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J.

SMIT

H.P.J.WIJN

Z
I
>3?-2i+tal-3-|

FERRITES
PHILIPS' TECHNICAL LIBRARY

About the book


In recent years

much

effort

has been
i.e.

put into research

on

ferrites,

ferromagnetic
their

oxides with iron as

main metallic component. This


resulted
in

has

many

interesting

and also
devices.

essentially

new applications

About ihe authors


J.

of magnetic materials to electrical

Due

to this research,

many
better

Smit and H.

P. J.

Wijn are both


the Research

properties of ferrites are

now

Research Physicists
Laboratories

in

understood than corresponding properties of metallic ferromagnetics.


Tn this book the characteristics of ferrites that are of importance for
application

of the

N.V.
in

Philips'

Gloeilampenfabrieken

Eindhoven,

Netherlands. Dr. Smit received his


physical
Delft in

purposes are presented

and discussed and, whenever possible,

engineering

degree

from
in
in in

explained

in

terms of intrinsic
in

1948 and his doctorate

properties.

These properties are


in

physics from

Leiden University

turn

treated

relation

to

the

chemical
structures

1956. Dr. Wijn took his degree

composition
of
the

and

crystal

materials.

The

physics in 1948 at Utrecht University

authors deal with


occurring

many

actual pro-

and

his doctorate at

Leiden

in

blems of the theory of phenomena


in

1953.

various

processes
is

of

magnetization. The subject

treated

on an intermediate
use
is

level

and more
physical

made of
than

simple

models

of rigorous

mathe-

matical derivations.

wags*

.'

PHILIPS

TECHNICAL LIBRARY

FERRITES

Distributors for United

Kingdom and
Ltd.

Eire:

CLEAVER-HUME PRESS
31, Wright's

Lane, Kensington, London, W.8.

FERRITES
PHYSICAL PROPERTIES OF FERRIMAGNETIC OXIDES
IN

RELATION TO THEIR TECHNICAL APPLICATIONS


BY

J.

SMIT
J.

AND
H. P.
PHILIPS

WIJN

RESEARCH LABORATORIES GLOEILAMPENFABRIEKEN EINDHOVEN - THE NETHERLANDS


N.V. PHILIPS'

1959

PHILIPS'

TECHNICAL LIBRARY

2.72-0

&3

HARRIS

COLL GE

PRESTON

*H7

c
Translated by: G. E. Luton, Eindhoven

Publisher's note:

This

book

is

published in English,

German and French

editions

U.D.C. Nr. 538.221:621.318.124

This

book contains 384

pages, 244 illustrations

N.V.

Philips' Gloeilampenfabrieken,

Eindhoven (Holland). 1959

This book or any part thereof must not be reproduced in any form without the written
permission of the publisher
Printed in the Netherlands
First published in 1959

The information

given in this

book does not imply freedom from patent

rights

S.

L,

SNOEK

(1902-1950)

Foreword
The most important advances made in ferromagnetism in the years since war have been in the field of magnetic oxides. Their development into
was
initiated

the last

useful materials

by the work of the

late J. L.

Snoek. The rapid

expansion of technology, especially high-frequency engineering, has been

a great stimulus to research on ferromagnetic oxides. Conversely the im-

provement of the

characteristics of these materials has

refined applications possible.

Much

progress has been

made increasingly made towards the

development of a theoretical description of the magnetic properties of these


oxides. In this respect the
tance.

work of L. Neel has been of fundamental imporAt the present time many of the properties of magnetic oxides are better

understood than the corresponding properties of metallic ferromagnetics.

For example the magnitude of the saturation magnetization of an oxide


with given chemical composition can be predicted far more accurately than
that of a metal or alloy.

The

original literature in this

new

field is

voluminous and readily acces-

sible (it is to

be found for example in the proceedings of the numerous con-

on magnetism of recent years). However, the authors felt that a definite need exists for a book which treats the subject of ferrites on an intermediate
ferences
level.

The term ferrites

will

be used to refer to

all

magnetic oxides containing

iron as major metallic component. This


this

book

represents an attempt to meet

need and to provide readers in an informal way with an insight into

the basic properties of ferrites.

The treatment

is

not exhaustive as regards

either the subject matter presented or the rigorousness of the theoretical devel-

opment of
authors.

basic concepts.

The

selection of material

and manner of presenand viewpoint of the

tation have been governed

by the

special preferences

The reader

will perceive that

some emphasis has been placed on work


is

carried out in the Philips Laboratories. If history


fication for this fact,
it

not a sufficient

justifirst

may

be recognized that the authors have

VIII

Foreword
these particular investigations

band information about

and thus should be

in a position to undertake a lively

and penetrating discussion of them.


details is

thorough familiarity with the experimental


since

of especial importance
their exact chemical

many properties of the ferrites strongly depend on

composition and microscopic physical structure. These factors in turn are


determined by the method of preparation.

The book
book

is

intended for

all

those
is

who

are actively interested in the

properties of ferromagnetic oxides. It


will enable

hoped that the arrangement of the


group, whatever his line of
interest to him.

any member of

this large

specialization, to find
c.g.s.

some chapters of special


is

The

practical

system of units

employed, that

is,

the various parameters are

expressed in terms of cm, ampere, volt, oersted, gauss and erg.


are indebted to
ries,

The authors

many

of their colleagues at Philips Research Laborato-

for useful criticism

and suggestions,

in particular to Dr. E.

W.

Gorter

and Dr. G. H. Jonker. The manuscript has been translated


acknowledge.
J.

into English

by

Mr. G. E. Luton, whose pleasant cooperation the authors


Smit

gratefully

H. P.

J.

Wijn.

May

1959

CONTENTS
Part A. Theory
Page
Chapter
I.

ON THE PROPERTIES AND THE ORIGIN OF


MAGNETIC FIELDS IN MATTER
The Magnetic Field
Energy of the Magnetic Field The Nature of Magnetic Moments
3.1.
3.2.
1

1.

