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Physics of Ferromagnetism5.0

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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

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

This page intentionally left blank .

1. A magnetic field can be produced by other magnetic poles or by electric currents.0126Oe. 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 . thin solenoid carrying an electric current. is placed in a uniform magnetic field H. and has the value It is also found that an electric current exerts a force on a magnetic pole. Consider two magnetic poles with strengths of ml (Wb (weber)) and m2 (Wb) respectively. giving rise to a couple or torque.) If a bar magnet of length / (m). the force F (N) acting on the magnetic pole is (/AO is defined so as to avoid a coefficient in (1. 1. 1 Oe = 79. whose moment is .) When a magnetic pole of strength m (Wb) is brought into a magnetic field of intensity H (A/m). each pole is acted upon by a force as indicated by the arrows in Fig.1 MAGNETIC MOMENT The most direct manifestation of magnetism is the force of attraction or repulsion between two magnets. see Appendix 6.1 MAGNETOSTATIC PHENOMENA 1. 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. which has poles m and —m at its ends.0 is called the permeability of vacuum. (1 Am" 1 = 4-n-X 1(T3 Oe = 0. The force F (N (newton)) exerted on one pole by the other is given by where /u. A uniform magnetic field exists inside a long.4).6 A rrT1. These are called 'Coulomb forces' by analogy with the Coulomb forces between electrostatically charged bodies. When a current of i (A) flows in the winding of a solenoid having n turns per meter. separated by a distance r (m). Generally a region of space in which a magnetic pole experiences an applied force is called a magnetic field.

where 6 is the angle between the direction of the magnetic field H and the direction of the magnetization (-mm -» +m) of the magnet.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). giving rise to a potential energy. As seen in (1. but no translational force. so that equations (1.4 MAGNETOSTATIC PHENOMENA Fig.1. 1.8) and (1. Thus a uniform magnetic field exerts a torque on a magnet. the work done by the torque (1. A magnet under the action of a torque in a uniform magnetic field.eld Fig. If no frictional forces act on the magnet. any kind of force which acts on the magnet involves m and / in the form of the product ml. We call this product a magnetic moment.5) and (1.8) is reversible. the torque exerted on a magnet in a uniform field H is given by irrespective of the shape of the magnet.2.2). 1. A magnet under the action of a translational force in a gradient magnetic gneticc field. it has the unit of weber meter (Wb m) In terms of M. 1. The translational force is given by in the ^-direction (Fig. A translational force acts on the magnet only if there is a gradient of the field dHx/dx. in practice it is rather hard to define the position of magnetic poles .6). The direction from the negative pole to the positive pole is defined as the direction of the magnetic moment.

we place at P another magnetic dipole M2. Now in addition to the moment Mj at the origin. 1. Both concepts are useful to calculate magnetic fields. A magnetic moment can also be produced by a closed loop carrying an electric current.8) as the definition of the magnetic moment.* However. the moment of force or torque. Figure 1. L. accurately. so that we can use equation (1. 1. Consider the magnetic field at a point P whose position is given by (r. because of the difficulty of realizing a 'point' pole. 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. we assume that the two *Some authors object to the concept of a 'magnetic pole' as unrealistic. A source of field meeting this condition is called a magnetic dipole. . 6) in polar coordinates.4). However. is a measurable quantity.4 shows a computer drawing of the lines of force calculated from (1. For simplicity we assume the size of the magnet / or of the closed current loop v^ is negligibly small compared with r. A magnetic moment produced by a closed electric current.13).3. 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. 1.3). 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.MAGNETIC MOMENT 5 Fig. which makes an angle 62 with r (for simplicity. 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.

and 91 = 62 = 6. . Maximum energy occurs at 6 = Tr/2.9). the potential energy of this system is given by If the two magnetic dipoles are equal in magnitude and parallel to one another. 1.4. dipoles lie in the same plane).14) becomes This potential energy is minimum at 6=0. as in the case of individual atomic dipoles in a ferromagnetic material. so that the configuration as shown in Fig. Computer-drawn diagram of lines of magnetic force produced by a magnetic dipole. This interaction between dipoles is called dipole interaction. (1.6 MAGNETOSTATIC PHENOMENA Fig.5(b) is unstable. so that the configuration as shown in Fig. so that M1 = M2 = M. 1.5(a) is stable. Using (1. 1.

the intensity of magnetization is given by If these moments have the same magnitude. usually denoted by /.2 X 10 29 (the moment of a single electron spin see (3.6). the coefficient in (1.17) (see Appendix 2 for energy conversions). (1. In the general case.14).19) simplifies to ..16) is (1..Mnn in a unit volume of a magnetic material. and are aligned parallel to each other (Fig. fixed. we have. (b) unstable. If M2 is antiparallel to MI} as is the case for atomic dipoles in an antiferromagnetic material (see Chapter 7). In (1. 1.M2.MAGNETIC MATERIALS AND MAGNETIZATION 7 (a) (b) Fig. There are strongly magnetic materials that are attracted by a permanent magnet. 1.7)) and r— 1A. the potential energy of the dipole interaction is given by 1..14).5(a). In Fig. Taking Ml = M2 = M = 1.. the coefficient in (1. M. When a magnetic material is magnetized uniformly. if we rotate M1 by a small angle 0j while keeping the direction of M-. we assumed that Afx and M2 are both in the x-y plane. 1. If there are magnetic moments M1.2 MAGNETIC MATERIALS AND MAGNETIZATION Magnetic materials are materials which are magnetized to some extent by a magnetic field. and weakly magnetic materials whose magnetization can only be detected by sensitive instruments.16) changes sign. the magnetic moment per unit volume is called the magnetic polarization or intensity of magnetization. from (1.5. Two arrangements of parallel dipoles: (a) stable.

Nm signifies the total quantity of magnetic poles existing in a unit volume of material. 1. only the surface currents remain uncompensated. 1. or the magnetic pole density. we have l/S elementary current loops per unit area of the cross section.9 X 102 gauss). Consequently uncompensated magnetic poles of surface density will appear at the ends of the specimen. Since neighboring currents cancel one another.20) . If we adopt the definition of equation (1. the concept of magnetization is also interpreted as a displacement of magnetic pole density p relative to — p by the distance / (Fig. we have Thus we can define the magnetization to be the number of magnetic poles displaced across a unit cross-section. we find from (1. and also that the cross-section of the elementary closed current is S (m2).12).7. we have from (1.22) with (1. Comparing (1.20) that the unit of / is Wbm~ 2 . Using equation (1.8. Concept of magnetization as a displaced magnetic charge density. p (Wb/m3).7).7) for the magnetic dipole.23). so that we have From this expression. which has the alternative and simpler name of tesla (T) (1T of I = W4/4ir gauss = 7. 1. 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. Concept of magnetization as an assembly of magnetic dipoles. where N is the total number of moments M in a unit volume.8 MAGNETOSTATIC PHENOMENA Fig. If we assume that there are n current layers per unit length along the direction of magnetization. Fig.20) In this expression. Since the unit of N is m~ 3 . we have from (1. and accordingly n/S elementary current loops per unit volume of the magnetic material.6. 1.

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

we can also interpret (1. Comparing Equations (1.29) is written as where ^ is called the magnetic permeability.34). 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 assume that the cross-section of the magnetic material is exactly the same as that of the search coil.9(b)). If we use (1.29). From a different point of view.2)). is proportional to the magnetic field.28).25) in Chapter 2. We call these quantities relative susceptibility and relative permeability. The units of x ar>d P are both Hm" 1 . 1.30) to mean that B can be regarded as the sum of the magnetization of a magnetic material and that of vacuum. In this case (1. 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.28) is written as If the magnetization. Using this quantity. the voltage is increased to where B is the magnetic flux density or magnetic induction.* n The product of B and the cross-section S is called the magnetic flux: The unit of flux is the weber. H. because vacuum is not matter.10 MAGNETOSTATIC PHENOMENA is produced across the coil by the law of electromagnetic induction. For a more detailed discussion of a practical case see Equation (2. and denote them x and ~jl. But we must remember that matter itself is an electromagnetic phenomenon. Therefore we can also measure x an^ M in units of /AO. 7. which is the same unit as /i0 (see (1. If we insert a magnetic material in the coil (Fig. (1. we have * In this case. so that we cannot specify the nature of vacuum on the basis of a naive concept of matter. we must believe that the vacuum is magnetizable! . respectively.27) and (1. we have where the proportionality factor x is called the magnetic susceptibility. t Some scientists feel that the magnetization of vacuum is a bad term. From the relationship in (1.26) in (1.

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.36)5 Fig. The difference between ^diff and ^-rev represents the susceptibility due to irreversible magnetization. The maximum value of the total susceptibility. Starting from a demagnetized state (7 = H = 0). 1. that is.3 MAGNETIZATION OF FERROMAGNETIC MATERIALS AND DEMAGNETIZING FIELDS Since ferromagnetic materials can be highly magnetized by a magnetic field.Beyond this region the processes of magnetization are no longer reversible. 1.11. while in the case of strongly magnetic materials. 1. Starting from the value of ^a. while xtm nas a sharp maximum. which is normally denoted by Js. they have relatively large magnetic permeabilities fL. / is a complex function of H (see Section 1. The slope of the curve OA is called the initial susceptibility xa. it is called the irreversible susceptibility ^irr. but along the minor loop BB'. so that (1. Initial magnetization curve and minor loops. the magnetization returns to zero upon removal of the field.3). ^rev has a decreases monotonically.34) holds only approximately in a limited range of fields. the magnetization increases with increasing field along the curve OABC and finally reaches the saturation magnetization. x and Jl are normally field-independent. (1. that is. If the field is decreased from its value at point B. Xditc and Xtot along the initial magnetization curve are shown in Fig. Their magnetization is changed by a magnetic field in a complex way. the slope of the tangent line drawn from the origin O to the initial magnetization curve. . not along BAO. In the region OA the process of magnetization is almost reversible. The slope BB' is called the reversible susceptibility XKV or the incremental susceptibility.10. which is described by a magnetization curve as shown in Fig. and ^tot goes to its maximum value ^max and drops off at / = /s. ranging from 102 to 106.MAGNETIZATION OF FERROMAGNETIC MATERIALS 11 In the case of weakly magnetic materials. 1. Changes in ^rev.10. the magnetization comes back. is called the maximum susceptibility Xma*> ^ is a good measure of the average slope of the initial magnetization curve. that is.

Various kinds of magnetic susceptibilities as functions of the intensity of magnetization.11. and at H = 0 it reaches the non-zero value /r (= OD). Hysteresis loop. 1.12 MAGNETOSTATIC PHENOMENA Fig. Further increase of the magnetic field in a negative sense results in a continued decrease of the intensity of magnetization. The absolute value of the field at this point is called the coercive force or the coercive field Hc (= OE). which finally falls to zero. not along CBAO. 1. of the magnetization curve is often referred to as the demagnetizing curve. the magnetization will change along FGC. DE. . the magnetization / gradually decreases along CD. Fig. 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. The closed loop CDEFGC is called the hysteresis loop. 1. This portion. If the magnetic field is decreased from the saturated state C (Fig.12).12. If the field is then reversed again to the positive sense.

The apparent magnetization curve of a material depends not only on its magnetic susceptibility. In order to calculate the demagnetizing field in this case. we use Gauss' theorem. This field is called the demagnetizing field. Demagnetizing field produced by magnetization perpendicular to the surface of a magnetic plate. which are used as permanent magnets. If the intensity of magnetization is 7. 1. Let us calculate the demagnetizing factor for a semi-infinite plate magnetized perpendicular to its surface (Fig.13. divided by /A O . 1. 1.MAGNETIZATION OF FERROMAGNETIC MATERIALS 13 The value of the saturation magnetization 7S does not exceed 2. but also on the shape of the specimen. which depends only on the shape of the specimen. so that we have where N is called the demagnetizing factor. That is. The value of relative maximum susceptibility also varies widely. whereas it is large for a thick and short specimen. the free poles which appear on its ends will produce a magnetic field directed opposite to the magnetization (Fig. 1. The intensity of the demagnetizing field H& is proportional to the magnetic free pole density and therefore to the magnetization.14). N approaches zero for an elongated thin specimen magnetized along its long axis. .14. Fig. which are used for motor and transformer core materials. For instance. Surface magnetic free poles and resulting demagnetizing field. while it ranges from 50 to 200 kAm" 1 (600 to 2500 Oe) or more for Alnico and Ba ferrites. then the surface density of free poles on both sides of the plate is +/ (Wb/m2) (see (1.5 T at room temperature for any material. Fig. from 10 to 105. but the value of the coercive field can vary over a wide range: it is about 8Am" 1 (= 0.24)).13). 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. When a specimen of finite size is magnetized by an external magnetic field.1 Oe) or less for Permalloy and steel containing a few per cent of silicon.

Assuming a uniform demagnetizing field in a general ellipsoid. In such a case. provided that the plate is sufficiently wide and thin. the magnetization is assumed to be uniform throughout the material. we have where k is the ratio of diameter to thickness. with the magnetization parallel to the plane of the surface. If the shape of the specimen is irregular. that is the ratio of length to diameter. we have The demagnetizing factor in this case is given by When we magnetize the plate parallel to its surface. together with experimental values obtained for cylinders of various k. the demagnetizing field is not uniform but varies from place to place in the specimen. for an elongated rotational ellipsoid (an ellipsoid with a circular cross-section) magnetized along its long axis. the demagnetizing factor is given by where k is the aspect ratio or the dimensional ratio.44) as a function of the dimensional ratio k. which can be simplified for special cases. In these calculations. Then Thus the demagnetizing factor depends upon the direction of magnetization.42) reduces to For a flat circular ellipsoid. The general result is in the form of a complex integral.2 Experimental values of N show considerable scatter depending on the method of measurement and the type of material.14 MAGNETOSTATIC PHENOMENA Applying this theorem to the closed surface shown by the broken line in Fig. 1.43) and (1. approaching the shape of a disk. The calculation of the demagnetizing factor is generally not so simple. we can prove that the demagnetizing factors for the three principal axes have a simple relationship .1 gives numerical values of the demagnetizing factor calculated from (1. In the special case of k » 1.1 For example. we cannot define a single demagnetizing factor. The only shape for which the demagnetizing factor can be calculated exactly is the general ellipsoid. (1. Table 1. and assuming that there is no field outside the plate other than the external field. the effect of the free poles is negligible.14.

00036 0. not the case.0000019 Oblate ellipsoid 0. the shape of the curve is sheared as shown by the broken line in Fig. however.0558 0.000784 0.0369 0.3333 0.0000009 Prolate ellipsoid 0. This is.2364 0.0172 0.040 0. we have from (1.MAGNETIZATION OF FERROMAGNETIC MATERIALS Table 1.00129 0. because H' is produced by the magnetization itself.00390 0.27 0.0203 0.001567 0.01532 0.0000066 0.1735 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.00617 0.3333 0.00776 0. That is.45) When a long cylinder is magnetized perpendicular to its long axis (which we take as the z-axis). If we plot a magnetization curve as a function of the external field.1248 0.1. published magnetization curves *It may seem that the real effective field should include H' in (1.15 as compared with the true magnetization curve shown by the solid line.000090 0.0000236 0. Nx = Ny = 0. The correction for converting the sheared magnetization curve to the true curve is called the demagnetizing correction or the shearing correction. Nz = 0.40).000392 15 From this relationship we can easily obtain the demagnetizing factors for simple ellipsoids with high symmetry. with increased susceptibility and remanence. As a result of this correction. .00675 0. the magnetization curve takes on a more upright form. 1.000430 0. Unless otherwise stated. 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. For a sphere in which NX = N =NZ.000125 0. so that we have When a semi-infinite plate is magnetized normal to its surface (which we take as the z-axis). so that 1 in agreement with (1. so that it produces only an internal force which has no effect on the magnetization.0696 0.000014 0.26).14 0. and Nx = Ny.0000036 0.00144 0.

even if it has a high susceptibility.025 Oe) to the saturated state. because if we superpose the body and the hole. we have a uniformly magnetized solid without free poles. 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. Shearing correction of a magnetization curve.16 MAGNETOSTATIC PHENOMENA / Fig. 1. In the case of a spherical cavity. We must keep this fact in mind when we use magnetic materials with high susceptibility. we must apply an external field which exceeds this value. Finally we consider the field inside a cavity in a material magnetized to an intensity 7 (Fig. which is 105 times larger than Hc. therefore. In general we cannot ignore the effect of the demagnetizing field. 1. Suppose that we magnetize a Permalloy sphere with Hc = 2 Am" 1 (= 0.16). the field is given by . A high field will be needed to magnetize a sample with a large demagnetizing factor. 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. and with the same magnetization as the material surrounding the cavity. the maximum demagnetizing field is given by In order to saturate this sphere. This must be true.15. Since the saturation magnetization of Permalloy is 1.16T (= 920 gauss). except that the poles are of opposite sign. otherwise the favorable properties of the material become useless. 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.

however. The problem of finding a distribution of electric potential is reduced to the problem of solving the Laplace equation under the given boundary condition.16. 1. where D is the electric displacement or electric flux density. there are dielectric materials distributed in an irregular manner. . so that (1. If we bore an elongated hole parallel to the magnetization. If we make a thin flat cavity perpendicular to the magnetization. the demagnetizing field of a specimen of irregular shape is not uniform. In the absence of true electric charge. so that (1. and a complicated distribution of magnetization results. Magnetic field inside holes in a magnetic body.55) for the given spatial distribution of s. Hm is the same as H' + H. and its direction is the same as that of the magnetization.MAGNETIC CIRCUIT 17 Fig. If.55) becomes or which is Laplace's equation.53) becomes In a uniform dielectric material we can put s = constant. On the other hand. This field is called the Lorentz field. 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.30). this is a fairly complex problem. 1. as given in (1. the field inside H^ is the same as Het{. we must solve (1.4 MAGNETIC CIRCUIT As mentioned in the preceding section. where <f> is the electric potential.

however. Therefore if conductors of irregular shape with different conductivities are distributed in a medium with finite conductivity. however. For a steady current. For instance. If we assume that the magnetization curve is given by a straight line without hysteresis. .85 X 10~12 FmT1). hence the actual situation is quite similar to that of a steady current in a Fig. Then (1. we can simply write where <f>m is the magnetic potential. If. the relation is always valid. If. 1.57) becomes which has exactly the same form as (1. the problem becomes very difficult.17.17. here the D vector leaks more or less into the vacuum. 1. A similar problem arises in finding the distribution of electric current density in a conducting medium. as in the two cases mentioned above. where there are ferromagnetic materials of irregular shape. Current distribution in a conductor of complex shape connecting two electrodes.60) becomes which is also of the same form as (1. Since the permeability of vacuum is not zero ( /AO = 4ir X 10~7 Hm" 1 ). /x is non-uniformly distributed. not true for dielectric materials. the conductor is surrounded by insulators. the situation is formally similar to the case of electrostatics. This is.55) or (1. however. the problem becomes very difficult. (1. In magnetism. the situation is quite similar to the case just mentioned.18 MAGNETOSTATIC PHENOMENA In magnetostatics. But actually the permeability of ferromagnetic materials is 103-105 times larger than that of vacuum. the situation becomes very simple.59). because the dielectric constant of vacuum is not zero (EO = 8. For ferromagnetic materials the situation is intermediate between these two cases. Since where a is the electric conductivity.54). the electric current is contained in the wire no matter how complicated the shape of the wire. if a conducting wire is placed in vacuum as shown in Fig.

corresponding to the resistance of the electric circuit. especially one of high permeability.18. In other words. corresponds to the total electric current.58) and (1. When (1. forms a circuit. if a magnetic material. The direction of magnetization should always be parallel to the surface of the magnetic material. The gray portions of the circuits are made from soft magnetic materials. Thus. we can define the magnetic resistance or reluctance as Corresponding to the electromotive force. The total flux in the circuit. One is magnetized by a permanent magnet.18 shows two typical magnetic circuits. The flux density B in the circuit corresponds to the electric current density i of an electric circuit.61) are compared. conductor. because otherwise free poles will appear on the surface. 1.MAGNETIC CIRCUIT 19 Fig. is found to correspond to the electrical conductivity a-. we can define the magnetomotive force in the circuit as . where S is the cross-section of the conducting wire. If B is uniform throughout the cross-section of the magnetic circuit. Two kinds of magnetic circuit. and the other by a coil. and ds is an element of length in the circuit. Figure 1. the magnetic permeability /u. the magnetic flux density B is almost fully confined inside the magnetic material. producing strong demagnetizing fields that act to rotate the magnetization parallel to the surface again. Thus we can treat the magnetic circuit and electric circuit similarly.

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

so that R'm is fairly large. 1. By using Kirchhoff s first and second laws.19. 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.MAGNETIC CIRCUIT 21 Fig. Generally /xr of a permanent magnet is very small... For a magnetic circuit containing a permanent magnet. Then where Hp is the field inside the permanent magnet and the integral is taken along the circuit excluding the permanent magnet. If a magnetic circuit has a shunt or shunts. just as we can an electric circuit.. however.<I> 2 . are the fluxes which leave the shunt point through the branches. Thus This relation corresponds to Kirchhoff s second law.. where <!> 1 .. It must be noted. 1.2. that a magnetic . Demagnetizing curve of a permanent magnet showing the operating point P. we have Kirchhoff s first law... we can solve any kind of magnetic circuit. because the electric current is zero.

<£„ (A). 1. Let the intensities of the free poles be m 1 .. • • •... Consider a system consisting of several permanent magnets (Fig.m 2 . In particular. Then the potential energy of the system is Since 0. the permeability becomes very small. In extreme cases. Assembly of permanent magnets. The presence of magnetic hysteresis also makes the situation more complicated. it is expressed as where rtj is the distance between the ith and the . <&. <£2. we can neglect the effect of hysteresis. when the product of the coercive field times the length of the circuit is negligibly small compared to the magnetomotive force..m.-.. • • •. is the potential due to the Coulomb interaction of free poles other than m ( . the leakage is so large than the actual flux is only a small fraction of the calculated value.'th free poles. ..20).22 MAGNETOSTATIC PHENOMENA circuit has more or less leakage of the magnetic flux. if a part of the circuit is magnetically saturated. so that the circuit is practically broken at this point. 1.5 MAGNETOSTATIC ENERGY Let us discuss the energy involved in a magnetostatic system. like an electric circuit dipped in an electrolytic solution. However.m n (Wb) and the magnetic potential at the position of each pole be $1.20.. 1.. If the free poles are Fig. The non-linear relationship between B and H also makes the problem more complex.

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

87) Then (1.95) By using this equation. we obtain (1.81) becomes (1.88) Solving (1. 1.88).944) where N is the total number of magnets.77) becomes (1. When the magnetization / is distributed over space.90) The magnetostatic energy can be expressed in terms of / and H instead of pm and <f>.24 MAGNETOSTATIC PHENOMENA Solving this equation. we have (1. Since the intensity of the magnetic field inside the sphere is given by (1. the magnetostatic energy is (1.93) and (1. Then the magnetic moment is (1.91) The difference in the magnetic potential between the positions of the positive and the negative magnetic poles is (1.21. Let the length of the kih magnet be lk and the magnetic poles at its ends be mk and — mk.89) The magnetostatic energy of the system is then (1. we can calculate the magnetostatic energy of the sphere shown in Fig. Then (1.92) where H^ is the component of the magnetic field parallel to the magnetic moment Mk.96) .

79) and (1.101) As a result.94) as (1. it produces additional magnetization /'. the divergence of the field due to pm is given by (1. Since the demagnetizing field is (1. and is zero outside the sphere.98) the magnetostatic energy is (1.22).1000) When the soft magnetic material is placed in the space. <f> or H always decrease. For example. respectively.95) denotes the permanent magnetization.95) can also be used to calculate the magnetostatic energy even when soft magnetic materials are present with the permanent magnets. 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. Let us calculate the magnetostatic energy for another example. In this case pm in (1. A magnetized ferromagnetic body of finite size.102) .99)5 where v is the volume of the magnetic body.22. When some soft magnetic materials are present in the system. Consider a magnetic body with demagnetizing factor N magnetized to intensity / (Fig. In the absence of the soft magnetic material.95) only through the change in <j> or H. so that the magnetostatic energy also decreases. the field is reduced to H' which is related to pm and p'm by (1.97) which agrees exactly with (1.79) signifies the pole density produced by the permanent magnetization only. the magnetostatic energy can be calculated from (1.MAGNETOSTATIC ENERGY 25 Fig. It should be noted that (1. and / in (1. 1.79) and (1.90). The effect of magnetization induced in the soft magnetic material comes into (1. 1. so that additional free poles p'm are induced: (1.

(1.104) The integration is carried out over the space where magnetic field H is present. We shall discuss this problem once again in Chapter 17 as what is known as the /j. Therefore.104) becomes (1. As seen from (1. 1.103) with (1.104) becomes (1. according to /' = xH'> so that. The magnetostatic energy can be also expressed in terms of B and H: (1.90) and (1.107) which is again in agreement with (1.26 MAGNETOSTATIC PHENOMENA The magnetization /' is magnetized by this resultant field H'. It should be noted that B in the integrand is calculated by excluding the permanent magnetization.* When no soft magnetic material is present. the magnetostatic energy of the system is also reduced by a factor l/Ji.105) gives (1.105) If there is some soft magnetic material.* correction. The energy stored per unit volume is given by (1.100).79) using the relation pm = divB. we have always div B = 0.108) *The reason is that (1. using (1.101). Accordingly the magnetic potential </> is also reduced to 1//Z times its original value. the magnetic field inside the sphere is given by (1.104) is deduced from (1.105).21. . If we include the permanent magnetization in B. the magnetostatic energy is stored in any space where magnetic fields exist.106) Considering again the example shown in Fig. B should equal n0H. Since this factor is substantially less than unity for most soft magnetic materials.102) becomes or f1 KVT) Comparing (1.97). (1. so that (1. we find that the field H' is reduced by a factor I//A from the field H.96) and is zero outside the sphere. we cannot ignore this effect in the calculation of the magnetostatic energy. hence (1.

must coincide with the result calculated from the Maxwell stresses. the line 7 = 7S. 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. . Since the volume of the cylinder is SI. In other words. 1. not necessarily true for actual ferromagnetic materials. This heat or energy is called the hysteresis loss and is given by which is equal to the area inside the hysteresis loop. we assumed that the energy supplied to construct the system is conserved and stored as magnetostatic energy. The energy supplied by this work is partially stored as potential energy and partly dissipated as heat which is generated in the material. If we consider a cylindrical section of magnetic material whose length is / (parallel to 7) and whose cross-section is 5. so that the resultant work must appear as heat. when the line of force expands perpendicular to the force. The forces calculated by the interaction between magnetic poles and the magnetic field. parallel to /. putting 7: = 0 and 72 = 7S.6 MAGNETIC HYSTERESIS In the preceding discussion. and the initial magnetization curve. an increase of magnetization. 7S.MAGNETIC HYSTERESIS 27 A line of magnetic force therefore tends to shrink so as to decrease the energy in (1. The work required for this transportation is H SIS. a tension given by acts parallel to the line of force. On the other hand. 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. Suppose that the magnetization is increased from / to / + dl under the action of a magnetic field H. the work required to magnetize the volume from the demagnetized state to saturation. is given by (1.23. the energy density (1.108) again decreases. Consider the work necessary to magnetize a ferromagnetic material. however.110) are called Maxwell stresses. 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. This assumption is. The stresses given by (1. or from the interaction between electric current and the flux density. This is equal to the area enclosed by the ordinate axis.112). a pressure expressed by acts perpendicular to the line of force. the potential energy must return to its original value. as shown in Fig. 57. In other words.108). 1.109) and (1. After one full circuit of the hysteresis loop.

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

115) over Fig. Comparison of hysteresis loops of hardened carbon steel and MK steel. however. Using (1.115) in the permanent magnet becomes /A 0 // 2 .26. does not produce a magnetic field in the air gap.25. 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. 1. Magnetic circuit containing a permanent magnet. H = 0. .104).104)). as shown in Fig. which. where P is the permanent magnet and S is soft magnetic material. Thus no magnetostatic phenomena will be observed. Comparison of hysteresis loops of soft iron and Permalloy. 1. Let us consider how a permanent magnet produces a magnetic field in the air gap of a magnetic circuit. Next we consider the performance of a permanent magnet as an energy source. Therefore the integrand in (1.24. 1. 1.26.MAGNETIC HYSTERESIS 29 Fig. Therefore we can stay that permanent magnets are the only source of magnetostatic energy. 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. Fig.

Accordingly the quality of a permanent magnetic material can be expressed by the maximum value of (BH). a small volume of material is needed to produce a given field in a given air gap. 1. because it has a large internal reluctance .30 MAGNETOSTATIC PHENOMENA the magnetic circuit excluding the permanent magnet. as shown by (1. The magnet with a small fi. it is essential to make the value of BT ( = /r) large. rather than at A' or A" where (BH) is lower. (1.119) means that the permanent magnet has greater effectiveness for larger values of the quantity —B-H (note that H < 0).27. In other words. The value of (B/f)max does not necessarily correspond to the magnetomotive force Vm. ~jl = ». the actual energy produced by a unit volume of the magnet is one-half of the quantity (BH).116) gives a good measure of the effectiveness of 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. this contribution should count as a part of the effectiveness of the permanent magnet. and the integration in (1. so that the permanent magnet must supply additional energy to magnetize it. . In order to obtain a large value of (BH)max.R'm. this is quite reasonable. This can be done by orienting the crystallites so that the magnetocrystaline anisotropy * In spite of this name. A large 7r can be achieved by making the value of 7S as large as possible. Now considering that for one circuit of the magnetic path. if a permanent magnet material has a demagnetizing curve as shown in Fig. the quantity U in (1. it follows that so that (1. Since the purpose of this magnetic circuit is to supply a magnetic field in the air gap.116) becomes where the superscript P means that the integral should be taken only over the permanent magnet. 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. For an ideal soft magnetic material.116) is non-zero only in the air gap. and finally to have the demagnetizing curve close to rectangular in shape. Therefore. but cannot produce a large magnetic flux.115) becomes Where G means the air gap and S means the magnetic material. Since the volume element di> is equal to the cross-section S times the line element ds.119). results in a large Vm. The final result (1. Even if the permeability of the soft magnetic material is finite. and for larger volume. so that H = 0 for a given B. and also by making the remanence ratio 7r//s as close to unity as possible. to have a large 77C.

Any change in the material that increases the remanence ratio will also tend to produce a rectangular demagnetizing curve.27. It must be noted here that the important coercivity is not the field at which / = 0. or jHc. Discuss this problem in terms of the energy. since where 7C is the value of / at B = 0. or superlattice formation). The value of BHC is. so as to align the easy axes parallel to the axis of magnetization. precipitation hardening. These points will be considered in more detail later. 1. magnetized to intensity I. (see Chapter 12) aligns the magnetization parallel to the direction of easy magnetization. while keeping the air gaps equal.PROBLEMS 31 Fig. 1.27. A high coercive field Hc can be achieved either by increasing internal stresses (caused by a crystallographic transformation. or by making the size of particles or crystallites less than the critical size for single domain behavior. but the field at which B = 0.1 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. How is the value of the moment changed in the limit of x ~* °°? 1. .2 Calculate the force needed to separate two semicircular permanent magnets of cross sectional area 5. limited by 7r. PROBLEMS 1. or by creating an induced magnetic anisotropy (see Chapter 13). or BHC. as shown in Fig. as shown in the figure. however. Demagnetizing curve of a permanent magnet. Thus BHC is also limited by /s//v We therefore see that high Is is essential for obtaining a high-quality permanent magnet.

Ferromagnetism (Van Nostrand.01 m. R. 2. fl = 500. 1. G.32 MAGNETOSTATIC PHENOMENA Fig.4 Using a permanent magnet material with a maximum BH product at B = 0. Tuebner. assuming that the magnetic circuit has no leakage of magnetic flux and no reluctance. How is the energy changed when the rod is dipped into a ferromagnetic liquid of relative permeability /I? REFERENCES 1.2 1. Druck von B.3 Calculate the intensity of the magnetic field in the air gap of the magnetic circuit shown in the figure. M. Theorie der Electrizitaet. Bozorth. Prob. S2 = 5 X 10 ~ 4 m2. New York. . Prob. Vol. i = 5 A. 1. S1 = 2.5 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. Use the values N= 200. R. Fig.5 X 10 ~ 3 m2. Becker.15T and // = 60kAm~ 1 . 1. 1933). we want to produce a magnetic field of 250 kAm"" 1 in an air gap of crosssectional area 12cm2 and width 14mm. /j = 1m.3 1. 1951). 1 (Verlag u. /2 = 0. Design the size and shape of the magnet.

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

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

by using a magnetic circuit. (Thin arrows show water flow.06-0.6 MAm" 1 (1-2T).1-10 T) can be produced. and magnetic fields from SOkAm" 1 to SMAm" 1 (0.12T) by using conventional permanent magnets.8-1. however. then we have where Hm is the field in the magnetic circuit. By these methods.PRODUCTION OF MAGNETIC FIELDS 35 Fig.) water through the conductor. open arrows show electric current. Naturally the cost of facilities and of electric power increase rapidly with the magnitude of the required magnetic field. and second to secure magnetic fields that do not vary with time. and the length of the air gap /a (see Fig. Various types of coil windings. so that (2. It is possible to produce fields of 50-100 kAm" 1 (0. 2.6) becomes .1 It is. a serious disadvantage in most cases that the field cannot be changed in magnitude or switched off. This field is small if the permeability of the circuit is sufficiently large. The advantages are first to avoid the use of electric power.2. current densities of 3-50 A mm"2 can be carried by the coils. It is also possible to produce a field of about 0. the electric current i.3). An electromagnet can be regarded as an apparatus to concentrate the magnetic flux produced by a coil into a small space. the length of the magnetic circuit / m . Magnetic fields can also be produced with permanent magnets. Then the first term can be neglected. because it gives an extremely uniform and time-independent magnetic field. 2. If the total number of turns in the windings is N.8 MA/m (1 T) by using a large iron magnetic circuit with permanent magnets as a source of magnetomotive force. Electromagnets are usually used to produce magnetic fields up to 0. Such a facility is particularly useful for proton resonance experiments.

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. 2. 2. Design of an electromagnet. Figure 2. as shown in Fig. the pole pieces can be tapered as shown in Fig. In order to make the maximum field as high as possible.S-l^MAm"1 (1-2T) using electromagnets. provided the magnetization is everywhere parallel to the cone axis.5-3T) by careful design. The magnetic field produced by the electromagnet then approaches a limiting value. independent of the properties and the shape of the magnetic circuit.0T) in a 5cm air gap. 2. Magnetic field as a function of magnetomotive force in an electromagnet. . The proportionality factor is given by l// a . and electric power consumption increase rapidly as the maximum field is increased beyond these values. 2.3. 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.m~1 (2.2 It is easy to produce magnetic fields of O. For example. cost.5 shows a large electromagnet which produces a maximum field of 2. and possible to attain 2-2.4. This simple linear relationship holds for any electromagnet up to some value of current or field.36 MAGNETIC MEASUREMENTS Fig. the permeability decreases. However.2 to lOMAm" 1 (4 to 12T) can be produced by means of superconducting magnets.6) is no longer negligible.4MA. The advantages of superconducting magnets are that: Magnetomotive force. Theory shows that the maximum field is attained when the tapered surface is a cone whose half-angle is 54.3.4.4MAnT1 (3. the size. so that the first term in (2. Ni Fig.7°. As the core approaches magnetic saturation.2 Fields ranging from 3.

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

This method is limited by the mechanical strength of the coil. the coil is damaged by the electromagnetic force acting on the lead wires. 2. for H = 56MAm" 1 (70T). Figure 2.7. For fields higher than 40MAm~ 1 (SOT). the switch E is closed. The so-called Cnare method4 utilizes the kinetic energy of the inward motion of a short metal cylinder called a liner.38 MAGNETIC MEASUREMENTS Fig. the coil is destroyed by the field even if it is made of high-strength materials. using either explosives or electromagnetic forces. then the switch C is closed and a large pulse current is sent to the coil D. When the current reaches its maximum value. First a large condenser B is charged from a source A. Circuit for generating a pulsed high magnetic field. 2. Magnetic fields higher than this limit can be produced by magnetic flux compression. Conceptual diagram of the Cnare method.110). First a liner is placed in a one-turn coil which is connected to a condenser bank through a Fig. The principle of this method is shown in Fig.8.7. 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. 2. For instance.8 illustrates the experimental arrangement for the Cnare method. This force results from the Maxwell stresses given by (1. in order to make the duration of the current pulse longer and also to prevent charging the capacitor in the opposite polarity. the Maxwell stress is calculated to be Since the yield strength of a strong steel is at most 150 kg mm 2. .

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

results in the electromotive force — d<l>/df in the search coil. One such instrument is the ballistic galvanometer. then from Kirchhoff s second law: If the flux has the value <t> (Wb) at t = 0 (so that i = 0). putting A3> = 2$. integration of (2. caused by removing the search coil from the magnetic field. An instrument that measures the electric charge Q by integrating the current i is called a fluxmeter. the maximum deflection of the galvanometer is proportional to the electric charge which passes through the coil. when the search coil is connected to a ballistic galvanometer. This instrument is a galvanometer having a moving coil with a large moment of inertia. &0.9). by reducing the intensity of the field to zero. Therefore. The proportionality factor can be determined using a standard mutual inductance M whose secondary coil is connected to the circuit (see Fig.11) results in Thus the total flux change is proportional to the electric charge Q which flows the circuit. If the electric circuit containing the search coil has resistance R (H) and inductance L (H). or by reversing the sense of the field. and becomes zero at t = 10 (so that i = 0 again). by rotating the coil by 180° about an axis perpendicular to the field. we have from which we can determine the magnetic field H. When a pulse of current flows through this coil in a time interval much less than the natural period of oscillation of the coil. the change in flux passing through the coil is measured by the deflection of the galvanometer. we have If the flux given by (2. or where k is the proportionality factor. When an electric current in the primary coil i0 is reversed. 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.13) and (2. Similarly when the flux change A<& occurs in the search coil. 2. The resultant deflection of the galvanometer.10) is reversed. . is proportional to this flux change.40 MAGNETIC MEASUREMENTS Any change in the magnetic flux passing through the coil. irrespective of the value of the inductance L.14). the deflection 0 is given by Eliminating k from (2. a flux change 2Mi0 occurs in the secondary coil.

MEASUREMENT OF MAGNETIC FIELDS 41 Fig. A commercially available fluxmeter is provided with a moving coil suspended in the field of a permanent magnet. or When there is a change in the magnetic flux through a search coil connected with this fluxmeter. the pointer will remain at any position on the scale. 2. A more automated recording fluxmeter will be described in Section 2. the DC current / (A) which flows through the plate will produce a DC voltage V (v) across the plate given by . that is Integrating (2. the Hall effect and the magnetoresistance effect.9.18). The third category of instrument. we have Thus the flux change is measured by the deflection of the moving coil. Magnetic fluxmeter circuit.3. When a magnetic field H (Am" 1 ) is applied perpendicular to a semiconductor plate made from Ge. can be used.10. The principle of the Hall effect is illustrated in Fig. or InAs. InSb. based on the galvanomagnetic effect. is commonly found in portable devices known as gaussmeters or field meters. The flux change caused by a rotation of the moving coil is designed to be proportional to its deflection. A fluxmeter is distinguished from a ballistic galvanometer by the fact that a fluxmeter ideally has no stable zero position. The suspension system provides a very small restoring torque on the coil. 2. Two different physical phenomena. 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.

0 T) or higher are commercially available. Magnetoresistive sensors have been used as read-out devices for magnetic bubble memories [see Chapter 22.42 MAGNETIC MEASUREMENTS Fig. 2. The magnetoresistance effect refers to the change in electrical resistance of a conductor subjected to a magnetic field applied perpendicular to the current. Li1. and the two kinds of carriers are combined and annihilated after being driven in the same direction by the magnetic field. The magnetoresistance effect is particularly large in Bi.1Oe) to 2.3 for ESR and in Chapter 4.10. the resonance frequency is proportional to the intensity of the magnetic field. The fourth category. and D2 contained in H2O. In both cases. Direct-reading Hall gaussmeters covering the field range from 8 Am""1 (=0. For these reasons. is used particularly for accurate calibration of other types of instruments.3] and for magnetically recorded tapes and disks.58Am'1 ( = l. and D2O. The principles will be explained in Chapter 3. LiSO4. Furthermore.804 ± 0. . The standard isotopes used for NMR are H1.1 for NMR. The standard material used for ESR is DPPH (a-diphenyl-/3-picrylhydrazyl) which resonates at 2. which is inconvenient for a general-purpose instrument. (2) measurement of the magnetic field produced by a magnetized body. LiCl. In this case the resistance change is proportional to H2. 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. magnetoresistance is rarely used for the direct measurement of magnetic fields.4 MAm"1 (= 3. galvanomagnetic effects are generally temperature dependent and also more or less subject to aging.001 MHz in a field of 79. (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.OOOOe). magnetic resonance phenomena.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. 2. Hall effect element.

2.33). the value of x' in (2. 2. The downward force is given by where I is the magnetization. from which we can determine the magnetic susceptibility x'• If. This force is counterbalanced by an automatic device described later. and (dH/dz) is the vertical gradient of the field. so that a current through the coil produces a vertical force on the coil. When the balance is in equilibrium.11.21). x> because of the demagnetizing field. When 7 is proportional to H. using (1. however. The coil is placed in the radial magnetic field of a loudspeaker magnet. we have from (2.MEASUREMENT OF MAGNETIZATION 43 Fig. v the volume of the specimen.22) is different from the true susceptibility. a specimen suspended from one arm of a balance is attracted downwards by the inhomogeneous field produced by an electromagnet. Magnetic balance. 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. As illustrated in Fig. The magnetic balance1 is the most common example of category 1. the current in the coil is proportional to .11. x is not not negligible as compared with 1 (say x> 10~2).

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

13. 2. 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. 2. and is magnetized to / (T) by an external field //ex. 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. Several manufacturers provide magnetometers of this type. As shown in Fig. The astatic magnetometer also falls into the second category. The principle of the third category (electromagnetic induction) is the same as that described in (2.2) above. the frequency is usually near 80 Hz and the amplitude is 0. 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 mm.13. Vibrating sample magnetometer (VSM). and convenience for measurements above and below room temperature. If the sample is driven by a loudspeaker mechanism. Note that the magnetic field just outside the specimen is the . In this device. perhaps 1-2 mm. in which case the frequency is normally somewhat lower and the amplitude larger.MEASUREMENT OF MAGNETIZATION 45 Fig. A mechanical crank drive can also be used.14). The vibrating sample magnetometer (FSM)10 is a modern version of this type of magnetometer. ease of operation. The advantages of this magnetometer are high sensitivity. 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. 2.1-0. This apparatus is still being used for the measurement of weak residual magnetization of geological specimens. the sample S is oscillated vertically in a region of uniform field.

The following is an example of the measurement of a magnetization curve as a function of the effective field He{{ for a spherical specimen. 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. Search coil. 2. but may be inconvenient to prepare. it has a well-defined demagnetizing factor (refer to (1.14. while the flux due to H is proportional to r2. same as the effective field Hei{ inside the specimen. especially as a single crystal. permitting measurement along many crystallographic directions in one single crystal sphere. A proper combination of two coils with radii r1 and r2 and number Fig. and is also unsuitable for measurements at low and high temperatures or under high pressures. Special combination search coils. The only disadvantages are a large demagnetizing factor and a certain difficulty in mounting and holding the sample during the measurement. and it is well suited for measurements at high and low temperatures or under pressure. On the other hand. requires only a small quantity of material (particularly advantageous for noble metals. . a spherical specimen has several advantages: it is relatively easy to prepare. rare earths and single crystals). 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. the flux which goes through the search coil is given by Then the flux due to / is inversely proportional to r.15. because the tangential component of the field is always continuous. 2.46)).46 MAGNETIC MEASUREMENTS Fig.15. 2.

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

. Since this unbalanced voltage is negligibly small. First the current i is passed through the primary coil. 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. Figure 2. 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 (2.11 Fig. 2. In the case of Fig.17. we have Integrating (2.16.32). so that the specimen S is magnetized.17 shows hysteresis loops obtained in this way for a Gd sphere at various low temperatures. which induces a voltage in the secondary coil This voltage almost compensates the voltage given by (2. which are used to generate a feed-back current i' in the primary coil of the mutual inductance L12.31) and (2. the signals proportional to / and i' are fed to an x-y recorder so that the magnetization curve is drawn. except for a small uncompensated voltage which keeps a current /' in the primary coil of L12. This deflection is sensitively detected by two photocells.28).and y-axes of an x-y recorder to draw an I-Heff curve. Hysteresis loops measured for Gd at various temperatures using special combination search coils. This gives rise to a voltage in the secondary coil This voltage deflects the galvanometer G. we have the relationship which shows that the flux change is proportional to the current change A/'. Pj and P2.48 MAGNETIC MEASUREMENTS specimen and a search coil. 2.34).

K. 2.26).25). which utilizes the Josephson effect. especially if the field is changed between readings. Chikazumi. and winding density n (turns m"1). If the search coil is removed from the specimen but remains in the magnetic field. 579. M. E. In this case. T. Katori. Instrum. Miura. PROBLEMS 2. Y.. 18 (1985). 3812.17 Counting these flux quanta gives a very sensitive measurement of the flux change and therefore of the magnetization of the sample. The principle of this method is to move a search coil with respect to a magnetized specimen by a fixed distance. Todo. and a SQUID magnetometer requires a long time for each magnetization measurement. The fact that the measuring apparatus must be at liquid helium temperature is clearly a disadvantage in many cases. 1174. the flux change is given by the first term of the final line of (2. and Y. If the air gap is / (m) long. Takeyama. S. and N. B 201 (1994).16 A very weak magnetic flux can be measured accurately by a superconducting quantum interference device (SQUID) magnetometer. Ishikawa and S. Hoshi. Takamasu. Phys. K. 6. Phys. C. H. Cnare. 155. Sci. T. H. . E. Appl. A.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. T. 3. and N. Matsuoka and Y. 2. Phys. Kakiuchi. Y. J. F. REFERENCES 1.2 A magnetomotive force M (A) is applied to an electromagnet made from highpermeability material. Nakao. (1965). K. Sakakibara. 5. measure the induced voltage with a digital voltmeter as a function of time. Nakagawa. T. Nojiri. Goto. 20. Herlach. S. four to five significant figures can be obtained by this method.REFERENCES 49 More accurate and stable measurement of magnetic flux is possible using a digital voltmeter.. K. J.1 Calculate the coil constant at the center of a one-layer solenoid of radius r (m). Soc. 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. the flux change is given by (2. or the specimen itself is removed from a fixed search coil. Miura. A. Goto. S. /. Haruyama. Cl-23. Japan. provided that the search coil is removed completely from the sample and out of the field.25) or the first term of (2. Uchida. Miura. /. de Phys. 45 (1984). 1018. and then integrate these values with respect to time with an analog or digital integrator. T. 37 (1966). Phys. Japan. Muto. 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. J. 1 (1962). In favorable cases. Kido. Appl. 4. Watanabe.. Physica. length 2-/J r (m)..

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

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

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Since the electron makes «/27r turns per second. 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. Fig. and e (C) is the elementary electric charge. its motion constitutes a current of —ea)/2Tr (A). One of the origins of the atomic magnetic moment is this orbital motion of electrons. Suppose that an electron moves in a circular orbit of radius r (m) at an angular velocity to (s"1) (Fig. .1 STRUCTURE OF ATOMS In the classical Bohr model of the atom.1) may be written as Thus we find that the magnetic moment is proportional to the angular momentum. Z electrons are circulating about the atomic nucleus which carries an electric charge Ze (C). where Z is the atomic number. where — e is the electric charge of a single electron. 3.3 ATOMIC MAGNETIC MOMENTS 3.1. (3. 3.1). 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). Bohr's atomic model. although their sense is opposite.

. 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. In other words. mh. it can be expressed in terms oi only the ordinate s as long as we treat only stationary states. is given by The eigenvalue of the angular momentum. and is given by where h is Planck's constant h divided by 2 77. or and / is an integer called the orbital angular momentum quantum number. 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.4) for P in (3.3). the s component of the angular momentum ps is expressed by the operator* where s is the circular ordinate taken along the circular orbit. which is normal to the orbital plane. the angular momentum is quantized. we have Thus the magnetic moment of an atom is given by an integer multiple of a unit which is called the Bohr magneton. Why the angular momentum of an orbital electron is quantized by h In quantum mechanics. so that only discrete orbits can exist. Substituting (3.54 ATOMIC MAGNETIC MOMENTS Now it is well known that the orbital motion of the electron is quantized.

The magnetic moment associated with spin angular momentum P is given by Comparing this equation with that of the orbital magnetic moment or (3. Besides the orbital angular momentum. so that its angular momentum is given by where s is the spin angular momentum quantum number and takes the values ±^. we find that the magnetic moment is again given by the Bohr magneton.STRUCTURE OF ATOMS 55 Fig. This concept was first introduced by Uhlenbeck and Goudsmit1 for the purpose of interpreting the hyperfine structure of the atomic spectrum. Explanation of a stationary state.19) into (3. However. In 1928. 3. we find that a factor 2 is missing in the denominator.20). 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.13).2. substituting P in (3. These conditions were proved by Dirac2 using the relativistic quantum theory. 3. the electron has a spin angular momentum. . we have or In order to satisfy (3. The magnitude of the angular momentum associated with spin is ft/2.16).3).14) to (3. Dirac2 provided a theoretical foundation for this concept by making a relativistic correction to the wave equation. we have or Thus the eigenvalue of L2 is an integer multiple of h.2. Applying (3.

The groups of orbits corresponding to n = 1.. can occupy the orbit defined by n and /. we can express (3.... The total angular momentum of one electron is defined by the sum of the orbital and spin angular momenta.0.19) in which s can take the values ±|..3(a) and 3. . with s = + \ and — \. which takes the numerical values 1. This is called spatial quantization. in the case of the d electron (/ = 2). The size of the orbit of the electron is defined by the principal quantum number n.2. and 0. electrons. The component of / parallel to the field. are called the s.p.d. —1. The coefficient of P in (3..4. or the magnetic quantum number can take the values For instance...3. Figures 3. the orbital moment can take five possible orientations corresponding to m — 2. are called the K. The spin angular momentum is defined by (3.3..g.. or in classical mechanics by the areal velocity... 3. m. The angular momentum is defined by the orbital angular momentum quantum number in (3.56 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. It .3 only two electrons.1. in a neutral atom Z electrons are circulating about a nucleus having an electric charge Ze (C)...3.3. As mentioned above. because the orbit precesses about the magnetic field.21) is calculated to be which is called the gyromagnetic constant.5). The shape of the orbit is determined by the angular momentum. the angular momentum parallel to the magnetic field is also quantized and can take 21 + 1 discrete states. shells. The electrons with / = 0. The orbits which belong to the principal quantum number n can take n angular momenta corresponding to / = 0. When a magnetic field is applied to an atom.2. so that where .39). Now let us examine the relationship between the electronic structure of atoms and their angular momentum..2. According to the Pauli exclusion principle.2.' is the total angular momentum quantum number..1.4.22).. L. In this case it is meaningless to discuss the azimuthal orientation of the orbit about the magnetic field. N. respectively. —2 as shown in Fig.21) as Thus we find the magnetic moment of an atom is closely related to the angular momentum of the electron motion. according to the classical model. 1. n — 1.f. A more exact definition of the g-factor is given by (3. M.4 show such precessions for m = 2. Intuitively this corresponds to discrete tilts of the orbital planes relative to the axis of the magnetic field.4. Using (3..1.

According to spatial quantization. and 5 for s. possible orbital angular momenta are / = 0. Therefore the total number of orbits belonging to one atom is given by Fig. . 3. Shapes of orbits for various magnetic quantum numbers.5 shows possible states belonging to the M shell. 1. I. The spin can take up an orientation either parallel (s = +\) or antiparallel (s = -\) to the magnetic field (Fig. p. Since the principal quantum number n of the M shell is 3.4. In other words. p. there are s. the number of orbits is 1.18. 3. and 2. Figure 3.STRUCTURE OF ATOMS 57 Fig. Spatial quantization for orbital (a) and spin (b) angular momenta. is interesting to note that these figures have some similarity with the atomic wave functions shown in Fig. respectively. 3. and s. and d.3(b)). That is. each orbital states consists of 21 + 1 orbits with different magnetic quantum numbers m. and d orbital states. each electron can occupy one state defined by n. 3.3. 3. When an atom contains many electrons.

because of a large Coulomb interaction with the unshielded nuclear charge. However. Z electrons occupy the possible orbital states starting from the lowest energy state. the atomic wave function of s electrons is very large in the vicinity of the nucleus. the total number is 2n2 = 2 X 32 = 18. we must take into consideration the interaction between these electrons. When a number of electrons are circulating around the same nucleus. from the lower n states to the higher ones. up to argon (Z = 18). as shown in Figure 3.21(c).5. This is the reason why the size of the atom remains almost unchanged from that of hydrogen. If. In an actual atom with atomic number Z. Table 3. because the effect of the inner electrons is simply to shield the electric field from the nucleus. In other words. 3. In the case of the M shell with n = 3.1 lists the electron configurations of the atoms which are most important in connection with magnetism. For this reason.58 ATOMIC MAGNETIC MOMENTS Fig. so that part of the orbit is close to the nucleus. the ordering of the energy levels remains unchanged. the charge distribution of the orbit deviates from spherical symmetry. 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. Figure 3. We see that the 3d orbit is circular. It must be noted that the energy defined by n is that of one isolated non-interacting electron. Various electronic states belonging to the M electron shell. as long as the inner electrons are distributed with spherical symmetry about the nucleus. Thus the energy of the 4s electron is lowered. Since two electrons with + and . the total number of electrons belonging to one neutral atom is equal to In2. whereas the 3s orbit is elliptical. the situation is changed. up to heavy atoms with many electrons. if the inner Z . however. As seen in this table. the 4s orbits are occupied before the 3d orbits are . the electrons occupy the states in the normal order.6 shows the shapes of various Bohr orbits.1 electrons form a spherical charge distribution about the nucleus. irrespective of the number of electrons. Therefore. This is the same as the electric field produced by a proton of charge +e.spins can enter into one orbit.

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

19 20 21 22 23 / 24 \ 25 26 27 28 29 V 30 36 .1.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 . 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 .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 . Electronic configuration of elements.

1. (contd.< 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 .„ 60 Nd 2 g 61 Pm 2 £ 62 Sm 2 2 3 63 Eu .Table 3. 57 La 2 2 58 Ce 59 Pr 2 . 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 .) _ 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 .

In the case of 5 electrons. When a number of electrons exist in an atom. in the case of the 4/ shell. producing no orbital moment. they occupy the states with a positive spin. 3.7. (2) The orbital vectors /. which would increase the Coulomb energy. 3. the magnetic quantum number m can take the values 3. 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. the maximum resultant orbit is L = 3 + 2 + 1 + 0 . In the case of 9 electrons. the electrons occupy states in the order of the numbers in Fig. -3. 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). The reason is that the electrons tend to take different orbits owing to the Coulomb repulsion.7).62 ATOMIC MAGNETIC MOMENTS Fig. 7 electrons have positive spin.8. —2. when the 4/ shell has 5 electrons. thus resulting i n L = 3 + 2 = 5 (Fig. and also the intra-atomic spin-spin interaction tends to align these spins parallel to each other. When the number of electrons is 9.2. In the case of the 4/ shell. 3. which has the capacity of accepting 14 electrons. (3) The third rule is concerned with the coupling between L and S. n.1. Russell-Saunders coupling. while the remaining 2 electrons occupy the states with m = 3 and 2. is less than half the maximum number. which is described as follows: (1) The spins s. When the number of electrons in the 4/ shell. 3. For instance. are arranged so as to form a resultant spin 5 as large as possible within the restriction of the Pauli exclusion principle.8). —1.1 = 5.0. the first 7 electrons occupy the half shell with positive spins. so that the resultant spin becomes 5 = \ — \ = f. thus forming 5 = f. or . the arrangement of these vectors are governed by Hund's rule5. For example. The reason is that the electrons tend to circulate about the nucleus in the same direction so as to avoid approaching one another. while the remaining 2 have negative spin.

when the Fig. it follows that / and s of a single electron are always opposite. / = 5 — f = f. 3. Since the orbital angular momentum of this electron points upwards (see Fig.VECTOR MODEL Spin angular momentum 63 Fig.9). because the spin angular momentum is opposite to the spin magnetic moment (see (3.20)). while when the number is 9.S. . Therefore when the number of electrons is less than half the maximum number. the electron senses a magnetic field H pointing upwards produced by the circulating nucleus with positive electric charge. / and s are opposite for all the electrons. As a result. However.8. n < 1. or n > 1. Then its spin points downwards. / = 5 + f = ^. When an electron is circulating about the nucleus (Fig. When the shell is more than half filled. 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.9. J = L . 3. So when the number is 5. Explanation of the l-s coupling. 3. Such an interaction is based on the s — I interaction of the same electron.9). J = L + S. Spin and orbital states of electrons in the 4/ electron shell. 3.

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.10. n. where a half-shell is just filled.10.29). while it is negative when n > 7. Spin S. thus resulting in parallelism between L and S. which have incomplete 4/ shells. The value of L increases from 0 at La to values of 3. /. as the number of 4/ electrons. The outermost electrons (5d)l(6s)2 2 are easily removed from the neutral atom. and then decreases towards 0 at Gd with 4/7. This state and also a completely filled 4/14 state are called 'spherical'. orbital L. changes as shown in Fig. Therefore the atomic magnetic moments of rare earth elements are more or less the same in both compounds and in metals. . so that its orbital magnetic moment is well preserved or 'unquenched' by the crystalline field. S increases linearly with n from La to Gd. The total angular momentum. while it is relatively large for n > 1. so that the only orbital momentum L comes from electrons with negative spin which point opposite to the resultant spin S.S for n = 0 to 7. and conduction electrons in metals or alloys. 5. while / = L + S for n = 1 to 14. Further increase in n results in a repetition of the same variation.64 ATOMIC MAGNETIC MOMENTS number of electrons is more than half the maximum number. 3. the sign of w is positive when the number of electrons n < 7. So / is relatively small for n < 7. and then decreases linearly to Lu. 3. because / = L . thus producing trivalent ions in ionic crystals. As mentioned above. L and J for rare earth ions. is increased. In terms of w in (3. the orbital momentum for the 7 electrons with positive spin is zero. Now let us calculate the values of 5. which has 4/14. which has 4/7. Fig. and total angular momentum 7 as functions of the number of 4/ electrons of trivalent rare earth ions. 6.

we have From the relationship between three sides and the angle ^ABO in the triangle A ABO.34) is called the saturation magnetic moment. Now let us discuss the magnetic moments associated with these angular momenta.7). Therefore the average magnetic moment becomes parallel to /. Comparing (3.VECTOR MODEL 65 Fig.11). Referring to (3. and also referring to the geometrical relationship shown in Fig.6) and (3. 3.11.11. 3.33). the vector L + 25 takes a direction different from / (Fig. Composition of atomic magnetic moment M. we have the spin magnetic moment Therefore.19) and (3. L and S precess about /. the total magnetic moment MR is given by When vectors L and S take different orientations. we have the orbital magnetic moment Referring to (3. we have Eliminating cos ZABO. 3.20). we have from which we obtain an expression for g: . and its magnitude is given by the projection on / or The magnetic moment given by (3. the vector L + 2S also precesses about /. however.34) and (3. Since.

1). p must be replaced by —ih(d/dq) (q is the positional variable). . y. respectively. or px.66 ATOMIC MAGNETIC MOMENTS In quantum mechanics. The calculation will be shown in Chapter 5. as will be discussed in Part III. Figure 3.65).10). Experimental values observed for trivalent ions * Let us deduce this relationship for orbital angular momentum L.* Then we have This relationship was first introduced by Lande empirically to explain the hyperfine structure of atomic spectra.6 If 5 = 0. and z. except that the magnetic moment is much more enhanced by the g-factor for heavy rare earths than for light ones.12 shows the effective magnetic moment calculated using (3. then J = L. so that it follows from (3. The shape of the curve is similar to that of L (see Fi 3. When a magnetic atom is placed in a magnetic field. while if L = 0.) Thus it is concluded that the eigenvalue of L2 is L(L + 1). the magnitude of the atomic moment deduced from the thermal average of magnetization is given by which is called the effective magnetic moment. and the position coordinates x. respectively. so that we have In polar coordinates.39) and (3. we must replace S2. y. Let the x-.and z-components of L be Lx. L(L + 1) and /(/ + 1).39) that g=l. we have (Examine this relationship for desired values of / and m in (3. so that g — 2. then / = 5. these components can be expressed in terms of the components of momentum p. 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.40) as a function of the number of 4/ electrons. py and pz. The solid curve represents the calculation based on Hund's rule. as In quantum mechanics. As a result. Then On the other hand. L2 and J2 by 5(5 + 1). we can write Executing this operator to the atomic wave function given by (3. Ly and Lz.65). This is exactly what we find in (3.

This discrepancy was explained by Van Vleck and Frank7 in terms of multiple! terms of these elements.vector modeldeell. tends to become Eu2+ or 4/7 by accepting an electron from the conduction band. result in an increase in the magnetic moment.12.. Effective magnetic moment as a function of the number of 4/ electrons measured for trivalent rare earth ions in compounds and rare earth metals.D. 3. In these elements. The broken curve in the figure represents this correction. while in the excited states. These divalent ions have the same electronic structures as Gd3+ and Lu 3+ . whereas Yb 3+ . The agreement between theory and experiment is excellent. Therefore.G. S and L make some small angle. thus producing a non-zero J. The electronic structures discussed in this section are often expressed in spectroscopic notation such as 2S1/2. The thermal excitation and the mixture of these excited states. thus showing the same effective magnetic moments.P. and reproduces the experiment well. in which S.F. whose electronic structure is 4/6. except for Sm and Eu. Eu3+. S and L almost compensate one another in the ground state.. The experimental points for metals.. The reason is that these ions are divalent in metals. except for Eu and Yb. or *Fg/2. because there is a tendency for atoms or ions to become spherical. tends to become Yb2+ or 4/14 in the same way. therefore. Fig. signify that . and comparison with the Hund and Van Vleck-Frank theories. in the compounds are also shown as open circles in the figure. shown as crosses in the figure. as seen in the figure. which is 4/13. are also in excellent agreement with the theory. 5DQ. respectively.

because the effect is extremely small. spin and orbital magnetic moments. The mechanism by which the magnetic atoms transfer their angular momentum to the crystal lattice will be discussed later in this section. In 1915.23). Consider the moment when the field (and therefore the magnetization) change direction from upward to downward. Barnett9 first succeeded in determining the g-factor by comparing the magnetization of two identical magnetic rods.11 The principle is illustrated in Fig. Then the associated angular momentum must also change. and accordingly the g-factor in (3. the natural period of oscillation was 26 seconds.14). A prefix to the capital letter represents 2S + 1. Electronic configuration and spectroscopic ground terms are given in Table 3. unsuccessful. Therefore the crystal lattice must rotate so as to compensate for the change in angular momentum of the magnetic atoms. This experiment was based on the idea that if the magnetic atoms in the bar have an angular momentum. Since this system is isolated mechanically. . the rotation of the bar should drive this momentum towards the axis of rotation.68 ATOMIC MAGNETIC MOMENTS L = 0. 3. The magnetization was also measured. and a suffix represents /. could be calculated.1. In the actual experiment done by Scott. the total angular momentum must be conserved. the axis always rotates perpendicular to the direction in which the force is applied (see Fig.22).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.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.3 GYROMAGNETIC EFFECT AND FERROMAGNETIC RESONANCE As noted in the preceding section.4. 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. 3. Many attempts* have been made to measure the g-factors of various magnetic materials in order to determine the contribution of these possible origins.2. The most successful measurement technique is known as the Einstein-de Haas effect. The difference gives the change in angular momentum. one rotating about its long axis and the other magnetized by an external magnetic field applied along its long axis. there are two possible origins for magnetism in materials.13.1. 3. respectively. This experiment was. The first such experiment was done by Maxwell. 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. however. so that the gyromagnetic constant in (3.™ which was developed more precisely by Scott. This relationship between rotation and magnetization is called the gyromagnetic effect.

Apparatus for observing the Einstein-de Haas effect.85 from g 5 10.and g'-values. the former is referred to as the g '-factor.91 1.91 1. is associated with the magnetic moment.5 1 7.19 g/(g ~ 1) 1.10 2.85 1. by the angle 6.21 2.99 1.GYROMAGNETIC EFFECT 69 Fig.01 2.5 . Comparison between g.5 0.5 from g' 4 7.10 2. Then a torque will act on M. 3. M.83 1.5 8 4. Values of these two quantities are listed for various magnetic materials in Table 3.10 2.13.99 1.21 2.91 1.18 2.90 1.84 g' 1.84 1.2.5 6 9 5 0. The g-factor can also be determined by a magnetic resonance experiment.91 1.5 8 4.2. P. experiment.92 1.12 2.83 1. g(%) Material Fe Co Ni FeNi CoNi Supermalloy Cu2MnAl MnSb NiFe2O4 g 2. as will be discussed below. the direction of this vector must change by L per unit second or Table 3.91 1.5 10.84 1. H. deviates from the direction of the applied magnetic field.98 1. Since an angular momentum. Suppose that the atomic magnetic moment.5 5 9. while the latter is called simply the g-factor.85 1.

Ferromagnetic resonance experiment. precessional motion will be induced for all the magnetic atoms.14. a>. we have that the time derivative of the angular momentum must be given by a torque. the magnetic moments of all the magnetic atoms in the material precess with the same angular frequency. no matter how the magnetic moment tilts from the direction of the field. 3. 3. when a magnetic field is applied to a magnetic material. and the intensity of the magnetic field applied perpendicular to the H vector of the microwave is increased gradually (Fig.15). 3.14. Processional motion of a magnetic moment. the vector L is perpendicular to P.44) is independent of the angle 6. so that the angular velocity of the precession is given by It is interesting to note that the angular velocity given by (3.15. Accordingly. (This relationship is a modification of Newton's second law of motion saying that time derivative of momentum is a force. and also to H. When the intensity H of the magnetic field reaches the value which satisfies the condition (3. . 3.f. if an alternating magnetic field of this frequency is applied perpendicular to the static magnetic field.) permeability shows a sharp maximum. Fig. so that the radio frequency (r. so that P must rotate about H without changing its angle of tilt 6 and its magnitude. In the actual experiment a specimen is attached to the wall of a microwave cavity.44). The trace of the point of the vector P is a circle of radius P sin 6.70 ATOMIC MAGNETIC MOMENTS Fig. Applying this law to a rotational system. a precession is induced.) As shown in Fig. Therefore.

3. and accordingly the value of g from (3.44). This phenomenon is known as ferromagnetic resonance (FMR). Ferromagnetic resonance curve (Hr: resonance field). we can determine v from (3. A more detailed discussion will be given in Chapter 20. 3. Figure 3. The actual precession is associated with various relaxation processes by which the system loses energy. .16.17. This is.22). however. we assumed that the magnetization reverses its sense upon the application of the magnetic field. true only if some relaxation process absorbs energy from the precessional motion and allows the Fig. Ferromagnetic resonance of a cylindrical ferromagnetic specimen.GYROMAGNETIC EFFECT 71 Fig.16 shows experimental results for Permalloy. In the preceding discussion of the Einstein-de Haas effect. The precessional motion described above is somewhat idealized. From the field at which resonance occurs.

The reaction of this relaxation mechanism causes the rotation of the crystal lattice of the specimen. For simplicity. or Accordingly the resonance frequency (3.47) is obtained as follows: Set the x-axis normal to the sample surface. The ferromagnetic resonance experiment was first performed by Griffith12 in 1946. The correct g-values were determined by Kittel13 by taking into consideration the demagnetizing field caused by the precessional motion. given by the sum of the torque from the external field and that from the demagnetizing field.72 ATOMIC MAGNETIC MOMENTS magnetization to relax towards the direction of the field. we have Solving this equation. we have the angular frequency Using equations (3. a similar calculation shows that Equation (3. and the z-axis parallel to the external field. When the magnetization tilts from the cylinder axis by the angle 6. Then we have for the equations of motion Eliminating Py from the above equations by using (3. 3.47). we can calculate the gyromagnetic constant and accordingly the g-factor.46) and (3. a demagnetizing field —7s(sin 0)/2/i0 is produced perpendicular to the axis.44) is modified to If the specimen is a flat plate and the external field is applied parallel to its surface. therefore.23).17). The torque acting on the magnetization is. . let us consider a cylindrical specimen (Fig.

Then we have Considering that g' = 1 for orbital motion and g' = 2 for spin.13"16 when a magnetic atom is under the strong influence of the crystal lattice.GYROMAGNETIC EFFECT 73 In addition to the demagnetizing field. The deviation of the g'-factor from 2 is apparently caused by a small contribution from the orbital magnetic moment. We also note that the sign of the deviation from a value of 2 is different for g. The restoring force acting on the magnetization can be equated to a hypothetical magnetic field acting parallel to the easy axis. The corresponding angular momenta will be (Ps)spin and (Ps)orb.and g'-values.54). which tells us that the origin of the atomic magnetic moment is not orbital motion but mostly spin.53) and (3. Van Vleck and others.2 together with the g '-values determined from gyromagnetic experiments. it orbital angular momentum is not conserved. 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. the magnetic anisotropy also influences the resonance frequency. so that only spin angular momentum contributes to the expression for the g-factor: Adding both sides of (3. respectively. and that from orbital motion by (/s)orb. The g-values obtained from ferromagnetic resonance measurements are listed in Table 3. as seen in Table 3. and H2 when the magnetization deviates towards the y-axis. because it produces a restoring torque tending to hold the magnetization parallel to the easy axis (see Chapter 12). the values observed for 3d transition elements are close to 2. As pointed out by Kittel. we have which can be written as . Let this field be Hl when the magnetization deviates towards the *-axis. Generally speaking. (3. the g-values obtained from magnetic resonance are greater than 2.2.3). Let the part of the saturation mangetization due to spin motion be (/s)spin. the g-values determined from magnetic resonance should be equal to the g'-values determined from the gyromagnetic experiment for the same material. If the magnetic atoms do not interact with the crystal lattice.52) is modified to On the other hand.

3. If we denote the ratio of the orbital contribution to the spin contribution by we can write from (3.2. The values are in excellent agreement. the potential energy is given by where r (m) is the distance between the electron and the proton.58) and (3.53) assuming s •« 1. These resonances are all concerned with electron spins. in which a single electron is circulating about a proton.52) and from (3.59) are also listed in Table 3. and s0 is the permittivity of vacuum . we can observe paramagnetic spin resonance. These values are all less than about 10%. In addition to the ferromagnetic resonance discussed in this section. The mechanism of quenching of the orbital moment must be known more precisely in order to understand the origin of magnetocrystalline anisotropy and magnetostriction. The quantity g is often referred to as the spectroscopic splitting factor. while the g'-factor is known as the magnetomechanical factor. antiferromagnetic resonance. so that they are called electron spin resonance (ESR). which will be discussed in Chapters 12-14. Now let us consider the wave function of a hydrogen atom. The values calculated from (3. together with the values directly determined from the gyromagnetic experiment.5).56) are listed in Table 3. We have learned that the orbital magnetic moment is mostly quenched in materials composed of 3d magnetic atoms.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.2. Since the electron is under the influence of the Coulomb field produced by a proton with electric charge +e (C). and ferromagnetic resonance (see Section 20.74 ATOMIC MAGNETIC MOMENTS The g' -values calculated using (3.

In classical dynamics. as shown for example by Fig.2. 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.62) is given in all textbooks on quantum mechanics. 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. the kinetic energy is given by \mv2 = (l/2m)p2. The suffixes n. orbital. Here we simply refer to the final solution. ®lm(d) is a function of the polar angle 9 from the axis of quantization. I. The solution of the Schrodinger equation (3. In quantum mechanics.1. where p is the momentum. 3. The specific forms of these functions involving the angles 6. and magnetic quantum numbers. and m are respectively the principal. The reason why these functions are characterized by these quantum numbers is that only functions characterized by these numbers express the stationary states.QUENCHING OF ORBITAL ANGULAR MOMENTUM 75 The state of the orbital electron is described by the wave function fy(. and <&m( <p) is a function of the azimuthal angle <p about the axis of quantization. (p are given by and .r). which is where Rn!(r) is a function of the radial distance from the nucleus r. as already explained in Section 3.64) is the same as the first term in (3.63).

1. d.76 m| ATOMIC MAGNETIC MOMENTS The term Pj (cos 6) is the /th transposed Legendre polynomial and given for / = 0. the azimuthal variations are smeared out.2. Note that if the square of wave functions with different m are added.69) express the eigenstates involving the azimuthal angle <p as discussed in Section 3. however. the sum becomes isotropic. we recognize that the wave functions for m = 0 in d or / electrons stretch along the z-axis or the axis of quantization. so that the directional distribution of the wave functions is expressed simply by rotating the functions (3. When the orbital magnetic moment remains unquenched. p.18. This is also the case if the square of wave . It is. either clockwise or counterclockwise. f electrons The functions (3. thus producing a circular current. meaningless to consider further details of this correspondence. such wave functions are circulating about the axis of quantization.4.69) about the axis of quantization as shown in Fig. The reader may recognize a similarity between these pictures and those of the Bohr orbits as shown in Fig. 3.1. In this figure. while those for m = 1 or the maximum values spread along the z-plane or the plane perpendicular to the axis of quantization. Accordingly.3 or s. 3.

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

their magnetic properties are influenced by these shapes. the orbital magnetic moments are strongly influenced by the crystalline field.19. thus cancelling their angular momenta. the Coulomb energy will be lowered. and accordingly no orbital magnetic moment arises. Referring to (3. Sometimes their orbital angular momentum is totally quenched. because the magnetic shells are exposed to the influence of neighboring atoms in the crystal environment. *The fact that (3. .68).78 ATOMIC MAGNETIC MOMENTS Fig. Suppose that two wave functions with m = + 2 and m = — 2 are superposed. We will elucidate the mechanism of quenching below. In the case of 3d electron shells. drawn by using ®2+2 m (3.69) and (3.19 illustrates the angular distribution of this wave function. This figure represents a standing wave constructed by a superposition of the oppositely circulating wave functions. the resultant wave function is given by Figure 3. Therefore neither angular momentum nor electric current is produced. 3. as shown in the figure. When such magnetic atoms are assembled into crystals.70). 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.70) is real means that the wave function is independent of time. The magnetocrystalline anisotropy of most rare-earth ions can be interpreted in terms of the atom shapes (Chapter 12).* Since this wave function spreads to avoid the anions (negatively charged ions) in the environment.

the wave functions </^.(r) in (3. because . the orbital magnetic moment will be quenched. but also includes exchange interaction. Finally. and L2n'^(t) is the Laguerre polynomial given by * This (/>„ is the same as that shown in Fig. which is given by the general form where x = Zr/a0. i/^ extend along the (110> directions. If the state expressed by one of these wave functions is stabilized by a ligand field. avoiding the principal axes with fourfold symmetry. and the latter dy.3 to discuss the mechanism of magnetocrystalline anisotropy. i/^. or the same neighbors at different distances. the d wave function can be written in terms of the following orthogonal real functions: Figure 3.QUENCHING OF ORBITAL ANGULAR MOMENTUM 79 In general. along the (110) and <100> directions. we shall elucidate the radial part Rn. a0 = 4Tre0h2/me2. 3. We shall also use the ligand theory in Section 12.20 shows the angular distribution of these wave functions.66). As seen in the figure. if/u extend along the principal axes. A better name for this interaction is the ligand field rather than the crystalline field.* The former are called ds. etc. covalent bonding.19. the energy of the nearest-neighbor interaction is different for ds and dy. when d electrons are placed in a crystalline field with cubic symmetry. Since the 3d magnetic atoms or ions have different neighbors. The origin of this interaction is not only the Coulomb interaction. while the functions i[/u.

68) and (3. The magnitude of the wave function is expressed by the density of drawing.6. (3. It is seen that the s function is large at the nucleus. In these patterns.21 shows a computer-generated pattern representing the spatial distribution of the atomic wave function (3.72).72) is given by Figure 3. The graphs shown below each pattern represent the radial variation of R(r). 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.66) calculated from (3.67). 3.80 ATOMIC MAGNETIC MOMENTS For a number or orbital electrons the functional form of (3. . the vertical axis is the z-axis or the axis of quantization.

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 81 Fig.1 Calculate the spectroscopic splitting factor (g-factor) for the neodymium (Nd) atom. The d(e) and d ( y ) wave functions of 3d electrons in a cubic ligand field.3 How strong a magnetic field must be applied parallel to the surface of an iron plate to . 3. Assume that g = 2. PROBLEMS 3. 3.20. 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.2Oe). 3.

3.21. Radial lines signify if/ > 0. 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. 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.

using microwaves with a wavelength of 3. 765. 73 (1948). N. Physik. 670. 152. 10. 245. Pauli. Rev. Mitchell. Verhandl. Einstein. Ges. Rev. 3. H. M. Barnett. de Haas. 1932). 111 (1915). 1116.. 610. 743. B-l) (1962). Mag.REFERENCES 83 observe ferromagnetic resonance. 101 (1956). A. J. Rev. Roy. 8. W.0 cm? Assume that g = 2. Proc. 270. 17. A. 6. J. All? (1928). Kittel. C. Proc. 61 (1925). Physik. 1. Con/.69) for m = 2. 1611. 82 (1951). by calculating the sum of the square of the wave functions given by (3. H. J. 158 (1946). Russell and F. 6. 13... Maxwell. 78 (1950). G. Einstein and W. A. Phys. 73 (1948). J. Linien Spektren und periodisches System der Elemente (Julius Springer. 173. p... 3. Physik. Polder. 1954). 9. Int. J. Verhandl. A. 1. 15. Deut. S. Physik. 155. . C.4 Show that the 3d5 electron shell is spherical. 542. 575. Z. Rev. Phys. 266. Rev. H. Suppl. 423. Phys. H. 14. Lande. 239. Soc. J. Berlin. E. Hund. Deut.. Z. 2.. Soc. C. 372. H. Nature. Electricity and magnetism (Dover. -1. and ignore the effect of magnetocrystalline anisotropy. p. Uhlenbeck and S. de Haas. Phys.. 5. Van Vleck. 0. 7. D. 953. 17 (1915).. 18 (1916). Phys. 31 (1925). Griffith. 12. 76 (1949). Oxford.. P. 4. Ges. Kyoto (7. Ges. Japan. Deut. 38. 18 (1916). Phys. Scott. and Cryst. J. 71 (1947). A. New York. Verhandl. Die Naturwissenschaften. A118 (1928). F. Astrophy.10 and 7S = 2. Physik. 16. Dirac. Van Vleck. Saunders.. 15 (1923). J.12T. Theory of electric and magnetic susceptibilities (Clarendon Press. 11. 351. G. Kittel and A. Phys. 13 (1925). REFERENCES G. 189. W. Rev. 1927). Goudsmit. and — 2. E.

nuclear magnetic moments make a negligibly small contribution to the magnetization of materials. 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. The quadrupole moment of the nucleus is given by where p is the electric charge density. Therefore. atomic magnetic moments originate from orbital or spin magnetic moments of electrons in unclosed electron shells.6.1 NUCLEAR MAGNETIC MOMENTS AND RELATED EXPERIMENTAL TECHNIQUES As discussed in Chapter 3.1. so that Q = 0 as seen from (4. The nuclear spin and the nuclear magnetic moment for various isotopes are given in Table 4. One nuclear magneton is given by where mp is the mass of the proton. so . and z the coordinate axis taken parallel to the nuclear spin. If the charge distribution has spherical symmetry it follows that r2 =x2 +y2 +z2 = 3z2. When Q > 0. atomic nuclei possess small but non-zero magnetic moments. The spin angular momentum of a nucleus is measured in units of h as in the case of the electron spin. and is denoted by the symbol /.1 to 5. from which we see that the magnetic moment is not necessarily proportional to the spin and sometimes even has opposite sign. or 1/1836.4 MICROSCOPIC EXPERIMENTAL TECHNIQUES 4. In addition to these moments. These moments are measured in nuclear magnetons.1) with the Bohr magneton given by (3. Accordingly. the g-value defined by takes various values ranging from 0. Comparing (4. The nuclear magnetic moment is also accompanied by a quadrupole moment.3). we see that the electron mass in the denominator is replaced by the proton mass. r the radial vector of the charge.7). the charge distribution of the nucleus stretches along the z-axis.

