe and Cr. For instance. this fact proves the validity of the Kondo theory. This curve is quite similar to the dependence of the gyromagnetic ratio on the number of 3d electrons measured for various magnetic 3d alloys. The origin of this phenomenon is that the magnetizations of the Fe layers on opposite sides of a Cr layer are aligned antiparallel as a result of a negative exchange interaction through the Cr layer. Magnetic tunneling is observed for two ferromagnetic metal layers separated by a thin insulating layer about Inm thick.MAGNETOELECTRIC EFFECTS 593 Fig.22 the Ap/p values amount to -100% near their Curie points (110-130K). Another magnetic semiconductor. Euj. 21. It was observed that the tunneling electric .8 shows the average Ap measured for various magnetic 3d alloys as a function of spontaneous magnetization. irrespective of the angle between the current and the field.

Thus we can express * When this value is used.7% at room temperature. If the effect of magnetization is simply to apply an internal magnetic field ju. The temperature dependence is mono tonic. This phenomenon was first observed by Julliere28 in an Fe-Ge-Co junction in 1975. where 0 is the angle between magnetizations in the metal layers. This effect is observed to exhibit an anomalous temperature dependence at the Curie point. In the case of ferromagnetic metals. an electric field is produced perpendicular to both the current and the magnetic field. Co. The thermoelectric power of ferromagnetic metals also depends on magnetization.32 The anisotropic effect can be described in a similar way to the magnetostriction or magnetoresistance effect.07 to the conduction electrons.5% at 77 K and 2. This is the Hall effect. Fe) junctions. we must look elsewhere for the origin of the extraordinary Hall effect.9. Since this is not the case. Slonczewski30 showed theoretically that the tunneling electric conductance varies as cos 9. it was found33 that the Hall electric field per unit current density depends not only on the magnetic field H but also on the magnetization /. . as shown in Fig.21). The magnitude of this effect is of the order of 1/tVKT 1 for Fe and Ni. When a magnetic field H is applied to a ferromagnetic metal perpendicular to the electric current.35 the value of R0 for Ni at room temperature was determined36 to be This value is the same order of magnitude as that of nonmagnetic transition metals such as Mn or Cu.0 = 1 in (21. Kaplus and Luttinger38 considered that the extraordinary Hall effect can be separated into the two parts: One due to the internal field p0I produced by the magnetization 7. Maekawa and Garvert29 observed hysteresis in tunneling resistance versus magnetic field for Ni-NiO-(Ni. R1 must be equal to R0. so that it can be expressed by where R0 is the ordinary Hall coefficient and R1 is the extraordinary Hall coefficient. Miyazaki et a/. The value of Rl for Ni at room temperature is This quantity increases with increasing temperature and exhibits an anomaly at the Curie point.594 VARIOUS PHENOMENA ASSOCIATED WITH MAGNETIZATION current between two metal layers depends on the relative angle between the magnetization in the two metal layers. and the other due to the spin-orbit interaction between 3d spins and conduction electrons. It should be noted that the value of R^ is one order of magnitude larger than that of R0. 21.31 observed a change in tunneling resistance for an 82Ni-Fe/Al-Al2O3/Co junction as large as 3.34 From the data of Smith. and has a maximum at room temperature. This is called the magnetothermoelectric effect. we must put ^.

When these quantities are small.9. we have and . but their directions are not parallel to each other. Temperature dependence of extraordinary Hall coefficient of Ni. If we write (21. Since R0 <c R\ except at very low temperatures.9. They considered that 3d electrons are conducting and their orbital motion is influenced by their own spin-orbit interaction. 21.37 where R0 is the ordinary Hall coefficient as given by (21. They showed that R\ is related to the resistivity by This relation holds well for various kinds of Ni alloys. 21. His calculation explains well the temperature dependence shown in Fig. Kondo17 considered that 4 s electrons are conducting and their orbital motions are influenced by the orbital motion of 3d electrons remaining unquenched.26) for each component in Cartesian coordinates.MAGNETOELECTRIC EFFECTS 595 Fig. the proportionality relationship holds between electric and magnetic quantities.23) and R\ is the extraordinary Hall coefficient due to spin-orbit interaction. respectively.39 The magnetoelectric polarization effect (ME effect) is the phenomenon in which a magnetic field H produces an electric polarization P or an electric field E produces magnetization /. He extended his theory to rare earth metals and explained the extraordinary Hall effect of Gd metal. the main part of R0 is R\. We can express these relationships as where a and a' are the ME tensor and EM tensor. In contrast to this theory.

H. In the latter material an interesting temperature dependence of the ME effect was observed near 10 K. /. The sign of 6 is positive when 6 has the same rotational sense as the electric current in the solenoid which produces the magnetic field.27) or (21. in which the plane of polarization of light reflected from a magnetic material rotates in accordance with the sense of magnetization. In spite of the fact that the frequency of precession motion of a spin is much smaller than the frequency of visible light.3 MAGNETO-OPTICAL PHENOMENA Magneto-optical phenomena can be classified into two categories: the magneto-optical effect in which the optical properties of a magnetic material can be altered by magnetic means. and the MKS (SI) values are 47r/c times the CGS values (c: velocity of light = 3 X 108 ms~*). and is expressed as where V is the Verdet constant. independently of the sense of propagation of the light. In the Faraday effect. The ME effect is observed only for ferro.or ferrimagnetic materials with low crystal symmetry. and to the field. Br. or I). it causes a large difference in absorption between two circularly polarized light beams. Co. these tensor component are dimensionless. The magneto-optical effects include the Faraday effect. The allowed transition .596 VARIOUS PHENOMENA ASSOCIATED WITH MAGNETIZATION Between the two tensor components a and a' we have the relationship The unit of these tensor components is sm" 1 or inverse velocity.43'44 21. each level splits into two levels 5 = — \ and + in the presence of a magnetic field H (Zeeman splitting). or Cu and X = Cl. In these materials one of the nondiagonal elements of the tensors in (21. and the photomagnetic effect in which a magnetic property of a magnetic material is altered by optical means.28) is nonzero. because this phenomenon is caused by the difference in absorption between two oppositely circularly polarized light beams. Fe. In CGS Gaussian units. 9. and the magnetic Kerr effect. of the plane of polarization is proportional to the path-length.4). Mn. due to the precession of spin. which have canted spin systems (see Section 7. ME effects are observed for boracite40 M 2 B 7 O 13 X (M = Cr. only the component of magnetization parallel to the direction of propagation of the light is effective in rotating the plane of polarization. and magnetite41'42 Fe3O4. This is due to the following mechanism: Suppose that a magnetic atom at an energy level A absorbs a photon ft a> and is excited to level B (see Fig. If the atomic spin is \. in which the plane of polarization of light transmitted through a magnetic material rotates in accordance with the sense of magnetization. Ni. In this case the sign of the angle of rotation is independent of the sense of propagation of the light. 21.10). the rotational angle. In both cases.

it . The magnetic structure of Er orthochromite (ErCrO3) was observed to change from antiferromagnetic to canted-spin upon illumination by light at 4. 21. Therefore the two transitions mentioned above must be caused by the absorption of oppositely circularly polarized light as illustrated in Fig. This is known as a selection rule in spectroscopy. so that the absorption of one circularly polarized light is greater than the other. For instance. we cannot regard this process as a photomagnetic effect. Since this is not an optical function. Photo-induced magnetic anisotropy (Section 13. 21. However. Generally speaking. or fro S = .\ at level A to S = \ at level B.2) and for detecting the sense of magnetization of recorded magnetic patterns in magneto-optical memory devices (see Section 22.47 Faraday rotation and magnetic Kerr effect are also used for observing magnetic domain patterns (see Section 15. In a magneto-optical memory system.3). thus resulting in a rotation of the plane of polarization of the light.10. Selective absorption of right-hand and left-hand circularly polarized light by a magnetic atom.2) is an example of a photomagnetic effect. The reason is thought to be the transfer of some 2p electrons from O 2 ~ to 6p orbits in Bi3+ ions. there must be a change in spin angular momentum. a magnetic signal is written using a laser beam (see Section 22. the Verdet constant of YIG is appreciably increased by the introduction of a small amount of Bi3+ or Pb3+ ions. Physically it corresponds to the law of conservation of angular momentum. however. the population between the two spin states at the level A is different. When a magnetic atom is magnetized. The Verdet constants have been measured for a number of transparent magnetic materials and are found to be impurity-sensitive. and this mixing of orbits enhances spin-orbit interactions.MAGNETO-OPTICAL PHENOMENA 597 Fig.2 K. because when circularly polarized light which has an angular momentum is absorbed by an atom. thus resulting in a nonzero rotation of the plane of polarization. the plane of polarization will rotate in the same sense during penetration to the skin depth and back to the surface. This is due to a change in superexchange interaction caused by light.10.46 Faraday rotation has been used for measuring magnetization in ultra-high pulsed magnetic fields.3). the role of light in this case is to locally heat the magnetic media above the Curie point so that the magnetization reverses on cooling in the demagnetizing field. between the two levels is either from S = \ at level A to 5 = — \ at level B.4. The mechanism of the magnetic Kerr effect is similar to the Faraday effect: when light is reflected at the surface of a magnetic material magnetized perpendicular to the surface.

