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F U N DA M E N TA L S A N D A P P L I C AT I O N S O F M AG N E T I C M AT E R I A L S
Fundamentals and Applications of Magnetic Materials

Kannan M. Krishnan
University of Washington, Seattle

3
 3
Great Clarendon Street, Oxford, OX2 6DP,
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and education by publishing worldwide. Oxford is a registered trade mark of
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© Kannan M. Krishnan 2016
Cover illustration: Ulla Kraitz’s rendering of the concept of Giant Magnetoresistance, discussed in detail in Chapter 13.
Kraitz also did the artwork for the Nobel Diplomas awarded to the 2007 Physics Laureates, Albert Fert and P. Grünberg.
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 To

Appa
Who so much wanted for me to write a book, but did not live long enough to see this one

Amma
Always a source of love, inspiration, and support

The teachers who have influenced me the most

Late Mr. T.B.V. Subhramanyam (HPS)
Professor H.S. Mani (IITK)
Late Professor L. Falicov (UCB)
Late Professor G. Thomas (UCB)
Who, hopefully, see some of themselves in this book

Generations of students at UCB and UW

For keeping me honest

and

M.N.
For simply being the magnet in most of my adult life
Contents

Table of constants (see inside front cover)

Preface xvii

1 Introduction to Magnetism and Magnetic Materials 1

1.1 Basic Electromagnetism 2
1.1.1 Magnetic Field: Biot–Savart and Ampere Laws 2
1.1.2 Magnetic Induction or Flux Density 4
1.1.3 The Magnetic Flux 6
1.2 Elementary Magnetostatics 7
1.2.1 Magnetic Charges: “Monopoles” and Dipoles 7
1.2.2 Magnetic Dipole Moment 8
1.2.3 Field Due to a Magnetic Dipole 9
1.3 The Magnetic Moment: Equivalence of Dipoles and Current Loops 11
1.4 Sources of Magnetic Fields 12
1.4.1 Field Generated by a Circular Current Loop 12
1.4.2 Field Generated by a Solenoid 14
1.4.3 Helmholtz Coils 15
1.4.4 A Planar Coil: Archimedean Spiral 16
1.5 Intensity of Magnetization 17
1.6 Relationship between Magnetization, Field, and Induction 18
1.7 Susceptibility and Permeability 20
1.8 An Overview of the Types of Magnetic Behavior in Materials 22
1.8.1 Diamagnetism 22
1.8.2 Paramagnetism 23
1.8.3 Ferromagnetism 23
1.8.4 Antiferromagnetism 25
1.8.5 Ferrimagnetism 25
1.9 Hysteresis 26
1.10 Work Done by the External Field in Hysteresis 28
1.11 Demagnetization 29
1.11.1 Calculation of Demagnetizing Factors 31
1.11.2 Gauss Law 34
1.11.3 Demagnetization Energy 36
1.11.4 Practical Consequences of the Demagnetization Field 37
1.12 Maxwell Equations 38
viii Contents

Summary 39
Further Reading 40
References 41
Exercises 41

2 Atomic Origins of Magnetism 47

2.1 Quantization of Energy 48
2.2 Quantization of Angular Momentum 50
2.3 Spatial Quantization of the Angular Momentum 50
2.4 One-Electron Wave Functions Subject to a Central Force 52
2.5 Relationship Between the Orbital Angular Momentum and the Magnetic Moment of an Electron 55
2.5.1 The Zeeman Effect: Evidence for Spatial Quantization 56
2.6 Electron Spin 57
2.7 The Stern–Gerlach Experiment 58
2.7.1 Nuclear Spin 60
2.8 The Spin–Orbit Interaction 61
2.9 The Electronic Structure of the Atom 63
2.10 Total Angular Momentum and the Magnetic Moment of the Atom 66
2.11 Quenching of Orbital Angular Momentum 71
2.12 Electron Paramagnetic Resonance (EPR) and Determination of the Landé g-Factor 73
Summary 75
Further Reading 75
Reference 75
Exercises 76

3 Magnetic Materials: From Isolated Moments to Ordered Arrangements 79

3.1 Langevin Theory of Diamagnetism 80
3.2 Introduction to Superconductors 82
3.3 Langevin Theory of Paramagnetism 84
3.4 Quantum Theory of Paramagnetism 87
3.5 Weiss Theory of Ferromagnetism 90
3.6 Law of Corresponding States 95
3.7 Mean-Field Approximation, Critical Phenomena, and Exponents 98
3.8 Exchange Interactions 102
3.9 Nature of the Exchange Integral and the Bethe–Slater Curve 105
3.10 Helical Structures 107
3.11 The Physical Meaning of Long-Range and Short-Range Forces 108
Summary 109
Further Reading 110
References 110
Exercises 110
 Contents ix

4 Other Ordered Magnetic Materials: Antiferromagnetism and Ferrimagnetism 115

4.1 Introduction to Antiferromagnetism 115
4.2 Molecular Field Theory of Antiferromagnetism 117
4.2.1 Temperature T > TN 117
4.2.2 Temperature T < TN 118
4.2.3 Field Applied Perpendicular to the Spin Lattice Direction 120
4.2.4 Field Applied Parallel to the Spin Direction (T < TN ) 120
4.2.5 Powder or Polycrystalline Samples 122
4.3 Spin-Flopping and Metamagnetism 123
4.4 Introduction to Ferrimagnetic Materials 124
4.5 Molecular Field Theory of Ferrimagnetism 125
4.5.1 At High Temperatures, T > TC 126
4.5.2 For Low Temperature, T < TC 127
4.6 Indirect Exchange Interactions 129
4.6.1 Super-Exchange Interactions 130
4.6.2 Double-Exchange Interaction 132
4.7 Role of Local Symmetry and the Environment 133
4.8 Determination of Magnetic Order: Neutron Scattering 136
4.9 Examples of Antiferromagnetic and Ferrimagnetic Materials 140
4.9.1 Rock-Salt Structures 140
4.9.2 Spinel Structure Compounds (Ferrites) 141
4.9.3 The Garnet Structure 145
4.9.4 Perovskites 147
4.9.5 Hexagonal Iron Oxide Structures 149
Summary 151
Further Reading 152
References 153
Exercises 153

5 Magnetism in Metals and Alloys 157

5.1 Introduction to the Electronic Structure of Metals 158
5.2 Free Electron Theory of Metals 159
5.3 Pauli Paramagnetism 163
5.4 Stoner Model of Ferromagnetism 165
5.5 Ferromagnetism of 3d Transition Metals and Alloys 168
5.6 The Slater–Pauling Curve 174
5.7 Spin Density Waves 176
5.8 The Indirect RKKY Interaction 178
5.8.1 Spin Glass and Frustration 180
5.8.2 The Kondo Effect 181
5.9 Amorphous Ferromagnetic Metals and Alloys 182
5.10 Examples of Magnetic Alloys 185
x Contents

Summary 187
Further Reading 188
References 189
Exercises 190

6 Magnetic Anisotropy 193

6.1 Magnetocrystalline Anisotropy 193
6.1.1 Cubic Crystals 195
6.1.2 Uniaxial (Hexagonal) Crystals 197
6.1.3 General Crystal Structures 200
6.2 Anisotropy Measurements 200
6.2.1 Torque Magnetometry 201
6.3 Determination of Anisotropy Constants from Magnetization 207
6.3.1 Fitting Magnetization Curves 208
6.3.2 Areas of Magnetization Curves 212
6.4 Anisotropy Field 213
6.5 Magnetic Resonance 213
6.6 Nature of Magnetocrystalline Anisotropy 214
6.7 Shape or Magnetostatic Anisotropy (Revisited) 217
6.8 Magnetostriction or Magnetoelastic Anisotropy 217
6.8.1 Phenomenological Theory of Magnetostriction (Magnetoelastic Energy) 221
6.8.2 Magnetostriction and the Effect of Stress 225
6.9 Mixed Anisotropies 226
6.9.1 An Example 226
6.9.2 A Graphical Solution 226
6.10 Anisotropy in Amorphous Magnets 227
6.11 Induced Anisotropy 228
Summary 229
Further Reading 229
References 230
Exercises 230

7 Magnetic Domains and the Process of Magnetization 234

7.1 The Domain Postulate 234
7.2 Contributions to the Domain Energy 238
7.2.1 Continuum Approximation of the Exchange Energy 239
7.2.2 Magnetostatic or Demagnetizing Energy (Shape Anisotropy) 241
7.2.3 Magnetocrystalline and Magnetoelastic Energy 244
7.3 The Bloch Wall 245
7.3.1 Wall Energy and its Optimal Thickness 246
7.3.2 Detailed Derivation of the Structure of a 180◦ Wall 248
7.3.3 90◦ Domain Walls 254
7.4 Bloch, Néel, and Cross-Tie Walls 257
 Contents xi