82 +2.1804 -0.32 +2.573 1.40361 -1.88 24. Various physical quantities of typical isotopes.271 +0.13 1.984 -0.47 +0.6 51.323 +1.97 100 22.14 8.90671 Quadrupole moment.2522 4.5 61.3436 +0.0 -0.3 -1.5131 -0.304 -0.58554 +0.26 -0.24 -0.994 -0.1766 -0.52 7.76 100 2.29 14.00282 0 +0.5 0 +0.42 10.12 30.3094 -0.857406 +1.60602 +1.4485 +4.46 +2.827 0 +3.82183 +5.231 +0.87 13.386 +0.242 -0.65 +4.53 4.7277 +1.8 100 100 1 85 Resonance frequency (MHz) for// = 10kOe (= 0.23 -0.65 57.9114 Element n (neutron) H C N 0 F Al P Cl V Mn Fe Fe*(14.242 5.1658 42.80 -0. Q/lO~ucm2 0 0 +0.615 -0.0802 g -3.134 -0.583 -0.2300 3.300 +0.36 +2.16 +2.0745 100 100 100 75.148 +3.4keV) Co Ni Ni*(67.68 -0.7 1.7078 3.0 +1.8091 -2.16134 -0.985 0.1866 -0.5899 +1.23 +0.2574 +1. 4.653 -0.14 15.3871 +0.7856 9.1763 11.3 +2.40361 -0.NUCLEAR MAGNETIC MOMENTS Table 4.22 +0.75 100 99.91 11.86 0.1 15.547 8.637 +0.72 -0. 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.34 Eu Gd Tb Dy Ho Er Tm Yb Lu Ir Pt Au Bi that the shape of the nucleus is a prolate ellipsoid.89370 +2.312 12.107 +0.161 -0.91314 +2. When Q < 0.25 — 69.8 0 0 -0.45656 +2.58 -0.329 -0.757480 +5.346 1.1.68 +1.0765 5.059 -0.1236 +0.4841 +1.534 1.5 33.5647 -0.49912 ±0. the charge distribution of the nucleus spreads along the x-y plane.7781 +4.43 1.052 +0.060 +1.608 -0.88 50.35 48.3590 +2.1).7937 +1.463 100 22.404 0.26332 +0.64140 +1.565 6.113 +1.1026 17.4037 +1.482 -0.21 — 100 1.412 38.375 0.54789 +1.1 +1.4709 +1.13166 +0.246 -0.1 2.7310 1. M/M N -1.239 0.92 +1.981 3.1546 +4.119 10.015 1.17 +0.84 1. 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 % — 99.1056 +2.88 1.113548 -0.82 47.82 0.6287 +3.080 -0.186 +1.26 +1.2 97.465 +1.9953 10.7361 6.857406 +0.911 100 12.14 -0.79277 +0.3849 +2. so that the shape of the nucleus is a flat oblate ellipsoid (see Fig.547 +2.4678 +0.5356 10.75 1.65 +3.255 +1.317 1.670 11.188 +0.130538 +3.1031 +1.702381 +0.0745 11.492 -0.404762 +0.0883 -0.273 0.09657 +0.422 1.06 4.28 0 +0.50 2.5 +1.35 0 +0.0902 -0.16 +0.064 -0.7739 40.64 10.261076 +1.21204 +0.529 99.1 +5.462 +0.215 +1.537 49.2261 +2.212 10.5758 6.8045 0.227096 -0.12 +1.52 -0.4keV) Cu Br Rh Pd Ag Sb 1 La Pr Nd Sm Spin.016 -0.86 52.86 9.0265 0 0.7958 MAm' 1 ) 29.94 100 14. .98 8. If the distribution of atoms surrounding the nucleus deviates from cubic symmetry.33 +0.9 +0.82628 +5.78 +0.63 1.21 -0.107 99.7 100 18.050 13.146 0 -0.74868 ±0.4 16.25 42.2696 -0.678 +2.

or Q > 0 and q < 0. this produces a gradient of the electric field 6E/dz0 along some specific crystal axis z0 at the nucleus. 4. the spin axis z tends to be parallel to the specific crystal axis z0. the nuclear spin precesses about the axis of H. 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.1 for various isotopes. Since the electric field along the z0-axis is given by E = —d<j>/dz0. The sign and magnitude of q are determined by the atomic arrangement in the environment of the nucleus under consideration. 4. This gives rise to a torque in addition to the torque produced by the magnetic field.e. as in the case of the electron spin. Since in NMR the size of the magnetic moment is smaller by a factor of 1/1836. there are various interactions with the environment. so that the nuclear spin is forced to rotate towards the z0-axis. When a nucleus having a nuclear magnetic moment as well as a quadrupole moment is placed in a material. the sign of the torque is opposite. the resonance frequency for NMR is much smaller than that for ESR. When Q < 0. On the contrary. while the magnitude of spin angular momentum is more or less the same.1.1. The resonance angular frequency for NMR is given by . If the nucleus is prolate. The resonance frequency can be determined by a method analogous to that used in electron spin resonance (ESR). The magnetude of this interaction is given by the energy e2qQ.1 Nuclear magnetic resonance (NMR) When the nucleus is placed in a magnetic field H. The value of Q is given in Table 4. Quadrupole moment of the nucleus and the field gradient at the nucleus. if q > 0. the electric field changes from place to place.86 MICROSCOPIC EXPERIMENTAL TECHNIQUES Fig. the negative field gradient is given by where q is the field gradient measured in units of . The resonance phenomenon and the experimental technique are known as nuclear magnetic resonance (NMK). everything is reversed.

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

because this component has nothing to do with the absorption or the dissipation of the energy (see Section 20. The spins with relatively fast precessional speed lag behind the central spin. or in the case of a non-uniform static magnetic field. The spin echo method provides information not only on the internal fields. all the spins are precessing in phase with the central spin. the central spin tilts by 180° through the z-axis (the axis parallel to the static magnetic field). The normal NMR method requires homogeneity of the sample material as well as of the static magnetic field. by selective absorption. This fact was first pointed out by Lamb6 and was experimentally verified by Mossbauer.3 Mossbauer effect The internal field for some isotopes can be measured by means of the Mossbauer effect. but also about the spin-lattice relaxation by which energy is transferred from precessional motion to the lattice. only the component parallel to the central spin is reversed. 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.7 To observe the Mossbauer effect. and about the spin-spin relaxation through which the energy is transferred between spins. The relaxation time involved in these processes is known as T! for the spin-lattice relaxation and as T2 for the spin-spin relaxation. 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.88 MICROSCOPIC EXPERIMENTAL TECHNIQUES Fig. so that after a time T (s). 4. By the application of the second high-frequency pulse with a double time-duration. This y-ray can be absorbed by another nucleus of the same species. 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. 4. The value of T2 can be obtained by observing the decay of the echo signal as a function of the time interval T (s). it is desirable to select an isotope with large mass which emits a low-energy y-ray and to place the isotope in a . Then the distribution of the spins is reversed from that before the application of the second pulse.2.5). The spin echo technique is useful for inhomogeneous materials. Schematic illustration of spin echo technique.1. thus giving rise to a sharp signal in the search coil. For the other spins. while those with relatively slow precessional speed precede the central spin. while the component perpendicular to the central spin remains unchanged.

NUCLEAR MAGNETIC MOMENTS 89 Fig. 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=\. 4. decays by electron capture with a half-life of 270 days to a second excited state of Fe57 with spin I=\. as shown in Fig.3. Co57 (which decays to Fe57) is particularly appropriate for the investigation of magnetism. The energy separation between the last two levels is 14. 4. 4.4 keV. One of the reasons for this is the difference in the size of the nucleus in the ground and the excited states.3. The isotope Co57. The energy scheme of the nuclear transition of Co57 to Fe57 is shown in Fig. the energy levels of the ground and the first excited are split by various effects into six levels. c. which gives rise to a difference in Coulomb interaction between the nucleus and surrounding electrons. because it allows detailed measurement of the internal field which acts on the nucleus of Fe57 in a magnetic material. One of the effects is the isomer shift. Among various possibilities. d) of the ground and excited states resulting from various interactions. If a nucleus of Fe57 exists in a magnetic material. which can be made by irradiation of Fe with 4MeV deuterons. solid with a high Debye temperature so that the nucleus is firmly bound. 4.3. which is a shift of the excited level upwards by 5 (Fig.3). Energe level scheme (a) of the nuclear transition of Co57 to Fe57 and energy levels (b. If for some reason the electron .

the energy is changed by where I2 is the component of the nuclear spin parallel to H^. as already mentioned in (a). the level is split into four levels with 72 = — f. In the excited state with 7 = f. 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 isomer shift can also be caused by a temperature difference or a difference in Debye temperature between the emitter and the absorber. which acts on the nucleus. As a result of these three effects. On the other hand. No quadrupole moment exists in the ground state.90 MICROSCOPIC EXPERIMENTAL TECHNIQUES density around the nucleus is different between emitter and absorber. the ground and the excited states are split into two. . Between these levels there are six possible allowed transitions which satisfy the exclusion rule A/ z = 0 or ±1.3(a) by the quadrupole moment of Fe57 in the field gradient q. 4. 4. 4. the energy level of 7Z < 0 is higher than I2 > 0 in the excited state. The valence of Fe57 can be estimated from the isomer shift. while it is negative for Iz = +\. or the rule of conservation of angular momentum. 4.3(d)). The mechanism of the internal field is explained in Section 4. Schematic illustration of the experimental arrangement for measurement of the Mossbauer effect.4.1. The second effect is the Zeeman splitting by the internal magnetic field //. This is called the quadrupole splitting. because the mass of the nucleus is changed during emission or absorption of the y-ray.4. the energy level is split into two levels with Iz = \ and —^.3.and fourfold levels (Fig. The energy levels are split as shown in Fig. the difference in Coulomb interaction should result in a shift of energy levels. From this shift we can determine the field gradient and deduce the identities of the lattice sites where Fe57 atoms are located. because the sense of Iz is reversed on excitation. —\. Fig. In this case. Since / = \ in the ground state of Fe57.\ and f as shown in Fig. 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. while the excited levels are split by The sense of the splitting is positive for Iz = ±|.

The hyperfine spectrum of Fe57 in iron metal. 2s. These s electrons are . is attached to a loudspeaker diaphragm.6). Moreover. 3. That is. 3. These values are generally tens of MAm" 1 (hundreds of kOe). or in terms of quantum mechanics. 4. the wave functions of these 5 electrons have high values at the nucleus (see Fig. The experimental procedure for observing the absorption lines is illustrated in Fig. The transmitted y-rays are detected by a counter and recorded as a function of the velocity. these s electrons can approach the nucleus (see Fig. the field gradient and the isomer shift. which is much larger than the Lorentz fields produced by these magnetic atoms or ions.4 Internal fields The values of internal fields measured by means of NMR and the Mossbauer effect are listed in Table 4. The internal field is thought to originate from the polarization of Is. the sign of the internal field is usually negative. which is of the order of Icms" 1 .5. when the source is moving with velocity v. The oscillation of the speaker modulates the y-ray wavelength through the Doppler effect. 4.3(d).21(c)).1. 4. and 3s electrons.10'11 In terms of classical physics. In this way we observe the six absorption lines shown in Fig. It is therefore possible for the y-rays emitted by Co57 to be absorbed by Fe57 in the magnetic sample material. or opposite to the Lorentz field.4. produced by Mossbauer effect measurement using a stainless steel source and a natural iron absorber 0. we determine the various parameters characterizing the internal fields. By analyzing these absorption lines.5. (After Wertheim8) The six transitions are observed as six absorption lines denoted by 1 to 6 in Fig. The y-ray source.025 mm thick. containing Co57. The most important of these is the internal field. the energy of the y-ray is modified by hv(v/c).NUCLEAR MAGNETIC MOMENTS 91 Fig.2 for various nuclei of magnetic atoms and ions. 4. 4. which is discussed in the following section.

while 3s electrons produce positive fields.2 ±0.5| |282| +279 ±44 +3500 + 550 +335 ±80 +4200 ±1000 polarized by the polarized d-electrons through the exchange interaction.5 -345 -17.9| |550| -41.5 -18. —112.5 ±1.6 -510 ±20 -37. .3 -280 -17. in the case of Mn 2+ .5 +1.92 MICROSCOPIC EXPERIMENTAL TECHNIQUES Table 4. Internal field Nucleus 57 Temperature (K) 0 0 0 0 78 78 room room room room 78 78 78 78 room 85 room 1.3 -81 + 4 -1.2 -215 -36.0 ±0.4 ±0.48 ±0.1 ±1.3 -342 |27.4 -280 ±5 -22.4 -312 ±5 -22.1 -515 -41. For instance.8 -190 ±10 < 0.12 -20. and in turn they polarize the nucleus through a mechanism called the Fermi contact.7 ±1.1| |339| -24.4.8 -200 ±10 -25.01 |212.6 -515 ±20 -40.6| 1157.1 -289 -6.5 ±1.08 +18. 2s.5 -320 -5.3 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. Generally speaking.1 ±1.51 |22.1 -540 |43.7 -460 |37.9 -550 -40.7| |12.3 + 0.6 -70 -17.8 < 10 -27.6 -220 -15.36 -217. I s and 2s electrons produce negative internal fields. the contribution of Is.9 + 0.7 ±1.4 -80 -13.2. The internal magnetic fields of several isotopes included in various magnetic materials (after Ishikawa9).2 -228 -23.6 -170 -6.6 -465 ±20 -16.64 ±0. which has no orbital moment.0 117.3| |468| -43. and 3s electrons are calculated to be —2.6 -510 ±20 -43.

the internal fields are as large as in ferromagnets. the magnetic structure of a crystal or the magnitude of the magnetic moment of an atom can be determined. The reason is that the radius of the 3d shell is smaller for Fe3+ than for Mn 2+ .7 to -43. A number of neutron-absorbing control rods limit the neutron density. which generate neutrons by chain reaction. The calculated value on the basis of exchange polarization is -50. It is seen in Table 4.2 that 119Sn in the ferromagnetic metals Fe. so that it interacts with and is scattered by the magnetic moments of magnetic atoms. The energy of neutrons produced by nuclear reaction is the order of 10 MeV. but not the overall magnetization. in spite of the fact that the electronic structures are the same. there are a number of rods containing nuclear fuel such as uranium. the orbital moment is almost quenched. which is smaller than the calculated value for Mn 2+ . because the frequency of thermal vibration is higher than that of the nuclear spins. This is because the internal fields reflect the ionic magnetic moments.913AfN. so that it penetrates matter without being influenced by the electric fields produced by electrons and ions. At the center of the reactor. -1400. The internal fields of Fe3+ in Table 4.6.9 MAm" 1 (-510 to -550 kOe). so that the internal field of an ion is caused by the polarization of its own d electrons. 4. Therefore the internal field in this case is a good measure of the ionic magnetic moment. because the positive contribution from the partially unquenched orbital moment is added to the contribution of the s electrons. On the other hand. In magnetic insulators. the neutron carries a nuclear magnetic moment of magnitude —1. Therefore the internal fields of paramagnets are generally very small. to keep it below a critical value. respectively. so that the internal fields come mainly from the exchange polarization of 5 electrons.2 range from -40.2 that 161Dy or 159Tb exhibit fairly large positive internal fields. in magnetic metals and alloys. The internal field of Fe2+ is much smaller than Fe3+. the polarization of the conducting s electrons is affected not only by their own ionic polarization but also by the polarization of their neighbors. Neutron beams can be obtained from a nuclear reactor.NEUTRON DIFFRACTION 1 93 and +59MAHT (-30. At temperatures above absolute zero.3 MAm" 1 (-630kOe). On the other hand. and +740 kOe). Co and Ni exhibits fairly large internal fields in spite of its non-magnetic nature. the internal field is proportional to the thermal average of the magnetic moment. By making use of this effect.11 in excellent agreement with the experimentally observed value -52MAH1-1 (-650kOe). 4. in antiferromagnets. These add up to —SSMAm" 1 (-690kOe).12 In the case of the 3d transition elements. It can be seen in Table 4. The orbital magnetic moment is caused by the orbital current.2 NEUTRON DIFFRACTION The neutron is an elementary particle which carries no electric charge. but this energy decays in heavy water at the center of the reactor to a value of the . as illustrated schematically in Fig. which produces a large internal field at the nucleus. However. the magnetic ions are always separated by anions.

This fact was first pointed out by Elasser13 and experimentally verified by Halban and Preiswerk. Generally speaking. as shown in Table 4.6. The first such experiment was done by Shull and Smart15 to detect the antiferromagnetic spin arrangement in an MnO crystal (see Chapter 7). 4. A neutron with energy near kT is called a thermal neutron. The scattering amplitudes are different for different atoms. in a manner analogous to the interpretation of X-ray diffraction results. and T is the absolute temperature of the heavy water (about 300 K). and the angle of diffraction is detected by a counter. either spin or orbital. where k is the Boltzmann constant. The density of thermal neutrons at the center of the reactor is in the order of 1014 cm"2 s"1.94 MICROSCOPIC EXPERIMENTAL TECHNIQUES Fig. This is reduced to 106-108 after reflection from the monochromator crystal. the intensity of the thermal neutrons is 1012-1014 cm~ 2 s"1 in the beam as it comes from the reactor. Nuclear reactor and double axis goniometer for neutron diffraction. The fact that the wavelength of thermal neutrons is close to the lattice constant of common crystals is quite fortunate for solid-state science. From this data the crystal structure and the magnetic structure can be analyzed.3. order of kT. This beam is diffracted by a sample crystal. and finally down to 104-106 after diffraction from the specimen. The wavelength of the thermal neutron is calculated by the de Broglie wave equation which gives a value of 1-2A. taking the neutron mass to be 1836 times the electron mass. The nuclear o .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. Neutrons are scattered by magnetic atoms in two ways: scattering by the atomic nucleus and scattering by the magnetic moment.

4.37 ^ /°-96 jo.8.35 -0.08 1. On the contrary. The reason is as follows: When the diameter of the scattering atom is the same order of magnitude as the wavelength of the radiation.27 0.35 0. only the magnetic scattering contributes to the change in diffracted intensity.23 Atom or ion Cr 2+ Mn2+ Fe (metal) Fe2+ Fe3+ Co (metal) Co2+ Ni (metal) Ni2+ scattering amplitudes.35 0.11)). C. the beams going through the right and left edges of the atom interfere with each other after scattering as shown in Fig.47 1.57 0.28 / \ J1'03 Magnetic scattering amplitude D (10 12cm) For 0 = 0 For sin 0/A = 0.3.7 shows the form factors for X-ray and neutron magnetic scattering as a function of sin 0/A. because neutrons are scattered magnetically principally by the outer electron shell. where 6 is the scattering angle. which varies with the scattering angle due to the size of the scattering body.45 0. For example. First we discuss the nature of magnetic scattering in method (2). the form factor for neutron scattering from the nucleus is independent of the scattering angle. are different not only in magnitude but also in sign. as seen in Fig.08 1. because the nucleus can be regarded as an infinitesimally small point compared with the wavelength of thermal neutrons.21 0.NEUTRON DIFFRACTION 95 Table 4.7. Figure 4.60 1.45 0. and this value is subtracted from the total intensity to determine the magnetic intensity.10 0. (2) The magnetic scattering can be suppressed by applying an external magnetic field parallel to the scattering vector. while X-rays are scattered by all the electrons. or perpendicular to the scattering plane. The decay of the form factor is faster for neutron magnetic scattering than for X-ray scattering.54 0. D. 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. (3) By using a polarized neutron beam and switching the direction of polarization. As seen in the figure.25 1. because a phase difference results. (HT12cm) 0.16 0. This phenomenon is quite similar to the diffraction of light after going through a small hole.51 0. 4. the form factor decreases with increasing scattering angle.57 0. Nuclear scattering amplitude C. C is negative for the Mn nucleus as a result of resonance scattering. When spin . Differential cross sections for nuclear and magnetic scattering (after Bacon16). The effective size of the atom for X-ray scattering is therefore much less than for neutron magnetic scattering.35 0. is given by a quantity called the form factor. f (see (4. The amplitude of the magnetic scattering.

or q = 0. (After Bacon16) Fig. X. and the reversed vector parallel to the projection of the unit vector of the atomic magnetic moment. The vector q can be expressed as as illustrated in Fig. We define the scattering vector. The magnetic scattering is proportional to the scalar product of q and A. e. on the scattering plane. is perpendicular to the vector q.10) is a factor which includes the unit vector parallel to the magnetic moment of the neutron.12) is a unit vector perpendicular to the scattering plane pointing from the incident side.. Also if the magnetic moment of the neutron. 4.8.7.96 MICROSCOPIC EXPERIMENTAL TECHNIQUES Fig. The scattering vector given by (4. For instance. in either a ferromagnetic or antiferromagnetic structure. no magnetic scattering occurs. 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. respectively. as where k and k' are unit vectors parallel to the incident and scattering neutron beams. A. if the atomic magnetic moment is perpendicular to the scattering plane. 4. and / is the form factor amplitude.9. q. Comparison of atomic form factors for X-ray and for neutron scattering. magnetic moments are arranged regularly. Illustration of the reason for the decay in form factor with increasing scattering angle. 4. The scalar product in (4. no magnetic scattering .

Relationship between various vectors involved in neutron diffraction: incident and scattered wave vectors.9.14). On the other hand. so both magnetic and nuclear scattering occur. occurs. magnetic scattering is effectively produced by neutrons polarized parallel to the projection of the atomic magnetic moments onto the scattering plane. K and the vector given by (4. q. k. k'. 4. 4. Suppose that the incident and scattering beams. (Note that if the atomic magnetic moments are perpendicular to some particular scattering plane. the magnetic scattering is maximized because q = \. and accordingly the scattering vector. One method for separating the magnetic scattering: (a) magnetic field H is applied perpendicular to the scattering plane. e. unit vector parallel to the magnetic moment. H. scattering vector. . In conclusion.) Now let us consider the method for detecting magnetic scattering in method (2). If the Fig. 4. so the magnetic scattering is completely eliminated.10.NEUTRON DIFFRACTION 97 Fig. which gives the maximum repulsion when the two dipoles are parallel to each other and perpendicular to the line joining them. e. when the magnetic field is applied vertically (see (b)). lie in the horizontal plane (see Fig. This fact can be interpreted in terms of the magnetic dipolar interaction (1. the magnetic scattering vanishes because q = 0. When a magnetic field.10). (b) field H is applied parallel to the scattering plane. magnetic scattering will occur from other scattering planes. is applied to magnetize the specimen parallel to the scattering vector (see (a)). The difference between the two cases gives the intensity of magnetic scattering.13).

(4. so that only the neutrons whose polarization is antiparallel to the magnetization of the monochromator can be diffracted. Including the nuclear scattering. the second term vanishes after averaging over all possible directions of X. When the incident neutrons are unpolarized. if C — D. so that an accurate observation of magnetic scattering is impossible. Otherwise (as in the case of Ni metal. we have for the total differential scattering where C is the nuclear scattering amplitude.) When a vertical magnetic field is applied to the monochromator as in Fig. Possible monochromators for neutron polarization are the (220) reflection from an Fe3O4 crystal and the (111) and (200) reflections from an Fe-Co crystal.98 MICROSCOPIC EXPERIMENTAL TECHNIQUES intensity of the magnetic field is adjusted to allow rotation of the magnetization towards the stable directions.11) can become equal to C at some scattering angle. unless D is much smaller than C.15) becomes less than 1% of the first term. (The form factor for magnetic scattering decreases with increasing scattering angle.3). polarized neutrons can be used to observe magnetic scattering. so that D in (4. Therefore.14) leads to Method (2) consists of altering q in (4. Accordingly. if there is an appropriate Bragg reflection. so that for neutrons whose polarization is parallel to the magnetization of the monochromator crystal. The precession finally reverses the direction of neutron spins at the end of the apparatus. 4. while for oppositely polarized neutrons.10(b). The inverter provides a high-frequency magnetic field perpendicular to the static magnetic field or the precession field. and induces resonance precession of the neutron spins. the second term in (4. Alternatively. Then (4. (The .15). we can separate the magnetic from the nuclear scattering. q = —1. This method was first proposed by Shull17 and executed by Nathans et a/. Figure 4.16) vanishes. The polarized neutron beam from the polarizing crystal retains its polarization direction in the collimating magnetic field. in which D was nearly equal to C. but the polarization can be reversed by the polarization inverter if necessary.18 They used Bragg scattering from a carefully selected monochromator crystal. where D is about 10% of C). we can get information on the magnetic anisotropy (see Chapter 12) or the canting of the spin system (see Section 7.11 illustrates the experimental arrangement for generating the polarized neutron beam.

In other words. such as ferromagnets. from —1 to +1.12. The wavelength of neutron beams remains unchanged by Bragg scattering. Fig. Triple axis goniometer for energy analysis in neutron scattering. 4. we can elucidate the dispersion relationship of the magnon or the quantized spin wave. On the other hand. and antiferromagnets.14) is changed by 4CDq. which is large enough to determine the intensity of magnetic scattering.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. The change amounts to 40% of C in the case of Ni metal. For instance.NEUTRON DIFFRACTION 99 Fig. Schematic diagram of a polarized neutron spectrometer. the velocity and therefore the kinetic energy of the neutrons is conserved. X. 4. (After Nathans et a/. . Such scattering is called elastic scattering. ferrimagnets. By measuring the change in wavelength as a function of wave vector in inelastic scattering.11. the neutron can excite spin waves in magnetically ordered systems.) By changing the direction of polarization of the neutron spins. in inelastic scattering a part of the kinetic energy is lost by conversion to some other form of energy. the total differential cross-section given in (4.

13. which can be measured accurately. When the rotational speed is correctly set. It has a magnetic moment whose magnitude is between that of the Bohr magneton and the nuclear magneton. a neutron which passes through the hole in a disk A (see Fig. the velocity of the neutron is determined. The wavelength of the scattered neutrons is determined by changing the angle of incidence of the analyzer crystal for a known Bragg reflection.13. 4. 4. Since a neutron of wavelength 1A has a velocity of 3. with mass about 207 times larger than the electron mass.13(b)).13. 4.96kms"1. 4. each of which has a single hole. the time required to travel the distance. as shown in Fig. The muons thus produced have high energy (about 100 MeV).9).12 shows a schematic illustration of a triple-axis goniometer for the observation of inelastic scattering. which disintegrate into neutrinos and muons. Another method to observe the change in wavelength is the time-of-flight (TOP) method. Principle of the time-of-flight (TOP) method. 4. say 1m.3 MUON SPIN ROTATION (/tSR) The muon is an artificially produced elementary particle. After these muons are introduced into a specimen. This method determines the velocity of the scattered neutrons. and have their spin axes antiparallel to their velocity.13(a)) can pass through the hole in disk B (see Fig. Muons are produced as follows: First high-energy protons collide with nuclei to produce mesons. they lose energy and finally come to rest at some point in the material. and the distance between the two disks. 4. The velocity of the neutron is determined by adjusting the rotational speed of a pair of disks. . from which the wavelength is found by de Broglie's relationship (4. Figure 4.100 MICROSCOPIC EXPERIMENTAL TECHNIQUES Fig. This particle can be used as a microscopic probe for detecting local magnetic fields inside magnetic materials. which is illustrated in Fig. Knowing this rotational speed. between the two disks is 252 ps.

^i~. 4.14. with positive electric charge +e (C). and the negative muon. Finally they stabilize to the Is ground state. The behavior of these muons in the specimen is quite different: The positive muons come to rest at an interstitial site in the crystal. A positive muon travelling from left to right passes through the counter D and stays in the specimen S. being repelled by the positively charged nuclei. Fig. The positive muon which stops at an interstitial site has its spin antiparallel to the incident direction. with negative charge -e (C)."1 . The negative muons are attracted to nuclei and take up orbital motion around a nucleus. There are two species of muons: the positive muon.15. p+. and also reduces the nuclear charge by e as a result of electrostatic shielding. 4. This phenomenon is called the pSR. This orbital muon adds a large magnetic moment to the nuclear magnetic moment of the host nucleus.14 is a schematic illustration of the /tSR apparatus. and then makes a precession motion about the magnetic field at this point. Figure 4. Conceptual diagram of the /xSR apparatus. thus producing a completely new artificial nucleus.MUON SPIN ROTATION ( M SR) 101 Fig. The precession frequency is proportional to the intensity of the magnetic field. Angular distribution of positrons emmitted from disintegrated ^u. whose radius is very small because of the large muon mass.

102 MICROSCOPIC EXPERIMENTAL TECHNIQUES A muon which passes through the specimen is detected by the counter X and is ignored. because the velocity of the incident muon is very large. and an electron neutrino ve. the muon eventually decays with a lifetime of 2. The Fig.16.20 and Nishida21) . During the precession motion. 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.2 /xs. 4. (After Yamazaki et al. an antimuon neutrino v^. and by the reaction turns into a positron e+.

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. 4.MUON SPIN ROTATION (/j. 4.20 and Nishida21) . as shown in the Fourier spectra of Fig. Fourier transform of Fig. 4.17. 4. but the frequencies obtained after Fourier analysis of the data are quite sharp. 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. The experimental points scatter a great deal. The data 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. Fig.SR) 103 positron tends to be emitted parallel to the direction of the spin of the muon.16. (After Yamazaki et a/.15 shows a polar diagram of W(Q).16 were obtained for metallic iron at various temperatures. Figure 4.16. Then we can observe a precession oscillation as shown in Fig.

Letters. Thesis (Tokyo University. Wertheim. Muon spin rotation spectroscopy (Adam Hilger. A. Anderson. 626. Soc. 6 (1958).. 17. Hahn. Halban and P. Rev. Phys.104 MICROSCOPIC EXPERIMENTAL TECHNIQUES 4. H. 1967).22 PROBLEMS 4. Phys. Shull. Y. Bacon. Neutron diffraction (Oxford. Hashimoto. E. C.. 203 (1936). 1256. J. Phys. L. Nishida. 21. Appl. Rev. S. Phys. 8 (1962). New York. 32 (1961). 124. G. . 76 (1949). 22. Nathans. Table of isotopes (6th edn. Z.. 10 (1959). 13. 110 (1958). O. G. as seen in Fig. and K. E. pp. E.090MN. Rev. Phys. 1963). Mattias and D. Hyperfine structure and nuclear radiations (North-Holland. New York. 5. 4.. the reader may refer to a reference book on this subject.5. Naturforsch. Preiswerk. M. T. Solids. 65. Amsterdam. 988-1011. W. Rev. 18. calculate the internal field (Am"1). 8. 3 (1959). 8-6-13. A. Chem. Nakai. Phys. 1690. Smart. 31 (1960). Yamazaki. E. Kondo. 138. /. and the isomer shift (mms"1). C. Bristol & Boston. Phys. 15. Portis and A. Rev. For further details. Phys. K. Physik. R. 12.. Z. Clarendon Press. Compt. Rev. Nathans.. Phys. Ishikawa. 20. (McGraw-Hill. G. 205S. and nuclear magnetic moment 0.17. Freeman. M. Nagamiya. Mossbauer. the quadrupole shift (J). 2. 164. G. K. Phys. 81 (1951). C... Phys. The relaxation mechanism of ^iSR can also be investigated by observing the decay of the precession. handbook. what temperature is required for the neutron bath? REFERENCES 1. 1968). 1280. American Inst. 149 (1959). 117. calculate the NMR resonance frequency for 57Fe in an internal field of — 27MAm~ 1 . /. 53B (1974). Lamb. Shull and J. Nagamine. G. 73. Gossard and A. /. Letters. Rend. 202 (1936). Watson and A. Phys. 118S. A. G. Appl. 19. 110S. E. 14. M. C.. 580. K.1 Knowing that the nucleus 57Fe has nuclear spin \. M. 1029. Phys. Portis.3 In order to produce a neutron beam which contains neutrons with an average wave length of 4 A. Phys. T. Marshall. Compt. 1955). Pigott. Shull. 4. 211.. R. 151 (1958). R. 11. 123 (1961). Schenck. Elsasser. M. Gossard. Shirane. 4. /. N. Hollander and Perlman. S. and A..2 Using the Mossbauer spectrum shown in Fig. 80 (1950). 4. 2nd edn. R. 1977). Chem. Japan. 38. Lederer. 10. Rend. 7.. 32 (1961). 16 (1961). 190. 6. 1091. Appl. 55 (1939). Sugimoto. and G. 9. K. L. G. Rev. 1985). Shull. C. W. W. 4. Metal Physics. Shirley. Solids. Crowe.. J. Wiley. 3. Phys. 16. A.16.

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

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According to Lenz's law.1). let us assume that the orbit is a circle of radius r (m). the orbit precesses about the applied field without changing its shape.1 which occurs in a material containing no atomic magnetic moments. the magnetic flux produced by this acceleration of an orbital electron is always opposite to the change in the external magnetic field. In other words. eu&B.5 MAGNETIC DISORDER 5. typically x~ 10~5. According to the law of electromagnetic induction. The relative susceptibility of such a material is negative and small. and that a magnetic field H (Am" 1 ) is applied perpendicular to the orbital plane. the change in the centrifugal force acting on the electron is given by which is just balanced by an increase in the Lorentz force. According to (5.3). which is in fact the case. with angular velocity . For simplicity. This is always true. 5.1 DIAMAGNETISM Diamagnetism means a feeble magnetism. so that the susceptibility is negative. 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. We assume that the radius r remains unchanged. and the velocity change Ay during the time interval A Ms given by where AH is the change in the magnetic field during A/. even when the orbital plane is inclined. an electric field E (VmT 1 ) is produced in such a way that so that The electron is accelerated by this field.

6) is replaced by x2 +y2. which is influenced by the band structure. so that r2 = x2 +y2= la2. Fig. each of which has Z orbital electrons.2 Diamagnetism is also exhibited by inorganic compounds.1 lists the . Table 5. the magnetic moment produced by the motion shown in Fig. 5. conduction electrons play an important role in producing diamagnetism. 5.6) becomes When a unit volume of the material contains N atoms.3). This relationship holds fairly well for materials containing atoms or ions with closed shells.2. but not when the field is parallel to the plane of the ring. 5.2). where the z-axisjs parallel_to the magnetic field (Fig. 5. Therefore (5. Referring to (1. benzene rings. This motion is called the Larmor precession (Fig. Larmor precession of a tilted orbit.12) and (5. act as closed shells.3). in which TT electrons are circulating just like orbital electrons.1. 5. They exhibit fairly strong diamagnetism when the field is applied perpendicular to the rings. so that r2 in (5.108 MAGNETIC DISORDER Fig. the magnetic susceptibility is given by where a2 is the average a2 for all the orbital electrons. For instance. we have X2 = y2 = z2 = a2/3.1 is given by In the case of a closed shell. Considering spherical symmetry. Mechanism of atomic diamagnetism.3 In the case of diamagnetic metals. electrons are distributed on a spherical surface with radius a (m).

5. Table 5. diamagnetic susceptibility is not strongly temperature-dependent.7 Xl(T -25 -35 -16 -14 -18 . Diamagnetism of spherically distributed electrons.9.4 . Relative diamagnetic susceptibility for various materials at room temperature.DIAMAGNETISM 109 Fig. even in the presence of an external field H (Meissner effect). the magnetic flux density. is always zero in the superconducting state.23 6 Reference \ ) 4 5 . B. Generally speaking. Superconductivity is also characterized by perfect diamagnetism: that is. is given by In other words. Superconductivity is the disappearance of the electrical resistivity at some (usually low) temperature called the critical temperature.1. /.7. Tc. values of diamagnetic susceptibility at room temperature for various materials. Materials Cu Ag Au Pb C (graphite) A12O3 H2O SiO2 (quartz) Benzene Ethyl Alcohol x (= ^TTX in cgs) .68 .3.7. Since in this case the magnetization.05 -16.9.

. 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. as does the direction of spin.110 MAGNETIC DISORDER Fig. as shown in Fig. 5. Temperature dependence of the critical field.4. the thermal energy shared for one degree of freedom is given by kT/2. 5. This table includes oxide superconductors with relatively high critical temperatures as first discovered by Bednorz and Miiller.5. Hc. of a soft superconductor. 5. where k is the Boltzmann constant. 5. but decreases gradually with increasing field as shown in Fig.4. 1. the position of each atom undergoes thermal vibration. Hc2. The magnetization curve of a superconductor is shown in Fig. so that magnetization.7. Let us assume a paramagnetic system containing N magnetic atoms each with magnetic moment M (Wb m). At room temperature. 7.These critical fields increase with decreasing temperature as shown in Fig. In this case.38 X 1(T23 JK" 1 . vanishes. 5. Fig. The critical field. Hcl. the magnetization does not drop to zero at the first critical field. called a Type II or hard superconductor. Hf. When the external field is increased to a critical field. 5. At absolute temperature T (K). There is another kind of superconductor. with their critical temperatures and critical fields. At a temperature above absolute zero.2 PARAMAGNETISM Paramagnetism describes a feeble magnetism which exhibits positive susceptibility of the order of . Table 5.2 lists typical superconductors.6. Hc.5. This type of superconductor is classified as a Type I or soft superconductor.^=10~ 5 -10~ 2 . and finally vanishes at the second critical field. increases with decreasing temperature. Magnetization curve of a soft superconductor. the superconducting state is destroyed.6 5. which we will refer to simply as spin.

Fig.40 9. the spins are distributed uniformly over all possible Table 5.8 (= llOkOe) — — — . 5. Such a magnetic field barely influences a thermally agitated spin system at ordinary temperatures.6.7. 5.20 18. Temperature dependence of the critical fields Hcl and Hc2 of a hard superconductor. H (Am"1).064 (= 803 Oe) 20. In the absence of a magnetic field. 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.1 10 40 100 110 Hc or Hc2 (0 K) 0.PARAMAGNETISM 111 Fig. Assuming that M= 1MB and H= IMAm" 1 .7 (=260kOe) 8.113MAm-1(=1420Oe) 0. Typical superconductors. We can calculate the magnetization of such a system more quantitatively using the Langevin theory. the potential energy is given by (1. Magnetization curve of a hard superconductor.9).2.8).25 7. 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. 5. the potential energy is given by which is about 250 °f the thermal energy at room temperature given by (5.12). 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. which is a moderately high field such as that produced by an electromagnet.164 (=2060Oe) 0.

The physical probability for a spin to make an angle between 6 and 8 + dO is. the points are gathered slightly towards H. 5.112 MAGNETIC DISORDER Fig.9).16) becomes . so that the probability for a spin to take this direction is proportional to the Boltzmann factor On the other hand. the magnetization due to the whole spin system is given by If we put MH/kT= a and cos 0 = x. we get -sin 0 = dx. therefore. For a spin which makes an angle 6 with H. so that (5. Angular distribution of paramagnetic spins in a magnetic field.8. is applied. so that the points of the unit vectors cover the sphere uniformly.8. the potential energy is given by (1. given by Since such a spin contributes an amount M cos 0 to the magnetization parallel to the magnetic field. orientations. When a magnetic field. 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. or 27rsin0d0. H. 5.

referring to (5.9. Figure 5. This means that as H.18) with respect to a. 5. cannot be realized in practice unless we use extra-high fields or cool the sample to extremely low temperatures. is increased. we have . For a field of the order of 1 MAm"1. or Therefore. Langevin function. the magnetization.17) is reduced to where the function in parentheses is called the Langevin function and denoted by L(a). given by (5.13) and (5. we have the numerator of (5. The integral in the denominator is calculated to be By differentiating both sides of (5. As a is increased. and accordingly a. (5. /.20) approaches NM. This saturation of the paramagnetic system.12). which corresponds to the complete alignment of all the spins.17).PARAMAGNETISM 113 Fig. L(a) approaches 1.9 is a plot of L(a) as a function of a. however.

The susceptibility is. The solid curves represent JBj(a) for J=\. and Gd3+. Fe3+. f. H. the average magnetization in a magnetic field. B}(a) can be expanded as . given by Thus we find that the susceptibility is inversely proportional to the absolute temperature. is given by where the function in parentheses is called the Brillouin function and is denoted by B y (a). Figure 5. In particular. and \ (note that in these ions L = 0.20) This means that the magnetization is proportional to the magnetic field. For a <s: 1.114 MAGNETIC DISORDER Therefore. For a •« 1. The functional form of B3(a) is similar to that of the Langevin function and in the limit of / -»°°. so J = S).25). as shown in (3. they coincide. we have from (5. the Langevin function can be expanded as so that retaining only the first term. only the linear part of L(a) near the origin is observed. if we set the z-axis parallel to the magnetic field.10 shows the magnetization curves of three paramagnetic salts containing Cr 3+ . In the above calculation. This relationship is known as the Curie law. All of the theoretical curves reproduce the experimental points quite well. a spin can have only discrete orientations because of spatial quantization. the z-component of M is given by where Jz can take only 2J + 1 values Therefore. therefore. we assumed that the spin can take all possible orientations. In reality.

28). we find that (5. E.22).27). we have Comparing this equation with (5. if we adopt only the first term in (5. Henry7) If we put / = oo in (5. we find that if we replace M in (5. II ferric ammonium alum. 5.24). Thus the Brillouin function includes the Langevin function as a special case (/ = <»).28) becomes equal to (5. (After W.28) for the Brillouin function in (5.24) by . and III gadolinium sulfate octahydrate. Magnetization curves of paramagnetic salts: I potassium chromium alum.PARAMAGNETISM 115 Fig.10. Considering that a = JMBH/kT.

24) holds. PROBLEMS 5.116 MAGNETIC DISORDER *ig. as shown in Fig. or we can get the saturation magnetic moment as already given by (3. is known as the Curie law. Orbital paramagnetism produced by orbital magnetic moments9 is also temperature-independent. and average orbital radius 0.1 Knowing that copper^has atomic number 29. from the saturation magnetization given in (5. In addition to Langevin paramagnetism.11. calculate its relative diamagnetic susceptibility. this temperatureindependent term must be subtracted before applying the Curie law.41). From the slope of this curve. l/x versus i curve tor Langevm paramagnet. When the effective magnetic moment is deduced from the temperature dependence of the paramagnetic susceptibility. we can calculate the effective magnetic moment. This is called Pauli paramagnetism? The susceptibility in this case is proportional to the density of states at the Fermi level. a change in temperature of a few hundred kelvin has only a small effect on the Fermi level.34).li. Use the following values: Avogadro's number N= 6.94gcm~3. atomic mass 63. density 8.27).5 A.29). 5. The quantity MeK is the effective magnetic moment as already given by (3.11 X 1(T31 kg. electric charge of electron e = 1.60 X 10~19 C. and electron mass m = 9. . (5. Therefore. On the other hand. Equation (5.02 X lO^mol"1. paramagnetic metals and alloys exhibit nearly temperature-independent paramagnetic susceptibility. For this purpose. so as to separate the Langevin term from the temperature independent one. which corresponds to several thousand K (refer to Chapter 8). we must measure the temperature dependence over a wide range of temperature. which gives the linear relationship between l/x and T.54. s.

R.. Phys. J. J. E.2 Calculate the relative paramagnetic susceptibility for an ideal gas. 4. J. Obata. Mod. Phys.. 5. Pauli. Rev. 4 (1936). Cleveland. E. 547. in which each molecule has a magnetic moment with J = 1. Magnetism and metallurgy I (ed.02 X 1023 mol"1. 11 (1956). Miiller. Z. A. R. 559. 15. Berkowitz and Kneller. Kubo and Y. 673. 189. L. J. Phys. at 1 atmosphere pressure and 0 °C. Phys. W. 252.. 7. G. Rev. 1972). REFERENCES 1. 1932). Z. Physik. 88 (1952). 2.41 at the above-mentioned temperature and pressure. 6. Vogt. Handbook of physics & chemistry (53rd edn. Oxford. 9. The 1 mol ideal gas takes a volume of 22. The theory of electric and magnetic susceptibilities (Clarendon Press. 41 (1926). 3. W.. W. 24 (1952).) (Chem.. Chem. . 81. Soc. 1969) p. Phys. 8. Van Vleck. H. g = 2. New York. Henry. B64 (1986). Japan. Rubber Co. Myers.REFERENCES 117 5. Pauling. Bednorz and K. Academic Press. Avogadro's number is 6.

Weiss1 in 1907. In this section we discuss the origin and nature of ferromagnetism in a narrow sense.3). In this book we describe either of these cases. This field was considered to align the neighboring spins parallel to one another. The physical origin of this interaction will be discussed in (6. It was found (as you will see later) that the molecular field coefficient w in (6.2. This also results in a spontaneous magnetization. The average magnetization under the action of an external field. wl.1). so that the molecular field cannot be attributed to a classical magnetostatic interaction. as ferromagnetism in a wide sense. or Note that this is just like the Lorentz field given by (1. 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. Weiss considered that a molecular field could be produced at the site of one spin by the interaction of the neighboring spins (Fig.6 FERROMAGNETISM The term ferromagnetism is used to characterize strongly magnetic behavior.1) is much larger than the Lorentz field coefficient l/(3p. both of which lead to the presence of spontaneous magnetization. H. Instead of a parallel alignment of all the spins. there can be an anti-parallel alignment of unequal spins. and a molecular field.0). which we call ferrimagnetism. such as the strong attraction of a material to a permanent magnet.1 WEISS THEORY OF FERROMAGNETISM The mechanism for the appearance of spontaneous magnetization was first clarified by P. 6. As discussed in Section 5. is given by . The origin of this strong magnetism is the presence of a spontaneous magnetization produced by a parallel alignment of spins. He assumed that the intensity of the molecular field is proportional to the magnetization. this term then includes both ferromagnetism and ferrimagnetism. He assumed that in a ferromagnetic material there exists an effective field which he called the molecular field.52) acting in a spherical hole in a magnetized body.

This state is called absolute saturation magnetization and denoted by I s0 . The intersection points O and P of curves (a) and (b) represent solutions. The state of thermal equilibrium represented by curve (a) is above point P' until P' reaches P. However. say P'. the equilibrium state is always closer to P. Equation (6.3) with respect to /.2) must satisfy (6. In this case. At T = 0.16). Let us first assume that H = 0. the slope of line (b) is zero. 6. Fig. or Is0=NM. Figure 6. the point O represents an unstable solution. The parameter in this case is given by Since (6. near the origin.WEISS THEORY OF FERROMAGNETISM 119 Fig. The molecular field acting at the site from which a spin is removed. Physically. the relationship (6.5) . because if the state changes from P to P". the alignment produces a non-zero molecular field which leads to more complete alignment. point P represents a stable solution. Graphical solution for spontaneous magnetization: (a) Langevin function (6.2) and (6. which requires that the state P' must always stay on the line (b)). we can solve (6.2) and (6.2.2) represents the Langevin function as shown by curve (a) in the figure. point O represents a completely random orientation of the spins. because if the magnetization happens to take some non-zero value. because an external field.4) becomes a straight line (b) through the origin. 6.4) as a function of a. Once there is some alignment of spins by random processes. where L(a) = l and I = NM. Such a solution can be obtained graphically.3) includes /. (b) function (6. Now let us consider the temperature dependence of spontaneous magnetization on the basis of this graphical solution. (6. H. On the other hand.4). is not necessary to produce a spontaneous magnetization. so that the point P goes far to the right.2 shows plots of (6. the state P' must rise along the curve b (this follows from the definition of a. similar to (5. and obtain The solution of (6.4) simultaneously with the same value of a.1.2).

22)). The points are experimental values for Ni and Fe. (After Becker and Coring2) As the temperature increases. 6. @ f . The temperature dependence of spontaneous magnetization obtained by this graphical method is plotted as a function of temperature in Fig.2.) The curves denoted by / = 1 and / = \ are the solutions using the Brillouin functions B^a) and Bl/2(a). compared with theoretical curves calculated from the Weiss theory using Brillouin functions with / = f. respectively. the slope of line (b) increases. This final temperature is called the Curie point.3 (see the curve denoted by / = oo. 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). instead of the Langevin function L(a). 1. the gradient of the initial slope of curve (a) in Fig. or . The experimental points for Ni and Fe are in better agreement with the curves J =\ and / = 1 than with the curve J = °°. or (see (5.120 FERROMAGNETISM Fig. In order to determine the Curie point. This means that the spatial quantization of spins is a more realistic picture than the classical view of unlimited spin orientations. and <». Temperature dependence of spontaneous magnetization. must be equal to the gradient of line (b) at T= ® f . 6.3. 6. and denoted by @ f . meaning that the spontaneous magnetization vanishes. the solution is always 7 = 0. At any temperature higher than the Curie point.

For iron.6) with (6. In this sense. At a temperature T *£. Thus the Curie point is a good measure of the molecular field coefficient w. 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.2 downwards and accordingly a shift of point P upwards. N = 8. Thus the magnetization I increases slightly. When.WEISS THEORY OF FERROMAGNETISM Equating (6. 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. we have (see (5.13).54 X 1028 m~3. which causes a shift of line (b) in Fig. .J= 1. The susceptibility in this case is given by On the other hand.27) for the Langevin function. we have Eliminating da/dH from (6.4).7). The physical origin of this enormously large molecular field is the exchange interaction. In order to measure this susceptibility accurately we must use a high magnetic field. 6. we call it the high field susceptibility. @ f . L'(«) is small enough to give a very small value for the susceptibility (6.28)).3).12) and (6. which will be discussed later. M = 2. using the values 0f = 1063K. we have where L'(a) is the derivative of L(a) with respect to a. So far we have ignored the effect of the external field.2MB. The effect of the external field is given by the second term of (6. from the definition of a in (6. we have 121 If we use the Brillouin function (5.14).

so that the denominator of (6. and may require the use of extremely high fields.16). the point P stays near the origin in Fig.3) in (6. where L'(a) = |. At T > @ f .2. T approaches 0 f . This is called the Curie-Weiss law. Let us discuss in more detail the shape of the magnetization curve near the Curie point. According to (5.22) or (5. the susceptibility is inversely proportional to the deviation of T from @ f .30). At T < 0 f .4.122 FERROMAGNETISMm Fig. 6. we have therefore .4. and noting that wI»H. 6. L'(«) = 5. which shows a divergence of the susceptibility at the Curie point.14) becomes That is. Separation of the two phenomena is difficult.14) tends to vanish and the susceptibility approaches infinity. where the magnetization is relatively small in comparison with the absolute spontaneous magnetization. Substituting (6.28). The temperature dependence of the susceptibility as predicted from these arguments is shown over the complete temperature range in Fig. so that (6. 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. Divergence of magnetic susceptibility in the vicinity of the Curie point. the quantity M in (6. some effects of technical magnetization may overlap with the high-field susceptibility. Taking into account spatial quantization.15) must be replaced by the effective magnetic moment given by (5. 6. however.

5.20).23) with respect to temperature. Magnetization curve at a tempera- ture near the Curie point.WEISS THEORY OF FERROMAGNETISM 123 Fig. This plot is called the Arrott plot. For more details the reader may refer to Kouvel and Fisher. we divide both sides of (6.7 (solid curve).4 Kouvel and Rodbell. such a relationship does not necessarily hold in every case. Extrapolating to H/I = 0.3 From the first term of (6.19) by / to give Therefore if I2 is plotted against H/I.6. we can determine the value of 7S. 6. By differentiating (6. 6. However. the magnetization is also affected by rotation against the magnetocrystalline anisotropy (Chapter 12). 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.6.6 The Curie point can also be determined by observing the anomalous specific heat. Fig. 6. For this purpose. so that the spontaneous magnetization must be determined by extrapolation from the high-field region.5 and Arrott and Noakes. This relationship between 7 and H is shown graphically in Fig. we obtain the specific heat . 6. Arrott plot. 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. we get the linear relationship shown in Fig. In practice. 6.5.

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

in which two kinds of atoms. as treated in Section 6. Applying this method to a spin system. an antiferromagnetic alignment of 5. and all the spins 5. while if / < 0. The magnitude of / is in the order of 103cm~1 (~103 K).. He suggested that between atoms with spins St and S. which results in ferromagnetism.. Therefore this approximation for treating short-range order is referred to as the Bethe-Peierls method. not just nearest-neighbor pairs. A similar phenomenon appears in a superlattice.17). so that when the temperature is near the Curie point. We will discuss the physical meaning of this interaction in Section 6. Peierls10 treated spin clusters in ferromagnetic theory. can take values only of \ or —\. Let us assume the Ising model11* in which 5 = |. Then the exchange energy associated with the spins 5. In the Weiss theory of ferromagnetism discussed in Section 6. A and B. except that the exchange interaction from the other spins is replaced by the molecular field. which is 103 times larger than the dipole interaction given by (1. If / > 0.1.. This is equivalent to the assumption that the value of / is the same for all spin pairs. This problem was treated by Bragg and Williams.8 using statistical mechanics in a similar way to the Weiss theory. This tendency to align the nearest-neighbor spins parallel (for positive /) causes complete parallel alignment of the entire spin system. and show using the Bethe-Peierls approximation how the spin clusters are created.3. the value of / is largest for nearest-neighbor spins. so that the z-component of 5. thus forming spin clusters. so that a ferromagnetic alignment is stable. there is an interaction with energy where / is the exchange integral. Since the exchange interaction is short-range. 5.1. 6. is called the Heisenberg Model. is given by *The case in which the spins can be oriented in all directions. are arranged in a regular alternating pattern. We assume that a particular spin 5. and S.9). the molecular field is assumed to be proportional to the average magnetization. This model is called Bethe's first approximation. In reality. near-neighbor spins still tend to remain parallel. however. where the parallelism of the spins is considerably disturbed. is stable and antiferromagnetism results. 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. the exchange interaction is short-range. 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.VARIOUS STATISTICAL THEORIES 7 125 The exchange interaction was first proposed by Heisenberg in 1928. . Sz. Bethe9 succeeded in calculating the degree of short-range order. The situation is also the same for S. the energy is lowest when St II S.

.28) and (6. Similarly the average value of S. remains in pi+ and pt_ as shown in (6. Then the probability that S. If p spins of the total of the z values of 5. = -\. has the value — \ is given by Therefore the average value of 5. = \.26) becomes Let us denote U in (6. take the value \.29). and as U~ if 5. then (6. has the value \ is given by and the probability that 5.27) as U+ if 5. is given by where the undetermined parameter.9. 6.126 FERROMAGNETISM Fig. Model for Bethe's first approximation. is given by which also includes the undetermined parameter Hm. Hm. while q spins take the value — |.

Hm becomes small. values of k&f/J are listed for various approximations. the energy per spin for S = \ is calculated as so that using (6.466 2. so that In the case of a body-centered cubic lattice.VARIOUS STATISTICAL THEORIES Since 5.312 1. and we have In the case of a two dimensional lattice. (S. and using (6'.443 1. Bethe's second approximation rigorously takes into consideration the influence of the second-nearest neighbors.36).> = (Sy). z = 6.30). The values of k@f/J for S = \ calculated by various approximations (after Oguchi15). we can calculate the spontaneous magnetization At a temperature near the Curie point. so that MBHm <§: kT.1.35) and (6. and 5. both of which are larger than the values given by (6. Approximations Weiss theory Bethe's 1st Bethe's 2nd Exact solution z =4 2 1.9) and taking Meft = 3MB.135 z =6 3 2. and 3 for z = 6. The exact solution is that given by Onsager12 for a Table 6. we get This gives the values 2 for z = 4. must be equivalent. In Table 6. and finally we get 127 From this relationship we obtain Hm as a function of temperature T.372 . z = 4.1. so that In order to compare this result with the Weiss theory.

21).2 for Fe. These exponents are called the critical indices According to the Weiss approximation.128 FERROMAGNETISM Fig. spontaneous magnetization. The temperature dependences of various physical quantities are altered by the appearance of parallel spin clusters. C. 6. Ni. two-dimensional lattice. Comparison of 7S versus T and \/x versus T curves for the Weiss theory and for Bethe's first approximations. as shown by the dashed curves in Figs 6. The Bethe approximation also explains the influence of cluster formation on the temperature dependence of energy and specific heat. and magnetic susceptibility.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. as shown by (6. This means that the Curie point is reduced for a given /. The extrapolated intersection is called the asymptotic Curie point (symbol 0a) to distinguish it from the real Curie point where the spontaneous magnetization vanishes. and we can clearly see a difference in the Curie points between the two approximations. 6. and also y = . which is clearly due to cluster formation above the Curie point. 7S. Fig. x> near the Curie point are given by and also at the Curie point where the exponents take the values given in Table 6. Experiments also show such a deviation.10 shows the temperature dependence of 7S for Weiss and Bethe's first approximations. For instance. fi=\. Let us assume that the temperature dependence of the specific heat.7 and 6. It can be seen that the value of k@f/J gets smaller as the order of approximation increases. The 1/x versus T curve calculated by the Bethe approximation shows a deviation from the linear Curie-Weiss law. 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.10. and Gd.

125 — a' < 0. This . According to the scaling law.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. but that it does appear in the Ising model or in the presence of a uniaxial anisotropy.EXCHANGE INTERACTION Table 6.17 0.5 a <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: 0.050 — 0. except for the values of the proportionality constant C.13 -0. 6.2.04 — 0.0294 for face-centered cubic lattices.) Weiss theory 0 t (K) 1043.5 y 1.34). Other strict statistical treatments also prove that no ferromagnetism appears in a two-dimensional lattice in the Heisenberg model. more accurate approximations based on the three-dimensional Ising model with S = \ give better values.1 5. This T 3/2 law holds fairly well experimentally. However.1174 for simple cubic.0 ± 0. In other words.14) and (6.2.33 1.51 ± 0.0 629.34 ± 0. in which the spins are connected in a chain.33 1. and 0.2.0587 for body-centered cubic.063 — ft 0.and two-dimensional spin lattices. 3 dimens. in a one-dimensional ferromagnet.02 1.104 ±0. If we assume that z = 2 in (6.2 3 y' = 1 as shown by (6. This law was deduced by Kadanoff et a/.32 ±0. 0. there exist the following relationships between these critical indices: The first two formulas hold well for various approximations.15).25 1 y' — — — 1. Materials Fe Ni Gd Ising model (S = |.6 292.2 ± 0.313 0. both of which tend to develop a parallel alignment of the spin system.060 — 0. These values are not in very good agreement with the experimental results. as verified by the numbers for the Weiss and Ising model given in Table 6.31 1 S 15 129 — 4.1 4. He concluded that no ferromagnetism appears for one. we find that the right-hand side vanishes. as listed also in Table 6.13 by assuming that the magnitude of the unit moment and the effective temperature depend on the size of the cluster. in which he assumed that the reversed spins propagate just like waves.262 ±0. Bloch14 treated the thermal disturbance of the spin arrangement at low temperatures using a spin wave model.02 0. Critical indices (after Oguchi ). no ferromagnetism appears.

respectively.45) is correct. The Pauli exclusion principle was first introduced to explain the multiplicity of atomic spectra.44). In other words. assumed to be 1A. Now let us consider the wave function of an atom with two electrons. the spins of these two electrons are parallel.q2). so that it is rather difficult to explain it in terms of classical physics. z) and a spin variable a ( = ± |). must be invariant for the exchange of the two electrons. the exchange interaction may be understood as follows: Suppose that two atoms with unpaired electrons approach each other. The value estimated from (6. <f/(q1. Therefore if this Coulomb energy is disturbed by the Pauli exclusion principle by a small factor. If the spins of these two electrons are antiparallel to each other. so that they form separate orbits. is the order of 1400 K. but it can be approximated by the product of two wave functions i/^^) of electron 1. 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. this wave function becomes i/f1(g2)'/'i(<7iX which is the same as before.17).By exchange of the two electrons.130 FERROMAGNETISM m interaction is due to a quantum mechanical effect. thus increasing the electrostatic Coulomb energy. t/fj. AJ7e. . thus reducing the Coulomb interaction. the probability of realizing this state. rather than condition (6. both of which can be expressed by a general coordinate q. y. The atomic wave function of an atom with a single electron is a function of a spatial coordinate r(x. which can be written as ^-^q^^^q^). or Since the two electrons are indistinguishable. say 1%. On the other hand. the electrons will share a common orbit. where q1 and q2 are the general coordinates of electrons 1 and 2.42) is 105 times larger that the magnetic dipolar interaction calculated from (1.q2).15 Let us elucidate how this principle is expressed in terms of the atomic wave function. o or The Pauli principle asserts that condition (6. which can explain the magnitude of the molecular field. however. they cannot share a common orbit because of the Pauli exclusion principle. the change in Coulomb energy. The reasoning is as follows: suppose that electrons 1 and 2 occupy the same state. one accepts the Pauli exclusion principle. &2(qi. If. and fy£q^) of electron 2. If. however. It is difficult to express this function exactly.

In order to realize this condition. that is According to (6.45). . (p(rl. Example For example.) and one containing the spin variables. In order to satisfy these conditions. The actual forms of these three terms are given by where Z is the atomic number (Z = 2 for He).q2\ . and the third term concerns the interaction between the two electrons. the second term concerns only electron 2. must be antisymmetric upon the exchange of the two electrons.45).45) asserts that the wave function of the two-electron system. 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.r2). (l/(q^. The wave can function $(qi. let us consider the case in which two electrons occupy the Is state of an He atom. the sign of these wave functions must be different.16 The relationship (6.q2) can b£b expressed as a product of two parts.EXCHANGE INTERACTION 131 according to condition (6. The Hamiltonian in this case is given by where the first term concerns only electron 1. it follows that This is another expression of the Pauli exclusion principle. resulting in a change in electrostatic interaction between the two electrons. Thus the symmetry of the spin variable can affect the symmetry of the part of the wave function containing the spatial coordinates. and r12 is the distance between the two electrons. while the state which is symmetric for the exchange of spin variables is antisymmetric for the exchange of spatial coordinates. ^(o-j. one containing the spatial coordinate. cr2).

54) and (6.55) are calculated as where . The energy of the state can be calculated by Assuming that <p1 and tp2 are normalized and also orthogonal. respectively. respectively.132 FERROMAGNETISM Suppose that the spins of two electrons are antiparallel. On the other hand. 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. the wave function must be symmetric for the exchange of spatial coordinates. the energies of the states given by (6. 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. the spatial wave function must be antisymmetric. if the spins of the two electrons are parallel.

H. 5. W. and J. Doring. Weiss. 18 (1967).. Camb. which was first given by Heisenberg. R. 31 (1925). 145 (1934). S. S. Hecht. 14. Phys. 151 (1935). A. Physik.7 clarified not only the nature of the molecular field in ferromagnetic materials. L. E. Letters.57). Soc. Proc. 2. and is called the exchange integral. R. Rev. 12. 16. J. P. L. V. but also the difference between ortho.. Statistical theory of magnetism (in Japanese) (Syokabo Publishing Co. Rev. This term signifies the energy produced by the exchange of two electrons between two orbits. which correspond to antiparallel and parallel spins. Rev. Letters. Lewis.2 Calculate a magnetization curve at the Curie point.] This treatment. respectively. Z.REFERENCES 133 In equation (6. 15. Kadanoff. Oguchi. the sign is + for the symmetric function (6. D. E. Z. However. 32. Swift. P. p. 540.. 215. Ferromagnetismus (Springer. and showed that Ju < 0. Physik. 8. Kane. Onsager. E.and para-helium. 1394. 65 (1944). Becker and W. Noakes. Proc. S. Z. 39 (1967). W. and K12 is the Coulomb interaction between these two electrons. W. . 253. Rodbell. A. Tokyo. J.55). Phys. calculate the molecular field at OK according to the Weiss theory. 13. Phys. Palciaukas. Would the accuracy of the value of the molecular field be increased or reduced when more exact statistical treatments were applied? 6.3 K. Rev. Gotze.. Pauli. W. D. and saturation moment Ms = 0. A150 (1935). Bloch. J.. E. 477..1 Knowing that nickel has the Curie point ®f = 628. Z. 699. 10. 206. The same situation was expressed in terms of the spins of two electrons. 7. Proc. 1970).57).54) and — for the antisymmetric function (6. Kouvel and M. Fisher. 136 (6A) (1964). 32 (1936). 661. In (6. 765.25). Rev. Use the first and second terms in the power series of the Langevin function with respect to a. 4. H 2 . Physik. Williams. Bethe. 786. 9. Soc. 61 (1630). Moreover. 49 (1928). Phil. 6. Phys. 31 (1925). Rayl. so that an antiparallel spin pair is stable and forms a bonding orbit. REFERENCES 1. 19 (1967). J. Rev. Phys. W. Berlin. 3. Arrott and J. Kouvel and D. Physik. Roy. 395. Ray.58). 108 (1957). Bragg and E.6AfB.. a similar treatment was applied to the hydrogen molecule. Ising. we find that the energies of the parallel and antiparallel spin pairs differ by 2/12.. Hamblen. F. Heisenberg. 117. Soc. A. /! and 72 are the energies of electrons 1 and 2. Peierls. In (6. Arrott. 552. Ju has no corresponding concept in classical physics. L. 1939). Mod. J=\. Phys. Phys. 6 (1907). in (6. A1626. PROBLEMS 6. 619. S1 and S2. respectively. Aspness. according to the Weiss theory. 11. J. R. T.

As expected. . This critical temperature is called the Neelpoint. 7. Figure 7. The spin magnetic moments of the Mn ions are arranged antiferromagnetically. Antiferromagnetic spin ordering was first verified experimentally in MnO by Shull and Smart. and the susceptibility increases. The crystal structure of MnO is such that Mn ions form a face-centered cubic lattice. where the antiferromagnetic structure appears. contrary to the case of the normal paramagnet. 7.3). as shown in Fig.1 using neutron diffraction. extra diffraction lines appear if magnetic ordering is present. as shown in Fig. neighboring spins are aligned antiparallel to one another so that their magnetic moments cancel. a number of extra lines are seen below the Neel point. Therefore the susceptibility in this case is smaller than for a normal paramagnet. and O ions are located between each Mn-Mn pair (Fig. Since the magnetic scattering of a neutron differs for + spins and . above some critical temperature.4 shows the neutron diffraction lines observed for MnO below and above the Neel point. Such extra lines are called superlattice lines. As the temperature increases. 7. Therefore an antiferromagnet produces no spontaneous magnetization and shows only a feeble magnetism. the susceptibility shows a sharp maximum at the critical temperature. The only difference is the presence of an ordered spin structure.1.spins. such spin ordering disappears completely. The relative magnetic susceptibility of antiferromagnetic materials.2. the same as for paramagnets. so that the temperature dependence of the susceptibility becomes similar to that of an ordinary paramagnet. When an external magnetic field is applied parallel to the spin axis. 7. as shown in the figure.1 ANTIFERROMAGNETISM In antiferromagnetism. Therefore. denoted by @ N . the spins which are parallel and antiparallel to the field experience almost no torque and so keep their ordered spin arrangement. ranges from 10 ~ 5 to 10 ~ 2 . Antiferromagnetic spin structure. However.7 ANTIFERROMAGNETISM AND FERRIMAGNETISM 7. the ordered spin structure tends to be destroyed. This is the characteristic feature of an antiferromagnet. x.1. because they reflect the presence of a structure larger than the basic Fig.

crystallographic unit cell. . Fig.3 The essential point of this mechanism is as follows: The O 2 ~ ion has electronic structure expressed by (ls)2(2s)2(2. Temperature dependence of magnetic susceptibility of antiferromagnetic materials. 7.>)6.3 was deduced by analyzing these superlattice lines. a superexchange interaction acts between Mn ions through the O 2 ~ ion. Crystal and magnetic structures of MnO. as shown in Fig. The direct exchange interaction between Mn ions is very weak.3. M1 and M 2 . an idea first introduced by Kramers2 and theoretically interpreted by Anderson. because it is interrupted by the interstitial O 2 ~ ions. The />-orbit stretches towards the neighboring Mn ions. 7. 7. The antiferromagnetic structure as shown in Fig.2.5. However.ANTIFERROMAGNETISM 135 Fig. 7.

One of the p-electrons can transfer to the 3d orbit of one of the Mn ions (say the Mj ion). so that its sense will be antiparallel to the total spin of Mn 2+ . (After Shull and Smart1).5. 120 K. ion through which exchange interaction acts between the spins . Neutron diffraction lines from MnO powder specimen observed below and above its Neel point.136 ANTIFERROMAGNETISM AND FERRIMAGNETISM Fig. 7. In this case the electron must retain its spin. 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. 7.4. The p-oibit of the O2 on magnetic ions Ml and M2.

These interactions can be expressed as molecular fields.1. S 2 ~. On the other hand. so that Therefore. As a result. the sublattice magnetizations of the A. Section 3.ANTIFERROMAGNETISM 137 (Hund's rule. The molecular field acting on the A site spins is given by where the inter-site interaction coefficient. The superexchange interaction acts also through S 2 ~.and B-sublattices are equal in magnitude and opposite in sign. The superexchange interaction is strongest when the angle Mj-O-lV^ is 180°. the remaining electron in the p-orbit must have spin antiparallel to that of the transferred electron because of the Pauli exclusion principle. Such a magnetization is called a sublattice magnetization. as shown in Fig. and as B sites the locations of the — spins. (7. and Se2~.1) and (7. the total spin of M t becomes antiparallel to that of M 2 . and becomes weaker as the angle becomes smaller.2). For more details the reader may refer to the review by Nagamiya et al. must be negative.5 The first theoretical treatment of antiferromagnetism was made by Van Vleck6 with later advances by Neel7 and Anderson. The exchange interaction with the other Mn ion (M 2 ) is therefore negative. and 7A and 7B are the magnetizations due to all the spins on the A sites and B sites. When the angle is 90°. we put Moreover.5) and (7. we can assume that W AA =WBB< and WAB = ^BA. and Br1" ions.1) for ferromagnetism. . 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.F°r simplicity. the interaction tends to become positive. WAB . respectively. 7.6) are of the same form as (6.8 Let us designate as A sites the lattice sites on which + spins are located in a completely ordered arrangement. 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. Se 2 ~. as in the Weiss theory of ferromagnetism.2) can be written as and The formulas (7. Cl1". It is experimentally verified4 that positive superexchange interaction at 90° increases in the order O 2 ~.

4) does not hold. similar to the spontaneous magnetization in ferromagnetism. 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. we have the magnetic susceptibility . 7A and /B are no longer symmetrical. and L(a) is the Langevin function. the sublattice magnetizations are given by Differentiating both sides with respect to H.7) and (7.2). we have Adding the two equations side by side. and vanish at a critical temperature. The Neel point is given by which is similar to equation (6. The sublattice magnetizations given by (7. which is the Neel point. as in (6.3). so that equation (7.138 ANTIFERROMAGNETISM AND FERRIMAGNETISM Therefore. 6. @ N . M is the atomic magnetic moment.8) decrease with increasing temperature (see Fig.8). and solving with respect to (dIA/dH) + (dIE/dH). When an external field is applied parallel to the spin axis.

Temperature dependence of reciprocal magnetic susceptibility for antiferromagnetic materials. The reason is that the intersite interaction coefficient.22) we have Then (7.14) can be expressed in a simple form If the temperature is well above the Neel point. the spin arrangement becomes random.15) gives a negative value provided that the intrasite interaction coefficient.19) gives a straight line which intersects the abscissa at T = 0a (see Fig. If Fig.ANTIFERROMAGNETISM 139 If we put and (7. (7.15). w2. wlt is relatively small. If we plot \/x as a function of T. @ a . so that from (5. 7. so that (7. is always negative. ( x\\ and x± are the magnetic susceptibilities measured by applying magnetic field parallel and perpendicular to the spin axis. the asymptotic Curie point. Unlike the case of ferromagnetism.17) becomes which has the same form as the Curie-Weiss law (6. . 7. is entirely different from the Neel point @ N .6).6. @ N .fpoiy is the susceptibility for polycrystalline material calculated by averaging x\\ and x± •) .

so that the point P in Fig.) Wj = 0. Table 7. 6. Typical antiferromagnetic materials and their Neel and asymptotic Curie points are listed in Table 7.6.19) with T replaced by @ N .2 rises along the curve L(a) and the value of L'(«) decreases from f.22 * Landolt-Bornstein. Temperature dependence of magnetic susceptibility of antiferromagnetic materials.140 ANTIFERROMAGNETISM AND FERRIMAGNETISM Fig.21) as 1/X-T. 3-148.17). 7.1. @a is negative and its magnitude is equal to the Neel point.6 is shown in Fig. 7.86 5. and finally in the limit T -» 0.15). or As the temperature decreases from the Neel point.95* 4. The %-T curve corresponding to Fig. . The susceptibility at the Neel point reaches a maximum. Magnetische Eigenshaften Vol II. as is given by (7. we have This behavior matches well the x~T curve in Fig.7.9) and (7. If we plot equation (7.7. we find that the curve for x\\ diverges as T tends to zero (Fig. Part 9. 7. Various constants for typical antiferromagnetic materials. 7.9 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 5.6). as easily found from (7.7. 7. the sublattice magnetization increases. As deduced from (7. (Symbols are the same as Fig. the susceptibility decreases with decreasing temperature. 7.6 3.1. (1962).

composed of the external field and the molecular field.22) becomes The direction of the sublattice magnetization must coincide with the resultant magnetic field. because the rotation magnetization of the sublattice magnetizations occurs even at 0 K (see Fig. 7.ANTIFERROMAGNETISM 141 Fig.8.8. Therefore Eliminating /A from (7. Rotation of antiferromagnetic spins in a magnetic field perpendicular to the spin axis. Suppose an external magnetic field. The sublattice magnetizations. When a magnetic field is applied perpendicular to the spin axis.25). 7. it follows that Using this relationship. (7.8). Hex. which are originally parallel to the y-axis. we have . Then the x.and B-sublattices are symmetrical. is applied parallel to the *-axis. 7.and y-components of the molecular field acting on the A-sublattice are given by Since the A. will rotate toward the x-axis as shown in Fig. the susceptibility may not vanish even at T = 0.

and B-sites in the ratio A: /A. the sublattice magnetizations are given by so that the spontaneous magnetization is At any temperature above absolute zero.7.9. 7. let us assume that only one kind of magnetic atom.6 and 7.9). of magnetic atoms is distributed on the A. as shown by the curve labelled 'poly' in Figs 7.2 FERRIMAGNETISM In ferrimagnets.and B-sublattices are occupied by different magnetic atoms and sometimes by different numbers of atoms. 2N. the measured susceptibility is the value averaged over the crystallites of all possible orientations. Spin structure of a ferrimagnet. where If all the magnetic moments are completely ordered.6 and 7.7. so that the antiferromagnetc spin arrangement results in an uncompensated spontaneous magnetization (see Fig.20). or Fig. Such magnetism is called ferrimagnetism and was treated by Neel. The total number. 7. . To describe this disordering. the A. the sublattice magnetizations are thermally disturbed. sometimes complete order may not be realized. with magnetic moment M. contributes to ferrimagnetism.142 ANTIFERROMAGNETISM AND FERRIMAGNETISM Therefore the susceptibility in this case is given by which is equal to the maximum susceptibility given by (7. 7.7 For simplicity. we introduce the normalized sublattice magnetizations. Actually the susceptibility in this case remains constant from the Neel point to 0 K as shown in Figs 7. and even at OK. In the case of a polycrystalline material. 7a and 7b.

multiplied by 2N. dl^/dH. and a and /3 are the intra-site coefficients normalized by w. we have Solving (7. 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. the term MH/kT must be added inside the braces { }.34) with respect to dIJdH. where C is given by The equation (7. Under the action of these molecular fields. using the approximation L'(«) = |. At temperatures above the Curie point.and B-sublattices. or where w is the absolute value of the molecular field coefficient between the A.FERRIMAGNETISM 143 The quantities 7a and 7b are interpreted as the average magnetic moment at each sublattice site. the sublattice magnetizations are calculated using common statistical procedures as In the presence of an external magnetic field H.35) can be simplified to where .

The relationship between \/\ and T given in (7. Temperature dependence of reciprocal susceptibility of a ferrimagnet. which has slope 1/C and intersects the ordinate at TL/XO. 0 f . the susceptibility becomes infinite at 0 f . The condition for producing this ferrimagnetism is 0f > 0.37) is graphically shown in Fig. The asymptotic Curie point in this case is given by while at the ferrimagnetic Curie point.33) under the assumption that T < 0 f .37) we have Solving this equation with respect to @ f . the magnitude of the third term in (7.41) therefore . so that the l/x~T curve departs from the asymptotic line and finally drops to zero at the Curie point.When the temperature is lowered from well above the Curie point. and ferrimagnetism appears. we have If 0( < 0.37) increases as the temperature approaches 0. 7. 7. so that from (7.37) becomes negligibly small. At high temperatures. so that the remaining terms are approximated by a straight line. The spontaneous magnetization in this case is given by where 7a and /b can be found by solving (7.10.144 ANTIFERROMAGNETISM AND FERRIMAGNETISM Fig. 1/^ = 0. while if 0f > 0. so that the critical condition 0f = 0 follows from (7. the paramagnetic state persists down to 0 K. the third term on the right-hand side of (7.10.

while for a < 0 and /3 < 0. the internal energy is given by which by using (7. If there is no external field.. In this case. it is evident that ferrimagnetism appears.43). If the absolute values of a and /3 become larger than the values that satisfy (7. so that The internal energy is then given by (III) Saturation in A sites only. The shape of the 7S-T curve depends on the combination of a. In this case we must have e internal energy is obtained by inserting (7.FERRIMAGNETISM 145 For a > 0 and ft > 0. we have The internal energy in this case is given by .46) in (7.43) gives the limiting conditions for realizing ferrimagnetism or paramagnetism: aj8 < 1. or (II) Saturation in both A and B sites. negative intrasite interactions may be suppressed. 7a and 7b take their maximum values.45). )3. (7. let us investigate how the values of 7a and 7b vary with the values of these variables. and p.43).45) with respect to 7a and 7b in the following four cases: (I) Paramagnetism. If the absolute values of a and /3 are smaller than the values that satisfy (7. By putting and minimizing (7.32) is converted to The stable values of 7a and 7b are calculated by minimizing (7.45) with respect to 7b. The most conspicuous macroscopic feature of ferrimagnetism is the appearance of various forms for the curve of the temperature dependence of spontaneous magnetization. the spin arrangement on the A and B sublattices becomes antiferromagnetic or non-magnetic. giving rise to spontaneous magnetization. A. To see how this works.

Case (IV) is realized in the region FCA. and IV in the a-/3 plane (see text). (For case II. III. 7. The paramagnetic case I is realized below the curve ACB.d < 2NM. First we assume that A < /JL. which is negative unless a > -/i/A and /3 > -A//x. because in this case the energies in the cases II. Similarly.49) is equal to {(«A + /LI)A + (/fyi + A)}/j. Case (II) appears in region ECF. and IV all give positive values. III.54) we know that a < -/A/A. or a/3 > 1.) This is consistent with the condition for the appearance of ferrimagnetism as mentioned just below (7. (IV) Saturation in B sites only. 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. and /x. a < 0 and /3 < 0. case (III) is realized in the region ECB. we can determine which case is realized for a given set of the parameters a. A. because I. In order to determine the regions in which the cases (I)-(IV) are realized.. 7. where a > -/A/A and /3 > —A/JA. we draw the line FC for which a = -/x/A. Equilibrium regions for four stable spin configurations I.43). The B site magnetization in this case is fully saturated. Let us discuss the problem on the a-p plane shown in Fig.11.146 ANTIFERROMAGNETISM AND FERRIMAGNETISM Fig. . ft. so that from (7. consider that the expression in parenthesis in (7.11. II. Ferrimagnetism appears in the region above and to the right of curve ACB. and the line EC for which /3 = -A//A.

The possibility of the occurrence of N-type behavior can be examined by investigating the sign of 7A — 7B near the Curie point. @c.22). The R-type appears when the sublattice with the larger moment is thermally disturbed more easily.and N-types in Fig. so that we have where C is given by (7. 7. In case (II). one sublattice is unsaturated and is easily thermally disturbed.12.12. producing various complicated temperature dependences of the spontaneous magnetization shown as R-. The P-type appears when the sublattice with smaller moment is thermally disturbed more easily. this occurs in all of region IV or the area FCA in Fig.36). In cases (III) and (IV).FERRIMAGNETISM 147 Fig. P. resulting in Q-type temperature dependence (see Fig. in which the sign of the spontaneous magnetization reverses at the temperature of the compensation point. 7. This occurs when /3 > — 1 in case (III). 7. both A and B sublattices are saturated. Four types of temperature dependence of spontaneous magnetization in ferrimagnets. The most characteristic temperature dependence is the N-type.11.33) can be approximated by the first term in (5. 7.12). and the spontaneous magnetization decreases as in the case of ferromagnetism. At T = 6f the Langevin function in (7. . At the compensation point.

or a = /3 = — 1. not only in region (III) but also in region (II). N-type temperature dependence results. as shown in Fig.59) gives the line SD which goes through the point S. and heated through the compensation point.148 ANTIFERROMAGNETISM AND FERRIMAGNETISM Fig. In Fig. but the spin direction varies from plane to plane such that the tips of . however.59) is positive.13.3).3 HELIMAGNETISM In a helimagnetic structure. so that using (7.14. as seen from (7.51). 7. In other words. Demonstration showing a reversal of spontaneous magnetization of a ferrimagnet with a change in temperature. 7S < 0 at T = 0. 7. 7. the saturation magnetization is measured in a fairly strong magnetic field. all spins in a layered crystal are aligned parallel within each c-plane. an N-type ferrimagnet is suspended freely by a thin thread in a weak magnetic field.56) we have or If the left side of (7. If. while 7S > 0 near © f . the various forms of Js vs T curves are illustrated by computer simulation10 for Ga-doped Yttrium-Iron-Garnet (YIG) (see Section 9. The magnetization always is aligned parallel to the field. the sample will rotate through 180° as the spontaneous magnetization changes sign. and has tangent A//t. 7. Above the line SH.13. The boundary condition (7.12. In the experimental determination of the temperature dependence. 7. as shown by the solid N-type curve in Fig. 7S > 0. ft > — 1. so that 7S < 0. Therefore in the region between the lines SD and SH. and is therefore always measured as positive.