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Secoi. For this purpose.22 ENGINEERING APPLICATIONS OF MAGNETIC MATERIALS Engineering applications of ferromagnetic materials are divided into three major categories: first is soft magnetic materials for AC applications in magnetic cores of transformers. sizes of transformers.d is hard magnetic materials for permanent magnets. excellent magnetic characteristics are more important than the cost of materials. inductors and related devices. and low hysteresis loss are required. high coercive field. Third is the semi-hard magnetic materials for magnetic recording. we must select suitable magnetic materials for particular applications based on a balance between competing requirements. From this point of view. it is customary to use wt%. we will omit 'wt' in the following description. For simplicity.1 Soft magnetic alloys (a) Silicon-iron alloys The addition of a small amount of silicon to iron results in higher maximum permeability. motors. high residual magnetization. Desirable properties for core materials are high permeability. inductors. lower magnetic loss and a substantial increase in electrical resistivity . moderately high coercive field and high residual magnetization are required. For this purpose. In the former case. In the latter case. Since no material meets all these specifications. low coercive field. In addition. up to many tons. so that magnetic cores must be magnetized to the maximum permeability point to make full use of the magnetization of the core material. Therefore high maximum permeability and low cost are necessary.1 SOFT MAGNETIC MATERIALS Soft magnetic materials are used for magnetic cores of transformers. and those for use in small. high induction and low cost are important factors. and generators. In the description of composition of practical alloys.6) are required. generators and motors are very large. so '%' will mean 'wt%.' 22. low-power devices where material costs are less important than magnetic properties. and accordingly high energy product (see Section 1. For this purpose. high permeability. low coercive field and low magnetic losses.1. motors. 22. we can classify soft magnetic materials in two groups: those for use in large machines where the cost of material is dominant.

The Curie point decreases from 770°C to about 500°C as the silicon content increases from 0 to 15%. well-oriented grains.1 shows composition dependence of various magnetic constants such as relative maximum susceptibility. meaning that the grains have the (110) plane parallel to the plane of the sheet. #max. and annealing for what is known as 'secondary recrystallization' to produce very large. (b) Iron-nickel alloys This alloy system is composed of two regions: the 'irreversible' alloys containing 5% to 30% Ni-Fe. for Fe with small additions of Si. 22. It was later found that this process works because primary recrystallization is inhibited by the presence of naturally occurring MnS particles.1. and the 'reversible' alloys from 30% to 100% Ni-Fe. Irreversible alloys . As seen in this figure. Hc. and the [001] easy axis parallel to the rolling direction. and hysteresis loss. Figure 22. Variation of magnetic properties of Si-Fe alloys with addition of silicon.4 also developed a new product called RGH using SbSe as an inhibitor.1 which lowers eddy current losses. silicon causes a decrease in saturation magnetization and an increase in brittleness. On the other hand.3 using A1N instead of MnS as an inhibitor against unwanted grain growth. Silicon is soluble in iron up to 15% Si. The maximum permeability is greatly improved by orientating crystal grains so as to align the easy axis of each grain in a unique direction. This process was improved by Taguchi and Sakakura. Imanaka et a/. annealing. Goss2 first produced 'grain-oriented silicon steel by a rather complicated process of hot-rolling. the soft magnetic properties are improved by the addition of Si. coercive field. Increasing brittleness makes high silicon alloys difficult to produce in the form of thin sheets. Wh. severe cold-rolling.SOFT MAGNETIC MATERIALS 601 Fig. and has better performance than conventional Goss steel. The product developed by this technique is called HIB (high bee) steel. The recrystallization texture is (110) [001]. so most commercial materials are made with Si contents from 1 to 3%.

Therefore the permeability has a maximum at 21. Because of this phenomenon. The alloy of this composition is made commercially under the name Permendur.35 and 14. Cr. This alloy is called Permalloy (see Fig. The crystal structure is bcc and FeCo superlattice forms below about 730°C at compositions around 50% Co.602 ENGINEERING APPLICATIONS OF MAGNETIC MATERIALS transform from fee to bee during cooling from high temperature. and also to increase electrical resistivity by a factor 4. Very high permeability is obtained only when the alloy is quenched from 600°C to suppress the formation of directional order (see Section 13. As reported by Elmen6 and by Masumoto. Actually. attains very high permeability without quenching. sharp maxima in x* and A'max are observed to occur at about 50% Co-Fe.12). 18. The reversible alloys are single phase fee solid solutions. which contains 5% Mo in 79% Fe-Ni.1). and 30% Fe. where both the saturation magnetization and the Curie point of the fee phase become very small and presumably drop off to zero. 8. the saturation magnetization at OK has a maximum at about 35% Co-Fe. and in aircraft equipment where light weight is important. various magnetic properties exhibit thermal hysteresis. The magnetocrystalline anisotropy and magnetostriction constants K and A go through zero near 20% Fe-Ni (see Figs 12. and this is the reason why these alloys are called irreversible alloys. As seen in the Slater-Pauling curve (Fig. and the average transformation temperature differs considerably between cooling and heating. (c) Iron-cobalt alloys Cobalt is soluble in iron up to 75% Co-Fe. This transformation occurs over a certain temperature range. The alloys near 30% Ni-Fe show a more rapid decrease in saturation magnetization with temperature than other magnetic alloys. or Cu is also effective in suppressing the formation of directional order. Alloys of this kind are called magnetic compensating alloys. Normally about 2% V is added to slow the ordering reaction and improve workability. where K1 goes through zero.11). so they can be used as shunts in magnetic circuits to compensate for the normal temperature change of magnetic flux. so that we can expect high permeability. The addition of a small amount of Mo. Other effects of adding Mo are to attain the conditions K = 0 and A = 0 simultaneously at the same composition. although the name is loosely applied to various Ni-Fe alloys. 45% Ni. In order to attain this characteristic. Its high flux density is useful for pole pieces of high-power electromagnets. Therefore Supermalloy. (d) Iron-cobalt-nickel alloys The best-known magnetic alloy which belongs to this system is Perminvar: 25% Co.5 The 36% Ni-Fe alloy where this anomalous behavior starts is called Invar and has nearly zero thermal expansion near room temperature. The maximum saturation value at room temperature occurs at about 40% Co-Fe.5 Fe-Ni. the alloy must be annealed for a fairly long time . The saturation magnetization at OK as a function of composition shows a simple variation following the Slater-Pauling curve except near 30% Ni-Fe.7 the unique feature of this alloy is its constant permeability over a wide range of magnetic induction.27).

1 0.1.0 0.2imp O.45 1. Heat H treatment c ^ 1 Name Content CO *a xmax (Am' ) (Oe) (T) (G) Iron Iron (pure) Si-Fe (random) Si-Fe (GOSS) 78Permalloy Supermalloy Permendur FeB amorphous10 0.1 2.79 2.5Ni 5Mo.05 0.73 .0 0.08 1710 1710 1570 1590 860 629 1950 1380 ®t (°C) 770 770 690 740 600 400 980 334 p (xlO~ 8 ) (tlm) 10 10 60 47 16 60 7 130 0.15 1.5 0. Magnetic properties of soft magnetic alloys (mostly from Bozorth9).97 2.05 2.002 0.00 1.Table 22.15 2.16 160 8 1.79Ni 50Co 8B6C 950 1480 +880 800 800 1050 600Q 1300 800 Q 150 10000 500 1500 8000 100000 800 680 5000 200000 7000 40000 100000 1000000 5000 80 4 40 8 4 0.OSimp 4Si 3Si 78.

however. should be proportional to the applied field. Also some compositions show relatively large aging and disaccommodation (Section 20. (a) Sendust11 The alloy containing 5% Al. Ferrites and other nonmetallic compounds are particularly good for high-frequency applications because of their high resistivity (see Table 22. 22. The eddy current loss is of primary importance. The necessity for this treatment was interpreted by Taniguchi8 as follows: all the spins in the domain wall are stabilized by a uniaxial anisotropy induced by directional ordering during the anneal. they have the disadvantage that the saturation magnetization is limited by the high content (about 25%) of non-magnetic metalloid elements. 10% Si and 85% Fe exhibits extremely high permeabilities Xa = 30000 and ^max = 120000 as cast from the melt.1. because this alloy responds strongly to magnetic annealing (see Section 13. so that they exhibit high permeability and low coercive field in addition to high electrical resistivity. (e) Amorphous magnetic alloys The preparation procedure and magnetic properties of amorphous alloys are described in Chapter 11. When the alloy is magnetized by a strong field the domain walls may escape from their stabilized positions and thus become incapable of giving constant permeability. 18. magnetic metals and alloys for AC use are always in the form of thin sheets or fine particles. Table 22. Amorphous alloys have small anisotropy.604 ENGINEERING APPLICATIONS OF MAGNETIC MATERIALS (for instance. . Then the hysteresis loop becomes a snake-shaped or constricted one as shown in Fig. and accordingly the resultant magnetization.1) effects.2). For power machines. and. They are mechanically strong. in order to reduce it. or rapid solidification processing. Amorphous alloys are successfully used in power transformers up to several kVA capacity. This behavior can be explained by the same model. It is also possible to make the hysteresis loop rectangular. because this composition just meets the conditions Kl = 0 and A = O. Since in this case the energy of the domain wall is a quadratic function of its displacement. the displacement. and some compositions have good corrosion resistance. The core materials are produced by continuous splat-cooling. and for small transformers and other devices operating at frequencies up to about 50 kHz.1 lists magnetic properties of various soft magnetic alloys. reduction of the various losses accompanying highfrequency magnetization is more important than static magnetic characteristics.1). 24 h) at 400-450°C. are coated with a thin electrically insulating layer and compressed into final shape.44. it is ground into small particles about 10 ju. after annealing. which.m in diameter.12 Since this alloy is very brittle. which keeps the domain walls in their original positions.2 Pressed powder and ferrite cores For high-frequency applications. in the form of long thin ribbons or sheets.