2.
3.

4
6 7

Spin moment

Quenching of the orbital angular momentum


Absolute magnitude of the angular momenta

.... ....

9
11

3.3. Spin-orbit Interaction 3.4.

13

Chapter

II.

THEORY OF FERROMAGNETISM
Diamagnetism, Paramagnetism and Ferromagnetism Exchange Interaction
Statistical
6.1. 6.2. 6.3. 6.4.
. .

4.
5. 6.

15 17 18

Theory of Magnetism
.

Langevin's theory ofparamagnetism

18

Weiss field theory offerromagnetism Paramagnetism above the Curie point


Criticism of the Weiss field theory

20 24 24
27 27
28

7.

Caloric Properties
7.1. Specific
7.2.

heat

Magnetocaloric effect

Chapter

III.
8.

FERRIMAGNETISM
Origin of Ferrimagnetism
8.1. Indirect

30 30 32

exchange interaction

8.2.
9.

Spin order

Weiss Field Theory Applied to Ferrimagnetism


9.1. 9.2.

....

34 34
38

Stretched configuration
Triangular configuration

10.

Paramagnetism above the Curie Point

42

Chapter IV.

MAGNETIC ANISOTROPIES
46
46
cubic crystals
11.1. Magnetocrystalline anisotropy

11. Description of Magnetic Anisotropics


11.2.

Induced uniaxial anisotropy

in

...

50

X
12.

CONTENTS
Origin of Crystal Anisotropy
12.1. Dipole-dipole interaction

52 52 54
55 55 57

12.2. Spin-orbit interaction


13.

Magnetostriction
13.1. 13.2.

Volume magnetostriction
Linear magnetostriction

Chapter V.
14. 15.

MAGNETIZATION PROCESSES
Weiss

Domain

Structure
wall)
.

60

The Domain Boundary (Bloch


Magnetization due to
16.1. Permeability
16.2.

64
.

16.

Domain Boundary Movement

69 69
73

Coercive force

17.

Magnetization due to Rotation of the Magnetization


Vector
75

X Chapter

VI.

DYNAMICS OF MAGNETIZATION PROCESSES


Ferromagnetic Resonance Conditions
18.1.

18.

78
.

Resonance

in

uniformly magnetized ferromagnetics

78

18.2. Influence

of the

Weiss domain structure on the

resonance conditions
18.3.

82 84 84
88
91

Magnetostatic modes

19. 20. 21. 22.

Ferrimagnetic Resonance
Spectroscopic Splitting Factor

Rotational Susceptibility

Wave
22.1.

Propagation in Magnetized Media

92 92
95

The wave equation


waves

22.2. Electromagnetic waves


22.3. Spin 23.

97
100
.
. .

Damping
23.1. General Properties 23.2. 23.3.

of complex susceptibility Phenomenological description of damping


theory

100

102
103

Damping

23.4. Instability at large amplitudes 24.

106
wall)

Dynamics of Domain Boundary (Bloch


24.1.

Movement

107

Wall

inertia

107
108

24.2.
24.3.

Damping of the wall movement


Wall resonance

110

CONTENTS
Part B. Measurements
Chapter VII.

XI

METHODS OF MEASURING FERROMAGNETIC


PROPERTIES
Measurement of Magnetization method 25.2. Methods utilizing the force
25.1. Inductive

25.

Ill Ill
acting on a body in a

non-uniform field
26.

115

Measurements of Magnetocrystalline Anisotropy Energy 116 26.1. Measurement of magnetic energy 116 26.2. Torque method 117 26.3. Torsion pendulum method 118
26.4. Determination

of crystal anisotropy from ferro119

magnetic resonance
27.

Magnetostriction
27.1. Displacement 27.2. Strain 27.3. Stress

119

measurements

119

measurements measurements
Initial

120
121

28.

Methods of Measuring Complex Various Frequency Ranges


28.1. Influence
bility

Permeability in
121

of demagnetization on the apparent permea121

28.2. Bridge 28.3.


29.

methods at lower frequencies

123

Wave methods at higher frequencies Loss Phenomena Related to the Dimensions of


Specimen
29.1. Skin effects
29.2.

127
the

132

and dimensional resonances

132 134

Eddy

current losses

Part C. Intrinsic properties


Chapter VIII.

INTRINSIC PROPERTIES OF FERRITES WITH SPINEL STRUCTURE


136 137
cell

30.
31.

Chemical Composition
Crystal Structure
31.1.
31.2.

Elementary

of the spinel The oxygen parameter u

lattice

137 139

31.3. Distribution

of the metal ions over octahedral and


140
145

tetrahedral sites
31.4. Ordering

phenomena

XII
32.

CONTENTS
Saturation Magnetization
32.1.

147

Magnetic ordering and saturation magnetization at

0K
32.2.

147

Temperature dependence of the saturation magnetization

155

33.
34.

Paramagnetism above the Curie Point


Crystal Anisotropy
34.1.
34.2.

160

162
162
165
168
171 171

Cubic crystal anisotropy

Induced uniaxial anisotropy


Properties

35. 36.

Linear Magnetostriction

Dynamic
36.2.

36.1. Induced ferromagnetic resonance

Domain

wall relaxation

175

Chapter IX.

INTRINSIC PROPERTIES OF FERRITES WITH

HEXAGONAL CRYSTAL STRUCTURE


37.

Chemical Compositions and Crystal Structures


37.1. 37.2. 37.3. 37.4.

177

Chemical compositions

177
179

Hexagonal close-packed structure


The magnetoplumbite structure Crystal structure of the compound

180

37.5.

Y = 5a2 Me 2.Fei2022 Mixed compounds

184 186 189


191
interactions
in

37.6. Identification of the hexagonal oxides

38.

Saturation Magnetization
38.1.