7.5 Domain Structures in Particular Configurations 260

7.5.1 Thin Films 261
7.5.2 Fine Particles 266
7.6 Coherent Rotation: the Stoner–Wohlfarth Model 271
7.7 Domain Wall Processes 280
7.7.1 Forces on a Domain Wall and the Potential Approximation 281
7.7.2 The Picture Frame Experiment 285
7.7.3 Interaction of Walls with Inclusions 287
7.7.4 Inclusions and Voids 289
7.7.5 Low Energy Domain Walls: the Wall-Bowing Approximation 290
7.7.6 Stress as a Hindrance to Wall Motion 292
7.8 The Magnetization Process 295
7.8.1 Magnetization in High Fields: Approach to Saturation 296
7.8.2 Magnetization in Low Fields: the Rayleigh Regime 297
7.8.3 Domains and the Magnetization Process 298
Summary 300
Further Reading 301
References 301
Exercises 303

8 Micromagnetic Imaging and Modeling 307

8.1 Introduction 308
8.2 Imaging Stray Magnetic Fields 310
8.2.1 Bitter Pattern Methods 310
8.2.2 Magnetic Force Microscopy 312
8.3 Imaging the Sample Induction Distribution 315
8.3.1 Interactions of Electrons with Magnetic Samples 315
8.3.2 Electron–Specimen Interactions in a TEM 317
8.3.3 Lorentz Microscopy: Fresnel and Foucault Imaging 319
8.3.4 Lorentz Microscopy: Differential Phase Contrast (DPC) Imaging 320
8.3.5 Electron Holography 322
8.3.6 Off-Axis Electron Holography 323
8.3.7 Coherent Foucault Imaging 325
8.3.8 Scanning Electron Microscopy—Types I and II Contrast 326
8.4 Imaging the Magnetization Distribution with Polarization Analysis 328
8.4.1 Secondary Electron Microscopy with Polarization Analysis (SEMPA) 328
8.4.2 Spin-Polarized Low Energy Electron Microscopy (SPLEEM) 331
8.5 Imaging using Sample–Photon Interactions: the Magneto-Optical Effect 333
8.6 Magnetic Imaging with Element Specificity 337
8.6.1 Principles of X-Ray Magnetic Circular Dichroism (XMCD) 338
8.6.2 Transmission X-Ray Microscopy (TXM) 341
8.6.3 X-Ray Photoemission Electron Microscopy (X-PEEM) 342
xii Contents

8.7 Basics of Micromagnetic Modeling 345

8.7.1 Energy Terms 346
8.7.2 Brown’s Static Equations 350
8.7.3 Numerical Micromagnetics: the Dynamical Equations 351
Summary 352
Further Reading 353
References 353

9 Fine Particles and Nanostructured Materials 358

9.1 Introduction 358
9.2 Classification of Fine Particles and Nanostructured Materials 360
9.3 Incoherent Magnetization Reversal: the Curling Mode 362
9.4 Superparamagnetism and the Blocking Temperature 364
9.4.1 Determining Size Distribution of Superparamagnetic Particles 370
9.4.2 The Blocking Temperature: Zero-Field-Cooled (ZFC) and Field-Cooled (FC)
Measurements 373
9.5 Coercivity of Fine Particles as a Function of Size 375
9.6 Magnetization Dynamics 377
9.7 Finite Size and Surface Effects 382
9.8 Inter-Particle Interactions 388
9.8.1 Magnetic Order Arising from Dipolar Interactions 390
9.8.2 Remanence Measurements and Interaction Effects 392
9.9 Ferrofluids 394
9.10 Response of Fine Particles to Alternating Fields 398
9.11 Mössbauer Spectroscopy 402
Summary 404
Further Reading 404
References 405

10 Magnetic Surfaces, Interfaces, and Thin Films 409

10.1 Introduction 409
10.2 Growth Methods and Modes 410
10.3 Electronic Structure and Magnetism 415
10.3.1 Energy Bands 415
10.3.2 Magnetic Exchange Splitting, δEex , Excitations, and Transitions 417
10.3.3 Magnetization, Curie Temperature, and Critical Behavior in Low Dimensions 421
10.3.4 Interactions and Coupling 424
10.3.5 Anisotropy and Magnetostriction 426
10.4 Thin Films 428
10.4.1 Metastable Phases 428
10.4.2 Critical Phenomena and Transitions from 3D to 2D Behavior 431
 Contents xiii

10.5 Magnetism in Two Dimensions: Monolayers, Ultrathin Films, and Interfaces 433
10.5.1 Monolayer Magnetic Moments 433
10.5.2 Surface/Interface Anisotropy and Perpendicular Magnetization 437
10.5.3 Domains and Two-Dimensional Magnetic Phase Transitions 441
10.6 Oscillatory Exchange Coupling 446
10.6.1 Experimental Observations 446
10.6.2 RKKY Description 448
10.6.3 Spin Polarized Quantum Well Description 453
10.7 Exchange Anisotropy/Bias 454
10.8 Exchange Spring 466
Summary 468
Further Reading 469
References 470

11 Hard and Soft Magnets 476

11.1 Introduction 476
11.2 Hysteresis and Operating Criteria for Hard Magnets 480
11.2.1 Demagnetizing Field and the Open Magnetic Circuit 480
11.2.2 Energy Density Product, BH 482
11.3 Magnetic Anisotropy and Mechanisms of Coercivity 484
11.3.1 Phenomenological Discussion 484
11.3.2 Atomic Description 487
11.4 Microstructure and Hard Magnetic Behavior 490
11.4.1 Brown’s Paradox 490
11.4.2 Exchange-Spring Magnets and Remanence Enhancement 492
11.5 Soft Magnets 494
11.5.1 Alternating Field Response and Eddy Current Losses 495
11.5.2 Random Anisotropy 497
11.5.3 Nanostructured Materials as a Route to Achieving Soft Magnetic Properties 498
11.6 Survey of Soft and Hard Magnetic Materials 500
11.6.1 Crystalline Soft Magnets 500
11.6.2 Amorphous and Nanocrystalline Soft Magnets 503
11.6.3 AlNiCo Permanent Magnet 505
11.6.4 FeCrCo Magnets 506
11.6.5 Pt–Co and Fe–Pt Alloys 506
11.6.6 Hard Ferrites (Hexaferrites) 508
11.6.7 RE–TM Permanent Magnets: Sm–Co and Fe–Nd–B Alloys 509
Summary 514
Further Reading 516
References 516
xiv Contents

12 Magnetic Materials in Medicine and Biology 519

12.1 Introduction 519
12.2 Magnetic Carriers for Biomedical Applications 526
12.2.1 Synthesis of Magnetic Nanoparticles 527
12.2.2 Core-Shell Structures 537
12.2.3 Biogenic and Biomimetic Synthesis 542
12.2.4 Design and Functionalization of Nanoparticles for in vivo Applications 545
12.2.5 Biocompatibility, Cytotoxicity, Biodistribution, and Circulation 550
12.3 Imaging 557
12.3.1 Magnetic Resonance Imaging 557
12.3.2 Contrast Agents in Magnetic Resonance Imaging 566
12.3.3 Magnetic Particle Imaging (MPI) 573
12.3.4 Optimizing Magnetic Nanoparticle Tracers for MPI 583
12.4 Separation and Diagnostics 590
12.4.1 Magnetic Separation 590
12.4.2 Forces on Magnetic Particles 591
12.4.3 Design of Magnetic Separators 593
12.4.4 Magnetophoretic Microsystems 596
12.4.5 Applications of Magnetic Separation 598
12.4.6 On-Chip Magnetic Biosensors 599
12.4.7 Magnetorelaxometry: Binding Specific Detection Methods 603
12.5 Therapy 606
12.5.1 Hyperthermia Treatment of Cancer: Biological Factors 606
12.5.2 Physics of Heating Ferrofluids with Alternating Magnetic Fields 610
12.5.3 Magnetic Fluid Hyperthermia (MFH) in Practice 620
12.5.4 Drug and Gene Delivery 626
12.6 Magnetoreception in Animals 630
12.6.1 The Earth’s Geomagnetic Field 631
12.6.2 Possible Mechanisms of Magnetoreception 632
Summary 639
Further Reading 641
References 642

13 Spin Electronics 655

13.1 Introduction 655
13.2 Fundamentals of Spin Transport 657
13.2.1 The Two-Spin-Channel Model of Conduction 658
13.2.2 Spin Asymmetry 660
13.2.3 Spin Polarization and Half-Metallic Ferromagnets 661
13.2.4 Spin Injection and Spin Accumulation 664
13.2.5 Spin Transport in Diffusive Systems: the “Standard” Model 667
13.2.6 Spin Injection and Spin Diffusion Length in Semiconductors 671
13.2.7 Spin-Dependent Tunneling 675
 Contents xv

13.2.8 Spin Transfer Torque: Current-Induced Magnetization Reversal and Domain Wall
Motion 679
13.2.9 Hall Effect, Anomalous Hall Effect, and Spin Hall Effect 685
13.2.10 Spin Caloritronics 688
13.2.11 Quantum Hall Effect and Topological Insulators 690
13.3 Two-Terminal Devices 692
13.3.1 Giant Magnetoresistance in CIP and CPP Geometries 692
13.3.2 Magnetic Tunnel Junctions (MTJ) and Magnetic Random Access Memories (MRAM) 698
13.3.3 Spin-Polarized Light Emitting Diodes 701
13.4 Three-Terminal Devices 702
13.4.1 The Johnson All-Metal Transistor 703
13.4.2 The Monsma Spin-Valve Transistor 704
13.4.3 The Magnetic Tunneling Transistor 706
13.4.4 The Datta–Das Spin-Field-Effect Transistor (SFET) 707
13.4.5 Spin-Polarized Injection Current Emitter (SPICE) Transistor 708
Summary 708
Further Reading 710
References 711