Mg-Mn ferrite is used as a rectangular hysteresis material.2. 50mol% ZnFe2O4.2 or Fig. The desirable properties for hard magnetic materials are high coercive field and high residual magnetization. 9. In Mg-Zn ferrites. the working point of the magnet should correspond to the maximum value of the energy product.17). no hopping motion of electrons occurs. and the oxide has extremely high resistivity and exhibits extremely low magnetic losses.7). (c) Garnets The crystal and magnetic properties of these oxides were discussed in Section 9. they are usually quenched from 800°C or slowly cooled in a nitrogen atmosphere to prevent segregation of a-Fe2O3 and occurrence of disaccommodation (Section 20. 22. because the 'natural resonance' shifts to higher frequency by an increase in Kl (see Section 20. so that it is used for bubble domain devices (see Section 22. Most commercial ferrites for this purpose contain Zn. Section 18.3. ferrites are electrically insulating. Maximum permeability occurs at 50-75 mol% MnFe2O4. which is the maximum rectangular area under the B-H curve in the second quadrant of the hysteresis loop (see Fig. so that they are suitable for extremely high-frequency uses (see Fig. Initial permeability is maximum at 30mol% NiFe2O4.1). However. However. Thin films of this crystal are optically transparent.1 to 1ft m (= 10-100 ft cm)). For most efficient use of the magnetic material. high permeability is realized at 50mol% MgFe2O4. so that they are extensively used as core materials. Single crystal garnets are used for microwave amplifiers. Since the metal ions are all triply charged. so that they are not suitable for extremely high-frequency use. high-frequency properties are better at higher Ni content.HARD MAGNETIC MATERIALS (b) Ferrites 605 As already discussed in Section 9. the resistivity is relatively low ( p = 0. 1.2 lists magnetic properties of pressed powder and ferrite cores. After being sintered at 1400°C. this ferrite can be sintered at high temperatures. for the following reasons: (1) The addition of Zn causes a decrease in the Curie point and brings the high permeability which is commonly attained just below the Curie point (Hopkinson effect.2 HARD MAGNETIC MATERIALS Another important engineering application of magnetic materials is as permanent magnets. 70mol% ZnFe2O4.3). Table 22.7). so that they are most suitable as high-frequency magnetic materials. Since only the doubly charged state is stable for nickel ions. . 20. Ni-Zn ferrites have extremely high resistivity. A figure of merit to express the quality of permanent magnet materials is the maximum energy product (5//)max. 9. Mn-Zn ferrites have relatively high saturation magnetization (see Table 9.3). (2) The addition of Zn causes an increase in saturation magnetization at 0 K (see Fig.27).2) closer to room temperature. 50-25 mol% ZnFe2O4. thus compensating a part of the decrease in saturation magnetization at room temperature caused by a decrease in Curie point.

Magnetic constants of pressed powder and ferrite cores. were developed.25 0.0 (T) 0.40 0. The origin of this magnetic annealing is the reorientation of the elongated precipitated particles (see Section 13. MK steel.14 and MT magnet (Fe-C-Al steel).1 Permanent magnet alloys As is well known in steel metallurgy.1) and it produces large internal stresses and at the same time finely divided elongated particles (see Fig. Originally the high coercivity of this magnet was thought to be due to large internal stresses. .13 Heat Name Sendust powder MnZn ferrite NiZn ferrite Ca added YIG Content 5A!. Since the coercive field for B. Cr steel and Co steel are all old permanent magnets utilizing this phenomenon.10Si 50Mn-50Zn 30Ni70Zn 0.15).1). he suggested that a single-domain structure of fine precipitated particles must be the origin of the high coercivity. which decomposes into two bcc phases during slow cooling from the high-temperature ordered bcc phase. Recently developed high-quality rare earth permanent magnets such as RCo5 and Nd15Fe77B8 meet both these requirements. This process is known as spinodal decomposition (see Section 13. Cooling this alloy from 1300°C in a magnetic field results in a rectangular hysteresis loop and accordingly a large value of (fi//)max. were used. Alnico. when a carbon iron is quenched from the fee phase.16 This alloy is also called Alnico 5. BHC.120))..25 0. MnAl.3. but later Nesbitt17 found that a high coercivity is also observed for an alloy of the same kind which has no magnetostriction.2. These later materials have higher coercivity but lower residual magnetization as compared with the alloy magnets. it transforms completely or partially to a bet phase called martensite.3.2. Accordingly. which is mechanically and magnetically hard. The MK magnet was invented by Mishima. 22. W steel. the aim in developing permanent magnet materials is to get the saturation magnetization as high as possible while maintaining high coercivity. first iron and its alloys such as KS steel. when the hysteresis loop is measured in the direction of the cooling field. invented by Honda and Saito. It has the approximate composition Fe2NiAl. etc. etc. 13..1 3. Other examples are KS magnet (Fe-Co-W steel).45 0. invented by Mishima and Makino15 which contain no expensive metals such as Ni and Co.17 (G) 360 200 320 135 ©f (°C) 500 110 130 287 p («m) 20 5x10" In the history of permanent magnets.606 ENGINEERING APPLICATIONS OF MAGNETIC MATERIALS Table 22. 800 1150 1050 HC & 80 2000 80 600 (Am" ) 100 8 240 1 ls (Oe) 1. and then compound magnets utilizing single domain characteristics such as Ba ferrites. cannot be greater than the value of the residual magnetization divided by /i0 (see (1.2% Ca+ Y3Fe5O12 treatment (°C) Press.

///.6. 4. it has good machinability and low density (3. thus resulting in a very low coercive field.and B-rich phases. This kind of magnet is described as having nucleation-controlled coercivity. which contain no obstacles to domain wall displacement.19 It has a magnetoplumbite-type crystal structure with the chemical formula BaO-6Fe2O3 (see Section 9. both of which have tetragonal crystal structures.5 gem"3). RCo5 and R2(Fe.20 MnAl is a ferromagnetic compound which includes none of the ferromagnetic elements (see Section 10.24 This phenomenon is considered to be due to the elimination of 'magnetic seeds' for the nucleation of reverse domains by the application of Hm. both compounds produce strong uniaxial anisotropies (see Table 12. the coercive field for /. and exhibit very high magnetocrystalline anisotropy. 8.3 and Strnat22).3).Co)17 magnets belong to this category.2. but even with 5% Co a usefully high value is obtained. . The largest (B/f )max is obtained at 15% Co. containing 0.2. The Nd15Fe77B8 magnet includes grains of the phase Nd2Fe14B with tetragonal crystal structure (Fig.3 Rare earth compound magnets RCo5 and R2(Co. These compounds have fairly large saturation magnetization (see Table 12. so that ferrite materials sintered into solid ceramic form can be used as permanent magnets.Fe)17 type compounds22 have a strongly uniaxial crystal structure (see Fig. less than that of Ba ferrite.7% carbon. This compound. One of the features of this type of material is that once the magnet is magnetized by a strong field. In the case of R = Sm.26). Strong internal stresses produced by this superlattice formation are supposed to be the origin of their high coercivity. 22. High coercivity is obtained because it is difficult to nucleate reverse domains. Necessary conditions for this are a defect-free structure of the crystals and also smooth grain boundaries containing Nd.25 Nd-Fe-B and Pr-Fe-B alloys can be prepared by the melt-spinning technique26 as well as by conventional sintering of powders. The anisotropy is uniaxial and also very large (see Table 12.. it will run across the grain. The grain size is much larger than the critical size for single-domain structure. so that the (BH)m3X values are one order of magnitude larger than those of previously available magnets.. //m. 22. 10.21 is inductionmelted and extruded at 700°C under a pressure of 80 kg mm"2.1). As discussed in Section 17. Moreover the crystal grains can be aligned by pressing in a magnetic field. respectively.4).10). In addition to excellent magnetic properties. which can increase (BH)max by a factor of 3.5 gcm"3. a sintered magnet can have a single domain structure. Fe-Pt and Co-Pt alloys form the superlattices FePt and CoPt.4). The melt-spun material is used in bonded magnets for accurately shaped parts. so that once a domain wall is created.2 Compound magnets Ba ferrite is a hexagonal ferrite invented by Philips investigators.HARD MAGNETIC MATERIALS 18 607 Fe-Cr-Co alloy is a deformable alloy magnet.23 This phase has a very large uniaxial anisotropy. increases with an increase of the maximum magnetizing field.

9 60 36 10 11 4.0C. Heat treatment (°C) 850Q 830Q 1150AQ.9 Name Composition Alloy magnets W steel 0. ISi 78Pt 23Co.1 Magnetic tapes and disks Magnetic tapes and magnetic disks are devices to record analog or digital signals magnetically by utilizing residual magnetization.31 0.0..9C.3 7.0C.60 0.6 12.45 1.8Al 24Co.3 for a number of permanent magnet materials.45 0.90 0.608 ENGINEERING APPLICATIONS OF MAGNETIC MATERIALS Hc B. steel 0. MK (AlnicoS) Fe-Cr-Co 0.6 5.7C. (T) 1.82 (Am" 1 XlO 2 ) 56 48 143 (Oe) 70 60 180 Table 22.0 4. 22.10Al.0 33.30Al.2 20.4 166 477 290 3.35Co 2.0 0.5 2.58 0.98 0.9C.0 5.3.8 1300AF.5 3.0A1 16Ni. 780FC 1000Q (B//)max Jm~3* XlO 3 ) 2.8.1 7.3 Superlattice magnets Pt-Fe Pt-Co 0.0 3.23Co.58 0.93 1.3Cr.6Cu 14Ni.15Co KS steel MT steel MK magnet Orient.6 Density (gcnT3) 8.0 3. 12Co.5%Cr 0.5Mo.5 8.77Pt 2O3 0.3.9 7.23 1250 1570 2070 2600 1200 1500 2560 7200 3300 9000 24 30 8. Magnetic properties of various permanent magnets.6W 3. The principle of these devices is .0 7.Cr.27 0.2 1.4 Compound magnets ferrite MnAl 70Mn.7Cr.8 1. 4W.5 1.3 200 160 446 438 464 250 200 560 550 580 8.3 6.0 0.1 4. 600B 600-540B 1.7C Rare earth compound magnets SmCo5 Sm2(Co.7 40 42 1.3Cu 28Cr.20 0.3 MAGNETIC MEMORY AND MEMORY MATERIALS 22.5Cr steel 15%Co 1. 9600 12000 The magnetic energy per unit volume is given by half of the value and is calculated as half of Various constants are listed in Table 22.7 7.3.Fe)17 Nd15Fe77B8 or l/8ir of GOe.8 (G Oe XlO 6 ) 0.