(c) Y3GaL1Fe39012 (P-type).15).HELIMAGNETISM 149 Fig. Computer simulation of temperature dependence of spontaneous and sublattice magnetizations in Ga-doped YIG: (a) Y3Fe5O12 (R-type). (d) Y3Ga2Fe3O12 (N-type). (b) Y 3 Ga 5 Fe 45 Oi 2 (Q-type). 7BB = 11. 7^ = 8. The resultant . This spin structure is also called a screw structure. 7.36cm-1 were assumed. •^AB = 25.10 the spin vectors of the spins along any line parallel to the c-axis describe a spiral or helix (see Fig.45cm-1.14.86 cm-1. 7.

and Q is a vector parallel to the z-axis with magnitude .11 and in MnAu2 by Villan12 and later by Kaplan. so that there is no spontaneous magnetization. A screw spin structure was first found in MnO by Yoshimori. y.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. is the vector drawn from the origin to a particular spin in the ith x-y plane. Then the x-.13 Let us suppose that all the spins are aligned parallel to one another in an x-y plane. Helimagnetism is found in many magnetic materials. magnetic moment of such a spin structure is zero over a sufficiently large volume of sample. with the x-axis.150 ANTIFERROMAGNETISM AND FERRIMAGNETISM Fig. In this sense. Screw spin structure in helimagnet. 7.15. and that the spins in the ith x-y plane make an angle </>.

66).3). The magnetization curve of this material is composed of a ferromagnetic part. it appears that ferromagnetism is parasitic on antiferromagnetism. . 7. 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.61) is constant for all spins in the same x-y plane. vanishes at the same temperature. @. The pitch of a stable helical spin arrangement is given by minimizing (7. © (see Fig. 7. Note that the second term of (7. which saturates in a sufficiently large field. of the latter part shows a maximum at some temperature. while that between second nearest-neighbor planes is antiferromagnetic. ^.25) to the helimagnetic case.4 PARASITIC FERROMAGNETISM Parasitic ferromagnetism is a term used by Neel14 to describe a weak ferromagnetism associated with antiferromagnetism in a-Fe2O3. so that the angle (f)i is constant with each x-y plane. while if n = 2. which demonstrates that this material is antiferromagnetic. or °°.17). The saturation magnetization. or so that we have Therefore the condition for the existence of a helical spin structure is In other words. 7.16). n (which is not necessarily an integer) expresses the pitch of the screw spin structure.PARASITIC FERROMAGNETISM 151 where n is the number of x-y planes required for the spins to rotate by ITT or 360°.63) with respect to Q. 7S. In the general case. the second nearest-neighbor interaction must be strong enough to satisfy (7. If n = 1. Applying the general expression for exchange interaction given by (6. /s. and a paramagnetic part. xH> which is proportional to the field (see Fig. 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. it is antiferromagnetic. Observing this phenomenon. the exchange interaction energy stored per unit volume is given by where N is the number of magnetic atoms and S is the spin. The helical spin structure appears also in rare earth metals. and C is the separation between neighboring x-y planes. The susceptibility. the spin arrangement is ferromagnetic.

This idea was deduced phenomenologically by Dzyaloshinsky. the antiferromagnetic spin axis rotates from the c-plane to the c-axis and the spontaneous magnetization simultaneously disappears.and inter-atomic l-s interaction between the two spins. 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°. 7.18). the actual reason was found to be the spontaneous canting of + and — antiferromagnetic spins.17. but the spin-canting also produces a small spontaneous magnetization in the c-plane.15 and theoretically by Moriya. where A5 is the tilt component of spin which contributes the parasitic ferromagnetism. It is interesting that the material a-Fe2O3 exhibits a phenomenon which demonstrates this mechanism: on cooling through a temperature of 250 K. Fig. . precipitated along its common crystallographic plane with the antiferromagnetic lattice of a-Fe2O3.16 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. The order of magnitude of Ag/g for 3d ions is 10~2-10~3. Magnetic susceptibility in a parasitic ferromagnet exhibits a maximum at the critical temperature at which saturation magnetization disappears. A non-zero value of D arises from an excited state and its perturbation mixed through the intra. Magnetization curve of a parasitic ferromagnet. the O-vector lies parallel to the c-axis.16. The Z)-vector lies in a direction which is determined by crystal symmetry. because any tilting of spins from the c-axis makes the vector 5j X S2 parallel to the c-plane.152 ANTIFERROMAGNETISM AND FERRIMAGNETISM Fig. and /super is the superexchange interaction between the two spins. which is called the Morin point.17 This proves the validity of the interaction given by (7. This is the origin of parasitic ferromagnetism. The order of magnitude of D is given by where Ag is the deviation of the g-factor from 2. Neel suggested that the ferromagnetism in this material is caused by a small amount of Fe3O4. If D< 0. 7. The agreement between the two quantities proves the validity of this mechanism. Table 7. 7. However.67). so that WD vanishes. For instance. so that the spin-canting occurs in the c-plane. in a-Fe2O3. the angle between S1 and S2 is not 0 or 180° (see Fig. This spin arrangement is almost antiferromagnetic.2 lists several materials which exhibit parasitic ferromagnetism and compares the values of AS/5 and Ag/g.

(After Moriya18) Material a-Fe2O3 MnCo3 CoCO3 CrF3 FeF3 * Livinson.19 AS/5 1.21. Moriya suggested that a strong crystalline field may be responsible for causing the spin canting. 7.MICTOMAGNETISM AND SPIN GLASSES 153 Fig.19 and 7. and spins Sj and S2. AS/S and Ag/g. This phenomenon is interpreted to mean that the ferromagnetic spins are interacting with the antiferromagnetic spins.6 XHT 2 1XHT2 2X1(T 3 * 3 Ag/g ~1X10~3 ~lXl(T3 — -1XHT2 ~1X1(T 3 Parasitic ferromagnetism appears also in NiF2. which are fixed with respect to the lattice. 7.4).2.19 and 7. A better term for parasitic ferromagnetism would be spin-canted magnetism. for which we expect that D = 0 from the crystal symmetry. showing the presence of unidirectional magnetic anisotropy (see Section 13. D.27"29 The reason for this decrease is the reversal of magnetization clusters caused by antiferromagnetic interactions. Typical helimagnetic materials and comparison between tilt of spin. . the spin system is frozen with no ordered structure. 7. Such magnetism is observed in Cu-Mn. Beck and Chakrabarti24) to describe a spin system in which various exchange interactions are mixed. Table 7.20 For further details of this topic. the decrease in magnetization disappears (see Figs 7. Diagram showing the relationship between the coefficient of antisymmetric interaction.20 for Cu-Mn24 and Ni-Mn25'26 alloys. The distinguishing experimental feature of mictomagnetism is that the magnetization drops abruptly when the material is cooled in the absence of magnetic field. The torque curve in this case contains a component with a period of 360°.20). The prefix micto is a Greek prefix signifying 'mixing'. If the material is cooled in a magnetic field. as shown in Figs 7.4 X H T 2-6XKT3 2 . which suggests the mechanism.18. A similar phenomenon was observed for Fe-Al. Fe-Al and Ni-Mn alloys. instead there is a shift of the hysteresis loop along the //-axis30 as shown in Fig. Waber and Beck23.20 Sometimes parasitic ferromagnetism is called weak ferromagnetism. see the review article. When the temperature is lowered. but this invites confusion with the weak ferromagnetism of metals.5 MICTOMAGNETISM AND SPIN GLASSES 'Mictomagnetism' is a term coined by Beck (Beck21'22.

6 at% Mn-Ni alloys in a magnetic field of 0.22. Sc and SD in the A-.and D-sublattices. (triangles) cooled in absence of magnetic field. as shown in Fig.26 . If Fig.154 ANTIFERROMAGNETISM AND FERRIMAGNETISM Fig. 7.19. Temperature dependence of magnetization measured for 24. 7. Temperature dependence of magnetization for 16. C.23'24 It should be remarked here that the antiferromagnetic arrangement is not strongly fixed in a face-centered cubic lattice.20. Suppose a face-centered cubic lattice contains spins SA. 7.7% Mn-Cu alloys: (a) heat-treated at 100°C. B-. SB. (circles) cooled in a magnetic field. curve be: cooled without magnetic field. (q) quenched.64 MA m"1 (8kOe): curve ac: cooled in a magnetic field.

70).4MAm" 1 (5kOe) from 300K to 1.8K.0 c .y A ).MICTOMAGNETISM AND SPIN GLASSES 155 Fig. we have The total exchange energy is then given by . and summing up by considering the relationship a? + fif + y. 5C and SD all have magnitude S. Solid curves: cooled in a magnetic field of 0.69) are reduced to Squaring the left-hand side of each equation in (7. and their direction cosines are given by (a A . Left: measured along the axis parallel to the field during cooling. Let us assume that spins SA. then any spin configuration satisfying keeps the total exchange energy constant./3 B ./3 D .8K.and z-components of (7.y D ).2. 0 A . y. Then the x-. (a c . Broken curves: similarly cooled without magnetic field. Hysteresis loops measured for disordered 26.30 the antiferromagnetic exchange interactions between all neighboring spins are the same in magnitude. 7. as will be shown below.21. Right: measured perpendicular to the field during cooling.5 at% Mn-Ni alloys at 1.y c ) and (a D . yB). SB. (a B .

156 ANTIFERROMAGNETISM AND FERRIMAGNETISM Fig. 7. Illustration of spin vectors in four sublattices in face-centered cubic antiferromagnet. 7. (d) spin axes are parallel to different (111) axes.69) is satisfied. Fig.23. 7. .23: (a) and (b) spin axis is parallel to [001]. the exchange energy remains constant. where N is the number of unit cells in the system. 7. (e) general case.24. The condition (7. (see (7.69) is shown as a vector diagram in Fig.23.69). Thus as long as condition (7.22. The relationship between four sublattice spin-vectors under the condition of equation (7. Figure 7. 7. Fig.24 shows special cases of Fig. Special cases in Fig. (c) spin axes are parallel to different (110} crystal axes.71)).

and D-sites are different chemical species. and the local spin configuration is easily disturbed. Experimentally. C. The difference between a spin glass and mictomagnetism is clarified if the critical temperature. Tc. [These spin configurations were already suggested by Kouvel and Kasper31 for Fe-Mn alloys. while (c) and (d) show all spins parallel to one of the (110) or <111>. 7. Figure 7. the value and sign of the exchange integral Jtj or the dipole interaction ltj (see Section 12. if the magnetic atoms in the A-. Figure 7. A similar phenomenon is also observed in mictomagnetism.26 shows an example for Fe-Au alloys.32 7.24(e) shows the case in which none of the spins are parallel to the principal crystal axes. thus resulting in mictomagnetism.3) depends on the chemical identity of the atomic pairs. the random spin arrangement is considered to be fixed.MICTOMAGNETISM AND SPIN GLASSES 157 Fig.] Figure 7. Solid curves: extrapolated to zero magnetic field. is plotted as a function of the magnetic impurity content. the . 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. Thus the antiferromagnetic spin arrangement in a face-centered cubic crystal has freedom to change its spin orientation without changing the exchange energy. B-.23: (a) and (b) show all spins aligned parallel to the z-axis or [001].32 Below the temperature of this maximum. Therefore.25.25 shows an example observed for dilute Fe-Au alloys. In the spin glass region below 12at% Fe. Tc. Temperature dependence of magnetization measured for 1 and 2 at% Fe-Au alloys in a weak magnetic field.38)). a sharp maximum is observed in the temperature dependence of susceptibility measured in a weak field.

find the nature of the spin arrangement at OK and the ratio of the ferrimagnetic Curie point to the asymptotic Curie point. The reason is that ferromagnetic clusters are coupled antiferromagnetically. in the ratio 3:2.2 Consider a ferrimagnetic material which has the same kind of magnetic ions in A and B sites. 7. where mictomagnetism exists. Assuming that the exchange interactions within the A and B sites are negligibly small compared to the exchange interaction between A and B sites. 7. find the values of the susceptibility which would be measured when a magnetic field is applied perpendicular to the spin axis at T=0. But Tc increases rapidly with Fe content above 12 at%.1 Consider an antiferromagnetic material which has a susceptibility. ^-0. for Fe-Au dilute alloys. and20 N . Compositional dependence of the transition temperature. For more details the reference book33 should be consulted. and the possibility of having a compensation point. . at its Neel point 0N. Tc. so that the interactions are strong. remains low because individual spins are randomly fixed. Tc. @N/2. PROBLEMS 7.32 critical temperature. 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 A and B sites are negligibly small compared to those between A and B sites. However.26.158 ANTIFERROMAGNETISM AND FERRIMAGNETISM Fig.

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

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In this Part. 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. bonding of various compounds and their magnetic behavior in Chapter 10.Part IV MAGNETIC BEHAVIOR AND STRUCTURE OF MATERIALS Since magnetism is closely related to the electronic structure of materials. . the magnetic behavior of metals. oxides and compounds is not the same. and the structure and magnetic behavior of amorphous materials in Chapter 11.

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

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

11) with respect to E. Using nf and referring to (8. 8.10) to be 20 000-50 000 K. however.2): the water level corresponds to the Fermi level. positively charged metallic atoms forming a crystal lattice. the wavelength becomes nearly equal to the lattice constant a. the total number of electrons is given by This relationship holds for any value of E. the Fermi level is given by Using the relationship (8. In order to calculate the total volume of water. 8. The Bragg reflection occurs when .3. we have This relationship g(E) is graphically shown in Fig. Corresponding to this quantity. The situation is analogous to a glass of water (see Fig. we need to know the cross-sectional area of the glass at each level. Consider a one-dimensional crystal lattice with lattice constant a along the %-axis. Slow electrons with long wave length or small k can move without being disturbed by such a crystal lattice.7). Referring to (8. 8.8). the electron wave tends to be reflected in a Bragg reflection. in addition to the free electrons. we define the density of states. and the total volume of water corresponds to the total number of electrons.BAND STRUCTURE OF METALS 165 Fig. If. In real metals we have. Similarity of water in a glass to free electrons in metals. g(E). where nt is the value corresponding to the Fermi level.10). The number of states between energy E and E + dE is given by g(E)dE. Differentiating (8. much larger than the thermal energy kT at room temperature. (8.2.9) becomes The value of E{ is estimated from (8.

is changed from Fig.5). As a result of the appearance of the energy gap.7 illustrates a band structure in which the + spin and — spin bands are shown separately.3 to Fig. . the stationary waves are formed. If a wave e'*x propagates in the +.t-direction. 8. As k approaches TT/CI.4. the first wave has its maximum amplitude between the lattice points. As a result. 8. 8. Since t/f 2 signifies the probability of the existence of electrons. 8. because there is no influence of the Bragg reflection. The modification is negligible for small k. the electron wave resonates with the lattice and the energy E increases discontinuously by A £ (Fig. the former wave has a higher Coulomb energy than the latter. 8. Next we consider how the situation changes when a magnetic field is applied.1. as is usual in resonance phenomena. At k = ir/a.166 MAGNETISM OF METALS AND ALLOYS Fig.6. 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. As shown in Fig. the density of states curve.4). then a wave e~lk* is produced by Bragg reflection. Let this energy difference be AS. g(£). while the second wave has its maximum amplitude at the lattice points. We call such a division into limited energy regions the band structure. Two modes of standing waves of wave functions in a crystal lattice. 8. the effect of the Coulomb interaction with the lattice lowers the energy and so increases the probability of free electrons existing at metal ions.4.14) and Fig. 8. Figure 8.3. the ordinate represents energy. In this case. 8. Density of states curve for free electrons. while the abscissa Fig. Let us consider how such an energy difference modifies the E-k curve in Fig. The reason for this discontinuity is that the reflected wave changes its phase angle by 180°.

represents the density of states of the + spin and — spin bands. 8.7. Mechanism for the appearance of magnetization by hand polarization. When a magnetic field H is applied parallel to the + spin (here we use the word spin for spin magnetic moment). Density of states curve for electrons in a metallic lattice. Fig. The E vs k curve for electrons in a metallic lattice.6.5.BAND STRUCTURE OF METALS 167 Fig. 8. . 8. the + spin band is lowered by an amount Fig.

it produces a special low-temperature heat capacity which is characteristic of metals. which will be transferred is given by the area between the old and new Fermi levels. 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. For instance.168 MAGNETISM OF METALS AND ALLOYS Therefore the electrons at the top of the . Such a modification of the electron distribution will be reflected in various physical properties. When the temperature is increased from 0 K. 8.1 When the temperature is raised from OK. so the thermal excitation caused by a temperature of several hundred K will have a very slight effect on the electron distribution. As mentioned previously.18) is approximately independent of temperature.8. as seen in Fig. so the susceptibility given by (8. the Fermi level corresponds to a temperature of order ten-thousand K.spin band will be transferred to the + spin band by reversing their spins. This is the origin of the Pauli paramagnetism. 8. the electrons in the vicinity of the Fermi level are excited across the Fermi level. so that The resulting increase in magnetization is given by Therefore the susceptibility is given by As will be mentioned later. however. An. 8. Fermi-Dime distribution function. the electrons are excited to levels higher than the Fermi level.8 for T = 0 (solid line) and for T > 0 (broken curve).8. the Fermi level is not strongly temperature-dependent. . so Fig. and is shown graphically Fig. The number of electrons. bringing their Fermi levels to a common value.

and dT/T= -dx/x. so that Putting (E — E{)/kT = x. T)/dTtt in the integrand of (8. we can regard g(E) as constant. Comparison between magnetic susceptibility and the coefficient of low temperature specific heat for Rh-Pd and Pd-Ag alloys. we have Fig.BAND STRUCTURE OF METALS 169 that the electronic heat capacity should be a good measure of the density of states at the Fermi level. from (8.20) with respect to T. 8. Then.21). dE = kTdx.9. we have the relationships E = E{ + kTx.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. so that where x0 = Ef/kT.20) is non-zero only in the vicinity of Ef. Let us next calculate this heat capacity. Since the derived function df(E.

Figure 8.170 MAGNETISM OF METALS AND ALLOYS This heat capacity increases linearly with increasing T. provided the density of states curve.9 shows a comparison between y and x observed for Rh-Pd and Pd-Ag alloys. is a good measure of the density of states at the Fermi level.18) is equally a measure of the density of states at the Fermi level. The proportionality factor j in (8. and is called the electronic heat capacity or the electronic specific heat. g(E). the Fermi level will shift slightly. has non-zero gradient at Et.2 We see a similarity between the two quantities.10). When the density of states is given by g(£).25) from (8. Subtracting (8.22)).27). this condition becomes which is modified by partial integration to (See (8. As a result of modification of the electron distribution near the Fermi level. g(Ef\ The susceptibility X given by (8. we have .23). The Fermi level of completely free electrons at T= 0 is given by (8. 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). the Fermi level Ef at T= 0 is defined by At non-zero temperature.

32) and (8. we must know the functional form of g(E). In the case of ferromagnetic metals. whether or not ferromagnetism appears can be determined only by g(£f). so that the splitting of the bands is much larger than in the case of paramagnetic metals.BAND STRUCTURE OF METALS 171 Since g(E) is almost constant between Ef(0) and E{(T).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. and (8.28) can be approximated as (Ef(T) — £f(0))g(Ef). so that Such a small shift of the Fermi level will cause only a weak temperature dependence of the Pauli paramagnetic susceptibility.31).30). In general. (8. The increase of the band energy by the transfer of An electrons is given by so that. the exchange field Hm is stronger than ordinary external fields by a factor of 102 to 103.32). the energy of the system is expressed by Therefore the criterion for the appearance or non-appearance of ferromagnetism is given by . For this purpose. the first term in (8.33). the number of electrons in the + spin and . However. referring to (8.

3'4 who treated ferromagnetism in metals in this way. by means of the coherent potential approximation. 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. Density of states curves for + and — spins for various Fe-Ni alloys.172 MAGNETISM OF METALS AND ALLOYS Fig.34) is lowered as the magnetization / is increased. This is the criterion for the appearance of ferromagnetism proposed by Stoner. as calculated by the coherent potential approximation. while if the < sign is satisfied.5'6 In this case. 8. According to this calculation. first the electronic structure of A atoms is calculated by .11. the energy (8.8 If the > sign is satisfied. Such a treatment is called the rigid band model. the energy increases as / appears and ferromagnetism is unstable. Density of states curves for Ni (solid curve) and for Fe (broken curves) as calculated for Ni-Fe alloys by the coherent potential approximation.8 Fig.10. On the other hand.7 we can treat the band structure by taking into consideration the electronic states of individual atoms. 8.8'9 In A-B alloys.

6 for Fe. respectively (in addition to the orbital magnetic moment). The three ferromagnetic elements Fe.6 per atom. and 2 Bohr magnetons. This is a famous graph. 8. Figure 8. The experimental points for Ni-Co alloys fall on the straight line connecting the points (27.spin bands. 0. If we assume that the number of 4s electrons is 0. however.10 The non-integral Bohr magneton numbers of 2.7.8 The important feature of this result is that the shapes of the density of states curves are different for + and spins. Actually. known as the SlaterPauling curve. 0. Then the average electronic structure is calculated by taking the weighted average of the A and B atom structures. 27. This method is somewhat similar to the Bethe approximation in the statistical treatment of ferromagnetism (see Chapter 6).11 shows the band structure for Ni and Fe separately.6) and (28. However. Looking at this graph. The situation is well described by plotting the saturation magnetic moment at 0 K as a function of number of electrons per atom. 1. This situation . The electronic structure of B atoms is calculated in the same way. 3. in the case of Ni-Cu alloys. and have respectively 4. Co.12 shows such curves plotted for various 3d transition-metal alloys. 3. respectively. which means that the 3d electron shell is just filled. 0) for Cu.1). then we can subtract 0.MAGNETISM OF 3d TRANSITION METALS AND ALLOYS 173 assuming an average electronic structure in the neighborhood of an A atom. the experimental points lie not on the straight line connecting the points (28. and 2 vacancies in the 3d shell (see Table 3. whereas there are big differences in the . and Ni exhibit ferromagnetism at room temperature. and also for different alloys constituents. and 0. Figure 8.2. but on the straight line connecting (28.6 Bohr magnetons.7MB and Ni atoms with 0. 0. these elements exhibit saturation magnetic moments of only 2.2.6 to obtain 10 electrons. It is possible to interpret this behavior to mean that Co atoms with 1.2 MAGNETISM OF 3d TRANSITION METALS AND ALLOYS Only the three transition elements Fe. and 28. and Ni are smoothly connected by two straight lines. with each atom keeping its individual moment.10 shows the density of states curves calculated by this method for Fe^Ni^ alloys. and 0.7. we have a consistent (coherent) solution. Co. we expect spin magnetic moments of 4. 1. 1. According to Hund's rule. The vertical lines signify the Fermi levels. which form band structures together with the 45 electrons. we see that the + spin bands of Ni and Fe are not very different. Equating this with the structures assumed in the calculation of the electronic structure of the individual atoms.7) for Co and (28.6.6) for Ni.6MB are simply mixed in the alloys. 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. Comparison with experiment will be made in the next section.6 and 18 (corresponding to the electrons in the filled shells of argon) from 28. Co. 0). and Ni are atomic numbers 26.6) for Ni and (29. at OK. Most magnetic alloys made for engineering uses contains one or more of these elements. Figure 8. The carrier of magnetism in this case is the 3d electrons.

Since the density of states at the Fermi level in the + spin band is fairly high.14 shows the density of states curve calculated by Wakoh and Yamashita14 for body-centered cubic iron.13 The shift of the .spin band are both filled.)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. This is actually the case for Co-Ni. 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. 8. electron vacancies appear only in the — spin band. 8.spin band.12.5 must produce vacancies also in the + spin band. The situation can be explained by assuming that the 3d electrons are itinerating in the 3d band which is common to all the atoms. Since. Figure 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. (After Bozorth10.6. Ni-Cu. As the electron number decreases from 28. Therefore the increase in total kinetic energy of the electrons (band energy) is relatively small. 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. where the + spin band and . except for NiCo-V. however. as seen in Fig. Ni-Zn and Ni-rich Fe-Ni alloys. NiCo-Cr11 and Fe-Ni(2). any decrease in the number of electrons above 1.5 electrons per atom. any . which is given by the difference in the number of electrons in the + spin and the — spin band. 8. In this situation. the total space in the peak at the top of 3d band is about 1. because the electron vacancies can be accommodated in a narrow space at the top of the .13. increases with a decreasing number of electrons at a rate of one Bohr magneton per one electron.spin band relative to the + spin band is very small.174 MAGNETISM OF METALS AND ALLOYS Fig. Therefore the magnetic moment in Bohr magnetons. Slater-Pauling curve.12. nature prefers a change to a crystal structure with a different density of states curve to an unnaturally large polarization of bands.

) further decrease in the electron number occurs mainly in the + spin band. This is the reason why the Slater-Pauling curve has a slope of +45° at the point representing Fe. (After Wakoh and Yamashita14. Density of states curve of Fe.MAGNETISM OF 3d TRANSITION METALS AND ALLOYS 175 Fig.) .14. Density of states curve of Ni. 8. (After Connoly13. 8. It is very interesting that the crystal structure changes from face-centered cubic to body-centered cubic at an electron concentration of 26.13. resulting in a decrease in magnetic moment.7. irrespective of the chemical Fig.

16 The solid curves represent the CPA calculation for magnetic moments of Fe and Ni atoms and their average.12 are more recent than those labelled Fe-Ni(l)]. a very low thermal expansion coefficient is measured at room temperature. Composition dependence of magnetic moments localized on Fe and Ni atoms in Ni-Fe alloys. the intensity of neutron small-angle magnetic scattering should be proportional to (5A — 5B)2. and also that these values change gradually with alloy composition. and its unusual thermal behavior is known as the Invar effect. the saturation magnetization should be proportional to CA5A + CBSB. 8. This behavior can be explained neither by a localized electron model nor by a rigid band model. From this information.8MB. 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 problem is further discussed later. 8. Figure 8. we can solve for SA and 5B for each alloy composition.12). This alloy is called Invar. 8.8 .1. If the spins SA and SB associated with A and B atoms are different in magnitude. as a function of composition in Ni-Fe alloys. At the peak of this curve.6MB. while that of Ni is about 0.15 shows the magnetic moments of Fe and Ni atoms determined in this way. the saturation moment drops sharply as the electron concentration is decreased and approaches the phase boundary [the points labelled Fe-Ni(2) in Fig. Experimental points are obtained by means of neutron small-angle scattering. where CA and CB are the concentration of A and B atoms.15 It is found that the magnetic moment of Fe is about 2. In the case of Fe-Ni. The magnetic moments localized on atoms of different chemical species can be determined by means of small-angle scattering of neutrons from disordered alloys.176 MAGNETISM OF METALS AND ALLOYS species in the alloy (see Fig. Fig.15. located at 35 at% Ni in Fe. On the other hand. The thermal expansion of Invar is apparently related to the instability of its ferromagnetism.

Cr. between them. Figure 8. 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.MAGNETISM OF 3d TRANSITION METALS AND ALLOYS 177 The solid curves in Fig. (Note that there is a vacancy accommodating two electron vacancies at the top of the . Fe-Pd. A«.15 represent the CPA calculation for the individual atoms and also the average magnetic moment. Fe-Ni.3). or Ti.19 A similar situation occurs in Ni-base alloys with non-transition elements such as Al. As explained in Section 4. 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 magnetic form factor for the scattering of neutrons depends strongly on the size of the 3d shell (see Figs 4. Actually.12). We see that not only the individual moments but also the behavior of the average magnetic moment are well reproduced by the CPA calculation.21 The reason is . This behavior was first treated theoretically by Friedel. 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. Mn. or Sn.2.8). 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. Each branch describes a sharp decrease in saturation magnetic moment produced by the addition of impurity atoms with fewer positive nuclear charges. i.spin band (broken curve in Fig.12). 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.16 summarizes the difference in the magnetic moment. AM. are all inconsistent with the Slater-Pauling curve. however.11 using a CPA calculation. between impurity and matrix atoms as a function of the difference in electron number.16 and later explained more quantitatively by Akai et al. Ga. which results in a sharp decrease in the average magnetic moment.e. since they sometimes couple ferromagnetically. so that the difference in nuclear charge 2e between Ni and Fe results in a difference in magnetic moment of 2MB. 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. Ge. There are many branches from the right-hand straight line of the Slater-Pauling curve (see Fig. because the addition of these impurities increases the average magnetic moment to some extent. Si.7 and 4. and Fe-Pt (underline means the main alloy constituent). 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. Manganese impurities are an exception. 8.11)). 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. 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. Sb. such as Fe-Co. 8. They showed that the magnetic moments of these impurity atoms are coupled antiferromagnetically with the ferromagnetic matrix moment. The points for Fe-base alloys in the third quadrant. V. 8.

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

**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

8 44.909 0.06 (Fe 2.8 27.5.192 MAGNETISM OF METALS AND ALLOYS Table 8.4 (Mn 3. .41 4.73 (Fe) 1.30) 4.83. Pt 0.6.15 2.37 Sat.5.0.2 0. Pd 0.51) 8.2 23.03) 4. 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) 1.70 (Fe 3.76 (Co) 1.72. so that the magnetocrystalline anisotropy (see Chapter 12) is quite large. Pt 1.04 (Mn 3.4 Ms per formula in MB 0. Ni 0.73.64.01 1.9) 4.42 (Co) 0.8 (Fe 2. Np.98 (Fe 0. Some Laves Table 8. form intermetallic compounds with transition metals.99.5).965 1.1 35.9.47) 4.66 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 .94 (Fe) 1.37 (Fe) 1. Ni 0. and Pu. V 0.93 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 2.52 2. Magnetic properties of RCo5 and similar compounds. Co 1. which require careful handling because of their radioactivity. Pt 0. For this reason some of these compounds show excellent permanent magnet characteristics.2 138 33.06 0.2 105 65.33. The R2Co17-type compounds have even better permanent magnet properties in some ways (see Table 8.77 1. Pd 0. Magnetic and crystal properties of ferromagnetic superlattice alloys. 104 104 104 104 104 104 104 105 105 105 105 105 unquenched.5 19.38 (Fe 2.18 (Cr 2.95 (Fe 3.26) 3.62) 0.2 0.27) 4. moment in MB at OK Ref. The actinide elements U.

8. H. Budworth. Ferromagnetism (Van Nostrand. Finally we will describe the ferromagnetic superlattice alloys containing only transition metals.3 show fairly high Curie points. Co-Cr. 83 Discuss the reason why the magnetic transition points of rare earth metals and alloys are well described in terms of the de Gennes factor. Phys. R..4 Explain why the magnetic moment of light rare earth atoms is parallel to that of transition metal atoms in intermetallic compounds. E. E{. Krumhansel. 1951) p. Phys. E. Kept. New York.. 2. 382.2 Referring to the Slater-Pauling curve in Fig. 8. and J. Kanamori. Soc. Soc.441. Fe3Pt exhibits Invar characteristic when it is atomically disordered. PROBLEMS 8.. J. CoPt makes an excellent (although expensive) machinable permanent magnet. Phys. 7. Hasegawa. Stoner. Elliot. Ni 3 Mn if ferromagnetic when it forms a superlattice. R. 46 (1974). Z. Phys. 31 (1971). Preston. D. The saturation magnetization of ordered FeCo is 4% larger than that of the disordered state. 259. Roy. because the exchange interaction between Ni-Mn pairs is ferromagnetic. Jo. 465. Hoare. Bozorth. 2 (1954). because the Mn-Mn interaction is antiferromagnetic. 33 (1972). The spin ordering is disturbed when the alloy is quenched from high temperature to attain the atomically disordered state. Kanamori. Proc. J. 339. E. E. Progr. Roy. W. As for Ni3Fe. 4. but have a rather small Fe moment. Mod. 9. A154 (1936).REFERENCES 193 compounds listed in Table 8. Japan. 5. 656. as listed in Table 8. as seen in UFe2. whereas that of heavy rare earth atoms is antiparallel. 81. and Fe-Cr alloys whose average saturation moment is equal to 1MB. C. M. Proc. and J.. 1599. . Stoner. Rev.. Acta Metal. 35 (1973).1 Assuming that the density of states of a non-magnetic metal is given by g(E) = g(E[XI + a(E — E{J) near the Fermi level.12. 3. A165 (1938). J. 43. Roy. 372. 1607. 41 (1927). C. 8. Pauli. Many investigations have been made on magnetic superlattice alloys. C. Stoner. Soc. A257 (1960). Japan. The ferromagnetic ThM5. C. find the alloy compositions of Ni-Co.. Physik. 7. E. 8. Leath. A. W. Hasegawa and J. 57. 11 (1948). L. 250. Stoner. P. REFERENCES 1. F. 6. detailed investigations have been made on the induced magnetic anisotropy (see Chapter 13).and Th2M17-type compounds (M = Fe and Co) are also listed in Table 8. Proc. Soc. calculate the temperature dependence of the Pauli-paramagnetic susceptibility of this metal. T. 10. A169 (1939). H.5.6. Soc. because they allow an examination of the relationship between magnetism and atomic pairs.

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1 we note the general features of oxide crystals. In order to construct oxides. molecule. while the radius of an M" + ion may be small as 0. Therefore oxides are expressed by the chemical formula MOX. 9. 9.4. we must insert M" + ions in such a close-packed oxygen lattice. There is more than one kind of interstitial site. * This does not mean that the size of the O atom is much larger than that of M atoms. are chemically combined with divalent oxygen ions O 2 ~. .32A. while the M"+ ion is small because it loses n electrons from the neutral atom. garnet ferrites in Section 9. When the third layer is placed on the second layer.1 CRYSTAL AND MAGNETIC STRUCTURE OF OXIDES When metallic ions with valence +«. where x = n/2. or M" + .6-0. The size of O 2 ~ is large because it has two extra electrons outside the neutral atom. If the atomic position in the third layer is the same as the first layer. 9.* The close-packed structure is illustrated in Fig. thus forming close-packed crystals. where the position of atoms in the third layer is different from that in either the first layer or the second layer. which are arranged in an ionic crystal. while (b) shows a possible placement of the dense packed second layer on the first layer. The radius of O 2 ~ is 1. In oxide crystals. 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. then discuss magnetic and crystalline properties of spinel ferrites in Section 9.2. Such a close-packed structure is face-centered cubic. When the oxides form solids. the unit of structure is not the MO. In Section 9. where (a) shows the twodimensional dense packing of spheres in the first layer.3.1. as shown in Fig. but individual ions M"+ and O 2 ~.8 A.2. Small M"+ ions occupy interstitial sites between them. one possibility is shown in (c). where x = 1-2. hexagonal ferrites in Section 9.5. the structure becomes hexagonal closed packed.9 MAGNETISM OF FERRIMAGNETIC OXIDES Most oxides are electrically insulating. the oxide MOX is produced. and finally other oxides in Section 9. but some oxides contain additional metal ions with n = 4 or 1. In most cases. This characteristic has been very useful in magnetic materials for communication and information devices. Therefore magnetic oxides such as ferrites exhibit very low losses when magnetized in high-frequency fields. large O 2 ~ ions are in contact with each other. The metal and oxygen ions are quite different in size. n = 2 or 3.

as will be discussed later. Table 9. in order of increasing x. but aligned at some arbitrary angle. with their crystal structures and some additional information.2. Site B is surrounded by six oxygen ions and is called the octahedral site. The tetrahedral site A and the octahedral site B in a face-centered cubic lattice. In addition to these two.. When the angle is nearly 90°.1.2. Fig. thus producing a canted magnetic structure (see Section 7. Stacking of atomic layers in close-packed structures. This displacement of oxygen ions is expressed in terms of the «-parameter. As mentioned in Section 7. It should be noted.1.3). because the surrounding four oxygen ions form a tetrahedron. but in all cases the metallic ions occupy one of these interstitial sites. . thus giving a ferrimagnetic structure. oxygen ions are still pushed outward because of their Coulomb repulsion. so that the oxygen ions tend to be pushed outward by the interstitial metal ions. the moments are neither parallel nor antiparallel. however. thus forming a ferromagnetic structure. When the angle M-O-M is nearly 180° the magnetic moments on the metal ions tend to be antiparallel.1 lists many magnetic oxides MO. There are many kinds of oxides. the moments tend to be parallel. because the surrounding six oxygen ions form an octahedron. magnetic moments are aligned by the superexchange interaction through the oxygen ions. 9. 9.. as described in Section 9. that even when the interstitial metal ion is absent. Site A is surrounding by four oxygen ions and is called the tetrahedral site.198 MAGNETISM OF FERRIMAGNETIC OXIDES Fig. there is a dodecahedral site. The size of these interstitial sites is generally fairly small. In some cases.

Yb. Ni.La 7 Sr 3 .Nd. Zn.Mg. Co (FR) M = Mn. garnet ferrites (Section 9.0 MO2 Crystal-type NaCl spinel spinel spinel spinel spinel Name ferrite cobaltite chromite manganite Examples (F: Ferro. Fe.33 MV2O4 1. and 16 metal ions on B-sites.Tm. Co.Fe 5 Zn 5 .Ni (FR) M = Co.33MMn2O4 1.Pb.Sm.Mn 5 Zn 5 (FR) M = Co.Eu.La. Co.Tb. 8 metal ions on A-sites. The unit cell contains 32 O 2 ~ ions. Ni 5 La 5 Ag 5 La 5 (FR) M = Mn. Ni. hexagonal ferrites (Section 9. Er. Fe.La 7 Ba 3 La 6 Pb 4 . for a total of 56 ions. etc.La 7 Cd 3 (F) M 3 = Gd 2 Co. Ni.Cu. However. the occupation of A sites by M 2+ ions and B sites by Fe3+ will give a net electrical charge of zero.50 M 8Ti 8Fe 4O3 1.Zn.Sm. Er. Since the numbers of nearest-neighbor O 2 ~ ions for A and B sites are in the ratio of 2:3. These ferrites are typical spinel-type oxides.Ni(FR) R = Y. Cu.La 7 Ca 3 . Ni (FR) M = Mn. Co (FR) M = Mn. Lu (CA) M = Bi. Crystal and magnetic structure of magnetic oxides MO. with the crystal structure shown in Fig. Fe.3).Lu(FR) R = Y.4). The open circles in the figure represent O 2 ~ ions.Ho.2 MAGNETISM OF SPINEL-TYPE OXIDES Spinel ferrites have the general formula MO-Fe 2 O 3 .33 M2VO4 1.33 MCr2O4 1.Gd.Ca.Ni. Such a configuration is called a normal spinel.. Yb. Ni. Cu.40CaFe4O7 1. 9. which form a face-centered cubic lattice.3. Fe. Co. Mg. 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.Dy. Co (FR) (FR) M = Ba. Fe 25 Zn 75 M = Mn.2). Fe.1. Fe.38 M 2 Ba 2 Fe 12 O 22 1.46 MFe12O19 1. many magnetic ferrites are inverse . Mg. 9. Co. Li 5 Fe 5 (FR) M = Mn. where M represents one or more divalent metal ions such as Mn.42M2BaFe16O27 1.Tb.50R3Fe5OI2 1. Ho. Fe.Gd.50MMnO3 1. Cd (FR) M = Mn.Eu.MAGNETISM OF SPINEL-TYPE OXIDES 199 Table 9.0 MO 1. Fe. Sr. FR: FerriCA: Cant-Magnetism) M = Eu(F) M = Mn. Fe. Co.33 M2TiO4 1. Tm.Ni.33MFe2O4 1. and other oxides (Section 9. x Formula 1.Ba 2 Fe.41 M2Ba3Fe24O41 1. Dy. Co. thus minimizing the electrostatic energy.. Cu (FR) M = Cr.50MMnO3 1. Mn.Mg.50RFeO3 1..33 MCo2 O4 1.Fe.5).Co 75 Fe 25 (FR) M = Mn.Ni.50M3MnO6 2. 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.

spinels. Since R0 = 1.1) can be rewritten as If we assume that u = 0. Spinel lattice.1) gives rA = 0. 9.32A.72 A. this means that 80% of the Mn ions occupy A sites.385.6 to 0.50A in most ferrites. Therefore when a metallic ion occupies an A site.2) gives rA = 0. (9. (9. which are suitable .385. Thus the A sites are much smaller than most metallic ions. (9. and r B = 0. Such a deformation of the lattice is expressed by the u-parameter. while in real ferrites u = 0. while the other 20% occupy B sites. and R0 is the radius of the O2 ions. rB = 0.4. It is interesting to note that ions occupying the A sites mostly have a spherical configuration: the electronic structure of Zn2+ is 3dw. In an undistorted lattice u = f = 0. Using this w-parameter.81 A.67 A.52A.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.380-0.375. with M = Zn. which is defined by the coordinate of the O 2 ~ ion as shown in Fig. is a normal spinel. 9. in which half of the Fe3+ ions occupy the A-sites and the remaining Fe3+ plus the M 2+ ions occupy the B-sites. whose radii range from 0.8 A.200 MAGNETISM OF FERRIMAGNETIC OXIDES Fig. Zinc ferrite. The Mn ferrites are 80% normal. it pushes the surrounding O 2 ~ ions outward. and a = 8.

and AA pairs.1 2.8 Density (gcm~ 3 ) 5.34 — 0.1. 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.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) — 4.3 7S r. Values of u are listed in Table 9.39 — 0.1 3.60 0. Magnetic and physical properties of spinel ferrites MFe2O4. Figure 9.39 8.385 0.6 2.24 5.17 ®f (K) — 300 585 520 585 455 — 440 670 575 w-parameter 0.381 — 0.42 5.52 4. (T) — 0.51 8.3 1. thus resulting in the magnetic arrangement given by Table 9.382 — .44 8. the main negative interaction acts between A and B sites.94 2.15 0. let us consider what kind of superexchange interactions are expected in this crystal structure.38 5.37 c:8. As mentioned in Section 7. BB.35 Lattice const.22 8.38 8.3 2.379 0.53 0.33 8.385 0.t.2.380 — 4. The following explanation was given by Neel2.29 5.381 0. so that we expect the AB pair to have a stronger negative interaction than the AA or BB pairs. let us discuss a possible magnetic structure of the inverse spinel. a (A) 8. 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.70 a: 8. In the inverse spinel ferrite. Before discussing the magnetism of ferrites. sizes to accept metal ions. Based on this idea.50 0.4.5 shows the angle and the distance between ions for AB.34 8. Definition of the w-parameter.33 5.75 — 0. 9.2 for various spinel ferrites.MAGNETISM OF SPINEL-TYPE OXIDES 201 Fig. who first developed the theory of ferrimagnetism.00 5.55 4.3 1.36 8.

Since Mn-ferrite is an 80% normal spinel. Co. This can be explained as follows: since M 2+ and Fe3+ ions are both 3d5 and have 5MB.6. (Modified from Fig. does not result in a change in molar magnetic moment. a partly normal spinel. the number of 3d electrons changes in order from 5 to 10. thus resulting in Mn 3+ and Fe2+. This occurs in the mixed MZn-ferrites: if x moles of Zn-ferrite (a normal spinel) is . If the ionic arrangement is a normal spinel. Cu. or a partial mixture of Mn2+ ions.and B-sites cancel one another. The molar magnetic moment of Mn ferrite is 4. 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. 32. 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. 9. 9. Ni. while if the arrangement is an inverse spinel. The real reason is that one electron is transferred from Mn 2+ to Fe3"1". Fe.1 in Smit and Wijn. An interesting feature of ferrimagnetic oxides is that the addition of a nonmagnetic oxide will sometimes result in an increase in molar magnetic moment. the molar moment should be given by which agrees with experiment.6MB.202 MAGNETISM OF FERRIMAGNETIC OXIDES Fig. both of which have 4MB.5.1) in which Fe3+ is 3d5 with a spin magnetic moment of 5MB and M 2+ has a magnetic moment of nME. Experimental points are very close to this theoretical line. Various paths for superexchange interactions in the spinel lattice. such an electron transfer results in a molar moment of 4 + 5 — 4 = 5MB. and Zn. and the magnetic moment n of the M ion changes from 5 to 0. If the identity of the M ion changes in the order M = Mn. smaller than the theoretical value 5MB. the molar moment is given by 4 + 4 — 5 = 3MB. Then we expect that the molar magnetic moment changes linearly from 5MB to zero as shown by the thick solid line in Fig.

heading toward a value of 10MB at x = 1. M falls below the line (9.1). as in Li-Cr ferrites .7 shows the variation of M with x for various kinds of mixed Zn ferrites. Yafet and Kittel5 explained this deviation in terms of a triangular arrangement of spins. Sometimes the N-type temperature dependence appears. Molar saturation moments of various simple spinel ferrites. 9. 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. however.MAGNETISM OF SPINEL-TYPE OXIDES 203 Fig. Ishikawa6 interpreted this phenomenon in terms of superparamagnetic spin clusters produced by the breaking of exchange paths by non-magnetic Zn ions (see Section 20.6.7). The R-type temperature dependence is commonly observed in spinel-type magnetic oxides.3 (Mark X is from Smit and Wijn. For small x.7). On the other hand. M increases along the line given by (9. Figure 9.1) added to 1 — x moles of M-ferrite (an inverse spinel). For large x.

eCrjeO4. since the Curie point is decreased by the addition of Zn.20). 9. . see Fig. Zn-ferrite is an antiferromagnet with a Neel point near 10 K.7. When cooled from high temperatures.2 summarizes the physical and magnetic properties of various spinel ferrites.4 (for x>l in Li0. the saturation magnetization at room temperature remains almost unchanged. 18. see Fig. it exhibits weak ferrimagnetism. Mn-ferrite has the highest saturation magnetization at 0 K of the simple ferrites.7. as shown in Fig. Fe-ferrite or magnetite (Fe3O4) is the oldest magnetic material known by man. Variation of molar saturation moment of various spinel ferrites with addition of Zn-ferrite. 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. However. 9. Mn-Zn ferrites are used in relatively lowfrequency applications. The Zn is added partly to increase saturation magnetization at 0 K.8). Similar behavior was found in Ni-Al ferrites. Mn-Zn and Ni-Zn mixed ferrites are widely used as soft magnetic materials for high-frequency applications because of their high electrical resistivity. Since the resistivity is relatively low. 9.7 Table 9.204 MAGNETISM OF FERRIMAGNETIC OXIDES Fig. To end this section we discuss features of some particular ferrites.5Fe2]5_.

so that the resistivity is extraordinarily low for an insulating material. . electrons 'hop' between these ions. this electron hopping ceases at 125 K. The temperature coefficient of resistivity even becomes positive (like a metal) at high temperatures. which is much higher than the theoretical value of 3MB. Co-ferrite has a saturation moment of 3. below which the resistivity increases abruptly and the crystal structure transforms to a lower symmetry. This temperature is called the Verwey point. As seen in Table 9. honoring the name of the discoverer of this transition.8. On cooling.94AfB. Temperature dependence of saturation magnetization of various Li-Cr-ferrites.MAGNETISM OF SPINEL-TYPE OXIDES 205 Fig.10 The ionic arrangement and crystal symmetry at low temperatures are not yet certain. This is due to a contribution from the orbital magnetic moment remaining unquenched by the crystalline field. Verwey proposed an ordered arrangement of Fe3+ and Fe2+ ions in the low temperature phase.4 Since Fe3+ and Fe2+ coexist on B-sites. 9.1).2 and Fig. Co-ferrite exhibits an extraordinary large induced anisotropy (see Section 13. Because of this contribution. 9.6.9 but this has been disproved by recent experiments.

The Curie points are low for all the chromites.8 ± 0. Ni.3.51 — .3 -600 -380 135 0 N = 10 0. we expect that the molar saturation moment should be given by Table 9.387 ± 0. where M represents a divalent metal ion such as Mn.0.327 w-parameter 0. For this reason. Li-ferrite is given by the formula Li 05 Fe 25 O 4 and has an inverse spinel lattice.43 1.2 -400 + 30 90 + 5 0. is the most common magnetic recording material.437 8. In most cases.00005 -310 55. The ionic arrangement is given by where V represents a vacancy. but if it is slowly cooled. The frequency limit depends on the Zn content (see Section 20.386 0.15 -570 80 ±10. Ni-Zn ferrites are used as magnetic core materials at high frequencies.3 lists various magnetic and crystal constants for several simple chromites. The Fe3+ ions in ferrites can be replaced by Cr 3+ . so that it exhibits ferrimagnetism. the lattice becomes tetragonal with a 5-6% distortion from cubic.00005 0. in the form of very small elongated particles. 20. in which some Mg2+ ions occupy the A-sites.n y-(gamma)-Fe2O3 is called maghemite and its crystal structure is an inverse spinel containing vacancies. they are normal spinels with Cr3+ ions on the B sites. The ionic distribution and accordingly the saturation magnetization and the Curie point depend on the temperature from which it is quenched. Mg-ferrite is an incomplete inverse spinel. the resulting oxides are called chromltes. Co. aligns antiparallel to that of 2Cr3+ on the B-site.14. nMB.3. Material MnCr2O4 FeCr2O4 CoCr2O4 NiCr2O4 CuCr204 ZnCr2O4 (K) (K) (MB) (A) 8. Fig. Magnetic and crystalline constants of various chromites.377 8. Cu-ferrite has a cubic structure when quenched from high temperatures.332 8.2 -650 100 0.12 Lattice ®a ®f M mol COnSt. Fe. If we assume according to Neel theory that the magnetic moment of the M 2+ ions. as will be discussed in Section 14. whose B-sites are occupied by Li1+ and Fe3+ in the ratio of 1:3.60 0. no electron hopping occurs because Ni exists only in the divalent state.248 ("17788 8. Cu.7. or Zn. the resistivity is therefore very high.3892 ± 0.17). This ferrite. The crystal structures are all cubic spinel. whose formula is given by MO-Cr 2 O 3 or MCr2O4. It is known that two kinds of ions in the B-sites form an ordered arrangement when it is cooled below about 735°C.206 MAGNETISM OF FERRIMAGNETIC OXIDES In Ni-ferrite. Table 9. This is the John-Teller distortion.

9). The trivalent rare earth ions. Ni. 1. or tetrahedral. Cu. Ho. while the molar saturation moments are as low as 0. are in poor agreement with (9. For M = Mn. manganese chromite.3 A.5 4. shows a spiral spin structure with the spontaneous magnetization parallel to (110) from which the Mn moment tilts by 68°.15 3.5. .4. Co.20 1.4.15 1. Lu. 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. Mn. The Fe3+ ions occupy 24d.14-1. or octahedral. Eu. Fe. MnCr2O4. and also 16a.16 Table 9.13-1.14 1. Various magnetic and crystal data are listed in Table 9. and the Cr moments tilt by 94° and 47°.-590 115 . Tb.85 1. the rare earths push the surrounding O 2 ~ ions outward. etc. For instance. probably owing to the formation of canting spin configurations.8 1.06 1. thus distorting the framework of the close-packed oxygen lattice.13 Manganites are spinel oxides containing Mn3+ with the general formula MO • Mn 2 O 3 or MMn2O4. occupy the 24c sites (or dodecahedral sites) which are surrounded by O 2 ~ ions forming a dodecahedron.0.05 1. 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 . or R3Fe5O12. Ni. The reason is that the chromites develop conical spiral spin structures at low temperatures.165 -392 80 -450 =200 <4 -450 -164 1.08 1. not only divalent M 2+ ions but also trivalent ions can be combined to make mixed spinel oxides.1.74 4. sites.0 1. respectively.MAGNETISM OF RARE EARTH IRON GARNETS 207 c/a 1. Zn.16 9. Since o the radius of the rare earth ions is 1. sites. the Curie points are as high as 170. 450 and 350 K.9 The experimental values. Gd.15 In these spinel-type oxides. which is much larger than that of the transition metal ions.35 4.105 -550 .06 . Cobaltites are spinel oxides continuing Co3+ with the general formula MO-Co 2 O 3 or MCo2O4. The molar saturation moment is generally small. Yb. etc.27 4. Magnetic and crystalline constants of various manganites.0 and 1.3 MAGNETISM OF RARE EARTH IRON GARNETS Ferrimagnetic rare earth iron garnets (RIG) are oxides with the formula 3R2O3 -5Fe2O3. Cd. R 3+ .5MB. respectively.0 ~ 1. Mg.14 14 0 N (K) Mmol (MB) Mef£ (MB) 5. where R stands for one or more of the rare earth ions such as Y. where M represents a divalent ion.55 00. however. Sm.1 . Dy. Fe.4 ~ 1. Er. Tm. where M represents a divalent ion such as Cr.

while the second . is given by where 7Fe is the total sublattice magnetization of Fe3+ ions on 24d and 16a sites. resulting in an N-type temperature dependence as shown in Fig. 9.9. As seen in this graph. 9. the magnetic moments of the R 3+ ions are large.19 As explained by Neel. Then the total magnetization is given by The first term on the right-hand side is the saturation magnetization.18 the magnetic structure of rare earth iron garnets consists of strongly coupled Fe3+ on 24d sites and Fe3+ on 16a sites. since only the exchange interaction between Fe3+ survives at high temperatures. Therefore. H. as the temperature increases.9. w is the molecular field coefficient. Generally speaking. the sublattice moment of the R 3+ ions decreases sharply. the R 3+ moments behave paramagnetically under the action of exchange fields produced by the Fe3+ spins. and x ls the paramagnetic susceptibility of rare earth ions. the Curie point is almost the same for all RIGs. Neel explained this situation by the formulation given below: the sublattice magnetization of the rare earth site under the action of the external field. Temperature dependence of molar saturation moment of various rare earth iron garnets. Since the intrasite interaction between R 3+ ions is very weak. so that the resultant saturation magnetization is parallel to the magnetic moment of R 3+ at low temperatures. and loosely coupled R 3+ on 24c sites which point antiparallel to to the ferrimagnetic component of Fe3+.208 MAGNETISM OF FERRIMAGNETIC OXIDES Fig.

2 1.533 6. Looking at the first term.040 0.35 12.7 -7. The garnet-type oxides contain only trivalent ions.29 12. This fact tells us that most of the orbital magnetic moment is quenched in this type of crystal.38 12. or to replace Fe3+ on 24d or I6a sites by A13+ or Ga3+. Dy. transparent.78 16.3 -1. or when Since x is tne paramagnetic susceptibility. 9.859 6.082 7.14 -0.43 2. (A) Density (gem.45 12.21 By such an introduction of non-magnetic ions. the magnetic moment of R 3+ .5. with no divalent ions.170 0.7 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.0 18. ' Mmol (OK.41 12.T) M(R3+ ) (OK.7 -5. we can control the compensation point. therefore.276 6.150 12. Tb. As seen in Table 9.07 R3+ Y Sm Eu Gd Tb Dy Ho Er Tm Yb Lu 7S (300 K. so that the value of w decreases and the condition given by (9.2 16.160 0. Therefore no electron hopping occurs and the resistivity is very high.9 and Table 9. is rather smaller than the value expected from Hund's rule for most rare earths. As seen in Fig. etc. so that — l/w > 0). etc.28 5.9 15. This temperature is the compensation point. This is because the spin S decreases.52 12. saturation magnetization.235 6. g-factor.MAGNETISM OF RARE EARTH IRON GARNETS 209 19 20 Table 9. Magnetic and crystalline properties of rare earth iron garnets.38 12. magnetocrystalline anisotropy. It is also possible to introduce Si 4+ or Ge 4+ ions together with the same number of Ca2+ or Mg 2+ ions.5.110 0.5. giving low magnetic losses even at high frequencies.436 6. so that ferromagnetic domains can be observed by means of the Faraday effect.2 10. This rather sophis- .0 5.0 -7.M B ) 0 0.150 0.653 6. as deduced from the molar saturation moment at 0 K. It is possible to mix several kinds of rare earth ions on 24c sites.005 0.2 0 5. we find that the saturation magnetization vanishes either when which is realized above the Curie point. MB) 5. lattice constant.128 term is the incremental magnetization induced by external fields when the material is nominally saturated. in the order Gd.48 12.13) is satisfied at a lower temperature.3 ) 0.110 0.3 -6.946 7.760 6. Thin garnet crystals are.019 0.1 -1.74 -7.33 12.52 12. it decreases inversely with the absolute temperature and it will satisfy the condition at some temperature (note that w < 0. 0C.169 6.110 0.078 0. the value of ©c decreases monotonically with the increase in the number of 4/ electrons in R.

and B-site ions half and half. Ni. Zn. is a common cubic spinel. Fe. in addition to Fe3+ and divalent metal ions. 9. which contain large 3+ metal ions such as Ba3+ on the substitutional sites in the oxygen layers (Figs. respectively.12 and 9.4 MAGNETISM OF HEXAGONAL MAGNETOPLUMBITE-TYPE OXIDES Magnetoplumbite-type oxides contain 2+ ions such as Ba2+. The 1:1 mixture of Fe2O3 and MO. Mg.210 MAGNETISM OF FERRIMAGNETIC OXIDES ticated materials technology has been utilized in developing bubble domain devices (see Section 17. 9. Sr 2+ or Pb 2+ . Sr 2+ and Pb 2+ are 1. The result is a hexagonal lattice for the layered structure. 9. Co. It is seen that an inter-oxygen layer contains either B-site ions exclusively or A.11 is simply a rotation of Fig. The ionic radii of Ba2+. and are therefore comparable to the radius of O 2 ~ (1. BaO and MO. Yand Z-types.32 A).32A.3 with the vertical axis perpendicular to (111) or an oxygen layer. Fig. Figure 9. The hexagonal oxides are composed of spinel layers (S-type) and hexagonal Rand/or T-type layers. M 2 + . W-. denoted by S. The hexagonal oxides thus produced are classified as M-.13). Ternary phase diagram of hexagonal ferrites. 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. Cu. etc. 1. where M represents Mn. 9. The crystal structure of S shown in Fig. these large metal ions occupy substitutional sites rather than the usual interstitial sites of the close-packed oxygen lattice. 9. according to the structures and concentrations of the layers containing the large metal ions.22 .27 and 1.3).10 shows a ternary phase diagram of these hexagonal oxides as a function of composition expressed as a combination of Fe2O3. Accordingly.10.43.

containing only Fe3+ metal ions. The layers denoted S* and R* have the atomic arrangement obtained by rotating the layers S and R by 180° about the c-axis. 9.10. 9. Crystal structure of cubic spinel drawn taking [111] as the c-axis.11.12. and R blocks containing Ba2+ and Fe3+. Atomic arrangement of R-type layers. 9.HEXAGONAL MAGNETOPLUMBITE-TYPE OXIDES 211 Fig.13. which is indicated as M on the left-hand edge of the phase diagram in Fig. 9. The M-type oxide has the formula BaFe12O19 or BaO-6Fe 2 O 3 . Fig. The small circles with arrows indicate magnetic ions and the directions of . The crystal structure of the M-type oxide is shown in Fig.14 as alternate layers of spinel blocks S. Fig. This oxide is a simple mixture of BaO and Fe2O3 and contains no MO. 9. Atomic arrangement of T-type layers.

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

2 Al compounds Elemental aluminum is purely metallic.1MB.3d TRANSITION VERSUS Illb GROUP MAGNETIC COMPOUNDS 225 B in Fe2B has the large value of 2. The saturation moment per Mn atom is about 1.24 MAm' 1 (28.1. and the saturation moment per Mn atom is 3.. and is ferromagnetic below its Curie point of 750 K.5MB. while Fell. has a moment of 1. has 2. but its chemical properties are sometimes electropositive and sometimes electronegative. It was observed that Fe-Al alloys with compositions between the two superlattices have an antiferromagnetic exchange interaction. MnAl is a metastable compound and is ferromagnetic below its Curie point of 650 K. 10.5 This was interpreted6 to mean that the outer electrons of B are polarized through covalent bonds by the magnetized Fe atoms. which is surrounded by four Fe and four Al nearest neighbors.2). The superlattice Fe3Al has the unit cell shown in Fig. On the other hand. the magnetic moment is concentrated on the Mn atoms. Ni.13 The /c-phase alloys with the general formula M 0 8 Mn 1 2 Al 2 (M = Cu.Fe) are also ferromagnetic14 with Curie points 300-400 K. Atomic arrangement of the superlattice Fe3Al and the Heusler alloy Cu2MnAl.3. while NiAl and also CoAl are paramagnetic.14MB. Co. and the localized moment at a Cu atom is no more than 0. FeAl. Iron-aluminum alloys exhibit ferromagnetism in the Fe-rich composition range.3. This material is used as a permanent magnet material (see Section 22. as shown in Fig. while the M atoms are nonmagnetic in all cases.31MB per Mn atom. The Curie point of this alloy is 610 K. is paramagnetic.20MB at room temperature. 10. 10.2kOe).15 Fig. According to neutron diffraction measurements. it is notable because it contains no ferromagnetic elements but nevertheless exhibits ferromagnetism12 in the ordered state. Neutron diffraction shows that Pel. .11 with an effective moment of 2. 10. so that it forms various compounds. which is surrounded by eight Fe nearest neighbors.7 Another superlattice. The alloy of composition Cu2MnAl is known as the Heusler alloy.46MB.3.8"10 The superlattice Ni3Al is ferromagnetic below its Curie point of 75 K.

1 Magnetic carbides All of these carbides are mechanically brittle.5 at% Mn.23 the C atoms tend to go into small octahedral sites rather than large tetrahedral sites in the body-centered cubic iron. fairly different from their asymptotic Curie points. This corresponds to a change in saturation moment of Mn from 1. This fact indicates that their spin arrangement is ferrimagnetic. The excess Mn atoms align their magnetic moments antiparallel to those of the other Mn atoms.1MB.2.5-70 at% Mn.1. The saturation magnetic moment extrapolated to 0 K is 0. and have metallic luster. 0a.0-68. some of them have ferromagnetic Curie points.5 emug' 1 ) and the Curie point decreases from 640 to 605 K as the excess Mn content decreases.0MB and Meff = 2. Therefore the saturation magnetization increases from 7.48 X 10"5 \Vbmkg~ 1 (56. and high melting points. but the absolute value of the moment was estimated to be 1. It is ferromagnetic below its Curie point of 210 K and has the moments Ms = 1. thus exhibiting ferrimagnetism.or ferrimagnetic phases have been found in the Mn-Ga series.226 MAGNETISM OF COMPOUNDS 10.5MB to account for its ferrimagnetic arrangement.0 at% Mn. It is ferrimagnetic below its Curie point of 690K.78MB per Mn. The ordered hexagonal s-phase exists at high temperature in the composition range 72. is a typical ferromagnetic carbide.1.. which are listed in Table 10. Cementite.05MB. There are many other ferromagnetic carbides.04 to 7. 10.3 Ga compounds Many ferro. while the effective moment is calculated from the linear part of the l/x~T curve is 3.58 to 1. As seen from this table.4 In compounds The compound Mn 3 In has the /3-brass type crystal structure. It was found that the internal field of the Fe atoms that are nearest neighbors of the octahedral C atoms is reduced from . Fe3C.20 There are Heusler-type ferromagnetic compounds Cu 2 MnIn 21 (@f = 500K) and Ni 2 MnIn 22 (@f = 323K).3 together with their magnetic properties.17 The f-phase has a -y-brass type cubic lattice at the composition 62 at% Mn.0 to 59. According to a Mossbauer experiment by Moriya et a/. It is weakly ferrimagnetic below its Curie point at 583 K. 9 f . This suggests that the binding force is partly metallic and partly covalent.16 There is also an e' -phase having the CuAu-type face-centered tetragonal lattice at low temperature in the composition range 72.76MB.02MB per Mn. It is ferromagnetic below its Curie point of 470 K. good electrical conductivity. so that it is rather ferrimagnetic.19 10. The l/x~T curve deviates downward from a linear relationship as the temperature is lowered from high temperatures to the Curie point.2 3J-IVb GROUP MAGNETIC COMPOUNDS 10.18 The face-centered tetragonal rj-phase with the CuAu-type ordered structure exists in the composition range 60-54. The saturation moment extrapolated to OK is 0.

Moreover.40. monoc. to a weak helimagnetism. Co. 353 K perov. 10.3. Crystal structures and magnetic properties of 3d-C compounds. the value in pure iron. For further details. Materials Fe3C Fe2C Fe2C Mn.0 4. This result agrees with the prediction by Bernas et a/.55 (ferr°~«r^ \ trans.3d-lVb G R O U P MAGNETIC COMPOUNDS 227 4 Table 10. a recent review25 (mainly on NMR investigations) should be consulted. and finally to semimetallic.75(Co). and that the amount of reduction is proportional to the number of nearest-neighbor C atoms. and finally to diamagnetism.0. Mn.4. Crystal structure and magnetic properties of ferromagnetic 3 J-Si compounds.55 0.4 Crystal structure Mn3Si Mn5Si3 (hex. Table 10.4 1.2 Magnetic silicides As mentioned in Section 8. In these compounds. to a weak ferromagnetism. or Ni.4 Materials Fe3Si Fe5Si3 Co2MnSi .89 5.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 1.1. beyond which it forms a number of silicides.20 1. At the same time. 3. the electrical properties change from metallic to semiconducting.2.54). and even when these metallic elements are mixed as solid solutions.72 1. fperov.70 3.) Cu2MnAl (Heusler) Curie point (K) 823 373 985 Magnetic moments per magnetic atom Ms (MB) Meff (AfB) 2. to a peculiar Pauli paramagnetism.0. The ferromagnetic silicides are listed in Table 10.1. As the electron concentration of M increases from Cr to Ni.24 for the compounds Fe 3 C 1 _ x B x (0 <x < 0.4. magnetic atoms occupy crystallographically different lattice sites and their magnetic moments are different from each other. this reduction rate is almost the same for all compounds in the Fe-C system.05.57(Mn) — 2. Crystal structure DOn hex.75 1.78 1. The MSi-type compounds retain the same cubic crystal structure (B 20 type) when M is Cr.2. Fe. the Fe-Si system forms a solid solution in the Si-poor composition range. the magnetic properties change from a special diamagnetism.

Most of the nitrides listed in Table 10.81MB. Thus the hexagonal compounds near Fe3Sn are ferromagnetic below the Curie point of 743 K. 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. with a Curie point as high at 761 K. NiCoSn is ferromagnetic below a Curie point higher than 830 K.1 Magnetic nitrides Ferromagnetic nitrides are listed in Table 10. For example. Cu2MnSn has a Curie point higher than 500K and Ms = 4. Materials containing even fairly large amounts of nitrogen retain a metallic luster and have magnetic properties qualitatively the same as the nitrogen-free material. Its Curie point and the saturation moment are reported by different authors to be 553 or 583 K and 2.31 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 creating electron vacancies in the Fe band.11MB per Mn atom.4. composed of low-spin-state iron atoms.10 or 1.2. The compounds FeNiGe.5 with their magnetic properties. 770K. fee iron is antiferromagnetic. the s^ phase (cubic) has a Curie point of about 760 K. The nitrogen atom is small. as shown in Fig. and Mn 34 Ge are ferromagnetic below their Curie points.2MB per Fe atom. and have magnetic moments Ms = 1.228 MAGNETISM OF COMPOUNDS 10. We see that one N atom occupies the body-centered site in face-centered cubic iron. Ni2MnSn has a Curie point of 342 K and Ms = 3. Co2MnSn has a Curie point of 811K and Ms = 4.69MB per Mn. both of which are ferromagnetic. so that it tends to go into the interstitial sites. Pd2MnSn has a Curie point of 189K and MS = 4.27MB per Fe atom. 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. we have ferromagnetic Heusler-like alloys.3 3d-Vb GROUP MAGNETIC COMPOUNDS 10. MnNiGe. respectively.26"29 10. similar to the Ge compounds.2.30 10.3 Ge magnetic compounds In the Fe-Ge system. thus . Fe167Sn is hexagonal (B 82 type) and ferromagnetic. A possible interpretation is that the N atom acts as an acceptor of electrons from Fe. As is well-known. In the vicinity of Fe2Ge. 10.28 By replacing Al by Sn in the Heusler alloy Cu2MnAl (see Section 10. and 870K. It is interesting to note that the introduction of only one N atom in a unit cell changes the weak antiferromagnetism to ferromagnetism.5 have the face-centered cubic structure of the Fe 4 N type. but the saturation moment decreases abruptly with increasing Ge content.23MB per Mn. Fe3Sn2 is a monoclinic compound.3.4 Sn magnetic compounds Sn forms a number of compounds with 3d transition elements. respectively. there are the /3 phase (hexagonal) and the rj phase.1). which is ferromagnetic below its Curie point of 612K. 360K.90MB and Meff = 2.79MB per Mn atom.

but still there is a possibility that this effect is caused by a lattice distortion or expansion. They ascribed this result to the appearance of the compound Fe8N.14 (mol) 3. M 2 P and M3P.90 2. In fact.5.15 1.3. which exhibit low-spin antiferromagnetism.0MB per formula unit.7 (OK) 9.-0.6 A. 10.02 (mol) 2.2 Magnetic phosphides There are three types of phosphides: MP.15 7. 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. FeMnP is ferrimagnetic below @f = 320 K. Many M 3 P Fig.98 0.6-2.t Fe3NiN Fe3PtN Fe2N78 Magnetism ferri ferro ferro ferri ferri ferro ferro ferro ferro 1. 3. For more details on magnetic nitrides a number of reviews31"34 may be consulted. while that of Fe4N is much larger. Crystal structure of Fe4N-type compounds.5.4.88 (mol) 3.tC. the lattice constants of fee Fe-Ni-Cr.3d-Vb GROUP MAGNETIC COMPOUNDS Table 10. Thus Fcj 2 Co 08 P has the Curie point 0f = 450 K and saturation moment MS = 2. Crystal and magnetic properties of magnetic 3d nitrides.8 0. CoMnP has @f = 583K and Ms = 3.31 Lattice type fee fee bet fee fee fee fee fee hep Curie point (K) 738 761 ca.2 MB for pure iron.201 (300 K) 2.-0.98.6-2.52.35 Some of the M 2 P type solid solutions containing different metals are ferromagnetic above room temperature. are about 3.479 7. 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. 10. MnP has a screw spin structure below 50 K which has been the subject of many investigations.8MB as compared to 2. .8 A. Fe-Mn-C and Fe-Mn alloys. Fe 18 Ni 02 P has ©f = 376K.0MB per formula.5 (Fe) suppressing antiferromagnetic interaction.

2) and also to the amorphous alloys containing B and P (see Chapter 11).35 .3. 10.84 — — — type compounds are ferromagnetic. Magnetic properties of M3P-type compounds. it Fig. MnAs exhibits an interesting magnetic behavior: on cooling. but slightly shifted to the left. as listed in Table 10. This curve is quite similar to the Slater-Pauling curve for 3J alloys (see Fig.12). 10. 10. This situation is similar to the case of borides (see Fig.3 Magnetic arsenides There are many magnetic compounds which have the NiAs-type crystal structure shown in Fig. the reviews by Watanabe and Shinohara34 and Hirahara35 should be consulted.5 as a function of the number of electrons in the M atom.35 Curie point 0.6. The saturation moment of M in M 3 P is plotted in Fig. 8. (K) 680 716 525 320 670 a (emug" 1 ) x47rX 1(T7 \Vbmkg~ 1 34 155. For further details on magnetic phosphides. and comparison with the Slater-Pauling curve.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) — 1.6.5.230 MAGNETISM OF COMPOUNDS Table 10.6. Saturation moment of M in M 3 P as a function of the number of electrons in the metal atom M. 10. This may be due to a transfer of some electrons from the P atoms to the matrix. 10.

7.6 3. In Cr-rich MnSb-CrSb solid solutions. with saturation magnetization 1.37'8 10.3.3d-Vb GROUP MAGNETIC COMPOUNDS 231 Fig. 10. This phenomenon was explained in terms of the exchange inversion.76 X 10~4 Wbmkg" 1 (= 140 emu g"1) at OK.3.6.7.5 2. which is caused by a combination of a distance-dependent exchange interaction and a spontaneous lattice deformation.0 4.23 2.5 Magnetic bismuthides MnBi has the NiAs-type crystal structure. which is stable below 633 K and exhibits Table 10. ferrimagnetism is realized at low temperatures and antiferromagnetism appears at high temperatures (Fig.4 Magnetic antimonides Magnetic antimonides are summarized in Table 10. Crystal structure of NiAs-type compounds (unit cell indicated by heavy lines).38'41 Crystal type NiAs NiAs CaF2 CaF2 CaF2 CaF2 Cu2MnAl Ni.In Curie point 0f (K) 586 313 490 750 500 470 410 830 Magnetic moments (MB) MsatOK Afeff 3.6 1. 10.9 1. 10.7).2 0.0 1.9 1. Crystal and magnetic properties of magnetic antimonides. undergoes a first-order magnetic transition at 313 K from paramagnetism to ferromagnetism.0/formula Compound MnSb MnAs05Sb05 CoMnSb NiMnSb PdMnSb Ni 16 MnSb Ni 20 MnSb NiCoSb .

28MB. The compound with x = 0.4 3d-Vlb GROUP MAGNETIC COMPOUNDS 10. However. has a Curie point @{ = 578K.6) and its stoichiometric compound has antiferromagnetic spin ordering. The Curie point determined by extrapolation is 750 K. 10.44 10.0.46 A detailed description is given in the review.7. Magnetic transition points as a function of composition x in (MnStOj.^CrSb)^42 ferromagnetism with a saturation moment of 3. but its saturation magnetization disappears once again on cooling to 483 K.95MB per Mn atom at 0 K. an effective moment Meff = 5. Similar magnetic behavior is observed also for the magnetic sulfides Cr^^S.93MB.232 MAGNETISM OF COMPOUNDS Fig.2) with the vacancies located in alternate c-planes.47 . or Fe7S8.125. For further information on this topic the review article45 should be consulted.8 shows the temperature dependence of saturation magnetization for CrS117. from which we see that the saturation magnetization disappears abruptly on cooling to 150 K. which is a natural mineral. and an average saturation moment per Fe atom of 0. has the composition Fe^S (x = 0-0.1 is also ferrimagnetic. thus producing a ferrimagnetic spin arrangement.4. 10. pyrrhotite.43 Magnetic writing of patterns was first achieved on evaporated thin films of MnBi. The compound with x .1 Magnetic sulfides The iron sulfide FeS has the NiAs-type crystal structure (see Fig. Figure 10.

9. the electrical properties change: FeS2 is metallic but the resistivity is fairly high. Similar to O. and their magnetic properties have been extensively investigated. The crystal structure of this compound is shown in Fig. which is used for heating elements. Some of the sulfide spinels are ferrimagnetic above room Fig. As M changes from Fe to Co. The MS2 compounds are known as pyrites. 10. 10. The magnetic properties also change: FeS2 is paramagnetic but its solid solution with CoS2 becomes ferromagnetic.8. together with the compounds with Se or Te which will be treated later. Several reviews48'51 are available on this topic.9.48 . NiS2 is semiconducting and highly resistive. and CuS2 is again metallic. S forms the spinel-type compounds A 2+ B 2 + S 4 . The solid solution with NiS2 exhibits antiferromagnetism. These compounds belong to the chalcogenide spinels.3d-Vlb GROUP MAGNETIC COMPOUNDS 233 Fig. Temperature dependence of magnetization of CrSj 17. Ni and Cu in increasing order of electron number. 10. CoS2 is more metallic and its resistivity is as low as that of Nichrome. This situation tells us that spin correlations in these compounds affect the electronic structure pronouncedly. Crystal structure of pyrite-type compounds MX2.

a number of reviews60'62 should be consulted. provided no evidence for such localized magnetic moments. In contrast to Fe3O4. Neutron diffraction.4. Fe3Se4 is ferrimagnetic below 314K. CuCr2Se4 (@f = 460 K).5 K) and HgCr2Se4 (@( = 120K) are chalcogenide spinels. and its saturation magnetization is 2. which corresponds to magnetite Fe3O4. with Mef{ = 5. They have a fairly large magnetoresistance effect (see Section 21. CrBr3. which may be explained as a difference between the moment of 2Cr3+ or 3MB X 2 = 6MB.74A. and Cr2Te3 are all ferromagnetic. however. CdCr2Se4 (0f = 129.2 Magnetic selenides There are many magnetic selenides. Fe3S4 remains cubic down to low temperatures without any phase transition. There are ferromagnetic halides such as RbNiF3. 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. They are representative magnetic semiconductors and their resistivity changes several orders of magnitude at their Curie points.2MB per mol formula unit. so that most of the chalcogenide spinels are semiconducting. so that they have saturation moment 6MB per mol. The tellurides Cr7Teg.59 The bonding in chalcogenide spinels has more covalent nature than in oxide spinels.234 MAGNETISM OF COMPOUNDS temperature.375. which is significantly larger than that of O 2 ". For more details. 1. 9. In fact.60"62 10.54'55 The saturation moment per formula unit is 5MB.32MB. The latter two are ferromagnets with parallel alignment of Cr3+ spins (3MB).32 A. the w-parameter of Fe3S4 is 0.1. Therefore the interstitial sites are large enough to accept metallic ions without any distortion of the lattice.5). its magnetic properties may be interpreted on the basis of band magnetism.43 Magnetic tellurides CrTe is ferromagnetic below the Curie point 333 K. Cr3Te4. Cr5Te6. 10.5 3d-VIIb (HALOGEN) GROUP MAGNETIC COMPOUNDS Most of the halides with 3d transition elements are antiferromagnetic.58 This material is also piezoelectric. The reason for this behavior has not yet been clarified.57 Greigite is ferrimagnetic below the Curie point @f = 606 K. so that it retains metallic conductivity at all temperatures. This parallel alignment is caused by a positive exchange interaction through the path Cr-Se-Cr. respectively. K2CuF4. which is the ideal value.56 One of the reasons is that the ionic radius of S 2 ~ is 1. The chalcogenide spinels TiCr2Te4 and CuCr2Te4 are both ferromagnetic below their Curie points of 214K and 365K. 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. Since this material has a high electrical conductivity. CrI2 and TiNiF3. and that of Cu2+ or 1MB.58MB. but their . making an angle of 90° (see Fig.60'62 10. The mineral Fe3S4 is called greigite. as explained in Section 7.2).

in which part of the Cu2+ is changed to Cu1+. many ferromagnetic rare earth compounds have Curie points below room temperature. Therefore they have no engineering applications.6 RARE EARTH COMPOUNDS All Laves compounds RA12 (R: rare earths) are ferromagnetic. Se) can be replaced by a halogen Y. resistivity increases abruptly. which have Curie points of 340 K and 260K. 10. Exceptional cases are the Th3P-type compounds Gd 4 Bi 3 and Gd4Sb3. The maximum Curie point 175 K is realized at R = Gd.69 . Yb. The resultant CuCr 2 X 4 _. The saturation moments are slightly smaller than Hund's values. t Y c is called a chalcogenide halide spinel. many magnetic halides exhibit one.10. In the limit of x -> 1. and at the same time the Curie point decreases abruptly.RARE EARTH COMPOUNDS 235 Curie points are all below room temperature. thus reducing vacancies in the conduction band and also decreasing resistivity.66 Fig. which contribute to conductivity.61 10. Crystal structure of R2Fe14B-type compounds6' and magnetic moments of individual atoms as determined by neutron diffraction. which has attracted much academic interest. However. Concerning this topic. except for those containing only nonmagnetic R = La. contribute also to the exchange interaction. and Lu.or two-dimensional spin ordering. respectively.65 Generally speaking. A part of the chalcogen X in a chalcogenide spinel CuCr 2 X 4 (X: S. Hirakawa63 and Urya and Hirakawa64 should be consulted. This fact indicates that vacancies in the 3d band.