Predominant

superexchange

the

various structures
38.2. Saturation

191

magnetization

of compounds with of compounds with of compounds with of compounds


with

M
193

structure
38.3. Saturation

magnetization

W
194

structure
38.4. Saturation

magnetization

Y
196

structure
38.5. Saturation

magnetization

Z
198

structure
39.

Crystal Anisotropy
39.1. Binding

202
to the c axis

of the magnetization
the basal plane

202
208

39.2. Anisotropy in 39.3. Origin

of crystal anisotropy

in

hexagonal oxides

210

CONTENTS
Chapter X.

XIII

INTRINSIC PROPERTIES OF FERRITES WITH

GARNET STRUCTURE
40. 41. 42.

Chemical Composition and Crystal Structure


Saturation Magnetization
Crystal Anisotropy
perties

212
212

and Ferromagnetic Resonance Pro214

Part D. Polycrystalline Ferrites


Chapter XI.
43.

STRUCTURE OF POLYCRYSTALLINE FERRITES


Isotropic Samples
43.1. Preparation 43.2.

216 216
221

Phase diagrams
Mechanical properties

43.3. Internal demagnetization 43.4.


44.

223

224
225

Crystal Oriented Samples

Chapter XII.
45. 46.

ELECTRICAL PROPERTIES
D.C. Resistivity 229 Frequency-Dependence of Conductivity and Dielectric Constant 236
46.1.

Experimental results

236
241

46.2.

Phenomenological theory

Chapter XIII.
47.

STATIC INITIAL PERMEABILITY

Static Initial Permeability at

Room Temperature ....


. . . . .

243 243

47.1. Ferrites with isotropic rotational permeability

47.2. Ferrites with anisotropic rotational permeability


48.

247 250

Temperature Dependence of Initial Permeability


48.1. Ferrites with spinel structure
48.2. Ferrites with

....

250 257
260 260 on the 262
265

hexagonal crystal structure

49.

External Influences

on the Permeability
a biased state
stress

49.1. Reversible permeability in

49.2. Influence
initial

of unidirectional mechanical

permeability

49.3.

The

initial

permeability as dependent on the method

of demagnetization
49.4. Stability

of the initial permeability

266

XIV
Chapter XIV.

CONTENTS

FREQUENCY-DEPENDENCE OF THE INITIAL


.

PERMEABILITY
50.

Magnetic Spectrum of Ferrites with Spinel Structure


50.1. Dispersion 50.2.

268

frequency

268

51.

276 Width of the dispersion region Magnetic Spectrum of Hexagonal Ferrites with the Basal
Plane as the Preferred Plane of Magnetization

278
axis

52.

Magnetic Spectrum of Hexagonal Ferrites with the c


as the Preferred Direction of Magnetization
Effect of Mechanical Stresses

283

53.
54.

on the Spectrum
losses

....

287
289 289

Relaxation Losses
54.1. Identification
54.2.

of relaxation

Phenomenological
process

description

of

the

relaxation

290
292

54.3. Relaxations in ferrous ferrites

55.

Induced Ferromagnetic Resonance

297

Chapter XV.
56.
57. 58. 59.

STATIC HYSTERESIS LOOPS


Coercive Force
301

60.

Remanent Magnetization Constricted Hysteresis Loops and Magnetic Annealing Effect of Uniform Mechanical Stresses on the Form of the Hysteresis Loop Permanent Magnets
.

306

310
317 319

60.1 Figures

319 of merit for permanent magnets 60.2 Permanent magnetic properties of hexagonal oxides 321

Chapter

XVI.

DYNAMIC PROPERTIES AT HIGH FIELD


STRENGTHS
and Distortion in the Rayleigh Region 327 327 and distortion
330
.

61.

Hysteresis Losses

61.1. Hysteresis resistance

61.2. Hysteresis constants 62.


63.

Frequency-Dependence of the Magnetization Curve


Ferrites
63.1.

333 338 338


341

under Pulse Conditions The shape of the pulse response curves

63.2. Switching times

64.

Total Losses

346
348

REFERENCES INDEX

365

CHAPTER

ON THE PROPERTIES AND THE ORIGIN OF MAGNETIC FIELDS IN MATTER

1.

The Magnetic

Field
electric currents.

A magnetic field is

produced by
is

The magnetic

field inside

a toroid or long solenoid

0.4

it

ni

and zero outside it. The field is here expressed in oersteds, the current i in amperes and the length / in cm; n is the number of turns. For a circular
current
i

with area

the magnetic

moment
iA.

is

defined as
(1.2)

M
This
is

= 0.1
is

because the magnetic

field at

a distance many times greater than

the radius of the circular current

equal to that of a mathematical dipole

with a magnitude given by (1 .2). Multiplying the numerator and denominator


in (1.1)

by

A and

then applying

(1.2),

we see that

the field (1.1) can also be

expressed in the magnetic

moment

per turn ^:
(1.3)

H=4n-
where

V is

the

volume of the solenoid.

In matter, atomic circular currents


ized by the magnetization

may occur. Their strength is characterM, which is the magnetic moment per cm3 Accor.

ding to

(1.3), then,

matter can provide an extra contribution to the

field

of

#mat

= 4irM.

(1.4)
is

One can

also say that a magnetization

equivalent to a

number of

ampere turns

(-)
V I

=10M.

(1.5)

/mat

The

is only an averaged field; in reality there will be conon an atomic scale. The total field arising from macroscopic currents (Ho) and microscopic currents together is called the induction

field

given by (1.4)

siderable fluctuations

B, so that for a toroid the induction in matter

is

B = Ho + 4wM.

(1.6)

PROPERTIES
is

AND THE ORIGIN OF MAGNETIC


is

FIELDS

[CH.

expressed in gauss, a unit which

exactly the same, however, as the

oersted.

The given derivation of (1.6) is valid only for a toroid or an infinitely long bar. If we compare a finite piece of matter, for example, an ellipsoid, with an infinitely long bar of the same cross-section (Fig. 1.1) we see that in the

Fig.