They are also used for recording digital signals for large-scale data storage for computers. so that usually both the tape and the magnetic head are moved. Then a residual magnetization corresponding to the signal wave form is left on the tape or disk. In order to reproduce the signal. The residual magnetization pattern recorded on a magnetic tape by a magnetic head. 22. 22. Magnetic tapes are used for recording audio signals (voice and music). shown in Fig. which in turn is magnetized by a signal current carrying the information to be recorded. Such a magnetic structure stores some magnetostatic energy. Magnetic powder or an evaporated magnetic thin film carried on a ninmagnetic tape or disk is maagnetized as it passes under a magnetic head.3(b). a magnetic reading head produces a voltage by electromagnetic induction when the recorded residual magnetization on the tape changes the magnetic flux in the head. taking into consideration the coexistence of a magnetic head and magnetic medium whose hysteresis loop is assumed to be as shown in Fig. A magnetic head utilizing the magnetoresistance effect is called an MR head. A magnetic disk consists of a rotating flexible plastic disk (floppy disk) or a rigid.3(a). a cylindrical head with multiple gaps is rotated. because of the increasing density of the recorded signal. and its . The result is shown in Fig.2.2. The signal from one track is converted to one horizontal visible line on the display tube. the running speed of the tape relative to the head must be high. Therefore instead of the induction method a static detection of the recorded signal using the magnetoresistance effect has been developed (see Section 21. The distribution of the recorded residual magnetization has been calculated by computer simulation. Then the signals are recorded along many narrow parallel tracks tilted with respect to the edge of the tape. The advantage of magnetic disks is that a desired portion of the stored information can be quickly retrieved without spooling through an entire reel of tape. thus reproducing the recorded picture.MAGNETIC MEMORY AND MEMORY MATERIALS 609 Fig. The speed of magnetic tapes and disks relative to the magnetic head is becoming smaller and smaller. 22. relatively thick disk (hard disk) coated with a layer of magnetic medium. For example. so that the induction voltage of the signal becomes smaller.2). and the tape is wound around the rotating head cylinder and moved in the opposite direction to the head surface motion. In this case. 22. tending to form closed magnetic flux paths. It is seen that the magnetization has a component perpendicular to the surface at all depths in the tape. Magnetic tapes are also used for recording video signals.

However. or the highest bit density. One possible solution is a thin film magnetic head floating aerodynamically above a smooth magnetic medium. the lines 1-4 are the magnetization process in a running tape).28 There is a physical limit to the minimum bit size.5). there are various technical limits in recording and reproducing magnetic signals.3.4.2 Magneto-optical recording The magnetic media used for magneto-optical recording79 are mostly R (rare earth)-Fe or R-Co sputtered amorphous thin films which have uniaxial magnetic anisotropy with the easy axis perpendicular to the film surface (see Section 13. before reaching this physical limit.610 ENGINEERING APPLICATIONS OF MAGNETIC MATERIALS Fig. a system which has been developed for large-scale hard disks. 22.30 The recording is exclusively digital: either . (b) the calculated distribution of residual magnetization in magnetic media. such as the miniaturization of the magnetic head and obtaining smooth contact between the magnetic head and the magnetic medium. Computer simulation of the distribution of residual magnetization in magnetic media: (a) assumed hysteresis loop (the dashed lines represent a complete hysteresis loop. 223. The most promising material has been TbFeCo. (After Shinagawa27) energy density becomes larger as the signal density becomes higher.

1 80 0.3).4 for powders.4(a)).15 120 0. and the polarization of the reflected beam is rotated oppositely for + and — recorded bits (magnetic Kerr effect. In order to write a signal. because the writing and detecting of the signal Table 22.1 > 2.0 1. and then a laser beam is focused on a narrow area to he'at it above the Curie point (Fig. . Magnetic constants of magnetic recording materials. induced by the demagnetizing field of the surrounding material. The advantages of magneto-optical recording are high-density memory storage and greatly reduced friction and wear.4.4. In order to detect the signal. a polarized laser beam is directed onto the magnetic media. Thus a + bit is written in.00 800 * In the case of packing factor 0.0 1. first all the area is magnetized downward.MAGNETIC MEMORY AND MEMORY MATERIALS 611 Fig.5 > 2. magnetization-up (+ ) or magnetization-down ( — ). 22. 22. After switching off the beam.5 ernug" 1 80 80 90 > 200 > 200 T G kArn' 1 Oe 20-31 20-80 16-64 20-72 8-80 250-390 250-1000 200-800 250-900 100-1000 0.* #c Materials •y-Fe2O3 powder Co-doped powder CrO2 powder Fe-Co powder Co-Ni thin FILMfilm Wbmkg" 1 X10~ 4 1. This rotation of polarization is detected by an analyzer and detector (Fig.30 200 1. (b) reading process. Magneto-optical recording: (a) recording process. this area cools down and a region of upward-pointing magnetization appears.1 80 0. see Section 21.4(b)).28 °i /. 22.

5.3). When the shift of a digital number is completed. Permalloy pattern for propagation of a bubble domain. In this way many digital numbers can be stored in the minor loops. In reading a digital number stored in the minor loops. Such a shift of bubble domains can follow a rotational rate as high as 100 kHz. In a memory storage system.31 It is a digital memory using bubble domains (see Section 17. amorphous alloys. while the number '0' is expressed as the absence of a bubble domain. the digital number T is expressed as the presence of a bubble domain. and is shifted to the next pattern during one revolution of the rotating field. etc. 22.) . and shifted to a major loop of Permalloy patterns. which is detected by a detector. Table 22.5. An example of a memory storage system is shown in Fig. (A bubble shifts to the next pattern by being attracted by a free pole appearing on the pattern during one revolution of a rotating magnetic field. 22. First a digital number is converted to a bubble domain array by the bubble generator. Mn-Zn ferrite. For details on bubble domain devices the reader may refer to Mikami.6.4 lists magnetic constants of various magnetic recording materials. Sendust.3 Bubble domain device This is an all-magnetic memory system with no mechanically moving parts. a bubble domain can propagate along a path defined by Permalloy patterns magnetized by a rotating magnetic field.32 Rotational field Fig. The bubble domain is attracted by the free pole appearing on a Permalloy pattern. produced on a garnet single-crystal film which is grown on a gadolinium-gallium-garnet single-crystal plate. and then each digital number is shifted to a minor loop.3. Materials used for magnetic heads are Permalloy. 22. 22.612 ENGINEERING APPLICATIONS OF MAGNETIC MATERIALS use highly focused laser beams and there is no physical contact with the magnetic medium. the gates to minor loops are opened. by opening all the gates to the major loops the digital number array is reproduced in the major loop. As shown in Fig.

Ferromagnetism (Van Nostrand. Kan. Kaneko. Kept. Graham.J. P. Stuyts. US Pat.. D. Physik. Fig. and G. 583. Snoek. Nakamura. Homma. 22. T. Saito. 557. 4. Bubble memory storage circuit. Bozorth. Tohoku Univ. Ohm. T. N. 13. Amsterdam. led to much useful understanding in solid-state physics and materials science. 80. Ferromagnetism (Van Nostrand. Kept. Masumoto. Goss. Handbook on magnetic substances (ed. Rathenau. K.. Sci. 10. . W. 1951) p. Tohoku Imp. G.. Am. Sakakura. H. numerically controlled machines. (Honda) (1936).. Sato. 32 (1961). 21 (1950). 1013. Tohoku Imp. Jr. R. 43 (1956). Obata.. Soc. 2351142 (1974). Tohoku Imp. Hatta.6. 515. G. Bubble domain devices were for a time used for telephone exchange systems. Sci.. 9. Taguchi and A. 23 (1935). W. T. 726. 12. Phys. Phys. W. J. J. and C. Asakura Publishing Co. Z. Imanaka. Franklin Inst. 17. 20. 647. van Oosterhout. Elmen. Nesbitt. 1951) p. Makino. so that the topic should not be ignored. Kept. J. N. H. Proc. J. as discussed in Section 17. H. Y. T. J. 1949). 8A (1956). 18 (1929)... Wilson. 435.. Univ. 4. Smit. 133 (1952). Mishima and N. 5 (1971). Princeton. S. Garter.. L. 870.. J. 1978) Sections 21. H. E. New developments in ferromagnetic materials (Elsevier. 8. A. Table 2. Princeton. W. 250. 417. Rev 13 (1952). E. Went. and K. N. MAG-1 (1978). Egami. 5. 15. 3. Sci. 1088. T. S. 879. Univ. AIP Con/. Kept. M. 9 (1920). M. 207 (1929). 19 (1932). IEEE Trans. S.REFERENCES 613 Fig. Germany Pat. Trans.. 19.J. Tokyo. No. 11. Kouvel and R. R. J. Nagashima. 206 (1928). 22. and T.10. Iron and Steel. Sci. L. REFERENCES 1. Research on bubble devices. J. 7. Rathenau. and A. Appl. Metals. Mishima. 173. Philips Tech. 2. S. G.. W. Bozorth. Taniguchi.3. M.. Honda and S. 195. Appl. Masumoto. W. 18. Univ. 16. 3159511 (1964). OLS No. 388. by Chikazumi et al. 6. but they have been largely replaced by semiconductor devices. 353. T. however. 317. 194. 14. etc.

2083. H. Pinkerton.. F. Asakura Publishing Co. M. MAG-5 (1969). Tanaka. /. J. Mag. J. 511. Section 26. 32. M. Appl. J. Kqjima. Croat. Kato. 54-7 (1986). Strnat. N. Phys. Tsukahara. Handbook on magnetic substances (ed. R. Nagao. Shinagawa. Handbook on magnetic substances (ed.. Kubo.. 28. 1975). M. S. S. Phys. Mag. Yamamoto. S. R. Fischer.. 25. 31. L731. Mag. H. and P. Sakamoto. P.614 ENGINEERING APPLICATIONS OF MAGNETIC MATERIALS 21. I. Tokyo. J.. S. Becker. Van Uitert: IEEE Trans. /. MAG-21 (1985). A. 22. Perneski.. Phys.. and Y.. by Chikazumi et al. G. N. 544. IEEE Trans. 1328. Tokyo. J. Section 26. E. T. Mag. Imamura. K. . 26. K. A.3. J. N. /. 9 (1969). J. 24. Ohta. 55 (1984). Matsuura. 55 (1984). by Chikazumi et al. and Y. MAG-8 (1972). W. 1551. Lee. 214. Iwasaki. Togawa. Sagawa. Kuno. Jap. 39 (1968). Chikazumi. F. IEEE Trans. Bobeck. S. Tanaka. F. Appl. 30. 29. Appl. Ohtani... /. 27. and I. 1270. 19 (1980). IEEE Trans. 2078. Mag. Remeika. Private communication. 1607.4. S. IEEE Trans. Herbst. Appl.. Phys. J. Asakura Publishing Co.. MAG-13 (1977). J.. Mag. Mikami. Imamura and C. 23. Mag. Fujimura. 1975). Mat. I. and T..