463.3 32.73 7.04 Density (gem.3 ) 7.93 8. . //a (see Section 12. 25 (1968). 255 (1962). 10.0 18.86 0. Cadeville and A.8. 3391.3 Ha (MAirr1) 3. There are cr-phase-like Fe groups composed of distorted hexagons. REFERENCES 1. N. Figure 10. J. 3. C.82 8.47 7. Myers.2.24 8. The compound with R = Nd is the main constituent of the Nd-Fe-B permanent magnet (see Section 22.00 11. and these Fe groups are separated by B-Nd layers. 10. are also extremely large. 2.77 8.8 17.13 6. Some of the anisotropy fields.7 12.68 Lattice constant a c Compound Ce2Fe14B Pr2Fe14B Nd2Fe14B Sm2Fe14B Gd2Fe14B Tb2Fe14B Dy2Fe14B Ho2Fe14B Er2Fe14B Tm2Fe14B Y2Fe14B 8.09 12. Rend. Soc.85 7.33 0. P.7 29.2). Myers.64 0.1 21.95 12.7 10 12 basal 6. The crystal and magnetic properties of R2Fe14B-type compounds are listed in Table 10.10.93 1.57 1. Phys.2 Describe the relationship between the period number and the crystal and magnetic structures of magnetic compounds.2).7 17.74 8. The atomic arrangement in this lattice is also very interesting.11 12.1 @f (K) 424 564 585 612 661 639 602 576 554 541 565 Other exceptional cases are the R2Fe14B-type compounds.3 12.8. all of which are aligned ferromagnetically. Ark.77 (A) 12.1 28 25 20 basal basal 3.69 We see that not only Fe atoms but also Nd atoms have fairly large saturation magnetic moments.86 0.75 8. Lundqvist and A. 20 (1961).82 8.02 8.28 Ms (MB mol) 22.6 25.80 8.79 8. 82.75 8.68 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. Mori and T.74 8.68 PROBLEMS 10. Japan.24 12.99 11.10 shows also the saturation moments of individual atoms determined by neutron diffraction.05 8. Fys.96 11.43 1.55 7.81 7. The Curie point of this compound was raised by introducing such B atoms.236 MAGNETISM OF COMPOUNDS Table 10.65 0.25 12.98 /8 (T) 1.1 Describe the relationship between the electronegativity of electronegative ions and the electromagnetic properties of magnetic compounds. The crystal structure is tetragonal (P42/mnm space group)67 as shown in Fig.09 1.16 1. N.05 12. J. Mitsui.77 8. Crystal and magnetic properties of R2Fe14B compounds.1 26. Compt.15 12.. P. M. /.

Tokyo. and Y. Ohoyama and K. G. 515. Tebble and D. Rev. 8. Soc. Soc.) (in Japanese) 7 (1961). 1969). Arrott. /. 410. by S. 8. 41. Soc. 36.40. Japan. Chikazumi et al. 1975) 7. Phys. J. Yasuoka. Asakura Publishing Co. 492. Sugihara. 21. 549. M. Phys. 120 (1960). H. Hirai. El. 1092..4.) (in Japanese). T. Japan. 38. by S. S. 605. 1663. 1257. 93. Maeda. Phys.) (in Japanese) 7 (1968). 29 (1958).4. Sato and A. Chikazumi et al. F. Phys. 16 (1961). Kept. New York. /. Ohoyama. Tokyo.. 35. p. Chikazumi et al. G. 125. Tsuboya and M. H. E.. Bean and D.. Japan. H. Adachi. Japan Metal Ass. Phys. Ann. 335. 24 (1963). Mag. H. Asakura Publishing Co.. Ito. Hirahara. 60. /. Phys. Phys. Phys. Myers. Hasegawa and I. Shinohara and H. Nagase. 1. 18 (1963). M. Tokyo. Handbook on magnetic substances (ed. Phys. 6. 32 (1971). 520. Soc. Kinzokubutsuri (Metal Phys. /. 13 (1958). Tokyo. 23. /. and A.. Yasuoka. 15. /. Phys. Asakura Publishing Co. 433. 664. Handbook on magnetic substances (ed. R. Phys. Japan. and R. Fujita. Japan. 24. Solids. Kittel. T. 10. S. Fruchart. 16. Sci. Soc. 39. Berger. 20 (1972). Chikazumi et al. K. /. Tsuboya and M. Chem. Asakura Publishing Co. /. Aoyagi and M. Sugihara. 17 (1962). Phys. E. Fujita. I. by S. 1. p. Sato and A. Phys. Kono. 28 (1967). Tokyo. 18. and T. P. A. Japan. Suppl. T. 114 (1959). and C. 1875. Y. W. 908.. I. Soc. 571. Sato. 152. 236. 18 (1963). 114 (1959). Japan. W. I. Arrott. Table 8. K. p. 20. Phys. 24 (1968)..33. J. Nakagawa. Sato and K. Handbook on magnetic substances (ed. . H.. 34 (1973). Watanabe and T. (1955). Ohoyama. Tsuboya and M. R. 17. 525. Soc. Solids. Katsuraki. 6 (1958). H. Phys. 22. A. Colloq.4. 9. Arrott and H. P. K. Watanabe. Tokyo. Appl. R. I. Adachi. 32. 1427. Soc. Kim and M. S... 172. 1072. Asakura Publishing Co. Mekata. Abe. Asakura Publishing Co. Endo. 385. K. K. 33. P. /. Tables 8. 1975) 8. Rev. A. T. Handbook on magnetic substances (ed. Feb.31. 7. /. A18. Y . Japan. Craik.4. Subst. Kanematsu and T. Roy. 543. 1444. Rev. 170. Watanabe. Materials (Wiley.REFERENCES 237 4. p.. O. 40. 17. Lett. 12. Chikazumi et al. 16 (1961). Fig. H. 20 (1965). G. 1534.. 12 (1977). /. Phys.. 1975) 8. Proc. Metals. Bernas. Nathans. /. Appl. by S.6. Kotaibutsuri (Solid State Phys. 1975) 8. 483. /. Japan. Cable. 17S B-I (1962). 29.28. K. J. Soc. Phys. Phys. Nihon Kinzoku Gakkaishi (J.1. Lab. 19. Wiener and J. T. Kanematsu. Soc. CI Suppl. 16 (1968). 13. 155. 1975) p. Sugihara. Japan Metal Ass. Shull. RITU. 126 (1962). Solids. Handbook on magnetic substances (ed. 1420. 3... M. 16 (1961)... G. 1975) 8. /. and K. Rev. H. and M. Pigott. Kotaibutsuri (Solid State Phys. 28..2. 38. Phys. 371.5. Chem. Soc. Ohoyama. Phys. H. H. Heusler. M. Takada. Tsuboya and M. by S. Watanabe. Tokyo. Phys. 17 (1962). 21 (1966). Chikazumi et al. 26. R.. 77. K. Phys. Kimura. Coles. Yasukochi. 8. J. H.. Tsuboya. T. Shinohara. Terada. Sato and K. and M. Kanematsu. I. Takahashi. C. Asanuma. 16 (1961). and H. 5. Mag. 27. Soc. Rodbell. B. Sugihara. 352. 37. A196 (1949). H. H. Shinohara. 31. Felcher. Suzuki. by S. Soc. Japan. p. Nihon Kinzoku Gakkaiho (Kept.) (in Japanese) 7 (1972). 25. Sugihara. 104. 30. K. Chem. 15 (1960). 18 (1963).. 143.4. T. H. p. 447. (1966). (ed. Japan. 540.3. 1096. Hume-Rothery. Chem. 11. Campbell. Takahashi. Moriya. /.\ 11 (1972). and K. Handb. Wilkinson. C. 19 (1934). 20 (1965). W. 14. Japan. 17 (1962). de Phys. Rev. 34.

Fujimura. Tokyo. Chem. M. 283 (1956). Inst. 1584. Herbst. Uda. 12 (1977). Phys. 138. 43.. 1975) 8. 1181. IEEE Trans. 42. K. Buturi (in Japanese). Hirakawa. C.. 11 (1956). F. Phys. 57 (1984) 4100. Miyatani. Con/. Chem. Methfessel. B. McGuire. 61. Phys. Nozaki. T. Buturi (in Japanese). Metal Phys. 3. K.. 55. Handbook on magnetic substances (ed. 45. H. G. Tsuya. /. K. Japan. . 46.. Wojtowicz. 69. 11 (1976). B. Miyatani. Watanabe. Tasset. Tsuya. Li. Givord. T. Phys. Hiraga. 29 (1974). 48. 28 (1957). Lehmann. 657.. 101. Adachi.. and M.238 MAGNETISM OF COMPOUNDS 42. Rev. 707.. 65. J. Yuzuri. T. M. 62. p.4. 60. C. Harder. 51 (1980). R. J. Tsubokawa.. 1083. Asakura Publishing Co. H. 840. Chem.. J. Sekizawa. and F.. White. /. 12 (1957). (in Japanese). Colominus. and J. by S. Chikazumi et al. J. S. Phys. M. Lotgering. Phys.. I. 11. S. /. Solid State Phys. Japan. W. S. 66. 44.. Mag. N. 63. M. F. 1964). 441. 557. Yamagushi. K. R. Croat. Yuzuri. Phys. Tsubokawa. Chikazumi et al. Buturi (in Japanese). 688. J. Nagasaki.2. 49. Hahn. H. and N. E. 25 (1970). Solid State Phys. 140. and W. 14. and S. Mag. and B. Res. F. Robbins. 47. F. 1033. (Nottingham. 35 (1964). Suits. Handbook on magnetic substances (in Japanese) (ed. Roberts. Tokyo. 385. Y. K. R.. C. 10 (1975). 56. Ogawa. 50. /. Sagawa. 67. Ogawa. Hirone. 5 (1970). Tokyo.. Urya and K. H. J. D. M. Handbook on magnetic substances (in Japanese) (ed. (in Japanese) 4 (1958). 57. Asakura Publishing Co. Adachi. /. Solids. Appl.. Buturi (in Japanese). N. Z. Hirone. M. H. K. by S. Foster. 513. Kelley. (in Japanese). 54... W. MAG-5 (1969). 52. 607. Phys. IEEE Trans. S. Sherwood. 518. Rev. Rev. Proc. Appl. Papers. Yelon. S. Solid State Phys. 1975) 10. Chikazumi et al. M. K. H. Spender. S. Soc. Maeda. MAG-20 (1984). 68. and E. 533. B29 (1984). 51. Phys. Williams. Sci. 28 (1973). 539. Matsuura. Phys. 62 (1968). Holtzberg. anorg. Morrish.. I.6. J. 24 (1969). Appl. 897. Yuzuri. and J.. 28 (1967). /. 4176. 59. 486. p. S. Can. P. C. 50 (1972). H. Yamamoto. 153 (1967).2. by S. de Lorent. Soc. (in Japanese). S. G. and A. Mag. J. Maeda. Coey. 104 (1956). 1975) 8. 2313. 53. 64. and K. H. F. Phys. 251. Solid State Phys. M. Int. 558. Appl. p. Hirakawa. Pinkerton. D. 58. Phys. Asakura Publishing Co.

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

Co. As seen from this graph. 8.4 electrons per atom.4 for a series (Fe 1 _. and V to Fe are interpreted by these authors as resulting from the fact that Mn.1. The behavior of the Curie point is quite different from Fig.4 .5 Figure 11.). 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. e ) in Bohr magneton for amorphous alloys (Fe1_.2) and Mn 3 P (see Fig.2 shows the Curie point of Fej^M. and 5MB.t:)08B01P0i as a function of average number of electrons in (Fe^^M^. respectively. Cr. Saturation magnetic moment per (Fe 1 _ jX M. 4. Cr.2). 11. This is analogous to the case of borides (see Fig.1 MAGNETISM OF 3d TRANSITION AMORPHOUS MATERIALS METAL-BASE Pioneering work on this subject was carried out by Mizoguchi et a/. and that of rare earth-base amorphous materials in (11. Mn. 10. and V. The steep decreases of the saturation moment caused by the addition of Mn. and then quenched from the melt by rapid compression between cold copper plates.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.5).eM. and V atoms have moments of 3.. Figure 11.. c M_ ( . 11. This shift can be accounted for by considering that B and P act as electron donors.240 MAGNETISM OF AMORPHOUS MATERIALS We shall discuss magnetism of 3d metal-base amorphous materials in (11. 10. and their magnetic moments are coupled antiferromagnetically with the Fe moment.1). shifted to the left by 0. amorphous alloys as a function of average number of electrons. melted in a plasma-jet furnace. where M = Ni. Cr. These raw materials were mixed.12).) 08 B 0] P 01 .

). of amorphous alloys of (Fe 1 _ A . the Curie temperature is as low as 85°C in an as-quenched sample.1 As seen in this graph. It should be noted that the Curie points of amorphous alloys are subject to change by annealing below the crystallization temperature. while it increases as high as 112°C after annealing for lOOOOmin at 200°C. The reason may be due to the appearance of . Figure 11. Curie point. This behavior is quite similar to that of Invar alloys (see Section 8. There is a tendency that the effect of annealing is more pronounced by increasing the annealing time at low temperatures. t ) 08 B 01 P 0 j as a function of average numbers of electrons in (Fej.MAGNETISM OF 3d TRANSITION METAL-BASE MATERIALS 241 Fig. This was suggested to be due to a compositional short-range ordering of different elements. 11.6'7 It is seen in this graph that the Fe moment drops sharply when the Si content is reduced below 0. while these are quite different for different crystalline alloys.6 at%. Figure 11.2). It is interesting to see how the magnetic moment changes when the metalloid element content is reduced. as a function of Si content. 0 f . (2) The changes in Curie point by the addition of various elements are rather smooth functions of electron concentration for amorphous alloys.3 shows the experimental results for the Fe27Ni53P14B6 system.. 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. the saturation moment of amorphous alloys is influenced by metalloid elements which act as electron donors to the matrix.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).^M.4 the crystalline alloys.M..2. As mentioned above.

6 . 11.242 MAGNETISM OF AMORPHOUS MATERIALS Fig. because the number of nearest neighbors in amorphous alloys is 11-13. The annealing times are indicated in the figure. Then a question arises why the magnetic moment of Fig.4.2MB).8 which is close to the value of 12 in the fee structure. Change in Curie temperature of amorphous Fe27Ni53P14B6 as a function of annealing temperature. on Fe atoms in Fe-Si amorphous alloys evaporated on cold substrates. The similarity between fee Invar and amorphous alloys seems reasonable. as a function of Si content. 11.3. M. The ordinate is normalized to MFe (= 2.1 the low-spin state of Fe atoms caused by an increase in the number of Fe-Fe pairs. Saturation magnetic moment.

2MB (see Fig. ferromagnetism of amorphous materials is not very different from that of crystalline materials.13 For more details. 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. For instance. However. Judging from this and other magnetic data. 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. the magnetic critical phenomena were investigated in Co01~B02f0^. It is interesting that two kinds of atomic magnetic moments are aligned antiferromagnetically in spite of the irregular spatial arrangement. depends considerably on the composition. From these facts.2). as discussed in Section 8. Fukamichi et al? discovered that Fej^B^ (x = 0. However. Figure 11. many investigations have been reported on this system. refer to various reviews.6 at% Si is 2. The temperature dependence of spontaneous magnetization of these amorphous alloys was found to be almost linear. and an expansion coefficient as low as that of Invar is found at x = 0. which is the same as that in fee alloys.4). it was concluded that the atomic magnetic moments and exchange interactions in these amorphous materials have fairly large fluctuations.8 MAm" 1 (lOkOe).. Since the first report16 of ferrimagnetic Gd-Co and Gd-Fe films sputtered onto glass plates. the internal fields of Fe075P015C0 x determined by means of the Mossbauer effect were found to be distributed over a fairly wide range.2. similar to that of Invar. Generally speaking. the atomic magnetic moment of Fe deduced from the internal field.14'15 11.18 The exchange interaction in this system has been interpreted in terms of a 'mean field model'. thus forming the usual ferromagnetic spin arrangement. . If the appearance of low spin states in Invar alloys is the origin of their low thermal expansion coefficients. when Si is replaced by Au. which is the same as that of bcc Fe where the number of nearest neighbors is 8. we know that the exchange interaction acts over long distances even between atomic moments arranged in an irregular manner.2).17.2 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. in spite of the irregular atomic arrangement.8MB.5 shows the temperature dependence of magnetization measured for (Gd 015 Co 085 ) 086 Mo 014 in a magnetic field of 0.11 etc. the magnetic moment of Fe becomes 2. not so simple. we would expect that the amorphous iron-base alloys would also exhibit some Invar anomaly. however. In fact. measured by Mossbauer effect. This is apparently the temperature dependence of magnetization for an N-type ferrimagnet (see Section 7. 11.21) amorphous alloys exhibit anomalous thermal expansion. The dashed curves in the same figure represent the temperature dependence of the sub-magnetizations of Gd and Co deduced theoretically.09-0. The situation is. In R-Fe amorphous alloys.w Fe08P013C007.MAGNETISM OF RARE EARTH AMORPHOUS ALLOYS 243 Fe in amorphous alloys containing more than 0.

This situation has been explained in terms of a transfer of electrons from Gd to Co.4 + 0.02MB in Laves GdCo2.1 State the major differences in magnetism between amorphous and crystalline materials and discuss possible reasons. 11.20 Such a decrease in local moment is suspected to be partly due to a disturbance of the parallel alignment of spins by local anisotropy.17 It is interesting to compare the amorphous RM 2 alloy prepared by sputtering and the crystalline Laves RM2 phase.55MB in both the amorphous and crystalline states. For instance.15MB.22 PROBLEM 11.19 The number of electrons transferred is smaller in amorphous alloys than in the crystalline state. .7MB in Co metal.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. the Co moment is 1. 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). but still lower than the value 1.14 However.244 MAGNETISM OF AMORPHOUS MATERIALS Fig. GdFe2 has an Fe moment of 1. in amorphous GdCo2.5. which is much higher than the value of 1. because the separation between Gd-Gd is larger in the former than the latter.

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

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

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the anisotropy energy is minimum when the magnetization points in either the + or — direction along the c-axis.) as The coefficients Kun (n = 1. For example... In other words. the angle between the c-axis and the magnetization vector. hexagonal cobalt exhibits uniaxial anisotropy with the stable direction of spontaneous magnetization. and decreases to its original value at 6 = 180°. parallel to the c-axis of the crystal at room temperature.. the anisotropy energy initially increases with 6. As the magnetization rotates away from the c-axis.) in these equations are called anisotropy constants.6.. and we call it a magnetocrystalline anisotropy.2. Using the relationships (12. We call an energy term of this kind a magnetic anisotropy energy.1) is converted to a series in cos nd (n = 2. then reaches a maximum value at 6 = 90°. or easy axis.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. Generally the magnetic anisotropy energy term has the same symmetry as the crystal structure of the material. 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..12 MAGNETOCRYSTALLINE ANISOTROPY 12. The simplest case is uniaxial magnetic anisotropy.4. 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.. If these .

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

y-.3 For [100]. in the x-. or in other words the energy is minimum. 12. plus a constant term 2\Kl.) where KI} K2. a1 = 1. £a < 0 for [111] as we see in (12. [010]. (Radial vector is equal to £a + 2|^j|. £a for [111] is higher than that for [100]. Polar diagram of the cubic anisotropy energy for K1 < 0 and K2 = 0. a2 = a3 = 0. (Radial vector is equal to £a + f/Cj. and z. for nickel at 23°C. If ATj < 0 as in the case of nickel.2 and. Polar diagram of the cubic anisotropy energy for K^ > 0 and K2 = 0.3 shows a polar diagram of the anisotropy energy. For iron at 20°C.9) (ignoring K2 and K3 terms). and K3 are the cubic anisotropy constants. so that [100] becomes the easy axis. and [111] directions are easy axes. so that E3 for [111] is lower than that for [100] and [111] and its equivalent [111]. Considering the cubic symmetry. [111]. and ignoring the K2 and K3 terms.2.2 shows a polar diagram of the anisotropy energy in this case. so that the value of E& given by (12. Figure 12.) Fig. 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. for Kl < 0 and K2=K3 = 0.5) is If K1 > 0 as in the case of iron. It is seen that the surface is convex for cube axes .5) plus a constant term equal to f ATj. [010] and [001] are also easy axes. and [001]) directions. It is seen that the surface is concave.(or [100]. 123. Figure 12.PHENOMENOLOGY OF MAGNETOCRYSTALLINE ANISOTROPY 251 Fig.

the magnetization rotates in some particular crystallographic plane. 12. (Radial vector is equal to £a + -^K2.or ferrimagnetic materials Kl > K2. Polar diagram of the cubic anisotropy energy for Kt = 0 and K2 > 0. we have from (12.5) Note that there is no contribution from the K-.252 MAGNETOCRYSTALLINE ANISOTROPY Fig. However. (Radial vector is equal to Ea + ^K2. the change in a formula for the K2 term is only ^ of that from the K1 term.6). and z-x planes. This is the case if the magnetization is confined to the {111} plane.5.) Fig. in many ferro. . then we have Using this relationship. In these cases.4 and 12. and even if K:=K2. Figures 12. however. 12. Polar diagram of the cubic anisotropy energy for Kl — 0 and K2 < 0. 12. so that the contribution of the K2 term can be ignored. the energy is equal to zero for all directions in the x-y. When. term. but Ea for (111) is highest in the case of positive K2 and lowest in the case of negative K2.) and concave for the (111) axes. 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. the K2 term is not necessarily negligible.t-axis (see Fig. y-z.4. and K2 < 0. let us consider the case in which the magnetization rotates in the x-y or (001) plane. Before examining the {111} plane. respectively.

12. Next we consider the (110) plane. If 6 is the angle of rotation of the magnetization from the z-axis in the (110) plane (see Fig. Fig.8).7. The direction cosines between coordinate axes of the old (x. then we have the relationship Using this relationship.y'.1*. The (111) plane in the old coordi* To construct such a table.6. we set up a new coordinate system (x'.. y.7). 12. For this purpose. Rotation of magnetization in the (001) plane out of the x-direction. Next let us calculate the anisotropy energy in the (111) plane. and K3) terms.c'-axis parallel to the [110] axis (see Fig. the y'-axis is in the (llO) plane. first we determine two axes. 12.y'. . and the .z') systems are listed in Table 12. sa' aan determine other direction cosines. we have from (12. z) and the new (x'.PHENOMENOLOGY OF MAGNETOCRYSTALLINE ANISOTROPY 253 Fig. K2.z'\ in which the z'-axis is parallel to the [111] axis. 12. Rotation of magnetization in the (110) plane out of the z-direction.5) the anisotropy energy which includes contributions from all three (K1.

254 MAGNETOCRYSTALLINE ANISOTROPY Fig. we have the direction cosines of magnetization in the old coordinates Using (12. 12.15) in (12.1. y'.5). then we have Referring to Table 12.8. z') with x' II [110] and z' II [111]. New cubic coordinate system (x1. Let 6 be the angle between the magnetization and the x'-axis in the x'-y' plane. . we have the anisotropy energy in the (111) plane in which only the K2 term has angular dependence and contributes to the anisotropy energy. nates is the x'y' plane in the new one.

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 .11).1.17) with (12.PHENOMENOLOGY OF MAGNETOCRYSTALLINE ANISOTROPY 255 Table 12. In summary. by comparing (12. the anisotropy energy can be expressed in the general form In the case of uniaxial anisotropy. we have In the case of the (110) plane. by comparison with (12. we have In the case of the (001) plane in a cubic crystal. we have In the case of the (111) plane.2).

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

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

and (111) planes. * 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. ignoring the K2 term. where the coefficients A2.19). which oscillates twice in the range Fig.A4. for 0=0-180°. Torque curve measured in (001) plane of 4% Si-Fe single crystal at room temperature (Chikazumi and Iwata). 6. so that we have F(x) = -dU(x)/dx. For example.25) as L ( 0 ) = -2v4 2 sin20-4^ 4 sin40-6^4 6 sin60-8y4 8 sin80. we have the relationship -F(x) Sx = SU(x).258 MAGNETOCRYSTALLINE ANISOTROPY is rotated by the angle 86. (12.26). 12. respectively. (12. The work done by the torque must equal the decrease in the anisotropy energy. where the coefficients are given by (12.10. In the case of cubic anisotropy.. and (12. (110). . If the potential energy is increased by 5U(x) when the body is displaced by Sx along the slope.••• . the torque is given by (12.27)..10 shows a torque curve (a plot of the torque vs. the torque can be calculated from (12. angle) measured for a single crystal disk of 4% Si-Fe cut parallel to (001).18). Then the torque L(0) must act on a unit volume of the specimen in a sense to decrease 6. of the field measured from the [001] axis. This angle almost coincides with that of the magnetization as long as the field is strong enough.17). the torque is given by (12.20). are given by (12. The experimental points are well fitted by (12.. the torque in the (001) plane is given by Figure 12. as a function of the angle of rotation.26) If the magnetization is rotated in a plane which includes the c-axis in a uniaxial crystal.21) for (001). so that or -L(0)50 = 5E(0).26).

the ratio of the first to the second peak. Since the amplitude is equal to K^/2. or if some induced magnetic anisotropy. we have . is present. 6 curve.67. and these peaks appear at 6 = 25. calculated from (12. 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.3°. It is.11. are both changed.5° and 71. the angle at which peaks appear. dangerous to estimate the value of K2 from these changes. however. and also the value of 6. 12. When K2 = 0. the torque curve is given by Figure 12.METHODS FOR MEASURING MAGNETIC ANISOTROPY 259 Fig.21) in (12.28). ignoring the K3 term.11 shows the torque curve. As the value of K2 increases. the ratio of the first peak to the second peak is 2. as discussed in Chapter 13. Torque curve calculated for (110) plane of a cubic crystal (the parameter is K2/Kl). Using the value of (12. In the case of the (110) plane. or L/Kl vs.26). 6 = 0-180°. where the parameter is the value of K2/Kl. the anisotropy constant K^ can be determined from the torque curve.

so that we have Therefore. which is slightly smaller than <p. and (/31.32) with respect to the angle 6. Therefore.10 It must be noted that when the magnetic field is not strong enough to align the internal magnetization in the field direction. Sa3. Definition of the angle 0 between spontaneous magnetization. We assume that the uniaxial anisotropy has the anisotropy constant Ku. The procedure for minimizing the energy (12. the magnetization rotates towards the field by the angle 6. Then the anisotropy energy is given by In addition. we must consider the field energy (see equation (1.9)). because the magnetization makes a nonzero angle <p — 6 with the field.260 MAGNETOCRYSTALLINE ANISOTROPY Fig. 12. The Fourier analysis can be performed by the calculation given by Chikazumi. and the z-axis (easy axis). As shown in Fig. In this case. 8a2. the value of K2 can accurately be determined by Fourier analysis of the torque curve to give the term in (12. or even if some induced anisotropy is present. and the easy axis is parallel to the z-axis.32) is as follows: If the direction cosines of the magnetization.12. a 2 . even if the plane of the sample is tilted from the (111) plane. H. we have . 12. if the magnetic field H is applied in a direction <p from the easy axis z. a3). which represents a torque curve oscillating three times in the range 8 = 0 to 180°. 7S. /32.32) should be zero when the direction of /s is in an equilibrium state. respectively. 7S are changed virtually by Saj. Let (aj. the total energy of this system is given by The direction of magnetization can be found by minimizing (12.29).9 or by a simple computer program. the uniaxial anisotropy may give rise to an apparent fourth-order anisotropy. the associated change in energy (12.12. /33) be the direction cosines of /s and H. and the angle ip between the magnetic field. and the z-axis.

the coefficients of Soj.36) by ISH. and 8a3. we have In order that (12. given by Multiplying (12. we put 2Ka/IsH=p (p <s 1). we have Substituting (12. and Sa3 must be zero.32). we have Putting each side of (12. which minimize the total energy (12. ( /A <K 1). into (12.39) for (12.38). we have where p Substituting (a l 5 a2. Sa2.34) by an undetermined parameter A and adding (12.32).35) be satisfied for arbitrary changes in Sa1. Therefore If the field is strong enough to satisfy ISH^>2KU. 5a2. a3). there must be a relationship between 5alt Sa2. and after dividing each side of (12.38). and Sa3.37) equal to 1 + /u.METHODS FOR MEASURING MAGNETIC ANISOTROPY 261 Since a^ + af + a| = 1. we have . we have Using (12.33).

11 . the torque curve exhibits hysteresis.42).12 When the magnetic field is so weak that the magnetization cannot rotate reversibly with the magnetic field. the actual rotation of the specimen from the direction of the field is given by <p. the term with twofold symmetry is not affected by the intensity of the applied magnetic field. Torque curve normalized per one Tb atom in a dilute Tb-Gd alloy. is determined by the relationship and then the torque curve is corrected by shifting the angle by <p . not 6. 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 torque curve shows some field dependence.11 In the case of a disk-shaped specimen. If the rotation of magnetization is associated with some loss of energy.12.41) as As seen in (12. Thus the torque is deduced from (12. because as seen in Fig.0. 12. <p . which is called rotational hysteresis. 12.6.13.262 MAGNETOCRYSTALLINE ANISOTROPY This energy is expressed as a function of the direction of the external magnetic field. which is a function of H.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. In order to correct for such a higher-order term. The term with fourfold symmetry does include p. not the direction of magnetization. This form is proper to express the torque curve. Fig.8 Figure 12. which will have some domains remaining at the edge even in high applied fields.

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. If the frequency of the microwave radiation field applied to the specimen coincides with the resonance frequency.41) should be replaced by j31. The fourth-order anisotropy thus produced is field-dependent. Therefore if the material has its own inherent Kw. If the easy axis of the uniaxial anisotropy is unique.13 the coefficient is different. resulting in the dominant contribution to the anisotropy from the second term. If the applied magnetic field is parallel to the easy axis. If the easy axis is parallel to the x. so that value of K^ changes its magnitude or sometimes changes its sign with a change in the intensity of applied field.5). . But if the easy axes are distributed on the x-. the uniaxial terms must cancel one other. a part of the microwave power is absorbed to excite the precession (see Section 3.METHODS FOR MEASURING MAGNETIC ANISOTROPY 263 whether internal or external.41). the resultant field-dependent Kl will be given by If Kw is small and positive. rotational hysteresis appears even when the field is strong enough to rotate the magnetization reversibly. /33 in (12.16 Magnetic anisotropy can also be measured by ferromagnetic resonance.1. because the anisotropy gives an additional torque to the spontaneous magnetization to rotate it towards the easy axis. y-. In ferromagnetic resonance. This effect is equivalent to a presence of the so-called anisotropy field.3). so that the average anisotropy is given by We see that the fourth-order term* in (12. The second term in (12. * In the original paper.or y-axis.42) shows the appearance of a higher-order term when the applied magnetic field is not strong enough.14 Alnico 515 and Co ferrite. or /32.44) has the same form as the cubk magnetocrystalline anisotropy (12. This phenomenon is called the torque reversal. Torque reversals have been observed for Fe2NiAl. Let us formulate the torque reversal by using (12. or z-axes in different places. the second term is simply a small correction as in the case of (12. the magnetic anisotropy influences the resonance field. This phenomenon will be treated again in Section 13. because higher order terms were ignored.42). the spontaneous magnetization precesses about the applied magnetic field with a frequency proportional to the magnetic field. Kl changes its sign from positive to negative as the field increases.

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.264 MAGNETOCRYSTALLINE ANISOTROPY Let us calculate the anisotropy field for a uniaxial anisotropy. Therefore we conclude that the resonance is expected to occur at a field less than the usual value by an amount Ha.46) and (12. Ignoring the higherorder terms in (12. we have which has the same form as (12.14).1).39). when magnetic anisotropy is present.51). we can simplify the anisotropy energy for small 8: On the other hand. 12.21) and (3.47). Substituting a.5) by (12. we first change the coordinate . if an anisotropy field exists. In the case of a cubic crystal.22)) which is given by The g-factor was defined in (3. in (12. when the magnetization is in a direction near [001]. the energy is expressed for small 6 by Comparing the terms in 0 2 in (12.47). so that the anisotropy field is given by When the magnetization is in a direction near [111]. we have Then the resonance field should be given by where the coefficient v is the gyromagnetic constant (see (3.

then use polar coordinates. . Then we have Using this expression in the first term in (12. system as shown in Fig. we can deduce the anisotropy constant. 12. we have the anisotropy field Therefore when the magnetic field is rotated from [001] to [111]. the resonance field should shift by Figure 12.47).51).15).METHODS FOR MEASURING MAGNETIC ANISOTROPY 265 Fig.15 shows the shift of resonance field observed for a single crystal of Fe3O4. and finally substitute using (12.8. when the magnetic field is rotated in the (001) or (110) planes. The polar and azimuthal angles of the magnetization in the vicinity of the z-axis.5). 12.14. we finally have Comparing this result with (12. as in (12.17 From such experiments.

is given by .15.3 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. (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. whereas the magnetic resonance exhibits different absorption peaks corresponding to the local anisotropies. Moreover.16 shows the rotation of ferromagnetic spontaneous magnetization. The magnetic anisotropy can also be determined by measuring magnetization curves. the torque measures only the average of the local anisotropy. whereas the resonance field measures the second derivative of the anisotropy energy.3).18 the exchange interaction between spins St and 5. if the specimen is inhomogeneous. Figure 12. which is composed of parallel spins. 12. Variation^ of the resonance field with a rotation of magnetization in (a) the (001) plane and (b) the (llO) plane.3. The reason that neighboring spins remain parallel is that a strong exchange interaction acts between spins (see Sections 6. According to Heisenberg's expression. 12. so that the anisotropy is different in different places. from one direction (a) to another (b). observed for a single crystal of Fe3O4.2.266 MAGNETOCRYSTALLINE ANISOTROPY Fig. We shall discuss this method in Section 18. 6.

12.MECHANISM OF MAGNETIC ANISOTROPY 267 Fig. When the magnetization rotates as shown in Fig. 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. because it has the same form as the magnetic dipole-dipole interaction (see (1. Therefore to explain magnetic anisotropy. Thus the exchange energy is isotropic. Rotation of spins in ferromagnetic spontaneous magnetization. 12.15)) if the coefficient is given by However. as The first term is independent of the angle <p. The second term is called the dipole-dipole interaction term. A pair of spins.17). so that it corresponds to the exchange interaction. where 5 is the magnitude of the spin and <p is the angle between S. and 5. after expanding in Legendre polynomials. we need an additional energy term which includes the crystal axes. Suppose that neighboring spins make the angle <p with the bond axis (see Fig. 12.16 from (a) to (b). so that if = 0 in (12..58) and the exchange energy does not change.17. . 12. all the spins remain parallel. through a change in the Fig. Then the energy of the spin pair is expressed.16.60). 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.

and then calculate the magnetostatic energy by using (1. If we extend the range of sum to the whole volume of the specimen. Before going into details of the spin-pair model. however. the convergence of the dipole sum with distance is not very rapid. Therefore the contribution of all the dipoles in the sphere of the radius r increases as In r with increasing r.59) is a higher-order term of the same origin. In reality. In the present case. let along the magnitude. In the case of pseudodipolar interaction. We cannot trust even the sign of such calculated results.59). we consider only the first nearest neighbors. A real calculation of magnetic anisotropy has been made for hexagonal cobalt.18). Therefore in order to calculate the dipole sum free from shape anisotropy. and is called the quadrupolar interaction. Such a logarithmic function increases only slowly.19 Some published papers show the calculation of the dipole sum only in the vicinity of an atomic site. Let (a l9 a 2 . first we consider a simple cubic lattice (Fig. Let us elucidate how magnetic anisotropy is constructed from the spin-pair energy given by (12. the range of interaction is truly short range. The third term in (12. a3) be the direction cosines of parallel spins. Such a model is called a spin-pair model. but the result can explain only a part of the experimental value. This corresponds to the shape anisotropy given by (12. In order to calculate the dipole sum. For spin pairs with bonding . it is tempting to assume that the main contribution comes only from the neighboring dipoles. we must calculate the contribution from a spherical shell with radius r.59) for all the spin-pairs in the crystal. Since the dipole field is inversely proportional to the third power of distance. we consider only the interactions between the first or at most the second nearest neighbors. The sum of dipole-dipole interactions between all the spin pairs in a ferromagnetic crystal is called the dipole sum. 12. For simplicity.23). so that it is not necessary to worry about the range of the sum. the dipole sum depends on the shape of the specimen. This is simply where i identifies the spin pair.268 MAGNETOCRYSTALLINE ANISOTROPY overlap of wave functions. so that the dipole sum increases only as (l/r 3 Xr 2 dr) = dr/r.94). The magnetic anisotropy is calculated by summing up all the spin pairs included in a unit volume of this crystal. 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). the convergence is still unsatisfactory. so we must calculate the contribution of all the dipoles in a large sphere. Since the pair energy for distant pairs is small. The magnetic anisotropy can be calculated by summing up the pair energy given by (12. let us consider how magnetic anisotropy is produced by the magnetic dipole-dipole interaction. and then increase r to infinity. we first calculate the magnetic field produced at one atom by all the surrounding magnetic dipoles. 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. however. Although special techniques have been used for such a calculation of the dipole sum. Such an interaction is called a pseudodipolar interaction.

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

which are expected to produce a large anisotropy.8A as compared to 1. the energy levels of d-electrons which are degenerate in the free ion state ((a) in Fig.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. metal ions occupy these small interstitial sites. For example. We shall discuss the behavior of the Co2"1" ions in the octahedral site. in which one Fe3+ occupies a tetrahedral site. thus forming a close-packed structure. in which atomic spins are close to one another. Cobalt-ferrite has the composition Co 2+ Fe2 + O 4 . 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. the magnetic anisotropy results from the behavior of non-spherical magnetic atoms in the crystalline field produced by the surrounding ions. The ds functions stretch along (110) axes.19.20). Interstitial sites in an oxide lattice: (a) tetrahedral site. We shall discuss how such wave functions result in a magnetic anisotropy in an oxide crystal. surrounded by four nearest neighbor O 2 ~ ions. 12. ferrites have the spinel lattice (see Fig. Since the divalent or trivalent metal ions (M 2+ or M 3 + ) are much smaller than the O 2 ~ ions (radius 0. There are two kinds of interstitial sites. however.20). This is not.19: one is a tetrahedral site. while the other Fe3+ and the Co2"1" occupy two octahedral sites.6-0. surrounded by six O 2 ~ ions. plus metal ions which occupy the tetrahedral sites and octahedral sites in a ratio of 1:2. 12. This model is called the one-ion model. In an oxide crystal. (b) octahedral sites. divalent oxygen ions (O 2 ~) are in direct contact to one another.270 MAGNETOCRYSTALLINE ANISOTROPY This spin-pair model is applicable to metals. they are squeezed into interstitial sites of the oxygen lattice. 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. 3. In general. 12. In all the oxides. and the other is an octahedral site. 12.32A for O 2 ~). . 9. Generally speaking. Fig. as shown in Fig. the case for oxides and compounds in which the magnetic atoms are separated by large negative ions. while the dy functions stretch along the cubic axes (100) (see Fig.3) consisting of a close-packed oxygen framework with face-centered cubic structure. In such a case.

MECHANISM OF MAGNETIC ANISOTROPY 271 Fig. so that they produce a trigonal field which tends to attract the electron along the trigonal axis.20. L is reversed. and A < 0.19(b)) are arranged symmetrically about the trigonal axis (the [111] axis in the same figure). the triply degenerate de levels are split into an isolated lower single level. The last electron which occupies the doubly degenerate levels can alternate between the two possible wave functions. while the remaining two electrons occupy the — spin levels (see Fig. 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. According to Hund's rule.20(c)). 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 second nearest neighbor metal ions surrounding an octahedral site (hatched circles in Fig. while the de wave function stretches between two cubic axes and avoids the O 2 ~~ ions. 12.67) becomes . S has a positive component parallel to the trigonal axis. This orbit produces an orbital magnetic moment ±L parallel to the trigonal axis. In addition to this. thus realizing a circulating orbit. Therefore the interaction energy in this case is given by21'22 In cubic crystal there are four (111) axes. L points in the + direction of this axis. 12. This orbital magnetic moment L interacts with the total spin S of the Co2+. the anisotropy energy produced by (12.29)) is expressed as Since the number of electrons in a Co2+ ion is more than half the number required for a filled shell. Such spin orbit coupling (see (3. L is parallel to 5 (Hund rule (iii)). If Co2"1" ions are distributed equally on octahedral sites with different (111) axes. When S is rotated so that it has a negative component. When. so that the Coulomb energy is relatively small and the de level is lowered. therefore. (c) trigonal field (arrows represent spins in a Co2+ ion). In consequence. 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. 12. Splitting of energy levels of 3d electrons by crystalline fields: (a) free ions. (b) cubic fields. the energy level of dy is increased.

the anisotropy constant in (12. )83). the magnetic anisotropy vanishes when the spontaneous magnetization disappears at the Curie point.25 Before closing this section. and the deviations . In fact. and this induced L gives rise to the magnetic anisotropy through the LS coupling. At temperatures above absolute zero. in any ferro. the orbital moment L is induced through the LS coupling. (04. For further discussion of various mechanisms of magnetic anisotropy. are not the same as those of the total spontaneous magnetization.68) becomes Since A < 0.272 MAGNETOCRYSTALLINE ANISOTROPY where 01. let us discuss the temperature dependence of magnetic anisotropy. Generally speaking. This explains the fact that many ferrites have negative Klt but the addition of Co tends to make K^ positive. magnetic anisotropy is produced through the interaction between spontaneous magnetization and the crystal lattice.59) is applicable over a wide range of temperature. (/31. The temperature dependence.27 Consider a ferromagnetic material with spontaneous magnetization produced by parallel spin alignment. the direction cosines of a local spin cluster. refer to Yosida and Tachiki. By Fourier expansion. j32. of the anisotropy is stronger than that of the spontaneous magnetization. 0 2 > ^s> and fy are the angles between S and the four (111) axes. a2.or ferrimagnetic material. «3).24 and Kanamori.70) is positive. In the case of metal ions other than Co2+. cos 6 \ is reduced to Therefore (12.23 Slonczewski. 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. We shall discuss this problem along the line proposed by Zener26 and developed by Carr. so that the temperature dependence of spontaneous magnetization should give rise to a change in magnetic anisotropy.

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. Therefore we have for n = 2 (uniaxial anisotropy) and for n = 4 (cubic anisotropy) Figure 12. etc. The larger the power of the angular function in ( >. Fig. The magnetic anisotropy is also influenced by other factors.21. the magnetic anisotropy averaged over all the spin clusters decreases with increasing temperature. therefore. Temperature dependence of observed K1 value for iron in comparison with the 10th power rule. the more rapidly the function < > decreases with increasing temperature. (After Carr27) . It should be noted.74). we have the relationship where K^ is the anisotropy constant for the nth power angular function. Therefore. temperature dependence of the valence states.27 thermal excitation of the electronic states of magnetic atoms. 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. 12.MECHANISM OF MAGNETIC ANISOTROPY 273 increase with increasing temperature. The agreement is satisfactory. even if all the coefficients in (12. According to an accurate calculation for the «th power function.59) are independent of temperature. such as thermal expansion of the lattice.

which is composed of the spin angular momentum 5 and the orbital angular momentum L according to Hund's rules (see Section 3. of 4/el.64 6 8 10.14 3. oxides. R S c Y L a Ce Pr Nd Pr Sm Eu Gd Tb Dy Ho Er Tm Tb Lu No. Table 12.6 9.50 — — — 7.and ferrimagnetic materials. 3+ Ions 5 L J g\//(/+D Meft/MB gJ 0 0 0 2.80 9.0 7.27 2. After discussing this topic. 12.0 9.34 10. and are well protected from the influence of the surrounding atoms.56 3 7/2 4.55 9.0 10.1 Uniaxial anisotropy The magnetocrystalline anisotropies of rare earth metals and alloys are extraordinarily large. because the orbital magnetic moments remain unquenched in these materials (see Section 8.274 MAGNETOCRYSTALLINE ANISOTROPY 12.4 0 0 0 0 0 0 0 0 0 0 3 5/2 2. because the magnetic moments are produced by 4/ electrons which are located relatively far inside the atoms. because generally the anisotropy constants are large.58 6 9/2 3.0 4.4.2.72 5 15/2 10.5 10.20 3.62 6 4 2.68 5 5/2 0.53 0 0 0 Metals MS/MB 0 0 0 — — — — — — 7.4 0 0 0 2.85 3 0 0. and the origin of the anisotropy is comparatively clear.94 3 6 9. The magnetic moments in this case originate from the total angular momentum.4 EXPERIMENTAL DATA Magnetocrystalline anisotropy constants have been measured for many ferro.74 10. First we consider the case of materials with uniaxial anisotropy. and compounds.40 0.0 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 . the orbital magnetic moments remain unquenched by crystalline fields. /.0 3.34 8.3).6 7.2 lists the angular momenta and magnetic moments for fifteen rare earth ions and Table 12.0 10.1 4. In this section we describe some of these results. (a) Magnetocrystalline anisotropy of rare-earth metals and alloys In rare-earth metals.54 5 4 3.60 6 15/2 9.00 0 7/2 7. we proceed to consider uniaxial 3d transition metals.2).00 7.60 3.52 3.0 9.72 0.20 10.58 5 6 7. Angular momentum and magnetic moment of rare earth ions and metals.

When a magnetic field is applied parallel to the c-plane. the magnetization is increased rather easily. the sample is magnetized only with great difficulty: only 80% of the saturation magnetization is attained in a field as high as 32MA. This proves that the orbital magnetic moments survive almost unchanged in the crystalline solids. 12. In Table 12. We can say that the spontaneous magnetization is confined in the c-plane by a strong magnetocrystalline anisotropy. whereas when the field is applied parallel to the c-axis. The orbital moment of Tb is L = 3.633 for a closed-packed hexagonal lattice. 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. Magnetization curve measured for a Tb metal single crystal at 77 K.22). the c/a value of the hexagonal lattice of Tb in 1. which is the maximum value. let us consider how Tb metals develops its enormous magnetocrystalline anisotropy. the lattice is compressed along the c-axis. rotation of the spontaneous magnetization tends to rotate the orbits in the crystal lattice. Terbium has hexagonal crystal structure. 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. thus giving rise to a change in electrostatic interaction between orbits and the lattice.ni"1 (400 kOe)34 (see Fig.34 metals (see also Table 8. For example. so that the orbital plane spreads perpendicular to / forming pancake-like electron clouds (see Fig 12. where the orbital magnetic moment remains unquenched.23). In other words. In such materials. 12.2. The anisotropy constant in this case is approximately /£u = 6 X 10 7 Jm~ 3 (6 X 108ergcm~3).59. respectively. On the other hand.EXPERIMENTAL DATA 275 Fig. If the c/a ratio were the ideal value .22. which is much smaller than the ideal value of 1.2).

22). Electron cloud of the 4/ electron of a Tb atom in a hexagonal lattice. it has no orbital moment (L = 0). thus attracting the clouds as shown in Fig. and accordingly exhibits no large magnetocrystalline anisotropy. in spite of the fact that the magnetization process is expected to occur exclusively by reversible rotation magnetization. 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 neighboring 3+ ions approach the electron clouds of the reference ion from above and below. 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.35 Since Gd has seven 4/ electrons. Therefore J is forced to point parallel to the c-plane. 12. At the same time. 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. 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. The same phenomenon was observed for Dy metal.23. .23). the reference ion and its neighbors would have face-centered cubic symmetry. 12. 12.23.276 MAGNETOCRYSTALLINE ANISOTROPY Fig. so that no uniaxial anisotropy should be produced. However. the lattice is plastically deformed: elongated by 7% along the c-axis and compressed by 6% parallel to the c-plane. if the lattice is compressed along the c-axis.

the electron cloud for m — 0 extends along the c-axis. thus making the c-axis an easy axis (D < 0). the magnetic moment of R is strongly coupled by the exchange interaction with the moment of Gd. when a small amount of another rare earth element. 12. The broken curve is for pure Gd. so that its exchange interaction is quite large.2 K for a 1. showing that a large anisotropy is produced by Tb. 12.24. Therefore. Since the c/a value of Gd metal is less than the ideal value of 1. On the other hand. -3 as the number of 4/ electrons per atom increases (see Fig. is alloyed with Gd.2. 12. as shown in Fig.2). Gd has the maximum spin (S = f ). 12. The solid curve is from a theory based on a rigorous calculation of 4/ orbits and their interaction with the crystalline field of Gd. When all the states less than half are occupied with seven electrons.11 Moreover. the amplitude of the torque curve is increased by a factor of five. According to Hund's rule (Section 3.24 shows the torque curve measured for an alloy of 1.36 The general form of this curve can be interpreted intuitively in terms of the electron clouds of 4/ electrons.8% Tb in Gd. The result is that Gd tends to exhibit an anisotropy characteristic of R. the resultant electron clouds become . Torque curve measured at 4.26).11 Figure 12. By adding only 1.25. The dashed curve is that for pure Gd. 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). From the uniaxial anisotropy measured in this case. so that the two rotate together when a field is applied. D.8% Tb.633. 12.1. The shapes of the electron clouds are independent of the sign of m.8% Tb-Gd alloy single crystal in a plane containing the c-axis. the 4/ electron successively takes states with magnetic quantum numbers m = 3.0.26. —2.EXPERIMENTAL DATA 277 Fig.26. as shown in Fig. R. —1. is deduced and plotted as a function of the number of 4/ electrons of R in Fig. the anisotropy constant per one R atom.

2. In fact. Since the shape of the electron clouds is independent of the sign of m. and 1 and a half in m = 0 will also result in a spherical electron cloud. 12. 12. a hypothetical group composed of one electron in each of the states m = 3. because L = 0. Uniaxial anisotropy constant D per one rare earth ion dissolved in Gd metal. the Fig.278 MAGNETOCRYSTALLINE ANISOTROPY Fig.11 spherical. Configurations of 4/ electron clouds for various magnetic quantum numbers. as a function of the number of 4/ electrons in the dissolved rare earth.11 .25.26.

5). so that the average radius of the 4/ orbits is relatively larger and the interaction with the crystalline field is larger. because they are divalent in the metallic state. The lines for all the other added elements except Fe have slopes steeper than that for Fig. Extrapolating these curves to zero absolute temperature. of cobalt alloys containing a small amount of Cr. Fe. The values of D are generally larger for « 4 y < 7 than for n4f > 1.12). Temperature dependences of the uniaxial anisotropy constants. except for Ce. In this connection. 12. and Sm.28.37 . 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. it is of interest to investigate how large an anisotropy would be found in hypothetical hexagonal iron or nickel. because Cu is nonmagnetic. this is expected.5) and between Ho and Er (n4f = 10. One of the reasons for this large anisotropy may be the low crystal symmetry.5 = 7 + 3. Ni. and accordingly are identical to Gd and La. or Cu.25 intersects the abscissa between Nd and Pm (« 4 y= 3. 12. that is. Cr and Ni. Mn. 12.37 Figure 12. The experimental points shown by crosses are in good agreement with the theory.27. The dot-dash line shows the calculated effect of simple dilution.EXPERIMENTAL DATA 279 theoretical curve in Fig. respectively (see Fig. the values of Kul at T = 0 were determined. This is because the nuclear charge is relatively smaller for n4f < 7. Pm. (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.27 shows the temperature dependences of the uniaxial anisotropy constants. Although it is difficult or impossible to produce hexagonal ferromagnetic 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. 3. and are plotted against the atomic percentage of added element M in Fig. Kul. Kul. measured for pure Co and for Co-alloys containing small amounts of Mn. The line for M = Cu is very close to that for simple dilution. the replacement of Co atoms by nonmagnetic atoms. The Z)-value is zero for Eu and Yb.

The atoms in an A-layer between B. 12. in close-packed hexagonal. It is interesting to note that Fe and Mn exhibit an anisotropy larger than Co. this change in crystal structure does not explain the dramatic change in Kal. In the case of the Co-Fe system.. and finally reaches a large negative value of —10. in which the crystalline field effect results in the following level scheme: m = +1 are the lowest. and m = 0 is the highest.2 X 105 Jm~ 3 . Figure 12. at 0 K for various Co-alloys as a function of the 3d metal alloys content. as a function of the number of 3d holes in M. The actual origin.280 MAGNETOCRYSTALLINE ANISOTROPY Fig. At the same time the crystal structure changes from closed-packed hexagonal to double hexagonal.37 simple dilution. and in the sequence ABACABAC.05at% Fe.39 (c) Magnetocrystalline anisotropy of rare earth-3d metal compounds The rare earth-cobalt compounds of the compositions RCo5 and R2Co17 have . deduced from the slope in Fig. This means that these elements make negative contributions to Kul. Uniaxial anisotropy constants. changes sign to negative. However. 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. Kul.28.. has not yet been clarified. since Kl for face-centered cubic Co is negative. in double hexagonal.28.29 shows a plot of the anisotropy constant per M atom. m = ±2 the next..1)..38 which contributes a positive Kul. 12. The difference between the two is that the stacking sequence of close-packed planes along the c-axis is in the sequence ABAB. The origin of this phenomenon must be due to atomic interactions of longer range than the second-nearest neighbors.and C-layers have the same nearest neighbors as in the face-centered cubic lattice (see Fig. at which point Kul decreases discontinuously. however. 9.

40 Compounds YCos CeCo5 PrCo5 NdCo5 SmCo5 Curie point (K) 978 673 921 913 984 M s /M B atOK per RCo5 per Co 7.5 Ku2atOK (MJm~ 3 ) ~0 ~0 18 19 ~0 .EXPERIMENTAL DATA 281 Fig.7 1. Table 12. Saturation moment and anisotropy constants of RCo5. M 2+ and Ba2+. 5 x l 0 6 J m ~ 3 at OK. and exhibits a very strong magnetocrystalline anisotropy.4.43 1.6). The ionic radii of Ba2+. which contains Fe3+.26). Sr 2+ . which are very large as compared with Table 12.43.6 10. and Pb 2+ are 1.3.44 1. The compounds of the R2Co17-type exhibit comparable values of magnetocrystalline anisotropy. 8. respectively. the anisotropy constants amount to 106-107Jm~3 (107-108 ergcm"3). or Pb 2+ . Sr 2+ . As seen in this table. which is the main constituent of NdFeB magnets.40 KulatOK (MJm~ 3 ) 6.32 A.42 (d) Magnetocrystalline anisotropy of hexagonal ferrites The crystal structures and magnetic properties of hexagonal ferrites were described in detail in Section 9.27.9 6.5 5.5 -7 -40 10.3 list various magnetic data40 for the compounds of the RCo5-type. and reaches +3.4 10. so that they exhibit strong magnetocrystalline anisotropies. but it changes sign at 126 K.4 7. The value of Kul is — 6 . 1.57 1. and 1.7 X 106 Jm~ 3 at 275 K.37 hexagonal crystal structure.32 1.29. This is due to a very strong crystalline field acting in a crystal of a very uniaxial nature (see Fig. The crystal structure is the magnetoplumbite-type hexagonal. 12. Uniaxial anisotropy constant per added 3d alloy atom in Co as a function of vacancies in the 3d band. has the tetragonal structure (see Section 10.41 The rare earth compound Nd2Fe14B.

In the case of positive Kul.282 MAGNETOCRYSTALLINE ANISOTROPY Table 12.478 0.56 Ku2 = 0. In this case.2 to 0. (T) 0. The frequency is related to the second derivative of the anisotropy energy (12.4.160 0. 43 43 44 44 43 43 43 43 43 43 43 6 9 8 0.478 0.0 0.415 0.395 Ku2 = 0.4 lists magnetocrystalline anisotropy constants measured at room temperature for various hexagonal ferrites.86 2.4. the anisotropy constants for these hexagonal ferrites are all of the order of 105 J m ~ 3 (106 ergcm"3).232 0.5 X 105 J m~ 3 .8 A).3 3. Table 12. because in spite of the presence of a cubic spinel phase the overall symmetry of the crystal is uniaxial.46 However. together with other magnetic properties.6-0.5 T. 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. 6. 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.339 430 280 390 130 340 410 the radii of Fe3+ and M 2+ . a similar calculation for the M-type compound led to Kul = —1. thus forming hexagonal crystal structures. Magnetocrystalline anisotropy of hexagonal ferrites at 20°C. the c-axis is the easy axis.1 KU1 + 2KU2 (10 5 Jm~ 3 ) /.150 0.6 -0.1) with respect to the polar angle. The magnetocrystalline anisotropy of these hexagonal ferrites is expressed by (12. but occupy substitutional sites in the layer parallel to (111) of the spinel phase.6 -1.46 Kondo47 showed that an Mn 2+ ion. (10s J m ~ 3 ) 3. and are comparable with that of O 2+ (1. These compounds are all ferrimagnetic with Curie points about 400°C and with saturation magnetizations at room temperature from 0. 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..8 ("O (Ref.32 A).285 0.1). As seen in Table 12.0 -2. Depending on the structures of the layers containing Ba2+. which has the opposite sign of the observed value. W-. Therefore these large metal ions cannot enter the interstitial sites in the closed-packed oxygen lattice. the compounds are classified into M-. and Z-types. while for negative Kul the c-plane is the easy plane. The actual origin of this anisotropy is considered to be an Fe3+ ion surrounded by five O 2 ~ ions. Y-. Ku. (0.75 -0.4 2. etc. so that it is proportional to Kul for a positive Kul and to Kul + 2Ku2 for a negative Kal. 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.9 -1. which has the same electronic . and their ratios to the spinel phase. From the calculation of a dipole sum.21 -1.

and the shape of the curve of easy axis angle vs temperature.49 The compound MnBi. It was observed for Fe7Seg that the temperature range for the rotation of the easy axis. The spin axis of the ferrimagnetic Fe7S8 tilts by 20° at OK. the anisotropy results in an easy cone of magnetization with polar half-angle sin"1 ^ —Kul/2Ku2. exhibits a very strong uniaxial anisotropy with the easy axis parallel to the c-axis.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.6 X 106ergcm~3). Ferroxplana.3). are used as permanent magnet materials (see Section 22. can produce the expected anisotropy.1 X 106 ergcnT 3 ) and Ku2 = 2.4. The compound Fe7Seg has a similar spin structure and also exhibits ferrimagnetism. Barium and strontium ferrites. which is a NiAs-type ferromagnetic compound (Section 10. which is antiferromagnetic.51 . which has antiferromagnetic spin structure (see Section 10. and gradually approaches the c-plane with increasing temperature.and ferrimagnetic compounds other than oxides was described in Chapter 10. When the anisotropy constants Kul and Ku2 have opposite signs.2(b)).4).50 When this compound is evaporated onto a glass substrate and annealed. 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.3).EXPERIMENTAL DATA 283 configuration as an Fe3+ ion. and reaches the c-plane at about 80 K. These phenomena were interpreted by the one-ion model of the Fe2+ ion surrounded by lattice vacancies.3. and then rotates discontinuously to the c-plane at 400 K. In the case of FeS. and mixing of the excited states. (e) Uniaxial anisotropy of magnetic compounds Magnetism of ferro. It has been demonstrated that 'magnetic writing' can be performed by using a magnetic needle to locally magnetize such a grain-oriented MnBi film. which has an easy plane parallel to the c-plane.2).46 The mechanism of the easy cone in Co2Y and Co2Z has been explained in terms of the Co2+ anisotropy48 discussed in Section 12.1 X 105 J m ~ 3 (9. rotates gradually towards the c-plane with increasing temperature. overlapping of the electron clouds with the surrounding O 2 + . the spin axis is parallel to the c-axis in the temperature range from 0 to 400 K. the c-axis is oriented perpendicular to the substrate surface. he considered a distortion of the ion. These useful properties are based on the strong magnetocrystalline anisotropy of these materials. has excellent high-frequency characteristics (see Section 20. and also the relationship 2|Xul| > \Ku2\ holds. depend on the ordering scheme of the lattice vacancies. The magnetocrystalline anisotropy of typical uniaxial compounds will be described here. which have the easy axis parallel to the c-axis. 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. The anisotropy constants measured for a polycrystalline material with the c-axes aligned parallel are X nl = 9.

because of its higher crystal symmetry.52 The exact nature of the variation depends on the annealing of the alloy. 10.32 shows the composition dependence of K^ of Fe alloys with the . The origin of the cubic anisotropy is not as clear as the uniaxial anisotropy. because many higher-order terms caused by various mechanisms can contribute to this anisotropy.1). Some of the experimental results will be summarized below. The anisotropy constant K1 of Fe-Al alloys decreases monotonically with the addition of nonmagnetic Al as shown in Fig. 12. Variation of Xt with composition in Fe-Al alloys (room temperature). (a) Magnetocrystalline anisotropy of 3d transition metals and alloys First we will discuss the anisotropy of iron alloys with body-centered cubic structure. which produces a superlattice as already explained in Chapter 10 (see Fig. 1230. 12. suggesting the formation of the superlattices Fe3Co and FeCo (Fig. cubic anisotropy is smaller than uniaxial anisotropy. (After Hall52) 12.4. Figure 12. The exact form of the decrease also depends on the annealing treatment. The K-t value of Fe-Co alloys also decreases with an increase of Co content. have cubic crystal structures with low cubic anisotropy (see Section 22.2 Cubic anisotropy Generally speaking.3). Therefore most soft magnetic materials. which exhibit high permeability and low coercive force. The value of Kl becomes more negative as the degree of order increases.31).30.284 MAGNETOCRYSTALLINE ANISOTROPY Fig.

55 When the alloy with composition Ni3Fe is quenched from about 600°C. The Ni-Fe alloys with face-centered cubic structures form the Cu3Au-type superlattice Ni3Fe. below which the ordering develops. Variation (After Hall52) of K^ with composition in Fe-Co alloys (room temperature) nonmagnetic elements Ti53 and Si.33. 12. in Fig. The variation of Klt however.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. as shown in Fig. as already discussed in Chapter 8. Variation of K^ with composition in Fe-Ti and Fe-Si alloys (room temperature).32. The ordering temperature of this superlattice is about 600°C.EXPERIMENTAL DATA 285 Fig. is much more steep. the value of K^ increases with the addition of nonmagnetic Ti. . it retains the disordered state. It is interesting to note that in the case of Fe-Ti alloys. 12. 12.31.

Variation of A^ in Ni3Fe as a function of logarithm of cooling rate in the range 600-300°C (room temperature). reflecting the instability of ferromagnetism due to the Invar characteristic57 (see Section 8. 12.2).1). The superlattice Ni3Fe. Fig. (After Bozorth56) .36.27 and Section 22. 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. Figure 12.12). 12. Similar behavior can be seen for Ni-Cr and Ni-V60 in Fig.36). 18.286 MAGNETOCRYSTALLINE ANISOTROPY Fig. and then once again from positive to negative at 20at% Co52'58'59 (Fig. In Ni-Co alloys. during which the superlattice is formed.35 shows the composition dependence of K^ for the ordered and disordered states. with the probability of 3:1. 12.33.56 Figure 12. K^ changes sign from negative to positive at 4at% Co.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. which the lattice sites are occupied by Ni and Fe at random.34. 8. but it increases with increased ordering. The anisotropy constant Kl in this state is very small or almost zero. 12. The Kl values of the Fe-rich alloys containing more than 65% Fe decrease once again with increasing Fe content.56 The alloy corresponding to K1 = 0 is called Permalloy. which exhibits extraordinarily large permeability (see Fig.

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

12. the shape of the ions which occupy A sites. One example is the anomalous behavior of K^ of magnetite or Fe3O4. when Co is added. Mn 2+ and Fe3+.2). Tv. The Fe2+ ions also make a large contribution to the magnetic anisotropy. decreases with decreasing temperature.3.288 MAGNETOCRYSTALLINE ANISOTROPY Fig.38. in which magnetic moments of Fe3+ ions on A sites couple antiparallel to those of Fe3+ and M 2+ on B sites. 12. the crystal transforms to a structure of lower . The magnetocrystalline anisotropy of ferrites is interpreted by the one-ion model as explained in Section 12. As explained there. Figure 12. such as Zn 2+ . (After Slonczewski24) remaining 8 Fe3+ ions and 8 M 2+ ions occupy B sites. Generally speaking. are spherical (see Section 3. 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\. or the Verwey point. It is seen that the contribution of Co2+ ions to K^ is positive for all the ferrites. as as shown in Fig. Mn 07 Fe 2i3 O 4 . Most ferrimagnetic ferrites have the inverse spinel structure. Below about 125 K.37 shows the contributions of Co2+ ions to Kl for Fe3O4. so that these ions do not make a large contribution to the magnetic anisotropy. The value of Kl is negative at room temperature. Temperature dependence of K1 for various spinel ferrites containing Co2+. begins to increase at 230 K and changes sign to positive at 130K. so that only the magnetic moments of M 2+ ions contribute to the net spontaneous magnetization. etc.37. MnFe2O4.

Ku. Let aa. so that the magnetocrystalline anisotropy becomes uniaxial. 12. The electrical conductivity has a similar temperature dependence. Kb. and ac be the direction cosines of spontaneous magnetization referred to the a-. with the same activation energy.39. If the K1 term is converted to the coordinate system for the low temperature phase.23 eV for Ka. and Kab correspond to K^ of the cubic phase.2). the magnitude of these constants should be in the ratio 3:3:10.EXPERIMENTAL DATA 289 Fig.61 The Kl values below Tv were calculated by (12. b-. and c-axes. Then the magnetocrystalline anisotropy energy is expressed as where a m is the direction cosine referred to the longest body-diagonal or [111]. The actual .61 as shown in Fig. was found to be expressed by the Arrhenius equation. It seems clear that this phenomenon is caused by a hopping motion of electrons between Fe2+ and Fe3+ on the B-sites. b-. The a-.77). The higher order constants Kaa.38. ab. The activation energy Q was found to be 0. Temperature dependence of K1 for magnetite (Fe3O4). and c-axes of the low temperature phase are almost parallel to the [110]. Therefore the origin of the magnetic anisotropy of the low-temperature phase is considered to also be related to Fe2+ ions on B-sites. 12. symmetry (see Section 9. The temperature dependence of these anisotropy constants.20-0. [110] and [001] axes of the original cubic structure. Kbb.

which is very close to the prediction. however. . in which some phonons accompanying a charge ordering are softened with decreasing temperature. We can regard the deviation of Klt A/Cj. 12.64 This transition may be a sort of structural transition. Then the Kl value can be calculated by the relationship which is plotted in Fig. 1239. disproved by later experiments.65 Miyata66 measured the temperature dependence of Kl for various mixed ferrites. from the broken curve connecting the points at high and low temperatures as caused by some clustering related to the Verwey transition. various physical quantities are condensed towards 81 K. which extrapolates to the abscissa at 81 K. Temperature dependence of magnetic anisotropy constants for low-temperature phase of magnetite (Fe3O4).6:3.62 The variation of K1 is regarded as one of the critical phenomena associated with this transition. and finally condensed to a low-temperature phase. the reciprocal of hKl is plotted against temperature as a solid line.290 MAGNETOCRYSTALLINE ANISOTROPY Fig.61 It is to be noted that these points fit well with the extrapolation of the K^ vs. This model was.61 ratio observed at 4. As a matter of fact.4:10.2 K was 2. In the same figure.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.62 The low-temperature transition of magnetite was first found by Verwey. T curve above 350 K.38 in the temperature range T < Tv.

EXPERIMENTAL DATA 291 Fig. (After Miyata66) . we see that the anomalous increase of AjSTj observed in Fe3O4 is Fig.40-12. Temperature dependence of K1 for MnFe2O4-Fe3O4 mixed ferrites. (After Miyata66) Figures 12. Ni.41.40. Temperature dependence of K1 for NiFe2O4-Fe3O4 mixed ferrites. 12.42 show the results for Fe3O4 with added Mn. 12. Comparing these graphs. and Zn.

while Fe2+ ions appear as soon as x is reduced from 1. (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. 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.43. Yosida and Tachiki23 summarized the origin of magnetic anisotropy as follows: (1) The contribution from magnetic dipole interaction is small. thus increasing the number of Fe24" ions. Magnetic ions other than Co2+ and Fe2+ do not contribute strongly to the magnetic anisotropy. in which no Fe2+ ion exists. (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. In the mixed ferrites MnJ.68 These facts tell us that the Fe2+ ions on B-sites contribute to a positive K^. The Ni 2+ ions go into B-sites and do not disturb Fe3+ ions on A-sites. whereas the Mn 2+ or Zn2+ ions go into narrow A-sites and change the instability of the lattice.O4. (After Miyata66) not very much influenced by the addition of Ni. If should be noted that mechanisms (2) and (3) are not realized for magnetic ions . 12.1)). as shown in Fig. the composition is MnFe2O4.Fe3_J. because they have ionic sizes larger than Fe+3. while this anomaly is completely suppressed by the addition of Mn or Zn. 12. the K1 value becomes more positive as soon as x is reduced from 1. they go into B-sites.42. A large positive shift of Kl was observed by this addition.292 MAGNETOCRYSTALLINE ANISOTROPY Fig. Temperature dependence of Kl for ZnFe2O4-Fe3O4 mixed ferrites. When Ti4+ ions are added to Fe3O4.67 For x= 1.

Fig. the 3d shell is deformable. For instance.44.44 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. 1 and f. (After Penoyer and Shafer67) with S = \.3_. In the case of Mn 2+ and Fe3+ with 3d5 (S = f).43. 12. Ni 2+ with 3d8 (S = 1) and Co2+ with 3d1 (S = f ) do not develop magnetic anisotropy from these mechanisms. Variation of Kl for MnxFe. Figure 12.23 We see that the agreement is excellent. 12. because these magnetic shells do not deform.EXPERIMENTAL DATA 293 Fig. Temperature dependence of Kl/Is for MnFe2O4 and the comparison with theory (solid curve).

(After Hansen69) (c) Magnetocrystalline anisotropy of garnet-type ferrites The details of this class of oxide have been described in Chapter 9. so that there is no electron hopping. with their spins antiparallel.70 . 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. Temperature dependence of K^ and K2 for YIG (Y3Fe5Oi2). 12. Since the Fe3+ ion has 5MB (Bohr Fig. 12. Temperature dependence of Kl for Sm 3 Fe 5 Oj 2 . Dy3Fe5O12 and Ho3Fe5O12.45. thus exhibiting ferrimagnetism. All the metal ions are trivalent and no divalent ions exist. The Curie point is 540-580 K. Five Fe3+ ions in a formula unit of R3Fe5O12 occupy 24d and 16 a lattice sites in the ratio 3:2.46.294 MAGNETOCRYSTALLINE ANISOTROPY Fig.

39 -0.3 ) -0. R3Fe5O12.3 ) -0.0005 21 Sm -400 -14.7 +500 Er 4.9).EXPERIMENTAL DATA 3+ 295 magnetons).05 +90 +0.14 -2. (10 5 ergcm. since the interaction between R3+ and Fe34" moments is weak.06 -0. and a contribution from R3+ ions.41 -0. these five Fe ions contribute 5MB to the resultant magnetic moment per formula unit at OK. 9. the contribution of the R 3+ moment decreases rapidly with increasing temperature.06 .2 80 320 80 300 80 300 4.021 -0. However. measured at various temperatures. the spontaneous magnetization of most garnet-type ferrites exhibits the N-type temperature dependence (see Fig.6 -0.44 -0.010 -76 Gd 4.36 -0.3 -0.56 -0. In other words.037 -0.2 77 295 4. and is compensated by the Fe3+ moment at a particular temperature called the compensation point.22 -0.023 -0.05 -120 -8 < -0. the magnetic moment of three R3+ ions on the 24c sites couple with this resultant Fe moment ferrimagnetically.5.(10 5 ergcm.06 -67 -0.06 K2 (104 JnT 3 ).082 -9. In addition.06 2. Magnetocrystalline anisotropy constants of garnet-type ferrites. because Y has no magnetic moment.70 R Y T(K) 4.2 80 300 Tm Yb ~0 +80 +0. Figure 12.2 77 300 77 293 4.25 -0.035 -0.7 < -0.2 77 295 4.45 shows Table 12. thus producing a large spontaneous magnetization at OK.30 -0.2 78 300 -2.17 -4 -0. The magnetocrystalline anisotropy of the garnet-type ferrites is composed of two parts: a contribution from Fe3+ ions.2 293 K1 (10 4 Jnr 3 ). The former contribution can be found experimentally by measuring the anisotropy of yttrium-iron-garnet or YIG.38 Eu -1.041 Tb Dy Ho -7.

12.1 X 105 Jm~ 3 . J. Phys. calculate the anisotropy field in the c-axis for cobalt. In contrast to this. Yamada and S. Instr. 15 (1976). 17 Suppl. Tajima. as shown in Fig. J.3 Assuming q = 3 X 10 ~ 25 J. Japan. R. 12.2 Knowing the values for 7S = 1. M. 8. 309. Soc. 4. The reason for this large contribution of R3+ is that the orbital moment becomes aligned with decreasing temperature.. T. 12.) (in Japanese). and K. 132-3. Phys. 1975. Jr.44. K. . Kouvel and C. /. S. Chikazumi. S. 711. /. is quite large and has a strong temperature dependence. No. 1964). thus giving rise to a large interaction with the crystalline field. 12. Phys. 477. 20 (1959). Kotai Buturi (Solid State Phys. Hofmann. 623. Ignore terms higher than K2. 13. 3. the magnetostriction constants (see Chapter 14) are also very large.5 lists the values of K^ and K2 at a number of temperatures for various garnet-type ferrites. R. (1970). T. J. Series in experimental physics (in Japanese). J. Japan. S. Chikazumi.71 and affect these anisotropy constants to a great extent (see Section 14. Grenoble Con/. Appl. 30 (1959). S. Penoyer. in volume quoted in Ref. /. what functional form should be expected for angular dependence of the anisotropy energy? Use the Zener-Carr formulation. Chikazumi. 12. 29 (1968). which has an orbital angular momentum L. Gengnagel and U. Abe and S. 17 (Kyoritsu Publishing Co. p. Physics of Magnetism (1st edn) (Wiley. and G. Graham. 11 (1956). 321 in volume quoted in Ref. Phys. 179. H. Appl. 91.6). above. 10. the contribution of R 3+ . 495. The origin of this anisotropy is the same as that of Fe3+ ions in the spinel-type ferrites. B-I (1962). 5. 39 (1968). Franse and G. Soc.4 If the temperature dependence of an anisotropy constant were the same as that of spontaneous magnetization. Physica. 9 (9). Japan. New York..296 MAGNETOCRYSTALLINE ANISOTROPY the temperature dependence of K1 and K2 of YIG.. Radium. 2. 4 above. C-I.1 When the magnetization is rotated in the (210) plane in a cubic crystal. so that they exhibit a monotonic temperature dependence similar to that in Fig. de Vries. Stat. Barnier. Chikazumi. Rimet. 306 in volume quoted in Ref. Y. Sol. Phys. Rev.. 9.. calculate the magnetocrystalline anisotropy constant Kl for a ferromagnetic metal with body-centered cubic structure (a = 3 A). 293-325. Pauthenet. 12. 13. PROBLEMS 12. S. D. pp. Phys. 409. Phys. 718. 340. 6. 15 (1960). 28 (1957). 4 above. In some cases. express the anisotropy energy as a function of the angle 9 between the magnetization and the [001] axis. Wakiyama and S. Table 12. Chikazumi. Proc. (1974). Toyama. Sci. F. p. Chikazumi. using the spin-pair model. Chikazumi.46. J. F. Japan. Soc. 7. REFERENCES 1. R.79T and Kul = 4. 1968). K. 11. Pearson. pp. 4. J.

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

979. Penoyer and M. 65. School Phys. Verwey and P. Chikazumi. W.298 57. Belov. Sou. W. Phys.. 1476. Rev. W. Y. 50 (1936). S. /. 61.. Soc. 71. F. 29 (1975). Chikazumi. Shiratori and Y. R. Shirane. 64. /. L. Rev. M. 20 (1980). 87. Shih. Japan. LXX (1978). 947. A. . 41 (1976). 68. Fujii. Geophys. 59. Soc. J. A. 67. N. 376. 41 (1975). and S. Physica. Pearson. 15 (1960). 48 (1980). F. Abe. MAGNETOCRYSTALLINE ANISOTROPY H. Miyata. 56. S. K. Phys. 4 (1965). Wakiyama and S. Phys. Japan. 66. 117. 51 (1937). Haayman. Akimitsu. J. Proc. Phys. 63. J. Popov. 62. Levitin. 70. Mat. Soc. Hansen.. F. Chikazumi. 58. Phys. and Yu. P. 1894. Z. Chikazumi. K. Japan. Jap. 16 (1961). 69. McKeehan. 30 (1959). 39 (1975). 1291.. Japan. No. Proc. Matsui and Y. T.. Appl. 1236S. G. 8 (1941).. J. JETP. Enrico Fermi. Syono. /. Soc. P. Phys. W. Phys. Japan. 136. W. 71. 33 (1962). Phys. Mag. J. /. Shafer. Kagawa and S. Y. AIP Con/. App. Gapeev. Chiba. K. Miyamoto. Phys. E. Chikazumi. Kino.. Int. 315S. S. K. /. Soc. /. 1975. K. Phys. J. Markosyan. R. 382. R. Mag. 60.

5 Permalloy which was cooled from 600°C (A) in a longitudinal magnetic field.1.1 shows the effect of magnetic annealing on the shape of the magnetization curve of a 21. The effect was first observed by Kelsall1 in Fe-Ni alloys. Curves A and C are measured after annealing in a magnetic field applied parallel and perpendicular. 13. but local easy axes were produced parallel to Fig. no field was applied during annealing. 13. This behavior can be attributed to an induced anisotropy whose easy axis is parallel to the direction of the annealing field. Figure 13. In the case of curve B. We shall discuss various types of induced anisotropy in this section. (B) in the absence of magnetic field.5% Fe-Ni alloy. and was investigated by Dillinger and Bozorth2 in detail.7 .1 MAGNETIC ANNEALING EFFECT The magnetic annealing effect is obtained by heating or annealing a magnetic material in an applied field. in that the induced anisotropy is produced by a treatment (often an annealing treatment) that has directional characteristics. Magnetization curves of 21. respectively. to the direction along which the magnetization curve is measured. and (C) with perpendicular (or circular) magnetic field.13 INDUCED MAGNETIC ANISOTROPY The induced magnetic anisotropy differs from the ordinary magnetic anisotropy discussed in Chapter 12. Not only the magnitude but also the easy axis of the anisotropy can be altered by appropriate treatments.

and AB pairs. and AB.9 The curve form is quite monotonic. This alloy. The directional order model was then reinterpreted in terms of atomic pair interactions whose magnitudes are different for different pairs. We ignore pair interaction terms higher than the quadrupole interaction. are different from one another. 14. This behavior is different from other magnetic alloys. It was discovered by Arnold and Elmen3 in 1923 that Ni-rich Ni-Fe alloys exhibit very high permeability. was investigated by many researchers with inconclusive results. Chikazumi7 found that the induced anisotropy tends to disappear as the alloy approaches the fully ordered state. and /AB. We assume that the coefficients of the dipole-dipole interactions (see (12. From the average susceptibility of curve C. Both models explained the fact that the induced anisotropy disappears when complete ordering is developed. Before going into details of this phenomenon. In a binary A-B alloy there are three kinds of atomic pairs. has unusual annealing behavior: high permeability is attained only when the alloy is quenched from high temperatures. Based on the fact that complete ordering decreases the specific volume of the alloy by 5 X 10"4. The open circles in Fig. This puzzle. reaching a maximum at a composition of 21. while the ordered phase model predicts a maximum at the Ni3Fe composition. the uniaxial anisotropy constant of the induced anisotropy is estimated to be 1 X 102 JnT 3 . let us describe the history of this alloy.24)). or Ni-Fe. and explained the induced anisotropy as the result of shape anisotropy of the second phase (see (12. Kaya8 assumed that ordering occurred by the growth of distinct volumes of the ordered phase. and nearly quadratic with respect to the Fe composition.9"11 We discuss the problem using the formulation first given by Neel.2 represent the maximum values of induced anisotropy constant observed after field cooling from 600°C at various cooling rates. as a function of Ni content in Fe. He tried to explain this phenomenon in terms of 'directional order'. where the degree of order is maximum. 1BB. because the strain model predicts a minimum at about 80% Ni where the magnetostriction constants go through zero (see Fig. Fe-Fe. This result conflicts with both the models. It was found that the order-disorder transformation takes place at about 490°C. 12.59)) of AA. he assumed that the length of an Ni-Fe pair is smaller than the length of other possible atomic pairs. most of which show improved soft magnetic properties after slow cooling or annealing. BB.300 INDUCED MAGNETIC ANISOTROPY the direction of spontaneous magnetization in each magnetic domain during annealing. BB.11). or an anisotropic distribution of different atomic pairs such as Ni-Ni. Then the anisotropy . given by l^. Slow cooling or annealing at intermediate temperatures greatly lowers the permeability. known as the 'Permalloy problem'. and Kaya5 investigated the process of formation of the superlattice in relation to changes in magnetic properties. The structure of this superlattice is shown in Fig. called Permalloy. Then directional ordering causes lattice distortion.5wt% Fe-Ni. 13. Later Dahl4 proved the presence of a superlattice in Ni-Fe alloys. and a long annealing time (about one week) at this temperature is required to attain the equilibrium state. where the ordering process starts. On the other hand. Tomono6 discovered that magnetic annealing is effective at 500°C.33. AA. which can produce an induced anisotropy through the magnetoelastic energy.

where z is the number of nearest neighbors. BB and AB pairs directed parallel to the ith direction. and NABi are the number of AA.MAGNETIC ANNEALING EFFECT 301 Fig. The total number of A sectors is also given by zA^. 13. where A^ and A^B are the total number of AA and BB pairs. 13. an AA pair has two A sectors. Thus the total number of A sectors is given by 2NAA + NAE. Note that A^..3): if we divide each atom into z sectors.1) where i denotes the pair directions. and A^Bi are not independent variables.. Nmi. for the following reasons (see Fig.2. Thus the total number of A sectors attached to the atomic pairs with the ith bond direction is where z is replaced by 2.9 energy due to an unbalanced distribution of three kinds of atomic pairs over differently oriented pair directions is (13. NBBi. and <pf is the angle between the magnetization and the ith bond direction. and attach each of these sectors to one nearest-neighbor bond. whereas an AB pair has one A sector. 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. A^. because each A atom has just two sectors attached to bonds in a single direction.