1.1.

Magnetized rotational

ellipsoid

com-

pared with a magnetized bar of infinite length (dashed). In the latter there are only internal lines

of force; with the ellipsoid the

lines are closed

around
arrows)

it.

The

stray fields

and the

internal de-

magnetizing

field (in

the opposite direction to the

may

also be

assumed as originating from

the fictitious poles

(+ and

at the ends.

ellipsoid the field

bar is

due to the (microscopic) "ampere turns" of the rest of the missing. This field would undoubtedly have been in the direction of the

magnetization.

On the

other hand, the field outside the ellipsoid

is

not zero;

we

find there the fields of the magnetic

are not cancelled out by those of the


lines

moments in the ellipsoid which now moments of the rest of the bar. The
field
it,

of force around the ellipsoid are closed loops. Leaving aside the
(1.6)

Ho, equation

would give

B=

47rMin the

ellipsoid

and zero outside

and does not apply. We correct this equation by introducing an extra field Hd. In matter, Hd is called the demagnetizing field, because it is usually opposed to the magnetization; outside matter it is usually called the stray
field.

In

all

we have

B=
Since the normal

H + HD + 4*M = H + 4irM.
Bn
,

(1.7)

component of the induction,

is

equal at both sides

of each surface element (continuity of the magnetic flux) the normal component of Hd makes at the edge of the specimen a jump of the magnitude 4irMn This makes it possible to compare Hd with the electrostatic field arising from electric charges. The charges are here fictitious magnetic sur.

face charges of the magnitude

= AM

(1.8)

1]

THE MAGNETIC FIELD

per

cm 2 where AMn is
,

the jump in the normal

tion (see Fig. 1.1). Positive

component of the magnetizaand negative charges are called north and south

poles respectively, and they are always present in equal quantities. If the

magnetization

makes no contribution
magnetic
field

not uniform, poles also appear inside the specimen. D to the integral of the tangential component of the along a closed curve:
is

Hm d/ = 0,

(1.9)

because the contributions of the atomic circular currents are cancelled out

by those of AttM
the

in the integral of the total field along a closed path.

For

H field of (1.7) we may therefore write

Hidl

= 0.4imi

(1.10)

where

is

the enclosed macroscopic current.

5 3 2
0.1

N An 5

u
0.01

b\

a=b

3 2
0.001

i
k

5 3 2
0.0001
1

11 31

I>

no

;> 3?

i>

1C

<

_;

i>

m
needle)

%
Fig. 1.2.

Demagnetizing

coefficient N/4ir

of ellipsoid of revolution along

the major axis (a) as a function of the ratio of the length of this axis
to that of the

minor

axis

(c),

for prolate ellipsoids (b

c,

and oblate

ellipsoids (a

b, disc).

PROPERTIES
It

AND THE ORIGIN OF MAGNETIC

FIELDS
is

[CH.

appears that only in a uniformly magnetized ellipsoid

Hd

uniform

and equal to

(The minus sign

will to M.) In general, be smallest along the major axis, for there are then relatively fewer poles and moreover they lie farthest apart. The three demagnetizing coefficients (Nx z) of an ellipsoid y and
is

used

Hm = -NM. opposed because Hm


is

(1.11)

differ in the three principal directions,

and

will

satisfy

Nx + Ny + N = 4w.
z

(1.12)

Some examples
sphere
infinitely

for special ellipsoids are:

long bar

infinitely large flat plate

NX = N = N = 4tt/3 Nx = Ny = 2TT N = Nx = Ny = N =
Z
z

4tt.

Fig. 1.2

shows for

ellipsoids

of revolution the demagnetizing coefficients


as a function of the variable ratio of the

along the major axis

(a) plotted

major to the minor axes


zing
field. It

(a/c) as derived

by Osborn [Os

1].

A uniformly magnetized ring has no demagnetihas, however, if the ring


8,
is

broken by

an

air

gap of width

which we assume to be

small compared with the thickness of the ring


(see Fig. 1.3). Since

Bn

is

continuous, the

field in

the

narrow gap

is

tion

in the material. If
it

uniform and equal to the inducno macroscopic currents

are present,

follows from (1.9) that


8)

Hdl-

(HD

+ 4nM)S = 0.
Fig. 1.3.

According to (1.1 1) this corresponds to a demagnetizing coefficient


Wring/417

Ring interrupted

by an

air gap.

8/1

(8

<

/)

(1.13)

2.

Energy of the Magnetic Field


flux

change in the magnetic

gives rise to

an

e.m.f. in the

Bn dA surrounded by a closed turn winding equal to

d$
At

10-8 V olt

'

(2.1)

{Bn

is

the normal

component of

on an element dA of a

surface through

the winding.)

2]

ENERGY OF THE MAGNETIC FIELD

The presence of a magnetic field represents a certain quantity of energy, work is performed in building it up with the aid of currents through coils. The Lenz opposing forces, then, are caused precisely by the voltages
for

according to
supplied

(2.1). If

the current through the coil


is eiSt

is i

amperes, the energy


current
i

by the

battery in the time St


field

= 0.U8& erg. The


cm3

excites the

magnetic

Ho, and

it

may

easily

be seen in the case of the


in order to raise

solenoid, for example, that the energy required per

the induction in an arbitrary point by

SB is

equal to

W= Ho
for which purpose the scalar product

SB,

(2.2)

must be taken, i.e. the component of SB along Ho. The total change of energy is found by integrating (2.2) over space. In the absence of matter, it follows that the total energy density
per

cm3

needed for building up the

field is

W=^Hl
57T

(2.3)

For the case of matter being

present,

SB

consists of

SB
Since

SHo

+ SHD + 4ir&M.
i.e.

we

are interested only in the total energy change,

integrated
is

over the whole space, the term with

8Hn makes no

contribution. This

consequence of the general law in vector analysis that

J
where the vector a
closed surface
is

abdV=0
i.e.