79) by considering that the magnetic potential difference between the magnetic poles ±75 is given by Hx. we have the relationship I = xHeS = xH-( */3/i0)/. the cross-sectional area of the permanent magnet must be . Since the magnetization / is attained by this effective field.1 When the sphere is magnetized to the intensity 7. Then we have The total magnetic moment of the sohere is • /\ When x~* °°> the moment becomes M= 4TrR3fj. Ni = 200 X 5 = 1 X 103 [A]. so that the magnetostatic energy is zero.SOLUTIONS TO PROBLEMS CHAPTER 1 1. 1. the field is calculated to be 1. and the reluctance. This expression can be deduced from (1. or from (1. which produces the Maxwell stress T\\ = ^fj.0)/2. we have the force acting between the two halves.2 The magnetic field produced in the air gap is given by // = ///n0.QH2 = (l/2ju.4 If there is no leakage of magnetic flux from the magnetic circuit. there are no free poles or there is no field in the space where / is present. this problem is interpreted as follows: Before the separation of the two halves. From the energy point of view. we have the total force F = (l//j. the effective field becomes Hetf = H — (l/3ja0)7.105).3 Using the magnetomotive force.0)72S.0H. When the two halves are separated by the distance x. the air gaps store the magnetostatic energy (l//A0)/2&c. Considering there are two gaps. 1. Differentiating this expression with respect to x.

the length of the permanent magnet parallel to the magnetization is given by 1.1(a).2 From (3. we have (Remark: This value is equal to the cosine of the angle between the central axis and the line connecting the central point O and the edge of the solenoid in Fig.99).39) 3.47) with respect to H. we have from (3. / = i/3r.1 By using z = 0. we have CHAPTER 2 2.44). we have 33 Solving (3.5 According to (1. 2.4 Adding and we find that all the ^-dependent terms vanish.) 2. CHAPTER 3 3. R = r in (2. . L = 6. 2_3 Refer to the text.2 From (2.616 SOLUTIONS TO PROBLEMS From Ampere's theorem.1 Using 5 = f. / = 4f.4). we have H = (Ni/l) (Am"1). we have Using 3.7).

1 Using g = 0. (D.94 X 106/63. 4. 2MH.5 from left to right correspond to the transitions CD. we have 5=1. 4. in Fig. we have from (4. from which we have H = 26. ®. (3). so that we have A £ = — O. we have v2 = 3kT/m or v = fokT/m . or (5) and ® corresponds to 4A£. (2).180. 43 From the relationship \nw2 = f AT.2 Using we have from .8) 5. taking the difference between CD and ®. H = -27 X 10 6 Anr l .1 Using N = 6. ®.9).47 XlO^m 3 . and the difference between (2) and (5) or (3) and (?).5 X 1(T10 m.2 X 10~27J. must be equal to the Zeeman splitting of the ground state. m = 9. or (5) and (3). we have from (5. Z = 29. Therefore the difference between (?) and (2).3. CHAPTER 5 5.l^cms"1 = — 9. we have T = h2/3mk\2 = 40 K. The difference between (D and (D.2 The absorption lines in Fig.2 MAm"1. Using this in (4.SOLUTIONS TO PROBLEMS CHAPTER 4 4.54 = 8. e = 1. respectively.11 X 10~31.60 X 10~19. we have Solving this equation.02 X 1023 X 8.090/\ = 0.5) 617 4. Moreover.6mms~'.39 cms"1. a = 0. which is 0.

Thus we find that 7a = 2NM.29). we have the magnetization curve I/NM = 1. 73 Since J2 = -(V3~/6)/1. from which we find that QC = 2w/12. . which is in region II. Therefore the value of / or Hm deduced from the experimental value of ®f becomes larger. Therefore we have from (7. x = C/(20N) = Xo.2) and (5.2 Since a = ft = 0. proportional to T2. 7.4) becomes / = NM(a/3) -H/w.Since the origin O is located in the region where 7S < 0 at T = 0 as well as T ~ 0f.65) cos QC = i/3~/2.38). we have Therefore the energy-dependence of the density of states becomes so that from (8. x=lx0 = 0. no compensation point appears.Thus we find that at T = 2® N .18) we have Thus we find that the susceptibility decreases with T.9).618 CHAPTER 6 6.1 We see in Fig.1 From (8. CHAPTER 8 8. 6. we have a = (45)1/3&1/3. Ib = -2NM.7 that x = Xo at T=0 and T=0 N /2.67^0. this ferrimagnet corresponds to the origin O in the a-ft diagram (Fig. we have SOLUTIONS TO PROBLEMS More accurate statistical treatment leads to a smaller value of k@t/J. 7. Comparing this with (6. 7.62) n = lir/QC = 12.4899CW from (7.2 At T = &f.h. Since wl = 0. (6.11). where h = H/NMw. Since A = f and /a = f. we find that ®N = -®a> so that x = C/(T + 0N). Using this in the above equation.41) and 0a = -0. we have from (7.19A1/3 . CHAPTER 7 7.1 From (6. Therefore at T = 0 N . so that ®f/®a = 1-02.22).4800O from (7. we have 0f = -0.39) with (7.

/.2 Af = 1MB is realized at electron numbers 27.7 and 25.y.z') plane is parallel to the (210) plane.y'. 26. 12. and 55at% Fe-Cr. z') plane.0) with respect to the cubic coordinates (x.y'.-«? = 1 and E. 12.-. m./? = E. = E.m .48).1 x x' y' z' y 1/i/S -2/1/5 0 z 0 0 1 2/i/5 1/1/5 0 12. has the direction cosines (2/i/5~. These numbers correspond to the alloy compositions 60 at% Ni-Co.4 Refer to the text.= 0.2 Using (12.. that is the x'-axis.1 Set the new coordinates (x'.y'.. From Table Sol. whose z'-axis is parallel to the z-axis and (0.1./.z'). 8.z\ The relationship between the cubic and new coordinates can be constructed as shown in Table Sol. 12.n.SOLUTIONS TO PROBLEMS 619 8. m.1 by using the relationship £. 90at% Co-Cr. we have the anisotropy field . «. CHAPTERS 9-11 Refer to the text.m} = £. respectively. Co-Cr and Fe-Cr alloys. = E.6. where /. Then the normal to the (0.1 for Ni-Co. we have the relationships Since we have Then the K^term of the anisotropy energy becomes 12. CHAPTER 12 Table Sol.l/i/5~. 83.and nt represent the direction cosines of new coordinate axes with respect to the cubic coordinates.

Let the angle between the spontaneous magnetization and the z-axis in the (110) plane be 6.4 Assuming n = 1. For [110] annealing ft = ft = (I/ /2 ) and 03 = 0.11) is expressed only by_the second term.11) becomes £ = «l"2 01 02 + «2«302 03 + «3 a l 03 01 = (1/2)ft ft sin2 6 + (l/v/2 )ft ft sin 6 cos 6 + (1/V2 )ft ft sin 0 cos 6.20). a3 = 0. that is ir/2. Then a1 = cos 6.1 Since kt = 0. Then we have <*! = a2 = (l/V2~)sin 9 and «3 = cos 6. Note that sin 00 = \/2~/\/3~. sin2S0 = 2\/2 /3. so that £ = 0. so that £ of the second term in (13.2 Let the angle between the *-axis and the spontaneous magnetization be 6.f i . a2 = sin 6.11) becomes Comparing this with (13. the induced anisotropy (13. [110] and [111] annealing are 0:1:2. 13. cos 00 = 1/V^. ft = 0. Therefore for [001] annealing ft = ft = 0. ft = ft = I/ . we have from (12. Therefore the ratios of the induced anisotropies measured in the (110) plane for [001]. Therefore the anisotropy energy (13.72) Therefore the anisotropy energy is given by CHAPTER 13 13. For [110] magnetic annealing. For [111] annealing 0i = 02 = 03 = (I/ &X so that where 00 is the angle between the [111] and the z-axis. cos200 = -|.620 12. so that where 00 is the angle between [110] and the z-axis.3 SOLUTIONS TO PROBLEMS Since the number of atoms in a unit volume is calculated by we have from 12. we have for <110> .

z'\ in which y' is parallel to [110]. the domain magnetizations in [100] and [100] change their directions to [010] by 90° wall displacement. we have E in (13. body-centered cubic and face-centered cubic structures given in Table 13.e. The relationships of the new coordinates and the cubic coordinates (x.1 By applying the magnetic field parallel to the [010] direction. we have Therefore so that we have the anisotropy energy CHAPTER 14 14. z' is parallel to [111]. k2 = f.28) and (13.3 Referring to (13. k1 = \. a'3 = 0. k2 = 0.y'. 13. and kt = -jk.3. 133 Let the angle between the spontaneous magnetization and [110] be 6. 3 in Table 13. we have for sc 0: £ = 0:1. 3.29) with slip system No. and for fee £ : £ + £ = 4:3. and the final elongation at saturation magnetization 7S is given by f A100. Considering that the magnetostrictive elongation is proportional to the magnetization /.3. the ratio of the induced anisotropies in <110> measured in the planes parallel to the (001) and (110) planes is given by k2/2:(kl/2+k2/4\ Then using the values of k1 and k2 for simple cubic. k2 = -j^.22). i. for bcc f : £ = 2:1. Table Sol. y. Then we have Since a{ = cos 6. we have . and set new coordinates (x'.28) where s is the slip density for slip system No. 13. k1 = 0.1.SOLUTIONS TO PROBLEMS 621 Comparing it with (13. z) are given by Table Sol. a'2 = sin 6.

we have for the second term of the anisotropy energy (12.14).1 Since the uniaxial anisotropy energy constant. so that sin(ir/4) = cos(ir/4) = l/v/2. so that we have For [010] elongation.2 Using (16.100) CHAPTER 16 16. the wall energy (16. Then the 180° wall energy (16. we have for a [010] domain Ea = — f A100cr.5 Using the values for Fe in Table 14.89). so that we have 14. 16. which is equivalent to (Oil). /32 = 1. Similarly. we have Ea = — ^A100cr.5) For (100).4 Putting direction cosines of (14. Therefore we have Ea = 0.3. i/»= 0 (see Fig.24). j3: = 1. Therefore we have Then the wall energy (16.47) gives y100 = 0.0.622 SOLUTIONS TO PROBLEMS 14. we have Since (alt a2. Ku. we find 143 Putting a1 = cos 6. a3) are (1. 14. and for a [001] domain Ea= — HA IOO O-. in this case is given by f ACT.49) and assuming a'3 = 0. we have from (14. which is equivalent to (010).33) and (14. Similarly for (110). a2 = sin 6.0) for a [100] domain. j3j = 0.43) For [100] elongation. so that sin \l/= 0. we have from (14.47) becomes 16.2 Referring to (14. i/f = ir/4.42) becomes . /32 = 0.