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

6).9) is expressed as . when we expand the exponential function. these atom pairs are locked in place. and they give rise to magnetic anisotropy which is calculated by putting (13. which depend on the crystal structure. their numerical values are listed in Table 13.MAGNETIC ANNEALING EFFECT 303 where AfBB is the total number of BB pairs. (13. as in which Putting we have the constants kl and k2. If 1'0 •« kT.8) into (13. (13.1.7) becomes After the alloy has been quenched. Using these constants.

304 INDUCED MAGNETIC ANISOTROPY Table 13. If /„ has the same sign as /'0. Values of k1 and k2 for various crystal types (cf. (13. which will be treated in Chapter 14. the . Crystal type Isotropic Simple cubic Body-centered cubic Face-centered cubic kr ^y | 0 -^ k2 3j 0 f -^ For an isotropic material. (13. Since the numbers of AA. hence where N is the total number of atoms per unit volume. the magnetostriction constants A100 and Am are related to the dipole interaction. the anisotropy constant becomes negative.11) becomes where <p is the angle between the magnetization and the direction of the annealing field. C| and 2CACB. As a matter of fact. the probability of finding BB pairs is proportional to CB.15). the average value of / is As we discuss in Chapter 14.10)). Neel estimated the values of Ij^. respectively. On using (13. BB. we can express the anisotropy constant as The composition dependence of this expression explains the experimental result shown in Fig. so that these magnetostriction constants of A-B alloys are also expected to change in a way similar to (13. where CB is the concentration of B atoms. and the easy axis develops parallel to the annealing field. / BB and 1AB from the composition dependence of magnetostriction constants. For a dilute and disordered solution of B atoms in a matrix of A. and AB pairs in disordered alloys are proportional to C\.2.1.13). 13.

is much smaller than the value at room temperature.38 X 10~23 JKT 1 . where /s is 0.50 T. 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 .12 These energy curves are obtained by integrating torque curves with respect to the angle.73)).18) is large enough to explain the experimental result. can be fitted with parabolic curves. and are then separated by Fourier analysis into the cubic crystal anisotropy and the induced uniaxial anisotropy energy curves. whereas it tends to deviate toward (111) for intermediate directions of the annealing field. is estimated from the value at room temperature given by (13.7 X 106 JnT 3 .50). shown in Fig. Figure 13. Using the 7S3 law (see (12.17). Using z = 12. k = 1. Denoting Ni as A. the value of 10.MAGNETIC ANNEALING EFFECT 305 composition dependence of these constants. 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.11) shows that the magnitude of the induced anisotropy depends on the crystallographic direction of the annealing field. and Fe as B. /FeFe and / NiFe . so that we have This formula will be described in detail in Section 14. less effective for (110>. The relationship (13.13)3 = 2. To compare experiment with theory. This figure also shows that the minimum point coincides with the direction of the annealing field for the three principal axes. the value l'Q at 700 K.14) as Since the experimental curve shown in Fig. Af=9.4 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. we can estimate the values of / NiNi . where Is is 1. Ku is calculated by (13.13 T.50/1. 14. we get the expression Using (14. 13.17Xl0 2 8 m" 3 . 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.2.2 is expressed as the coefficient given by (13. It is seen from these curves that magnetic annealing is most effective for (111) annealing.0 X 107 X (0. and least effective for (100>. At the temperature at which the alloy is normally annealed.11. or 1'0. as Nl'0 = 3.

20) and (13. 13. This agrees qualitatively with the experimental results. The deviation of the minimum point of the energy curve. In order to fit the theoretical curve to the experiment quantitatively. for three principal directions of the annealing field. On comparing (13.5. however.6.11) with the parameters deduced from the best fit to the experimental curve B. The solid curves B in Figs. not satisfactory. in Fig. 13.1. 13.5. however.11) we have.4 and 13.5 . we find that k ^ : k2 = 1:8. 6.. A0.11) and qualitatively explains the experimental curve B.4. Quantitatively. 13. Curve A is the theoretical curve deduced from (13.306 INDUCED MAGNETIC ANISOTROPY Fig.12 the minimum point. the experiment shows a larger directional dependence. Curve A is the theoretical curve deduced from (13. as shown in Fig. Magnetic anisotropy energy induced by magnetic annealing of a (110) disk of Ni3Fe. The agreement is. we find that the ratio of the Ku should be 2:3:4 for the three principal axes. is plotted as a function of 8. On putting into these formula the theoretical values of k1 and k2 listed in Table 13. from the direction of the annealing field.

13. Induced anisotropy constant as a function of crystallographic orientation of the annealing field.2. They found that the material responds to magnetic annealing only when it is more or less oxidized.P. which measures the quality of a permanent magnet material. their results are listed in Table 13. That is. 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).21 who found that the coefficients of the first and second terms. The values of the ratio k1: k2 have been measured by several investigators12'16 for a number of alloys. Single crystal experiments were made for the same system by Penoyer and Bickford. even for face-centered cubic alloys. have different composition dependences.12 are drawn using this ratio. which have been used as oxide permanent (O..18 Magnetic annealing has been found to be effective also for some ferrites. as shown in Fig. 13.9 to 9. In other words. For further details refer to Ferguson17 and Iwata.7). The induced anisotropy was measured for Fe-Co ferrites by lida et al. such as Co ferrites.8.19 This annealing has been used to improve the (5//)max or energy product.5.6. 13. The values for body-centered cubic Fe-Al alloys are also quite different from the theoretical ratio of 0:1. the magnetic annealing of ferrites is effective only in the presence of lattice vacancies.) magnets.MAGNETIC ANNEALING EFFECT 307 Fig. F and G. or k1 and k2 times the proportionality factor outside the parentheses in (13.20 who discovered that the effect is sensitive to the partial pressure of oxygen during cooling (Fig. F increases as the square of .

4 1:1 Investigator Chikazumi12 Aoyagi eta/. If all the Co2"1" ions are distributed equally along the four equivalent (lll)s.14 Aoyagi etal.3-2. this unbalanced distribution of Co2"1" ions results in an induced anisotropy.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. When this ferrite is cooled in a magnetic field. *i:*2 Material Polycrystal Ni3Fe 20%Co-Fe 12.u Aoyagi etal. 13. Since the axis of the uniaxial anisotropy of Co2+ ions is parallel to (111). the Co2"1" ions tend to occupy the octahedral sites whose (111) axis is nearest to the magnetic field. Theoretical and experimental values of the ratio kl:k2.0 1:2.2.6 1:1.308 INDUCED MAGNETIC ANISOTROPY Fig.9-2.69)). The doublet thus produced gives rise to a uniaxial anisotropy with its axis parallel to (111) (see (12.6. whose energy levels are split as shown in Fig. Angle of difference.u Suzuki15 Chikazumi and Wakiyama16 . the F or kl Table 13.3-9.12 the Co content.20(c).13 Aoyagi et a/. between the direction of annealing field and the easy axis of the induced anisotropy as a function of crystallographic orientation of the annealing field.6 1:3. so as to lower the anisotropy energy. the uniaxial anisotropies cancel out because of the cubic symmetry. while G increases linearly with the Co content. A0. Slonczewski22 explained this behavior in terms of the one-ion anisotropy of the Co2+ ion on the octahedral sites. After cooling. 12.4 1:8.5 1:3.

which has constant permeability over a wide range of applied fields.8. This explains the linear dependence of the G term on the composition.ROLL MAGNETIC ANISOTROPY 309 Fig. whose composition is 50% Fe-50% Ni. 13.20 term should vanish just like the directional order in the body-centered cubic lattice. then recrystallized to give a (001)[100j crystallographic texture. The presence of lattice vacancies is assumed to speed the diffusion of ions. 13. This alloy. they produced a new magnetic material called Isoperm. Effect of magnetic annealing of Co-Fe ferrites under various partial pressures of oxygen.23"25 Oxidation was also found to be necessary for the magnetic cooling of Ni-ferrites. Magnetization . This one-ion induced anisotropy should be proportional to the available number of Co2+ ions. 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.2 ROLL MAGNETIC ANISOTROPY It was discovered by Six et al.27 in 1934 that a large magnetic anisotropy is created during the process of cold-rolling iron-nickel alloys. and finally cold-rolled again to about 50% reduction in thickness.7. The quadratic composition dependence of the F term was ascribed to directional ordering of the Co2+-Co2+ pairs. is first strongly cold-rolled. as seen in Fig.26 13. Actually the F term is very small compared with the G or k2 term. Utilizing this effect.

Fig. Magnetization curve and domain structure of Isoperm. Variation of coefficients F and G (which are proportional to kl and fc2.28 in 1940. 13. They concluded that this anisotropy cannot be explained in terms of the coupling between magnetostriction and internal stresses.310 INDUCED MAGNETIC ANISOTROPY Fig.9.9). and by Rathenau and Snoek29 in 1941. Detailed investigations of this phenomenon were made by Conradt et a/. giving rise to a linear magnetization curve (Fig. 13. .8.21 parallel to the rolling direction takes place exclusively through domain rotation. respectively) with change in Co content in Co-Fe ferrite. 13.

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

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

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

which is Using (13.11(a). The anisotropy energy is expressed as Table 13. the roll magnetic anisotropy in this case is calculated as and .34).n3) are the direction cosines of the normal to slip plane of the z'th system.is the short-range order parameter. Assuming these two kinds of anisotropy. type). The anisotropy given by (13. provided that /0 > 0. 2. the atomic relation between the two sides of the slipped plane becomes disordered. The number of BB pairs produced in a unit area of the slipped plane is where a. a3) for all the slip systems. we observe slip bands as shown in Fig. a 2 .11(b)). signifying an abundance of BB pairs and thus rendering the hard axis normal to the slip plane. 13. We call this type of anisotropy short-range order (fine-slip) type (S.n3i) and the coefficients in each term of &(«!. In the case of rolling on the (110) plane in the [001] direction. 5 contribute to the roll deformation (see Fig. we can deduce the relationship between rolling reduction r and the slip densities st.314 INDUCED MAGNETIC ANISOTROPY PY in other words. 4. The comprehensive explanation for this is that.n2i. 13. we can explain all the experimental facts for rolled single crystals. By a simple calculation.n2.4 lists the values of (nlt. when only short-range order prevails in the crystal. which proves that the slip systems 1. if slip takes place in a crystal with short-range order. The average anisotropy of these three BB pairs is given by where (nl.30) is a uniaxial anisotropy with the axis normal to the slipped plane.C.

type) of anisotropy for each slip system (see (13. The effects of heat treatment will be explained later. or (110). the anisotropy grows monotonically. a^) in the expression for short-range order-coarse slip type (S. Of siip system 1 2 3 4 5 6 7 8 9 Coefficients in g(a 1 .33)). but at high reductions it tends to decrease again. If we measure the anisotropy in the rolling plane.4. With increasing reduction in thickness by rolling. In other words. (13.( a i> a2.36) shows that the S. Equation (13. This is probably due to the destruction of ordering by severe rolling. the observed Ku is negative.a 2 .F.12 shows the variation of Ku produced by (110)[001] rolling. As expected. No.C.C.ROLL MAGNETIC ANISOTROPY 315 Table 13. a3 ) nj n2 n3 a a 2 3 a 3ai a a \ 2 10 11 12 In the case of Fe-Ni alloys. which have a positive /0 as given by (13. Figure 13.17). the plane perpendicular to the rolling direction becomes an easy plane. both types result in an easy axis perpendicular to the rolling direction. type has the hard axis parallel to the z-axis.35) shows that the L. . Direction cosines of the normal to the slip plane and the coefficients of each term in g. type has the easy axis parallel to [110].

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. it is possible that four slip systems contribute to the deformation. 13. Then the maximum shear stress acts on a slip plane tilted 45° from the rolling plane. the same as for (110)[001] rolling. In the case of (001)[110] rolling. Fig.31 . in the case of (110)[001] rolling.12.11(a)). as verified by the observation of slip bands on the side surface of the rolled slab (see Fig. the slip plane makes an angle of 35. 13.11.5° with the rolling plane. 13. This kind of slip is called easy glide.316 INDUCED MAGNETIC ANISOTROPY Fig. operate. Actually. the slip plane rotates and its tilt angle approaches 45°. which encourages continued slip on the active slip system.13(b)). 13. 13.13(a)). Variation of the uniaxial anisotropy constant of roll magnetic anisotropy with the progress of (110)[001] rolling Ni3Fe crystal. In contrast. 13. This kind of slip is called cross slip. 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. The slip plane in this case makes an angle greater than 45° from the rolling plane (see Fig.13(a)). or 4 and 5 (see Fig. 1 and 2. (a) Slip bands and (b) slip systems for (110)[001] rolling. only two of the slip systems. however. As a result of the rolling deformation.

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

Therefore dislocations tend to occur in pairs in an ordered alloy. Variation of the uniaxial anisotropy constant due to roll magnetic anisotropy with the progress of (001)[110] rolling Ni3Fe crystal. If.27) decreases as S increases.14. the easy axes of the resulting grains may be aligned to some extent parallel to the magnetic field. This treatment can be applied to Alnico to improve its permanent magnet .318 INDUCED MAGNETIC ANISOTROPY Fig. 13. by Chin. however. in which elongated precipitate particles are aligned by a magnetic field during the precipitation process. In other words.33 Takahashi34 used electron microscopy to observe dislocations produced by compression. First we treat the induced magnetic anisotropy of precipitation alloys.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. and investigated their relationship to the created magnetic anisotropy. This results in a net macroscopic induced anisotropy in the material. such as wire-drawing. The roll magnetic anisotropy was measured also for body-centered cubic alloys. p0 and therefore p in (13.32 This kind of investigation has been extended to other kinds of cold-working.31 second following dislocation. so as to make the stacking disorder between the pairs as short as possible. crystal growth or a phase transformation takes place at a temperature below the Curie temperature. keeping Sp0 nearly constant. 13.

v).CRYSTALLOGRAPHIC TRANSFORMATIONS 319 characteristics.15 show elongated precipitates in field-cooled Alnico. in addition to Fe. the shape anisotropy should disappear. when the surface is a {111} plane.3.1 Induced magnetic anisotropy in precipitation alloys In 1932 Mishima35 invented a very strong magnet called MK steel. When the precipitate particles are densely packed as in Fig. 13. or Fe3O4.24) should be replaced by a function which has the general behavior of v(l . It is also observed that ferrimagnetic garnets exhibit growth-induced anisotropy with the easy axis normal to the surface. Then if v becomes 1. we cannot ignore the magnetic interaction between particles. The difference between the last two cases is that the cobalt transformation requires the physical displacement of atoms. Ni. This alloy transforms to a superlattice with tetragonal crystal structure during neutron irradiation. Therefore the spontaneous magnetization is different in the two phases. but the precipitates contain more Fe and Co. an induced anisotropy is observed when polycrystalline cobalt is cooled through the transformation temperature in a magnetic field. At the opposite extreme. while the matrix contains more Ni and Al. and is weakly magnetic or nonmagnetic. meaning that the entire sample consists of the precipitate phase. changing the ionization state of both ions. the anisotropy should be proportional to the precipitate volume. and a uniaxial anisotropy is induced if a magnetic field is present during irradiation. A similar phenomenon is observed for magnetite. this alloy consists of Al. Photograph (a) shows a cross-sectional view and (b) a side view of the elongated precipitates. and are ferromagnetic. As suggested by its name. 13. if v is very small.40) . 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. Both the precipitates and the matrix have bcc structures. and a shape anisotropy as given by (12. The electron micrographs of Fig. which is known as Alnico 5 in Europe and the United States. Jones and Emden37 applied this procedure to Alnico and obtained a rectangular hysteresis loop with a large value of (5//)max.24) is produced. and Co. Therefore v in (12. The anisotropy constant in this case is given by (13. at least over small distances. whose crystal structure changes from cubic to a lower symmetry at about 125 K. It is observed that the precipitates are always elongated parallel to the (100) direction which is nearest to the field applied during cooling. 13.15. A third case is the phase transformation in cobalt metal from fee to hep (with uniaxial anisotropy) at about 400°C. Let v be the volume fraction of precipitates. 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. 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. but it separates into two phases by precipitation below 900°C. Above 1300°C it consists of a homogeneous solid solution with bcc crystal structure. while the magnetite transformation takes place purely by the transfer of electrons from one ion to another (electron hopping).

In this case the magnetostatic energy is increased by the fluctuation in composition if the fluctuation occurs along the direction of magnetization. the precipitation results in a change in lattice constant. This can result in a special kind of precipitation. and if the Curie point depends strongly on the composition. In the commercial heat treatment of Alnico 5. the alloy is first annealed for 30 min at 1250°C to produce a homogeneous single phase structure. precipitation occurs if the free energy of the system decreases when an atom is transferred from the matrix phase to the precipitate phase. respectively. the local saturation magnetization will vary strongly with the local composition and therefore with position.13 MAm" 1 (1600Oe): (a) cross-sectional view. In general. a fluctuation in composition perpendicular to the direction of magnetization will not affect the magnetostatic energy. (b) side view of the elongated precipitate particles. however. the second derivative of free energy with respect to concentration must be negative.6 wt% Al. and then cooled slowly from 900 to . The mechanism of growth of the precipitate particles was explained by Cahn38 as spinodal decomposition. If spinodal decomposition occurs near the Curie point of an alloy. 5wt% Ti. 3wt% Cu. However.39 where 7S and 7S' are the saturation magnetization of the matrix and the precipitate phases. This precipitation process is called spinodal decomposition. 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.1 wt% Si. If. 6. and results in a very regular. quenched to 950°C to prevent the precipitation of the fee gamma phase. Therefore in order to initiate precipitation. an increase in elastic energy will oppose the process of precipitation. Electron micrographs of Alnico 8 (36wt% Co. 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.320 INDUCED MAGNETIC ANISOTROPY Fig. 0. and Nz is the demagnetization factor (along the long axis) of an isolated precipitate particle. 13.15. For this reason the precipitate particles are elongated only along the direction of magnetization. 14wt% Ni. small-scale precipitate structure. balance Fe) annealed at 810°C for lOmin in a magnetic field of 0.

5. During these magnetic heat treatments many small precipitate nuclei are produced.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]. The magnitude of ^u decreases as /3 increases from 0 to 45°. the precipitates continue to grow in an anisotropic way even without the presence of a magnetic field.1. The magnetocrystalline anisotropy of this material determined by magnetization . respectively.2 . 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. the easy axis of the induced anisotropy deviates by an angle a which is always less than /3 as shown in Fig.CRYSTALLOGRAPHIC TRANSFORMATIONS 1 321 700°C at a rate of 0.05 and 0. The final size of the particles is somewhat less than about 1000 A long and 100 A in width..16. for i =x. This results from the fact that the long axis of the precipitates approaches the nearest (100). y and z. d = 200-600A.12MAm'1 (1500 Oe). where i represents x. It was discovered by X-ray diffraction that the crystal had divided into three regions. l/d = 3-5. 0. The degree of order. and each occupying a different volume fraction vt. determined by X-ray diffraction. and also requires an increase in elastic energy.2 Induced anisotropy produced by neutron irradiation It was discovered by Pauleve et al. This heat treatment is called aging. y or z.05. each with its tetragonal c-axis parallel to one of the original cubic [100]. so that the increase in elastic energy is smaller when the precipitates elongate parallel to (100). A single crystal disk cut parallel to (Oil) was irradiated at 295°C by 1. were 0.01. For Alnico with higher Co content.21 ± 0. 5. also may vary between the three regions.21 + 0.3. 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. This is partly due to the development of an irregular geometry of the precipitate particles. Ku = (1. The long axis of these precipitates is parallel to the (100) direction which is nearest to the direction of the applied magnetic field. In one case.32 + 0.39 The magnetic anisotropy thus produced is hardly changed by further aging with a magnetic field applied perpendicular to the easy axis. the magnetic heat treatment is performed at 800-820°C.41 that neutron irradiation of 50 at% Fe-Ni alloy results in the formation of a tetragonal CuAu-type superlattice. Once the precipitate nuclei have formed.7.3 Ks' in a magnetic field stronger than 0. Iwama et al.6) X 105 Jin" 3 for v = volume fraction of precipitate = 0. [010].40 observed that a slower cooling rate gave larger induced anisotropy and also large dimensional ratio (length //diameter d) of the precipitate particles. 13. This formation of precipitate nuclei is most effective at a temperature just below the Curie point of the precipitate phase. or [001] axes. The reason for this is that the elastic modulus is smaller along (100) than along (111). 13. because any change in particle shape requires diffusion of atoms over long distances corresponding to the particle size. The values of u.1-0. 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].

of the easy axis from [100] as functions of the angle ft between the magnetic field applied during cooling and [100].3 X 106ergcm"3).16. but when the magnetic field is in some other direction. The values from magnetization curves are . and 20%. which makes [110] a hard axis.40 curves was found to have the easy axis parallel to [100]. These values. This reasoning is similar to that of the torque reversal discussed in Section 12.5Ks"1 in a direction ft from [100]. When the external field is parallel to [100]. which are deduced from magnetization curves. so that the spin distribution is determined by a balance of the local magnetocrystalline anisotropy. and the magnetostatic energy. the external field energy. and the angle. and the hard axes parallel to [110]. a. The anisotropy constant.2 X 106ergcnT3) and K^ = 2. [010]. The uniaxial anisotropy constant. all the spins are also aligned parallel to [100]. Ku. respectively. the exchange energy. The anisotropy constants were determined to be Kul = 3.322 INDUCED MAGNETIC ANISOTROPY Fig. 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. and finally annealed for 16h at 600°C. and that the volume fractions of the [100]. and [001] regions are 60%. The anisotropy was determined from torque measurements on a (100) disk of Alnico 5 which was homogenized for lOmin at 900°C. it was concluded that the size of the ordered regions is about fifty lattice constants. cooled in a magnetic field of 0. 13. As a result of this analysis.64 MA m"1 (8kOe) at a rate of 0.2.2 X 105 J m ~ 3 (= 3. 20%.3 X 105 JnT 3 (= 2. ^ul[010] and ATul[001]. Kul[ of the ordered region with its c-axis parallel to [100] is larger than those of other regions. are slightly different from those deduced from torque curves. the spins will take a transitional distribution.

which is interpreted in terms of the induced anisotropy due to directional order in the binary alloy. at which the phase transformation takes place. the major effect of irradiation in a magnetic field is to alter the volume fractions of the three kinds of ordered regions. . because in this composition range Ku of the hep phase keeps the same sign at all temperatures above room temperature. which is only 7% of the estimated value. because Ku of the hep phase changes sign between the phase transformation temperature and room temperature.3 X 10 4 Jm~ 3 (=2. A large induced anisotropy constant. or by a strong irradiation in space. In either case it is an interesting story.17 shows the dependence of Ku determined in this way.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. the observed induced anisotropy may be far from the final value. so that Ku is extremely small. the induced anisotropy continues to increase with irradiation. 3. The sign of Ku is negative from 100 to 95% Co. there are four possible orientations for the c-axis of the transformed hep Co. Since. rather than to alter the anisotropy constants or the directional order in each region. 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. the phase transformation occurs below room temperature. however. It was also observed that the temperature dependence of the induced anisotropy is proportional to that of the magnetocrystalline anisotropy of pure Co. For compositions below 80% Co.42 Recently it was reported that the ordered phase of 50%Fe-Ni is found in iron meteorites. 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.3x 10 5 ergcm~ 3 ). and depends on composition as C(Co)2C(Ni)2.3. Figure 13.3X 10 5 ergcm~ 3 ). was observed by Graham49 for polycrystalline pure Co after it was cooled in a magnetic field of 0.24 MAm" 1 (= 3000 Oe) through the phase transformation point.44"47 The ordering may have been produced by annealing over astronomical time periods. as a function of Co content in Ni.CRYSTALLOGRAPHIC TRANSFORMATIONSO 3 while those from torque curves are In conclusion. of the single crystal magnetocrystalline anisotropy of the alloy with the same composition.3 X 10 5 Jm~ 3 (=3. The sign of Ku is positive from 95 to 70% Co. The maximum value of the induced anisotropy constant is 2. 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. Based on this experiment. — 2 X 104 Jm~ 3 . Since there are four (111) axes in an fee grain. 13.

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

13. The resulting mixture of two kinds of twinned regions will result in a uniaxial anisotropy with the easy axis parallel to the c-axis.and c-axes are the hard. The magnetocrystalline anisotropy energies in the (110) plane are plotted in Fig. The anisotropy constants observed52 at 120 K.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. b. 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. In order to establish a unique b-axis.28) and obtained the record value of Ku = 1. In addition to the twins with different a-.18 for all the possible twins. If the magnetic field applied during cooling is accurately parallel to one of the (100) directions. b-.3 X 10s J m ~ 3 (= 1. respectively. The crystal axes or a-. However. see Fig.3. are given by where the symbol * indicates values at 4. there is another class of twins. It was found that when a magnetic field is applied parallel to one of the (100) axes during cooling through the transition point. Fe2+ and Fe3+ ions form an ordered arrangement on the B sites.4(b)). b-. both of which are perpendicular to the c-axis. so that no atomic migration is required. observed the same effect for Fe-Co alloys with the double hep structure (ABAC stacking sequence. intermediate.CRYSTALLOGRAPHIC TRANSFORMATIONS 51 325 Wakiyama et al. Since Ka > Kb > 0. the c-axis is established parallel to this (100) as mentioned above. we find that the a-. which is just below the transition point. or sub-twins. and easy axes.54 considered that as a result of this quenching of the electron hopping. the c-axis of the low temperature phase is established parallel to this <100>. and c-axes.75).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. 13. and c-axes of each twin with respect to the cubic axes are listed underneath the graph. The magnetocrystalline anisotropy of this low temperature phase is given by (12.55 No final conclusion has been reached on this point. Verwey et al. but the b-axis becomes parallel to one of the two possible (110) directions. 12. this proposed ordering scheme has been disproved by later experiments. in which .6at% Fe.2 K.3 X 106 erg cm'3) for an alloy of Co-1.

the c-axis tilts by 0.23° or -0.326 l. This is actually the case. The twins thus developed have the c-axis parallel to the (100) which is nearest to the magnetic field during cooling. 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 anisotropy energy for twins 1 and 1' is considerably lower than for the other twins. the anisotropy energies of the twins with dashed numbers (shown by dashed curves) differ slightly from the solid curves for the non-dashed numbers. so that we expect the twins 1 and 1' will develop uniquely. Because of a small difference due to the Ku term.23° out of the z-axis in the z-a plane. where all the indices are referred to the cubic axes.75)) with a different axis and are indicated by a dashed number under the graph. If a magnetic field is applied in the direction 9 = 40° out of the (100> during cooling through the Verwey point.55 These twins have a Ku term (see (12. The dashed curves with dashed numbers refer to sub-twins which have uniaxial anisotropy with different easy axis. The numbers on the curves refer to twins whose axes are shown in the table underneath the graph.Or INDUCED MAGNETIC ANISOTROPY Fig. 13.18. and the fe-axis at 0=90° in the {110} plane .

and twin 1 is uniquely selected.52 Even if the stress is negligible. while twin 1' elongates parallel to [111]. the space between the specimen and the aluminum rings is very small (less than 0.4%). In order to remove the twin 1'. 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. Ferromagnetic resonance absorption curves observed for magnetite at temperatures below the Verwey transition point.CRYSTALLOGRAPHIC TRANSFORMATIONS 327 Fig.19). so that the resonance occurs at a higher field. we can utilize _the difference in deformation of the two twins: twin 1 elongates by 0. 13. The effect of a compressive stress on Ku was estimated by changing the magnitude of the stress. 13. The anisotropy constants given by (13. and was found to be negligible. The peaks at the higher field are due to the original twin.43) were determined for such a squeezed specimen.19.4% parallel to [111].56 containing the c-axis and the magnetic field during cooling. while heating the specimen from -195°C to -181°C (Fig. In a freely supported specimen. He observed a shift of the resonance line of lower fields by applying a magnetic field parallel to a new (100). 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. 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. which has its easy axis perpendicular to the field and contributes a negative anisotropy field. Bickford56 observed this switching phenomenon by means of ferromagnetic resonance. corresponding to the . so that the generation of more than one twin was impossible.

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.20. Switching of the c-axis of the low-temperature phase caused by rotation of magnetization in the (001) plane of magnetite. This means that the change is not caused by changing the magnitude of the anisotropy in each twin.3) containing more than two kinds of rare earth ions sometimes exhibit a uniaxial anisotropy in addition to cubic magnetocrystalline anisotropy. corresponding to the resonance field minus the anisotropy field. as shown in Fig. Yamada showed that the switching occurs at the angle where the anisotropy energies of the two twins become equal.59'60 . 13. This uniaxial anisotropy has its axis parallel to the direction of the crystal growth. He explained this phenomenon in terms of the displacement of twin boundaries. but by the growth of a new twin at the expense of the old twin. which has its easy axis parallel to the applied field and contributes a positive anisotropy field. The peaks at the lower field are due to a new twin. 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.3.58 and is therefore called the growth-induced magnetic anisotropy. The numerical values on the torque curves give the magnetic field in which the torque was measured.5 Growth-induced anisotropy The rare earth iron garnets (see Section 9. as observed through a change in torque curves.5 resonance field plus the anisotropy field. He also found that switching occurs between 77 and 120 K if the nucleus of a new twin is present. so that the resonance occurs at a lower field. The torque changes abruptly when the switching occurs. Yamada57 observed the switching phenomenon by means of a torque magnetometer. 13. 13.328 INDUCED MAGNETIC ANISOTROPY (001) Fig.20.

while the growth direction becomes the hard axis if the film plane is parallel to {100}. 13. so that the magnetization of the particle is forced to align parallel to the direction of the field applied during cooling. the growth direction becomes the easy axis if the plane of the thin film is parallel to {111}. Cobalt metal undergoes no crystal transformation in this temperature range. 13.64 In general.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. photo-induced anisotropy. These are: (1) (2) (3) (4) (5) exchange or unidirectional anisotropy. is grown epitaxially onto gadolinium-gallium-garnet (GGG). when there is a large misfit of lattice parameters between the substrate and the garnet film. 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. rotatable anisotropy. 13. 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 .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. it exhibits a unidirectional (as opposed to a uniaxial) anisotropy. is antiferromagnetic with a Neel point at about 300 K. which covers the surface of Co particles. 6-7/Lim thick. induced anisotropy in amorphous magnetic alloys. but the cobalt monoxide CoO.4 OTHER INDUCED MAGNETIC ANISOTROPIES Here we shall discuss induced magnetic anisotropies other than the categories already described in Sections 13. it was observed by torque measurement that when a thin film of Sm 0 4Y 26 Gaj 2 Fe 3g O 12 (Sm-YIGG). 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. After cooling in a magnetic field down to a temperature well below the Neel point. mictomagnetic anisotropy. When an external magnetic field is applied out of the easy direction as . the larger the difference in size between the two kinds of rare earth ions. which tends to hold the magnetization in the direction of the field applied during cooling.63 If was also observed that in the case of growth plane parallel to {111}.21(a)).4.3. a fairly large uniaxial anisotropy is induced by stresses through magnetostriction.1-13. For instance.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 growth-induced anisotropy.

shown in Fig. the magnetization of the particle rotates and makes an angle 8 with the spin axis of CoO. The dashed curve was observed for the same specimen cooled without magnetic field. 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. 13. 13. The magnetic anisotropy thus produced is called the exchange anisotropy. thus increasing the exchange energy at the surface.22. dashed curve: cooled in absence of magnetic field. depending on the total surface area of the particles and therefore on the average particle size.21.330 INDUCED MAGNETIC ANISOTROPY Fig. 13. Hysteresis loop observed at 77 K for a slightly oxidized Co powder. 13. the hysteresis curve shifts to the left along the abscissa as shown by the solid curve in Fig. Spin arrangement in a Co particle coated with CoO.65 . Solid curve: cooled in magnetic field. The anisotropy energy thus produced has the form The value of Kd is of order 1 X 105 Jm 3. The reason for this shift is that the magnetization of Fig.22.21(b). As a result of this anisotropy.

Therefore if an electron absorbs this light.3 X 10~19 J or 2. 13. 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. It was also observed that a rotational hysteresis (see Sections 12. it has more than enough energy to overcome the normal binding energy that holds the electron in the atom. As described in Section 9.67 Fe-Al. a magnetic anisotropy can be induced.OTHER INDUCED MAGNETIC ANISOTROPIES 331 the Co particle tends to point in the + direction due to the exchange anisotropy.direction. and that the hysteresis does not disappear even in a high magnetic field. One of the photomagnetic effects is photomagnetic annealing. This phenomenon may be useful for some magnetic logic system.68 and Fe^CNij^Mnj). This phenomenon was first observed in yttrium-iron-garnet (YIG) by means of ferromagnetic resonance by Teale and Temple. This induced anisotropy is called the photolnduced magnetic anisotropy.2 Photoinduced magnetic anisotropy By illuminating some transparent ferromagnets in a magnetic field.2 and 18. we find the corresponding temperature to be 24 000 K. and their spins are aligned antiparallel. independent of the direction of the magnetizing field.6) is associated with the torque curve of this material. . If such a shifted hysteresis curve can be obtained at room temperature.1 eV. the magnetic Fe3+ ions in YIG occupy 24d and 16a lattice sites in the ratio 3:2.direction in order to reverse the magnetization into the . [ ] and ( ) signify the 24c.3. so that h v for visible light with a wavelength of 600 nm is calculated to be 3.70"72 Another effect is the polarization-dependent photoinduced effect.69 in all of which some antiferromagnetic interactions exist. it becomes possible to have a material in which the remanent magnetization always points in one specific direction.70 The energy quantum of light of frequency v is given by h v. in which the spontaneous magnetization is stabilized by new ion distributions produced by illuminating an appropriate magnetic material with non-polarized light. When Si ions are introduced into YIG. so that the ion distribution is changed to where x is the number of Si atoms per formula unit. This distribution can be described by the following formula: where { }.65 Exchange anisotropy was also observed in an Fe-FeO system66 and for many ferromagnetic alloys such as Ni-Mn. 16a and 24d sites. they occupy 24 d sites selectively. respectively. thus exhibiting ferrimagnetism. so that an excess field must be applied in the . Equating this energy with kT.4. in which polarized light can selectively excite electrons from the ions on some lattice sites. Nonmagnetic Y 3+ ions occupy 24c sites.

the Fe2+ ion is anisotropic.73 The four 16a sites which are the nearest to the Si4+ ion have their special axis parallel to different (111) directions. A spherical specimen of YIG with added Si is mounted on a torque magnetometer and cooled to 4. the distribution of Fe2+ and Fe3+ ions on 16 a sites is random. The specimen can be irradiated by polarized infra-red light in a magnetic field applied by .23 shows the positions of all the lattice sites in a garnet crystal.73 Suppose that an Si4+ ion occupies the 24d site at the center of the cube. so that if the magnetization is parallel to.24 shows an experimental arrangement for observing the polarizationdependent photomagnetic effect. a 16a site is surrounded by six O 2 ~ ions octahedrally. Position of each sublattice site in the garnet structure. The lattice site from which the electrons are excited is called the photomagnetic center.73 As explained in Chapter 12. 13. but as the temperature is lowered. In other words.332 INDUCED MAGNETIC ANISOTROPY Fig. 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. As seen in the figure.23. It is clear from experiments that this special (111) is the easy axis of the Fe2+ ion on this site. Figure 13.99 A. There are four equivalent 16a sites. while the length of the other edges is 2. Figure 13. say. [111]. the 16a site which has its special axis parallel to [111] is the most stable site for an Fe2+ ion. The shape of this octahedron is considerably distorted: the length of the edge of the face parallel to (111) is 2. Fe2+ ions tend to be attracted by electrostatic forces to Si4+ ions on the 24 d sites. In photomagnetic annealing. anisotropy is induced in the direction of the magnetization during illumination.68 A.2 K in liquid helium. thus increasing the number of Fe2+ ions which have their easy axis parallel to the magnetization. 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. At high temperatures.

45).25. measured from [001]. 13. In other words.45). Lc in equation (13.72 an electromagnet. Lc = 0. <t>. 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. Anisotropy constant.24. Fig.2MAm"1 (= 15kOe) parallel to [001] or [110].72 . When a specimen of YIG with Si content x = 0. of polarization-dependent photomagnetic induced anisotropy as a function of the direction of magnetization during illumination. 13.OTHER INDUCED MAGNETIC ANISOTROPIES 333 Fig. Experimental arrangement for observing polarization-dependent pbotomagnetic effect. the torque curve was given by only the first term in (13.034 was irradiated for four minutes with nonpolarized infra-red light in a magnetic field of 1.

. The mechanism of the excitation of electrons from the photomagnetic center is discussed from a more microscopic point of view by Alben et a/. . the curve is shifted upwards. as shown by the crosses in the figure. as shown by the open circles in the figure. When the magnetic field was applied in a direction making the angle $ with [001]. The same experiment was repeated with plane of polarization of the infra-red light perpendicular to [111]. One of these is the anisotropy produced by control of the angle of incidence during evaporation. The sinusoidal curve shown with solid circles in Fig. the metal vapor impinges onto the substrate in a direction tilted from the normal to the surface. This is due to a decrease in Fe2+ on the site whose special axis is parallel to [111]. On the other hand.43 Rotatable magnetic anisotropy in anomalous magnetic thin films In magnetic thin films. 13.334 INDUCED MAGNETIC ANISOTROPY This is reasonable. The uniaxial anisotropy of a film produced in this way 78 Fig.76 that is. <l> curve is shifted downwards. Lc was nonzero. The interpretation is that electrons are excited from the photomagnetic centers with the special axis parallel to [111] more effectively. when the light is polarized with the polarization perpendicular to [111]. which are symmetrical with respect to [001] or [110].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.AT A. 13. The resulting Lc vs. resulting in a decrease in the number of Fe2+ ions on this site.26. because there are two (111) axes in the (110) plane.25 is a plot of Lc as a function of <t>. 13. because the two (111) axes in the (110) plane are no longer symmetrical with respect to the applied field. various magnetic anisotropies can be produced by varying the preparation procedures. Columnar structure produced by incident-angle evaporation.

77 which is clearly observed by electron-microscopy as shown in Fig.78 Even when the direction of evaporation is accurately normal to the substrate surface. This anisotropy is called the rotatable magnetic anisotropy.27. 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.79 has its easy axis parallel to the direction of inclination of the incident vapor. The dependence of this anisotropy on alloy composition is different from that of directional order. Ku. Ku. The anisotropy constant. In all cases the field strength is 20kA m . O Evaporated onto the substrate kept at 20°C in a magnetic field.28. which is shown by dashed curves.1 (= 250Oe).2)). 13.2779 as a function of Ni content in Fe-Ni alloy films for various evaporation conditions. The magnetization in each . the easy axis can be rotated by applying a strong magnetic field.26. as a function of Ni content (dashed curves show the anisotropy produced by directional order (see Fig.81'82 The structure of this domain will be described in detail in Section 17. if the film is magnetized parallel to its surface during the evaporation an in-plane anisotropy is produced. X Evaporated onto the substrate kept at 300°C in a magnetic field. in several ways: the magnitude is much greater and there is a non-zero value in pure Ni. Induced anisotropy constant. 13.. of anomalous Fe-Ni magnetic thin films evaporated under various conditions.4. Moreover.OTHER INDUCED MAGNETIC ANISOTROPIES 335 Fig. 13. so that now we simply glance at a conceptual view as shown in Fig. The anisotropy is apparently caused by the shape anisotropy of a tilted columnar structure.60 It was found that the rotatable anisotropy is caused by stripe domains. 13.

82 domain deviates from the plane of the film. 13. (c) observed after removal of a very strong magnetic field perpendicular to the original stripes. 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. (b) observed after removal of a relatively strong magnetic field perpendicular to the original stripes. alternatively upwards and downwards.28. the magnetostatic energy due to surface free poles. which is produced by the columnar structure. This deviation is caused by presence of an anisotropy with its easy axis perpendicular to the film surface. and the exchange Fig. The spin structure of the stripe domain is determined by a balance of the perpendicular anisotropy energy. Spin structure of stripe domains.29.82 .336 INDUCED MAGNETIC ANISOTROPY Fig. 13.

This explains the mechanism of rotation of the easy axis. and magnetocrystalline anisotropy. while the coupling of the Mn-Mn pairs is negative. This anisotropy also depends on the pre-annealing treatment that determines the degree of ordering. so that their spins tend to align ferromagnetically. and tends to vanish as the degree of order approaches unity.6 MA m^ 1 (20kOe). Ni and Mn atoms form a Cu3Au-type superlattice as shown in Fig. This is the origin of the anisotropy caused by stripe domains. and smallest for (111). the origin of this induced anisotropy is to be attributed to a spin rearrangement rather than to an atomic rearrangement. thus changing the total energy. Measurements on a single crystal show that this induced anisotropy is largest when the cooling field is applied in the (100) direction. Mn-Mn pairs exist. The appearance of the unidirectional anisotropy suggests the presence of some antiferromagnetic interaction. Ku.82 When a weak magnetic field is rotated in the film plane. K^. Kd. 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. 12. 13.29(a) shows a photograph of stripe domains as observed by the powder-pattern technique. the exchange coupling of the Mn-Ni and the Ni-Ni pairs is positive.87 Since no atomic migration can occur below room temperature. A neutron scattering experiment showed directly that some of the Mn spins are antiparallel to the spontaneous magnetization. and continues to increase up to a field of 1.5). as well as uniaxial anisotropy. intermediate for (110).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)).OTHER INDUCED MAGNETIC ANISOTROPIES 83 337 energy.88 this induced anisotropy contains unidirectional anisotropy.33. In this alloy.84 The appearance of this anisotropy has interfered considerably with the development of magnetic thin film computer memories. the stripes are disturbed (see the photo (b)).4. According to the experiment by Satoh et a/. 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 rotatable anisotropy is observed only for anomalous magnetic films. and their negative interaction disturbs the ferromagnetic spin arrangement and produces mictomagnetism (see Section 7. On the other hand. in which no Mn-Mn nearest neighbor pairs exist. Figure 13. Such a rotation of magnetization relative to the stripes changes the spin structure. When the alloy is perfectly ordered. so that their spins tend to align antiferromagnetically. if the alloy is partially ordered.85'86 that when a partially ordered Ni 3 Mn is cooled from room temperature to 77 K in a magnetic field. a weak uniaxial anisotropy of the order of 103 J m ~ 3 is induced. This fact also suggests that the phenomenon depends strongly on the antiferromagnetic interaction of . and the alloy is ferromagnetic. the magnetization rotates with the field without changing the direction of the stripes. The value of K1 depends strongly on the intensity of the magnetic field used in the measurement of the anisotropy. Therefore all the interactions between spins are positive.

tCo1_J. B-B. 13. Ku. which are treated in Chapter 11. First we discuss the anisotropy induced in amorphous alloys composed of 3d transition metals containing 10-20 at% of metalloid elements such as B. Numbers in the figure are the temperatures in °C at which the magnetic annealing was performed. In the concept of directional order discussed in Section 13. This is the . N. in which ferromagnetic clusters are coupled antiferromagnetically with one another to minimize the pseudodipolar interaction between clusters during cooling in a magnetic field.92 as a function of x. increases as x decreases from x = l. As in the case of magnetic annealing of crystalline alloys. and A-B pairs are constants. induced in amorphous materials of composition (Fe^Nij^ggBjo and (Fe. Figure 13. Ku.)goB2091 and (Fe.30 shows the uniaxial anisotropy constant. no detailed theoretical treatment has been published.1. some mechanism specific to the amorphous structure can also be considered.cCo1_. Mn-Mn pairs.4.cNi1_. However.89 This induced anisotropy is considered to be caused by rearrangement of the mictomagnetic spin system. a uniaxial anisotropy can be induced during preparation or by magnetic annealing.2 K. induced by magnetic annealing of the alloys with compositions (Fe. The only difference is that a nonzero anisotropy is found even at x=l. we assumed that the pseudodipolar interactions of A-A.)78Si10Bi2 9 as a function of x.)78Si10B12.1.l. prepared by quenching from the melt. Uniaxial anisotropy constant. 13JO. suggesting that a major part of this induced anisotropy is caused by directional order.5 Induced anisotropy of amorphous alloys In amorphous alloys. This may be attributed to directional ordering of the nonmagnetic metalloid atoms. However. the anisotropy constant. Polycrystalline samples were also measured over a wider temperature range down to 4. Ku.338 INDUCED MAGNETIC ANISOTROPY Fig. Si or P.

because every A-A pair has identical length and symmetry. as do all A-B and B-B pairs. only one kind of magnetic atom pair exists. Kelsall.95 Stress-induced anisotropy96 and exchange anisotropy97 have also been found in amorphous materials. but a slight change in the length of the pairs to decrease the total pseudodipolar interactions can cause the induced anisotropy. 279. Amorphous materials prepared by quenching will crystallize if heated above some critical temperature. however. (111)[110].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. it was found that even below this crystallization temperature a long annealing causes a change in the average atomic volume (structural relaxation). The reader may refer to the review by Eschenfelder" on these topics. 285. Arnold and G. because the sign of Ku depends on the presence of a DC bias voltage during sputtering. not so simple. 6 (1935). 13. W. the induced anisotropy was measured in the (001) and (110) planes. Dillinger and R. Franklin Inst. F. a body-centered cubic and a face-centered cubic lattice. For x=l.98 The mechanism is. Physics. Bozorth. 5 (1934). Calculate the induced anisotropy energy expressed in terms of the angle of rotation of magnetization in the (111) plane. [110] or [111]. Calculate the ratio of the induced anisotropy constants for the three cases. REFERENCES 1. 195 (1923). assuming only nearest neighbor interactions. PROBLEMS 13. However. 3. However. D. Calculate the ratio between the two values for a simple cubic.REFERENCES 339 case for crystals. J.1 After a single crystal of a body-centered cubic alloy is cooled in a magnetic field applied parallel to [001]. H. the induced anisotropy is measured by rotating the magnetization in the (110) plane. 621.. Physics. . Elmen. J. However.94 The relationship between this microscopic structure and the macroscopic magnetic properties has also been discussed. in amorphous materials the distances between nearest neighbors are variable. so that the pseudodipolar interaction is not the same for every A-A pair (similarly for every A-B and B-B pair). The anisotropy constants determined for two planes are generally not the same. 13.2 After a binary alloy with a cubic lattice was annealed in a magnetic field applied parallel to [110]. This phenomenon has been interpreted in terms of a columnar structure as well as by directional order. not only the magnitude but also the sign of Ku is different for different preparation conditions. 2. M.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. Evaporated or sputtered Gd-Co or Gd-Fe films exhibit a uniaxial anisotropy with the easy axis perpendicular to the film surface. 169. A. G.

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3). The magnetostrictive strain changes with increasing magnetic field as shown in Fig. and finally reaches a saturation value A. 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. so that the elongation of the radius PP" in the direction AB is given by Fig. thus resulting in a deformation of the specimen as a whole (Fig. . the details of which are described later.2).14 MAGNETOSTRICTION 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. Although the deformation is small. in the range 10~5 to 10"6. The point P is displaced in the ^-direction by PP' = e cos <p. Magnetostrictive elongation as a function of applied field. when it is magnetized to saturation (Fig. 14.1. The deformation SI /I due to magnetostriction is usually very small. 14. A deformation of this magnitude can be conveniently measured by means of a strain-gauge technique. magnetostriction is an important factor in controlling domain structure and the process of technical magnetization. which is an exact sphere with radius 1 when it is nonmagnetic but is elongated by SI/I = e in the direction of magnetization. or along the x-axis. 14.1 PHENOMENOLOGY OF MAGNETOSTRICTION Magnetostriction is the phenomenon whereby the shape of a ferromagnetic specimen changes during the process of magnetization. 14. In order to calculate the dependence of the strain on the direction of magnetization. we consider a ferromagnetic sphere.1.

. 14. the average deformation is given by the average of (14.3. When the domain magnetization is distributed at random in a demagnetized state as shown in Fig. thus Fig.2.1). Rotation of domain magnetization and accompanying rotation of the axis of spontaneous strain. 14. Elongation of the radius of a sphere with unit radius in the direction making angle <p with the axis of spontaneous strain. 14.344 MAGNETOSTRICTION Fig.2(a).

as shown in Fig. if i// = 0.4). 14. 14.PHENOMENOLOGY OF MAGNETOSTRICTION 345 Since in the saturated state. First we consider a ferromagnetic material with uniaxial anisotropy. Assuming isotropic magnetostriction.2(b). (14. During this process no magnetostrictive elongation occurs. At higher fields. let us consider how the magnetostrictive elongation changes as a function of intensity of magnetization. Rotation of the spontaneous magnetization 7S by an applied field H in a uniaxial crystal. such as cobalt. We call this quantity the isotropic magnetostriction. We have assumed here that the spontaneous strain f A is constant. 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.6) gives A(S///) = 0. If the magnetic field H makes an angle \\i with the easy axis (Fig. because the magnetization is everywhere (except within the domain walls) parallel to the easy axis. until the magnetization reaches the value 7S cos i/f. in other Fig. that is.4. 14. the domain walls separating anti-parallel domain magnetizations. that is. the domain magnetization rotates towards the direction of the applied field. during this process the elongation changes by If H is parallel to the easy axis. irrespective of the crystallographic direction of the spontaneous magnetization.

there is no change in the length of the specimen from the demagnetized state to saturation. the magnetizations at which the displacement of 180° walls is complete.6) gives A(S///) = §A. The 81/1 vs / relation for this crystal is shown by the dashed curve in Fig. assuming that all wall displacements are finished before the onset of rotation magnetization. we have. simply by averaging the above values. Magnetostriction of a uniaxial crystal as a function of the intensity of magnetization. 14. if H is perpendicular to the easy axis. thus If i// has some value between 0 and Tr/2. Since.5. are given by The changes in 81/1 are shown graphically in Fig. 14. For a polycrystal. .5 as a function of magnetization for various values of i/f. so that the average elongation is Fig. For a cubic crystal with Kl > 0. On the other hand. we put / = 7S cos <p in (14.5. in this case magnetization takes place entirely by rotation. (14. 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.1). that is. 14.346 MAGNETOSTRICTION words.

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

where 9 is the angle between 7S and H. Magnetostriction expected for (111) magnetization under the assumption of isotropic magnetostriction. We call this anisotropic magnetostriction.577/s. When the crystal is magnetized parallel to [111]. so that This relationship is shown graphically in Fig. . At the end of this stage I = Is/i/3= 0. 14. Then domain magnetization will rotate towards the direction of H. The experiment for iron reveals similar behavior. just opposite to the case of [100] magnetization. because /s is always parallel to one of the (100) directions throughout the entire magnetization process. Figure 14. A slight positive elongation due to 90° wall displacement occurs in the early stage of magnetization.8). [010] and [001] domains. Fig. [010] and [001] domains by the displacement of 180° walls at a sacrifice of [100]. while Akulov4 fitted the points to a straight line.7.7.9 shows the experimental result for [110] magnetization. the domains are first reduced to [100]. but the sign of the elongation is negative (see Fig. we must understand the physical origin of the magnetostriction. while a fairly large contraction is observed later during the rotation process. Thus the sign of A as well as its magnitude depends on the crystallographic direction of magnetization.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. 14. during this process / = /„ cos 6 and also 81/1 = f A(cos2 9 — f). 14. In order to discover the origin of the anisotropic magnetostriction. assuming the displacement of domain walls. and fitted the experimental points to a theoretically deduced parabolic curve.

as in magnetic anisotropy.2 MECHANISM OF MAGNETOSTRICTION Magnetostriction originates in the interaction between the atomic magnetic moments. 14. (Figure after Becker and Doring. Experimental magnetostriction data for <110> magnetization of iron.6 which was developed in his paper on magnetic annealing and . (Figure after Becker and Doring. We discuss the origin of magnetostriction following the treatment of Neel. Experimental magnetostriction data for (111) magnetization of iron.9.MECHANISM OF MAGNETOSTRICTION 349 Fig.2 Experimental points according to Kaya and Takaki5) Fig. 14.8.2 Experimental points according to Kaya and Takaki5) 14.

the crystal lattice will be deformed when a ferromagnetic moment arises. The first term. if the crystal is strained. When the crystal is strained. When the distance between the atomic magnetic moments is variable. that is whereas.350 MAGNETOSTRICTION Fig. A spin pair with a variable bond length. its bond length r0 will be changed to r0(l + exx) and . 14. we express the pair energy as Let (<*!. eyy. but normally their contributions are small compared to those of the second term. is the exchange interaction term.17) becomes Now let us consider a deformed simple cubic lattice whose strain tensor components are given by exx. /33) those of the bond direction. the interaction energy (12. Then (14. a2. r. if. ezz. Thus the crystal deformation caused by the first term does not contribute to the usual magnetostriction. y32. For instance. and can be regarded as the principal origin of the usual magnetostriction. a spin pair with its bond direction parallel to the *-axis has an energy in the unstrained state given by (14. and angle.59) may be expressed as where r is the interatomic distance (Fig. surface anisotropy. Neglecting these higher-order terms. exy.10. because such an interaction tends to change the bond length in a different way depending on the bond direction. = 0.18) with 8. but it does play an important role in the volume magnetostriction. = 1. and ezx. each pair changes its bond direction as well as its bond length. eyz. g(r). which is discussed in Section 14. it is independent of the direction of magnetization. If the interaction energy is a function of r. The second term represents the dipole-dipole interaction. /39 = R.10). The following terms also contribute to the usual magnetostriction. between parallel spins and the bond. «3) denote the direction cosines of domain magnetization and (/3j. which depends on the direction of magnetization. 14.5.

Then the pair energy (14. for a cubic crystal. and c12 are the elastic moduli. Adding these for all nearest neighbor pairs in a unit volume of a simple cubic lattice..18) will be changed by an amount Similarly. ezx. for the y and z pairs. the crystal will be deformed without limit unless it is counterbalanced by the elastic energy which.. it increases rapidly with increasing strain and equilibrium is . Since the magnetoelastic energy (14...y j83 = \ezx).23) is a linear function with respect to exx. eyy. we have where The energy thus expressed in terms of lattice strain and the direction of domain magnetization is called the magnetoelastic energy. (32 ~ \ex. is given by where c n . Since the elastic energy is a quadratic function of the strain.MECHANISM OF MAGNETOSTRICTION 351 the direction cosines of the bond direction will be changed to (/3 t = 1. Similar calculations for the bodycentered cubic and face-centered cubic lattice yield the same expression (14.23) with for the body-centered cubic lattice and for the face-centered cubic lattice. c 44 .

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

Putting (14. = ft =l/i/3~ (i = 1.32).33) and (14. The elongation in [110] is not independent of A100 and AU1.34). 2. a3 = y33 = 0 in (14.25) and (14.MECHANISM OF MAGNETOSTRICTION becomes 353 If the domain magnetization is along [100]. By using A100 and A m . and 3) in (14.24). we can express A100 and Am in term of the coefficients of the pair energy: . (14. the elongation in the same direction is obtained by putting a Similarly.35). but is related to them by as will be found by putting a1 = ftl = a2 = /32 = 1/^2.26) into (14. the elongation is calculated to be by putting a.32) into (14. when the magnetization is along [111].32) can be expressed as 4 Thus the magnetostriction of a cubic crystal may be expressed in terms of A100 and A m . (14.

Fig. Composition dependence of the magnetostriction constants A100. (After Lichtenberger7 for solid curves and Kim et al.11. 14.38). A110.39) to those for Am. The condition for isotropic magnetostriction is thus expressed by equating the expressions for A100 given by (14.) . (14. it is hard to attribute any significant physical meaning to the isotropic magnetostriction.37). The final form is the same as that of the isotropic magnetostriction given by (14. Since the coefficients of the pair energy and the elastic moduli included in these expressions are entirely independent of each other. it can be seen by putting (14. and A nl for Ni-Fe alloys.2 K for less than 44% Ni.40) into (14.1).35) becomes where 6 is the angle between the direction of domain magnetization and that of the measured strain.8 for dashed curves measured at room temperature and dot and dashed curves measured at 4. For isotropic magnetostriction. where the magnetostriction is isotropic at 15% and at 40% Fe-Ni. and (14.354 MAGNETOSTRICTION If (14.Figure 14.36) that ^ = ^100 = ^111 = ^110.11 shows the dependence of magnetostriction constants on the alloy composition for iron-nickel alloys.

2. In a hexagonal crystal. and 3). = 6. even if A100 =£ A m .MECHANISM OF MAGNETOSTRICTION 355 For polycrystalline materials.11. because the deformation in each grain is averaged to produce the overall magnetostriction. the expression for the magnetostriction of a cubic crystal becomes more complicated than (14.16). from the composition dependence of A100 and Ain observed for binary alloys. The average longitudinal magnetostriction is calculated by averaging (14. As seen in Fig. If we take into account the third term of (14. it is possible to deduce its coefficient.35) for different crystal orientations. 14. respectively. /. the magnetostriction is isotropic. assuming a. (i — 1. thus In the preceding discussion we considered only the dipole-dipole interaction term in (14.35): where and h1 and h2 are related to A100 and Am by hl = (3/2)A100 and h2 = (3/2)Am. 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. by setting the z-axis parallel to the c-axis.16). the composition dependences of A100 and Am can be .

48). the probabilities of finding AA. . As discussed above. If the atomic distribution of A and B atoms is completely random. Neel6 deduced the coefficients. 2CACB. AB and BB pairs are proportional to CA. respectively. the Is.52) with (14.39) for an fee lattice.356 MAGNETOSTRICTION Z approximated by quadratic functions. we have If we assume that the elastic moduli of Ni-Fe alloys are the same as those of Ni. the composition dependences in the fee region are expressed by where CNi and CFe are the fractions of Ni and Fe. for all three possible kinds of atomic pairs. the origin of magnetostriction is the magnetoelastic energy. we can determine from which we have for Ni-Fe alloys. respectively. as given in Table 14. Therefore the average / is given by Similarly the average dl/dr is given by Solving (14.4. In Ni-Fe alloys. and C\. This value was used for estimating the induced anisotropy due to directional order in Ni-Fe alloys in Chapter 13. we have Comparing (14.3 in Section 14. where CA and CB are the fractions of A and B atoms. Using these relationships.

thus changing its resistance. For more details the reader may refer to the review by Kanamori.MEASURING TECHNIQUE 357 which is the magnetocrystalline anisotropy of the deformed crystal.12). by AS/S = A///. 14. and a decrease in cross-sectional area. A calculation of magnetostriction was made by Tsuya11 for ferrites using a one-ion model.35) is reduced to Fig. S. However. 12. Usually the value of the gauge factor ranges from 1. the resistance wire in the strain gauge is also elongated. but the value for A U1 and its temperature dependence were not satisfactory.3. and also that the effect of strain is only geometrical.13 14. an elongation of A///. as shown in Fig.8 to 2. the direction cosines of the magnetization are given by (12.12. is called the gauge factor. sometimes called a resistance strain gauge. The proportionality factor between A/// and AR/R.12.14 .5. we cut a disk parallel to (110) from a single crystal and cement a strain gauge parallel to [100] or [111].2.3 MEASURING TECHNIQUE A convenient means for measuring magnetostriction is the strain gauge technique. is made of a small piece of paper or polymer sheet. When a specimen to which this strain gauge is cemented is elongated. Paper strain gauge. Therefore the microscopic origin of magnetostriction is the same as that of magnetocrystalline anisotropy. The calculated A100 agreed with experiment. Slonczewski12 calculated magnetostriction in Co ferrites using the one-ion model discussed in Section 12.14-15 A strain gauge. on which a thin serpentine resistance wire or foil is cemented as shown in Fig. where R is the resistance of the strain gauge.7. 14. the agreement with experiment was not satisfactory. then rotate a magnetic field in the plane of the disk. Jn order to determine A100 and A U1 in a cubic material. so that the elongation given by (14. If we denote the angle between [001] and the magnetization by 6. If we assume that Poisson's ratio is 0. which means that the volume of the gauge material does not change during elongation. and measure the strain parallel to [100] or [111]. should result in a gauge factor of 2.

if the specimen is too thick.57). the rigidity of the specimen is altered by the presence of the strain gauge. Equating the amplitude of this term to f 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. The data in this case is shown as curve B in Fig. so as to experience the same magnetic field and the same .14 When the strain gauge is parallel to [001]. This curve has the functional form cos26.55) gives Figure 14. Equating the amplitude of this curve to f A m . so that we have where 90 = 54. Magnetostriction measured as a function of the angle of magnetization from [001] for 3.56). For the strain gauge parallel to [111]. 14. so that the sensitivity of the strain gauge is reduced. which makes the determination of saturation magnetostriction difficult (see Section 14. in agreement with (14.93 at% V-Ni alloy. we put /3j = /32 = 0.5). Changes in gauge resistance are measured in a bridge circuit.13 shows the experimental result of magnetostriction measured for 3. so that (14. On the other hand.13.7° in agreement with (14.a N Fig.55). (B) parallel to [111]. which has a minimum at 54. Moreover.93% V-Ni (110) disk: (A) elongation parallel to [001]. the volume magnetostriction is increased. 14. Curve A shows the elongation parallel to [001] as a function of the angle 6. three dummy gauges completing the bridge may be cemented onto a nonmagnetic disk placed near and parallel to the specimen. The functional form of curve A is well fitted by cos26. To compensate for resistance changes due to temperature and to magnetic field. and /33 = 1. the demagnetizing factor becomes so large that it may be difficult to reach magnetic saturation. we can determine A1U. we put ^ = )32 = ft = l/i/3~ in (14.13.7°. we can determine A100.

the gauge factor is influenced by the magnetic field and by temperature.1 Magnetostriction of uniaxial crystals (a) Magnetostriction of rare earth metals Heavy rare-earth metals with more than seven 4/ electrons such as Gd. in which the magnetostrictive strain changes the gap between two conducting plates and hence changes the capacitance.4 EXPERIMENTAL DATA 14.4. Magnetostriction measurements can also be made by a capacitance technique.16 . Ac.EXPERIMENTAL DATA 359 temperature as the specimen. and Tm exhibit ferromagnetism at low temperatures (Section 8. Temperature dependences of magnetostriction constants AA. For wire and ribbon samples. Except for Gd.14. Ho. these metals have unquenched orbital magnetic moments which give rise to large magnetocrystalline anisotropies. Gadolinium is an exceptional case.1. Tb.14 Strain gauges made of semiconductor materials are also available. Details are given by Wakiyama and Chikazumi. but correspondingly high values of magnetoresistance and temperature coefficient of resistivity. AB. Er.3).(a)). some strain gauges are made with the gauge factor quite insensitive to both magnetic field and temperature. they have very high sensitivity (gauge factor over 100). Even in this case. so that they can be magnetized to saturation only in very high fields (see Section 12. 14. because it Fig. and AD observed for gadolinium single crystal. 14. which may be too small to mount a strain gauge. a sensitive length-measuring device called a linear variable differential transformer (LVDT) may be useful. so that a calibration is needed. However. Cy.4.

c33 = 3. Temperature dependence of magnetostriction constant observed for polycrystalline cobalt in various magnetic fields20 (numerical values of H are in Oe (= W3/4irAm~1J).14 shows the temperature dependences of magnetostriction constants (see (14.15. a NiAs-type compound.4) and MnBi.5 -1099 -1233 -70. even though there is no orbital magnetic moment. For other rare earth metals (with nonzero orbital magnetic moments) it is hard to determine accurate values of magnetostriction constants.3) are listed in Table 14. extrapolations to 0 K from the small values near the Neel points give very large values.2.58.16'17 Note that the magnitudes of some of these constants are as large as 100 to 200 X 10~6.17 Ho18. c44 = 0. c13 = 1. 14.2 ) . and is easily magnetized to saturation in any crystallographic direction. Magnetostriction constants and elastic moduli of hexagonal cobalt. Er.5 X KT 6 105xlO~ 6 120 126 126 -82 -108 -128 -52XMT6 -200 cn = 3. The Table 14.5X10~ 6 5 -32. 14.5 -52 -66 5 -88. (c) Magnetostriction of hexagonal oxides and compounds Magnetostriction constants of a hexagonal ferrite BaFe18O27 (see Section 9.65.20 The magnetostriction constants and elastic moduli measured for single crystals are listed in Table 14.15.03.45)) of Gd. c12=1.07. some thousands times 1(T6 for Dy. Therefore magnetostriction can be measured without any difficulty.1.21 t\ Oj A^ Ag A£ Aj) 200 0 -200 400 -16. However.76 X 10 u Nnr 2 (Xl0 12 dyncm. has no orbital moment (L = 0).1.17'19 (b) Magnetostriction of cobalt Cobalt transforms from fee to hep at about 420°C on cooling. (see Section 10. The magnetostriction constant of polycrystalline cobalt changes its sign at this transformation point as shown in Fig. Figure 14.360 MAGNETOSTRICTION Fig.

20.4. C ll ^12 C 44 Metal A100 Am 6 X 10 Nnr (x!0 dyncm.19). Effects of dilution with nonmagnetic elements such as Cu.4. 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. respectively.18 / . together with those of nickel. In all these cases.21-14.16 for Fe.43)) are shown in Fig. Compounds BaFe18O27 MnBi AA 13XlO~ -800 6 AB 3 X 1(T -210 6 Ac -23X10" 640 Ref. respectively. It is interesting that the values of A100 for Fe-Si and Fe-Al increase with a dilution with these nonmagnetic elements. Magnetostriction constants for Fe-Ni alloy are already shown as a function of Table 14.4.24. Magnetostriction constants of hexagonal compounds.29 The magnetostriction constants of Fe-Ti alloys exhibit fairly complicated composition dependences (Fig.2 ) 6 n 2 12 Ref.17.3.60 1. although the magnetocrystalline anisotropy constants of these materials are almost the same (see Sections 12.9 -21.2X10' -24. Cr. The effect of dilution with nonmagnetic elements such as Si.7 X l O ~ -45. The temperature dependences of five constants are shown in Fig. 6 3xlO~ 22 23 constants of MnBi are two orders of magnitude larger than those of BaFelgO27. V. 24 Fe Ni 20. the magnetostriction constants are also influenced by heat treatments. The magnetostriction constants and elastic moduli observed for nickel at room temperature are listed in Table 14. Temperature dependences of five constants (see (14.3. with addition of Ti. Contrary to iron. 14.3.19.46 1. 14. Magnetostriction constants and elastic moduli of iron and nickel (room temperature). the saturation magnetization stays almost constant.3 2. and Ti on A100 and Am of Fe are shown in Figs 14.2.18. while the Curie point increases. Since the Fe-Al alloy develops the superlattice Fe3Al. 14.EXPERIMENTAL DATA 361 AD 6 Table 14.12 \ 2. and 14.41 1. both the constants A100 and Am are negative.50 1.2).1(d) and 12. the magnitude of the magnetostriction decreases monotonically with dilution. 14. reflecting a monotonic decrease of the saturation magnetization. 14.2 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. and Ti are shown in Figs 14. Al. In the case of Fe-Ti alloys.1(e)).

which is an anisotropic ion and can be responsible for the large magnetostriction.33'34 Magnetostriction constants of Ni-Co and Fe-Co alloys are shown as a function of composition in Figs 14. the magnetostriction constants are insensitive to heat treatments.Fe3_J.43) by A^ = hlt A2 = 2h2. In the case of Ti. A100 decreases and A ni increases with the formation of the superlattice Ni3Fe. except for some ferrites containing Fe2+ ions. In the case of Co.0. .) composition in Fig. respectively. and A5 = 2hs.64MAm"1 (= 8kOe).11. Despite the formation of the superlattice FeCo37 (see Section 8.27 shows the composition dependence for MnA. (b) Magnetostriction of spinel-type ferrites The magnetostriction constants A100 and Am are listed for various spinel-type ferrites in Table 14. the introduction of Ti4+ may give rise to a change in valence from Fe3+ to Fe2+. Figure 14. The isotropic magnetostrictions are realized at 60 and 85% Ni.362 MAGNETOSTRICTION Fig.4. except for very large values for ferrites containing Co or Ti. 14.O4.7) and the accompanying lattice softening may also contribute to the large magnetostriction. both constants change abruptly as x becomes smaller than 1. 14. A4 = H4.26. In the vicinity of 75% Ni. which contribute to large values of magnetocrystalline anisotropy and magnetostriction. A3 = h3. a fraction of Fe3+ ions on the A sites change to Fe2+ ions.16. 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. Similar to the composition dependence of K1 of the same system. Particularly in those ferrites containing more than 50% Ti.48 Also the Fe2+ ions on the A sites tend to produce the Jahn-Teller effect (see Section 14.3 may contribute to these large values. Most of the constants are of the order of magnitude of 10~5.4).25 (The constants in the figure are related to those in (14. the one-ion anisotropy of the Co2+ ion discussed in Section 12. Most ferrites have negative A100. and isotropic magnetostriction occurs.25 and 14.

.5.28 shows the temperature dependence of magnetostriction constants of YIG containing only nonmagnetic yttrium. but for those garnets containing rare earth ions with nonzero L the values are very large at low temperatures.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. With the addition of anisotropic Tb. Figure 14. This is due to the fact that the paramagnetic rare earth ions are strongly magnetized by the exchange field at low temperatures. the values at low temperatures become very large as seen in Fig.59 14.17. A change in magnetostriction by replacing Fe3+ with Ga3+ in YIG or by an increase in x for Y3Fe5_jGa_. The values at room temperature are of the order of magnitude of 10~6-1CT5.5 VOLUME MAGNETOSTRICTION THERMAL EXPANSION AND ANOMALOUS In the preceding sections we assumed that the volume of a ferromagnet remains .O12 was also measured. 14. Composition dependence of magnetostriction constants of Fe-Si alloys. 14.VOLUME MAGNETOSTRICTION 363 Fig.29 which shows the temperature dependences of magnetostriction constants.

14.364 MAGNETOSTRICTION Fig.16). g(r). r. Composition dependence of magnetostriction constants of Fe-Al alloys (room temperature).30). the fractional volume change is given by Using the spontaneous strain tensors given by (14. this term depends on the length of the bond. However.28 constant during the process of technical magnetization.58) that However.16). we find from (14. in (14. or the distance between the paired spins. )33). For the spin pair whose bond direction is given by the direction cosines (/31. This term describes the exchange interaction between spins. First we discuss the effect of the first term. In terms of strain tensors. we have ignored the first term and all terms higher than the second term in (14. j32.18. We call this phenomenon the volume magnetostriction. a change in the pair energy is given in terms of the lattice strain by . and is independent of the direction of the spins relative to the bond direction. These terms can produce a small but nonzero change in volume with magnetization.

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

or the sum of the magneto-volume and elastic energies. Minimizing the total energy.31 Summing up the pair energies for all the nearest neighbor pairs in a simple cubic lattice. we have which is called the magneto-volume energy. 14.32 . Composition dependence of magnetostriction constants of Ni-Cu alloys (room temperature). Fig.22.366 MAGNETOSTRICTION Fig. Composition dependence of magnetostriction constants of Ni-Cr alloys. 14.21.

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

368 MAGNETOSTRICTION Fig.25. 14. we have the volume change This is the volume magnetostriction produced by the appearance of spontaneous Fig.35 Adding up these terms.26. Composition dependence of magnetostriction constants of Ni-Co alloys (room temperature).36 . Composition dependence of magnetostriction constants of Fe-Co alloys (room temperature). 14.

14Fe2.0704 Li0.7 1.63FeL26Mnj.3 47 142 170 990 Am 6.2 4.56Ti0.1 -19. but is nonzero when the material is ferromagnetic.6 110 -38.4.7 37 -3. g.VOLUME MAGNETOSTRICTION Table 14.ioFe2.53) is replaced .35Fe2. the coefficient.0 -12.8 45 36 3 -2.2 0. g. (14. is independent of at.nO. and (14.5 -26 -5 -0.52).5Al0.51). In other words.43Zn0. the coefficient.1 -16. Using this relationship. 20°C 20°C Ref. Then the internal energy associated with the spontaneous magnetization is given by where z is the number of nearest neighbors.5 -210 -109 -27.5 -22 49. The coefficient.6 3.3 2.3504 Li05Ga14FeL1O4 Ti018Fe282O4 Tio56Fe244O4 A100 -31Xl(T 6 -20 -590 -42 -57. 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. is regarded as the average exchange interaction energy.1504 Lio. in (14.5 Xl(T 6 78 120 -14 4. g. Magnetostriction constants of spinel-type ferrites (mainly after Tsuya49). Composition MnFe2O4 Fe3O4 Co08Fe22O4 NiFe2O4 CuFe2O4 MgFe2O4 Li05Fe25O4 Mn 06 Fe 24 O 4 Mn028Zn016Fe237O4 Mn104Zn022Fe182O4 Mgo.5 -10.9 109 86 92 (330) Temp. Co 032 Zn 022 Fe 22 O 4 Co01Ni09Fe2O4 Li0. Similarly we have and These are the volume changes produced by the appearance of ferromagnetism.

and has no sharp peak at the Curie point. which is a 34 at% Ni-Fe alloy used as a low thermal expansion material (see Section 8. or where Cp is the anomalous heat capacity per unit volume due to the appearance of ferromagnetism.. (Data after Miyata and Funatogawa43) by E.69) results in an anomalous thermal expansion coefficient.2). 14. 14.30 is much larger than that of Ni. c n and c12. In fact. This relationship can also be deduced from thermodynamic considerations.27. Also. using the relationship between the bulk modulus. 14.370 MAGNETOSTRICTION X Fig. Dependence of magnetostriction constants on the composition x in Mn^Fcj^O. the anomalous thermal expansion coefficient of Ni shown in the inset of Fig.30 is quite similar to its anomalous heat capacity. Since the magnetic internal energy depends on temperature through a change in spontaneous magnetization. we have for all crystal types where (a = 8 v/v. The anomalous region shown by the hatched area in Fig. and the elastic moduli..30 shows the temperature dependence of thermal expansion coefficient for Invar. covers a wider temperature range. the volume change given by (14. This behavior can be interpreted in terms . 14. The main graph in Fig. c.

RIG 371 A100 Am 6 (K) 6 Ref.5 -4.0XHT -1.3 -7.0 1.7 4.0 9 0 9 2A 78 196 300 0 55 78 196 300 0 50 50 50 50 50 50 55 TmlG YbIG 25 10.8 -4.4 -7.2 54 DylG -1400 67 -10.6XKT -3.4 -14.6 -3.3 HoIG -1400 -169 -46.61"3 A theory based on the spinfluctuation model can also explain this phenomenon.1 -5.1 -4.1 -8. Magnetostriction constants of garnet-type ferrites (after Tsuya57.5.0 -19.4 -4.7 0 2420 78 196 300 78 196 300 4.2 -10.7 5. Hansen58).4 9 5 4 4.8 78 196 300 4.4 159 110 86 51 21 49 21 4 -3.2 56 50 50 50 50 50 18.4 -8.2 52 50 50 53 50 50 50 TbIG 1200 4. Temp.6 -5.5 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.3 -3.4 3 -550 560 65 12 -145 -21. YIG SmlG EuIG -1.5 20 4 5 1 78 196 300 50 50 50 78 196 300 50 50 50 4.5 -3.64 .4 -183 -28.9 1.1 -4.1 2.9 -11.9 -2.5 -82.9 5 4.3 1.1 -1.2 55 50 50 50 50 50 50 -330 ErIG 630 -450 -56.0 1.3 -5.2 51 GdIG 7.2 78 196 300 78 50 97 -31 196 300 4.1 9.VOLUME MAGNETOSTRICTION Table 14. and a high-spin state with a large magnetic moment and large atomic volume.6 -12.3 5.2 -31.

0. the energy of spontaneous magnetization is given by Fig. which causes an increase in spontaneous magnetization.OO)58 (Data after Belov et al.372 MAGNETOSTRICTION Fig. 0. Temperature dependence of magnetostriction constants of TbxY3_.00. H. can also be changed by the application of an external field. 14.29.t.58 (Data after Hansen59) The exchange energy. 1.60) .26 and O. Temperature dependence of magnetostriction constants of YIG.65.28. g.54. 2.50. 2.17.Fe5O12 U-values are from up to down: 3.12. 1. 14. In the presence of a high magnetic field.

Temperature dependence of the anomalous thermal expansion coefficient for Ni and Invar..43).16).73) (other than the constant term) is Comparing with (14.30. The volume magnetostriction depends also on the shape of the specimen. the volume change is spherical. where w is much smaller . which are the direction cosines of the observation direction. (1 + «). For the simple cubic lattice..62) and (14. referring to (14. Let us proceed to the volume magnetostriction that arises from the quadrupole interaction q(r) in (14.74) does not contain any /3. 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. the main term in (14.69). 14. The anomalous thermal expansion and the forced magnetostriction are essentially isotropic.69).23)). this term produces a volume magnetostriction given by Using the relationships (12. The h3 term in (14. Consider a ferromagnetic specimen of nearly unit volume. we see that this effect is caused by a rotation of the spontaneous magnetization against the magnetocrystalline anisotropy. it is called the crystal effect. so that. because they are caused by the isotropic exchange interaction.68). corresponds to this effect. which does not contain any /3.VOLUME MAGNETOSTRICTION 373 Fig.61 (see (6. This effect is isotropic: in other words. because (14.

the volume magnetostriction is small when the magnetic field is reasonably weak. and considering M ~ I. /. 14. Fig.32 shows the volume magnetostriction observed for two iron samples with different demagnetizing factors. because the forced magnetostriction is linear with H (see (14.65 . In summary. 14. the magnetostatic energy is given by where M is the magnetic moment of the specimen as a whole. First the volume increases proportionally to H2 as a result of the form effect. It should be noted that the form effect produces not only volume magnetostriction but also normal linear magnetostriction. When the specimen is magnetized to saturation. The sign is negative for iron and nickel.31.75) for E in (14. the volume magnetostriction of a specimen with a finite size is expected to change as a function of external field as shown in Fig. Substituting U in (14. the volume change decreases and then increases linearly due to the forced magnetostriction. In this case.374 MAGNETOSTRICTION than 1. Schematic variation of the volume magnetostriction with increasing magnetic field. we have We call this effect the form effect. but it becomes comparable to the linear magnetostriction when the magnetic field is stronger than 1 MAm"1 (about 104 Oe). N. and with demagnetizing factor. and then the crystal effect appears in the region of rotation magnetization. When this sample is magnetized to an intensity of magnetization. depending on the sign of q (or of Kj) and that of dq/'dr.72)). 14.69). Generally speaking. The sign of the crystal effect can be either positive or negative. or to H2 if the magnetization curve is linear. this volume change also reaches a saturation value The feature of this effect is that the volume change is proportional to I2.31. For a specimen in the form of a rotational Fig.

32. (a) k = 16. (Data after Kornetzki66) ellipsoid with the long axis parallel to the x-axis. Then we have Since the demagnetizing factor of the elongated ellipsoid is given by (1.78) and (14.79). Experimental data on the field dependence of the volume magnetostriction for two iron specimens with different dimensional ratios.78) becomes where a is given by . Let the length of the specimen be / and the diameter d.9. 14. we have Using (14.VOLUME MAGNETOSTRICTION 375 Fig.6.43). the demagnetizing factor depends on the strain as where k is the dimensional ratio or aspect ratio (length/diameter). (b) k = 41. (14.

a mechanical stress is expected to have some effect on magnetization. The measurement of the anisotropic form effect is discussed by Gersdorf.376 r MAGNETOSTRICTION (N = dN/dk\ Ignoring the volume magnetostriction.67 14. Using these relationships in (14.23) we have the magnetoelastic energy . cr (Nm~ 2 ). Then the tensor components are given by a-fj = crjijj. The resultant strain can be found by minimizing the total energy or Solving (14. In order to avoid this effect in measuring the ordinary linear magnetostriction. sn. 544 are the elastic constants. Let the direction cosines of this tension be (y^ y2. is acting on a ferromagnetic body. which results in a strain with components where su. Suppose that a stress. y3). we have where exx is the longitudinal magnetostriction. we must use a specimen with a small demagnetizing factor.6 MAGNETIC ANISOTROPY CAUSED BY MAGNETOSTRICTION Since a magnetostrictive elongation is caused by magnetization. and eyy or ezz is the transverse magnetostriction. and eyy and ezz should become more negative. Such an effect is called the inverse effect of magnetostriction.85). the magnetostatic energy is expressed in terms of strain tensors as Therefore in order to decrease the magnetostatic energy. Magnetostriction plays an important role in determining domain structures through this effect. exx should become more positive.