(2.4)
if

divergence-free (no sources or sinks),

for each

J andA

= 0,

as holds for each

B field,

and where the vector

is

curl-free (no eddies),

i.e. if

for each closed curve jbi&l


fulfils this

= 0. According

to (1.9), every demagnetizing field


in (2.2)

condition.

As a consequence,

Ho may be replaced by the total field H. In our case, Ho is the divergence-free vector (Ho = Bin the absence of matter) and Hd is the curl-free
vector (see
(1.9)).

The work performed on matter by the current


SWmat

is

therefore
(2.5)

= HoSM.
calculate the total

By

integrating to

8M

in (2.5)

we can

be performed to produce the magnetization. For this know the relation between Ho and M. Now, in the case of ferromagnetics the value of is not determined by Ho but, as we shall see in Chapter V, by the field which consists of Ho and Hd together. Thus

that must purpose we must

work

S JFmat

= HSM - HD 8M,

(2.6)

PROPERTIES

AND THE ORIGIN OF MAGNETIC


solely

FIELDS

[CH

where

HBM does not depend upon the shape but


term of
(2.6) is the

upon the

material.

The

last

demagnetizing energy. This can easily be

calculated for an ellipsoid, since

HD = -NM which, after integration, gives (2-7) WA = WM*


era

of the ellipsoid. This energy therefore represents extra work to be more general expression for the demagnetizing energy, which performed.
per

cm3

also holds for arbitrary shapes,

may

8(B- Ho - Hd)
SHo

for

SM in

the last

be obtained by substituting (1/4tt) term of (2.6). The terms with SB and


contribution, according to (2.4), so

integrated over space

make no

that there remains

07T

which

is

comparable with

(2.3).

Equation

(2.7) is valid for

each point of

must be the ellipsoid, while (2.8) is valid for each point of the space and energy. The integrated over it in order to find the total demagnetizing
total field
field

energy

is

then given by an expression like

(2.3)

or (2.8) for the

H.
shall

We

now

consider the energy of a permanent magnetic dipole

in

a constant magnetic
magnetic
is

field H. When H, the work performed on the dipole, according to (2.5), this case, as with HSfi, where Sfi is the change, due to rotation, in p. In

a magnetic

moment

aligns itself in a

field

the force of gravity for example,

we can introduce a potential which is equal,


work performed on
the dipole

to within a constant, to the opposite of the

by the field during rotation of the vector. This then becomes

V = -fiH
and
is

(2.9

at

minimum if p and H are parallel;

this is the position

of equilibrium

of the dipole.

3.

The Nature of Magnetic Moments

In

we

calculated the magnetic field due to circular currents.

We saw that

in the example of an in finitely long bar a field 4ttM is directly associated with a magnetic moment per unit volume M, so that the circular currents

on which
. .

based can and must be omitted from the field equation to circulair currents (1 10) In principle the magnetic moment can also be due instance, in the case of eddy currents or on a macroscopic scale, as it is, for
this field is

3]

THE NATURE OF MAGNETIC MOMENTS

currents in a superconductor. In such cases

it is not usually referred to as a magnetic moment, the currents being retained explicitlx in the equatione from which can be determined. This separation is quite arbitrary, however.

The magnetic moments of

interest to us

come from

electrons in their atomic orbits (diameter

^ KH

the motion of the cm) or from their spin

motion. It has been found that in ferromagnetics the magnetic moment due to orbital motion is of the order of only 10% of the total moment, the predominant part being due to spin. We shall therefore give a brief qualitative semi-classical treatment
3.1

of the origin of electron spin.

SPIN

MOMENT

After the existence of electron spin was postulated by Uhlenbeck and Goudsmit in 1925, in order to explain gas-discharge spectra, it was explained by

Dirac in 1928 with the aid of relativity theory and quantum mechanics. In the theory of relativity the parameter pair E,t (energy, time) is treated
in the as a fourth dimension

same manner as the pair p,x (momentum, position); time is regarded and energy is the momentum conjugated with it.

E,t should therefore occur in the equations in the same way as p,x. With the classical energy equation for a particle with mass in a potential field V

P E-this is

2m

V=0
new equation
in which p also occurs an operator). This constant can

not the case,

for

occurs linearly and/? quadratically. Dirac


(really

solved the difficulty by postulating a


linearly, multiplied

by a constant

only be the velocity of the particle, because v bEkin /bp is still valid, is equal to the velocity of light c, so that, according to Dirac, the observable values (eigenvalues of the operator) of each component of

and

the velocity can only be c.

Only one component can be "measured"


(i.e.

at

the same time, the others remaining then undetermined

c). This

is

an

unexpected

result,

but

it

leads directly to the existence of the spin. In order

to visualize the spin of an electron

moving with a macroscopic velocity v


spiralized, so that,
is less.

we must assume that the path of a particle (<^c) is not straight, but is in some way

We

in Fig. 3.1.

although the microscopic velocity is c, the drift velocity thus have a translation plus a rotation, as shown schematically In general the sense of the rotational motion will not be defined,
field the state

but with the application of a magnetic


electron has

with the one direc-

tion of rotation will have lower energy than the other

moment

/*.

and thus the an angular momentum / and associated with it a magnetic The magnitude of the angular momentum may be estimated

PROPERTIES
v
_

AND THE ORIGIN OF MAGNETIC


Fig. 3.1.

FIELDS

CH.

Schematic representation of the


electron.

internal

motion of an
its

The electron
c,

moves

in

path with a velocity


is v-

while
is

the translation velocity

The

spin

in this case perpendicular to the plane of

the figure.

the energy of in the following way. According to the theory of relativity, 2 have with the velocity of light, is mc . mass m, which actually moves

We

seen that

energy mc 2 then p is also possible. By analogy, therefore, a state with established the should equally be possible. With this statement, Dirac

E is

comparable with p.