5).4 Since the stable 90° walls make ±62° with the x-y plane (see Fig.75 X 10~21 X 0. 16.SOLUTIONS TO PROBLEMS If we put sin <p = x.37).15).40 X I04/S2rf(l .25XHT 1 2 X6X10 4 = 1. .21 and equation (16. Fig. we have A = 2 X 3.40xl0 4 / s 2 d(l-sin2</>).sin20)/(l +7s2/4/i0A:1).22X 10~3 Jm' 2 .2 In case (i). so that em = 5. n = 2 and a = 3 X 10"10 in (16. we find that the domain width d depends on Ka as K^/4.25 X 1(T12.66)). Since the wall energy depends on Ka as -^K^.47).40 X I04/S2d(cos 4> . In this case we must take into consideration the fj. as shown by (16. showing the dependence on the wall energy as -Jy. 17. Therefore we have the wall energy (16.sin <£)2 = 5.4 CHAPTER 17 17.34 X 1.30).55) y100 = 2 X V6.52/3 X 10~10 = 6.10) where /s is replaced by <a.38 X 10~23 X 800 = 3. Therefore the magnetostatic energy per unit area of the 90° wall is given by em = 5.1 The magnetic pole density appearing on the 90° wall is given by u> = ±/s(cos 4> — sin 4>).31) where /A* is given by (17. we have jT = 0. The magnetostatic energy per unit area of the 90° wall is given by (17.124° = 56°.3 Putting 6{ = 527 + 273 = 800 in (16.* correction (17. Sol. 16. the above integral is converted to f _ 1 x d x and finally we have 1 2 623 16. the inner angles of the ^-domain are 62° X 2 = 124° and 180° . 16.75 X HT21 J. Using this value and S = \. the domain width d is given by (17.

20 = 5.26) becomes A = 2/(l + 4.14. 173 Using 7S = 1. so that x = f + f = 12. where ^wall = 20. cos2 0 = sin2 6 = \.31X10-" = 0.0 times. cos2 6 = f. so that cos 6 = I/ \/2. we must take into consideration /*.624 SOLUTIONS TO PROBLEMS In case (ii).* given by (17. we have from (18.76).82/(2 X 4. so that the critical radius for single domain particle (17.95 X 1(T6. so that x = T + (5 x f ) = 8-8. the magnetostatic energy must be 0. only 180° wall displacement occurs.1 X 105) = 3.For polycrystalline cobalt.1 X 10s in (17. only magnetization rotation occurs. so that A is proportional to Ka.36). For 6 = 30°.8. CHAPTER 18 18.0 times the value of 20 A given by (17. which is equal to 100 A or 0.20 times the value for an isolated single domain particle. sin2 0 = |.5. When the magnetic field makes an angle 6 with the c-axis. Therefore the critical size for polycrystalline iron must be 5. Using this correction in (17. 1 in the denominator can be ignored. so that /I* = 1 + 3.26).14) = 0. so that x = (20 X f) + f = 16. 17. sin2 0 = f. the relative susceptibility is expressed by X = XwaiiCos 2 0 + J rot sin 2 0. cos2 0 = £. 183 Note that when H is parallel to the c-axis. For 6 = 45°. For 0 = 60°.39). so that .29).389. we have 18. Similarly in the p* correction A (17.33 mm. Therefore we find in (17.3.2 Since / = a/2 and 9 = ir/4. while when H is perpendicular to the c-axis.01 Aim. *rot = 5.37) that the domain width d depends on Ku as *V 4/^1/2^-1/4.66) //0 = 2v/2"y180o/(/sa). Ka = 4. we have X = 1.75) must become 1/0.4 According to (17. The /A* correction (17. where 1 can be ignored.86).95 X 10-6/4irX io~ 7 = 4. we have the domain width = 3.1 Since the residual magnetization remains in the positive direction in each particle.

Referring to the solution of (18. Sol. and finally comes back to the +x-direction.5 From (18. Since 7A and /B are 2:1 in magnitude. —x.1 Since there is no magnetic anisotropy.4 625 Since Nz = 0. After the field is rotated towards y. 19. during which / increases from NM/3 to NM linearly with H.1 19. 7A makes the angle 30° with H and its magnitude is (i/3 /2)wIA. When a field slightly more than /s/4ju0 = KU/IS is applied in the x-direction. the magnetization which makes an angle +45° with the —^-direction reverses its direction by irreversible magnetization rotation (see Fig. and decreases to zero. and finally become ferromagnetic at Hs.SOLUTIONS TO PROBLEMS 18. we have the average susceptibility X = I1/Hl = Xa + TiHl. Since Hs is proportional to /S( = /A = ~\IB$> tne fom1 of the Hs vs T curve is Q type (see Fig. Thus the susceptibility increases linearly with an increase of H^. 18. is increased. the shape anisotropy constant is deduced from (12. we can conclude that the residual magnetization of 2/s/ir is produced in the direction 45° from the +.22).24) as Ku = I?/4n0. spins on both the sites cant towards H. we have . As the field.1).1 Using the approximation for /c «: kT in (20. CHAPTER 20 20. Fig.2 The triangular arrangement starts at the field //cl = (w/3)NM and ends at Hc2 = wNM. 18. Sol.t-axis towards the —y-axis.29). the spin axis is always perpendicular to the field while the field is weak. H. 19.107). the magnetization which makes angles between —135° to 45° to the +*-axis remain.1). —y. CHAPTER 19 19.

626 SOLUTIONS TO PROBLEMS Using these relations in (20.105 X 105 X 2 X (-1 X 102) = -2. . Since 00 = 60° and 9 = 120°.98) to= co0 = 1.105 X 105 X 2 X 1) = 0. and j'b p = Eb. there is no flux change. we have from (20.91) and (20.9(X2*:umax//s) by a factor 20.33 X 10-6(lntan30° .In tan ( 9/2)) = -6.95) t = (In tan ( 00/2) .0.549) = 6.00715.3 Outside the moving wall. we have Since j'a p = Ea. Let the induced field above and below the wall be Ea and Eb.33 X 10~6 X (-0. respectively.In tan 60°) = -6. Therefore the total eddy current loss per unit area of the plate is given by 20. so that the induced electric field must be constant. Since a «K 1.549 .26) we have 20.86). then we have Let the current density above and below the wall be *'a and ib.2 The coefficient of In t in (20. By the condition for steady current.21 X 107 s~l. we have a = (47r)2 x10~ 7 X 1 X 108/(1. we can solve for Ea and Eb as respectively.95 X 10~6 s.98(2Kamax/Is) is larger than that for H = 0.00715 X 2.33 X 10~6 s. respectively. we have from (20.4 From (20.21 X 107) = -6. respectively. and T= TO = -1/(0.36) for H = 0.

52 X 106 X 6.0 X 10~9 m = 80A.52 X 10 . we have the differential equation Integrating each term with respect to t.95 X 1(T6 = 24.147). .4. this is converted and calculated to be s = v/4ir\ = 10/(4<7rX 1 X 108) = 8. we have from which we have Using (20.138) and (20.5 Putting a = H = 0 in (20. 20. the number of turns during this time is given by ft = 3.SOLUTIONS TO PROBLEMS 6 627 Since the precession frequency /= <u/27T= 3.129).

quadrupole moment Hall coefficient. orbital angular momentum magnetic moment Bohr magneton number in a unit volume.Appendix 1 SYMBOLS USED IN THE TEXT A exchange stiffness constant B Blt B2 C D E EH Ea Emag ^•magei £an £CT F H Hm H0 Hc H / /s 70 7r /rh / K KI} K2 Ku Kd L M Ms N Nc P Q R Rm 5 T magnetic flux density magnetoelastic constants Curie constant. total angular momentum magnetic anisotropy constant cubic magnetocrystalline anisotropy constants uniaxial anisotropy constant unidirectional anisotropy constant torque density. area. critical field for superconductivity or spin flopping anisotropy field intensity of magnetization saturation (spontaneous) magnetization saturation magnetization at OK residual magnetization rotational hysteresis integral exchange integral. magnetic scattering amplitude for neutrons energy density. demagnetizing factor. power activation energy. radius reluctance long-range order parameter. specific heat. electric field. total number of turns number of carbon atoms in a unit volume angular momentum. nuclear scattering amplitude for neutrons electric flux density. spin angular momentum absolute temperature . Young's modulus magnetic field energy density magnetic anisotropy energy density magnetostatic energy density magnetoelastic energy density magnetic after-effect anisotropy energy density magnetostrictive anisotropy energy density force magnetic field molecular field critical field coercive field.