14 Magnetic Information Storage 716

14.1 Introduction 716
14.2 The Basic Principles of Magnetic Recording 717
14.3 Physics of Magnetic Recording 720
14.3.1 Field Efficiency of an Inductive Head 720
14.3.2 Karlquist Approximation of the Field of a Ring Head 721
14.3.3 The Write Process: Width of a Recorded Transition 723
14.3.4 The Readback Process Using an Inductive Head 726
14.3.5 The Readback Process Using a Magnetoresistive Head 729
14.3.6 Noise Sources 735
14.3.7 Thermally Activated Magnetization Reversal 738
14.3.8 The “Trilemma” in Hard Disk Magnetic Recording 741
14.4 Perpendicular Magnetic Recording 743
14.5 Materials and Structures: Recording Media 746
14.6 Approaches to Increasing Areal Densities in Magnetic Recording 749
14.6.1 Antiferromagnetically Coupled (AFC) Media 749
14.6.2 Composite Exchange-Spring Media 750
14.6.3 Heat-Assisted Magnetic Recording (HAMR) 753
14.6.4 Bit-Patterned Media (BPM) 755
14.7 Magneto-Optic Recording 758
14.8 Solid-State Non-Volatile Magnetic Memory 760
14.8.1 Magnetic Random Access Memory (MRAM) 761
14.8.2 Toggle MRAM Device 762
xvi Contents

14.8.3 Spin Transfer Torque Magnetic Random Access

Memory (STT-MRAM) 764
14.8.4 Current-Driven Domain Wall Motion and Related Devices 766
Summary 769
Further Reading 770
References 771

Afterword 775
Index 777
Preface

Magnetism is subtle in its manifestations. Driven electronically, it is weak com-

pared with electrostatic interactions. Quantum mechanical in nature, its origin is
in the Pauli exclusion principle and the existence of electron spin. However, it is
also known for a variety of both classical and quantum mechanical effects, arising
from both short- and long-range forces, and is widely associated with “micro-
structure” or the morphological arrangements of magnetic moments (domains),
as well as phases, grains, or individual atoms themselves. These are, in part, the
reasons for the richness of structures and properties encountered in magnetic sys-
tems from which various useful technological and biomedical applications arise.
These are also, in part, the reasons why the magnetic behavior of materials is
poorly understood and many fundamental questions remain unanswered.
This book provides a comprehensive discussion of magnetism, magnetic ma-
terials, and related applications. The logical train of thought progresses in four
parts from physics of magnetism (§1–5), magnetic phenomena in materials (§6–
8), size and dimensionality effects (§9–10), and applications (§11–14). Beginning
with a description of magnetic phenomena and measurements on a macroscopic
scale, this is followed by discussions of intrinsic and phenomenological concepts
of magnetism, such as electronic magnetic moments, and classical, quantum, and
band theories of magnetic behavior. It then covers ordered magnetic materials,
emphasizing their structure-sensitive properties, and magnetic phenomena, in-
cluding magnetic anisotropy, magnetostriction, and magnetic domain structures
and dynamics. There then follows a comprehensive description of imaging meth-
ods to resolve magnetic microstructures (domains), along with an introduction to
micromagnetic modeling. Size (small particles) and dimensionality (surface and
interfaces) effects—the underpinnings of nanoscience and nanotechnology, that
magnetism brings into sharp focus—are then explored in some detail. The hall-
mark of modern science is its interdisciplinarity and hence, after covering the
required background material to establish a solid foundation, the second half
of the book discusses in substantial depth, with extensive bibliography, infor-
mation technology, spin electronics—encoding information using the electron
spin state—and the future of biomedicine, via recent developments in magnet-
ism. Modern materials, with tailored properties, require careful synthetic and
characterization strategies; the book also includes relevant details of the chem-
ical synthesis of small particles and the physical deposition of ultrathin films.
In addition, details of state-of-the-art characterization methods and summaries
of representative families of materials, including tables of properties, where ap-
propriate, are presented. Finally, CGS equivalents (to SI) are regularly inserted,
xviii Preface

in the hope that if one were to be referring to works of a recent antiquity this
feature would be useful.
Overall, the text is comprehensive and written with readers of different back-
grounds in mind. It is based on more than two decades of teaching this material,
and offers a focus that is not easily available elsewhere. The introductory subject
matter, covered in the early chapters, does not assume any knowledge of mag-
netism and is presented carefully with adequate exercises to serve as a useful text,
particularly for students of applied magnetism. The target readership is wide, and
the text would be a useful addition to lecturers of senior undergraduate courses
in physics, engineering, materials science, biology and bioengineering, radiology
and medicine, and of graduate courses in these disciplines. In addition, research
students, post-doctoral fellows, supervisors, and those crossing over from physics
and engineering to biology and medicine, or vice versa, would find this text to be
an excellent reference.
This book has grown out of courses taught at the University of Califor-
nia, Berkeley and the University of Washington, Seattle. It began in the early
1990s, at UC, Berkeley, as a set of notes for a one-semester (16 weeks) course,
for both undergraduate seniors and graduate students, in various science and
engineering disciplines. Lectures over the first 12 weeks covered essential con-
cepts in §1–7, §9, and §11, followed by selective discussions of information
storage technologies (§14), spin electronics (§13), and other applications by in-
dustry experts and student presentations. Subsequently, I also offered a more
advanced one-semester graduate course at UCB emphasizing the second half of
the book (§8–14). Such a two-semester course will do proper justice to the subject
matter at hand, and the book is ideally suited for it. Since 2001, at the University
of Washington, Seattle, I have been teaching a one-quarter (10 weeks) version of
this course. This is much more challenging, not only because of the limited time,
but also due to the addition of newer topics, such as developments in nanotechnol-
ogy (§9–10), applications in biology and medicine (§12), and spintronics (§13).
The best way to teach this subject in a single quarter is to selectively discuss the
important concepts (§1–7), depending on student background, in eight weeks,
and in the remaining two weeks give an elementary overview of the biomed-
ical (§12) or physical (§11, §13, and §14) applications of magnetic materials based
on student interest. Needless to say, this book encompasses much more than these
courses.
In writing this book, in addition to my teachers to whom this book is dedi-
cated with gratitude, I have benefitted immensely from various colleagues who
most generously gave of their time in reviewing chapters, particularly in their
areas of expertise. I thank them most sincerely. In alphabetical order they
are: Dr. Samuel Bader (§10), Professor Yuping Bao (§12), Professor Xavier
Batlle (§9), Professor John Chapman (§1–4), Dr. Peter Fischer (§7–8), Dr. R. M.
Ferguson (§12), Dr. Emad Girgis (§13), Professor Erol Girt (§14), Dr. Axel Hoff-
mann (§13), Professor Albrecht Jander (§1), Dr. Samuel Jiang (§11), Professor
Laura Henderson-Lewis (§2, §5), Professor Anil Kumar (§6), Professor Amilcar
 Preface xix

Labarta (§9), Professor Yasukazu Murakami (§8), Professor Anna Samia (§12),
Professor Rudolf Schäfer (§7–8), Professor Daisuke Shindo (§8), Professor Rob-
ert Stamps (§10), Dr. Bruce Terris (§14), Dr. Jan-Ulrich Thiele (§14), Professor
John Weaver (§12), and Dr. Wei Zhang (§5). In addition, I am deeply indebted
to the anonymous OUP reviewer and Professor Honglyoul Ju who read the en-
tire manuscript. The critical reading of the manuscript by all these colleagues
has resulted in many changes, corrections, and improvements; however, I am en-
tirely responsible for any remaining omissions, errors, or mistakes, and will be
more than happy to address them in subsequent revisions. In my teaching and
research, I have also benefitted immensely from interactions with generations of
students and post-doctoral fellows, as well as numerous collaborators, over the
past three decades. The list is too long to acknowledge them individually, but
many of their feedbacks, thoughts and inputs are reflected in this book. The book
was written during residencies at the Rockefeller (Bellagio) and Whitely (Friday
Harbor) Centers; in particular, I have spent many productive months at the lat-
ter and simply cannot imagine completing this book without access to this idyllic
retreat. Finally, I am grateful to Professor Eugene Haller for encouraging me to
teach the first such course on magnetic materials at UCB, and to Sonke Adlung of
OUP, for his inimitable style of encouragement and patiently leading me through
the publication process.