If,

however, the

momentum +p

occurs,

existence of a

new

state

a particle which, as

was

of the electron, which can be related to the positron, later demonstrated experimentally, has the same
sign. All that

mass as the electron but a charge of opposite

concerns us here
.

2 occur two energy levels, mc is that in the description of the electron there one state According to Bohr, it is possible to cause transitions from the

to the other by

means of electromagnetic radiation of frequency

v,

which

follows from

hv

= E -E = 2mc
1 2

(3.1)
sec).

where h

is

Planck's constant (6.625

10" 27 erg

Now

it is

reasonable

this v will also be to assume, because there are only two energy levels, that argument applies in the derivathe frequency of the spin motion. A similar momentum J is tion of the precession frequency (see 20). The angular the angular equal to the mass times the square of the velocity, divided by

frequency

a>

2ttv.

The

velocity here

is c,

so that, according to (3.1)


(3.2)

^"c*_
2mc*\h

where h

= h/2n,

corresponding to
v in (3.1) is

=\
(

if

/=

hS.

The frequency
orbit

very high
(1

= 2x

102/sec)

and corresponds

to that of very hard

gamma quanta

MeV). The average radius of the

may be

taken as
rsp in

= - = = 2x 10- 11
w
2mc
Of

cm,

known

as the

Compton

wavelength.

course, as in the case of the

Bohr

orbits in the

hydrogen atom, we must not think here of a


is

precise, sharp

a zero point motion, just as that of the electron orbit. The difference is that in this lowest state in the hydrogen atom. in the Is state
spin motion

the

motion can show angular momentum, due

to the fact that there

is

3]

THE NATURE OF MAGNETIC MOMENTS


c,

9
so that the

always one component of the velocity which has the value


"orbits" cannot have reversal points. bably of the order of 10 -13 cm.

The

size

of the electron

itself is

pro-

For a normal orbital motion the ratio y between the magnetic moment and the angular momentum is equal to
yorbit

e/2mc.
is

(3.3)

For the spin motion, however, the relation


yspm
i.e.

= e/mc

(3.4)

twice as large, as follows from Dirac's theory. This

may also be expressed


(3.5)

by the factor g in
y

= g e/2mc,
for the orbital motion.

being 2 for the free spin and

Owing

to the fact the

that the charge e of the electron

is

negative, the magnetic

moment and

momentum are of opposite sign. No simple explanation can be given for this deviating value of the g factor. The magnetic moment of the electron
angular
is

called the

Bohr magneton, and Hb

is

given by the equation

eh

= 9.27
and

2mc
if

10- 21 erg/gauss.

(3.6)

In 19 we shall see that


factor

spin

orbital

motion are both present the g

may have an

arbitrary value.

3.2.

QUENCHING OF THE ORBITAL ANGULAR MOMENTUM


first

In most magnetic materials containg elements of the


metals (Ti to
is is

group of transition
electrons

Ni and

also

Cu) the resultant

orbital

moment of the
that the orbital

much

smaller than the spin


is

moment; we say then

moment
field).

"quenched". This

a consequence of the electric fields at the position

of the ions, caused by the surrounding ions (known as the crystalline


Disregarding magnetic
effects,

a state (orbit) in which an electron travels

round in a
is

certain sense has exactly the


i.e.

same energy as the same

orbit with

the opposite sense of rotation,

such a state with an angular

momentum

doubly degenerate (both

states

have the same energy). This degeneracy


be non-uniform; for
less positive,

can be removed by the


instance
it is

crystalline field. This field will

strongly positive in the direction of negatively charged neigh-

bouring ions (repulsion of the electron) and negative, or at least


in directions in between.

motion can now be

utilized in

The above-mentioned indeterminancy in orbital quantum mechanics by so superposing the

10

PROPERTIES
states as to

AND THE ORIGIN OF MAGNETIC


orbits.

FIELDS

[CH.

two

produce two different


will

In the one state the positions

of high potential

be avoided as

much

as possible (orbit a in Fig. 3.2)


field.

so that this state will have a lower energy than the original in this

The other state is then left with precisely the unfavourable positions (orbit b) which results in an equally higher energy. The energy splitting AE is of the order of 10- 12 erg. These new states can have no angular momentum.
the opposite direction still disregarding magnetic effects had of motion would also be possible and we should have four states instead
If they

of two.
This superposition of states has some resemblance with the combination
into one standing

wave of two waves

travelling in opposite directions.

The

average charge distribution of the travelling waves is uniform, that of the standing wave is non-uniform. According to old quantum theory the electron

moving

in a

Bohr

orbit

is

associated with a

wave such

that the length of the

-*

AE

Fig. 3.2.

atively

Removal by the crystalline field of the orbital degeneracy caused by the four negcharged ions in the corners. Orbits a and b are turned exactly 45 with respec-

to each other.

The

resultant energy

change

is

shown.

circumference of the closed orbit


is

is

equal to an integral
/

number
/

of wave

lengths. The s state additional and corresponds to = 0, and should be regarded as a zero point motion. The state with = &p state, = 2 a d state etc.
/
1 is

is

When two
angular
It is clear

such waves propagating in opposite directions (opposite values of


are combined, a standing

momentum)

wave

results with 2/ nodes.

that the energy of such a charge distribution will

tation in a non-uniform crystal field with the proper symmetry.


state

depend on its orienFor instance zp


is

does not combine with a

field

of cubic symmetry and the degeneracy

3]

THE NATURE OF MAGNETIC MOMENTS

11

not removed. A Estate, however, is affected by such a field. The five fold energy
level is split

up into a doublet and a triplet. This partial degeneracy which still


cube planes have

exists is due to the fact that equivalent orbits lying in different

equal energy. The degeneracy can be further removed by superimposed


crystal fields of lower

symmetry. If

this is

not the case a partial occupation

by electrons leaves the lowest state of the total electronic system degenerate, which may possess orbital angular momentum. This situation occurs e.g. for divalent cobalt ions in octahedral sites in compounds. The states of the doublet are called non-magnetic and a combination of
of the
triplet states

them does not


3.3.

give rise to angular

momentum.