/32. current density macroscopic current density microscopic current density Klirr factor. slip density. magnetostriction constants for five constant expression current. z z a («!. thickness. electric field gradient radius. y2. distance. damping factor direction cosines of magnetization molecular field coefficients damping coefficient of domain wall. probability coefficient of quadrupole interaction. compressibility. ratio of orbit to spin magnetostatic energy per unit area 629 . a2. roll reduction displacement. variables of Langevin and Brillouin functions. length. orbital angular momentum quantum number magnetic pole. packing factor direction cosines of observation direction and the annealing field surface density of domain wall energy direction cosines of atomic pair thickness of domain wall. m. n p q r s s n . pair energy Cartesian coordinates number of nearest neighbors curvature of potential valley. s12 t . ^ 13 (/3 X . c 44> c12 d e / g h i i ma imi k / m n /. /33) •y (•)/!. coefficient of the shape effect (magnetostriction) coefficient in law of approach to saturation elastic modulus. electronic charge frequency g-factor. light velocity elastic moduli domain width strain. magnetic quantum number number of turns per unit length. Boltzmann factor coefficient of dipole-dipole interaction. anisotropy energy function. spin quantum number elastic constants time velocity. skin depth. thermal expansion coefficient. loss angle surface density of energy. domain wall mass. y..APPENDIX 1 U V Vm W Wh Wt Z a b c c n . exchange term Planck's constant. dimensional ratio. principal quantum number direction cosines pressure. volume molecular field coefficient. s44. «3) a.73) S B em energy thermoelectric power magnetomotive force work hysteresis loss rotational hysteresis loss atomic number lattice constant. w x.

spin-orbit parameter relative number of Fe3+ ions on A and B sites permeability relative permeability permeability of vacuum initial permeability maximum permeability gyromagnetic constant resistivity volume density of magnetic pole electrical conductivity. relaxation frequency. /J. fj. <j> X X i// 0 ®f ®N @a <t> APPENDIX 1 wall energy per unit area ratio of delayed to instantaneous magnetization Rayleigh constant angle (particularly between magnetization and the field) magnetostriction constant. mass magnetization relaxation time angle (azimuthal). JL /i0 Ha /imax v p pm cr T if. short-range order parameter.630 ew f 17 0 A A. tension. magnetic potential magnetic susceptibility relative magnetic susceptibility angle Curie point ferromagnetic Curie point Neel point asymptotic Curie point magnetic flux .

Ref.16542 X 10~ =2.61151 XlO 1 9 7.27396 X 10~5 cm~' K J cal =0.7854 X 10~ = 1 * The values in this table are based on the recommendations of the CODATA task group.69506 = 1 =1.2999 X 10"24 = 1.72426 X 10 = 1 = 2.Appendix 2 CONVERSION OF VARIOUS UNITS OF ENERGY* MA/mt eV 1 1.03040 X 1023 = 4. t This column expresses the value of the magnetic field H.86177 X 10~4 0.23985 X 1(T4 0.70450 = 0.37477 X 10" = 1 = 1.5806 XlO 2 2 = 2. when it acts on 1 Bohr magneton (MB). 7.58668 = 0.7476 X 10~24 = 1. which gives the corresponding energy MEH.10631 X 1023 = 3. .84407 = 1.1604X104 = 1.8292 X 10~20 = 1.80655X104 =1.43872 = 1.50341 X 10 = 0. Table IV (1973).60218 X 10~19 =3. CODATA Bulletin 11. 1973.98646 X 10~23 =4.38071 X 10"23 =3.5901 XlO 2 3 23 24 = 0.1840 = 1 =3.3900 X 10'1 = 8.18473 23 23 = 0.62415 XlO 1 9 2.

67259 X KT11 Nm 2 kg~ 2 /i = 6.99792458 XW8ms~1 g = 9.80665 m/s2 G = 6.18401(15° cal)-1 k = 1.Appendix 3 IMPORTANT PHYSICAL CONSTANTS* Velocity of light Acceleration due to gravity Universal gravitation constant Planck's constant Mechanical equivalent of heat Boltzmann's constant Value of kT at 0°C Avogadro's number Electronic mass Electronic charge (absolute value) Ratio charge/mass Faraday constant Bohr magneton Gyromagnetic constant Flux quantum ' Mostly from CODATA 1986.6485309 X 10" Cmor 1 MB = 1.1093897 X 10~31 kg e = 1.60217733 X 10"19C e/m = 1.1 F = Ne = 9.6260755 X 10-34Js h = h/2ir= 1.771 X10~ 21 J N = 6.10509896 X 105g mA~' s~ l 00 = h/2e = 2.75881962 X 1011 Ckg.05457266 X 10-34Js J = 4.06783461 X 10~15 Wb .380658 X K T ^ J K . c = 2.1 kT0 = 3.0221367 X 1023 mol' 1 m = 9.16540715 X 10~29 Wbm v = 1.

^f 16 Rubidium 5s 85..89 Q ^ Strontium 5s2 87. N 2 He izi Q-I I I TT i IS2 -268.85 12 Mg 3i2 24.098 0.174(q) 26 on PO °Q 'Kurchatovium — i 2 2 I 6d 7s ! 104 Ku ..34 3.07 ' Actinium 1050 i 2 3200 .5 Barium 1640 725 Q Hafnium XV 72 Hf 5d26s2 178.9054 1.87 Q 19 K 774 20 Ca * 40.4678 1.. °-9712 4s .40 Q 678.r2 47.9055 6.60 38 Sr ^ 769 MJ3 21S© Yttrium 4d'5s2 88. 0:534 - .55 4 2 Calcium W84 839 /?/ ^ " Scandium 3d4j 2 44.! 57 Ta =^? 1^ u 920 | Lanthanum " 5d6f2 86 \1 I \\ .0079 I 0.Appendix 4 PERIODIC TABLE OF ELEMENTS AND MAGNETIC ELEMENTS la Ha .62 2..49 13.0763(-260) 4He 11 Na 3s 22.9 Q 500 © 1090 | 1.5 22 Ti IVa 328? „?.54 Q n7s 12/8 0 i i 1H I TT j I IS i Hydrogen -252.305 2 ' J L^l.873 Cesium 28.81 Magnesium 648-8 .19(-273) I I 1..65 39.992 21 Sc Ilia 2332 O 0 «39 Titanium 3rf24. L74 0 Potassium 63.2 £ "* *> -195 © 882.0254 ! 5(?) IMO 700 89-103 (Actinides) X.90 4.98977 Sodium 97. Lithium ian« 180. 0.4 56 Ba 6s2 137.9559 2.9059 4 478 - 39 Y 333? ' 40 Zr 1523 © WSs2 91. -%^' 138. ^T . .00260 I .53 37 Rb 38.93 -m i 26 Mpa 3Re ft -272.22 6.3 2227 4602 57-71 (Lanthanides) Francium (223) 87 Fr (667) 88 Ra 2 (27) Radium 226..„ ' t DC A -RP 2970 .Q7n 1347 r> nBeryllium f 1.08 1.f.87'' Helium •> & _ 2 5 9 1 4 11 H2 © M 4.'105 Ha — Hahnium — _ i ' i I >! 89 Ac i 6d7s 27) 0.44 Zirconium ^T @ 8?Q o 55 Cs 6s 132.

0482 4 2 76o m fifin ^T 64 ° J^Q ^ ° 57J® . subl.9064 8.7 Mra = 0.207 20. mag.7 2 113 ssis ' 93 Np 2 Neptunium D 5f 6d7s 237.016(a) 101 312? ° Q Promethium ~1080 4f6s2 (145) — 61 Pm 24&o(?) 4f5d6s2 7° 140.2 140.2 i . moment (emu/g) Is : satur. mag.85 19. SDW (MB) CT : mass mag.00 2 2 90 Th 4790 l750 Protactinium <1600 5f 6d7s 231.24 7.3 1244 i962 26 Fe Iron 3rf54s2 55.12 0 6.0359 2 2 91 Pa - 92 U Uranium 5f6d7s 238.847 7.20 \M± = 2. = 1. (K) .66(3).6 73 Ta 2 5425 996 H Tungsten 5d46s2 183. fee hex 6« =67 >15GPa M± = 0.01 5 2617 4612 43 Tc Technetium 4d 5s (97) — 5 2 2172 4877 0 44 Ru Ruthenium 4d 5s 101.07 12.1580 order CTO = 221. Msd = 0.0381 11.87 3380 H I890 24 Cr Chromium 3d5% 51. moment (MB) Ms : satur.9414 5. spin flip pt.53 75 Re 3180 0 5627 Osmium 5d"6s 190.7? nonferro| magnetic . (K) Mctt: effect.996 7. (T) Via £r APPENDIX 4 .94 9. M.14 2672 !857 H 25 Mn Manganese 3rf5452 54.9380 7. trans. fy : Curie pt. moment (MB) M+ : antif. 6. pt.769(a) 59 Pr 3212 60 Nd v Neodymium 4/<6.216 M.25 9. = 1040.7 aMn QN = 95 Ms =2. 22. moment (MB) Msd : amp. = 1.634 Magnetic parameters 6W : Neel pt.4 4 2468 4742 El 42 Mo Molybdenum 4d 5s 95.86 I535 1400 qln 2750 1100DT DP 705 41 Nb Niobium 4d 5i 92.029 18.9479 16.6. mag. MIV = 0.2 144. = 123 K wavelength X H = 21 lattice c.57 .3 74 W 3410 H seeo Rhenium 5d56s2 186.0.1 7 23 3900 10 H Tantalum 5d%s2 180.5 76 Os 3045 5027 58 Ce Cerium 3257 798 Praseodymium93l 4/36.9. P spin density wave 9W = 311 wavelength X± =27 lattice c.768^) „ ^ (8^ \> g° Thorium 6d 7s 232. j^ ^Mn-f6w=480? bcc MeH = 3.59 Via Vila 23V Vanadium 3rf34s2 50..9077 6. (K) 9/fl : ferro-antif.2 pMn no magnetic IsW =2.