89) becomes where <p is the angle of the magnetization measured from the axis of stress. cu. Then we have the relationship so that (14. This difference in energy between domains results in a force acting on the 90° domain walls between them.33) and (14. thus producing changes in magnetoelastic and elastic .MAGNETIC ANISOTROPY CAUSED BY MAGNETOSTRICTION 377 The coefficients B1 and B2 are related to A100 and Am by (14. the lattice distorts. (14. because as the magnetization rotates. In other words. and c44 and sn.89) leads to Let <p be the angle between [111] and a. For simplicity. Using this relationship between cn. If instead of fixing the direction of magnetization. a magnetic anisotropy is produced. When the easy axis is parallel to [111]. Hereafter we use (14. A100 = Am = A. for the [010] and [001] domains we have and respectively.89). according to (14. (14. <r.96) when we discuss the effect of stress on magnetization.93) becomes This relationship holds always if we define <p as the angle between the magnetization and a. Magnetostriction can also influence the cubic anisotropy.88) can be rewritten as For a ferromagnet with K^ > 0 such as Fe. a domain with magnetization parallel to [100] has energy Similarly.34). the energy changes as the magnetization rotates. we assume isotropic magnetostriction. s12. This is a kind of uniaxial magnetic anisotropy. and su* (14. Then. we fix the axis of stress.

28) becomes A£ = A^Ufcf + a\a\ + a ^ a f ) .378 MAGNETOSTRICTION energies. Substituting the strain tensor in the magnetoelastic energy (14.23) using the strain tensor components in (14. 3 (see (12.100) gives This value is small compared with the observed value of -5.7)).7 X 103 J m but is not negligible.33) and (14.34). Therefore the observed magnetocrystalline anisotropy constant must be compared with the theoretical value using the correction given by (14. we have We have also a change in elastic energy from (14.27): Thus a change in the total energy (14. (14.3 for Ni. where AKl is given by from the relationships (14. Using the values of Table 14. .100).30).

If the cubic crystal is elongated along the z-axis (c > a). occupies an octahedral site in a cubic crystal. For example. . because Fig.t 2 — y2 has a lower electrostatic energy than the other.68 Intuitively this phenomenon is interpreted as a deformation of the lattice by anisotropic electron clouds of 3d electrons. three d levels are lowered and two d levels are raised by cubic crystalline fields. the magnetostriction is produced by a balance between a decrease in the magnetoelastic energy and an increase in the elastic energy. Then the dy function with 2z 2 -. Then nine electrons distribute on five energy levels according to Hund's rule as shown in Fig. as shown in Section 3.20). This is the Jahn-Teller distortion. Therefore the ninth electron occupies this level. the elastic modulus corresponding to this deformation decreases with a decrease of temperature towards this transition point.2) observed at room temperature is due to this effect.ELASTIC ANOMALY AND MAGNETOSTRICTION 379 14. A typical example is the John-Teller distortion. 14. the balance of the two energies results in a nonzero distortion of the crystal. Since such a deformation of the crystal increases the elastic energy.7 ELASTIC ANOMALY AND MAGNETOSTRICTION In this section.2. we discuss several topics on the relationship between elasticity and magnetostriction of magnetic materials. One of the dy functions has the form x2 — y2 and stretches along the x. Splitting of the dy levels of the Cu2+ ion on the octahedral site. the magnetostriction must increase. suppose that the Cu2+ ion.and y-axes. The tetragonal distortion of copper ferrite (see Section 9.33. which has nine 3d electrons. 14. while the other dy function has the form 2z2-x2-y2 and stretches along the z-axis (see Fig. At high temperatures this material is cubic.33. One of the mechanisms that can cause a decrease in the elastic moduli is a structural phase transition. 3. 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. When a cubic phase at high temperatures transforms to phase with lower symmetry at some transition temperature. As noted in Section 14. As discussed in Chapter 12.or _y-axis.4. so that the total energy of the occupied levels is lowered as the lattice is elongated along the z-axis. Therefore if the elastic moduli are decreased for some reason.

69 (Data of AE effect from Koster70) .4. Schematic diagram of stress-strain relationships for ferro and nonferromagnetic materials. Comparison between the AE effect and A for Fe-Ni alloys. so that the elastic modulus cn is reduced.380 MAGNETOSTRICTION Fig. A value of magnetostriction observed for Ti-ferrite (see Section 14. the thermal excitation to the excited dj level lowers the total energy levels by reducing the separation of the two levels. 14.35. Figure 14. This phenomenon is called the lattice softening. However. The elastic moduli of ferromagnetic materials are reduced to some extent due to magnetostriction.2(b)) is considered to be due to lattice softening caused by Fe2+ ions on the A sites. 14.34. there is still a tendency for the lattice to deform to a tetragonal structure.34 shows the stress-strain curves for ferromagnetic and Fig.

Takaki. REFERENCES 1. where magnetization can rotate freely. 227. 1966). thus resulting in a decrease of the Young's modulus.. Proc. W. Physik. 4. 96 (1954). 1939). J.5 Calculate the value of AX^ for iron at room temperature. 1959) Chap. 287. Nl. Phys.. W. Soc. 10 (1932).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]. Sci. Phys. P. 44 (1978).REFERENCES 381 nonferromagnetic materials. Carr. estimate the order of magnitude of the dipole-dipole interaction. which demonstrates the proportionality between LE/E and A in Fe-Ni alloys. 7. Cleveland. Phys. Lichtenberger. which exhibit the A£ effect. C. Kaya and H. y. 45. Calculate the elongation measured in the [010] direction as a function of the intensity of magnetization in that direction. Ann. 14. 274. 570. S. a mechanical vibration produces eddy currents through the rotational vibration of magnetization. W. N. F.35. and h3 is magnetized to its saturation by a constant magnetic field which makes an angle 6 with [100] in the (001) plane. Chikazumi. the magnetostriction contributes an additional strain irrespective to the sign of A. . Berlin. Phys.71'72 PROBLEMS 14. M. Becker and W. Z. L. Kim. 9. 10. This phenomenon is called the AE effect. Webster. Matsui. Heisenberg. Japan.. and z domains? Assume \100<r*K. Boring. D. Rev. J. L. E. 78. 14. instead of nonmagnetic 18-8 stainless steel. (London). Ferromagnetismus (Springer.K1. 14. 143 When a single crystal sphere with magnetostriction constants hlt h2. S284. A109 (1925). Hokkaido Univ. 1152. 15 (1954). 8. 5. It is naturally proportional to the magnitude of A as shown in Fig. which results in an additional internal friction. In ferromagnetic metals. Turbine blades are usually made from magnetic 13% Cr stainless steel. Radium. 3. Magnetic properties of metals and alloys (American Society of Metals. 69 (1931). 69 (1931). 6... 10. J. how do the elongations parallel to [100] and [010] change as a function of 07 14. Handbuch der Physik (Springer-Verlag.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 . Phys. R. Berlin. Akulov. 2.4 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. 225. Fac. Soc. and S. Mason. XIII/2. At moderate stresses. 302. /. Neel. because vibrational energy is more strongly absorbed in a magnetic material because of this effect. Z. W. Roy. 2 (1935).

35. New York. F. 15 (1960). 8. J. K. Appl. J. 1210... Japan. 99 (1955). 139 (1965).. Petrakovski. Jones. M. K. Tsuya. B. 48 (1980). Japan. Zijlstra. 18. Soviet Phys. Phys. W. McSkimin. Phys. Appl. 17 (1962). /. T. J. Soviet Phys. 29. S. W. 41.. Phys.. Soc. Stull. L.. Phys. 34. 33... Clark. G. Tohoku Univ. 97. 18 (1955). Kainuma. Williams. Miyata and Z. Yamamoto and T. K. Williams and A. 51. Sherwood. /. 42 (1971). H. 51. 899. 816. 23. . J.. Phys. 36. Lee. Inst. 89 (1953). 2544. Phys. Soc. Pavlovic. 31. C. 40. /. Phys. J. J. 19. Carr and R. M. Rev.. 53. I. 616. Tatsumoto and T.. F. Nakamichi. /. 17. V. Phys. G. J. H. 431. 38 (1957). Rev. C. R. Phys. A216. Chap. 1303. Japanese J. Chem. Chap. 46. Ferrites (1970). J. Appl. 1963). 27. Tohoku Univ. 11 (1959).. 328 (in Japanese). T. 13. Soc. Appl. R. 1138. Soc. K. Callen. Phys. H. DeSavage. Rev. 34 (1963). 20 (1965). N. 42. and E. S. Syono. I. Geophys. by S. Japan. L. Rev.... 11 (1972). 18 (1963). A. 168.. 44. Phys. K. M. Vol. Soc. Int. and O. Rept. Tsuya. 25 (1953). 852. Goldman. 15. 14. Inc. J. Ishizumi. Rev. Pappis. Soviet Phys. 1975. Phys. 1968). H. B. V. Boothby. 822. 1001. 40 (1969). J. 1673. and J. 39 (1968). Fonton and A. Phys. 406.. Tilden. 1325. Bozorth. S. Shimizu. R. Repts. Appl.. Bozorth and J. /. Borzorth. Alstad. 9 (1967). Phys. Prog. Phys. Wakiyama. 576. N. Res. Phys. 279. N. J. Appl. Appl. /. M. Yamamoto and T. Zalesskii. 571. Japan. Phys. Y. R. Y. Phys. E. 80 (1950). Miyajima. 39. B8 (1957).9 (in Japanese). Okamoto. Phys. Hall. MAGNETOSTRICTION N. E. 6 (1903). R. A. C. Vol. Kotyukov. Rev. 32. p. 624. Inst.. Funatogawa. Phil. 301. 392. 10 (1963). 17. Donne. Experimental Physics Series (Kyoritsu Publishing • Co. E. M. 99 (1955). N. 138 (1965). 4 (1965). J. A. J. Spring Meeting of Phys. Chikazumi.. J. 48. 15 (1960). Rev. Phys. 21. p. Appl. M. 28 (1957). Legvold. 30. Mitsuoka. Phys. Honda and S. Table 13. 47. C. J. and S. 707. White. L. Appl. Appl. Soc. R. 1236. Sci.. Rhyne and S. 4. Chikazumi. Solids. A1243.. R. 49. 4486. 449: Sci.. Slonczewski. /. J.. Smith and R. /. S.. K. 42. G. Phys. 1975). ed. Chem. Ohta. E. L. E. p. Chikazumi. R. 20. Experimental methods in magnetism. Res. and J. Rhyne. 29 (1958). 39 (1968). Phys. Walker. 165. 1967). Appl. Soc. Nakamichi. Clark. 28. Lett. R. Mod. G. Phys. 127. Phys..Y. Jr. Appl. T. 6 (1963). Tsuya. Solids. 153 (1967). 1283. Phys. /. 38. /. 573. Phillips and R. R. Phys. 37 (1966). Arai.382 11. L. 228. W. G. N. /. 2 (Wiley-Interscience. Williams. Wakiyama and S. S. Japanese!. 71. J.. Conf. 509.. Rev. Magnetism (Academic Press.. Chikazumi et al. Kanamori. L. F. 34 (1973). Comstock. and N. 52. 16. /. 12. Phys. 22. Phys. 10 (1968). Rept. JETP. Rev. Rev. C. (Asakura Publishing Co. Bozorth and T. Mag. Tokyo. 13 (1958). 310S. W. Arai and N.. M. S. Appl. S. 445. Hall. Rev. 43. 1788. J. E. Solid State.. Lett. M.. 83 (1951). /. A472. G. Vol. 28 (1957). Handbook on magnetic materials. Phys. 30 (1959). Phys. 45. 14. 26. Benninger and A. Appl. 140 (1965). A. Rhyne. and A. 26 (1955). J. Nilsen. Tsuya. 161. 184. 1588. Smoluchowski. G. Phys. Legvold. 50... 25. Phys. Bozorth. 1. Solid State. Japan. Chan. Pavlovic. Proc. 335. 37. Japan (1973). Bickford. Wakiyama and S. Magnetism. Walker. Japan. 3 (1964). 30 (1959). 24. and R. Phys.. lida. Phys. 14 (1959). and R.

35 (1943). 51 (1951). Mag. J. Popov. Soc.12 (in Japanese). 157. 82 (1963). 45 (1974). Appl. J. Mag. Soc. Mag. (London). III/12a. 611. Mech. Matsui and S. M. 45 (1978). 62. R. Tsuya. Appl. 55. 59. Table 13. Z. R. Phys. DeSavage. 56. A. Phys. LXX (1978). 60. Hansen. C14 (1981). K. Chikazumi. R. 70. 37 (1966). 383 V. 117. L. p. Belov. JETP. I. D. 87 (1933). JETP. 63. Stoelinga. W. Appl. Rathenau. 3737. 41 (1975). Appl. B. Phys. 68. H. 3638. Koster. 381. Proc. 20 (1953). Ferromagnetismus (Springer-Verlag. Lazan and L. Comstock and J. R. ASTM. A.. Sokolov and T. H. 61. M. (London). Hien. M.. (Asakura Publishing Co. S. 560. P. Japan. Hasegawa. Phys. Berlin. 65. Sou.. N. 38 (1967). 131. Doring.. W. N. Physica. 1978). A. Phys. ed. Princeton. 220. 1130. Proc. Handbook on magnetic materials. J. Becker and W. . 458. 72.. 66. 56. H. 57. Weiss. Clark.REFERENCES 54. by S. A. Z. J. Landolt-Bornstein (Springer-Verlag. and G. 15-18 (1980). 855. P.. 2793. p. 986. Sou. Kawakami. 281. Phys. and S. /. /. Tsuya. Raymond.J. Proc. F. Cochardt. Bozorth. Mat. M. /. 58. Jahn and E. L. Metalk. 196. Soc. Enrico Fermi. 67. E. School Phys. Proc.. K. /. Gapeev. S. W. Phys. N. Physik. A. Ferromagnetism (Van Nostrand. Kornetzki. 1951). Levitin. 27 (1961).. 1939). P. R. Chikazumi. Demer. 194. 1975).. 1324. Phys. R. J. A161 (1937). 25 (1967). Gersdorf. F. Berlin. and Yu. Hansen. Z. 64. Part a. Int. Markosyan. /. 71. Oxides & Related Comp. p. Roy. Teller. 69. /. Chikazumi et al.

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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.Part VI DOMAIN STRUCTURES Ferro.

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so that the axis of tension becomes an easy axis.1. 15. but people at that time tended to believe that ferromagnetic domains were small enough to be regarded as a mesoscopic feature. Barkhausen was a famous vacuum tube engineer. Cj (see Fig. Then they applied a strong local field Fig. 15. It means that the magnetization of a ferromagnetization specimen takes place in many small discontinuous steps. At the time. they reduced the field to zero and applied a small reverse field.1). the volume of a single domain was estimated to be about 10 ~ 8 cm3.1 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. This effect is called the Barkhausen effect. 15. because the spontaneous magnetization takes different directions in different domains. Barkhausen effect.5% Fe-Ni alloy with a very small magnetocrystalline anisotropy and a positive magnetostriction. it was thought that each step in magnetization corresponds to the flip of a complete domain. In 1919 Barkhausen2 discovered that the magnetization process in ferromagnetic materials takes place in many small discontinuous steps. After removing the domain structure by magnetizing the whole wire to saturation in a long solenoid. He connected a loud speaker to the circuit and heard a roaring noise like the sound of waves on the sea shore. 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.2). This is called the Barkhausen noise. . Later this volume was found to be simply the volume traversed by a domain wall released from some constraint. Permalloy is a 21. From the magnitude of a single step.15 OBSERVATION OF DOMAIN STRUCTURES 15. In 1931 Sixtus and Tonks3 succeeded in producing a large domain in an elastically stretched Permalloy wire.

The reason may be that the sizes of the observed domains were too large according to the then-current concept of domain structures. 15. and a single domain wall travelled along the wire. 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. Sixtus and Tonks also observed that the shape of the domain wall is concave. Sa and S2. Some improvements were made by Elmore. but no definite conclusion was drawn for about seventeen years. The first attempt to observe ferromagnetic domains directly under a microscope was made by Bitter4 in 1931 and independently by Hamos and Thiessen5 in 1932.388 OBSERVATION OF DOMAIN STRUCTURES Fig. with a small coil.6 both in the techniques for preparing the collidal ferromagnetic suspension and for electropolishing the crystal surface. as shown in the inset of Fig. he hesitated to conclude that these were real images of domain walls.2.3(a). in this case a complicated layer of surface domains prevents the observation of the underlying simple domain structure. During this period. to reverse the magnetization. One block of the maze pattern is about 10~2 to 10~ 3 mm in width. C2. This experiment was the first measurement of the speed of domain wall motion. 15. This technique of observing domain structure is called the powder-pattern method. this is in good agreement with the domain volume estimated from the Barkhausen . 15. so that the volume of a single block was estimated to be about 10~8 cm3. one thing that was confusing the investigators was the appearance of the maze domain pattern as shown in Fig. Although some micrographs in Bitter's paper revealed domain walls. This is because the magnetization reversal toward the center of the wire is damped or retarded by local eddy currents. The main reason may be that the surfaces of the single crystals used were not oriented so that they contained a magnetic easy axis. The speed of the wall displacement was determined by measuring the time interval between the signals arising in two separate search coils.2. They observed that a reverse domain nucleated at C 2 . This phenomenon can be considered as a large Barkhausen effect. 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. Large Barkhausen effect. Many investigations were made thereafter using the same technique.

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

An electrolytic solution is made by mixing phosphoric acid (85%) and solid chromic acid in the ratio 9 to 1 (by weight). Fig.5 shows an example of a complicated domain pattern observed on a tilted crystal plane. Fairly heavy currents in the range 10-20Acm~2 are used to polish the specimen. It is also necessary to remove residual stresses introduced during the process of cutting. Figure 15. we must cut a crystal along a crystallographic plane that contains at least one of the easy axes. with a large copper plate serving as the cathode of the electrolytic cell (Fig. Before observation of domain patterns. 15. which is held in the electrolyte by tweezers or a clamp connected to the anode of the power supply. For this purpose.390 OBSERVATION OF DOMAIN STRUCTURES Fig. . Preparation of Fe3O4 precipitate. The solution is contained in a beaker of 100-600 ml capacity. the electrolyte should be completely removed from the specimen by washing with distilled water. the best means is electrolytic polishing using high current density.6). so as to produce a large potential drop near the specimen. many small surface domains appear.5. 15. Complicated domain pattern observed on a crystal surface which makes a fairly large angle with an easy axis (4% Si-Fe). The area of the cathode should be fairly large compared to that of the specimen. In order to observe a well-defined domain pattern.4. 15.

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. in which the light strikes the sample surface at a small angle. Method of electrolytic polishing. To observe the domain structure. which is set under the microscope. A small electromagnet as shown in Fig. First the specimen is placed on the magnet. Figure 15. 15. Small electromagnet for the observation of domain patterns. 15.9 shows an example of the domain pattern observed on a (001) surface of a 4% Si-Fe crystal.8).6.HISTORY OF DOMAIN OBSERVATIONS 391 Fig. The most convenient means to determine the axis of magnetization is to observe the striations which appear perpendicular to Fig. or light lines under dark-field illumination. we use a reflecting or metallurgical microscope. The black straight lines are the domain walls and the arrows show the direction of spontaneous magnetization in each domain. increases the optical contrast and makes the domain walls more easily visible. thus the domain walls are visible as black lines under normal illumination. Sometimes a dark-field illumination system. at a magnification of 70-150 times. The ferromagnetic colloidal particles are attracted to the domain walls where the gradient of the stray field is maximum. 15.7. 15. .7 is convenient for applying a horizontal or a vertical magnetic field to the specimen.

the magnetic flux emerges from the groove as shown in Fig. 15. The black line at the center is drawn as a schematic illustration of the appearance of a mechanical scratch. Williams et al. thus collecting the colloidal particles. The irregularities which cause the striations are thought to be non-flatness of the electropolished surface and inhomogeneity in alloy composition. This behavior of a scratch is shown schematically in Fig. Domain pattern on (001) surface of 4% Si-Fe crystal (retouched).n devised a Fig. . and is not visible (Fig.10(b)). The same thing happens at a groove made deliberately by scratching the electropolished surface with a fine glass fiber. 15.8. 15. 15. The reason is that magnetic free poles appear at irregularities which are perpendicular to the local magnetization. 15.10(a). In order to find the sense of the local magnetization.9. if the scratch is parallel to the domain magnetization. If the groove is perpendicular to the domain magnetization. the domain magnetization. does not attract colloid. it induces no free poles. Powder-pattern method.9.392 OBSERVATION OF DOMAIN STRUCTURES Fig.

The magnetic Kerr effect is the rotation of the plane of polarization of light on reflection from the surface of a magnetized material. 15. Figure 15. The light reflected by the specimen reaches the observer after going through the half-silvered mirror. The powder pattern technique was adopted for electron microscopy by making a replica of the surface after the powder dried.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.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. 15.10. 15. so that they can be used at any temperature. Magnetic flux line around a mechanical scratch: (a) scratch perpendicular to the domain magnetization. Figure 15. Small spike domain induced by a thin magnet wire.12(a) shows a polarizing microscope as used for the observation of magnetic domain structures. clever technique using a thin permanent magnet needle: if the S pole at the end of the needle approaches a domain surface. The light from the lamp is polarized by a polarizer. (b) scratch parallel to the domain magnetization.12 illustrates a domain observation system using the Kerr effect.11). analyzer.MAGNETO-OPTICAL METHOD 393 Fig. These effects do not make use of a colloidal magnetic suspension. and eyepiece.11.12(b) . indicating the sense of domain magnetization. 15. and projected onto the surface of the specimen. Fig. reflected by a half-silvered mirror. Figure 15. the field produced by this S pole induces a spike-like reverse domain which points in the direction of domain magnetization (Fig.

Figures 15. the arrangement shown in Fig. If the magnetization lies parallel to the surface. for the case of magnetization perpendicular to the surface. In this apparatus the polarizer and the analyzer must be arranged so as to satisfy the law of reflection. Domain structures in transparent ferromagnetic materials such as iron garnets can be observed by this method. shows rotation of the polarization axis in opposite senses on reflection from domains magnetized in opposite directions. domains of the other sign will appear darker. so that the magnetization has a nonzero component parallel to the beam. so that the magnetization can lie perpendicular to the c-plane. and for stronger contrast. 15. In this case we must use a polarized incident beam making a small incident angle with the surface. the size and shape of domains vary with sample thickness. so that the other set appears relatively light. If the analyzer is adjusted for maximum transmission of light reflected from domains of one sign.4.12(a) will not reveal the domain structure. Alternatively. 15. The construction of the apparatus is the same as that for the Kerr effect. We shall see the reason in Chapter 17.1(e) MnBi has its easy axis parallel to the c-axis. and its magnetocrystalline anisotropy is enormously large. (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.3 LORENTZ ELECTRON MICROSCOPY In magnetic thin films which are thin enough to allow the transmission of an electron . Figure 15.13(a)-(c) show the domains observed for specimens of different thickness. the analyzer can be adjusted for minimum transmission from one set of domains. The Faraday effect is the phenomenon by which the polarization axis rotates during the propagation of light through the material. 15.394 OBSERVATION OF DOMAIN STRUCTURES Fig. except that the incident polarized light passes through the specimen as in a biological microscope. As explained in Section 12.12.13 shows the domain structures observed by this device on the c-plane of MnBi. in spite of a large demagnetizing field.

the domain structure can be observed using the electron microscope. Domain structures observed by the magnetic Kerr effect on the c-plane of MnBi plates: (a) the thickest plate. (Due to Roberts and Bean16) beam. 15.17 If the objective electron lens is defocused slightly from the specimen film.LORENTZ ELECTRON MICROSCOPY 395 Fig. (c) the thinnest.13. 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. (b) intermediate. the domain walls appear as .

5. This method is called Lorentz microscopy. from which we can deduce the direction of magnetization. Principle of Lorenz microscopy. If the objective lens is focused at infinity. from which we know that the magnetization lies in four equivalent crystallographic directions. as illustrated in Fig.15 shows an example of domain structures observed in a Permalloy thin film of thickness 600 A. the method known as transmission Lorentz scanning electron microscopy (SEM) overcomes this difficulty.19 We see many domain walls appearing as black and white lines. However.14. 15.4. 15. as will be described in Section 15. 15.14. back or white lines. a parallel electron beam focuses to a spot (a diffraction spot). The strong point of this method is its high magnification. The inset shows the diffraction pattern.18 The spin structures of the cross-ties perpendicular to the main domain walls will be explained in Section 16. Figure 15.16 shows a Lorentz micrograph observed for a single crystal film of iron parallel to the (001) plane.396 OBSERVATION OF DOMAIN STRUCTURES Electron beam Fig. Figure 15. but because of the defocusing it is not possible to observe well-defined crystalline and magnetic structures at the same time.4 SCANNING ELECTRON MICROSCOPY Scanning electron microscopy (SEM) enables the observation of domain structures in .

they are deflected by the Lorentz force in directions which are different in different domains. Domain pattern observed in a Permalloy film of thickness 600 A. when electrons penetrate into a tilted ferromagnetic specimen. The electron beam is scanned over the specimen surface and the deflected electrons are collected by the electron detector. 15. 15.17. 15.16. Fig. Domain pattern observed in a (001) iron single crystal film of thickness 2500 A. This method is called reflection Lorentz SEM. The electron beam in the display tube is synchronized with the scanning electron beam in the electron microscope. Some of the domains deflect the electrons towards the surface of the specimen. while other domains deflect the electrons more deeply into the specimen.18. and its diffraction pattern (inset). and its intensity is modulated by the number of collected electrons.18 thick specimens by using the deflection of electron beams.SCANNING ELECTRON MICROSCOPY 397 Fig.19 . As shown in Fig. Then the domain structure is reproduced as a black and white pattern as shown in Fig. 15.15.

15. see the nucleation and motion of the domain walls. From such a wave form we can. An AC magnetic field is applied to the sample at a frequency which is a small multiple of the scanning electron beam sweep frequency.18. Instead of reflecting electrons from a bulk specimen. 15. 15. By a refinement of this method it is possible to observe the dynamic behavior of domain walls.20 .398 OBSERVATION OF DOMAIN STRUCTURES Fig. In this method. an electron Fig.19.3). The principle of the observation of domain walls in a thick specimen using scanning electron microscopy. we can utilize the Lorentz deflection22 from a magnetic thin film (see Section 15. Domain pattern observed on a Si-Fe plate. and the domain walls appear as sinusoidal waves as shown in Fig. if the wall motion is sufficiently repeatable.17.

the strong point of this method is that the electron beam can be sharply focused on the film. The secondary electrons are collected and accelerated towards a thin-film target made of gold.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. 15.21 beam is scanned over the specimen film.24 Figure 15.SCANNING ELECTRON MICROSCOPY 399 A Fig. D .19. Another method for observing domain patterns on bulk specimens is spin-polarized SEM. in which the electron beam is slightly defocused from the film.23 We call this method transmission Lorentz SEM. under a potential gradient that produces an electron wave with a wavelength of the order of the atomic radius of gold. As a result of interference scattering. Thus well-defined structural and micro-magnetic structures can be observed on the same pattern. is detected by a Mott detector. As compared with the usual Lorentz microscopy. the brightness of the electron beam in the display tube is modulated according to the diffraction angle to make the domain pattern visible. 15.20. the sense of which is different for different domains. The principle of the Mott detector. 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. the cross-section of the scattering beam depends strongly on the scattering angle at some specific W Fig.

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

The principle is to utilize the change in the diffraction angle of the diffracted X-rays due to a strain in the crystal.23. 15.X-RAY TOPOGRAPHY 401 Fig. Domain pattern observed by means of X-ray topography on a Si-Fe (001) plate 120/Am thick. As shown in Fig. 15. the X-rays Fig.5 X-RAY TOPOGRAPHY X-ray topography was invented by Lang26 to investigate the distribution of internal strains in a crystal. 15.22. Principle of X-ray topography. 15.27'28 .22. also we can see the spins inside the 180 degree walls. Figure (c) illustrates the spin map as deduced from these experiments.

so that the diffracted X-rays are blocked by the slit S and cannot reach the film B. 15.6 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. as shown in Fig. the distribution of the internal strain in the specimen appears as a black and white pattern in the film B. The strong point of this method is that it allows the observation of the interior domain structure. the diffraction angle is changed. If the specimen A and the film B are displaced at the same velocity. 120 yum thick. but a strain image caused by magnetostriction. 15. thus being deflected in the same way as a beam of light passing through an optical biprism.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. this electron Fig. In order to produce a good coherent electron beam.24.29 .30 The electrons tend to be attracted towards the gold wire from both the electrodes.24. If the crystal is distorted. Figure 15. This is not a magnetic image. Schematic diagram of electron-hologram formation.23 shows the domain pattern observed by this method for a (001) single crystal plate of Si-Fe. The actual construction of the electron biprism consists of two earthed parallel electrodes with a positively charged thin gold wire inserted between them.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. 15.

and after overlapping with the reference optical beam reproduces a real image of the specimen. The reason for this will be explained below.ELECTRON HOLOGRAPHY 403 Fig.32 Suppose that the electron waves P and Q in Fig. According to quantum mechanics. (a) Lorentz image and (b) electron interference fringes as observed by electron holography for an amorphous film of (Co094Fe006)7QSilnB11. Several domain walls can be observed. A laser beam with the same wavelength as that of the electron beam used to produce the hologram is passed through the hologram plate. which have the same phase . The hologram exposed on the photographic plate is developed and transferred to an optical system to reproduce a real image of the specimen. The magnetic structure in these photographs will be discussed in Chapter 16.31 microscope uses field emission from a sharp cold tungsten cathode. 15.25(a) shows a Lorentz micrograph produced in this way from an amorphous film of composition (Co094Fe006)79Si10B11. when an electron passes through a space where the vector potential A exists. Figure 15. interference fringes as seen in (b) are formed. and the integration is along the electron path.26. Therefore when the reference optical beam is directed almost parallel to the beam passed through the hologram. The holograph contains information not only of the real image but also of the phase difference of the electron waves. 15. These fringes run parallel to the magnetization in the film.25. the electron wave undergoes a phase shift given by where h is Planck's constant divided by 2ir.

15. at z = 0. $ in (15. we see by putting the final term in (15. In other words. 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. if neighboring interference fringes correspond to P' and Q'.. we have * Since B = curl A. 15.2) equal tO 27T.26.1) along ABCD is given by <j)A • ds = fl curl. A dS = fj Bn AS = AO. . If the saturation flux density Bs in the film is the only magnetic flux penetrating the area PP'Q'Q.3) must be twice the flux quantum.404 OBSERVATION OF DOMAIN STRUCTURES Fig.27 two electron waves PP' and QQ' passing through a magnetic thin film of thickness d form two neighboring interference fringes. From (15. If this phase difference were ITT.4). travel through the magnetic field and reach P' and Q' at z = z0. where AO is the magnetic flux penetrating the area ABCD. which is just twice the flux quantum h/le. the integration in (15.1). we have where / is the separation between the two fringes. Illustration of phase difference between two electron waves. Suppose that in Fig. From (15.

Z. 6. 5. 53. 486. 796. Phys. Phys. 153. Phys. S. M. Magnetic flux in a magnetic thin film. Z. For instance. Phys. R.. Lifshitz. 38 (1931). Weiss. Sowjet U. 1903. British J. IEEE Trans. which exist where the lines of flux emerge. 1291. 43 (1933). Griffiths. H. 96 (1935). 155. J. 442. Sekiya. MAG-15 (1979). 523. 9 (1958). Neel. 5 (1944). 8 (1935). Tonks. Appl. Japan. Phys. Phys. Hamos and P. Phys. Barkhausen. Phys. 39 (1932). D. Lifshitz. 54 (1938). Phys. 337. 89 (1934). (15. Landau and E. Phys. 401. However. 90 (1934).. 62 (1942). Rev. On the other hand. 265. if the flux caused by the magnetization in the film leaks into space and comes back through the area PP'Q'Q. L. J. 757. C.. S. 279. Phys. Suzuki.REFERENCES 405 Fig. 8 (1944). 241. f. 4. Williams. 3. 2. M. 357. 930. S.. 9. /. 71 (1932). J.. 309. when we observe the flux in space. Shockley. if there is leakage flux in the area PP'Q'Q. Kaya. Sixtus and L. 661..5). Elmore. 37 (1931). Soc. 51 (1937). V. and the separation of the fringes is inversely proportional to Bs.. Kaya and J. Phys. Mag. L. d. /. L. 507. Bitter.27. USSR. 982. and W. Rev. so that the separation / becomes larger than (15. the fringes run parallel to the magnetization.. 551. Phys. the interference fringes run along the lines of flux density. H. F.. Bozorth.. Rad. This method is useful for finding the location of free magnetic poles.4) decreases. is uniform. K. 11.5) does not hold. Rev. /. 42 (1932).. 10. 20 (1919). J. Phys. Z. 7. P. <E> in (15. Rev.. Therefore it the thickness of the film. W.. 12. 6 (1907). . Z. 15. 10 (1955). Thiessen. A. 410 (1932). J. 419. 8. 70. E. Chikazumi and K. Z. REFERENCES 1. 53 (1938). 75 (1949). Craik and P. 931.

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

or magnetoelastic energy. 16. are increased.16 SPIN DISTRIBUTION AND DOMAIN WALLS 16. as shown in Fig. In an infinitely long. If this disk is uniformly magnetized to saturation along a diameter. which modifies the complete parallel spin alignment. As a result. magnetocrystalline energy. and the demagnetizing field Af/s/ju. 16. Fig. In a ferromagnet of finite size.2. the spontaneous magnetization is aligned parallel to the long axis.1. such a single domain produces surface free poles which give rise to magnetostatic energy. The stable spin distribution is determined by minimizing the total energy Consider a ferromagnetic disk of radius r and thickness d. free magnetic poles N and S appear at the edges. U3.99) given by where v is the volume of the disk given by Fig.1. thin ferromagnet. the spin distribution must be altered.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. i/mag. In order to reduce t/mag. exchange energy.0 appears opposite to the spontaneous magnetization 7S. Ux. Ua. . so that there is a magnetostatic energy (1. thus forming a single domain. 16. Circularly magnetized disk (no free poles). Uniformly magnetized disk (single domain structure).

in addition to the spin S. This formula shows that the exchange increases as the square of the angle (p. Let us calculate the sum of the exchange pair energies between 5.4) reduces to where S is the magnitude of the spin. In other words.2. a' can be expanded as where (x. which increases as the square of the strain in the lattice. Instead. the exchange pair energy given by (16. and that of Sj at Q.44) or found from Table 1. the exchange pair energy (16. According to a detailed calculation by Weiss. The value of / is related to the Curie point as listed in Table 6. if we assume S = 1 for iron. it follows that When the angle tp between spins S. There is no divergence of magnetization and therefore no free poles.8). be a'. the exchange energy stored in a pair of spins 5. and can be calculated using equation (1. and its z nearest neighbor SyS. 16.7) can be expressed in terms of a and a' as cos <p = a • a'. This is analogous to the elastic energy. One possible spin configuration that eliminates magnetostatic energy is the circular configuration shown in Fig. and S.. In a cubic lattice. Similarly the exchange energy density can be expressed in terms of the spin distribution in the lattice. using the relationship (16. at Q. and Sj is small. by the distance r-t.1. at P be a.7) can be expressed in terms of a. Umag = 0. In a ferromagnet. Since cos <p in (16.5. is given by where / is the exchange integral. As discussed in Section 6. The elastic energy density can be expressed in terms of the strain tensor as shown in (14. we find another spin at Q' which is located —r . y-.1 for various statistical approximations. If we assume the variation of a is smooth and continuous.4 Let a unit vector parallel to the spin S.. neighboring spins make some non-zero angle. / > 0. A general discussion of magnetostatic energy is given in Section 1.27).2.408 SPIN DISTRIBUTION AND DOMAIN WALLS The demagnetizing factor N can be approximated by that of a thin oblate spheroid.3 the relationship between / and the Curie point is given by For instance. which is separated from S. z •) are the components of the distance r. so that some exchange energy is stored.

body-centered cubic.9) over all the atomic pairs in a unit volume. differentiating (a • a) = 1 twice with respect to x. The number of atoms in a unit cell. 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. = 4 for a face-centered cubic lattice j Summing (16.3). n. Calculation of exchange energy in a given spin distribution. and the facecentered cubic lattices.13). where a is the lattice constant or the length of the edge of a unit cell.12) becomes where A is given by . from P (see Fig. the exchange energy density becomes On the other hand. 16.8) over Q and Q' vanish.MICROMAGNETICSs 409 Fig.3. we have Using (16. is given by n = 1 for a simple cubic lattice \ = 2 for a body-centered cubic lattice > . (16. 16. so that the summations of the second terms in (16.

15. 6. we have so that In addition to this. 15. as shown in Fig./'dr = 0.3). the spin direction is parallel to the edge. z) with the origin at the center of the disk and the z-axis perpendicular to the plane of the disk.and y-axes.410 SPIN DISTRIBUTION AND DOMAIN WALLS The terms such as da/dx correspond to the strain in an elastic body. we have Since where i and j are unit vectors parallel to the x.15) is called the exchange stiffness constant. with areas where the spin direction changes sharply. depending on whether the sense of spin rotation is clockwise or anticlockwise (see Section 15. and the expression (16. If we rewrite (16.21) that the average exchange energy density t/ex/i> increases as the radius r decreases. 16. At the edge of the film. da/dz = 0. respectively.2. The actual domain structure in an amorphous film as seen in Fig. The spin configuration in the intermediate region is not circular but rather rectangular. so that from (16. da. Let us calculate the exchange energy of the spin configuration shown in Fig.25(a). This is because the exchange energy density £ex given by (16. the spins are forced to align parallel to one of the easy axes.14) using cylindrical coordinates (r. When the magnetocrystalline anisotropy is large. In this sense the coefficient A in (16. however. In such regions there appear black or white lines in a Lorentz image. the domain structure in a disk with cubic .25(b) shows such a circular spin configuration at the center.14) is similar to that for the elastic energy density which is expressed as a quadratic function of strain tensors.20) is large where r is small. As a result.16) we have Therefore the exchange energy of a disk with radius r and thickness d is given by We see from (16. so as to reduce the magnetostatic energy.

a considerable amount of elastic energy must be stored in the crystal.5.6. some magnetostatic energy is stored. Because of the free magnetic poles appearing at the edges of the disk. These transition layers are called domain walls.5.2. 16. and the elastic energy will be concentrated into the small flux-closure domains. this term is also . If each domain elongates as required by the magnetostrictive strain. 16.4. Since the magnitude of A is generally small. after Bloch5 who first investigated the spin structure of these transition layers in detail. In order to keep the domains in contact with each other. Sometimes they are referred to as Block walls.) In this case the deformation of the bulk sample will be determined by the magnetostriction of the main domains. 16. Domain structures of a disk with cubic magnetocrystalline anisotropy.7).2 DOMAIN WALLS At domain boundaries there are transition layers where spins gradually change their direction from one domain to the other. (Domains with antiparallel magnetization have the same strain.1). We shall discuss this problem in Section 16. however. In addition to this. 16. which are forced to strain so as to fit the deformation of the main domains (Fig. the magnetostrictive strain does not actually cause gaps to appear. Consider next the case of a ferromagnet with a large magnetostriction (A > 0). Fig. the crystal will separate at the domain boundaries as shown in Fig. the domain walls which separate the neighboring domains store energy which is called domain wall energy.4. However. 16. 16. We have discussed here various domain structures and the various kinds of associated energies. while that of a uniaxial crystal becomes as shown in Fig. 16.DOMAIN WALLS 411 Fig. We shall treat this problem in Chapter 17. 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. the total energy is distributed among these associated energies in appropriate ratios. crystal structure and large crystal anisotropy becomes as shown in Fig. Real domain structures will be determined by minimizing the total energies given by (16. In the equilibrium state. Domain structures of a disk with uniaxial magnetocrystalline anisotropy.

8.7)). so that an abrupt change in the angle <p increases exchange energy to a great extent. between spins on the neighboring two layers is given by ir/N. 16. . sometimes used to describe one particular type of domain wall.412 SPIN DISTRIBUTION AND DOMAIN WALLS Fig.6. 16.7. Therefore the angle (p. the thicker the wall.8.5). 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. Since the number of atoms in a unit area of one layer is given by I/a2. Rotation of spins in the domain wall. the number of nearest neighbor spin pairs in a unit area of the wall is given by N/a2. 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. Fig. Let us calculate the domain wall energy using a simplified model: as shown in Fig. 16. Postulated domain structures of a disk with a large positive magnetostriction (unrestrained magnetostrictive deformation leads to the formation of gaps at the domain boundaries). the spins change their direction in steps of equal angle from (p = 0 to 180° over N atomic layers. Expected domain structure of a disk with normal magnetostriction (elastic energy is concentrated in the small fluxclosure domains). Let us consider a simple cubic lattice with lattice constant a. to distinguish it from another type called a Neel wall (see Section 16. Fig.. 16. In other words. the smaller the exchange energy.

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

The angle of spins between two neighboring layers is given by (d<p/dz)a. 16. Let us solve this problem using the variational method.9. It is interesting to note that yex and ja are equal in the equilibrium state. the energy of the wall per unit area is calculated as In the above model.9). Actually. 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.* For iron. if the anisotropy energy measured as a function of the angle of spin. is denoted by g(<p). . we assumed that the rotation of spin occurs at a constant rate. however. the two terms are numerically equal in the equilibrium state with respect to changes in x.414 SPIN DISTRIBUTION AND DOMAIN WALLS Fig. Set the z-axis perpendicular to the wall surface. the orientation of each spin in a wall is determined so as to minimize the total energy. 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. 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. so that the exchange energy is expressed as JS2a2(d<p/dz)2. <p(z).

the integrand must always be zero.15). Since the exchange interaction is isotropic.DOMAIN WALLS Therefore the total energy becomes 415 where A is the exchange stiffness constant given by (16. that is This equation is usually called the Euler equation of the variational problem. the total energy of the wall is changed by which should vanish for the stable spin arrangement.16 X 10~21 (see (16. regardless of its orientation in the lattice.33) for a small variation of the spin arrangement inside the wall. 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. Multiplying by (d(p/dz) and integrating from z = —<*> to z = z.35) requires that In order that this condition be satisfied for any selection of S<p(z). so that Next the stable spin configuration can be obtained by minimizing the total energy (16. 5 = 1. a = 2. we have . When the angle tf> of the spin at z is varied by 8<p. For iron.6)). Then the vanishing of (16. / = 2.9 X 1(T10 and n = 2. the value of A is the same for any wall.

Modifying (16. this becomes We shall calculate this function for several examples later. Let us treat the domain wall of a ferromagnet which has uniaxial anisotropy.416 SPIN DISTRIBUTION AND DOMAIN WALLS Here the origin of g(<p) is defined to be the value at <p = + ir/2. 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. so that g must be zero for <p = 90°.10. so that g = 0 inside the domains at z = +°°.40). where the anisotropy energy is the highest.39) tells us that the anisotropy energy density is equal to the exchange energy density at any part of the wall. and vice versa. because the origin of <p is defined to be the hard axis.10.33). Then (16.44) is graphically shown in Fig. Referring to (16. The relationship (16. 16. the spin rotation is most rapid at the center of the wall.39). 16. The thickness of the wall is strictly speaking infinite.41) becomes The relationship between <p and z given by (16. As discussed above. we have On integrating. From this fact we can see that the spin rotation is more rapid at any position where the spin has a higher anisotropy energy. where the anisotropy energy approaches zero. as indicated by the dashed line in Fig.1). The rate of spin rotation at z = 0 is given by so that the thickness of the wall is given by . The anisotropy energy in this case is expressed as This expression differs from the usual one such as the first term in (12. we obtain. for the total surface energy of the wall given by (16. and tends to vanish far from the center of the wall.

16. Variation of spin direction within a 180° wall in a ferromagnetic crystal with uniaxial anisotropy.180° WALLS 417 Fig. while a wall between [100] and [010] is a 90° wall. such as nickel. magnetic free poles would appear along the curved portion.3 180° WALLS Magnetic domain walls are classified into two categories: 180° walls separating two oppositely magnetized domains.2 and 16. [010]. 16.27). 16. 16. [010]. as in iron. In the case of a ferromagnet having its easy axes parallel to (111). 16. as seen in Fig. and [001]. and 90° walls separating two domains whose magnetizations make a 90° angle. all domain walls other than 180° walls are classified as 90° walls. 109°. In this section we treat 180° walls. it appears as a straight line. there are three kinds of domain walls: 180°.3(b). This expression is the same as (16.12(b). The energy of the wall can be calculated by using (16. which was deduced from the simplified model shown in Fig.29). and 71°. 15.8. [100].43) in (16. The reason is that if the wall were curved as shown in Fig.11). Let us consider the geometry of a 180° wall separating [100] and [100] domains in a cubic ferromagnet with K1 > 0. Consider a cubic ferromagnet having its easy axes parallel to <100>.42): which is also nearly equal to (16. There are six possible directions of domain magnetization: [100].3). Similar results are obtained for domain walls in materials with cubic anisotropy (see Problems 16. If we observe such a wall on the (001) surface. they share the property of being sensitive to mechanical stresses. giving rise to a demagnetizing field opposite to the magnetization . [001]. A domain wall between [100] and [100] domains is a 180° wall. as seen in the domain pattern observed on the (110) surface of Permalloy (Fig.10. Commonly.

11.418 SPIN DISTRIBUTION AND DOMAIN WALLS Fig. when the wall is observed in a direction parallel to the domain magnetization.13. because this curvature does not result in the appearance of any magnetic free poles Fig. However. the cross-sectional view of the wall can be curved as shown in Fig.12. 16. Therefore the wall is straightened as shown in Fig. . Diagrams showing how domain walls are flattened to decrease magnetostatic energy. 16.6 in the swollen part of the domain.12(a). Domain pattern observed on the (110) surface of ordered Permalloy. 16. 16.

16. This curvature does increase the total area of the domain wall. Possible curvature of a domain wall.14. irregular distribution of internal stresses or alloy composition. Let the angle between n and y-axis be i/>. We set new coordinates (x'. The spins in the wall rotate about n as shown in Fig. on the wall. and accordingly the total wall energy.5). so the wall tends to decrease its surface area unless there is some reason to sustain the curvature. 16.419 Fig.14. . The angle i/< indicates the direction of the normal to the wall surface. the normal n must lie in the y-z plane. and the dependence of the wall energy on its crystallographic orientation. z').yr. n. Imagine a cylindrical 180° wall between [100] and [100] domains as shown in Fig. in which the *'-axis is parallel Fig. As explained above. 16. The magnetocrystalline anisotropy energy is given by as shown in (12. 16. Possible mechanisms for sustaining curvature in the wall result from the presence of inclusions or voids. with the *-axis parallel to the magnetization. A cylindrical domain wall. and consider how the wall energy depends on the crystallographic direction of the wall normal.9 to avoid the appearance of magnetic free poles in the wall.13.

the wall energy (16.42) becomes Putting sin i/> cos if> = s. sin q> = t.53 If the plane of the wall is parallel to the x-y plane (i/> = Tr/2).49). <p. the direction cosines with respect to (x. the wall energy is maximum at if/ = 45°. in terms of new direction cosines as Using the angle.15. so that The change in j during the rotation of the wall from tj/ = 0 to 90° can be calculated using (16. 16. or cos <p d<p = dt. 16. As seen in this graph. it follows that s = 0. z) are expressed as Considering that 0:3 = 0 in the wall. or parallel to the x-z plane (i/f = 0). where the wall is parallel to (Oil). we have from (16. y. Using direction cosines ( a ( .54) and is shown by the solid line in Fig. a'2.48) is expressed. through the use of (16. the anisotropy energy (16.420 SPIN DISTRIBUTION AND DOMAIN WALLS to the jc-axis. as indicated in Fig. we have so that the anisotropy energy in the wall is expressed as Using this expression. The maximum value is . a'3) with respect to the new coordinates.9.

Configuration of 180° walls in a (Oil) single crystal plate. dashed line. Fig.16.34) and K\ given by (12.17. 16. 16. 16. we have and Therefore the 180° wall tends to become parallel to {100}. Dependence of 180° wall energy on the orientation of the normal to the wall surface. total wall energy (energy per unit area X total area) for a wall in a (Oil) single crystal plate.180° WALLS 421 Fig. in the case of a single crystal plate cut parallel to (Oil). Orientation of a 180° wall in a (Oil) single crystal plate.6). wall energy per unit area. For iron. the 180° wall tends to tilt so as to minimize the total energy (= wall energy X total area) as shown in Fig.16. . using values of A given by (16.15. The total energy is given by Fig^ 16. Solid line. However.

In the case of i/f = 45°. the spin rotation is separated into two stages.52) in (16. of course. 16.17. the field is applied parallel to the magnetization of the intermediate domain. the domain between the two 90° walls is highly strained. This is one possible mechanism for nucleation of 90° walls in the process of demagnetization.41) to give Figure 16. thus making possible the zig-zag shapes shown in Fig. When. In an actual ferromagnet with nonzero magnetostriction. whereas in the case of i/> = 2. However.7 The geometry of spin rotation in a 180° wall is solved by using (16. a 180° wall is expected to split into two 90° walls.15 the function U/Qd) is shown as a dashed curve.87°. the presence of a tilt was confirmed by observing the position of 180° walls on the top and bottom surfaces of a thin crystal. because of the appearance of strong magnetic free poles on a plane perpendicular to the direction of magnetization. It is almost impossible to observe such an end-on or cross-sectional view of the zig-zag wall. the two 90° walls cannot move very far apart. 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. the spin rotates smoothly. Accordingly the wall has two stable orientations. where the rotation rate should be very small. In Fig. the double wall may be separated into two independent 90° walls. the wall tends to separate into two 90° walls. thus generating a new domain which is magnetized perpendicular to the original domains. For a material with small magnetostriction. In order to reduce this energy. however. In the case of t/j = 0.4 90° WALLS A 90° domain wall separates domains whose magnetizations make an angle of 90° . so that the spin direction approaches another easy axis.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. on the magnitude of the magnetostriction constants of the material.87°. In this case the wall is nearly parallel to (010). 16.4 The magnitude of this effect depends. 16. [001]. which has two minima at t// — 13° and <{/— IT. so that it must store a magnetoelastic energy density |{(f)A100}2 X (cn — c12).18 shows the angle of spin rotation <p as a function of z (normalized) for t/f = 45° and if = 2.

n. /33).61). Geometry of spin rotation in a 180° wall making angles i/» = 45° and i/» = 2. Let the two magnetizations on both sides of the 90° wall by ll and 72.19) be (<*!. Let the angle between the normal to the wall. The 90° wall is oriented so as to make the normal component of magnetization the same on both sides of the wall. and the angle between the normal. and those of the magnetization of one domain be ( f t l t /32. 16.y'. a2. n. But the 90° wall has the freedom to change its orientation about this bisector (Fig. We shall discuss these matters in this section. the details are somewhat different. 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. and the domain magnetizations be 6. where a^ = 0. to avoid the appearance of magnetic free poles on the wall surface. with respect to (x'. (or near 90°). and the normal to the plane which contains the two magnetizations be i/f. a3).90° WALLS 423 Fig. 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. n. a 2 = sin i//. 16. a3 = cos i/». from which we have (16. This condition does not uniquely specify the orientation of the wall. /33 = 0.87° with the (001) plane (K1 > 0).19). However. In order to see the rotation of spins in the wall more *Let the direction cosines of the normal to the wall. /3j = /32 = 1/V^. The fundamental properties of 90° walls are similar to those of 180° walls. Then we have cos 8= al/3l + a2f}2 + a 3 /3 3 .18.z') (see Fig. 16. so that cos 0=(l/v^)sin i/». .

19. Let us assume that the azimuthal angle of the magnetization about the z-axis changes from <f»l to <£2 (<j)l = — $2).20) be (a1. .424 SPIN DISTRIBUTION AND DOMAIN WALLS Fig. and 7i . y. 16. z. 16.72). From a consideration of the geometry. z) (see Fig. fa. Diagram showing possible orientation of a 90° wall which has no magnetic free poles.20.62). * Let the direction cosines of the two magnetizations with respect to (x.^2 = cos "> so that sin2 0(cos2 (j>1 — sin2 $[) + cos2 8 = 0.* we have The angle between the spins in neighboring atomic layers in the 90° wall is given by Fig. let us choose new coordinate axes so that the x-y plane is parallel to the plane of the wall as shown in Fig.Since the two magnetizations are perpendicular. a^ + /^i ft + 7iT2 = 1> where al = a2 = sin 8 cos <t>lt fa = .ft2 = sin 6 sin 4>i. 16. yj) and (a2. easily. from which we have (16. 16. Directions of magnetization on both sides of a 90° domain wall.20. /32. the magnetization makes the angle 6 with the normal to the plane wall. As defined above.

Fig.21.21.64). y. The 90° wall energy.5). we get the wall energy as a function of the angle ^ as shown in Fig.65). so that the larger range of integration makes the wall energy larger in spite of the smaller value of sin2 6. as a function of orientation of the wall. using the first term of the magnetocrystalline anisotropy given by (12. 16. U. On the other hand. is minimum for i// = 0. minimizing the sum of the energies (16. if the anisotropy energy density is expressed as a function of the two angles 6 and (j). the total energy of the wall is given [similar to (16. The reason for this is that the rotation of the spin in the wall is only 90°. </>). where the plane of the wall is parallel to the magnetization of the domains on either side.42) for the 180° wall]. for \\i = 90°. . where a is the spacing of the atomic layers. By using this result. then the anisotropy energy per unit area is given by The spin rotation in the wall can be found by the variational method. the total change in the azimuthal angle is 180°. the wall energy per unit area.63) and (16. As seen in this graph. 16. The energy per unit area parallel to the average zigzag wall. y.90° WALLS 425 sin 9(d<f)/dz)a. 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. g(6. is minimum at fy = 62°. On the contrary. by By the numerical calculation of (16.

22) in order to attain the minimum total wall energy. 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. 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). The observed zigzag angle is plotted as a function of the distance from the scratch in Fig. 16.21 as a function of if/. U. 16. 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. It is observed that the zigzag angle is nearly 106° at places far from the scratch. 16. Figure 16. . which we call the zigzag angle. each segment must be out of the (001) plane. When we observe these zigzag walls on the (100) crystal surface (the y-z plane in Fig. thus resulting in zigzag-shaped walls. The reason for the variation of the zigzag angle. is minimum at if/ = 62°. Since in this case 90° walls must stretch along the z-axis. is 106°.22). As seen in this graph the energy. 16. that the stable configuration of the 90° wall is a zigzag shape. 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. 16. CD. 16. 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. may be understood as follows: a tension stress is produced in the region around the scratch.22. It is concluded. 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. composed of alternate segments each making an angle i/f = +62° with the x-y plane.22). the angle CD between the zigzag line segments. but becomes smaller at places nearer to the scratch.24.426 SPIN DISTRIBUTION AND DOMAIN WALLS Fig. therefore. Domain structure induced by the application of a mechanical scratch on a (100) surface of 4% Si-Fe crystal. These domains are connected by closure domains at the crystal surface to avoid the appearance of magnetic free poles.

16. discourages the closure domains.24.8 . thus Fig. Variation of zigzag angle and calculated internal stress as a function of a distance from the scratch. Txx. This tension. however. 16.23.90° WALLS 427 Fig. Zigzag domain walls produced by a mechanical scratch on a (100) surface of 4% Si-Fe crystal (Chikazumi and Suzuki8). This tension is the main origin of the underlying domains parallel to the x-axis. because their magnetizations are perpendicular to the tension. because the magnetostriction constant parallel to <100> is positive. so that the normal components of magnetization across the zigzag walls are no longer continuous. which has only the component Txx underneath the maze domain. Therefore the closure domains tend to become shallower.

27). are in fact composed of fine zigzag lines. The result shows that the maximum value of the internal tension is 90kgmm~ 2 . This experiment was performed for the purpose of clarifying the nature of maze domains (see Fig.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. However. A tilted 90° wall as observed for an iron whisker. these surface free poles have little effect.25.3(a)) observed on mechanically polished crystal surfaces. 16.428 SPIN DISTRIBUTION AND DOMAIN WALLS Fig. 16. The total magnetic free pole on a zigzag segment is independent of the angle t/>. the zigzag angle is expected to decrease close to the scratch.31).9). Neel pointed out that in the case of very thin films. Let us calculate the energy of the Neel wall for a uniaxial ferromagnet. In thick samples. 16. such a spin rotation must produce free poles on the sample surface where the domain wall terminates. 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. 16.9 producing magnetic free poles on the zigzag walls. by . The domain patterns observed on each surface of the crystal revealed that the 90° wall tilts as shown in Fig. The tilt of 90° walls was also observed on iron whisker crystals. 16.25. 16. grown by the reduction of ferrous bromide by hydrogen gas at about 700°C. but in thin samples their contribution to the total energy of the system may not be negligible. which normally appear to be poorly defined and thick. 15. The zigzag angle was theoretically calculated as a function of TXJC. In contrast to the spin rotation in the Bloch wall (Fig. so that a decrease in the angle results in the same number of free poles spread over a larger wall area. in good agreement with the calculation. Since Txx increases nearer to the scratch. The exchange energy stored in a unit area of this wall is given.9 The crystal is a few millimeters in length and has a rectangular cross-section. and the latter a Block wall (see Fig.26). It was found by a careful observation of the powder pattern using a dilute colloidal suspension that the walls of maze domains. 16.10 We call the former type of wall a Neel wall. the spin rotation in the Neel wall occurs in a plane containing the normal to the wall (Fig.& The value of Txx deduced from the observed value of the zigzag angle is also plotted in Fig. similarly to (16. thus reducing the magnetostatic energy. which is close to the yield strength of the material.24.

16.32).27. by In addition. . The anisotropy energy per unit area of the wall is given. the Neel wall stores magnetostatic energy due to the demagnetizing field Fig.SPECIAL-TYPE DOMAIN WALLS 429 Fig. Spin rotation across a Neel wall (the rotation occurs in the plane of the page). similarly to (16. (b) Neel wall (Chikazumi). by where g(0) is given. 16.26. Two types of spin rotation across a magnetic domain wall. for uniaxial anisotropy: (a) Bloch wall. similarly to (16.43).

47).29. the Bloch wall has an additional magnetostatic energy due to free poles at the film surfaces. 16.430 SPIN DISTRIBUTION AND DOMAIN WALLS Fig. so that all the equations from (16.72) with (16. which was assumed to be 1 in (16. decreases with a Fig.70). we find that the Neel wall always has higher energy than the Bloch wall.47). Spin configurations inside and outside the cross-tie wall. On the other hand. because the demagnetizing factor. which increases with a decrease of film thickness as shown by the curve a in Fig.11 .33) to (16.28.68) and (16.28. the wall energy of the Neel wall is given by Comparing (16.69). In the case of magnetic thin films.47) hold in this case by using the substitution Therefore.10 This term has the same functional form as (16. 16. referring to (16. the magnetostatic energy of the Neel wall decreases with a decrease of film thickness. N. 16. (b) Neel wall. Dependence of the wall energy on film thickness (a) Bloch wall.

29 appears.28.SPECIAL-TYPE DOMAIN WALLS 431 Fig. where the energies of both types of domain wall are comparable. Figure 16.12 decrease of film thickness as shown by the curve b in Fig. (b) interference fringes. 16. while the Neel wall is stable for relatively thin films. where the direction of spin changes discontinuously. a cross-tie wall as shown in Fig. Electron interference micrographs of a cross-tie wall as observed for a Permalloy film: (a) Lorentz image. Therefore the Bloch wall is stable for relatively thick films. Bloch-type and Neel-type spin configurations appear alternatively along the wall.31. The value of y is the direction cosine of spins with respect to the normal to the page. For films of intermediate thickness. Leakage field-free spin configuration of a Bloch wall. 16. 1630.13 .30(a) shows a Lorentz image of a cross-tie wall observed for a Permalloy film. while (b) shows interference fringes Fig. 16.11 In this wall. The spin arrangement on both sides of the wall is modified and results in cross-ties.

16. Brown. J. /. B25 (1982). 9. D. 1493. Weiss. REFERENCES W.. Phys. and H. Phys. Phys. Jr. P. 163 Calculate the energy of a 180° wall which is parallel to (100) of a bcc ferromagnetic crystal with 5 (spin) = \. Smith. Micromagnetics (Wiley-Interscience. D. 28 (1957). 1. 8. 16. Matsuda. L.. W. 0f (Curie point) = 527°C. Phys.31. 10. Suzuki. E. 6. O. W. 888.. there is an infinitely long x-domain touching both crystal surfaces with a quadrilateral cross-section surrounded by y-domains. Such an asymmetric spin configuration was experimentally'verified by electron microscopy. Appl. Soc. Phys. 58 (1940). f. Shinagawa. T. Mag.. Appl.. B.432 SPIN DISTRIBUTION AND DOMAIN WALLS as observed by electron interference microscopy which show the same spin configuration as the postulated structure in Fig. C. S. 241 (1955). Appl. Bloch. Solidi. /. 918. a (lattice constant) = 3 A. 7. S. Phys. 736. Calculate the inner angles of the cross-section of the ^-domain perpendicular to its length. 14. This paper ignored the H* -correction. Fujiwara. 525. Phys. 17 (1978). 160. R. or vice versa.. I. F. Mod. Osakabe. formulate the energy of a 180° wall which is present in this crystal. Neurath. Jr. /. 523. Graham.. Stat. It is a line boundary in a domain wall. Phys. 541. 85 (1952). 21 (1949). 533.2 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. 74 (1948). 12. 3. Phys.30(a). C.. 13. K. Goodenough. Compt. Chikazumi and K. A..... Endo. Appl.29. Rev. Chikazumi and K. 29 (1958). Brown. 6799.. 1291. 38 (1970). 1963). Phys. Suzuki. 29 (1958). 4. Fukuhara. and J. F. H. Tonumura.Y. A. Jr. 10 (1955).1 Assuming that a ferromagnetic crystal with isotropic magnetostriction constant and with negligibly small magnetocrystalline anisotropy energy is subjected to a uniform tension cr. /. Neel.. T. 32 (1962). Phys. 5.4 In a single crystal plate parallel to the (001) plane. Rev. 16. Graham. W. 74 (1932). /.. Jap. R. 11 (1940).3 . Hubert. 699. E. as shown in Fig. Japan. . Phys. Suzuki. Tanabe. IEEE Trans. 295. Z. N. Hubert13 theoretically predicted a leakage field-free spin configuration of a Bloch wall. Jr. The line in either a Bloch or a Neel wall where the spin rotation changes from right-handed to left-handed. 141. N. Chikazumi. Rend. 294. F. Rev. MAG-15 (1979). DeBlois and C. In Fig. D. 16. Rev. which is described in a later paper: S. and Kl = 6xl0 4 Jm. 2. Bloch lines appear as bright spots or dark spots from which cross-ties emerge.. Phys. Kittel. A. is called a Bloch line. 11. 16.14 PROBLEMS 16. Assume that the effect of magnetostriction can be ignored. Rev. Huber. and the magnetocrystalline anisotropy is expressed only by the first term. Appl. and P.

For simplicity we assume that the crystal extends indefinitely in the —z and also in the ±x. CD.and ferrimagnetic materials are divided into multiple domains. in which there are many plate-like domains with magnetization 7S along the +z or — z direction. In this section we discuss how the magnetostatic energy is reduced by the appearance of domains. in which the spontaneous magnetization takes different orientations. 17. As shown by (1.1.1. The magnetic potential must satisfy the Laplace equation Fig. is given by where m is an index that numbers the domains. First we calculate the magnetostatic energy of the domain structure as shown in Fig. Then the surface density of magnetic free poles.77). .and +y-directions. We assume a crystal with a surface parallel to the x-y plane at z = 0.17 MAGNETIC DOMAIN STRUCTURES 17. The domains are separated by 180° walls lying parallel to the y-z plane. the magnetostatic energy is given by where <p is the magnetic potential. 17. Free poles on the crystal surface produced by the plate-like or laminated domains.1 MAGNETOSTATIC ENERGY OF DOMAIN STRUCTURES Ferro. The reason for the existence of domains is that the magnetostatic energy is greatly reduced. Let the thickness of each domain be d.

we have The solution of the Laplace equation (17. the potential must be symmetrical with respect to the plane z = 0.8) as . so that Using this relationship in (17. In order to prove that (17.6). In the present case. The value of 9 at z = 0 is obtained from (17. where magnetic free poles exist.3) and find that (17. The coefficients An are determined to satisfy the boundary condition (17. It must satisfy the boundary condition at z = 0.7) for <p in (17.3) must have the form where n is an odd number. 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.1) in (17.6).7) and (17. because the free poles are confined to this plane.3).3) holds. Using (17.4). we may use (17.434 MAGNETIC DOMAIN STRUCTURES in all space other than at the crystal surface.7) is a solution of (17.

10). as shown in Fig. magnetic free poles are confined in the crystal . obtaining for the checkerboard pattern and for the circular pattern. results in a decrease in the magnetostatic energy. (17. In these cases.11). All three formulas (17. 15.2). Such wavy domains were observed in MnBi.11) and (17. The energy is rather closer to that of the checkerboard pattern (17. In all the cases considered above. 17.12) with (17. A decrease in d. d. therefore. 17.3.1. because the N and S poles are mixed more densely.2 and the circular pattern as shown in Fig. Checkerboard domain pattern.13(c). Goodenough2 showed that a wavy pattern as shown in Fig. the spontaneous magnetization lies perpendicular to the crystal surface.12) show that the magnetostatic energy is proportional to the size of the domains. 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.MAGNETOSTATIC ENERGY OF DOMAIN STRUCTURES 435 Fig.4 has a much lower magnetostatic energy than the plate-like or laminated domain structure of Fig. The above calculation was carried out by Kittel.11) and (17. Using (17. 17. d.2. we see that the magnetostatic energy is greatly reduced by mixing N and S poles more closely.10). 17. 17.1 who also extended the treatment to the checkerboard pattern shown in Fig. Comparing (17.

as shown in Fig. in the crystal each domain magnetization is rotated non-uniformly by the demagnetizing field resulting from the free poles at the crystal surface. However. if the easy axis makes an angle other than a right angle with the crystal surface. Laminated domains with magnetizations making a small angle 6 with the surface. 17. Circular domain pattern. 173.6(a)).4.5. 17. This results in a reduction of magnetostatic energy. Let the angle of inclination of the easy axis from the crystal surface be 6. Wavy domain pattern. giving the magnetostatic energy per unit area However. 17. . where there is a discontinuous change in magnetization. surface. Fig. Then the surface density of free poles is given by If the magnetization is fixed in the easy axis (Fig.5. 17. as shown in Fig.10). the surface density of magnetic free poles is obtained by the substitution 7S -»7S sin 6 in (17. the demagnetizing field in each domain will rotate the magnetization out of the easy axis. thus producing a volume distribution of free poles.436 MAGNETIC DOMAIN STRUCTURES Fig.

Fig. As mentioned in Section 1. 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. It must be noted that there is some increase in anisotropy energy in case (b). The permeability p* is not the real permeability.MAGNETOSTATIC ENERGY OF DOMAIN STRUCTURES 437 + + + + + Fig. 17. 17. 17.7).4) must be replaced by This means that the permanent free poles give a divergence of B which does not include the permanent magnetization. It is easily shown that the total number of free poles is the same in Figs. .6(b). 17.6. It is easy to see that the magnetostatic energy is much lower for (b) than for (a). 17. because free poles with the same sign tend to repel one another. 17.* correction. Model for /a. (b) the local magnetization is rotated out of the easy axis by the demagnetizing field. because the magnetization is rotated away from the easy axis. which results from domain wall motion. but a special permeability resulting from rotation of the magnetization. Fig.5: (a) The direction of magnetization is fixed. This produces a volume distribution of magnetic free poles instead of a planar distribution.6(a) and (b). Then the boundary condition (17. 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(b). equivalent to Fig.7.5. Distribution of magnetization vectors in a domain in Fig.

* = (JL* is no longer symmetrical for z > 0 and z < 0.5). Using these relationships in (17.23). we have Therefore (17. Let the solution for ^t* = /AO be The solution for /u. is no longer symmetrical with respect to the plane z = 0. we have Since (17. we have On the other hand. thus . we find Similarly from the Laplace equation for z < 0. <p.22) and (17.15). so that we can assume the form Using this formula in (17.9). we have Comparing (17. the potential must satisfy the Laplace equation for z > 0.4) and (17.16) must satisfy the conditions (17. so that Similarly in the case /A* = /A O .21) becomes The potential at z = 0 is obtained by multiplying A by (17.5) does not hold.18). z)/<?z. so that the relationship (17.438 MAGNETIC DOMAIN STRUCTURES In this case the magnetic potential. we have and where fz signifies df(x.

29) gives JL* = 45.1-17. However. and (17.22. the total domain wall area per unit volume is increased by reducing the width of the domains.26) gives A = 1 and there is no such correction. (17. As seen from the preceding calculations. On the other hand.82) we have In the case of the 90° wall on which magnetic free poles appear. Using these values.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. of the domains. 17. This correction is called the mu-star correction. by putting 00 » 7r/4 in (18. Let us calculate the value of JL* for iron. when the magnetization is perpendicular to the crystal surface as in Figs. so that the factor A given by (17. irrespective of the geometry of the domain structure. the crystal on both sides of the wall has /x*. The equilibrium size of the domains is determined by minimizing the sum of the magnetostatic energy and the total wall energy. and (17. its importance was first pointed out by Kittel.26) is 0.103)). such as the zigzag 90° domain walls in Fig.1 17.82) in which 60 ~ Tr/2).4.0435. .15 (T).2 X 104 Jm~ 3 and spontaneous magnetization 7S = 2. the magnetostatic energy is always proportional to the width. a very small value. d. 16. /I* = 1. Therefore such a correction can never be ignored when the fields produced by free poles cause a rotation of the magnetization.2 SIZE OF MAGNETIC DOMAINS As mentioned previously.SIZE OF MAGNETIC DOMAINS 439 Therefore the magnetostatic energy (17. so that we have The value of /A* is determined by the rotation of the magnetization out of the easy axis (see (18. which has magnetocrystalline anisotropy K1 = 4.14) must also be multiplied by A. a ferromagnetic body is divided into many domains in order to reduce the magnetostatic energy. Therefore the magnetostatic energy is reduced by reducing the width of the domains. so that When the magnetization makes 45° with the crystal surface.

8(b). d. 17. Consider a ferromagnetic plate with thickness / having an easy axis perpendicular to the plate.10).8(a). The magnetostatic energy of such a free pole distribution is given by (17. both of which produce demagnetizing fields -/S//AO m tne plate. 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.8.10). (b) multi-domain structure.36). The equilibrium domain width. as shown in Fig. so that the total wall energy per unit area of the plate is given by where y is the wall energy. free poles exist on the top as well as on the bottom surfaces. is given by minimizing the total energy or Solving (17. so that the magnetostatic energy per unit area of the plate is given by two times the results of (17. In the present case. (a) Single domain structure. the total domain wall area is l/d. or On the other hand. we can ignore the interaction between free poles on the two surfaces. If / » d. we have . If the entire plate consists of a single domain as shown in Fig. 17. 17. N poles appear on the top and S poles appear on the bottom surfaces.440 MAGNETIC DOMAIN STRUCTURES Fig.

the total domain wall area is twice as large as that of the laminated domains. 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.35).15. Actually. On the other hand.01 mm. 17. we observe a checkerboard-like domain pattern on the c-plane of a cobalt single crystal. given by (17.2.9(a). y. 17.32) is evaluated as Therefore the energy of the equilibrium domain structure is about 1/10000 of that of a single domain.45) with (17.6 X 10~ . In the case of the checkerboard pattern shown in Fig. or /.39) for any value of /s. 17.01 (m) is calculated to be Thus the magnetic domain width is small. We therefore conclude that the checkerboard domain structure will never exist. but increases .39).45) is larger than (17. however. we find that (17. as shown in Fig.SIZE OF MAGNETIC DOMAINS 3 441 In the case of iron. /s = 2.33). so that the domain width in a plate with / = 1 cm = 0. of the order of 0. The total energy of this domain structure is evaluated by using (17.9(b)). 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. to give The magnetostatic energy of the single domain given by (17. y100 = 1.37) in (17. We see that the width of the domains is small at the surface perpendicular to the c-axis. or Minimizing the total energy leads to an equilibrium domain width so that the total energy becomes Comparing (17.

The strain in the closure domain is given by exx = 3A100/2. (After Y. Since the closure domain must be compressed into a triangular form which matches the major domains.12. 17. so that if the magnetostriction constant is positive. .10 is a sketch of the domain structure at the crystal surface. and no magnetostatic energy is stored. In general. ferromagnetic materials exhibit magnetostriction. Domain pattern observed on cobalt crystals with the crystal surface (a) perpendicular to the c-plane and (b) parallel to the c-axis. the formation of magnetic free poles can be avoided by generating closure domains with magnetizations parallel to the crystal surface. The surface domains exist only to a limited depth. 17. the closure domains tend to elongate parallel to the crystal surface.9. 17. In this case no free poles appear. 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. some magnetoelastic energy is stored. the width of the domains will be determined by a balance between the magnetoelastic energy and the wall energy. Takata) gradually with increasing the distance from this surface. Figure 17. as shown in Fig. so that the total domain wall area is not as large as that assumed in the above calculation. In a cubic crystal such an iron or nickel where the number of easy axes is more than one. 17. however.442 MAGNETIC DOMAIN STRUCTURES Fig.11. as shown in Fig. In this case. Schematic illustration of the surface domain structure below the crystal surface perpendicular to the uniaxial easy axis.10.

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. Closure domain structure of a cubic single crystal. 17.12.11. A100 = 2. Here c u is the elastic modulus of the crystal. y = 1. with the neighboring major domains.41 X 1011. cn = 2.6 X 10 3. so that Fig. . 17. Hypothetical magnetostrictive elongation of a closure domain.SIZE OF MAGNETIC DOMAINS 443 Fig.07 X 10 5.

For instance.1). In a uniaxial crystal such as cobalt. . the magnetostatic energy of the domain structure without closure domains is calculated by putting /s = 1. The closure domain in this case stores magnetic anisotropy energy.38). 17.54). This value is of the order of 0. we find that the structure with closure domains has lower energy.55) with (17.33). giving Comparing (17. The anisotropy energy stored per unit area of the crystal surface is given by For cobalt Ku = 6. the shape of the closure domains is greatly modified. When the easy axis tilts from the normal to the crystal surface. thus where Kul and Ku2 are the anisotropy constants defined by (12. Powder pattern of closure domains observed on the (100) surface of an Fe + 4% Si crystal (Chikazumi and Suzuki).14 shows a fir-tree pattern.3)).79 in (17. for the (001) surface of an iron single crystal containing a small amount of silicon.13.444 MAGNETIC DOMAIN STRUCTURES Fig. and is much larger than the case of (17. The total energy is given by which is much lower than (17. Fig. as shown in Fig.0 X 105 (see (12.13. it is also possible to produce closure domains which are magnetized in hard directions.5 mm. 17.39). 17. so that On the other hand. Such closure domains are actually observed.

Schematic illustration of fir-tree domains.15. Fig. 17. 17. suggested the possibility of utilizing it as .19).15. which is the closure domain structure observed on a tilted (001) surface of an Fe or Fe + Si crystal.BUBBLE DOMAINS 445 Fig. The domain boundaries of the fir-tree pattern tilt from the main domain wall by some angle.4 who discovered the bubble domain. 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). 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 tree-like domain serves to transport a part of the free poles appearing on the crystal surface from one domain to the neighboring domain.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 structure is illustrated in Fig. 16. The observation of well-defined domain patterns and the interpretation mentioned in this section were developed by Williams et al? 17. Bobeck.14. 7.

The resultant demagnetizing field is given by If r = h/2. . The surface tension of the domain wall tends to reduce the bubble radius. so that N is approximately f.446 MAGNETIC DOMAIN STRUCTURES Fig.16.0. The reason is as follows. whereas that in (c) is given by -2NIs/ju. The demagnetizing field in (b) is given by /S//AO. 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). (b) a magnetic field without bubbles. Figure 17. A superposition of (b) and (c) is equivalent to (a).17. where r is the radius of the bubble and h is the thickness of the plate. 17. the shape of the bubble may be regarded as a sphere. Surface free poles and the demagnetizing field of a bubble domain: (a) a bubble domain.16 shows the structure of the bubble domain.17. 17. (c) a hypothetical bubble domain with double magnetization. As shown in Fig. The latter effect is due to the fact that the internal magnetic field in the bubble domain is parallel to its magnetization. a digital memory device. 17. Structure of a bubble domain. Fig. while the magnetostatic energy of the magnetic free poles tends to increase the radius. where N is the demagnetizing factor of the bubble domain.

HA. as functions of the reduced radius. On the other hand. y/2/sr + bias field.18 shows the left-hand and right-hand side values of (17. In order to stabilize the bubble. These points represent equilibrium states. which tends to decrease the radius of the bubble. #-» 1. being 0 for r = 0. For r -»oo. N=^.56) and (17.//*„. P and Q.so that the left-hand side of (17. As in the case of a soap bubble. the inner pressure of the magnetic bubble is given by y/r (Nm~ 2 ). r/h. Fig. Fig. so that this value approaches -/s/ju.0. Comparing this with the pressure on the wall produced by a hypothetical field Hy. is a function of the radius of the bubble. N. so that the left-hand side of (17.57). These three fields must be balanced. Demagnetizing field. which favors the magnetization in the bubble. we must apply a bias field -Hb. which is 2IsHy (see (18. giving Using (17.59) is 7s/3ju. Therefore the demagnetizing field in the bubble tends to increase its radius. Hb. (17. where (17.59) is satisfied. we have where the negative sign means that the effect of the field is to reduce the radius of the bubble.4)).0.BUBBLE DOMAINS 447 Therefore we find that the demagnetizing field given by (17.59) is /. 17.58) becomes The demagnetizing factor.56) is positive. the domain wall energy y (Jm~ 2 ) gives rise to a surface tension. 17. The two values are equal at two cross-over points. and surface tension field. r/h.59) as functions of the reduced radius.18. For r = h/2. .

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

5) is used to create the bubble domains. In this case a growth-induced anisotropy (see Section 13.3). The necessary condition to create a bubble domain is that a large perpendicular anisotropy exists in the crystal. Variation of orientation of spins in the midlayer of the bubble domain. Three kinds of bubbles are seen in the photograph.20.9 or a thin Permalloy film is evaporated on top of the crystal.BUBBLE DOMAINS 449 Fig. Specifically. The contrasts of these bubbles illustrated in (a). (b) a hard bubble (N = 3).5). which exhibits a feeble spontaneous magnetization by spin-canted magnetism. corresponding to N = 1. and (c)'. 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.2kOe). and (c) can be interpreted assuming the spin structure as shown in (a)'.10 The soft magnetic layer is effective in removing the complicated spin structure of the hard bubbles. In order to suppress the appearance of hard bubbles. (b). (a) a normal bubble (N = 0). 17. —1. because their movement is abnormal. the perpendicular anisotropy of a surface layer of the crystal is erased by ion bombardment. and 0.74MAm"1 (=9. . hard bubbles are undesirable for such devices. because some normal wall nuclei are created in the soft layer and propagate downwards through the wall to destroy the unstable spin structure. under the application of a bias field of 0. respectively. in a Co thin film with the c-axis perpendicular to the film surface. (b)'.0. or One crystal that meets this condition is orthoferrite (see Section 9. However. the anisotropy field 2KU/IS must be larger than the demagnetizing field Is/fj.3. 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.