SPIN-ORBIT INTERACTION
of electron velocity
will also

If magnetic effects are present a reversal

change

the energy, and the above reasoning

is

of a crystalline

field there

can

still

no longer valid; even in the presence be some orbital angular momentum.

is a magnetic effect due to which again has a relativistic origin. is This interaction may be compared with the Lorentz force, which corresponds to an electrical field strength

Irrespective of the internal magnetic fields there

what

known as

spin-orbit interaction,

E=(vxH). 10.-8
This follows from Maxwell's theory, or from the theory of

(3.7)

relativity,

a coordinate system moving with a velocity v relative to another system, an extra electrical field-strength prevails equal to (3.7),

which

states that in

if

Tis the magnetic field-strength in that other system.

By analogy with this,

there exists in the one system a magnetic field-strength

H = -(vxE)/9.W2,
if Eis

(3.8)

the electrical field-strength in the other system.


is

The

spin of the

moving
is

electron

subject to this field,

so that according to (2.9) the energy

E*.o.

= -fi(vxE)/9.10U,
is

(3.9)

to

which a factor

i, the

applying in the case of the

Thomas factor, g factor.

added for reasons similar to those

In general it may be assumed that the electrical potential of an atomic core


is

mainly spherically-symmetrical. The

electric field is

then radially oriented,

so that

a .o.

=2mc
r

(i(pXr)l9.WU

12

PROPERTIES
there
is

AND THE ORIGIN OF MAGNETIC


atom an

FIELDS
and

[CH.

and hence

in the

interaction between spin

orbital

moment of

the

form

E
In this expression of the iron group
5.036

s .o.

= A L S.
momentum and
A
is

(3.10)

is

the orbital angular

an energy
(1

quantity which depends


it is

upon

the ion concerned; for the transition metals


erg

of the order of 10" 13 erg. (See Table 3.1)

xlO

15

cm-

1
).

TABLE
SPIN-ORBIT

3.1

PARAMETER
ion

FOR VARIOUS IONS OF THE IRON GROUP IN CM">


Configuration
A

(cm- 1 )
154
150 87 57

Ti

3d
3rf3

ym
Cri
Ci-iiMn 111

2Z> 3/ 2

3rf 2 3

F2

*F3I2

Fe Fe 11

m Mnn

3d*

Wo

3d5 6S 5I2
3d<5 5Z> 4

Co"
Ni 11

3cP 4F9/2 3d* 3p4


3rf9 2 Z> 5 /2

Cu"

-100 -180 -335 -852

The

effect

of an interaction (3.10)

is

that the original situation existing


field is restored to

before the splitting action


so that the
first

of the crystalline

some

extent,

two

states acquire

slight orbital
h,

moment

again,

approximation to (X/AE)

where the
If,

original orbital

amounting in moment was h


states

or a multiple thereof (max. 2 for the iron group). In the same approximation
the spin orientation has not changed.
therefore, only

one of the

by an electron, there will be some orbital moment present, the direction of which will depend upon the sign of A. If both orbits are occupied by an electron, the orbital moments again offset each other, so that the interaction (3.10) has no effect. This occurs in filled shells, for example in Mn n or Fe 111 in which all spins are parallel and all orbits of the 3d shell are singly occupied. Intermingling no longer has any effect in this case and the charge distribution is and remains spheri(that with the lower energy) is occupied
,

cally symmetrical.

The admixed orbital angular momentum is antiparallel to the spin moment (A > 0). For more than half-filled shells, the direction of the resultant spin is determined by that of the half-filled shell. These do not,
however, contribute to the orbital

momentum,

so that the resultant orbital

momentum
to

is

parallel then to the resultant spin

moment, corresponding

an

effective negative A.

3]
3.4.

THE NATURE OF MAGNETIC MOMENTS


ABSOLUTE MAGNITUDE OF THE ANGULAR MOMENTA
is

13

It

was

stated in 3.1 that the actual velocity of the electron

c,

corres-

ponding to an angular
find that only

momentum

of h/2.

Now this holds for each compowe

nent of the velocity (along three axes perpendicular to each other) but

one component can be measured at a time; the others remain indeterminate and are either + c or c. This is a consequence of Heisen-

berg's uncertainty principle.


fore,

be

c2

but 3c

2
.

In the

The square of the total same way it appears, as a

velocity will not, thereresult of this, that each

component of the angular momentum is /i/2, but that only one component can be measured at one time. The square of the length of the angular mo-

mentum

vector

is

then

/i 2 ,

for

= \: + S = S(S +
z*

Sx*
.

Sy*

1)

(3.11)

and not S2 The expression postulated in (3. 1 1) has general validity, and applies
also to the spin

moment of

several coupled spins. Let there be

2S

spins in

the z direction, then

SX
since,

(SX \

+ ^2 +

...)

Sxx

+ Sxz +

is

owing to the lack of correlation between the motion of the individual


double-product terms cancel out on the average. This applies
direction, while

spins, the

also to

they

Sz 2

= Sz

so that (3.11) follows here too. With


less.

increasing

the indeterminancy becomes relatively

For

similar reasons,

an expression analogous to

(3.11) applies also in the

case of pure orbital angular

momenta:

x+a

UL +

1).

(3.12)

Fig. 3.3. Possible orientations of

an

angular

momentum
an

vector

with

respect to
(z axis).

axis of quantization

The semi-integral numbers can occur


only for spin (S

/2

represents the

case of three mutually parallel spins).

14

PROPERTIES
values of
1,

AND THE ORIGIN OF MAGNETIC

FIELDS

[CHI

The
(2L

Sz

or

Lz

which can be determined by measurement, ascend in

steps of

1)

S - 1, 1) or 2, ... (-S), thus totalling (25 which corresponds to as many positions of the resultant vector
for example S,

with respect to the z axis (see Fig.