0 c.4 7.9665 18.22 22.t.8 2732 1453 0 29 Cu Copper Id104s 63.8) sse.9254 8.895(a) H 94 Pu Plutonium 5f"7s2 (244) _ 3232 64i 95 Am Americium 5f7s2 (243) 2607 994 96 Cm Curium 5f6d7s2 (247) 1340 97 Bk Berkelium 5f>7s2 (247) m 4510 319 d 206 Z 122 Z7 .p.25 7.) n cubjc / = hex /S20 =1. Afeff = 3.38 6.193(-38.7870 a =161.44 3727 1966 # 46 Pd Palladium 4d10 106. p. (°C) mn(°C) electronic structure atomic weight density (g cm'3) (° C.9 765 77 Ir Iridium 5d76s2 192. Symbol b.16 3140 47 Ag 1552 ^ silver 4dl°5s 107.933 2567 1083 0 30 Zn zinc 3dl°4s2 65.87 62 Sm Samarium 4/66i2 150.92 907 419. Z7 monoclinic VIH .70 8.58 45 Rh Rhodium 4d*5s 102.708 fee CT = 164. 1597 64 Gd 822 3233 13H 0 65 Tb 3041 Terbium 4f96s2 158.t.9055 12. otherwise r.37 U 3827 1772 ° 79 Au Gold 5rf106s 196.APPENDIX 4 Co fee .616 515 1395 Contents in each frame Atomic Number.9332 8. OH orth.ss -38.492 2212 48 Cd 961.59 14. (°C) 1Symbols for Crystal types ^ diamond 0 fee A rhombohedral H bee D tetragonal 0 hex.40 8.8 M S = 1-739 crystal type trans.93 $ Cadmium 4dl°5s2 112. @ 28 Ni Nickel 3ds4s2 58.868 10.65 320.96 5.245 Gadolinium 4f5d6s2 157.4 12.546 8.57 M S O = 0.09 21.9 Ms = 1.p.71 2870 1495 (® ^ . rhomb.61 ^ ^62834 ~ ' « =58.88 2807 1064 0 80 Hg Mercury 5dw6s2 200.253(a) 1360 Europium 4/76s2 151.15 6 635 Ni fee Metf = 1.536(a) 1778 63 Eu 1072 a.42 4130 78 Pt 2410 Platinum 5d96s 195. hex. Ib lib 27 Co Cobalt 3dJ4s2 58.

7 444.535 t IVb 2550 2330 6 C Carbon 2s22p2 12.9342 9.78 32 Ge Germanium 4s24p2 72.U-i 8 O Oxygen 2*22/>4 15. rt ° A ^ 31 Ga Gallium 4s24p 69.30(3) 231.2^4 78.37 11.97 Bn P 2270 Antimony 5s25p* 121.98154 2.2.93 2403 29.82 684.9994 1.011 3.3 A iseo Polonium &26p4 (209) 84 Po 254 962 Dysprosium 4/106s2 162.20.75 6.61 2080 50 Sn Tin 5s25p2 118.97376 2.799 67 Ho 2720 ^ 1470 Erbium 4/126s2 167.1 ^ko DId K '.559 66 Dy 2335 0 1409 Holmium 4/"6s2 164.52 (diamond) f Vb 4827 3550 » 0 ( VIb -195.8 -249.8 -209.9216 5. (red) (black) D 2467 660.062 68 Er 2510 69 Tm 1727 1522 0 Thulium 4/136$2 168.28 49 In 156.72 5.14(-273) 15 P phosphorus 3.568(-273) 16 S Sulfur *V ^^ 2.086 2.96((3) -182.2 11.42 2355 1410 n ' .0067 1.78 83 Bi 271.69 .96 -218.6 D 280 44.96 4.07(a).9 217 93 gi ^ & A Indium 5s25p 114.V 30.636 APPENDIX 4 Illb 5 B Boron 2s*2p 10.86 81 Tl 303.50 O mo Bismuth 6j26p3 208.4 -229.67 H9.26 9.342 327.59 5.82 7.1 0 -237.86 .5 J?0 0 1457 82 Pb Lead 6s26p2 207.81 2.62 51 Sb 630.46 2830 937.8 A n Thallium fe26p 204.60 6.0(a) U2 m 7 N Nitrogen 2*22p3 14.4 33 As Arsenic 4s24p3 74.210.73 613 sublimate 34 Se Selenium 4.70 14 SI Silicon 3^ 28.50 8.69 7.37 13 Al Aluminum 3s>3P 26.74 A 1750 52 Te 5s25p4 127.1.9804 9.25 Tellurium 449.5 989.318 1545 98 Cf Californium 5/°7i2 (251) — 99 Es Einsteinium 5/"7s2 (254) — 100 Fm Fermium 5/127^2 (257) — 101 Md Mendelevium 5f37s2 (258) .9304 8.

7 -189.1 -m.5(-273) 17 Cl Chlorine 3s23p5 35.9045 4.842 l656 ' O ? 42 ~ 0 ' 102 No Nobelium 5/147s2 (255) — 103 Lr Lawrencium 5f146d7s2 .30 — -107.67 ' R Bromine 4s24p5 79.2 -246.5 *2 54 Xe Xenon 5s25p6 131.2(-273) 35 Br 58.179 1.4(-273) 36 Kr -152.94 184.6 -100.99840 1.948 1.6 Q-J 531 Iodine 5s25p5 126.9 Astatine 6s 6p (210) 2 5 85 At 337 302 86 Rn Radon 6s 6p (222) 2 6 -6i.04 6.204(-245) 18 AT Argon 3s23p6 39.453 2.14 -219.35 H3.65(-233) -185.904 4.APPENDIX 4 637 Vllb 9 F Fluorine 2s22p5 18.97 9.05 -248.959(a) 1193 71 Lu 3315 824 66Q Lutetium 4f"5d6s2 174.80 3.78 -7-2 Rr2 Krypton 4s24p<> 83.s -71 70 Yb Ytterbium 4/146s2 173.30 -156.62 10 NC Neon 2s22p6 20.98 C2 0 -188.2(-273) -34.

257 X10" 2 (12.257 XHT 9 1.257 X 10~8 1X10 9 10 7.33 X10 4 7. T (tesla).96 XlO" 1 1.257 X 1(T6 = /x in CGS 7.579 X 10~8 7.96 X10 8 7.96 X10 2 1X10 4 1. MX (maxwell).96 X 10s Magnetic potential <U A Magnetomotive force Fm I Magnetic susceptibility x Hm" 1 Relative susceptibility x Permeabmty n Hm" 1 Relative permeability JL Permeability of /AO vacuum = 4irX 10~ 7 Hm" 1 Demagnetizing factor N Rayleigh constant TJ H/A Reluctance Rm H'1 Inductance L H Anisotropy constant K\ Jm .96 = W2/4ir. 1X10" 1 1.33 X10 7 1. 1. fl (ohm).^X m COS 1.96 X10 7 1X10~ 9 .96 X10 6 1X10 8 7. Oe (oersted) 1. ergcm"3 ncmOe' 1 Wb (weber).577 6. A (ampere).257X10 6.257 = 4ir/10. . A -^ F Energy density £m j/ Ordinary Hall coefficient R fln^A' 1 1. H (henry).96X10 3 Oe'1 gilbert MX" l abhenry .Appendk 5 CONVERSION OF MAGNETIC QUANTITIES-MKSA AND COS SYSTEMS Quantity J Magnetic pole MagneticFLUX Magnetic moment Magnetization Magnetic FLUX flux density Magnetic FIELD field Symbol MKSA unit y m $ M 7 B H Wb Wb Wbm T T Am' 1 Conversion ratio MKSA value COS value COS value MKSA value 1.257 X 1(T7 1X 10~8 1.33 = W3/(4Tr)2.96xl(r' COS unit MX G G Oe GILBER ° 7.257 X10 ~ 3 1 X 10~4 7.579 X 10~5 .257XlO~ 4 =1 1.579 = (4ir)2/W2. J (joule). 7.96x10 7 . G (gauss). 6.

30 Oe = 1.26X10. the symbol fi0H should be used and is preferably called an 'induction field'. coil = 1.6Oe = 1.Appendix 6 CONVERSION OF VARIOUS UNITS FOR MAGNETIC FIELD Am" 1 (ampere per meter) ImAm1 Oe (oersted) 5 T* (tesla) 9 Remarks lOmAm.1 lOOkAm" 1 IMAm" 1 lOMAm. but sometimes can be used as a unit of magnetic field.6kOe = 1. * T is a unit of magnetic flux density.6 fj-T earth mag.0e= 1.1 lAm.T 1 X K T 5 G = 1-y (gamma) = 1.26 MOe = 126 T can be produced by flux compression. In this case.26X10" 8 T = 1.26T can be produced by electromagnets = 126kOe = 12.26mOe =1.6mOe = 1.126 mT = 12.126T / permanent magnets = 12.26X10-4 Oe = 1.1 IkAmT 1 lOkAm.6mT^ can be produced by = 1-26kOe = 0.26/iT = 0.1 100 MAm" 1 = 1.26X10.6T can be produced by supercon.1 lOOmAm.7 T = 12. field = 0.1 lOOAm.26xlQ.15-0.26mT = 126Oe = 12.126 Oe = 12.1 10 A m .26Oe = 0. .

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281t CeFe2 180t. 309f. 307. 442f. 593 CdMn2O4 207t Ce 64f. 282t BaNi2Fe16O27 (Ni2W) 282t Ba 2 Ni 2 Fe 12 O 22 (Ni2Y) 214t. 331. 190t Ce2Fe14B 236t Co 69t. 214ft Ba3M2Fe24041 (Z) 210f. 487f. see magnetic borides Ba ferrites. The general metallic elements are indicated by M. 213ft Ba 2 M 2 Fe 12 O 22 (Y) 210f. 503t. 270. 288f. 588 Co alloys 279f Co-added Fe3O4 288f Co-added MnFe2O4 288f Co-added Mn 07 Fe 23 O 4 288f Co-doped powder 611t Co ferrite. 282t. 282t. 205. 283 Ba3Co2Fe24O41 (Co2Z) 215t. 218f CdCr2Se4 234. a-Fe2O3 (hematite) 92t. amorphous 403f Co21Ge2B6 224t Co-M alloys 279f. 280f Co-Mn alloys 174f . 215ft Ba2Mg2Fe12O22 (Mg2Y) 214t. 360ft. 211. Bold page numbers indicate the pages where detailed explanatio