Kannan M. Krishnan
Seattle, April 2016
 Preface xix

Labarta (§9), Professor Hiroyuki Murakami (§8), Professor Anna Samia (§12),
Professor Rudolf Schäfer (§7–8), Professor Daisuke Shindo (§8), Professor Rob-
ert Stamps (§10), Dr. Bruce Terris (§14), Dr. Jan-Ulrich Thiele (§14), Professor
John Weaver (§12), and Dr. Wei Zhang (§5). In addition, I am deeply indebted
to the anonymous OUP reviewer and Professor Honglyoul Ju who read the en-
tire manuscript. The critical reading of the manuscript by all these colleagues
has resulted in many changes, corrections, and improvements; however, I am en-
tirely responsible for any remaining omissions, errors, or mistakes, and will be
more than happy to address them in subsequent revisions. In my teaching and
research, I have also benefitted immensely from interactions with generations of
students and post-doctoral fellows, as well as numerous collaborators, over the
past three decades. The list is too long to acknowledge them individually, but
many of their feedbacks, thoughts and inputs are reflected in this book. The book
was written during residencies at the Rockefeller (Bellagio) and Whitely (Friday
Harbor) Centers; in particular, I have spent many productive months at the lat-
ter and simply cannot imagine completing this book without access to this idyllic
retreat. Finally, I am grateful to Professor Eugene Haller for encouraging me to
teach the first such course on magnetic materials at UCB, and to Sonke Adlung of
OUP, for his inimitable style of encouragement and patiently leading me through
the publication process.

Kannan M. Krishnan
Seattle, April 2016
Introduction to Magnetism
and Magnetic Materials 1
1.1 Basic Electromagnetism 2
This chapter introduces different kinds of magnetic materials and their response
1.2 Elementary Magnetostatics 7
to magnetic fields. To understand these interactions we begin with a brief de-
1.3 The Magnetic Moment:
scription of magnetic fields (H) and how they are generated in a controlled and Equivalence of Dipoles and
well-defined manner. Following this, we describe the response of the material to Current Loops 11
the magnetic field, called magnetic induction, B, including the contribution of 1.4 Sources of Magnetic Fields 12
the substance (be it a gas, solid, or liquid). However, in free space H and B are 1.5 Intensity of Magnetization 17
different measures of the same field related by a constant, μ0 , the permeability 1.6 Relationship between
of free space. We develop two different formulations, starting either with cur- Magnetization, Field, and
rent carrying wires and the forces between them (SI units)1 or with interactions Induction 18

between magnetic “poles” (CGS units, highlighted in a grey background). In 1.7 Susceptibility and Permeability 20

this process, we describe the magnetic dipole moment, m, the elementary mag- 1.8 An Overview of the Types of
Magnetic Behavior in Materials 22
netic quantity of interest in materials and its volume average or magnetization, M,
and establish the inter-relationship between these fundamental magnetic param- 1.9 Hysteresis 26

eters: B = μ0 (H + M) in SI and B = H + 4πM in the CGS system of units. Note 1.10 Work Done by the External Field
in Hysteresis 28
that even though this book emphasizes SI units, it is important for a practicing
1.11 Demagnetization 29
magnetician to be conversant with both sets of units, their respective formula-
tions, and the conversion from one to the other; in fact, if one is referring back to 1.12 Maxwell Equations 38

works of even recent antiquity or, for that matter, engaged with others involved Summary 39

in related technologies today, familiarity with both systems of units will be most Further Reading 40
helpful. References 41
We distinguish between applied, Happ , and demagnetizing, Hd , fields, as well Exercises 41
as the related field, Hin , inside the body,2 and also between the intrinsic response
of the material and experimental measurements of samples in terms of the appro-
priate susceptibility, χ (= M/H ) and permeability, μ(= B/H ). Following these
definitions and presentation of conceptual ideas, we provide a general overview
of the variety of magnetic behavior observed in different materials, that includes
diamagnetism, paramagnetism, ferromagnetism, antiferromagnetism, and ferri-
magnetism. These topics are covered in detail later, but here the goal is to
obtain a physical sense of the wide range of magnetic materials before they
are discussed in detail in subsequent chapters. We then introduce hysteresis in
ferromagnetic materials and the structure-sensitive properties defined by vari-
1
Systeme International d’Unites, or the
ous points on the hysteresis curve. This is followed by a description of the role
International System of Units.
of demagnetization and the associated magnetostatic energy in ferromagnetic 2
Later, we define Happ = H0 , and typic-
and ferrimagnetic materials for objects of simple, well-defined shapes such as ally, Hin = Happ + Hd .

Fundamentals and Applications of Magnetic Materials. First Edition. Kannan M. Krishnan.

© Kannan M. Krishnan 2016. Published in 2016 by Oxford University Press.
2 Introduction to Magnetism and Magnetic Materials
i n
d
Hx
L netic order by neutron diffraction (§4.8), and various methods of domain imaging
Hx
x
Figure 1.1.1 A solenoid (L  d) gen-
erates a field, H, that is a product of
the number of turns, n, per unit length
and the current, i. A plot of the field
strength, Hx , as a function of position
is shown below. The field is fairly uni-
form near the center of the solenoid but
shows a significant gradient dHx /dx at
the ends (see §1.4.2 for further details).
Note that the ordinate axes could equiva-
lently be scaled to represent the flux
density, Bx (= μ0 Hx ), where μ0 is the
permeability of free space.
3
Hans Christian Oersted (1777–1851),
Danish physicist and chemist. The unit of
magnetic field, Oe, in CGS units honors
his discovery.
4
Jean Baptiste Biot (1774–1862) and
Felix Savart (1791–1841) developed this
law together in 1820.
5
We shall follow the convention,
|A| = A, for all vectors in this book.
6
The vector product, a ⊗ b, is a vec-
tor, c, perpendicular to both a and b
with magnitude ab sin θ , where θ is the
angle between a and b. A right-hand
rule determines the direction of c. Note
that the vector product anti-commutes:
a ⊗ b = – b ⊗ a.
ellipsoids of revolution. Finally, we present an overview of the practical conse-
quences of demagnetization and conclude by presenting Maxwell equations, in
differential form, accompanied with a brief discussion.
Readers interested in the principles behind various practical induction, field,
and magnetization measurement methods, including assorted magnetometry, will
find the book by Kalvius and Tebble (1979) very useful. However, Hall effect
(§13.2.9) and magnetoresistance (§13.3) measurements, determination of mag-
(§8) are discussed later in the book. Those familiar with these elementary con-
cepts may skip this chapter, but mastery of this material is essential as it is the
foundation on which we build the rest of the book.
1.1 Basic Electromagnetism
1.1.1 Magnetic Field: Biot–Savart and Ampere Laws
Imagine the years 1819–20. Hans Christian Oersted,3 a then obscure professor
at the University of Copenhagen, was lecturing on the physics of electrostatics,
galvanic or continuous currents from batteries, and magnetism. Even though
there was then no apparent connection between electricity and magnetism, he
intuitively tried a novel demonstration. He placed a thin compass needle in close
proximity to a wire through which he passed a current. To his surprise, the com-
pass needle showed a large deflection when the current carrying wire was aligned
along the direction of the needle; in fact, when he reversed the direction of the
current, the needle had a similar deflection but in the opposite direction.
From this fortuitous beginning of electromagnetism we have come a long way;
it is now well known that magnetic fields are produced whenever there are charges
in motion. The most common example is the solenoid (Figure 1.1.1), which is
used to produce a field, H, inside itself by passing a current, i, through its wind-
ings. If the solenoid is “infinite” in length, L  d, the magnitude of the field,
H = ni, where n is the number of turns per unit length. It follows that H is meas-
ured in units of [Am–1 ] (in the SI system). Permanent magnets also produce a
magnetic field in their vicinity, but even in such cases the magnetic fields can
ultimately be attributed to (atomic) charges in motion (§2).
Two simple laws, that are equivalent, can be used to calculate the fields
generated by current carrying wires in various configurations. To calculate the
magnetic field from a current circuit, we start by defining the contribution from
an element, δl, of a wire carrying a current of positive charge, as shown in
Figure 1.1.2a.
The first, Biot–Savart4 law, states that the field, dH, at an arbitrary position, P,
given by R (R = R û)5 with respect to δl, is given by the vector or cross product6
1
dH = iδl ⊗ û (1.1.1)
4πR2
 Basic Electromagnetism 3

P Figure 1.1.2 The Biot–Savart law il-

(a) (b) dθ
dH
θ lustrated for a current carrying wire.
(a) The field, dH, defined at an arbitrary
R a point, P, due to the current, i, of positive
a R Rdθ
charge from an element, δl, of the wire.
û (b) A magnified image showing the de-
i i
tails of the geometry used in calculating
δl θ δl
the field for a wire of infinite length.

or in the alternative, but equivalent, form

1
dH = iδl ⊗ R (1.1.2)
4π|R|3

This simple inverse square law is introduced here without proof. The Biot–
Savart law is valid for steady or for sufficiently slowly changing currents; however,
it places no restrictions on the speed of the charges for it can even be relativistic.
Strictly speaking, other conditions are required for the law to be valid; we will not
address them here and such details can be found elsewhere [1]. Its effectiveness
is demonstrated by applying it to a number of simple current circuits later, but
first, we will illustrate its usefulness by determining the field due to a conductor of
infinite length carrying a current, i (Figure 1.1.2). Applying the Biot–Savart law,
(1.1.1), to the wire of length, δl = cos
Rdθ
θ
, and carrying out the cross product, we get

i Rdθ i
|dH| = sin(90◦ – θ) = cos θ dθ
4πR2 cos θ 4πa
where dH, as shown in the figure, is out of the plane of the paper and a/R = cos θ.
For an infinite wire, –π/2 < θ < π/2, and integrating over the range of θ , we get
 π/2 π/2
i i i
|H| = cos θdθ = sin θ | = (1.1.3)
4πa –π/2 4πa –π/2 2πa

Thus, the magnetic field is defined in units of [Am–1 ] and the direction of H is
consistent with the right-hand rule for a current flow of positive charges. Alterna-
tively, the strength of the magnetic field due to the current, i, in the wire can also
be determined by the second, simple, Ampere7 law, which states that the integral
of the field along any closed path is equal to the current enclosed by it:

H · δl = i (1.1.4)
closed path

For the infinite wire carrying a current, i, applying Ampere law to a closed circular
path of radius, a, gives

i
H · δl = 2πaH = i or H = , (1.1.3a) 7
Andre-Marie Ampere (1775–1836),
closed path 2πa French physicist.
4 Introduction to Magnetism and Magnetic Materials

which is identical to the earlier result, (1.1.3), obtained by applying the Biot–
Savart law.