4.11 Figure 17.21.3). (b) and (c) are interpreted by assuming the spin structure (a)'. This spin . (b)' and (c)'.4 STRIPE DOMAINS Stripe domains are associated with a rotatable magnetic anisotropy discovered in anomalous magnetic thin films (see Section 13.2 kOe). Three kinds of bubbles (a). 17. Stripe domains appear when the perpendicular anisotropy is not greater than the value that satisfies (17.450 MAGNETIC DOMAIN STRUCTURES Fig.60). respectively.74 MAm" 1 (= 9. 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. (Courtesy of D. The broken arrow indicates a Bloch line. Watanabe). 17.22 shows a schematic illustration of the spin distribution in stripe domains.

as . The magnetic anisotropy energy is expressed in terms of the angle. 9.10): where the value is doubled by considering the effect of free poles on both sides of the thin film. as in (17.7) and averaging over one wavelength. 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. 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.STRIPE DOMAINS 451 Fig.22. 17. 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. When 6 <s: 77/2.

is obtained by minimizing w with respect to A. whereas the spontaneous magnetization rotates with the external field. the condition w > 0 reduces to When a rotating field of moderate intensity is applied to the stripe domains. the configuration of stripe domains remains unchanged.61) and averaging over one wavelength of the spin oscillation. The wavelength. giving Using this value. The exchange energy per unit area stored in this spin system is calculated. we have the anisotropy energy per unit area as where h is the thickness of the film. If w > 0.452 MAGNETIC DOMAIN STRUCTURES Using (17.14).61) in (16.w represents the function in parentheses. A. to be The total energy is given by where . using (17. In this process some magnetostatic energy is . the stripe domain appears.

thus finally resulting in a single domain structure.37).DOMAIN STRUCTURE OF FINE PARTICLES 453 Fig. 13. (17. 17.5 DOMAIN STRUCTURE OF FINE PARTICLES As discussed in Section 17. the domain width is related to the thickness of the crystal.44). If the field exceeds some critical value.3. 1200A thick. an additional magnetic anisotropy energy is created. 17.29.23. Lorentz electron micrograph of stripe domains as observed on a 95Fe-5Ni alloy thin film.67). This is the rotatable anisotropy discussed in Section 13. which means that the easy axis of this anisotropy is changed.4. as seen in (17. Stripe domains observed by the powder pattern method were shown in Fig. Figure 17.2. and (17. Murayama12 calculated this spin configuration more precisely by using a variational method. because some magnetic free poles appear at the domain boundaries. In other words. keeping its shape unchanged.49). the domain width is always proportional to i//. I. Therefore when the size of the particle is decreased. For instance. the stripes rotate. the domain width decreases more gradually than the size of the particle.13 added to the energy given by (17. Consider a spherical ferromagnetic particle with radius r.23 shows a Lorentz electron micrograph of stripe domains as observed on an Fe-Ni thin film. If this sphere is divided . We have assumed that the variation of the spin-canting angle is sinusoidal.

the magnetostatic energy is roughly estimated to be d/2r times the value for a single domain particle. into multiple domains. 17. the total wall energy is roughly estimated as On the other hand.454 MAGNETIC DOMAIN STRUCTURES Fig.24). each of width d (see Fig. giving The total energy of the particle is minimized by the condition giving .24. 17. Relationship between the size of ferromagnetic particles and the width of magnetic domains.

74) we have The presence of a single domain structure was first predicted by Frenkel and Dorfman14 in 1930.16 and Stoner and Wohlfarth. so the number of domains in the sphere decreases as shown in Fig. attaining finally the single domain structure below a critical radius.25.17 It was pointed out by Kittel15 that single domain structures are also expected for ferromagnetic fine wires and thin films. further detailed calculations were made by Kittel.DOMAIN STRUCTURE OF FINE PARTICLES 455 As the radius r of the particle is decreased. Goto) . d = 2rc.19 (Courtesy of K. 17. so that from (17. Electron micrographs of powder patterns (Colloid SEM) of Ba-ferrite: (a) for relatively large particles showing a multi-domain structure.24. Figure 17. At this critical radius. (b) for relatively small particles showing a single domain structure. and more than ten years later. rc.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. the width of the domains is decreased proportional to Vr. 17.15 Neel.

the . the magnetostatic energy is reduced by the magnetostatic interaction between particles. while in photo (b) a flux line emerges outside a thin platelet. Electron interference fringes observed for Co platelets showing lines of magnetic flux inside and outside the platelets.26 shows electron interference micrographs of Co platelets with different thicknesses. The situation is also the same for a ferromagnet that contains many nonmagnetic inclusions or voids. showing a single domain structure (see photo (b)). In photo (a) we see that the lines of magnetic flux are confined inside a relatively thick platelet. 17.20-21 (Courtesy of A. separated by a nonmagnetic matrix.18 We see many domain walls on a relatively large particle. showing that this platelet tends to have a single domain structure. The thickness of the platelet in (b) is about one quarter of that of (a).26. showing a multi-domain structure (see photo (a)).20'21 In the preceding discussion we treated an isolated particle. Tonomura) scanning electron microscope (Colloid SEM). if the direction of the easy axis changes from grain to grain. so that the critical size for a single domain structure is more or less increased. showing the magnetic flux lines inside and outside of the platelet. In an assembly of single domain particles.19 Figure 17.456 MAGNETIC DOMAIN STRUCTURES Fig. but only a cluster of magnetic powder on a small particle. Even in a purely magnetic material.

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

the normal n to the grain boundary. or z-direction (/ or . and the direction of magnetization 7j in the left-hand grain. or 3). /33) with respect to the cubic axes of the left-hand grain. 17. If y3 > y2 > y\ and /3. the axes of easy magnetization are (100).y^) with respect to the right-hand grain (Fig. because this is the easy axis closest to II. Crystal orientations on both sides of a grain boundary.y\.28).80). = 1. the direction of magnetization. 72.458 MAGNETIC DOMAIN STRUCTURES Fig. 17. y. Let the direction cosines of the normal to the grain boundary be (/31.27. > y3. When the magnetization is in the r'th easy axis in the left-hand grain and the . Angles of magnetizations of the neighboring grains as measured from the normal to the grain boundary. 2. 17. y-. and that the total domain energy is lower by a factor l/\/2 . For crystals with positive K^ such as iron. it follows that Thus we find that the magnetostatic energy of a uniaxial polycrystal is about one-half that of the isolated grains. Therefore from the calculation in (b) above. hence the magnetization in either grain can lie along the x-. Fig.29 shows the three crystal axes (x. we find that the domain width in a polycrystal is about /2 times larger than the domain width in isolated grains. /32. The free pole density on the grain boundary is then given by .'th easy axis in the right-hand grain.28. Figure 17. For a cubic crystal.y-i. in the right-hand grain should be parallel to the z-axis. the probability of having a good continuity of magnetization across the grain boundary is much greater. and (. If the individual grains are separated from one another. which has three or four axes of easy magnetization (depending on the sign of the anisotropy). z) of the right-hand grain. 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.

29. respectively. 2. and JC-direction. thus On averaging a>2 with respect to /?.DOMAIN STRUCTURE IN N O N . to minimize the surface density of free poles appearing on the grain boundary.. then &> changes its sign. 17. is parallel to the y-axis. If ft is less than y3. If the domain magnetization 7j in the first grain is in the region indicated by 1.84) over all possible orientations of the right-hand . f» becomes smaller when the magnetization in the right-hand grain. we have On averaging each term in (17. and 3.I D E A L FERROMAGNETS 459 Fig. < (y3 + y2)/2. Then If /3. If /3. 72. y-. the domain magnetization 72 in the second grain must be parallel to the z-. the Ac-direction becomes the most favorable for /2. is further decreased and it happens that ft < (y2 + Ti)/2.

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^.

10. 18. The range of integration in (18.9. the magnetization remains parallel to [111] when the applied field was in the first quadrant (the area marked with circles) in Fig.12). and <p0 is given by Similarly. The range of integration in (18. 18.10). and average over the circled area. Fig. 18. The average z-component of magnetization. is given by where <p is the azimuthal angle of the field measured from the (110) plane. If we let the angle between [111] and the applied field be 0. and <p0 is given by . which is the residual magnetization. the z-axis.10. we find the residual magnetization to be where tp is the azimuthal angle about [111] measured from the (Oil) plane.MAGNETIZATION CURVE AND DOMAIN DISTRIBUTION 473 Fig. Let the angle between the z-axis and the direction of the applied field be 6. in the case of K^ < 0 (easy axes parallel to <111».

The reason is that this alloy is magnetically very soft. v-. and z-magnetizations at the residual point is parallel to the long axis of the cylinder (Fig. while in the former case it is three.12).10). Let the magnetization components parallel to the x-. Therefore. 18. In the above treatment. thus increasing the magnetostatic energy. It is reported1 that Permalloy has residual magnetization as small as 7% of the saturation magnetization.2). respectively. the magnetostatic energy of the free poles which appear on grain boundaries is 20-50% of that of an isolated particle. 7r. and /. in spite of the fact that the largest deviation angle is 55° in both cases. Thus the value of 7r/7s is in the range 70-90% for cubic ferromagnets. is given by the formula where 7S is the saturation magnetization. As we discussed in Section 17.11 shows the experimental plot 7r as a function of !/(/ + m + n). In real polycrystals. Isoperm. or the lack of mobility of the domain walls. we ignored the influence of free poles which may appear on the grain boundaries. The reason is that in the latter case the number of easy axes is four. Otherwise nonzero free poles appear on the side surface of the cylinder. and 72. the residual magnetization is reduced by this effect. Accordingly the shape of the hysteresis loop is more rectangular than in materials with uniaxial anisotropy. domain walls will be generated to create domains of reverse magnetization. and z-axis be Ix. Then we have the relationships from which we can deduce (18. Iy.6. m. and n are the direction cosines of the long axis of the cylinder with respect to the cubic axes. Kaya2 measured the residual magnetizations of variously oriented cylindrical single crystals of iron. The value of the residual magnetization is influenced by the shape of the specimen. where we see that the experiment is well expressed by (18. unusual values of 7r/7s may be obtained. In ferromagnets with a special anisotropy. and discovered a rule called the Imn rule or Kaya's rule: The residual magnetization.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. Actually. if the cubic anisotropy is predominant. which is made by rolling a grain-oriented Ni-Fe alloy (see Section 13. so that the magnetization is easily reversed. Kaya explained this rule by assuming that the vector sum of the x-. because of the difficulty of nucleating reverse domains. In any case. the reduction of the residual magnetization is incomplete. however. sometimes the free poles which appear at residual magnetization reverse a part of the magnetization to reduce the magnetostatic energy. has .14). thus reducing the magnetostatic energy. y-. Figure 18.14). The probability of selecting the nearest easy axis is larger when there are more easy axes.

and n are the direction cosines of the cylinder axis with respect to the cubic crystal axes. if the easy axis of the induced anisotropy is parallel to one of the other cubic easy axes. if the easy axis of the induced anisotropy coincides with this cubic easy axis.1. Permalloy annealed at 490°C exhibits an /r//s value of about 30%. grain-oriented Si-steel (see Section 22. in addition to some cubic anisotropy with positive K^ As the field is reduced from a high value.MAGNETIZATION CURVE AND DOMAIN DISTRIBUTION 475 Fig. However.12.1). so that the value of 7r//s is almost 100%. On the other hand. 18. so that the residual magnetization (measured after magnetizing parallel to the rolling direction) is almost zero. Bozorth3 explained this phenomenon as follows: This alloy exhibits an induced uniaxial anisotropy as a result of the annealing (see Section 13. Fig.1) has its easy axis parallel to the rolling direction.11. The relationship between residual magnetization and crystal orientation of cylindrical single crystals of iron. . The orientation is expressed by !/(/ + m + n). Distribution of magnetizations in an elongated cylindrical specimen with positive K^ (Kaya's rule). 18. m. the domain magnetization rotates back to the nearest cubic easy axis and stays in this direction. (After Kaya2) its easy axis perpendicular to the rolling direction. where /.

thus giving no contribution to the residual magnetization. the most unstable magnetization is reversed first.476 TECHNICAL MAGNETIZATION Fig.6. we have the relationship so that therefore . the 7r//s value becomes We expect the same situation for a sample of iron under elastic stress. Figure 18. Next we shall discuss the polar distribution of domain magnetizations at the coercive field point. Let the half-polar angle of the cone of the reversed magnetization be 00.13. Then the distribution of magnetization is shown at point E in Fig. As seen in Fig. Since the probability that the easy axis of the induced uniaxial anisotropy coincides with one of the cubic axes is f. when the field is increased in the negative direction from the residual magnetization. 18. 18. Since the reversed magnetization is equal to the unreversed magnetization at the coercive field. 18. Values of Ir/Is for various categories of ferromagnetic materials.13 summarizes the predicted values of 7r//s for various magnetic materials. the domain magnetization which points in the positive direction is most unstable.6. the magnetization will split into plus or minus directions along this preferred easy axis. If the easy axis of the uniaxial anisotropy is distributed at random and the magnetization reversal occurs by wall displacement.

once it has been brought to the coercive field point. and the coercive field is the field needed to move a 180° wall making 45° with the positive direction. This field is about 0. However. are reversed first by . Next we discuss the case of a ferromagnet in which a cubic magnetocrystalline anisotropy is predominant. A permanent magnet is often magnetized after it is assembled into a device. which make small angles with the positive field direction.MAGNETIZATION CURVE AND DOMAIN DISTRIBUTION 477 Fig. irrespective of magnetization mechanism. starting from the coercive field. If we try to attain the same domain distribution from the demagnetized state. we need a fairly strong field to reverse the directions of domain magnetizations which are almost perpendicular to the field direction.14. 18.4 It should be noted that this process of remagnetizing permanent magnets is effective. 18. Thus the half-polar angle of the cone is 45°. When the field is increased in the negative direction from the residual magnetization to the coercive field.14. whose distribution is almost the same as that of the residual magnetization. which requires the application of a large field. only 0. Change in domain distribution during the magnetization process. For example. Finally the sample reaches point H. except for a grain-oriented uniaxial magnet. As shown in Fig. Let us consider the magnetization process which may occur when the field is increased in the positive direction from the coercive field point E.12MAm""1( = 1500Oe) larger than Hc. it can be easily remagnetized by a relatively weak field.24MAm~ 1 (= 3000Oe) is required to magnetize to residual magnetization. only reversible magnetization rotation occurs from the point E to F (where H = 0). the most unstable domain magnetizations.SOMAirT1 ( = 10 000 Oe) to magnetize to saturation from the demagnetized state. which is the magnetization pointing in the negative direction (point G in the diagram). a Ba-ferrite magnet with coercive field Hc = O. assuming uniaxial anisotropy and magnetization occurring by domain wall displacement.lZMAmT 1 (=1500Oe) requires about O. because the field must overcome the demagnetizating field. But if the magnet is first magnetized and then brought to the coercive field point by applying an appropriate reverse field. Further increase in H in the positive direction causes a reversal of the most unstable magnetization.

478 TECHNICAL MAGNETIZATION 180° wall displacement. 18. the magnetization reversal is exclusively performed by magnetization rotation. must be reversed to get to the coercive field point.433/s. if Kl < 0. in the case of uniaxial crystal anisotropy.19) does not include a complicated integration with respect to the azimuthal angle as in (18. In the case of an assembly of single domain particles. 18.10). Thus we have the relationship from which we have Equation (18. Similarly. The former method consists in heating the .832/s.15 summarizes polar diagrams of magnetization distribution at residual magnetization and at the coercive field for various categories of magnetic materials.9). As will be discussed in Section 18. and is reversed first. magnetization at an angle of 45° to H is most unstable. the coercive field state is attained when half of the residual magnetization 0. and its physical meaning. There are two methods of demagnetization: thermal demagnetization and AC demagnetization. because 00 < 35° (see Fig. or 0. Figure 18. Therefore we have the relationship from which we have Again the equation (18. is reversed.21) includes no complicated integration with respect to the azimuthal angle.866/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. because 00 is less than 45° (see Fig. or 0. so that half of this value.416/s.3. If /C: > 0. or an elongated particle with uniaxial shape anisotropy.10). the residual magnetization is 0. Finally we discuss the process of demagnetization or of obtaining zero net magnetization. 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.

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

16.480 TECHNICAL MAGNETIZATION Fig. AC demagnetization must be performed by using a rotating field of decreasing magnitude instead of an AC field along a fixed axis.2 DOMAIN WALL DISPLACEMENT When a domain wall moves in a large plate of a homogeneous magnetic material. This situation corresponds to a sphere placed on a level surface. 18. 18. Variation of angular distribution of magnetization during AC demagnetization. The wall therefore does not return to its original position after the field is removed. the wall must settle at the position . 18. about which position its displacement becomes reversible for small displacements. then the sphere will settle in a concave depression. s. as shown in Fig. assuming random uniaxial anisotropy and magnetization occurring by domain wall displacement. which has no stable position. Let us assume that the wall energy per unit area. Similarly the displacement of the wall becomes reversible only when the wall energy varies from place to place. this case.17. the surface of the plate must be uneven. the wall energy is independent of its position. When there is no external magnetic field. Suppose that a plane wall moves. the wall is in neutral equilibrium. In order that the sphere have a position of stable equilibrium. sw. In other words. keeping its shape unchanged. changes as a function of position.

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

Becker and Doring6 explained the ratio given by (18. however. using picture-frame single crystal specimens cut out of a bulk single crystal of Si-Fe as shown in Fig. because the domain structure is not the same for the three picture-frame specimens.482 TECHNICAL MAGNETIZATION Fig. Williams5 measured initial permeability parallel to (100). Method of cutting picture-frame single crystals with sides parallel to (100). the last assumption is quite doubtful. He discovered that the initial susceptibility was not constant.31). (110) and (111). In the (110) crystal. so that Thus we have the relationship (18.18.33) as follows: in the case of the (100) crystal. a 180° wall runs parallel to the edge. . irrespective of direction of the applied field. In order to check this. is not necessarily in disagreement with the theoretical treatment given above.18. so that cos2 6= 1. Therefore we expect that the initial susceptibility is constant.33) from (18. domain walls are parallel to either one of the three easy axes. 18. However. so that In the (111) crystal. but varied as This result. provided the total domain wall area S is the same. 18. domain walls are parallel to either one of the two easy axes which are closest to (110) edges. {110} or (111) from a bulk single crystal.

18. (18. If the wavelength of the stress variation is sufficiently larger than the wall thickness. we can regard the anisotropy given by (18. so that Thus the initial susceptibility is again constant. s.39) can be expanded near 5 = 0 as . When the easy axes are randomly distributed.7 This idea was developed by Kersten. as The anisotropy constant therefore varies as This form is assumed for simplicity. as first pointed out by Kondorsky. irrespective of the field direction.55) as Assuming that K1^> \a.8 whose treatment may be described as follows: he assumed that the internal stress varies as a function of displacement.17 is the presence of randomly distributed internal stresses. Then the wall energy is deduced from (16.38) as remaining constant throughout the wall. although the functional form is generally different between anisotropy energy and the magnetoelastic energy.DOMAIN WALL DISPLACEMENT 483 In the case that K1 < 0.31) becomes One mechanism for generating variations in wall energy as shown in Fig. easy axes are parallel to (111). we have Thus in all the cases. (18.

/. 7S = 2.41) is expressed in terms of 8 as Moreover.46) or Fig. When the wavelength. the above calculation is not applicable. is large. 8. 16.25). is smaller than the thickness of the wall.484 TECHNICAL MAGNETIZATION Comparing (18. if we assume that a domain wall exists at every energy minimum.07 X 10~5. and also that the wall energy varies similarly in the x-. y-. it follows that Using (18.43) and (18. the effect of the stress will be smoothed over by the effect of the exchange interaction.46) by assuming that A100 = 2.36) According to this expression. we can estimate that JL&« 200. Therefore the minimum susceptibility is realized when / ~ 8. /. so that the wall becomes easily movable again. However. giving Since there are contributions from other mechanisms such as 90° domain wall displacement and magnetization rotation. a~ 50kgmm~ 2 = 5 X 108 Nm~ 2 . This is because the wall is easily displaced when the wall energy changes slowly with position. the susceptibility is large when the wavelength of stress variation. Ordinary soft steel or iron exhibits /Za ~ 100 ~ 200. so that this estimate seems reasonable.16. we have Based on (16. .18. so that We can estimate the value of the initial susceptibility for iron from (18. our assumptions of internal stress and total domain wall area are fairly arbitrary. If / < 8. so we cannot have great faith in the calculation. and z-directions. we can express the thickness of the domain wall approximately as so that (18.44).40) with (18. we have from (18.

18. 17.52) leads to the susceptibility .19.19. 18.51) to give In many cases we have cos2 0= f (see (18.9 aand Kersten10 proposed a new mechanism of reversible wall displacement as shown in Fig. Actually.DOMAIN WALL DISPLACEMENT 485 Fig. This was first pointed out by Neel.5) acts on the wall. A 180° wall bulging under the action of a magnetic field. (18. 18. The wall shown in Fig.33. When a field H is applied in a direction which makes the angle 6 with the magnetization /s. a pressure given by (18. 18.19 is pinned at the side edges but is free to bulge under the action of the field pressure.32). 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. the wall is deformable. so that the wall bulges in a cylindrical form as shown in Fig. Let us assume a domain wall pinned from place to place as shown in Fig.13. If the radius of curvature is r.50) is modified using (18. so that (18. The increase in magnetization produced by this wall bulging is where S is the total domain wall area per unit volume. Since s is approximately related to r and / by (18. as shown in Fig.35)).34) and (18. however.48) and (18. 16.19.10 We assumed above that the wall is rigid and undeformable.

A.15)). When the field becomes strong enough to drive the domain wall out of the stable pinned region. the initial susceptibility increases with increasing temperature and exhibits a sharp maximum just below the Curie temperature. 18. we have the relationship Figure 18. further increase in . For simplicity. so that we have Well-annealed pure iron exhibits xa ~ 10 000.21. is proportional to 7S2. let us treat a rigid plane wall.5)). Ni. or because A is proportional to S2 (see (16. Generally speaking. which displaces without any deformation. 7S = 2. the wall displaces irreversibly and does not return to its original position even after the field is removed. y = 1. he assumed that the exchange stiffness constant. or If the wall reaches the point sl where the gradient is maximum. Kersten10 treated this phenomenon. which is given by (16. a pressure acts on the wall (see (18.53).59).486 TECHNICAL MAGNETIZATION If we assume that voids or nonmagnetic inclusions (pinning sites) are distributed in a simple cubic array with spacing /.6 X 10 3. This phenomenon is called the Hopkinson effect. and Co fitted to formula (18. Therefore the wall energy changes with temperature as Using this expression in (18. varies with the displacement s as shown in Fig.47) for a 180° wall. Th£ mechanism described here is considered to contribute to this high initial susceptibility. Suppose that the wall energy.53) leads to In the case of iron. which displaces until the restoring force becomes equal to the pressure. ew. When a field is applied. In order to describe the temperature dependence of the wall energy.15 (Wbm 2). we have Then (18. Excellent agreement is seen.20 shows the temperature dependence of x* for Fe. and we can assume from the observation of domain patterns that / = 10 ~ 4 (m).

Solid curves represent the theory (see (18.59)).10 field intensity causes an irreversible displacement of the wall to the next equilibrium position. . Temperature dependence of the relative initial susceptibility for iron. s2.21. If the field is reduced to zero. the wall comes back to the nearest stable point. Thus the critical field. at which the wall is swept out of the crystal is determined by the maximum gradient of the curve in Fig. so that we have If we assume that the variation of the wall energy is caused by variations in the Fig. 18. H0. where K = Kl +K2 for cobalt. Further increase of the field will bring the wall to the next equilibrium position.21. 18. where the condition (18.60) is satisfied for a new field.DOMAIN WALL DISPLACEMENT 487 Fig. cobalt and nickel. 18. Positional variation of the wall energy and the irreversible displacement of the wall. s0. but not to the original position. s3.20.

we assume that A = 10 5.63) also becomes maximum. so that H0 (18. r. Kersten11 measured the coercive field of Ni as a function of the internal stress (see Fig. however. does not satisfy the equilibrium condition (18. Curve a shows the result for a Ni wire which was stretched plastically by various amounts. so that the radius of the wall decreases as H is increased. The radius of curvature of the cylindrical wall. where sw = j. the wall is plane (curve a). so that the wall must expand irreversibly to the next pinned points. 18. while curve b is for a cold-rolled Ni plate that was annealed for various lengths of time to release the internal stress.61).42)). For H = 0. the maximum gradient of the wall energy is given by where S is the wall thickness (see (18. Figure 18.488 TECHNICAL MAGNETIZATION internal stress as shown by (18. Therefore the critical field is obtained by putting r = 1/2 in (18.64).48). 7S = 1T. H. cos0~l. Using this expression in (18. the wall energy is maximum when / ~ 8.39). is increased. is inversely proportional to H as shown in (18. As the field. up to curve c where the radius r is equal to half the distance between the two pinned points.48).23 shows the cross-sectional view of a domain wall with both ends pinned. Further increase in H causes an increase in r. and also we adopt a maximum internal stress cr0 = lOOkgmrcT 2 = 109 NnT 2 . we have As already mentioned.22).64) becomes which is about the average coercive field of alloy permanent magnets. the wall bulges under the action of the pressure (18. so that the numerical value of (18. Both curves agree well with (18. Next we shall discuss the critical field for a pinned domain wall.48) to give . which. Therefore we have For ordinary ferromagnets.5) as shown by curves b and c.

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

88) for At/. 00. H. Then the energy of the field is reduced by 2/s/f cos 912r. if the interval between Fig. Therefore the irreversible expansion of the wall will occur before the wall leaves the pinning points. However.490 TECHNICAL MAGNETIZATION field.24. Suppose that the wall is displaced by the radius r of the pinning point under the action of the field H. and if this value exceeds At/. H0 on the angle.69). .71)). Dependence of the critical field. The critical field in this case is given by the condition or If we use (17. (18. 18. between the field and easy axis of the uniaxial anisotropy (see (18. the wall bulges in a cylindrical form.67) becomes which is much smaller than (18. the wall will leave the pinning point. Let the energy of pinning be At/ at each pinning site.

24. Generally speaking. The energy density in this case is given by where Ku is the uniaxial anisotropy constant. for domain wall displacement. giving Fig.25. Moreover. it can be magnetized only by rotation of the domain magnetization. 18. the domain magnetization 7S rotates from the easy axis by the application of a magnetic field H.25. the critical field is proportional to I/cos 6. the domain magnetization 7S rotates from the easy axis to a direction which makes the angle 9 with the field (Fig. The equilibrium direction of magnetization can be found by minimizing the energy (18. This is equal to Kul for uniaxial magnetocrystalline anisotropy. and equal to f ACT for magnetoelastic energy due to stress a. then when the field makes an angle 00 with the easy axis.72) with respect to 0. This mechanism is called magnetization rotation. First we discuss reversible magnetization rotation. roll magnetic anisotropy. 18. 18. for uniaxial anisotropy. If the magnetic anisotropy is uniaxial. Thus the critical field is larger for larger 00. and rotates back to the easy axis reversibly upon removal of the magnetic field. . and the applied magnetic field H makes an angle 90 with the easy axis. As shown in Fig. and shape magnetic anisotropy of elongated precipitates. Let this value be H0 y . the wall leaves the pinning points before the irreversible expansion point is reached.MAGNETIZATION ROTATION 491 the pinning points is smaller by two orders of magnitude. the critical field is given by which is shown graphically in Fig. 18. For instance.3 MAGNETIZATION ROTATION If a ferromagnetic medium contains no domain walls or only immobile domain walls.25). Magnetization rotation away from an easy axis. 18. H0 is smallest when the field is applied parallel to the easy axis. a uniaxial anisotropy can arise from various induced anisotropies such as magnetic annealing.

the magnetization decreases along the same linear curve. Numerical values are the angles between the field and the easy axis. we have from (18. When the magnetic field is removed. As 00 is reduced. decreases as seen in the magnetization curves calculated from (18.74) in Fig.9). and for a Co single crystal with the c-axis perpendicular to the magnetic field. Solving for x in (18. or the susceptibility. 18.26).26. It is interesting that for 00 = 30° and 60°.73) Putting this in (18. Magnetization curves due to magnetization rotation against the uniaxial anisotropy. Such linear magnetization curves are observed for a stretched nickel wire (A < 0).74).26. 18. in contrast to the case of 00 = 90°. which is a cold-rolled grain-orientated Fe-Ni alloy (see Fig. . for a Permalloy wire annealed with an electric current flowing through itself (see curve c in Fig. we have from (18.26. the magnetization does not saturate. Putting cos 6 = x. for Isoperm. 13. we have The magnetization curve can be obtained by plotting x as a function of p as shown in Fig.73) where p=IsH/Ku. we have which is a linear magnetization curve (see Fig.1). 18. while the slope of the magnetization curve. 18. For the case in which 00 = 90°. with almost no residual magnetization. 13.75). for which the magnetization saturates completely at H = 2KU/IS. the residual magnetization increases.492 TECHNICAL MAGNETIZATION Fig.

As mentioned in the previous section. so that condition (18.82) becomes For iron in which 7S = 2. the susceptibility due to wall displacement is quite structure- .73) becomes or The initial susceptibility is obtained from (18.K\A0 2 as shown in (12.79) we have In the case of cubic anisotropy with positive KI} the anisotropy energy is expressed as . (18.MAGNETIZATION ROTATION In very weak magnetic fields (H <. KU/IS\ 8 ~ 60. so that (18.2 X 104 / m~ 3 .52). so that the initial susceptibility is given by In the case of negative Kl the anisotropy energy is expressed as — (2. so that the initial susceptibility is given by In the case of a random distribution of the easy axes. much larger than the value given by (18.75) as so that from (18.84) gives Since iron usually exhibits relative initial permeability of 100-200. sin2 0 0 = f. there is no doubt that domain wall displacement contributes to the mechanism of magnetization at low fields.85).K\/3)A02 as shown in (12. If we put 493 the anisotropy energy in (18.15 T and Kv = 4.55).72) is expressed as Ku&62.

while K1 = 420 Jm~ 3 (see the curve for the disordered state in Fig. and A is zero at 19% Fe. This value is too large to permit such a high permeability. Double heat treatment means that the specimen was annealed for 30 min at 1000°C. as follows: In Fe-Ni alloys K^ is zero at 24% Fe. Annealing means prolonged annealing below 500°C after annealing at 1000°C. the relative permeability of Fe-Ni alloys depends upon the heat treatment: The maximum value of about 10 000 is observed at 22% Fe. 14. 18. 18.494 TECHNICAL MAGNETIZATION Fig. so that it can increase indefinitely by improving the homogeneity of the material. As shown in Fig.27.35). Thus we can say that the susceptibility due to magnetization rotation is the lower limit of the initial susceptibility. This value of stress is about 1% of ordinary working stresses. we can calculate the value of K using (18. while A = 7 X 10~6 (see Fig.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 the high permeability is not due to magnetization rotation. Assuming that this value is due to magnetization rotation. as discussed previously. 12. At 24% Fe. cooled slowly to 600°C. Kl = 0. where K^ is almost zero. .1.84) with JLa = 10000. On the other hand. At 19% Fe the magnetoelastic anisotropy is zero irrespective of stress. Furnace cooling means cooling from 1000°C in the furnace. sensitive. and then quenched on a copper plate kept at room temperature.27. Initial permeability of Fe-Ni alloys (After Bozorth12). Therefore we must consider wall displacement. the susceptibility due to magnetization rotation depends only on the magnitude of magnetic anisotropy and is insensitive to the homogeneity of the material. and 7S = 1.

In order to obtain high permeability. cooled slowly down to 600°C. is applied in the -x-direction. an induced anisotropy Ka{ with the easy axis randomly oriented is produced. This local anisotropy cancels the cubic anisotropy from place to place in a composition range where K! « Kuf. irreversible magnetization takes place by domain wall displacement. Further annealing or slow cooling results in the development of directional order. thus resulting in easy rotation of magnetization locally. Irreversible magnetization rotation in an elongated single domain particle. Figure 18. irreversible magnetization occurs by magnetization rotation. P . In ordinary ferromagnetic materials. the treatment is the same. First we treat the case of uniaxial anisotropy. 18. Next we discuss irreversible magnetization rotation. while in single domain particles. with the magnetic field. 18.27. thus creating a uniaxial anisotropy much larger than the cubic anisotropy.28 shows an elongated single domain particle whose long axis makes an angle 6Q with the Ac-axis. the alloy must be annealed at 1000°C for 30min. 18. For uniaxial anisotropies other than shape anisotropy. as seen in the dashed curves in Fig. By this treatment. directional order develops in this alloy system.MAGNETIZATION ROTATION 495 However. the spontaneous magnetization rotates to the direction which makes the angle. H. The energy density of this system is given by The equilibrium direction of the magnetization is obtained by minimizing this energy. This picture can explain why such a high permeability is obtained reproducibly in a definite composition range. creating an induced magnetic anisotropy Kuf which stabilizes the magnetization parallel to its direction during annealing. 6. Therefore the high permeability is reduced. and then quenched at a moderate rate to room temperature (double heat treatment). When a magnetic field. with the easy axis in the direction of the long axis of Fig.28.28. there is another possibility involving magnetization rotation: As explained in Chapter 13. giving E Fig.

and it is unstable when With increasing field H. increasing the angle 6. and adding them together. so it must be that Differentiating (18. 18. and then suddenly rotates towards the —^-direction.89) can be expressed as Squaring both sides of the two equation in (18. the magnetization changes from a stable to unstable equilibrium. or the critical field. the magnetization rotates. We see that p.92) we can solve for sin20 0 from (18.90). In other words. this condition gives Equations (18. At this instant.496 TECHNICAL MAGNETIZATION When this is a stable equilibrium. is minimum when 00 = 45°.88). when the field makes the angle 45° the magnetization reversal occurs at the smallest critical field.88) and (18. which is given by .29. H0. we have an equation for sin2 6 from which we have Using (19.90). to get This relationship between p and 00 is shown graphically in Fig.

52). 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^. The critical field becomes larger as 60 deviates from 45°.93)). the anisotropy energy is given by (12.MAGNETIZATION ROTATION 497 Fig.55) when /s is close to an easy axis. on the orientation of the applied field (refer to (18. 18. Since the functional form of the anisotropy is more complex. 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. We discuss only the case in which the field is applied opposite to the magnetization pointing parallel to one of the easy axes. the situation is not so simple.29. H0. so that the total energy is given by . At 00 = 0° or 90°. Since the anisotropy energy with positive Kl is approximately expressed by (12.

104). which starts at point B. the second term becomes significant because of the appearance of irreversible magnetization. we expect a reasonably good permanent magnet material. In the lower half of the loop.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. and K^ = 104 ~ 10s JnT 3 . In the reversible magnetization region where H is small. the magnetization changes approximately as given by (18. so that the magnetization is described by where /j and Hl are the amplitudes of / and H. Thus if such an irreversible rotation magnetization is realized. so that H0 = 104 ~ 105 Am" 1 (= 102 ~ 103 Oe). respectively. the second term changes its sign. When H is decreased. the magnetization changes along a loop as shown in Fig. With increasing amplitude of H.30. Therefore if H is oscillated about the origin. the magnetization is well approximated by the first term. 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 .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. These values are in the range for permanent magnet materials. 18. This phenomenon was investigated by Lord Rayleigh13 a long time ago. 18. In the common ferromagnets 7S = 1~2T.

30.105) and (18. By analyzing this waveform.RAYLEIGH LOOP 499 Fig. because it causes not only power losses but also a distortion of the waveform. 18. Thus the flux density B is expressed by Calculation shows that and The quantity tan 8 is called the loss factor. we find that the phase of the fundamental waveform of / is shifted by the angle 8. The quantity k given by (18. and has a nonzero value when there is hysteresis loss.31 shows how the waveform of / is distorted by the Rayleigh loop when a pure sine wave of H is applied.112) is called the Klirr factor. we can rewrite (18. Using (18. The hysteresis loss is calculated to be which shows that the loss increases rapidly with an increase of the amplitude //j. Rayleigh loop.106) as ascending pa: desebnding pa These curves are called the Rayleigh loop. Figure 18. it is a . The appearance of this hysteresis loop is undesirable for magnetic cores. and also there appears a third harmonic wave sm3a)t.107).

1831. Now we can derive the second term in Rayleigh's equation from this model.60) is satisfied. 18. On the other . H0. for then the voltage induced by the third harmonics is shorted in the delta circuit. The origin of the Rayleigh loop is the same as that of the ordinary hysteresis. similar to the Gaussian distribution function centered at HQ = 0.2. where dew/ds = 0. say A.61). Let us consider the mechanism in terms of wall displacement. In the present case. If the field is increased from H to H+dH. Distortion of the wave form of magnetization by the Rayleigh loop when a pure sinusoidal field is applied. 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. The critical field to get over a maximum. HQ is limited to a small range. the point rises along the slope. As discussed in Section 18. In Fig. the wall is held at the place where condition (18. the longer the jump in each discontinuous displacement. measure of the third harmonic relative to the fundamental frequency.500 TECHNICAL MAGNETIZATION Fig. say to B. At H= 0 the wall stays at a point. and displaces discontinuously from the maximum to the next positive slope. It should be noted that the stronger the field.32. ds^/ds is plotted as a function of the displacement s. where /(//„) is a function of H0. Let the number of maxima that have critical fields between H0 and H0 + dH0 be /(//0)d//0. The only difference is that the amplitude of the field is very small in the case of the Rayleigh loop. the point displaces from B to C -» D -> E. the number of walls which are released should be proportional to /„ dH. so that we can postulate that f(H0)) is a constant. With an increase of the field. say /0. is given by (18. 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. With further increase of H.

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

Now we apply the field Hl in the + direction. 18. Changes in magnetization with field according to the Preisach model.502 TECHNICAL MAGNETIZATION Fig. .34.33. A shifted rectangular hysteresis loop. reversing the — magnetization below the Fig. so that the boundary lines AOB are shifted by H^ to A'O'B' (see Fig.34 (b)). 18. 18.

1 200 4300 150000 0. Parameters of Rayleigh loops Material /Za 15 TJ* 103 per Am Hper —— Oe) 4ir 25 0.104). It is also possible to regard the Preisach model as an assembly of small magnetic particles with various rectangular hysteresis loops.1. the shift b is caused by the magnetic interaction from the neighboring particles.34 (f)).0013 Wh f o r A / = l ( r 4 T = 1/477 gauss /uJm 3( X10/xerg cm 3) 2. In this section we examine the rotation of the magnetization under such circumstances.34 (c)).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 . Let the angle between magnetization and the magnetic field be 6. 18. This corresponds to the Rayleigh relationship given by the second term in (18. In this case. ferromagnetic materials are generally magnetized to their saturated state. or to H2 (see Fig.0001 0.34 (c). line O'B' to +. If the field is decreased to —H^ the boundary lines are shifted to A"O"B" (see Fig. The magnetization reversal occurs from one end of the triangular area. 18. Then the component of magnetization in the direction of the field is given by .LAW OF APPROACH TO SATURATION 503 Table 18. 18.32 0. 18. thus resulting in an increase in the number of — magnetized units.013 0. where all possible wall displacements have taken place and the magnetization is pointed almost parallel to the applied field.5 LAW OF APPROACH TO SATURATION Under a moderately strong field. It is the rate of increase of jua by an increase in the amplitude of H.13 3. The Preisach model is essentially the same as the explanation given above with respect to Fig. The parameters of Rayleigh loops measured in various magnetic materials are listed in Table 18.6 0. 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. and the magnetization change is proportional to the area of AO'C'O"".32.1. 18.41 0.0005 0.014 0.25 0.

we have where Now we solve for the actual form of C for cubic anisotropy. 18.116).504 TECHNICAL MAGNETIZATION Fig. The torque exerted by the magnetic field is counterbalanced by the torque resulting from the magnetic anisotropy (see Fig. Since the magnetization rotates along the maximum gradient of the anisotropy energy in the vicinity of H. tp) are the polar coordinates of the magnetization.35.118) in (18. Rotation of magnetization against the magnetic anisotropy. Since £a is normally . where (6. 18. it can be found from (18.117) to be where On substituting (18.35): where E& is the anisotropy energy. Since 6 is very small.

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

18.129).121). This means the presence of the a/H term.506 TECHNICAL MAGNETIZATION Then (18. is The last term. The experimental points are well fitted by straight lines. From (18.7). Using the values of b thus determined we can calculate from (18. A close inspection of the graphs in Figs. instead of measuring / itself. averaging over the all possible orientations of the individual On putting this in (18. The first term. This means that the experiments are well described by the b/H2 term in (18.37 show dl/dH as a function of 1/H3 for iron and nickel. we obtain This result coincides with that obtained by Becker and Doring16 by an entirely different method.128) the values of Kv We obtain (at room temperature) These values are in fair agreement with the values given in (12. \oH.129).129).37 reveals that the experimental points deviate from the linear relationship near the origin. The law of approach to saturation. Czerlinsky17 measured dl/dH in the high-field region.124) becomes For a polycrystal. we have Figures 18.36 and 18. This term cannot be explained in terms of a uniform .6) and (12.36 and 18. obtained by experiment. has been discussed by many investigators. a/H. as we shall see later. is caused by an increase of the spontaneous magnetization itself. 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.

. Both calculations are very complicated. small spike domains. If local internal stresses caused by dislocations or lattice vacancies fix the direction of the local magnetization firmly. The same thing is also expected for the magnetization surrounding a special precipitated particle producing an exchange anisotropy (see Section 13.120). Since a constant restoring force or torque leads to the b/H2 term. as already discussed in (18. magnetization rotation. Brown18 explained the a/H term as the result of the stress field about dislocations.0. because this leads to the b/H2 term.LAW OF APPROACH TO SATURATION 507 Fig. For instance. so that here we show only the basic ideas of the two interpretations. 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. the work necessary to magnetize the specimen to complete saturation diverges. as shown by Thus we must conclude that the term a/H is valid only within some finite range of field strength.36. As pointed out by Neel.4. Law of approach to saturation for iron (Czerlinsky17). we must assume the presence of a restoring force which increases as the magnetization approaches saturation. 18.1). 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. which remain around voids at high fields.

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

acting between second nearest neighbor spins. 19. 7A and 7B. At the same time 7A tilts from the +77-direction under the action of the molecular field from the B sublattice. This interaction is equivalent to a magnetic field of several hundred MAm" 1 (several MOe). 7A and 7B. Let us consider a ferrimagnet consisting of two sublattice magnetizations. As the field is increased.2). and tilts from the -77-direction. The two sublattice magnetizations are aligned antiparallel by the superexchange interaction (see Section 7. Therefore the technical magnetization for ferrimagnetic materials behaves in the same way as that for ferromagnetic materials.2 SPIN FLOP IN FERRIMAGNETISM Ferrimagnetism is the result of two uncompensated sublattice magnetizations. aligned antiparallel and having different magnitudes (/A > |/B|). However.5 Experimental data on metamagnetic magnetization processes for various antiferromagnetic materials are given by Jacobs. A theoretical investigation of this behavior was made in 1968. Jj.1). while — w is the inter-sublattice molecular field coefficient (w > 0). the effective fields which 7A and 7B feel are given by Taking the difference on each side in (19. If 1/A| > |7B|. /2.SPIN FLOP IN FERRIMAGNETISM 521 exchange energy. The spontaneous magnetization is the difference between the two sublattice magnetizations (7S = 7A |7B|) (see Section 7. Further increase in 7:7 causes a rotation of 7A and 7B towards the field. The molecular fields acting on these sublattices are expressed as where WA and W B are the intra-sublattice molecular field coefficients. a ferrimagnet responds to a high magnetic field quite differently from a normal ferromagnet. in addition to the first neighbor exchange. while 7B is aligned antiparallel.4 A theoretical treatment of metamagnetic magnetization processes in antiferromagnetic materials is given in a detailed review. 7A is aligned parallel to the magnetic field. as long as the field is moderately weak.7 but experimental studies have been started only recently when ultra-high magnetic fields become available. In an external field 77. resulting in a ferromagnetic arrangement (see Fig.11). 7B becomes unstable. we have therefore .6 19.6). Thus 7A and 7B form a canted spin arrangement. so that a ferrimagnet behaves like a normal ferromagnet in magnetic fields of moderate strength.

We can find 77cl. by putting 7 = |7A| — |7B| to give In the same way.13) in (19. at any temperature. |/A| and |/B| have constant magnitudes independent of the angles between /A. In other words. by putting 7 = |7A| + |7B|. Using the relationship (19. Since 7A and 7B must be parallel to 77Aeff and HBeK respectively.12) is satisfied only when both sides of the equation are zero. However. at which the linear magnetization curve begins and the field.7. do depend on temperature. The magnetization composed of 7A and 7B is given by which is proportional to H. these sublattice magnetizations have different directions. so (19. as long as the canted-spin arrangement exists. the left-hand side of (19. independent of temperature. 19. to give . Canted spin arrangement. we can find 77c2.7. Thus the magnetization curve of a ferrimagnet must be the same straight line with susceptibility.11). This means that |/A| and |/B| are determined by their own magnitudes.6.522 SPIN PHASE TRANSITION Fig. we have This relationship is shown in a vector diagram in Fig. at which it ends.12) must be parallel to 7A. I/TV. Thus in the canted-spin arrangement. In the canted-spin arrangement. 19. 7B and H. 77c2. Ferrimagnetic spin-flopping: (a) Fig. independent of the intensity of the external field. the field. 77cl. 19. whereas the right-hand side must be parallel to 7B.

respectively. The number of nearest neighbor /-sites of an /-site. 5 is the spin of an Fe ion (5 = f). resulting in a spontaneous magnetization of 5 Bohr magnetons per formula unit associated with one Fe ion (see Section 9.SPIN FLOP IN FERRIMAGNETISM 523 Since |/A| and |/B| depend on temperature. Three Fe ions on the 24 d sites and two Fe ions on the 16a sites are coupled antiferromagnetically.21) and .18) and this 5-value. 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. we can express the exchange energy density for a-a interaction as where N is the number of Fe ions per unit volume.20). Using this formula. these critical fields are also dependent of temperature. Yttrium iron garnet (YIG) is a ferrimagnet with the chemical formula Y3Fe5O12.10) by converting the sublattice names from A and B to d and a. for the 16a and 24 d sites are given by The exchange energy between the /-site spin St and the . where Y is nonmagnetic while Fe is magnetic. Comparing this expression with (19. is given by -2JijSiSj. where Jtj is the exchange integral.. Using (19. site spin 5.3).. (19. A computer simulation of such spin-flop behavior is shown below. Since we have where AfB is the Bohr magneton. z.

10). 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. Ido and Ia0 for YIG.26) and (19. or the temperature dependence of Id and Ia can be found by successive integrations of (19.8. The spontaneous magnetization of a ferrimagnetic garnet is given by where According to (19.22). Anderson8 assumed the following two sets of values for the exchange integrals for YIG: and The results are plotted in Fig.27). which shows the temperature dependence of Id . Hmd and Hma are given by Starting from the initial values at 0 K.524 SPIN PHASE TRANSITION (19. 19.

These graphs show field dependences of normalized values of sublattice magnetizations.27).29)). and the inclination of the magnetization curve.8 The dashed curves assume the values of set B.for set A.26). The temperature dependence of 7S thus obtained is in good agreement with the experimental values of Anderson. the solid curves are calculated by using set A (see (19. where the spin canting takes place. together with (19. the values of //cl and Hc2 . their z-components and the resultant magnetization. which ignores Jaa and Jdd. calculated by using the values Jtj for set A (see (19. Temperature dependence of normalized sublattice magnetization calculated by using two sets of exchange integrals.SPIN FLOP IN FERRIMAGNETISM 525 Fig. Nevertheless the temperature dependence of 7S thus obtained is not so different from the solid curve. However. 19. stay constant as mentioned before. and temperature dependence of the spontaneous magnetization.8. Figures 19. cannot be accurately determined by such a procedure. This means that values of the three /i.9 and Ia as well as the spontaneous magnetization 7S.16)).11). the magnitude of the sublattice magnetizations. Another method for determining the value for w or Jad is to observe spin flopping in a high magnetic field (see (19.9 The solid curves assume the values of /(j. respectively. in which the molecular fields Hm are replaced by the effective fields /feff in (19. The magnetization curve in high magnetic fields can be simulated by using (19.9(a) and (b) show the results for YIG at 100 K and 200 K.29)) and the dashed curves are drawn using set B (see (19. and a different value for Jad.15) or (19. In the field range Hcl <H<Hc2.30)).

526 SPIN PHASE TRANSITION Fig.29) for YIG: (a) at T= 100 K. (b) T= 200 K. Figure 19.9.9 are different at different temperatures. . Magnetization process during spin flopping calculated by using the exchange integrals (set A) in (19.10 shows a spin-phase diagram in which the traces of //cl and Hc2 are drawn in the H-T plane. 19.

SPIN FLOP IN FERRIMAGNETISM 527 Fig. 19. 19.10.9 This spin-phase diagram is difficult to verify experimentally. 0 f .11. 19. It is interesting to note that this boundary continues above the Curie point. Spin phase diagram constructed for YIG by using the exchange integrals (set A) in (19. This means that above the Curie point the material is paramagnetic in zero field.10 is the phase boundary at which the ferrimagnetic spin arrangement changes to ferromagnetic. Conceptual spin phase diagram for an N-type ferrimagnet. and Fig. . The dashed curve in Fig. but becomes ferrimagnetic in an applied field up to the phase boundary (dashed curve). because it requires very high magnetic fields.29).

they dilute the Fe ions on d.9'10 In an N-type ferrimagnet (see Section 7. A part of the spin phase diagram for DylG constructed by using two sets of exchange integrals.1 (= 1 MOe). and Hcl = 0 as found by (19.and d-sites is weakened.16). and a comparison with experiments. ©c. go to zero at the compensation point. Therefore spinflopping can be observed in a relatively weak field near the compensation point.2).|/B| = 0 at the compensation point.528 SPIN PHASE TRANSITION Fig. shown by solid and open circles. Figure 19. The dashed critical curves are calculated on the basis of this two sublattice model. Figure 19. The critical fields. so that the exchange interaction between a. Above TQ. The solid circles . Hcl and Hc2. When nonmagnetic Ga ions are added to YIG.and a-sites. 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.12 shows a part of the spin phase diagram observed for DylG. They are in poor agreement with experiments. it is always ferromagnetic in a nonzero field.12. 19. In this case spin-flopping can be observed in a relatively weak magnetic field such as 80MAm. |/A| .11 is a conceptual spin phase diagram of an N-type ferrimagnet. which is an N-type ferrimagnet.11 The unit of the exchange integrals is cm ferromagnetic in higher fields.

For example. . y. In 3d transition metals. the exchange integrals Jad — — 25.4). 12. the atomic rf-wave functions are split into de and dy states under the influence of the cubic crystalline field (see Section 3. the energy difference is rather small between the ground state with J = \L\ — \S\ and the first excited state with / + 1.30). it is necessary to observe spin-flopping in pure YIG. while the latter is called the low-spin state. The situation is the same for the Co3+ ion. By fitting a calculated Hcl versus temperature curve to the experiment.13(b)).HIGH-FIELD MAGNETIZATION PROCESS 11 529 were measured by means of Faraday rotation (see Section 21. because interactions between Dy and other spins are introduced. When such an ion is located on an octahedral site in an oxide. The former state is called the high-spin state.or z-axis. because L'(d) decreases as T2. For instance. This means that such an experiment is not very satisfactory for measuring exchange integrals.6cm"1 and Jaa = —6. this is not necessarily true. we obtain the solid curves in the Figure. According to Hund's rule. the ground state for Eu 3+ has \L\ = \S\ = 3.2cm" 1 were determined. The reason for this is that we assumed the atomic magnetic moment to be independent of the field.29) and (19. Unlike sets A and B in (19. thus resulting in a non-magnetic ion. 19. 19. in which L and 5 make some angle. This results in a magnetic moment of 4MB. which shows XQ ~* 0 as T -> 0. Md. Therefore by selecting 6 parameters (sets A and B) in the figure we can easily fit the experiment with the calculation.13(a). as shown in Fig.2). all the + spin levels are filled first and then the lowest — spin level is occupied. however. Moreover. the level splitting due to the crystalline field is too large. This has been done by applying ultra-high magnetic fields12 up to 350 T (see Section 2. The value of Jdd cannot be determined. the two + spins which occupied dy levels fall into the lowest ds levels (see Fig. the atomic magnetic moment of rare earth atoms is generally well described by Hund's rule (see Section 3. In Sm3+ and Eu 3+ ions.3 HIGH-FIELD MAGNETIZATION PROCESS As discussed in Section 18. L is generally quenched by the crystalline field. while the first excited state with / = 1 is higher than the ground state by 600 K or about 700 MAm"1 (= 9MOe).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. however. which fit the experimental points reasonably well. 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. 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 high-field susceptibility is given by (18.3). because the sublattice magnetization on the d-site.133). is saturated during the spin flopping at low temperatures.5. it may find a nearest neighbor O 2 ~ ion on the x-. In some real magnetic materials. If. the number of parameters is increased.1). so that / = 0. In order to determine exchange parameters. Suppose we place an Fe2+ ion that has six 3d electrons on the octahedral site.20).

the high-spin states are split into 2J + 1 levels in a magnetic field H with J2=J. Level splitting and electronic states of Fe2+ or Co3 + (d6) ions on octahedral site: (a) high-spin state. According to statistical mechanics.. Assuming the energy of the low-spin state to be zero. Variation of level splitting between low-spin and high-spin (/ = 1) states with increasing magnetic field. The energy separation between the two states is denoted by At/.-J. the high-spin states are split into three levels with Jz = 1..13.. For simplicity. (b) low-spin state.530 SPIN PHASE TRANSITION Fig. . whose separations increase with increasing field H.0. -1. 19.14. Saturation magnetization of these two-spin-state compounds changes considerably with temperature and applied magnetic field. 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. 19.U/kT\ so that the probability of Fig. Figure 19. Generally speaking.. the probability of obtaining the state with energy U is proportional to the Boltzmann factor exp( .J~1. let us assume that the magnetic moment of the low-spin state is zero. while that of the high-spin state is gJME.14 shows the variation of the energy levels of the two-spin states for /=!.

at high temperatures such as Fig.15.0086 eV (corresponding to 100 K). . However. 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. 40.15 up to 300MAnT1 (=3.33) for T = 4. Temperature dependence of saturation magnetic moment with / = 1 calculated by assuming A U= 0. the field dependences of the saturation magnetic moment Ms calculated from (19. 100 and 200K are plotted in Fig.75 MOe). 19. At 4K. 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.0086 eV (100 K).

The nonzero atomic magnetic moment remains in low fields.45). measured at 4K. Co. 0. 0.35.9MB. 0. and Ni at 4.1. 19. (from top to bottom x = 0. The composition dependence of the high field susceptibility could be . Co ions with many Se neighbors tend to take the low-spin state14 with zero magnetic moment. 0. which is a pyrite-type compound.532 SPIN PHASE TRANSITION Fig.14 100 and 200 K the transitions are spread out and the curves resemble the Brillouin function.16 shows the magnetization curves for CoS2__tSeA. When Se is added.2. because there are still some high-spin Co ions with a small number of Se neighbors. Invar is an alloy of 35at% Ni-Fe whose thermal expansion coefficient at room temperature is almost zero. The values measured for Fe.2K. 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. 0. Figure 19. 0.28. it has a number of practical uses.375.28. If the magnetic material containing such two-spin-state ions is ferromagnetic.30. 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.17 The high field susceptibility. with the Co ion having an atomic magnetic moment of 0.25. 0.. The compound CoS2 is ferromagnetic.40 and 0.15'16 Recently this characteristic was alternately interpreted in terms of the temperature dependence of local magnetic moment in spin fluctuation theory.2K are18 This phenomenon is interpreted as an enhancement of the band-polarization by the external field. we must consider the effect of the molecular field and use H + wI for H. as seen for the curves for x > 0. Magnetization curves measured for CoS2_^Sex at 4.

temperature and magnetic field are two major parameters: Temperature ranges from 0 to 1000 K. the magnetization curve of a ferromagnet above its Curie point. well accounted for in this way. a high magnetic field influences the magnetic structure as the temperature does. 19. the populations of the spin states in a magnetic field H are described in terms of the parameter a = MH/kT. which is called the paraprocess. In the usual statistical theory of ferromagnetism. the energy of a magnetic moment of 1MB in a magnetic field of SOMAnT1 ( = 1 MOe) corresponds to 68K. For example. Figure 19. the shape of the curve changes with temperature. Therefore one is tempted to consider that the field H and temperature T are not independent parameters to describe the magnetic state. an ultra-high magnetic field of 800 MAm" 1 (= 10 MOe) corresponds to 680K. while magnetic field ranges from 0 to IMAnT 1 (= 13kOe). Since. This additional experimental parameter may be useful for checking various statistical theories (see Section 6. all the curves would be identical. however.17 shows the paraprocess of a ferromagnet calculated by the Weiss approximation. In the statistical mechanics of spin systems. However. 19. If the paraprocess were described by a unique function of H/T. The abscissa is MH/kT. depends independently on H and T. this is not the case. Therefore all magnetic phase transitions can be caused by applying an ultra-high magnetic field as well as by temperature.2). As seen in the figure. The parameter on each curve is the value of T/@f.SPIN REORIENTATION 533 Fig. however.17.19 As discussed above. Paraprocess calculated for a ferromagnet by the Weiss approximation.4 SPIN REORIENTATION Spin reorientation is defined as a transition of the state of magnetic ordering between .

In the case R = Dy. not only the exchange interaction but also the magnetic anisotropy plays an important role.23 Figure 19.22 Many RCo5-type intermetallic compounds (see Section 12. Similar phenomena are observed for other magnetic orthoferrites. or a change in the orientation of the spin axis.18. In order to explain all the phenomena reasonably. Rare earth orthoferrites are magnetic oxides with composition given by RFeO3 (R: rare earth). but their transitions occur at low temperatures. 19.23 . they have orthorhombic crystal structure (see Section 9. the c-component (7S = y 72 + 72 ).3). and 7C. In the case R = Sm.21 This is a spin reorientation corresponding to a second-order phase transition. Figure 19. canted.20 In these phenomena. an antisymmetric exchange interaction (see Section 7.19 shows the temperature dependence of spontaneous magnetization measured for a spherical specimen of DyCo5 hung by a thin thread perpendicular to Fig. ferrimagnetic or ferromagnetic). Ia. the spontaneous magnetization.4) undergo second-order type spin reorientations. 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. Because this crystal structure is a distortion of the cubic structure.4) acts on the antiferromagnetically arranged Fe34" spins. and then the spontaneous magnetization rotates gradually until it reaches the c-axis at 367K (rSR2).and Dy-spins are coupled ferrimagnetically on the a-axis below 325 K (rSRj).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.18 shows the temperature dependences of 7S. we must assume that the Dy spins have taken a conical spin arrangement above rSR1.534 SPIN PHASE TRANSITION two of the possible magnetic structures (antiferromagnetic. thus resulting in a canted-spin arrangement with a small spontaneous magnetization. Spin reorientation of DyCo5 caused by temperature change. the a-component of 7S. Co.

CrSj 17 (see Section 10. It is also interesting that |/s| depends on the intensity of the field in this temperature range. The sublattice magnetizations of the A. Assuming the molecular field constant to be —w. and rotates with increasing temperature until it reaches the c-axis at TSR2 = 285 K. Assume that the magnetic anisotropy is negligible. 193 Consider a possible engineering application of spin reorientation. 19.23 the a-c plane.12). 7. There are a variety of spin reorientations. . In the case R = Nd.4). etc. change in sign of the anisotropy constant. how many degrees does 7A tilt from 77? Find the magnitude of 77 in this case. PROBLEMS 19.1 Draw the spin-phase diagram for an antiferromagnet containing N magnetic ions each with magnetic moment M. Temperature dependence of /s measured for a spherical specimen of DyCo5 freely rotatable about an axis perpendicular to the a-c plane.and B-sublattices are given by 7A = \ NM and 7B = — \NM at T= 0 and 77 = 0. 19. we shall not go further into the details of such behavior. the spontaneous magnetization is parallel to the fe-axis below TSR1 = 245 K.4) and MnAs (see Section 10.3) undergo a first-order type spin reorientation. When 7B is perpendicular to H.24 Some magnetic materials such as FeRh (see Section 8.19. draw a high field magnetization curve at 0 K.PROBLEMS 535 Fig. and the temperature dependence of /A = —7B is the Q-type (see Fig. The numbers identifying the various curves are the angle 6 measured from the c-axis.2 Suppose a ferrimagnet contains N magnetic ions with a magnetic moment M in a unit volume.to the c-axis with increasing temperature from TSR1 to rSR2. including reorientation of the easy axis. It was observed that the specimen rotates from the a. However.

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

and also depends on the final magnetic state at H2. There is an immediate change in magnetization. while changes due to aging are not recoverable by purely magnetic means. and is suddenly changed to H = H2 at t = 0. 20. Suppose that a magnetic field H = H1 is applied to a magnetic material. or crystal phase transition.2) may cause a delay in magnetization. This phenomenon is sometimes referred to as magnetic viscosity. In the simplest case. 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. Magnetization may also be affected by purely metallurgical phenomena such as precipitation. The time-varying part /„ can be written generally as The magnitude of /„ is a function of /.. diffusion. such as near the residual magnetization or the coercive field.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. In(t) can be expressed by a single relaxation time T. are usually known as aging. the value of /„ is very small. For example. /„ may be fairly large. /n. but there is an additional change. 7j. while if the final state is in a field range for irreversible magnetization. 20. Eddy currents (see Section 20.20 DYNAMIC MAGNETIZATION PROCESSES In this section we treat time-dependent magnetization processes. . to give where 7n0 is the total change in magnetization from t — 0 to °°.1. These processes become particularly important when the magnetization must change rapidly. not including /. if they occur slowly at or near room temperature. as in high-frequency or pulsed fields. but this kind of purely electrical phenomenon is regarded here as distinct from magnetic after-effect. this kind of magnetization change is also excluded from the definition of magnetic after-effect. if the final state is in the field range for magnetization rotation. occurring over time as shown in Fig. Structural changes like those in the previous sentence.

Magnetic after-effect observed for a low-carbon iron.1 The curves measured at various temperatures can all be fitted with straight lines corresponding to a (log In)-t relationship.1. where the Rayleigh term (the second term in (18.104)) is Fig.1 .2) describes the experiment well.2 shows a semi-log plot of /„(/) vs time measured for pure iron containing a small amount of carbon.538 DYNAMIC MAGNETIZATION PROCESSES Fig.2. The applied field in this experiment is in the initial permeability range. Figure 20. 20. This means that (20. 20. Time change in a magnetic field and the associated change in magnetization.

Then changes in magnetization are delayed so that where S is the delay expressed as a phase angle. we call this angle 8 the loss angle and tan d the loss factor. to give Suppose that an AC magnetic field expressed as is applied to a magnetic material. 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. observed for a low carbon iron.4) and (20. Then we find and Since the appearance of a nonzero angle S results in a power loss.6). Figure 20.1 .MAGNETIC AFTER-EFFECT 539 negligibly small.3. Temperature dependence of the loss factor.3) for DC magnetization. If we denote this ratio as £. The value / n0 //j was 30%. we consider a differential equation which leads to (20. 20. The numerical values are the frequencies of the AC field in hertz. In order to express this phenomenon mathematically. we use (20.3 shows the temperature dependence of the loss factor measured at Fig. In order to find the angle S and the amplitude /„. tan 5.5) in (20.

as a function of reciprocal temperature. a model proposed by Snoek2 is helpful. Snoek's model of magnetic after-effect. We see that both groups of experimental points fall on the same straight line. tan 8 becomes very small for large T. because the relaxation time T varies with temperature.5. If we consider (20.4 shows the logarithm of relaxation time. 20. Logr vs 1/T curve obtained from semistatic (open circles) and high-frequency measurements (center-dot circles). because the denominator increases as r 2 . while the denominator stays almost constant. suppose a heavy ball is placed on a concave Fig. Each curve shows a maximum at some temperature. . as determined from AC measurements as well as from semistatic measurements.7) to be a function of T. because the numerator becomes small. Figure 20.1 various frequencies for low-carbon iron.4.2. 20. which means that both phenomena have the same origin. For small T. 20. 20.5. tan d becomes also small. The maximum occurs for Therefore we can determine the relaxation time from the angular frequency of the maximum at a particular temperature. As shown in Fig. while the numerator increases only as T.1 the same material used in the semistatic measurement shown in Fig.540 DYNAMIC MAGNETIZATION PROCESSES Fig. In order to understand the nature of this phenomenon.

the second term of (20. If the relaxation times are distributed over a wide range.11) becomes If we set (20. In general the relaxation times are distributed over some finite range. we have. when the viscosity decreases at high temperatures. we can conveniently use In r as a parameter instead of r.13) can be expressed as . from (20. The magnetic after-effect is not necessarily described by a single relaxation time. Since g(T)d(lnr) = (g(r)/T)dT. On the other hand. At an intermediate temperature. again resulting in very low loss. resting on the concave surface.MAGNETIC AFTER-EFFECT 541 surface covered with a layer of thick mud. the motion of the ball is most severely damped. the ball will move on the hard mud surface with very low loss. If we put t/T=y. changing its equilibrium position. for TJ < T< T2. 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. If the ball is displaced by a lateral force H. This is the reason why the loss factor has a maximum at an intermediate temperature. and a very large loss results. This corresponds to the semistatic magnetic after-effect.10). 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). As the viscosity of mud increases at low temperatures. 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. the ball will move through a low-viscosity mud layer. it will sink gradually into the layer of mud.

3. we see that A/ n decreases linearly with time t. This magnetic loss is also independent of the angular frequency ca. r2. and finally tends towards to zero according to for T! < r2 <K f. log £ measured at 55°C for well-annealed carbonyl iron. 20. T2 = 0.0048s. then A/ n varies proportionally to In t. Figure 20. or for TJ •« t <. E . Richter-type magnetic after-effect. however. the loss factor will be maximum at a frequency where 1/ca lies between TI and T2. F Fig.542 DYNAMIC MAGNETIZATION PROCESSES The function N(a) is expressed approximately by Using these formulas. According to (20.6. and it reproduces the experiment very well.14s. The solid curve represents the function (20. 20. If this material is magnetized by an AC magnetic field. We see in Fig. or for t <sc TJ < T2. we expect that the loss factor tan 8 will be zero when T becomes very large at low temperatures.15) drawn by assuming TI = 0.6 shows the time decrease of magnetization vs.4 so that it is referred to as the Richter-type magnetic after-effect. This loss is referred to as the Jordan-type magnetic after-effect.7). This type of magnetic after-effect was investigated by Richter. that some non-zero value remains even at OK.

identified as x-. Figure 20.7. and z-sites in Fig. y-. «2. The physical mechanism of the magnetic after-effect was proposed by Snoek2 and later corrected by Neel. and Nz. which are very small compared with an iron atom. and for rl •« t «: T 2 . «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 .20). Then the anisotropy energy is given by where (o^. in a unit volume of the iron lattice. we have where S is called the magnetic viscosity parameter. There are three kinds of interstitial sites. Magnetic after-effect for Alnico V. the pseudodipolar interaction of the Fe-Fe pairs in the ^-direction is changed.E MAGNETIC AFTER-EFFECT 543 0 Fig.5 The origin of this magnetic after-effect is that the distribution of relaxation times is very large: TJ. and z-sites be Nx. If many carbon atoms occupy x-sites preferentially.6 The carbon or nitrogen atoms.8.7 shows the time variation of magnetization as a function of log t observed for Alnico V. occupy interstitial sites in the body-centered lattice of iron. 20. respectively. This type of magnetic after-effect is often observed for permanent magnet materials. Ny.18) holds. while T2 is sufficiently large. the volume in which T is equal to \/u> is constant independent of a>. In such a case. so that tan 8 becomes independent of (a. The experimental points lie very well on straight lines.1). is very small. In this case (20. thus inducing a uniaxial magnetic anisotropy (see Section 13. y-. 20. verifying (20. Let the number of carbon atoms on the x-.

atom. 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. Three kinds of interstitial lattice sites for carbon atoms in body-centered cubic iron.22). Now we consider the process by which carbon atoms change their position from the given distribution Nx. At thermal equilibrium at a temperature satisfying the condition lc <zz kT. The potential barrier between x.544 DYNAMIC MAGNETIZATION PROCESSES Fig.8. It is given by Q + (f . 20. Fig.9).and y-sites. 20. and Nz at t = 0 to thermal equilibrium at t = °° given by (20.a|)/c and Q + (f . the distribution of carbon atoms is given by where the subscript °° indicates an equilibrium value after a sufficiently long time. Q + (| . Ny.al)lc.9. 20. This height is also influenced by the orientation of the domain magnetization.a32)/c for the three kinds of lattice sites. .

This equation explains the relationship between log T and l/T shown in Fig. First we discuss the effect of such diffusion of carbon atoms on magnetization rotation. If the magnetocrystalline anisotropy is much greater than anisotropy resulting from the carbon atoms. in this case. From the slope of the log T vs l/T curve. Since the angle of the final rotation is small. the anisotropy energy given by (20. and gradually approaches the final direction. £acc in (20.21) changes with time as where c is a coefficient that includes the relaxation time. When a field drives a domain wall to a new place. or K^s>Nlc.25) is readily solved as where Ea0 is the anisotropy energy at t = 0 and Thus the time variation in the anisotropy is. 20. neglecting the higher order terms and using the relation Nx + Ny+Nz = Nc. the domain magnetization rotates instantaneously to the equilibrium direction upon the application of a magnetic field.25) can be regarded as constant. we expand the exponential functions in (20.22) in power series of lc/kT.4. kT.height of barrier). which is equal to 0.99 eV in this experiment. we have Assuming that lc «. This value agrees well with the activation energy for diffusion of carbon atoms in body-centered cubic iron. 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. described by a single relaxation time. we have Since Ny and Nz change with time in a similar way. Then (20. we obtain the activation energy Q. The effect of diffusion of carbon atoms on the displacement of domain walls is more complicated.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( . the carbon . and.

in which state the energy of the system is given by where v is the volume of the particle. This phenomenon is caused by thermal fluctuation of the magnetization of an isolated single domain. thermal activation will allow the domain magnetization to rotate over the potential barrier. This phenomenon is similar to Langevin paramagnetism (see Section 5. Such a rearrangement of carbon atoms changes the wall energy through a change in the anisotropy energy.88). by letting 00 = 0. If. If the magnetization is reversed to the negative direction. such coherent rotation is not able to overcome the potential barrier. to give [7max = vI2H2/4Ku at cos 0 = ISH/2KU. If the intensity of the field is less than the critical field H0. 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. its radius is In such particles the domain magnetization is always thermally activated.546 DYNAMIC MAGNETIZATION PROCESSES atoms in the wall rearrange their lattice sites so as to stabilize the local orientation of spins inside the wall. 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. At room temperature T=273K. Since the former is less than the . At temperature T each spin is subject to thermal agitation whose energy is kT/2 per degree of freedom of motion.2). the directions of spins in the wall are changed by an angle comparable to IT. the energy becomes The potential barrier between the two states can be easily calculated from (18. and the wall starts to move gradually. so that it is called superparamagnetism? When a magnetic field of intensity H is applied in the negative direction. so that for Ku = 105 J/m3. the critical volume becomes If we assume that the particle is spherical in shape. 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. If the length of such a gradual displacement is larger than the wall thickness. Neel7 proposed another type of magnetic after-effect called the thermal fluctuation after-effect. so that £aoo in (20. respectively. kT= 3. the magnetization will stay in the positive direction. Since usually the height of the potential barrier is much larger than kT/2. however.87) and (18. and oscillating. We refer to the magnetic after-effect caused by diffusion of carbon or nitrogen atoms as the diffusion naf after-effect. The coherent rotation of all spins included in this particle is also thermally activated and has energy kT/2.77 X 10~21 J. Neel6 made a detailed calculation for such a gradual displacement of the wall.25) must be regarded as a function of time.

MAGNETIC AFTER-EFFECT 547 latter.18). it follows from (20. H0 . 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. 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.34) is expected to cover a very wide range. or the values of Ku. are scattered around average values. 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. If we let Kum3X and t>max denote the maximum values of Ku and v.33) is quite similar to (20. If the field is increased to just below the critical field. the value of r given by (20. and the time change in magnetization in this case is expected to be proportional to log t as shown by (20.24). if H is close enough to the critical field. If the particles volumes v.32) becomes sufficiently large compared to the second term to permit us to neglect the second term. Neel7 estimated that a particle of volume 1 X 10 ~ 24 m3 exhibits a relaxation time T~ 10"l s at room temperature.34) .2KU/IS. the important difference between the two is that the activation energy in (20.34) includes H. Although the form of time change of N+ given by (20. Thus the condition TJ •« t <c T2 is always valid for a practical duration of measurement. whereas a particle of volume 2 X 10~24 m3 exhibits T ~ 109 s (several tens of years) under the same conditions. 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. the first term of (20.

or the magnetic viscosity parameter. the slope of the A/ n — log t curve. 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. and then later from B to C. in the latter type any memory of the previous state would be destroyed by changing the magnetic state. We see that the permeability changes significantly for a long period of time.11 Under a fixed magnetic field of 0. The important difference between the diffusion after-effect and the thermal fluctuation after-effect is as follows: In the former type. When the ball is displaced to a new place. After some period of time the ball will sink into the mud layer and will lose its mobility. When a domain wall is pinned by a small obstacle. In this case the viscosity parameter S decreases with increasing temperature.18).20). For instance. We can regard the ball in this model as representing a domain magnetization driven by an external field against the . 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.4 MAm"1 (5 kOe) a domain of 10 /j. it can be moved fairly easily on the surface of the mud layer by an external force.10'12 A thermal fluctuation after-effect can also be considered for domain wall displacement. However. Neel12 called the former type the reversible after-effect. if the magnetization is changed from state A to state B. hence the superposition principle is not valid for the latter type. the wall can be released by a thermal disturbance.ct and the latter the irreversible after-effect. This is actually the case for permanent magnets such as Alnico V (see Fig. 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. 20.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. Therefore in the former type. Snoek used the model shown in Fig.7). some materials exhibit a quite different temperature dependence of the parameter S. S in (20. the history of the previous magnetization distribution is retained by a non-magnetic mechanism. 20. In this sense Snoek13 named the phenomenon disaccommodation. in a Pt-Co alloy the parameter S decreases rapidly with increasing temperature. 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. such as the distribution of carbon atoms. is expected to be proportional to the absolute temperature T. This phenomenon is called the superposition principle. we have According to this conclusion.5 to explain this phenomenon. Figure 20.548 DYNAMIC MAGNETIZATION PROCESSES On putting these two expressions into (20. In contrast. m in diameter was observed to increase to about 100 pt m in a time of about 3 min. 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. The result was interpreted in terms of temperature dependence of the "activation volume".9 This phenomenon was interpreted in terms of Neel's disperse theory.

carbon atoms will diffuse into energetically favorable sites. stabilizing the domain magnetization as it exists. similarly to (18. Let us consider this phenomenon in terms of diffusion of carbon atoms. 20. Suppose that the magnetization lies parallel to [100] in a material with K1 > 0. The final distribution of the carbon atoms is calculated by putting al = 1. a2 = «3 = 0 in (20.82). Disaccommodation observed for Mn-Zn ferrite. Therefore. we have the anisotropy energy where A 6 is the angle of deviation of magnetization from [100].22) to give Expanding these exponential functions and putting the results into (20. After some period of time.MAGNETIC AFTER-EFFECT 549 Fig. the susceptibility due to magnetization rotation is given by .21). a part of which can be changed by diffusion of C or some other structural change.13 magnetic anisotropy.10.

its value is given by (18. 20.43). where N is the total number of iron atoms in a unit volume = 8.25). The local anisotropy energy is changed by so that the wall energy is changed by Comparing (20. This time we regard the ball as representing a domain wall. Since the susceptibility is inversely proportional to a.43) with (18. the spin in the wall rotates by the angle if we postulate uniform rotation of the spins across the wall. When the wall is displaced by a distance A s. 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. the susceptibility change is provided . Therefore we cannot explain a large disaccommodation as shown in Fig.5 X 1028 m~ 3 .10 by this magnetization rotation model.53)). which is smaller than the thickness of the wall 8.01 at%. we can estimate the induced anisotropy at 300 K as which is lower than the magnetocrystalline anisotropy K1 by a factor 10 3.550 DYNAMIC MAGNETIZATION PROCESSES If we assume that the concentration of carbon atoms is 0. each spin in the wall is stabilized by a local anisotropy given by (20.38). If «0 is caused by internal stress. Let us consider next the displacement of domain walls.31). and also Mc « 107 (see (14. as shown by (18. then NC/N = 1 X 10~4. After the wall has remained for a prolonged time in the same place.

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

there is no flux change. so that the magnetization is damped away inside the cylinder. magnetization mostly occurs by domain wall displacement. so that the magnetic flux penetrates completely through each lamination. If dl/dt is sufficiently large. and electrically isolated from its neighbors. Since the eddy current that flows around a cylinder of radius r produces a magnetic field only inside this cylinder. where R is the radius of the wall. the skin depth is calculated to be The magnetic cores of AC machines are usually made of laminated thin sheets of magnetic metal. treated as a constant. hence . In Fig. given by Thus the eddy current loss is proportional to the square of the rate of the magnetization change. Its value is independent of the size or shape of the specimen. this means that the loss can be decreased by subdivision of the material into electrically isolated regions.11(a). In Fig.51) that the power loss is proportional to r\. The power loss per unit volume is.11(b) a ferromagnetic cylinder is separated into two domains by a cylindrical 180° domain wall. therefore. In real ferromagnets. It is also seen in (20.552 DYNAMIC MAGNETIZATION PROCESSES where p is the resistivity. The magnetic field produced by the eddy current always opposes the change in magnetization. we considered a homogeneous change in magnetization. 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.17 The depth 5 is called the skin depth. 20. 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. each sheet thinner than the skin depth. 20. as long as the skin depth is sufficiently small compared to the diameter or thickness of the specimen. Inside the wall. This is also true for an alternating magnetization. When a magnetic metal with p = l X l O ~ 7 n m and JL = 500 is magnetized by a 50Hz AC magnetic field. This is the reason that ferrites are more useful at high frequencies than ferromagnetic metals and alloys. the power loss increases proportional to the square of the frequency as long as the flux penetration is complete. the eddy currents become strong enough to give rise to a magnetic field that is comparable to the applied field. That is. for r < R. It is natural that the loss is inversely proportional to the resistivity.

it follows from (20. Eddy current in a cylindrical specimen with magnetization changing (a) homogeneously.11. and (b) by wall displacement. for (20.18 Outside the wall.12.48) that or Thus the average power loss per unit volume is given by If we use the rate of magnetization change. A single crystal of Si-Fe cut into a picture-frame shape with (100) legs. Fig. 20. we have . 20.56).EDDY CURRENT LOSS 553 Fig. and its domain structure. for r > R.

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. this energy must appear as heat produced by the eddy current.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. we have which shows the proportionality between v and H. The proportionality between v and H can easily be inferred from the model shown in Fig.11(b).12).51). There was very good agreement between the calculated and observed behavior of the wall in this cylindrical case also. since the surface tension of the wall helps to diminish its area. It is now known from this experiment that the anomaly results from ignoring the localization of eddy currents at the domain walls. 20.13(a). This fact was first experimentally verified by Williams et a/. Williams et al. 20. 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.554 DYNAMIC MAGNETIZATION PROCESSES Thus we find that the power loss depends on R. and they showed that the calculated power loss is in good agreement with the observed one.56).13(b) when a strong magnetic field is applied. 20. On average.62) with (20. The reason is that the eddy currents are localized at the wall and such localization gives rise to a larger power loss. When a cylindrical wall with radius R is expanding with the velocity dR/dt. which was known as the eddy current anomaly. so that Comparing this with (20. 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. . Thus on equating (20. the power supplied by the magnetic field per unit volume is Since there is no change in the potential energy. the position of the wall. we find that the power loss is four times larger than that for a homogeneous magnetization change. because the power loss is proportional to i2. They also found that the wall shrinks into a cylinder as shown in Fig. The cylindrical wall vanishes very rapidly. 20. Before the success of this experiment.

Figure 20. since it depends not only on the shape and the distribution of domain walls. Distribution of eddy current in a cylindrical specimen for homogeneous magnetization and for wall displacement. Let us now assume Fig. It is seen that the eddy current changes discontinuously at the location of the domain wall. 20. Cross-sectional view of a domain wall moving (a) at low speed and (b) at high speed. 20. .EDDY CURRENT LOSS 555 (b) Fig. The calculation of the distribution of eddy currents is very difficult for an actual material which contains many walls. but also on the dimensions and external shape of the specimen.11.14. This discontinuity. Ai. 20.14 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.13. is easily found by letting r = R in (20.

We call the eddy current due to homogeneous magnetization the macroscopic eddy current.556 DYNAMIC MAGNETIZATION PROCESSES Fig. and also cannot distinguish the two categories of macroscopic and microscopic eddy currents. the paths of eddy currents are complicated because of the presence of many non-conducting inclusions. since plus and minus values of imi cancel each other. 20. we cannot ignore the third term in (20. If there are a large number of domain walls. the individual microscopic eddy currents become small. For such a case we can calculate the power loss as the sum of those of the macroscopic and microscopic eddy currents. The power loss is then given by where the integration should be made over a unit volume of the specimen. 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. z ma . or if the separation of domain walls is comparable to the size of the specimen. and the deviation from macroscopic eddy current due to wall displacement the microscopic eddy current.3 HIGH-FREQUENCY CHARACTERISTICS OF MAGNETIZATION In this section we summarize various losses and resonances that appear in high- . For this case we can approximate the power loss by a macroscopic eddy current. / mi . 20. the third term should vanish.15 for homogeneous magnetization. If. 20. 20. and accordingly the velocity of an individual wall is small. Spatial distribution of macroscopic and microscopic eddy currents. If the spatial variation of the macroscopic eddy current is gentle compared to that of the microscopic eddy current.15.15.65). This is a natural conclusion because this presence of a large number of domain walls means that the magnetization is quite homogeneous. that the distribution of eddy currents is shown by curve a in Fig.64). as seen in (20. as it is in Fig. however.

Desirable properties for soft magnetic materials are high permeability and low loss. the most important loss is the hysteresis loss. it plays an important role in the high-frequency range. so it corresponds to the normal permeability: if there are no losses. 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. is mostly damped in this range and is replaced by magnetization rotation. and is thus expressed as B = B0e*ia'~s\ The permeability is then If we put (20. as discussed in the preceding section.'. and accordingly in the Rayleigh region. the loss factor due to the hysteresis loss depends on the amplitude of magnetic field. The permeability /A" expresses the component of B which is delayed by the phase angle 90° from H. very thin Permalloy sheets (approaching 10 ^tm) are . The presence of such a component requires a supply of energy to maintain the alternating magnetization. The ratio AI" to /*' is. from (20. as will be discussed later. If the amplitude of magnetization is very small.66) becomes In these expressions /// expresses the component of B which is in phase with H. because the wall displacement.67). If a magnetic material is magnetized by an AC magnetic field H = H0eltat. The hysteresis loss becomes less important in the high-frequency range. and so tan 8 is also called the loss factor. regardless of the origin of the delay. we should have /A = /j. The next important loss for ferromagnetic metals and alloys is the eddy current loss. which is the main origin of the hysteresis. In the low-frequency region.HIGH-FREQUENCY CHARACTERISTICS OF MAGNETIZATION 557 frequency magnetization. Let us consider what kinds of losses appear as the angular frequency « is increased. the magnetic flux density B is generally delayed by the phase angle 8 because of the presence of loss. as distinguished from the other types by reducing the amplitude of H towards zero. The quality of soft magnetic materials is often measured by the factor p/tan 8. For instance. Since a power loss of this type increases in proportion to the square of the frequency.

The origin of this phenomenon is considered to be the building up of an electromagnetic standing wave inside the core. Magnetic cores composed of fine metallic particles ('dust cores') are also made for the purpose of reducing eddy currents. However. Since the relaxation time decreases with increasing temperature. Thus metallic cores tend to be replaced by ferrite cores for high-frequency applications. as will be discussed later.3 for a low-carbon iron. In contrast.17). The loss factor due to ionic diffusion exhibits a maximum at room temperature only for very low frequencies (as low as a few herz). if the material contains excess Fe2+ ions. the resistivity of magnetite (Fe3O4) is fairly low (10~4 £1 m = 10~2 ft cm).25 X 2. so that even bulk material can be used as a magnetic core. The Ni-ferrites have resistivities as high as 107 ft m (= 109 ft cm). 20. A similar phenomenon is also observed for Ni-Zn and Mn-Zn ferrites at — 150°C at a frequency of several kHz. as shown in Fig. Some of the garnet crystals are transparent to visible light. which shows a maximum at a certain value of to. Hence the wavelength in the material is given by . and therefore no electron hopping occurs.16 shows a drop of permeability between 1 and 2 MHz for an Mn-Zn ferrite core with cross-section dimensions of 1. so that it does not contribute to the high-frequency loss at room temperature. It is estimated that this temperature maximum would be shifted to room temperature at a frequency of several hundred megaherz.7). however. Vacuum evaporation. this phenomenon cannot be distinguished from the natural resonance which occurs in this frequency range. The relation between tan 8 and the relaxation time r is given by (20. sometimes their permeability drops at a certain frequency.20 This drop in permeability is shifted to a higher frequency when the size of the cross-section is reduced. where e and /I are the relative permittivity and relative permeability. if ferrite cores are used for a large-scale machine. Magnetic after-effect also gives rise to a magnetic loss. but the resistivity is of the order of 1 ft m ( = 102 ft cm). tan 8 exhibits a temperature maximum when measured at a fixed frequency. The most effective means of avoiding eddy currents. For instance. However.19 The origin of this phenomenon in ferrites is considered to be the diffusion or 'hopping' of electrons between Fe2+ and Fe3+.558 DYNAMIC MAGNETIZATION PROCESSES produced by rolling to reduce eddy currents. however. The velocity of an electromagnetic wave is reduced by a factor (ejl)'1 as compared with that in vacuum.3) contain no divalent metal ions. is to use electrically insulating ferromagnetic materials such as ferrites and garnets. Mn-ferrites with excess Fe content are used to attain increased permeability. 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. as discussed in Section 20. The resistivity of a typical ferrite is about 104 ft m (=10 6 ftcm). eddy current losses are observed. so that they exhibit extraordinary low magnetic losses.1. electroplating and sputtering are also effective in preparing very thin metal films which are used in high-speed and high-density memory devices. Figure 20.5 cm2. the rare earth iron garnets (see Section 9. 20. so that they can be and are used extensively at high frequencies (see Fig. Since. respectively. Even in this case. In this case the eddy current loss is not negligible at frequencies over 100 kHz.

The ordinate is normalized to the value at 1kHz.49). e~ 5 X 104. If. if we assume /= 1.' and /A" observed for Ni-Zn ferrites with various compositions. Snoek22 explained this fact in terms of the resonance of magnetization rotation under the action of the anisotropy field. Generally. The resonance frequency can be obtained by setting H = 0 in (12.16 is recognized as the resonance type. This phenomenon is called dimensional resonance. It is commonly known that yu.' and //' (or \' and ^") vary with frequency as shown later in Fig.5 MHz. giving rise to a standing wave. the electromagnetic wave will resonate within the core. to give where v is the gyromagnetic constant given by . For Mn-Zn ferrite. if some kind of resonance is induced at frequency fr (Hz is replaced by /. Figure 20. Ji ~ 103.HIGH-FREQUENCY CHARACTERISTICS OF MAGNETIZATION 559 Fig.20 where c is the velocity of light in vacuum and / is the frequency. 20.23.21 The curve forms are also of the resonance type.17 shows the frequency dependence of /J. the dimension of the core is an integer multiple of the wavelength A.6 cm. and Hr by /r). therefore. the wavelength A is found to be 2. 20.16. Dimensional resonance observed for Mn-Zn ferrite cores with different crosssections. /x'j. permeability drops off and magnetic loss increases at very high frequencies because of the occurrence of a magnetic resonance. It is seen in this graph that a ferrite with high permeability tends to have its permeability decrease at a relatively low frequency. 20. The form of the experimental curves in Fig.

we can calculate the anisotropy field from (12.2 (A).9:24. the magnetization rotation about the easy axis will resonate with the field.7:16. resulting in abrupt changes in yj and /A". we have from (20. 24. the anisotropy field is given by (12.56) as Using this value and assuming that g = 2. or This value is in the range of frequency where resonance occurs. 20.5:33.71) is applied.17. 39. This phenomenon is called natural resonance. 20.71). therefore. If we take K1= — 5 X 102 Jm~ 3 .53) or . a high-frequency magnetic field with angular frequency given by (20.4 (D).3T for Ni-Zn ferrite. 31. This can be explained as follows: If we assume that KI > 0.21 If.17 that the higher the permeability. remainder Fe2O3. We see in Fig. 20. the lower the frequency where natural resonance occurs.0:9.5 (C). as seen in Fig.9 (B). 48.560 DYNAMIC MAGNETIZATION PROCESSES Fig. 7S = 0.7 (E).17.2:0. Natural resonance observed for Ni-Zn ferrites with different compositions: Mole ratio of NiO: ZnO = 17.

we have the relationship If. for random distribution of in-plane easy axes in a polycrystalline material. H&2 > Hal. to give In order to eliminate KI} we multiply (20.79). the permeability due to rotation in the plane is given.82). therefore. and fjb = 4ir X 10~7 /I. It was confirmed experimentally that the natural . 20. this limit is higher than the Snoek limit given by (20. Then the resonance frequency is given.HIGH-FREQUENCY CHARACTERISTICS OF MAGNETIZATION 561 so that the resonance frequency increases with an increase of K1 as On the other hand. by On the other hand. we have The dashed line in Fig. and using a = 2irf. The condition expressed by (20.78) together.3 T.77) and (20.1 lists various magnetic parameters for two Ferroxplanas.4) called Ferroxplana. similar to (3.81) and (20.' drops to one-half its maximum value. Assuming that 7S = 0. the permeability decreases with an increase of Klt as we know from relation (18. It was discovered that this limit can be overcome by using a special magnetocrystalline anisotropy. It is therefore predicted that no ferrite can have a permeability higher than the Snoek limit.17 is drawn by connecting the points where /u. by From (20.80) coincides approximately with this line: this line is called the Snoek limit.23 Table 20.51). so that the permeability may be high. to obtain The same relation holds for K^ < 0. Let the anisotropy field for this magnetization rotation be H3l. while that for rotation out of this plane be Ha2. magnetization rotation in this plane can occur easily. If the anisotropy in the c-plane is small. which exhibits an easy plane perpendicular to the c-axis.84). assuming the occurrence of magnetization rotation. One of the materials that satisfies this condition is a magnetoplumbite-type hexagonal crystal (see Section 9. as long as a cubic magnetocrystalline anisotropy is present.23 This anisotropy is a uniaxial anisotropy with ^u < 0.

however. which has dimension s"1. the resultant vector given by both terms in braces represents the component of 77 perpendicular to 7.85) represents the component of H parallel to 7.32 X 102 Oe) l^XlO'Am.5xl0 4 0e) 2100MHz 1000 MHz resonance occurs at frequencies higher than the Snoek limit.1 (=1. a gyroscope performs a precession motion under the action of an external torque. The factor v is the gyromagnetic constant given by (20. The — sign comes from the fact that the angular momenta of electron spins are opposite to their magnetic moments.3. which are the origin of magnetization. The equation of motion may also be written as as shown by Kittel.25 Since the second term in braces in (20. The factor A. This component of 77 exerts a . it has been difficult to reduce the resistivity and accordingly the loss factor of these materials.OxWAnr1 (= 1.562 DYNAMIC MAGNETIZATION PROCESSES Table 20. thus approaching the axis about which the precession occurs. and is called the relaxation frequency. the magnetization moves towards — (7 X (/ X 77)).25xl0 4 Am. but tends to rotate toward the external torque if its free precession is restricted by some boundary condition. The second term describes the damping of the precession motion in the direction (/ X H). Various constants and resonance frequency of two types of ferroxplana Co2Ba3Fe24O41 Saturation magnetization/s Anisotropy fields Hal tfa2 Resonance frequency /r Theory Experiment 0. This situation is described by the Landau-Lifshitz24 equation where / is the magnetization vector and H is the magnetic field vector.3 X 102 Oe) 1. we discuss the dynamic character and switching mechanism of a spin system.1 X 10s Am' 1 (=1.1. Practically.72).4 SPIN DYNAMICS In this section.09 T (=72G) 0.43). or in the direction — (7X77).27 T (=2150) l. defines the degree of damping action. As discussed in Section 3.4xl0 4 0e) 3700MHz 2500MHz Mg2Ba2Fe12O22 0. The first term represents the precession motion of the magnetization (see (3. 20. so that they cannot be used at very high frequencies. the magnetization moves in a direction perpendicular to both / and H.1 (= 0.

85) can be derived from this equation by neglecting the higher-order terms in a 2 . If we put this assumption is equivalent to a 2 < s l . Thus the magnetization performs a precession motion under the action of the external force and the damping.84) and (20. In other words. Suppose that a static magnetic field H is applied parallel to the —z-direction. so that the exact equation of motion should be This equation was first derived by Gilbert and Kelley.85) is mathematically equivalent to (20.84). It is easily verified that (20. it is implicitly assumed that the first term (called the intertial term) is much larger than the second term (called the damping term). the damping should act not only on the precession motion.84) or (20. we have where This solution represents the precession motion of magnetization keeping a fixed angle . however. First we consider the precession motion. Strictly speaking. the damping should act on the resultant motion of the magnetization d//df.25 Equations (20.84) and (20. In equations (20.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. neglecting the damping action. The equation of motion is given by which can be written for each component of Cartesian coordinates: On solving this equation.85). but also the motion induced by the second term in (20.85).

20. 20.18. Precession motion of magnetization in the absence of damping.85). dl /dt and dI2/dt.87) for each component of the Cartesian coordinates as On solving these equations with respect to dlx/dt. an external field cannot rotate the magnetization towards the field direction.18). It should be noted that without damping. In the . we obtain If we start from (20. we obtain a similar set of equations.84) or (20. We rewrite (20. The two sets of solutions are the same when a 2 « 1. with (1 + a 2 ) everywhere replaced by 1. with respect to the z-axis (Fig. the precession motion will decay unless there is a source of external energy to maintain it. If a non-zero damping acts on this precession motion.564 DYNAMIC MAGNETIZATION PROCESSES Fig.

The motion of magnetization for small damping.20. Solving the differential equations (20. 20. general case including a 2 » 1.19. This switching motion of magnetization becomes more viscous as the relaxation frequency becomes large. and the magnetization rotates more directly towards the —z-direction without making many precession rotations (Fig.93). 20. Fig. we obtain where Q is a function of time and is given by and 00 is the initial inclination of magnetization.97) and (20. 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. 20.SPIN DYNAMICS 565 H Fig.93) with respect to Ix(t\ Iy(t) and Iz(t). however.20). we know from (20. it turns out that \/u>» T. 20. hence the magnetization performs a number of precession rotations before it finally points to the -z-direction (Fig. (20. The motion of magnetization for large damping. we must use (20.98) that 1/w = ar. If a2 » 1.19).91) and TO is If a 2 « 1. so that !/&>«: T.96).

21. 20. The relaxation time for switching of magnetization as a function of the relaxation frequency. for 7S = 1 T. because the magnetization performs too many precession rotations. In Fig. The minimum value of T is given by which can be estimated.51) is. The graph shows that the relaxation time T is minimum when or This condition is called critical damping. The fastest switching is therefore attained for an intermediate value of the relaxation frequency. which includes the relaxation frequency A (see (20.98)).566 DYNAMIC MAGNETIZATION PROCESSES Fig.6 MAm and g = 2. becomes very large if the relaxation frequency is too small. 20. . as 1 ( = 20 000 Oe) The condition for critical damping (16.21. the relaxation time T is plotted as a function of TO. taking a strong magnetic field Hz — 1.

we see that the relaxation frequency due to eddy currents given by Using the values 10 ~ 7 H m. The demagnetizing field due to the total eddy currents is calculated from (20.3. One of the reasons was to take advantage of their eddy currents to obtain critical damping. the motion can be maintained only if energy is supplied to the system by an oscillating or rotating magnetic field. the relaxation frequency as determined for nickel ferrite from the width of the resonance line is 107-108 Hz.104) and (20. thus the radius of the metal wire.103).87) that the damping action is equivalent to the presence of the demagnetizing field.FERRO-. and w its angular frequency about the z-axis. In order to produce a . Let H0 be the amplitude of the rotating field.107) must be equal to the value given by (20. AND ANTIFERROMAGNETIC RESONANCE The fundamental concept of spin resonance has already been described in Section 3. 20. If a damping force acts on the precession motion.88). We call this the uniform mode or Kittel mode. must be In the past. There we assumed that all the spins forming the spontaneous magnetization maintain perfect parallelism during precession. r0. FERRI-. it is easily seen in (20. Consider a thin metal wire. Starting from (20.105). AND ANTIFERROMAGNETIC RESONANCE 567 For instance. we have the uniform mode of precession expressed by (20. magnetic thin films and thin wires were investigated as possible fast switching devices. On comparing (20.91).50) as On the other hand.90) with the angular frequency at resonance given by (20. One method to obtain critical damping is to use eddy current damping.5 FERRO-. which is insufficient for the critical damping. the relaxation frequency (20. we obtain In order to attain critical damping. FERRI-.

as If we apply a static magnetic field parallel to the z-axis. The components of the torque acting on the magnetization vector are then expressed.568 DYNAMIC MAGNETIZATION PROCESSES Fig. the Landau-Lifshitz equation (20. 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. Torque components exerted on magnetization /s by the rotational field H0. . In the stationary state. in cylindrical coordinates. for each component. non-zero torque on the magnetization vector. 20. 20.22.22).84) becomes.

so that </> becomes -90°.114). tan </> becomes infinity. tan (j> changes to minus infinity.FERRO-. where Hr is the resonance field. This value is calculated by putting </> = 45° in the equation for x" m (20. 20. as shown in Fig. FERRI-. while x" nas a maximum at Hz = Hl. so that (f> becomes 90°.23.111) with (20.23 for various values of a. The width of the absorption peak at half the height of the maximum value is called the half-value width. the width of the absorption peak increases. because at this value sin2 <f> becomes half its maximum value 1. As Hz increases and becomes equal to HT in (20. 20. we have from which we obtain and for 6 •« TT.113). AND ANTIFERROMAGNETIC RESONANCE 569 Comparing (20. Then tan 0 = 1 in (20. As soon as Hz becomes larger than HT. As the parameter a or the relaxation frequency T increases.117).117) changes sign at Hz = Hr. so that the half-value width is given by . The real and imaginary parts of the susceptibility are expressed as or from (20. These susceptibilities are plotted against the DC magnetic field Hz in Fig.110). Therefore x' m (20.114).

55 X 105 Am' 1 . from the half-value width. etc. 20.25T.23. A. In the vibration of a string. and we have Thus we can determine the relaxation frequency. A# = 5. Dependence of the real and imaginary parts of the rotational susceptibility. various higher-order harmonic standing waves are .59 X 103 Am" 1 . and g = 2. electron hopping between Fe2+ and Fe3+ ions. on the intensity of the DC field. 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. Hr = 2. x' and x". near the resonance field HT (numbers on the curves are values of or). generation of spin waves caused by inhomogeneity of the material. Hz. 7S = 0. For Mn-Zn ferrite.570 DYNAMIC MAGNETIZATION PROCESSES Fig. generation of lattice vibrations caused by magnetoelastic coupling.

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

25.1) and (7. The negative exchange interaction acting between 7A and 7B tends to align the two magnetization vectors antiparallel. 0) mode. the magnetic amsotropy. These three effects. and a magnetic field H is applied parallel to the z-axis. the external field. i.e. 20.26.572 DYNAMIC MAGNETIZATION PROCESSES Fig. The configuration of inplane component of magnetization in each cross section of a spherical specimen corresponding to the (4. we assume uniaxial anisotropy with its easy axis parallel to the z-axis. can combine to cause the same precessional speed of 7A and 7B about the z-axis keeping the angle between the two magnetizations constant. 20. so that the anisotropy field is given by . (After Walker28) Fig. and the exchange interaction.. and H^ and 7fmB the molecular fields.2).84). which are as shown in (7. H^ and #aB the anisotropy fields acting on the A and B sublattices. 3. respectively. For simplicity. Neglecting damping terms in (20. we have the equations of motion for two sublattice magnetizations: where H is the applied field.

AND ANTIFERROMAGNETIC RESONANCE 573 Fig. FERRI-. Antiferromagnetic resonance. or We assume that the external field H is applied in the + z-direction. Then the components of (20.FERRO-.26.120) become . where //a is the absolute value of the anisotropy field. Let Hm be the absolute value of the exchange field acting between the two sublattices. 20.

Since this mode stores exchange energy. in this case we find that 0A = 0B from (20. so that such a resonance mode cannot be excited by an external RF field. the angular momenta of the two sublattice magnetizations are almost compensated near the compensation point. and obtained beautiful agreement with experiment. 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. The latter mode is caused by division of the spin axis between the two sublattice magnetizations.574 DYNAMIC MAGNETIZATION PROCESSES The components of the two sublattice magnetizations are given by where / is the absolute value of spontaneous magnetization.36'37 Observation of this phenomenon in GdIG was in good agreement with theory. In such a case the resonance frequency of the exchange mode drops down into the microwave region. as is known from (20. In addition to this mode. another resonance is observed at higher frequency in the infrared region. which has a fairly small exchange interaction that allows the observation of resonance in the microwave region.6 EQUATION OF MOTION FOR DOMAIN WALLS It was first pointed out by Doring39 in 1948 that a moving domain wall exhibits .124). The theory was extended by Yosida33 to a more general type of anisotropy. Ferrimagnetic resonance34'35 is essentially the same as ferromagnetic resonance. In the case of the N-type ferrimagnet. in the sense that the spontaneous magnetization precesses as a whole about the external field. we call it the exchange mode.127). However. as is the case for antiferromagnetic resonance. He treated the resonance of CuCl 2 -2H 2 O. On putting these equations into (20.128).38 20. however.

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

v = 2.49 X 10~n. This energy is proportional to v2 and corresponds to the kinetic energy of the wall. Furthermore. v. and fj. In this case the wall has an additional energy Since as shown in (16.6 X 10~3.576 DYNAMIC MAGNETIZATION PROCESSES where Iz is the z-component of magnetization induced in the wall. the wall continues to move even without any external magnetic field.42)). by Comparing these equations. which results in a displacement of the wall in the z-direction. from (20. we have . A = 1. we find This means that the wall must have a z-component of magnetization in order to move with nonzero velocity.136) and (20. if the wall has a z-component of magnetization. by For a 180° wall in iron. We can express it as where m is the virtual mass of the wall per unit area and is given.137).0 = 4irX 10~7.91).21 X 105. This phenomenon is described as the inertia of the domain wall. The rotational velocity of this precession is. with y = 1.134) becomes where y is the wall energy per unit area (see (16. This angular velocity can be related to the translational velocity of the wall. This field acts on each spin so as to induce precession motion in the x-y plane. through comparison of (20.39). (20.

Formally it can be expressed in terms of the relaxation frequency A which appears in the Landau-Lifshitz equation (20. the origin of the wall damping is the same as the damping acting on the precession motion of the magnetization. and we have For iron. we have )3 = 1. by On comparing (20. we have For Ni-ferrite with . p = 1 X 10~7. The z-component of (20.15 (T). and assuming ln(r 0 /R) ~ 1.EQUATION OF MOTION FOR DOMAIN WALLS 577 Next we consider the damping term /3(ds/df) in the equation of motion (20. with /s = 2.129) becomes For eddy current damping we can compare (20. For highly insulating materials such as ferrites. we have Even if we assume that the radius is as small as R = 1X10 6 (=1 /im). 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. a quantity of work given by which is dissipated as heat.140) with (20. (20. using (20.140). in one second.129).8X102. If we neglect the first and third terms.63).145) and (20.84).84) gives Thus the internal magnetic field does.146).

On the other hand.29 shows the wall velocity as observed in the shrinking of bubble domains (Section 17. shows a monotonic increase in velocity with increasing field.84 for magnetite and £ = 0.61) and (20. The third term in (20.3). Iz. observed for a hard bubble in which spin rotation is not so easy as in a normal bubble. 20. Curve (a).26 for Ni-ferrite. we can determine )3 = 4. 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. This value is much smaller than the value obtained for the eddy currents in a very thin iron wire. reaches the saturation magnetization. shows that the velocity exhibits a maximum and then decreases with increasing external magnetic field. we have Using this relationship.06 even after the effect of eddy currents is subtracted from the observed value.61). 20.28. Gait40 measured the velocity of a domain wall in single crystals of magnetite and Ni-ferrite. He found the values of c at room temperature to be 0. cut in a picture-frame shape as shown in Fig. In the preceding discussion. The value of j8 for magnetite is as large as 4. Figure 20. The latter value is of the same order of magnitude as the value of (20. when the z-component of magnetization. Therefore. 7S.5m2 s^A'1 (= 20000cms -1 Oe"1) for Ni-ferrite. On comparing (20. The origin . observed for a normal bubble.148). which was deduced from the relaxation frequency.578 DYNAMIC MAGNETIZATION PROCESSES Fig.140).41'43 Actually this characteristic was observed for a garnet crystal film with very low magnetic losses. the wall velocity is expected to saturate and then decrease with an increase in the external magnetic field.129) signifies the restoring force acting on the wall. Ferrite single crystal in picture-frame shape.24m2 s-'A" 1 (=1900 cms" 1 Oe~ 1 ) for magnetite and 2. the wall velocity is determined by the demagnetizing field inside the wall which is produced by the z-component of magnetization. curve (b). and confirmed the validity of (20.28.

we have here This means that the wall will oscillate about an equilibrium position.46) and (16. the equation of motion (20. from the comparison of (16.47). as so that the mass becomes . The factor a is related to the permeability /A by (18. Domain wall velocity of a shrinking bubble as a function of magnetic field.EQUATION OF MOTION FOR DOMAIN WALLS 579 Fig. where y is expressed. (b) hard bubble. » ^-a) to give The mass m is given by (20. If we neglect the second term and the right-hand term.36) ( /JL.44 of this force is given in Section 18. 20.2 for several examples.129) becomes On solving this differential equation. as observed for a garnet crystal film with very low magnetic losses: (a) normal bubble.29.138).

the power loss should also be larger for wall displacement than for magnetization rotation. In order that the magnetization changes by 7S per second. the magnetization is switched to [100]. while wall displacement requires 7r/(255)rads~ 1 . wall displacement is more rapidly damped than is magnetization rotation. the angular velocity of spins in a wall is much larger than that for magnetization rotation.580 DYNAMIC MAGNETIZATION PROCESSES On putting (20. 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. 20. For instance. it turns out that SS~ 10~4 for 8= 10~5 mm.79) for the natural resonance derived on the basis of magnetization rotation. Since the power loss in the wall is proportional to w 2 or (SS)~ 2 .1 mm. wall displacement could survive to high frequencies. the quantity SS is the fractional volume of wall per unit volume of the specimen. the total loss is expected to be proportional to (SS)"1. except for the factor \/5S. Solve for the time change in the anisotropy energy. This would require that the wall spacing be very small.1 After magnetizing a single crystal of carbon-iron parallel to [010] for a long time to its saturation. 20.156) This relationship is similar to formula (20. the difference between the two mechanisms would be large. One of the reasons for this is the high original value of permeability. For the example mentioned above. Since S is the total area and S is the thickness. 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.155) into (20. assuming diffusion after-effect and also lc <s kT. we obtain ( (2001 ft>0v/7l = 0.46VSS v/. hence the wall resonance frequency is expected to be lower by a factor 102 than in the case of natural resonance. so that the specimen would be filled with domain walls and the wall displacement would become practically equivalent to incoherent magnetization rotation. For a given amplitude of magnetic field.153) and (20. If this value could be increased to approach 1. therefore. (20. Thus magnetization rotation becomes more important at high frequencies.2 Suppose that an aggregate of aligned. The reason is that for a given amplitude of magnetization. since the specimen contains only one domain wall.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 . long. if S8 is very small. but also it is partly because 58 is very small (10~6). magnetization rotation requires an angular velocity (ir/2)rads"1.//40. PROBLEMS 20.152). On the other hand. the angular velocity is 104 times larger for wall displacement than for magnetization rotation. However. note that these differences between wall displacement and rotation depend on the value of 55. How fast is the magnetization change if the intensity of the field is maintained at 89% of the critical field. if the spacing of the walls is 0. By the same reasoning. 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.

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

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

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

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This entropy is controllable by an external magnetic field. so that the entropy becomes Thus the entropy is reduced by the application of a magnetic field. In other words. when H increases and the magnetization saturates at 7S. so that the entropy becomes On the other hand. magnetic materials have additional entropy due to the presence of spins. we have the entropy S for a given I. Adiabatic demagnetization is a method to create a low temperature by manipulation of this extra entropy. In this model.2) containing N spins in a unit volume. where M is the magnetic moment of one spin and N+ + N_ = N. 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. the number of ways of realizing this combination is expressed by Using Stirling's formula ln(«!) = n In n — n. N_. the number of + spins. each spin magnetic moment (simply called 'spin' hereafter) can take either a + or — direction. magnetization). or N+ = N_ = N/2. we assume an Ising model (see Section 6. N+. When N+ and N_ are given. When a magnetic field H is applied in the + direction. When H = 0. N_ = 0 and 7V+ = N. For simplicity. The entropy 5 is generally given by k In W. increases. the spins can undergo thermal motion. where k is the Boltzmann factor and W is the number of different ways of realizing the state (in this case. . 7 = 0.1). Consider a paramagnetic material composed of a number of spins.1 MAGNETOTHERMAL EFFECTS In magnetic materials. decreases. while the number of — spins.21 VARIOUS PHENOMENA ASSOCIATED WITH MAGNETIZATION 21. thus the magnetization increases.

is given by (18. In this temperature range the Curie-Weiss law (6. the high field susceptibility. Since the magnetization of a paramagnet is a unique function of H/T (see Fig.01 K can be attained by adiabatic demagnetization. The approach to low temperatures is limited by the interaction between magnetic ions. is applied to a paramagnet. using nuclear magnetic moments with very small interactions.586 VARIOUS PHENOMENA ASSOCIATED WITH MAGNETIZATION First a strong magnetic field. wl and H are comparable in magnitude. H. the internal energy is changed by (see (6. At magnetization levels approaching saturation. the molecular field wl is much larger than H. 5. must be held constant (see (21. Therefore the heat generated in a unit volume is given by At T «: @ f . a temperature as low as 0. /. so that neglecting H in (21. /.u. the heat change is zero. In an adiabatic process. This is the principle of adiabatic demagnetization. so that we have . In the case of a ferromagnet. The work done by the field must be converted to heat. ^0.10).3)). 5.22)). In order to keep the same entropy. so where dS is the entropy change. The work d W done by the field (per unit volume) is given by On the other hand. which magnetizes to the intensity. such as CrK alum. the temperature T decreases as the field H is reduced.15) holds. and the field is reduced (adiabatic process). keeping the temperature constant at T (isothermal process). Super-low temperatures in the range of . Then the paramagnet is thermally isolated from the heat reservoir. the magnetization. the spin entropy contributes to the magnetocaloric effect.9 or Fig.10) we have At T > ®f.K (= 10~6 K) have been obtained by means of nuclear adiabatic demagnetization. so that H cannot be neglected. Using a paramagnetic material containing a dilute concentration of magnetic ions. Q: which is transferred to the heat reservoir to keep the temperature constant. Suppose that the magnetization is increased by SI under the application of a magnetic field H.133). Therefore the entropy must be kept constant during adiabatic demagnetization.

it becomes .11) in terms of H. we obtain The temperature change is given by where C. is the specific heat for constant /. If we express (21.8). It is seen that the proportionality factor between 8T and 5(/2) is constant below 360°C. Figure 21.MAGNETOTHERMAL EFFECTS 587 Fig.1 shows the magnetocaloric effect observed for Ni below and above its Curie point of 360°C. 21. while it increases with increasing T. (Experiment by Weiss and Forrer.14).1 after Becker and Doring2) Using the expression for the Curie point (6.14) that the temperature change is proportional to 72 below and above the Curie point.11) and (21. Temperature change caused by magnetization in Ni at temperatures near the Curie point as a function of the square of magnetization/density ( p : density).10). as expected from (21.1. (21. It is predicted from (21.11) and (21.12) is converted to the form Using this in (21.

The curves are quite similar to the temperature dependence of the high field susceptibility (see Fig. Since L'(«) approaches zero more rapidly than T does as T-»0. The temperature of a ferromagnet is also changed by the generation of heat associated with technical magnetization processes.2 shows the temperature dependence of the magnetocaloric effect as measured for Ni. The temperature change due to this magnetothermal effect is the order of 0. This corresponds to the heat generated by the hysteresis loss.15)). (Experiment by Weiss and Forrer. 8Q given by (21.001 K. Co. Detailed investigations were made by Bates and his collaborators7 for Fe. This phenomenon has been investigated by a number of workers4"6 for carbon steel. Temperature dependence of magnetocaloric effect in Ni. (21. nickel and pure iron.2. The prediction is thus that 8Q has a maximum at the Curie point and decreases with either decreasing or increasing temperature.9 Figure 21.1 after Bozorth3) (see (6.4).6 MAm"1 (= SOOOOe). showing the expected behavior. 6. much smaller than the magnetocaloric effect. and Ni. 21. an irreversible increase in temperature is . The temperature change at the Curie point is 0.85 K for Ni and 2K for Fe at // = 0.16) becomes very small at low temperatures. On the other hand. Numerical values in the figure are fields in Oe or (103/4ir) (Am"1).3 shows the temperature changes observed for Ni as it is cycled around the hysteresis loop. so that the temperature will increase continuously if the material is cycled around the hysteresis loop. Investigations were also extended to ferrites8 and permanent magnets. The temperature change due to this magnetothermal effect is partly irreversible.588 VARIOUS PHENOMENA ASSOCIATED WITH MAGNETIZATION Fig. Figure 21.7 In addition to the reversible change in temperature (magnetocaloric effect) occurring at high fields. so that SQ becomes very small again.14) becomes At very high temperatures. the denominator becomes larger more rapidly than the numerator as the temperature increases. at T > @ f .

4.MAGNETOTHERMAL EFFECTS 589 Fig. increasing the entropy of the spin system and resulting in an absorption of heat. 21. like a decrease in molecular field. 21. opens up the angular distribution of spins.3. (After Okamura6) . Magnetothermal effect in Fe as a function of the applied field.4 shows the magnetothermal effect observed for Fe. and the rotation of magnetization results in a decrease in anisotropy field. This heat change is caused by magnetization rotation against the magnetocrystalline anisotropy. The work done by the magnetic field is mainly used to raise the anisotropy energy. Since the anisotropy field is changed by \H= -WK^/3^ (see (12. Figure 21.57)). Reversible changes in temperature are observed not only at high fields but also in very low-field regions near the origin. (After Townsend5) observed at the coercive field. which. Magnetothermal effect in Ni as a function of the applied field. during the magnetization rotation from Fig.

and in this sense is quite similar to Ni which has ten electrons outside the argon shell. Mott explained the temperature variation of resistivity fairly well by this picture. ®f= 1043 K. The same effect is also observed in the forced increase of spontaneous magnetization by the application of high magnetic fields. Mott13 interpreted these phenomena in terms of the scattering probability of the conduction electrons into 3d holes. 21.16) to be When K^ < 0.2 X 104. the heat generated during this process is calculated from (21. as measured by Englert. including magnetoresistance. In Fig. magnetic tunneling. however. the magnetothermoelectric effect. Experimental separation of the reversible and irreversible temperature changes was attempted by Bates and Sherry.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. the magnetization rotates from <111> to <100>. Kv = 4. If the material is ferromagnetic. so that the scattering of 4s electrons into the plus (magnetic) spin state is forbidden.6 shows the field dependence of resistivity of Ni parallel and perpendicular to the magnetic field.10 21.5 the ordinate scales are adjusted so that the resistivities are equal at the Curie point of Ni.5 X 106 Jdeg"1 m~ 3 . Hall effect. Pd has ten electrons outside the krypton shell. The first case causes a temperature dependence of resistivity in ferromagnetic metals resulting from the temperature change in spontaneous magnetization. so that the temperature change is calculated to be which is in good agreement with the heat absorption seen in Fig. Figure 21.4. in which both the plus and minus spin states of the upper 3d levels are vacant. It is seen that the resistivity of Ni is considerably reduced by the appearance of spontaneous magnetization below its Curie point. the resistivity always decreases with an increase in spontaneous magnetization. ME effect. etc.0025 and C = 3. Figure 21. so that SQ is still negative. For iron. He considered that d electrons are localized at the lattice sites and interact . L'(a) ~ 0. and the other is the dependence of resistivity on the orientation of the magnetization (anisotropic magnetoresistance effect).12 It is seen that irrespective of the direction of the applied field with respect to the current. This scattering is.5 compares the temperature dependence of the reduced resistivity of Ni and Pd. T= 300 K. 21. Kasuya14 interpreted these phenomena by a picture quite different from the Mott theory. permitted in a nonmagnetic metal. half of the 3d shell is filled.590 VARIOUS PHENOMENA ASSOCIATED WITH MAGNETIZATION (100) to (111).

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

the Mott theory is considered to be invalid. respectively. Temperature dependence of 3Apnl for Fe and Fe-Al alloys.a3) and (/3j. 21. 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.15 in accordance with the Kasuya theory. These coefficients have been measured in Fe and Ni single crystals by a number of investigators.7 shows the temperature dependence of Ap m as measured for Fe and Fe-Al alloys by Tatsumoto et a/. because both quantities depend not on the sense but only on the direction of spontaneous magnetization. The second case of magnetoresistance.16 electrons are considered to be scattered by the irregularity in the polarization of 4/ elections. Figure 21. /32. The numerical values are in the range 0. at least for rare earth metals. Since the 4/ electrons are completely localized. can be described in a similar way to magnetostriction. The change in resistivity is described as where (alt a2.592 VARIOUS PHENOMENA ASSOCIATED WITH MAGNETIZATION Fig.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 .1-4%. the anisotropic magnetoresistance effect.7. /33) are the direction cosines of spontaneous magnetization and electric current.

The magnetoresistance effect is particularly large for magnetic semiconductors such as chalcogenide spinels (see Chapter 10). They found that the resistance of the film drops to about half of its original value upon the application of a magnetic field. irrespective of the angle between the current and the field.MAGNETOELECTRIC EFFECTS 593 Fig. 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. In fact. Magnetic tunneling is observed for two ferromagnetic metal layers separated by a thin insulating layer about Inm thick. 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. This curve is quite similar to the dependence of the gyromagnetic ratio on the number of 3d electrons measured for various magnetic 3d alloys. after Jan19) magnetic moment. Similar phenomena have been observed for various combinations of ferromagnetic and antiferromagnetic metal multilayers.8.^Gd^Se.23"26 Recently a giant magnetoresistance effect has been found in multilayer magnetic thin films. For instance. which are composed of alternating thin layers of Fe and Cr. 21.20 Since the deviation of the gyromagnetic ratio from 2 is a good measure of the remaining orbital moment. Another magnetic semiconductor. the origin of which has been discussed by a number of investigators. exhibits very large temperature dependence of resistivity and also a very large magnetoresistance. this fact proves the validity of the Kondo theory. Kondo explained the magnitude and the temperature dependence of this effect satisfactorily. Euj.22 the Ap/p values amount to -100% near their Curie points (110-130K). It was observed that the tunneling electric . Figure 21. Magnetoresistance effect as a function of the mean number of Bohr magnetons per atom observed for various magnetic 3d transition alloys.8 shows the average Ap measured for various magnetic 3d alloys as a function of spontaneous magnetization. This phenomenon was first discovered by French scientists27 in 1988 in multilayer Fe-Cr films. in In-doped CdCr2Se421 or HgCr2Se4. (Smit18.

as shown in Fig.31 observed a change in tunneling resistance for an 82Ni-Fe/Al-Al2O3/Co junction as large as 3. we must put ^. When a magnetic field H is applied to a ferromagnetic metal perpendicular to the electric current. This phenomenon was first observed by Julliere28 in an Fe-Ge-Co junction in 1975. 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. and has a maximum at room temperature.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. Fe) junctions. Thus we can express * When this value is used.5% at 77 K and 2. and the other due to the spin-orbit interaction between 3d spins and conduction electrons. 21. Miyazaki et a/. so that it can be expressed by where R0 is the ordinary Hall coefficient and R1 is the extraordinary Hall coefficient. The value of Rl for Ni at room temperature is This quantity increases with increasing temperature and exhibits an anomaly at the Curie point.7% at room temperature. Maekawa and Garvert29 observed hysteresis in tunneling resistance versus magnetic field for Ni-NiO-(Ni. In the case of ferromagnetic metals. The temperature dependence is mono tonic.34 From the data of Smith. This is the Hall effect.0 = 1 in (21. 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.07 to the conduction electrons. It should be noted that the value of R^ is one order of magnitude larger than that of R0. Co. This is called the magnetothermoelectric effect. R1 must be equal to R0.21).594 VARIOUS PHENOMENA ASSOCIATED WITH MAGNETIZATION current between two metal layers depends on the relative angle between the magnetization in the two metal layers. 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 /. If the effect of magnetization is simply to apply an internal magnetic field ju. we must look elsewhere for the origin of the extraordinary Hall effect. Since this is not the case. Slonczewski30 showed theoretically that the tunneling electric conductance varies as cos 9.9.32 The anisotropic effect can be described in a similar way to the magnetostriction or magnetoresistance effect. . The magnitude of this effect is of the order of 1/tVKT 1 for Fe and Ni. The thermoelectric power of ferromagnetic metals also depends on magnetization. an electric field is produced perpendicular to both the current and the magnetic field.

When these quantities are small. They considered that 3d electrons are conducting and their orbital motion is influenced by their own spin-orbit interaction. Temperature dependence of extraordinary Hall coefficient of Ni. His calculation explains well the temperature dependence shown in Fig. but their directions are not parallel to each other.9. 21. He extended his theory to rare earth metals and explained the extraordinary Hall effect of Gd metal. the proportionality relationship holds between electric and magnetic quantities. If we write (21. 21. Kondo17 considered that 4 s electrons are conducting and their orbital motions are influenced by the orbital motion of 3d electrons remaining unquenched.23) and R\ is the extraordinary Hall coefficient due to spin-orbit interaction. we have and . We can express these relationships as where a and a' are the ME tensor and EM tensor. They showed that R\ is related to the resistivity by This relation holds well for various kinds of Ni alloys.26) for each component in Cartesian coordinates. Since R0 <c R\ except at very low temperatures. respectively. In contrast to this theory.9.37 where R0 is the ordinary Hall coefficient as given by (21.39 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 /.MAGNETOELECTRIC EFFECTS 595 Fig. the main part of R0 is R\.

in which the plane of polarization of light reflected from a magnetic material rotates in accordance with the sense of magnetization. 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.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 magnetic Kerr effect.27) or (21. of the plane of polarization is proportional to the path-length. because this phenomenon is caused by the difference in absorption between two oppositely circularly polarized light beams. Fe. and magnetite41'42 Fe3O4. /. each level splits into two levels 5 = — \ and + in the presence of a magnetic field H (Zeeman splitting). Co. and the MKS (SI) values are 47r/c times the CGS values (c: velocity of light = 3 X 108 ms~*). The magneto-optical effects include the Faraday effect. The ME effect is observed only for ferro.10). In both cases. these tensor component are dimensionless. ME effects are observed for boracite40 M 2 B 7 O 13 X (M = Cr. it causes a large difference in absorption between two circularly polarized light beams. and to the field. only the component of magnetization parallel to the direction of propagation of the light is effective in rotating the plane of polarization.28) is nonzero.4). due to the precession of spin.or ferrimagnetic materials with low crystal symmetry. the rotational angle. In the latter material an interesting temperature dependence of the ME effect was observed near 10 K. Ni. In the Faraday effect. or I). Mn.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. In these materials one of the nondiagonal elements of the tensors in (21.43'44 21. In CGS Gaussian units. 9. 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. Br. 21. In spite of the fact that the frequency of precession motion of a spin is much smaller than the frequency of visible light. independently of the sense of propagation of the light. and is expressed as where V is the Verdet constant. or Cu and X = Cl. H. which have canted spin systems (see Section 7. in which the plane of polarization of light transmitted through a magnetic material rotates in accordance with the sense of magnetization. The allowed transition . If the atomic spin is \. and the photomagnetic effect in which a magnetic property of a magnetic material is altered by optical means. In this case the sign of the angle of rotation is independent of the sense of propagation of the light.

\ at level A to S = \ at level B.2 K. so that the absorption of one circularly polarized light is greater than the other.3). Physically it corresponds to the law of conservation of angular momentum. Since this is not an optical function. The Verdet constants have been measured for a number of transparent magnetic materials and are found to be impurity-sensitive.2) and for detecting the sense of magnetization of recorded magnetic patterns in magneto-optical memory devices (see Section 22. Generally speaking. Selective absorption of right-hand and left-hand circularly polarized light by a magnetic atom. there must be a change in spin angular momentum.47 Faraday rotation and magnetic Kerr effect are also used for observing magnetic domain patterns (see Section 15. In a magneto-optical memory system. 21. 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. Photo-induced magnetic anisotropy (Section 13. we cannot regard this process as a photomagnetic effect.4. and this mixing of orbits enhances spin-orbit interactions. This is known as a selection rule in spectroscopy.MAGNETO-OPTICAL PHENOMENA 597 Fig. This is due to a change in superexchange interaction caused by light. however.10. 21. the Verdet constant of YIG is appreciably increased by the introduction of a small amount of Bi3+ or Pb3+ ions. For instance. the population between the two spin states at the level A is different.3).46 Faraday rotation has been used for measuring magnetization in ultra-high pulsed magnetic fields. or fro S = . the plane of polarization will rotate in the same sense during penetration to the skin depth and back to the surface. between the two levels is either from S = \ at level A to 5 = — \ at level B. Therefore the two transitions mentioned above must be caused by the absorption of oppositely circularly polarized light as illustrated in Fig. 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. a magnetic signal is written using a laser beam (see Section 22. it . When a magnetic atom is magnetized. thus resulting in a nonzero rotation of the plane of polarization. The magnetic structure of Er orthochromite (ErCrO3) was observed to change from antiferromagnetic to canted-spin upon illumination by light at 4.10. thus resulting in a rotation of the plane of polarization of the light. However. because when circularly polarized light which has an angular momentum is absorbed by an 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.

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and S.. Rev. 688. Phys. 466. Miyamoto. 295. Chikazumi. /. K. 37. 49 (1988). 1154. Shirai. Pugh and N. 42. Pugh.. Theoret. 12 (1973). Shindo. K. M. and S. G. Progr. 1779. M. Ariga. S. 80 (1950). Y. 46 (1979). Y. M. Nakao. 47. 660. E. and S. N. T. Japan. 19. 37 (1966). Appl. and H. E. 55 (1986). ed. Schmid. Miyamoto. Miura.. H. 45. Kaji. M. Y. K. Handbook on magnetic substances. Phys. 1389. Rev. Kobayashi. A. by S. Tsushima. /. M. Kondo. 39. 48. Chikazumi et al. 48 (1980). No.. Rev. Rostoker. 30 (1910). Phys. I. 28 (1962). Rostoker. 846. Egawa. Morita. Japan. Rev. Y. Siratori. Phys. 47 (1979). Teranishi. Chikazumi. Soc. Mod. Chikazumi. 38. T. R. Kimura. E. and S. Phys. 95 (1954). de Phys.. Smith. Rieder. J. 1947. J..REFERENCES 35. 25 (1953). 599 A. Takeuchi.3.. Phys. Otuka. Phys. C8-953. Iwashita. Luttinger. 1404. Japan. H.. Jap. Kohn. Phys. 235. Taniguchi. Phys. 43. (Asakura Publishing Company. S. Solid State Comm. Japan. 44. Phys. Tokyo. Goto. Appl. Kita. 46. K. 38 (1981). /. Shindler. Phys. A. 41. Soc. 1. and S. /. Soc. and N. Shinagawa. Asher. and A. 36. I. E. J. Y. . 40. and K. Kurita. W. Miyamoto. E.. Kaplus and J. Soc. Toyokawa. Sugano. K.1. T. Tasaki. J. 1975).

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

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

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

05 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 0.05 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 0.00 1.0 0.79 2.OSimp 4Si 3Si 78.5 0.1 2.97 2.002 0.15 1.45 1.0 0.1 0. Magnetic properties of soft magnetic alloys (mostly from Bozorth9). 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.Table 22.73 .5Ni 5Mo.15 2.2imp O.

(a) Sendust11 The alloy containing 5% Al. and accordingly the resultant magnetization. however. are coated with a thin electrically insulating layer and compressed into final shape. should be proportional to the applied field. Ferrites and other nonmetallic compounds are particularly good for high-frequency applications because of their high resistivity (see Table 22. the displacement. 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. Table 22. The core materials are produced by continuous splat-cooling. because this composition just meets the conditions Kl = 0 and A = O.m in diameter. The eddy current loss is of primary importance. and. 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 11.12 Since this alloy is very brittle.44.2 Pressed powder and ferrite cores For high-frequency applications. and some compositions have good corrosion resistance. Since in this case the energy of the domain wall is a quadratic function of its displacement. reduction of the various losses accompanying highfrequency magnetization is more important than static magnetic characteristics.1. magnetic metals and alloys for AC use are always in the form of thin sheets or fine particles. For power machines. Then the hysteresis loop becomes a snake-shaped or constricted one as shown in Fig. . and for small transformers and other devices operating at frequencies up to about 50 kHz. Also some compositions show relatively large aging and disaccommodation (Section 20.1) effects. in order to reduce it.604 ENGINEERING APPLICATIONS OF MAGNETIC MATERIALS (for instance. 10% Si and 85% Fe exhibits extremely high permeabilities Xa = 30000 and ^max = 120000 as cast from the melt. Amorphous alloys have small anisotropy.1 lists magnetic properties of various soft magnetic alloys. in the form of long thin ribbons or sheets. 24 h) at 400-450°C. or rapid solidification processing. 18.1). it is ground into small particles about 10 ju. This behavior can be explained by the same model. 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. 22. It is also possible to make the hysteresis loop rectangular. They are mechanically strong.2). which. after annealing. which keeps the domain walls in their original positions. Amorphous alloys are successfully used in power transformers up to several kVA capacity. they have the disadvantage that the saturation magnetization is limited by the high content (about 25%) of non-magnetic metalloid elements. because this alloy responds strongly to magnetic annealing (see Section 13.

so that they are suitable for extremely high-frequency uses (see Fig. so that they are most suitable as high-frequency magnetic materials. . this ferrite can be sintered at high temperatures. After being sintered at 1400°C. so that it is used for bubble domain devices (see Section 22. Section 18. For most efficient use of the magnetic material. no hopping motion of electrons occurs.1 to 1ft m (= 10-100 ft cm)). (c) Garnets The crystal and magnetic properties of these oxides were discussed in Section 9. ferrites are electrically insulating. and the oxide has extremely high resistivity and exhibits extremely low magnetic losses. Mg-Mn ferrite is used as a rectangular hysteresis material.3. 9.17). In Mg-Zn ferrites. Mn-Zn ferrites have relatively high saturation magnetization (see Table 9. 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.7). so that they are extensively used as core materials. Maximum permeability occurs at 50-75 mol% MnFe2O4. 70mol% ZnFe2O4.2 HARD MAGNETIC MATERIALS Another important engineering application of magnetic materials is as permanent magnets. so that they are not suitable for extremely high-frequency use. 22.3).2. The desirable properties for hard magnetic materials are high coercive field and high residual magnetization. thus compensating a part of the decrease in saturation magnetization at room temperature caused by a decrease in Curie point. 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. 9.1).HARD MAGNETIC MATERIALS (b) Ferrites 605 As already discussed in Section 9. Ni-Zn ferrites have extremely high resistivity. because the 'natural resonance' shifts to higher frequency by an increase in Kl (see Section 20.3). 1. 50mol% ZnFe2O4. high permeability is realized at 50mol% MgFe2O4.2 or Fig. Single crystal garnets are used for microwave amplifiers. Since the metal ions are all triply charged. the resistivity is relatively low ( p = 0. Initial permeability is maximum at 30mol% NiFe2O4. However. the working point of the magnet should correspond to the maximum value of the energy product.7).2) closer to room temperature. (2) The addition of Zn causes an increase in saturation magnetization at 0 K (see Fig.2 lists magnetic properties of pressed powder and ferrite cores. high-frequency properties are better at higher Ni content. A figure of merit to express the quality of permanent magnet materials is the maximum energy product (5//)max. Thin films of this crystal are optically transparent. 50-25 mol% ZnFe2O4. Most commercial ferrites for this purpose contain Zn. Since only the doubly charged state is stable for nickel ions.27). Table 22. However. 20. which is the maximum rectangular area under the B-H curve in the second quadrant of the hysteresis loop (see Fig.

17 (G) 360 200 320 135 ©f (°C) 500 110 130 287 p («m) 20 5x10" In the history of permanent magnets. when a carbon iron is quenched from the fee phase. . which is mechanically and magnetically hard. etc.2.0 (T) 0.25 0.1 3.3. he suggested that a single-domain structure of fine precipitated particles must be the origin of the high coercivity. first iron and its alloys such as KS steel. MnAl.40 0. MK steel.. Originally the high coercivity of this magnet was thought to be due to large internal stresses.2% Ca+ Y3Fe5O12 treatment (°C) Press. were developed. it transforms completely or partially to a bet phase called martensite. Cooling this alloy from 1300°C in a magnetic field results in a rectangular hysteresis loop and accordingly a large value of (fi//)max. The MK magnet was invented by Mishima.1 Permanent magnet alloys As is well known in steel metallurgy. W steel. It has the approximate composition Fe2NiAl.16 This alloy is also called Alnico 5. These later materials have higher coercivity but lower residual magnetization as compared with the alloy magnets. Alnico. invented by Mishima and Makino15 which contain no expensive metals such as Ni and Co. BHC. This process is known as spinodal decomposition (see Section 13. and then compound magnets utilizing single domain characteristics such as Ba ferrites.3. the aim in developing permanent magnet materials is to get the saturation magnetization as high as possible while maintaining high coercivity.10Si 50Mn-50Zn 30Ni70Zn 0. Accordingly.15).14 and MT magnet (Fe-C-Al steel). 13. Recently developed high-quality rare earth permanent magnets such as RCo5 and Nd15Fe77B8 meet both these requirements. when the hysteresis loop is measured in the direction of the cooling field. The origin of this magnetic annealing is the reorientation of the elongated precipitated particles (see Section 13. 22. were used. etc. cannot be greater than the value of the residual magnetization divided by /i0 (see (1..13 Heat Name Sendust powder MnZn ferrite NiZn ferrite Ca added YIG Content 5A!. Other examples are KS magnet (Fe-Co-W steel).1).120)). Since the coercive field for B. Cr steel and Co steel are all old permanent magnets utilizing this phenomenon. but later Nesbitt17 found that a high coercivity is also observed for an alloy of the same kind which has no magnetostriction. 800 1150 1050 HC & 80 2000 80 600 (Am" ) 100 8 240 1 ls (Oe) 1.45 0.2.1) and it produces large internal stresses and at the same time finely divided elongated particles (see Fig.606 ENGINEERING APPLICATIONS OF MAGNETIC MATERIALS Table 22. which decomposes into two bcc phases during slow cooling from the high-temperature ordered bcc phase. Magnetic constants of pressed powder and ferrite cores.25 0. invented by Honda and Saito.

both of which have tetragonal crystal structures. and exhibit very high magnetocrystalline anisotropy. RCo5 and R2(Fe. the coercive field for /. Strong internal stresses produced by this superlattice formation are supposed to be the origin of their high coercivity.3 Rare earth compound magnets RCo5 and R2(Co. One of the features of this type of material is that once the magnet is magnetized by a strong field. As discussed in Section 17.3).1). so that once a domain wall is created.. The anisotropy is uniaxial and also very large (see Table 12. 8. High coercivity is obtained because it is difficult to nucleate reverse domains. In addition to excellent magnetic properties. both compounds produce strong uniaxial anisotropies (see Table 12. so that ferrite materials sintered into solid ceramic form can be used as permanent magnets. so that the (BH)m3X values are one order of magnitude larger than those of previously available magnets. //m. The melt-spun material is used in bonded magnets for accurately shaped parts. thus resulting in a very low coercive field. These compounds have fairly large saturation magnetization (see Table 12.2. which can increase (BH)max by a factor of 3.25 Nd-Fe-B and Pr-Fe-B alloys can be prepared by the melt-spinning technique26 as well as by conventional sintering of powders. .6.26). In the case of R = Sm. a sintered magnet can have a single domain structure. increases with an increase of the maximum magnetizing field. but even with 5% Co a usefully high value is obtained. Necessary conditions for this are a defect-free structure of the crystals and also smooth grain boundaries containing Nd. less than that of Ba ferrite. it has good machinability and low density (3. 22. 10.10).HARD MAGNETIC MATERIALS 18 607 Fe-Cr-Co alloy is a deformable alloy magnet. which contain no obstacles to domain wall displacement.and B-rich phases.2 Compound magnets Ba ferrite is a hexagonal ferrite invented by Philips investigators.5 gcm"3.Fe)17 type compounds22 have a strongly uniaxial crystal structure (see Fig. ///.19 It has a magnetoplumbite-type crystal structure with the chemical formula BaO-6Fe2O3 (see Section 9. This kind of magnet is described as having nucleation-controlled coercivity. respectively.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.3 and Strnat22). 22.. containing 0.7% carbon.23 This phase has a very large uniaxial anisotropy.4). The largest (B/f )max is obtained at 15% Co. Moreover the crystal grains can be aligned by pressing in a magnetic field. The Nd15Fe77B8 magnet includes grains of the phase Nd2Fe14B with tetragonal crystal structure (Fig.4). This compound.20 MnAl is a ferromagnetic compound which includes none of the ferromagnetic elements (see Section 10.21 is inductionmelted and extruded at 700°C under a pressure of 80 kg mm"2. it will run across the grain.5 gem"3). Fe-Pt and Co-Pt alloys form the superlattices FePt and CoPt.Co)17 magnets belong to this category. The grain size is much larger than the critical size for single-domain structure. 4.2.

0 0.6 5.5 3.3 6.7 40 42 1.8.3 for a number of permanent magnet materials.93 1.7C.2 20.0 4.Cr.35Co 2.4 166 477 290 3.5 2.1 7.58 0.0 5.31 0.3 200 160 446 438 464 250 200 560 550 580 8.0 33.8Al 24Co.58 0. 4W. 22.6W 3. 780FC 1000Q (B//)max Jm~3* XlO 3 ) 2.30Al.4 Compound magnets ferrite MnAl 70Mn.0C.23 1250 1570 2070 2600 1200 1500 2560 7200 3300 9000 24 30 8.6 Density (gcnT3) 8.Fe)17 Nd15Fe77B8 or l/8ir of GOe.5Mo. Magnetic properties of various permanent magnets.9 Name Composition Alloy magnets W steel 0.23Co.3 7..2 1.45 0.82 (Am" 1 XlO 2 ) 56 48 143 (Oe) 70 60 180 Table 22.3Cu 28Cr.0 3. 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 22.60 0.98 0.1 4.9 60 36 10 11 4.8 1300AF.8 1.0 7.3.6Cu 14Ni.0 0.608 ENGINEERING APPLICATIONS OF MAGNETIC MATERIALS Hc B.10Al. steel 0.0A1 16Ni.3.8 (G Oe XlO 6 ) 0.0C.3.5%Cr 0. Heat treatment (°C) 850Q 830Q 1150AQ.3 Superlattice magnets Pt-Fe Pt-Co 0. The principle of these devices is . 600B 600-540B 1.90 0.20 0.15Co KS steel MT steel MK magnet Orient.9C.77Pt 2O3 0.3 MAGNETIC MEMORY AND MEMORY MATERIALS 22.27 0.9C.9 7.7 7.0 3.5Cr steel 15%Co 1. MK (AlnicoS) Fe-Cr-Co 0.0.45 1.3Cr.7Cr. (T) 1.6 12.1 Magnetic tapes and disks Magnetic tapes and magnetic disks are devices to record analog or digital signals magnetically by utilizing residual magnetization. 12Co.7C Rare earth compound magnets SmCo5 Sm2(Co.5 1. ISi 78Pt 23Co.5 8.

the running speed of the tape relative to the head must be high. 22. They are also used for recording digital signals for large-scale data storage for computers. shown in Fig. The signal from one track is converted to one horizontal visible line on the display tube. a cylindrical head with multiple gaps is rotated. relatively thick disk (hard disk) coated with a layer of magnetic medium. and its . Magnetic tapes are also used for recording video signals.MAGNETIC MEMORY AND MEMORY MATERIALS 609 Fig. Then a residual magnetization corresponding to the signal wave form is left on the tape or disk. The speed of magnetic tapes and disks relative to the magnetic head is becoming smaller and smaller. because of the increasing density of the recorded signal. In this case. Therefore instead of the induction method a static detection of the recorded signal using the magnetoresistance effect has been developed (see Section 21. and the tape is wound around the rotating head cylinder and moved in the opposite direction to the head surface motion. It is seen that the magnetization has a component perpendicular to the surface at all depths in the tape. The result is shown in Fig. 22. 22. Such a magnetic structure stores some magnetostatic energy. so that the induction voltage of the signal becomes smaller. For example. 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.2.3(b). which in turn is magnetized by a signal current carrying the information to be recorded. tending to form closed magnetic flux paths. 22. In order to reproduce the signal. The residual magnetization pattern recorded on a magnetic tape by a magnetic head. thus reproducing the recorded picture. The distribution of the recorded residual magnetization has been calculated by computer simulation.3(a). 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. Magnetic tapes are used for recording audio signals (voice and music). Then the signals are recorded along many narrow parallel tracks tilted with respect to the edge of the tape. A magnetic head utilizing the magnetoresistance effect is called an MR head. so that usually both the tape and the magnetic head are moved.2. Magnetic powder or an evaporated magnetic thin film carried on a ninmagnetic tape or disk is maagnetized as it passes under a magnetic head. taking into consideration the coexistence of a magnetic head and magnetic medium whose hysteresis loop is assumed to be as shown in Fig.2). A magnetic disk consists of a rotating flexible plastic disk (floppy disk) or a rigid.

Computer simulation of the distribution of residual magnetization in magnetic media: (a) assumed hysteresis loop (the dashed lines represent a complete hysteresis loop.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. a system which has been developed for large-scale hard disks.30 The recording is exclusively digital: either . 22.610 ENGINEERING APPLICATIONS OF MAGNETIC MATERIALS Fig.5). However.28 There is a physical limit to the minimum bit size. 223.4. the lines 1-4 are the magnetization process in a running tape). One possible solution is a thin film magnetic head floating aerodynamically above a smooth magnetic medium. The most promising material has been TbFeCo. such as the miniaturization of the magnetic head and obtaining smooth contact between the magnetic head and the magnetic medium. or the highest bit density.3. (After Shinagawa27) energy density becomes larger as the signal density becomes higher. there are various technical limits in recording and reproducing magnetic signals. (b) the calculated distribution of residual magnetization in magnetic media.

00 800 * In the case of packing factor 0. In order to write a signal. because the writing and detecting of the signal Table 22.28 °i /.15 120 0.* #c Materials •y-Fe2O3 powder Co-doped powder CrO2 powder Fe-Co powder Co-Ni thin FILMfilm Wbmkg" 1 X10~ 4 1.3). a polarized laser beam is directed onto the magnetic media. After switching off the beam. Magnetic constants of magnetic recording materials. 22. induced by the demagnetizing field of the surrounding material.4(a)).4 for powders. . This rotation of polarization is detected by an analyzer and detector (Fig. 22.1 80 0. (b) reading process. and the polarization of the reflected beam is rotated oppositely for + and — recorded bits (magnetic Kerr effect. magnetization-up (+ ) or magnetization-down ( — ).0 1.4.1 80 0.5 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 0.30 200 1. see Section 21. this area cools down and a region of upward-pointing magnetization appears. and then a laser beam is focused on a narrow area to he'at it above the Curie point (Fig. Magneto-optical recording: (a) recording process. Thus a + bit is written in.5 > 2.0 1.1 > 2.MAGNETIC MEMORY AND MEMORY MATERIALS 611 Fig. In order to detect the signal. first all the area is magnetized downward.4. The advantages of magneto-optical recording are high-density memory storage and greatly reduced friction and wear. 22.4(b)).

22. 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. An example of a memory storage system is shown in Fig. In this way many digital numbers can be stored in the minor loops. In reading a digital number stored in the minor loops. etc.5. For details on bubble domain devices the reader may refer to Mikami. and shifted to a major loop of Permalloy patterns. First a digital number is converted to a bubble domain array by the bubble generator. a bubble domain can propagate along a path defined by Permalloy patterns magnetized by a rotating magnetic field. When the shift of a digital number is completed.3 Bubble domain device This is an all-magnetic memory system with no mechanically moving parts. (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.31 It is a digital memory using bubble domains (see Section 17. Materials used for magnetic heads are Permalloy.5. 22.3. In a memory storage system. Sendust.32 Rotational field Fig.3). Mn-Zn ferrite.) . Such a shift of bubble domains can follow a rotational rate as high as 100 kHz. The bubble domain is attracted by the free pole appearing on a Permalloy pattern.4 lists magnetic constants of various magnetic recording materials.612 ENGINEERING APPLICATIONS OF MAGNETIC MATERIALS use highly focused laser beams and there is no physical contact with the magnetic medium. 22. As shown in Fig. produced on a garnet single-crystal film which is grown on a gadolinium-gallium-garnet single-crystal plate. 22. by opening all the gates to the major loops the digital number array is reproduced in the major loop. and is shifted to the next pattern during one revolution of the rotating field.6. Table 22. amorphous alloys. which is detected by a detector. Permalloy pattern for propagation of a bubble domain. the gates to minor loops are opened. and then each digital number is shifted to a minor loop.

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

S. L731. Tokyo. Asakura Publishing Co. Mikami. Phys. S. Sagawa. Croat. and Y. by Chikazumi et al. M. 39 (1968). J. Phys. S.. /. Nagao. A. Kubo. W. 2078. 9 (1969). Mag. 511. G. and T. Lee.. Mat.. 31. 25. Kuno.. Ohtani. S. H. Becker. . Herbst. 1551. 1975). IEEE Trans. N. /. J. Mag.. 29. Appl. J. Mag. Bobeck. F.. MAG-8 (1972). 1975). Fischer. T. Mag. F. 19 (1980). F. Appl. Imamura and C. 23. Phys. and I. Phys. N. Asakura Publishing Co. Ohta. K. Sakamoto. Yamamoto.. Pinkerton. 26. Handbook on magnetic substances (ed. Shinagawa. K. 27. IEEE Trans. 1607.. 55 (1984). Perneski.. J. Private communication. Tanaka. A. MAG-21 (1985). M. J. Remeika. Imamura. R. 54-7 (1986). Appl. Van Uitert: IEEE Trans. Kqjima. 32. 2083. I. Matsuura. Strnat. H. 1270. Iwasaki. 1328. S. 24. Handbook on magnetic substances (ed. Fujimura. Togawa. N. /. E. I.614 ENGINEERING APPLICATIONS OF MAGNETIC MATERIALS 21. Tokyo. Mag.3. M. Kato. and Y. J. by Chikazumi et al.. 30. 55 (1984). MAG-13 (1977). R. Tanaka.4. Section 26. Jap. Tsukahara.. and P. S. P. J.. Chikazumi. Mag.. 22. IEEE Trans.. J. Section 26. IEEE Trans. J. MAG-5 (1969). /. Appl. 544. Mag. 28. 214.

QH2 = (l/2ju. Considering there are two gaps.0H. Differentiating this expression with respect to x. This expression can be deduced from (1. or from (1. this problem is interpreted as follows: Before the separation of the two halves. 1. Then we have The total magnetic moment of the sohere is • /\ When x~* °°> the moment becomes M= 4TrR3fj. we have the relationship I = xHeS = xH-( */3/i0)/. the cross-sectional area of the permanent magnet must be . When the two halves are separated by the distance x. which produces the Maxwell stress T\\ = ^fj. and the reluctance.SOLUTIONS TO PROBLEMS CHAPTER 1 1. the effective field becomes Hetf = H — (l/3ja0)7. the air gaps store the magnetostatic energy (l//A0)/2&c.3 Using the magnetomotive force.2 The magnetic field produced in the air gap is given by // = ///n0. we have the force acting between the two halves.0)72S. we have the total force F = (l//j. so that the magnetostatic energy is zero. 1.1 When the sphere is magnetized to the intensity 7. From the energy point of view. there are no free poles or there is no field in the space where / is present. Ni = 200 X 5 = 1 X 103 [A]. the field is calculated to be 1.0)/2.79) by considering that the magnetic potential difference between the magnetic poles ±75 is given by Hx.4 If there is no leakage of magnetic flux from the magnetic circuit.105). Since the magnetization / is attained by this effective field.

/ = i/3r.2 From (2. CHAPTER 3 3. we have H = (Ni/l) (Am"1). L = 6.4 Adding and we find that all the ^-dependent terms vanish. 2_3 Refer to the text.) 2. 2.5 According to (1.44).99).47) with respect to H. the length of the permanent magnet parallel to the magnetization is given by 1. we have 33 Solving (3.1(a). R = r in (2.1 By using z = 0.7). . we have Using 3.4).1 Using 5 = f. we have CHAPTER 2 2. / = 4f. we have from (3.39) 3.2 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.616 SOLUTIONS TO PROBLEMS From Ampere's theorem.

6mms~'. 2MH.54 = 8.39 cms"1. we have from (5. and the difference between (2) and (5) or (3) and (?).090/\ = 0. Moreover. e = 1.2 The absorption lines in Fig. must be equal to the Zeeman splitting of the ground state.5) 617 4. we have Solving this equation. ®.2 Using we have from .SOLUTIONS TO PROBLEMS CHAPTER 4 4. which is 0.l^cms"1 = — 9.5 from left to right correspond to the transitions CD. we have v2 = 3kT/m or v = fokT/m . we have 5=1.11 X 10~31. The difference between (D and (D. (D.5 X 1(T10 m.60 X 10~19.2 MAm"1. 4.180. in Fig. we have from (4. or (5) and (3). (2). Therefore the difference between (?) and (2).47 XlO^m 3 . H = -27 X 10 6 Anr l .1 Using N = 6.1 Using g = 0. a = 0.2 X 10~27J. we have T = h2/3mk\2 = 40 K. CHAPTER 5 5. (3). or (5) and ® corresponds to 4A£. so that we have A £ = — O. from which we have H = 26. ®. Z = 29. m = 9. 4.02 X 1023 X 8.9). taking the difference between CD and ®. Using this in (4. respectively.94 X 106/63.3. 43 From the relationship \nw2 = f AT.8) 5.

x = C/(20N) = Xo. 7. 73 Since J2 = -(V3~/6)/1. no compensation point appears. Since wl = 0. (6.4899CW from (7. we have a = (45)1/3&1/3. Therefore the value of / or Hm deduced from the experimental value of ®f becomes larger. Since A = f and /a = f.2 Since a = ft = 0.Thus we find that at T = 2® N .62) n = lir/QC = 12. we find that ®N = -®a> so that x = C/(T + 0N).h. we have SOLUTIONS TO PROBLEMS More accurate statistical treatment leads to a smaller value of k@t/J. Therefore at T = 0 N . which is in region II.2) and (5. Thus we find that 7a = 2NM.4800O from (7. Comparing this with (6. Using this in the above equation.9). from which we find that QC = 2w/12. CHAPTER 8 8.39) with (7.618 CHAPTER 6 6. we have from (7. 7. x=lx0 = 0.7 that x = Xo at T=0 and T=0 N /2. Ib = -2NM. 6. .18) we have Thus we find that the susceptibility decreases with T. we have Therefore the energy-dependence of the density of states becomes so that from (8.Since the origin O is located in the region where 7S < 0 at T = 0 as well as T ~ 0f.29).1 From (6.22).11).1 We see in Fig.38).19A1/3 . Therefore we have from (7. proportional to T2.41) and 0a = -0. CHAPTER 7 7. where h = H/NMw. we have the magnetization curve I/NM = 1. 7.1 From (8. this ferrimagnet corresponds to the origin O in the a-ft diagram (Fig.2 At T = &f.4) becomes / = NM(a/3) -H/w. we have 0f = -0.65) cos QC = i/3~/2.67^0. so that ®f/®a = 1-02.

that is the x'-axis.-.y'.z') plane is parallel to the (210) plane.and nt represent the direction cosines of new coordinate axes with respect to the cubic coordinates.0) with respect to the cubic coordinates (x.n. whose z'-axis is parallel to the z-axis and (0. 83.1 Set the new coordinates (x'.z'). has the direction cosines (2/i/5~. CHAPTER 12 Table Sol.m . 8.1 by using the relationship £. and 55at% Fe-Cr./? = E. = E.-«? = 1 and E. These numbers correspond to the alloy compositions 60 at% Ni-Co.2 Using (12. m.. 12.y.6.y'.7 and 25. m.48). From Table Sol. 12. Then the normal to the (0.2 Af = 1MB is realized at electron numbers 27. «. 90at% Co-Cr.4 Refer to the text.y'.= 0.1. we have the relationships Since we have Then the K^term of the anisotropy energy becomes 12.l/i/5~. where /. respectively. 26. z') plane. = E.1 for Ni-Co..m} = £.z\ The relationship between the cubic and new coordinates can be constructed as shown in Table Sol. we have the anisotropy field . Co-Cr and Fe-Cr alloys. CHAPTERS 9-11 Refer to the text. 12.SOLUTIONS TO PROBLEMS 619 8.1 x x' y' z' y 1/i/S -2/1/5 0 z 0 0 1 2/i/5 1/1/5 0 12././.

so that £ of the second term in (13. the induced anisotropy (13. cos 00 = 1/V^. so that £ = 0. Therefore the ratios of the induced anisotropies measured in the (110) plane for [001]. that is ir/2. [110] and [111] annealing are 0:1:2.11) becomes Comparing this with (13. Let the angle between the spontaneous magnetization and the z-axis in the (110) plane be 6. ft = 0. so that where 00 is the angle between [110] and the z-axis. Then we have <*! = a2 = (l/V2~)sin 9 and «3 = cos 6. Then a1 = cos 6. a2 = sin 6.4 Assuming n = 1.f i . sin2S0 = 2\/2 /3. Therefore for [001] annealing ft = ft = 0.2 Let the angle between the *-axis and the spontaneous magnetization be 6. For [110] magnetic annealing.620 12.11) 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 6.3 SOLUTIONS TO PROBLEMS Since the number of atoms in a unit volume is calculated by we have from 12. cos200 = -|. Note that sin 00 = \/2~/\/3~.20).1 Since kt = 0.72) Therefore the anisotropy energy is given by CHAPTER 13 13. 13.11) is expressed only by_the second term. Therefore the anisotropy energy (13. we have for <110> . For [111] annealing 0i = 02 = 03 = (I/ &X so that where 00 is the angle between the [111] and the z-axis. For [110] annealing ft = ft = (I/ /2 ) and 03 = 0. a3 = 0. ft = ft = I/ . we have from (12.

z'\ in which y' is parallel to [110].22).29) with slip system No. k2 = -j^. 13. and for fee £ : £ + £ = 4:3.3. a'2 = sin 6. we have . z' is parallel to [111]. Then we have Since a{ = cos 6. k1 = \. 13. z) are given by Table Sol. k1 = 0.e.SOLUTIONS TO PROBLEMS 621 Comparing it with (13. k2 = 0.1. y. The relationships of the new coordinates and the cubic coordinates (x. k2 = f.3 Referring to (13. 133 Let the angle between the spontaneous magnetization and [110] be 6. for bcc f : £ = 2:1. and set new coordinates (x'. 3 in Table 13. Considering that the magnetostrictive elongation is proportional to the magnetization /. Table Sol. a'3 = 0.28) and (13.3. 3.28) where s is the slip density for slip system No. we have E in (13.1 By applying the magnetic field parallel to the [010] direction. i.y'. and kt = -jk. body-centered cubic and face-centered cubic structures given in Table 13. the domain magnetizations in [100] and [100] change their directions to [010] by 90° wall displacement. we have Therefore so that we have the anisotropy energy CHAPTER 14 14. 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. and the final elongation at saturation magnetization 7S is given by f A100. we have for sc 0: £ = 0:1.

we have for the second term of the anisotropy energy (12.3.47) becomes 16. 14. Similarly for (110).1 Since the uniaxial anisotropy energy constant.100) CHAPTER 16 16. j3: = 1. so that we have For [010] elongation.14).5 Using the values for Fe in Table 14. Similarly. we have from (14. the wall energy (16.4 Putting direction cosines of (14. a3) are (1.5) For (100). we have Ea = — ^A100cr. in this case is given by f ACT. we have Since (alt a2. 16. so that sin \l/= 0.0) for a [100] domain.89). Ku. and for a [001] domain Ea= — HA IOO O-. which is equivalent to (Oil). j3j = 0.622 SOLUTIONS TO PROBLEMS 14. so that we have 14.2 Using (16. i/»= 0 (see Fig.47) gives y100 = 0. we find 143 Putting a1 = cos 6. /32 = 0.0. Therefore we have Then the wall energy (16.43) For [100] elongation.42) becomes . i/f = ir/4. Therefore we have Ea = 0. /32 = 1. so that sin(ir/4) = cos(ir/4) = l/v/2.24). a2 = sin 6. we have for a [010] domain Ea = — f A100cr.33) and (14. we have from (14.2 Referring to (14. which is equivalent to (010). Then the 180° wall energy (16.49) and assuming a'3 = 0.

52/3 X 10~10 = 6.sin20)/(l +7s2/4/i0A:1). Using this value and S = \. n = 2 and a = 3 X 10"10 in (16.15).75 X HT21 J.4 Since the stable 90° walls make ±62° with the x-y plane (see Fig. Therefore the magnetostatic energy per unit area of the 90° wall is given by em = 5.66)). Since the wall energy depends on Ka as -^K^.47). Sol.25XHT 1 2 X6X10 4 = 1.22X 10~3 Jm' 2 . we have jT = 0. the above integral is converted to f _ 1 x d x and finally we have 1 2 623 16.30).4 CHAPTER 17 17.10) where /s is replaced by <a. we find that the domain width d depends on Ka as K^/4.34 X 1. the domain width d is given by (17. the inner angles of the ^-domain are 62° X 2 = 124° and 180° .37).5).21 and equation (16. Therefore we have the wall energy (16.124° = 56°. . 16. The magnetostatic energy per unit area of the 90° wall is given by (17.75 X 10~21 X 0. we have A = 2 X 3.40 X I04/S2rf(l .55) y100 = 2 X V6. 16.25 X 1(T12.* correction (17. In this case we must take into consideration the fj.sin <£)2 = 5.2 In case (i).SOLUTIONS TO PROBLEMS If we put sin <p = x.40 X I04/S2d(cos 4> . showing the dependence on the wall energy as -Jy.40xl0 4 / s 2 d(l-sin2</>). 16. Fig.38 X 10~23 X 800 = 3.1 The magnetic pole density appearing on the 90° wall is given by u> = ±/s(cos 4> — sin 4>). as shown by (16. so that em = 5. 17.31) where /A* is given by (17.3 Putting 6{ = 527 + 273 = 800 in (16.

which is equal to 100 A or 0. Using this correction in (17.14) = 0. 183 Note that when H is parallel to the c-axis.39). For 0 = 60°.76). sin2 0 = f. so that /I* = 1 + 3. we have from (18. Similarly in the p* correction A (17.26).37) that the domain width d depends on Ku as *V 4/^1/2^-1/4. we have 18. so that x = f + f = 12.624 SOLUTIONS TO PROBLEMS In case (ii).0 times.5.3.01 Aim. where 1 can be ignored. only 180° wall displacement occurs.82/(2 X 4. so that . we must take into consideration /*.86). so that x = T + (5 x f ) = 8-8.14.33 mm. so that x = (20 X f) + f = 16. so that cos 6 = I/ \/2. 17.20 times the value for an isolated single domain particle.66) //0 = 2v/2"y180o/(/sa). The /A* correction (17.0 times the value of 20 A given by (17. while when H is perpendicular to the c-axis.389. only magnetization rotation occurs. the relative susceptibility is expressed by X = XwaiiCos 2 0 + J rot sin 2 0. the magnetostatic energy must be 0. For 6 = 30°. When the magnetic field makes an angle 6 with the c-axis. For 6 = 45°.1 X 105) = 3. we have X = 1.26) becomes A = 2/(l + 4.36). sin2 0 = |. Therefore we find in (17.31X10-" = 0. so that the critical radius for single domain particle (17. cos2 6 = f. Ka = 4.29). CHAPTER 18 18. 1 in the denominator can be ignored. so that A is proportional to Ka.8. Therefore the critical size for polycrystalline iron must be 5. we have the domain width = 3.75) must become 1/0.95 X 1(T6. cos2 0 = £.2 Since / = a/2 and 9 = ir/4.20 = 5.1 X 10s in (17.4 According to (17. 173 Using 7S = 1.For polycrystalline cobalt.* given by (17.95 X 10-6/4irX io~ 7 = 4. where ^wall = 20.1 Since the residual magnetization remains in the positive direction in each particle. *rot = 5. cos2 0 = sin2 6 = \.

1 19. Fig. Sol.2 The triangular arrangement starts at the field //cl = (w/3)NM and ends at Hc2 = wNM.SOLUTIONS TO PROBLEMS 18.1 Since there is no magnetic anisotropy. Thus the susceptibility increases linearly with an increase of H^. and decreases to zero. Since 7A and /B are 2:1 in magnitude. 19.1 Using the approximation for /c «: kT in (20. 18.5 From (18. and finally become ferromagnetic at Hs. After the field is rotated towards y. the magnetization which makes an angle +45° with the —^-direction reverses its direction by irreversible magnetization rotation (see Fig.t-axis towards the —y-axis. the shape anisotropy constant is deduced from (12. As the field. the spin axis is always perpendicular to the field while the field is weak. 18. Since Hs is proportional to /S( = /A = ~\IB$> tne fom1