Note that in CGS units,8 the Ampere law is written as


H · δl = 4πiabamp (CGS) (1.1.5)
closed path

where the dependent unit of current is abamperes (= 10 A). If the inde-

pendent unit of current, Amperes, is used, the Ampere law in CGS units
becomes

H · δl = 4πi/10 (CGS) (1.1.6)
closed path

It is then easy to show that the field (CGS) for a point at a distance a from an
infinite wire is

2i
H= Oe. (1.1.6a)
10a

Comparing (1.1.3a) and (1.1.6a), we can show (left as an exercise to the reader)
that the conversion from CGS to SI units is

1 A/m = 4π × 10–3 Oe.

1.1.2 Magnetic Induction or Flux Density

8
In §1 only, discussions of CGS units
are shown in a grey background.
9
Nikola Tesla (1856–1941), Serbian-
American physicist, electrical engineer,
and inventor of the alternating current in-
duction motor and numerous other elec-
tromagnetic devices.
10
Hendrik Anton Lorentz (1853–1928),
a Dutch physicist, who shared the 1902
Nobel Prize in Physics with Pieter Zeeman.
Magnetic induction, B, also called the flux density, or flux per unit area, is defined
as the response of the medium to a magnetic field, H. It is worth mentioning, at
the outset, that there is a general lack of unanimity in the literature regarding the
names for B and H, but not on what the symbols represent; for there is uniform
agreement regarding the relationship between, B, H, and the magnetization, M
(defined in §1.5), as stated in SI units in (1.6.1) or CGS units in (1.6.2).
The ratio between B and H is called the permeability, μ. In SI units, free space
is also considered a medium with permeability, μ0 (the origin of this is explained
below). The unit of magnetic induction is the Tesla9 = [Wb m–2 ] = [V s m–2 ] and
is defined in terms of the Lorentz10 force it imparts on a straight current wire, l,
carrying a current, i:
FL = il ⊗ B (1.1.7a)
Definition: A magnetic induction of 1 Tesla imparts a force of 1 N on a 1 m length of
conductor carrying a current of 1 A in a direction perpendicular to the direction
of induction.
 Basic Electromagnetism 5

Now, consider two parallel wires of infinite length, separated by a distance, a,

with currents i1 and i2 flowing through them. A finite segment, say L2 , of wire #2,
will experience a field H21 = i1 /(2πa) from wire #1, with a resultant force

K · 2 · i1 i2 L2
F21 = (1.1.8)
a

If the constant of proportionality, K, is set equal to 1, then the currents have to be

defined in dependent units of “abamperes”. Alternatively, if the current is defined
independently in the SI units of Amperes, then K = 10–7 . To avoid the appearance
of 4π elsewhere (Heaviside11 rationalization), it is included in this constant and
K = μ0 /4π, where μ0 = 4π × 10–7 [V s A–1 m–1 ] or Henry/m, written as [H m–1 ].
This is the origin of the permeability of free space, μ0 , in the SI system. Further
useful and humorous discussions on dimensions and units in magnetism can be
found in a well-known tutorial paper [2].
In free space, the induction, B0 and the field, H0 , are linearly related

B0 = μ0 H0 (1.1.9)

and the force on a current carrying wire, l, is then given by

FL = il ⊗ B0 = μ0 il ⊗ H0 (1.1.7b)

If we consider the motion of a single charge, e, with velocity, v, then we get

FL = μ0 ev ⊗ H0 = ev ⊗ B0 (1.1.7c)

This Lorentz force, FL , forms the basis of a number of magnetic imaging methods
using electron beams and is discussed further in §8.3.2. Further, since FL is always
orthogonal to the velocity, v, a free electron in motion subject to an external field
will have a circular orbit. It is easy to show (see Exercise 1.10) that the radius of
this orbit, known as the cyclotron radius, is given by

me v
rcyclotron = (1.1.10)
|e|B

where me and –e are the mass and charge of the electron, respectively
(see §13.2.11).
Before we move on, some caution is advised. We need to stop and ask, what
is the definition of the field, especially inside a magnetic material of finite size
and well-defined shape? So far, we understand that in free space an applied field,
H0 , gives rise to an induction, B0 = μ0 H0 . If we insert a magnetic solid into this
free space, the field and induction inside it, given by Hin and B, may be very dif-
ferent from H0 and B0 , respectively. All the magnetic moments inside the solid,
11
not only respond to H0 , but now produce additional magnetic fields inside the Oliver Heaviside (1850–1925).
6 Introduction to Magnetism and Magnetic Materials
12
Wilhelm Eduard Weber, German
physicist (1804–1891) who worked closely
with C.F. Gauss.
13
Michael Faraday, British physicist,
chemist, and philosopher (1791–1867).
solid (in fact, they also contribute to the field outside the solid) as well. This is
commonly known as the demagnetizing field, Hd , introduced in §1.11, which op-
poses the magnetization, M, and depends on the macroscopic shape of the solid.
Furthermore, depending on the distribution of the magnetic moments in the solid,
the magnetic field inside may vary from point to point. In the special case of a
solid, whose shape is approximated as an ellipsoid, with the magnetic field ap-
plied along a principal direction of the ellipsoid, then throughout the interior of
the sample the field will be uniform and given by
Hin = H0 + Hd = H0 – Nd M (1.1.11)
where, Nd is the demagnetization factor (see §1.11). Note that when the magnet-
ization is very small compared to the applied field, |M|  |H0 | = |B0 |/μ0 , we
can assume that the internal and applied fields are the same, Hin = H0 . This ap-
proximation is generally valid for weakly magnetic materials such as diamagnets
(§1.8.1) and paramagnets (§1.8.2), but not for ferromagnets (§1.8.3).
1.1.3 The Magnetic Flux
Magnetic flux, , in SI units is measured in units of Webers12 [Wb] and is defined
on the basis of the Faraday13 law of electromagnetic induction, which states that
the voltage induced in a current loop of N turns is proportional to the rate of
change of the magnetic flux, , enclosed by it and is in a direction opposing the
flux change, or
V = – N d/dt (1.1.12)
Definition: A Weber [Wb] is a unit of magnetic flux which when reduced to zero in
one second induces an e.m.f. of one volt in a one-turn coil through which the flux
passes.
The induction, B, as defined in the previous section, is equal to the flux per unit
area, or flux density. Hence, B = /A (Tesla = Webers/m2 ) and for uniform B,
(1.1.11) gives
dB
V = – NA (1.1.13)
dt
from which the units of B are [V s m–2 ]. This simple law, relating a time-varying
magnetic induction to the generation of an electrical voltage (and thus an electrical
current/signal in a simple circuit), forms the basis of a wide variety of magnetic
measurements, and even a recently developed biomedical imaging method, called
magnetic particle imaging (§12.3.3).
 Elementary Magnetostatics 7

1.2 Elementary Magnetostatics

1.2.1 Magnetic Charges: “Monopoles”

and Dipoles
If one were to play around with bar magnets it can be seen that the magnetic
effects are strongest at the ends. Historically, these ends were called “poles”
and they were always observed to occur in pairs of equal strength and op-
posite polarity, i.e. dipoles. However, even though isolated magnetic poles or
“monopoles” have not been observed, it was found that the interaction be-
tween magnets may be explained, in a manner similar to simple electrostatics,
in terms of an inverse square law force between the ends of a dipole taken
singly, one at a time:
p1 p2
F= r̂ (CGS) (1.2.1a)
r2
The constant of proportionality has been set equal to 1 and the pole strength
is defined as a dependent unit.

Definition: A unit pole exerts a force of 1 dyne on another unit pole at a distance
of 1 cm from it.

Continuing the analogy with electrostatics, the interaction between

“poles” is divided into two parts: (1) a pole generates a magnetic field,
p1
H1 = r̂ (CGS) (1.2.2)
r2
and (2) the field interacts with a second pole

F2 = p2 H1 (CGS) (1.2.3)

Definition: A unit pole in a field of 1 Oersted experiences a force of 1 dyne.

Therefore, the unit of pole strength is [Dynes/Oe] in CGS and the force ex-
perienced by a hypothetical unit positive pole placed at any point determines
the direction and magnitude of the field at that point.
Alternatively, the magnitude of the field, |H| = H , can be defined quan-
titatively as the number of lines of force per unit area; thus, 1 Oe = 1 line
of force/cm2 . Hence, for a unit pole, H = p/r 2 = 1/r 2 = 1 Oe at r = 1 cm and,
by definition, H = 1 Oe = 1 line of force/cm2 . The surface area of a sphere
of radius, r, is 4πr 2 and if r = 1 cm, area = 4π. This implies that 4π lines of
force emanate from a unit pole. In this manner we can reason that the total
flux, , from a “pole” of strength, p, is equivalent to 4πp. The underlying
spherical symmetry is the origin of 4π when the basic relationships, (1.6.2),
are formulated in terms of point “charges” in the CGS system of units.
Another random document with
no related content on Scribd:
Aunt Sophia Primshock’s eyes, if it could not sneak in through her
ears. On the very next morning after Pee-wee’s brief career upon the
stage he received the following letter:

My dearest nephew Walter:

We were so pleased to see in the Council Fire column of a
newspaper that you have been awarded the scout badge for first
aid to animals. Prudence is so proud of her cousin that she
cannot wait to see you and tell you so. When we think of all the
cruelty that is inflicted on poor dumb creatures, and sometimes
by boys, it makes me very happy to think that my very own
nephew stands as the champion of the beasts and birds, and
will not harm them or allow anyone else to harm them. That is
better than selling sausages like a pedler, and if it is true that
they are made of dogs it makes one’s heart ache to think of it.
We want you to come here and see us very soon, and you must
stay for several days.
Your proud and happy
AUNT SOPHIA

Enclosed in the envelope was another missive, rather more formal

in tone, which read:

TO WALTER HARRIS, SCOUT:⸺

The Humane Committee of the Girl Scouts of North Deadham
invite you to attend their rally on Saturday evening, July the
tenth, and to accept the Black Beauty Cross of Mercy, for
friendship and kindness to dumb creatures. This cross is given
only by the North Deadham organization, to those rendering
conspicuous service in the field of humanity by championing our
dumb friends who cannot speak for themselves.
Katherine Kindheart
Sympathea Softe
Dorothy Docile
Prudence Primshock
Committee
 The hero’s acceptance of this invitation was a little disconcerting,
but it did not dim his glory. On the contrary (so far as his own efforts
were concerned) it increased his glory. He wrote:

Dear Aunt Sophia and Prudence and that Committee too:

I got that animal first aid badge so now I have ten badges
only I didn’t get it yet but anyway, I’m a star scout. You have to
have a general knowledge of farm animals and I know a lot
about them and I was kicked by a cow and she spilled the milk. I
like milk too. I know what’s good for colic and you have to know
that and it’s good for a horse. I don’t mean colic.
Once when I was drowning some kittens I saved two so that
was a kind act to those two and that counts. It counts one point.
I fixed a tin can that was tied to a dog’s tail because it was tied
too tight. I know all about the different knots, too. Once I
grabbed a bat because I thought it was a dish rag hanging up. I
bet most girls wouldn’t be kind to mice especially rats.
If a horse falls down you have to take off his harness and the
thing that goes kind of alongside his neck comes off like
suspenders. Anyway I like a belt better on account of wearing
my belt axe. Gee whiz I like girls and every kind of animals, only
they’re scared when they get in a rowboat.
I read that story about Black Beauty that your badge is
named after. I like elephants better. If you have a parrot you
better not swear because he learns it. Scouts have to cut birds
up in sections so as to tell the different parts of them. I’m going
to wear that Black Beauty badge alongside my star badge. I’m
going to go on the train that gets there in time for supper.
With love,
WALTER HARRIS
 First Aid
Physical Development
Personal Health
Public Health
Life Saving
Astronomy
Swimming
Forestry
Dairying
Animal First Aid that makes ten.
P. S. I don’t mean you have to cut birds up alive only in pictures.

Aunt Sophia put on her spectacles and scrutinized this letter

curiously, but in the end her eyes dwelt fondly on the words at the
end of the list of badges. Pee-wee always thus summarized his
glories, even in school examination papers. She gazed at the words
Animal First Aid and was reassured.
As for Sympathea Softe and Katherine Kindheart and Dorothy
Docile, they were greatly edified by the imposing list of Pee-wee’s
triumphs.
“Physical Development,” said Dorothy, in whispered admiration; “I
just bet he’s tall and dark, with a splendid chest. One can be big and
gentle at the same time.”
“Of course,” said Sympathea, “look at elephants; they’re as gentle
as can be.”
“Oh, I hope he isn’t like an elephant,” said Dorothy; “they’re so
clumsy. And they just eat, eat, all day. They just live on peanuts.”
“I pictured him as tall and lithe,” said Miss Katherine Kindheart;
“like a—like a tree. I think that one familiar with forestry is almost
sure to be tall. The swimming award too! Oh, I just long to see him. I
think that forestry is such perfectly scrumptious word too. Forestry! It
sort of reminds me of Daniel Boone and Buffalo Bill—calm and
stately; you know what I mean.”
“Or General Pershing,” said Sympathea.
“Or Eugene O’Brien,” said Dorothy, who was something of a
movie fan.
 “Oh don’t you just long to see him?” they all asked each other.

1 Pioneer scout; a lone scout; one without troop or patrol affiliations.

 CHAPTER IV—HE ADVANCES
Pee-wee started for North Deadham in full scout regalia, carrying
a duffel bag instead of a suitcase, wishing to detach himself as much
as possible from the manners and customs of civilization. A new
feature of his motley array was a can-opener dangling from his belt,
intended to suggest the rugged scout’s dependence on his own
culinary art in the dense wilderness. It was rather suggestive of
Heinz 57 varieties.
On the train he made some memorandums in his scout report
book looking to the future government of his new patrol. The
following is a sample.
If any hop-toad can’t learn the pace he has to have his legs tied
together for an hour.
Every feller that gets a new hop-toad gets a piece of chocolate but
he has to give it to his patrol leader for the treasury.
If a hop-toad can’t croak like a frog he has to be turned over on
his back and somebody sit on him till he croaks.
A hop-toad has to be given to the tom-cats if he can’t learn
because the tom-cats want more because they only have six.
On account of going fast hop-toads have to have sticks in their
mouths.
I’m going to try to get tents near where the Robins were before the
other fellows chased them away.
When the train stopped at North Deadham, the girls of the
Humane Committee saw descending from it a diminutive figure clad
in khaki, and Solomon in all his glory was not arrayed like him. His
scout report book bulged out of his pocket, his jack-knife and his
compass and his can-opener jangled in a kind of martial tune, his
step was the step of a conqueror. Beneath his flapping scout hat his
curly hair showed and upon his face was a frown, a terrible frown,
the frown of a hero.
The only discordant note in the martial figure that he presented
was the stick of lemon candy which he was sucking. During his ride
various articles, chiefly edible, had been left upon his lap for
inspection, and he bought them all, and they now bulged and
protruded here and there upon his scout attire.
Removing the stick of lemon candy from his mouth, he
contemplated the girls who had come to meet him, uttered the single
word “Hello” and replaced the candy in his mouth.
“Did you ever in your life?” gasped Sympathea.
“He is certainly not an elephant,” said Dorothy.
“Or a Daniel Boone or a Buffalo Bill,” chimed in Miss Kindheart.
“I’d rather be myself than them,” said Pee-wee.
“Yes, why?” asked one of the reception committee anxiously.
“Because they’re dead.”
“Oh, we’re so glad to see you, Walter,” said Cousin Prudence,
embracing him till he rattled like a Ford car; “I thought you’d never,
never, come to see us. And you’ve won the animal first aid badge!
Oh, isn’t that perfectly wonderful!”
“I won a lot of others too,” Pee-wee said; “I’ve got nine badges.
See them on my sleeve? When the tenth one is put there I’ll be a
star scout. I’m going to be a patrol leader, too. I lost a marshmallow
on that train. Are you going to have that meeting to-night?”
“We certainly are and you’re going to be the main attraction.
You’re going to sit on the stage! Isn’t that just perfectly fine? I don’t
believe you’ve ever been on a stage, now have you? Do you think
you’ll be afraid?”
It was very hard for Pee-wee to admit that there was anything in
the world he hadn’t done; and to have it intimated that he, the actor
in Double-crossed, had never been on the stage, was as much as he
could bear. But he remembered his voluntary promise to his mother
and modified his answer.
“Sure, I’ve been on platforms and they’re the same as stages,” he
said; “only they’re kind of different. When we get our awards we
have to go on platforms. Do you think I’m scared of audiences? Gee
whiz, they won’t hurt you. I’m not even scared of bears and they’re
not as bad as audiences, that’s one thing sure.”
“But I mean a regular stage,” chirped Sympathea, “with woods
painted in back and everything.”
“I’ve even been lost in the woods,” Pee-wee announced proudly.
“Do you think I’m scared of painted woods? You can’t get lost in
those. I’ve been—I’ve been—famished in the woods, when I was
lost.”
“I thought scouts never got lost,” Miss Dorothy Docile carolled
forth.
“That shows you don’t know anything about them,” Pee-wee said
disdainfully; “they know all about getting lost; they get lost better than
anybody else. Then they find their way out by resourcefulness. Do
you know what that means?”
“Isn’t that perfectly wonderful?” said Miss Katherine Kindheart.
“That’s nothing,” Pee-wee said; “you go around in a circle when
you get lost; do you know why?”
“No, do tell us.”
“Because your heart is on your left side. You have to know all
about astronomy if you’re a scout.”
“That isn’t astronomy, that’s anatomy,” said Cousin Prudence.
“Woods is my middle name,” said Pee-wee.
“Isn’t that a perfectly lovely name?” said Sympathea. “Walter
Woods Harris.”
“I don’t mean it’s really my middle name,” Pee-wee said. “Suppose
I was crazy about mince pie. I’d say my middle name was mince pie,
but it wouldn’t be Pee-wee, I mean Walter Mincepie Harris, would it?”
“And do you really go round in a circle when you get lost?” Cousin
Prudence asked him.
“S-u-re,” said Pee-wee conclusively, “your left side goes ahead of
your right side—”
“And what becomes of your right side?” Katherine asked.
“It comes along after your left side,” Pee-wee explained.
“And doesn’t it ever, ever catch it?”
“No, so that’s why you go round in a circle; see? Now I’ll close my
eyes and try to go straight. I’ll show you.”
 The demonstration of this item of scout lore was highly
satisfactory and very scoutish; for scouts are supposed to smile and
Pee-wee’s escort of honor did more than that, they screamed.
Closing his eyes, Pee-wee strode forward verging more and more
toward the curb until he stumbled and went head over heels into the
gutter, where his feminine admirers gathered about him, clamoring to
aid the hero.
Pee-wee was equal to the occasion. “A scout is supposed to
spread mirth,” he said, rising and brushing the mud from his regalia.
He had certainly spread mirth as thoroughly as the mud was spread
upon his scout uniform. “I’ll tell you something else about anatomy
too,” he said. “Just then when I fell down in the mud it reminded me
of it. Do you know how many muscles it takes to make a smile?”
“No, do tell us,” said Cousin Prudence as she brushed him off,
laughing uncontrollably.
“Thirteen,” said Pee-wee.
“No wonder you were unlucky,” said Sympathea, shaking with
laughter.
“It takes sixty-four muscles to make a frown,” Pee-wee continued.
“So you’re doing a lot of extra work if you frown,” he added, pulling
up his torn stocking.
The girls’ Humane Committee must have been of an economical
turn, for they did not use sixty-four muscles, or anything like that
number. They roared and screamed, and held their sides and
brushed him off and readjusted his official junk upon his diminutive
person, and just kept on laughing and laughing and laughing.
 CHAPTER V—HE STORMS THE INNER
FORTRESS
Having risen from the gutter like so many world heroes who began
as poor boys, Pee-wee proceeded to expatiate on the honorable
company which had come out of that lowly and muddy abode into
the dazzling halls of fame.
“That’s where Mr. Temple began who started Temple Camp,” he
said. “Wait till I see if I’ve got my money all right; I’ve got seven
dollars and fifty-two cents not counting my ticket because my father
paid for that. I’ll treat you all to sodas.”
“Oh I just couldn’t eat a thing while I’m laughing so,” Miss Dorothy
Docile explained; “thank you just as much.”
“Can’t you eat when you’re laughing?” Pee-wee asked
incredulously.
“No, can scouts eat while they laugh?”
“S-u-re, they can eat while they’re sleeping even. If you dream
about eats they taste just as good don’t they?”
“Can they eat while they’re going around in a circle?” Sympathea
asked mischievously. “You know we’re girl scouts, but we really don’t
know much about girl scouting, because we’ve only just started.
Don’t you think our Black Beauty award is a splendid idea?”
“Sure, I have lots of dandy ideas,” Pee-wee said; “but anyway
you’ve got a right to kill snakes—snakes and mosquitoes. But I
haven’t got any right to kill a lion.”
“Oh, I hope you never did that,” said Cousin Prudence.
“Sure I didn’t,” Pee-wee assured her.
If any proof of his courage was required, he gave it in his martial
advance up the wide, old-fashioned, thickly carpeted stairway which
led to the inner fortress where Aunt Sophia Primshock sat bundled
up in a big wheel chair. No weapon had she but her spectacles, but
she used those in such a way as to make her terrible to behold. Her
eyes made sudden flank movements around the side of them; they
went “over the top” as well; and peered straight through them in a
way of terrible scrutiny.
Aunt Sophia Primshock had all kinds of money and several
different kinds of rheumatism. As fast as there was a new kind, she
secured it. She was very deaf, but not too deaf to hear Pee-wee. It
was not quite as bad as that. Next to her collection of rheumatics
was her collection of cats. In the august presence Pee-wee now
appeared in all his scout glory—marred only by a hole in his stocking
—followed by Cousin Prudence.
“I am very glad to see my nephew,” said Aunt Sophia, as Pee-wee
advanced to receive her kiss, “and I am not only glad but proud to
call him my nephew,” she added. “I don’t know much about this
scouting, I’m afraid it makes boys a little wild. But when a boy
registers his friendship for dumb creatures I am proud, more than
proud, to call him my nephew. You have seen the girl’s committee?
They are dear, sweet girls, all of them.”
“Oh yes, he fell for us, Mother,” said Prudence.
“Fell for you?”
“Yes, he fell all over himself, but he isn’t hurt.”
“And what is better still, he would not inflict any hurt,” said Aunt
Sophia. “And what a fine boy he is, eh Prudence? A splendid, kind,
humane boy, with a heart—”
“On his left side, Mother,” said Prudence; “he proved it to us and
we know he has a heart.”
Aunt Sophia smiled indulgently. Like most persons who are under
the spell of one idea she was not even curious about matters in
general. It was perfectly evident that she had captured the helpless,
struggling, little Girl Scout troop and turned it into a humane society.
There was no doubt that the “committee” had originated in that
solemn apartment.
“You can kill snakes because they kill birds,” Pee-wee said; “and
cats kill birds too.”
There was no answer to this so Aunt Sophia said, “I was so happy
when I heard—saw it printed in a newspaper—that my nephew had
won the badge for first aid to dumb creatures.” (Aunt Sophia always
called animals dumb creatures.) “That is better than running after
circuses and going to—to shows. Isn’t it? I had a brother, a very dear
and promising brother, many, many years ago, and he joined a
troupe of play actors, which made his poor mother very, very sad.”
Pee-wee wriggled nervously but listened with respect. “The scout
boys, they don’t—they don’t fill their brains with—with wild west
shows? What is that you have there?”
“That’s my handbook, and this is my scout report book,” Pee-wee
exclaimed, glad enough to expound the ins and outs of scouting.
“Ah yes, and if you do a kind act you jot it down?”
“Sure.”
“Let me see them,” said Aunt Sophia holding out her hand; “my
arm is very stiff. Did you bring me my tea, Prudence dear?—I eat
very little and go about almost none at all. I am very, very stiff.”
“That’s because you don’t sleep outdoors,” Pee-wee said. “I bet if
you went scout pace you wouldn’t be stiff. Do you want me to show
you how?”
“Goodness gracious no, my dear! Let me see what is in the books
—”
“Rolling down hills is good too,” said Pee-wee; “I bet if you try that
you won’t be stiff. Lots of scouts roll down in barrels, because that
shakes them up. I’ll get a barrel for you if you want to try it.”
Aunt Sophia did not want to try it, but she was presently to be
shaken up in quite another way. Gazing with increasing severity
through her spectacles she saw sprawled upon the page the
dreadful words.

If any hop-toad can’t learn the pace he has to have his legs
tied together for an hour.
Every feller that gets a new hop-toad gets a piece of
chocolate—
If a hop-toad can’t croak like a frog he has to be turned over
on his back and somebody sit on him till he croaks.
 Aunt Sophia looked up, dumbfounded, speechless. She
readjusted her spectacles, as if even they might be deceiving her,
and read:

A hop-toad has to be given to the tom-cats—

She read no more. Rather she saw the page in a kind of trance.
Her astonished eyes jumped from one blood-curdling memorandum
to another, picking out the more heartless words and phrases. Given
to the tom-cats ... chased the Robins away ... turned on his back till
he croaks ... hop-toads ... sticks in their mouths....
Horrors, oh horrors! Here before her very eyes was a series of
recipes for cruelty! Directions, suggestions, memorandums written in
cold blood for the torture of hop-toads!
Pee-wee sensed the situation, but it was too late. The hop-toads
were already on their backs, the sticks were in their mouths, they
were croaking, or being fed alive to tom-cats, the robins had been
chased from their nests and their little ones, the boys were standing
around eating chocolate while the toads suffered, the massacre was
on.
“I’ll tell you all about it,” Pee-wee said, facing the awful face of his
outraged aunt. “You see hop-toads, they’re really not hop-toads; do
you see?”
“I do not see,” said Aunt Sophia.
“I’ll tell you all about it. Scout patrols are named after animals;
there’s a patrol at Temple Camp named the Robins, see? My new
patrol is going to be named the Hop-toads, because they’re all going
to be good at scout pace, see? Gee whiz, you don’t care if we make
fellers hold sticks in their mouths, do you? Because they can run
better that way. A hop-toad means a—a scout. I’m a hop-toad.
Maybe I don’t look like one but I am.”
Aunt Sophia was just about convinced—by a very, very narrow
margin. She was convinced, but she remembered the awful things
upon that fly-leaf. She was still a little, just a very little, suspicious.
But she accepted Pee-wee’s explanation....
 CHAPTER VI—CARRIED BY A MINORITY
That same memorable Saturday was the day on which Pee-wee’s
troop was to go to its summer quarters at the beloved Temple Camp.
As every scout knows, Temple Camp is a little in from the Hudson
River in the neighborhood of Catskill.
North Deadham is about thirty-five miles north of Bridgeboro.
Roughly speaking, North Deadham would be on a line between
Bridgeboro and Temple Camp. The brilliant idea of spilling the beans
in North Deadham is attributable to Artie Van Arlen, patrol leader of
the Ravens—Pee-wee’s own patrol.
“What do you say if two or three of us start hiking on Friday and
camp along the way and bang into North Deadham in time to foil our
young hero?” said Artie. “Foiling is his middle name, so we’ll try a
little of it. Then we’ll wrap him up and take him along to camp with
us. What do you say?”
“You mean hike all the way?” asked Connie Bennett of the Elks.
“Sure.”
“Declined with thanks,” said Connie. “Let him stay there a while.
What’s the use of starting out hunting for trouble? He’s wished onto
the Ptomaine Committee or whatever they call it; let them worry for a
while.”
“Anybody in the Silver Foxes want to hike it?” Artie asked.
“We promised Mr. West of the West Shore Railroad, we’d go that
way,” said Roy; “we can’t break our words. The train will be waiting
for us.”
“Some scouts!” said Grove Bronson of the Ravens.
“I’d just love to stop at North Deadhead for our young hero,” said
Hunt Ward of the Elks, “but you know how the directors of the
railroad would feel.”
“Sure, a scout’s honor is to be trusted,” said Roy.
 “How about his feet?” Artie shot back. “Can you walk from the
station to the train? You make me tired, you fellows.”
“If you’re so tired what do you want to hike for?” Roy asked.
“You’re so wide awake and full of pep, what do you want to go to
Fried ham or Dead-ham for? I should worry about Deadville or
whatever you call it. Right away when we get rid of Pee-wee you
want to go and get him. They’ve just had whooping cough at Temple
Camp; isn’t that bad enough? The raving Ravens are raving again,
no wonder the railroads are losing money with the Raven Patrol
walking all over the country.”
“Who’ll volunteer?” Artie said.
“A large chunk of silence,” said Roy.
“I won’t,” called one.
“Neither will I,” shouted another.
“Not for mine,” piped up a third.
“We’ll all volunteer not to hike,” said Roy. “Let the scouts in the
books do the hiking.”
“I will,” said Grove Bronson.
“He hasn’t got the railroad fare,” shouted Roy.
“All right,” said Artie, “you and I’ll hike together, Grove; we’ll take
the north turnpike—”
“Be sure to put it back when you get through with it,” said Roy,
“and give our kindest regards to the animated animal cracker and if
you’re going to hike from Deadtown to camp the best way is to follow
the Franklin Turnpike as far as Idaho and take the second turn to
your left. That’ll take you into the Great Salt Lake. Don’t hurry, take
your time.”
“The pleasure is ours,” said Artie.
“If you don’t get to camp till next summer it’ll be all right,” said Roy.
“Tell Pee-wee he’ll find us near the lake and we hope he’ll drop in.”
 CHAPTER VII—MENTAL TELEGRAPHY
Thus it happened that while Scout Harris, friend and champion of
the dumb creatures, was preparing to receive the tribute that was
due him, two scouts of his patrol were tramping along the dusty road
as the sun went down, on the last part of their long hike to North
Deadham. They crossed the frontier of the village unnoticed. The
only sentinel there was a rooster on a fence and he was asleep at
his post, or rather his perch.
The invading column passed through McCrockett’s Lane and
rested under a weeping willow tree, where they kindled a little fire
and brewed some coffee and fried some bacon. If the weeping
willow could but have known their business it would have laughed
rather than wept.
Their supper finished, the invaders trampled the fire out and
played mumbly peg under the tree just as if nothing were going to
happen. Scout Harris said afterward that just at that time (seven
thirty) a strange desire for fried bacon came over him and that he
smelled coffee. Thus soul speaks to soul across space in the mystic
realm of scouting!
At exactly eight o’clock by a cow-bell in a neighboring field,
verified by their own trusty scout watches, the invaders followed a
northwesterly course through the village square into Gordon’s Hollow
and thence to Main Street and to a certain commissary where they
made ready for the terrible work in hand by two stimulating ice cream
cones, which sent the blood coursing through their veins and gave
them strength and courage.
Passing the district school with great caution they succeeded in a
skilfully conceived flank move around the entire police department,
who was standing on a corner talking with an unsuspecting citizen.
This was at exactly seven minutes after eight by the town hall clock
which wasn’t going, no doubt in honor of the great occasion.
 Singular to relate, at precisely four minutes after eight by Pee-
wee’s reliable scout watch, and just as he was starting with his
cousin Prudence for the church lecture hall, he was conscious of a
shivering and decided to return and get his scout jacket. It was at
that very moment that the invading legion partook of ice cream
cones. Perhaps it was only a coincidence but so strong was the
thought of ice cream cones in Pee-wee’s mind that he bought two
(treating his cousin Prudence) on their way to the church. A most
singular and harrowing thing to relate is that these two separate
parties almost met in Pop Carroway’s Candy Parlor.
The lecture room of the church was ablaze with light from eight
kerosene lamps. One of these had a reflector on it, to be used
perhaps as a sort of spotlight on the hero’s entrance.
Aunt Sophia, by reason of her collection of aches and pains, did
not attend this gala meeting. She stayed at home with her cats. But
the minister was there and the Girl Scouts from South Deadham and
Deadham Centre were there.
This gay outpouring of nearly fifty people was not exactly in honor
of Pee-wee. It was a Girl Scout rally intended to stir up interest in the
local movement. But since Pee-wee, like a true scout, was always
prepared to take whatever came along, he appropriated all the stray
glory that was floating around.
Being the only boy in town, he was something of a lion and was
viewed with becoming awe by the spectators as he sat wedged in
between his cousin Prudence and one of the other girls on the
platform. His martial appearance was somewhat modified when he
pulled up his rebellious stocking, but his frown was terrible and his
belt axe was so skilfully displayed as to strike dismay to the most
courageous heart.
His nine merit badges (the final badge still lacking) were revealed
upon his sleeve. He and the two maidens who flanked his sturdy
form occupied but two chairs and from the rear of the little meeting
room Artie Van Arlen and Grove Bronson, lurking there unseen,
beheld the picture of these three as a sort of human sandwich (the
kind sold at railroad stations) with the middle part of almost
microscopic proportions. All of the valor in Scout Harris’s diminutive
body seemed to be squeezed up into his head by the flanking
pressure of his feminine hostesses and he gazed out upon the
assemblage, silent, uncomfortable, terrible.
The organization business of the evening being concluded and a
couple of songs about the woods having been sung, Miss
Sympathea Softe arose, replaced a straying lock of hair with skilful
daintiness, wriggled a little with becoming stage fright, and
proceeded to explain the happy idea which the Girl Scouts had hit on
in the Black Beauty Award.
 CHAPTER VIII—A PREDICAMENT
“Humanity and kindness,” she said in finishing, “are as broad as
the skies. So we planned not to confine our award to our local circle
or even to Girl Scouts everywhere. There are Boy Scouts as well
and we must not forget them.”
“There are more of them than there are Girl Scouts,” Pee-wee
spoke up, “because I can prove it—”
“And their activities are reported in newspapers throughout our
country—”
“They’re in Boys’ Life too,” Pee-wee announced vociferously, to
the great amusement of the audience.
“The Boy Scouts,” continued Sympathea, “have an award called
the First Aid to Animals Badge. It is the intention of our little troop to
tender the Black Beauty Cross to every scout winning that award.
The first one that we are going to honor is the cousin of one of our
members, Prudence Primshock; a scout from Bridgeboro, New
Jersey, a star scout who has won the badge that stands for
humaneness in his troop—Walter Mincepie Harris—”
“Good night, he’s disguised as a mince pie,” Grove whispered to
Artie; “the plot grows thicker, as Roy would say.”
“Excuse me,” said Sympathea blushing, “I mean Walter Woods
Harris. I’m just a little nervous and (great and reassuring applause) I
hardly know what I’m saying. We all know that Boy Scouts are
heroes, that their hearts are always on the left, I mean on the right, I
mean they’re in the right place. Walter—Scout Harris, will you please
stand up and—”
“Hold while there is yet time!” came a voice from the rear of the
little lecture room. “Water Mincepie Harris is not what he seems! He
has disgraced the beloved mince pie and he is trying to deceive you
all!”
“It’s Grove Bronson!” shouted Pee-wee, jumping from his seat.