3.3).

The values of L are

alwaysintegers.

The

positions of the vectors as


it

drawn are only average

positions. In reality

were a zero point motion around them. Moreover, the whole figure should be thought of as arbitrarily rotating around the z axis.
there occurs as

CHAPTER

II

THEORY OF FERROMAGNETISM

4.

Diamagnetism, Paramagnetism and Ferromagnetism

We have seen in Chapter I that a magnetization M can occur in matter as the

result

of a more or

less parallel

alignment of the elementary magnets present

therein (electron orbits or electron spins).

To produce

this

alignment

it

will

generally be necessary to apply a magnetic field

H. The magnetization M,

when

relatively small, is

then often found to increase proportionally with

//according to

M= ^
cm
3.

(4 1}

where x is the (constant) susceptibility per B is found from (1.7) to be

In that case the induction

B=
The constant is Depending upon
/u.

(1

+ A-n X)H =

imH.

(4.2)

and /x 1. called the permeability. In vacuo, x be the sign and the magnitude of x> three cases may

distinguished:
a)

Diamagnetism x

<

F r

this

phenomenon

to occur there need be

no permanent dipoles present. The magnetic field induces a magnetic moment that is opposed to H. This is really the most natural form of magnetism and occurs in principle in all substances. It is a direct consequence of one of the most fundamental laws of nature, which states that any change gives
rise to forces

which tend to counteract

this change.

This

is

here expressed

in Lenz's law, according to which the magnetic flux contained


circuit tends to
tries

by a closed

remain constant, since the induced electromotive force (2.1) to change the current in such a way as to oppose the flux variation.
is

The value of x

usually of the order of

lO -5

it is

very small compared

with the other contributions to x f r the materials with which cerned here, and will therefore be disregarded.
b)

we

are con-

2 Paramagnetism x 0, but small (e.g. x < 10~ )- I Q this case magnetic moments which are already present (from electron orbits or spins) but which

>

have a random orientation, are to a slight extent aligned in the alignment being opposed by thermal agitation.
c)

field, this

Ferromagnetism. In the so-called ferromagnetic materials, just as in

paramagnetic materials, magnetic moments are also present, the difference being, however, that the spins of neighbouring ions are already more or
less parallel.

This does not


(i.e.

mean

that the whole specimen

is

necessarily

uniformly magnetized

any arbitrary piece of

soft iron is

no magnet),

16
for if
it

THEORY OF FERRO MAGNETISM

[CH.

II

were, the finite dimensions would give rise to large "demagnetizing

forces (see Fig. 1.1). Internally, too, a great deal of demagnetization

would

occur as a result of inhomogeneities and imperfections in the specimen. For


this

to

more favourable energetically for the material subdivide itself magnetically into a large number of small regions, known
reason
it

is

usually

as Weiss domains, after Pierre Weiss,

who

first

postulated their existence


is

in 1907. Within each domain, the size of which


0.1

of the order of 0.001 to

mm,

the magnetization

is

uniform but the direction of this spontaneous


usually

magnetization varies from one domain to another such that, in the absence

of an external

field,

there

is

no

overall magnetization
1

left.

The

application of an external field of the order of

to 100 oersteds

may

often be sufficient to remove the


practically to saturation.

domain

structure

and to bring the material

Thermal agitation has no effect on the magnetizing process of these large conglomerates of spins. Thus the material has a high
permeability

(maximum

10 6 ).

Another typical property of ferromagnetics is the occurrence of hysteresis, is not associated with one specific value of the i.e. each value of the field induction B, the latter depending upon the previous history, that is upon the fields which have been applied previously. For example, with a given field

the induction will be larger if the material


is first

saturated in a strong

field in the direction

of

H than if the

material were

first

saturated in the

The graph which shows the relation between B and is known as the hysteresis loop
opposite direction.
(Fig.
4.1).

This

hysteresis

is

the

result of irreversible magnetization

processes, which, since they cause

energy dissipation, adversely affect


the quality of coils in which these
materials are employed as cores.

On
it is

the other hand, the non-reversibility


also has
its

useful side, because

due to

this

phenomenon

that after

magnetization and subsequent reduction of the field to zero, there


still

is

some magnetization left, which means that such a material has permanent magnet properties.

15
Fig. 4.1. Hysteresis loop

of an annealed

iron specimen.

[5

EXCHANGE INTERACTION
5.

17

Exchange Interaction

The spontaneous magnetization of a Weiss domain is produced, as we have seen in 3.3, mainly by the magnetic moments of electron spins. However, notall spins of the electrons of an atom or ion can be parallel. Accordingto the Pauli principle two electrons in a system cannot be in the same si ate. The state of an electron is determined on the one hand by the orbit in which it moves, and on the other by the direction of its spin. As was shown in 3.4,
there exist only

two

states for the spin

of one electron (S

-J):

parallel

or anti-parallel to a certain direction. Each orbit, then, can be occupied


the case, for reasons of

by two electrons with opposite spin. In most atoms this is as far as possible economy in energy, so that there is no or only one uncompensated spin left. Exceptions are found in the transition metals, for example in the iron group (VtoNi) where the five circular orbits from the third shell (3d orbits) have equal energy. In these atoms it appears to be

more advantageous, owing to quantum mechanical reasons, for the spins of the 3d electrons to be parallel (one of the Hund rules). The maximum magnetic moment per ion or atom is then 5 ix B (e.g. Mn11 or Feni). For more than five
electrons in the

3d shell the resultant moment decreases again; for instance, Co11 in the 3d1 state has a moment of 3/j.b- It may be said that, in consequence
of the Pauli principle, the mutual spin orientation of the electrons imposes a restriction on their orbital motion. Since two electrons strongly repel each
other

(Coulomb

force) this will certainly affect the energy.

Now,

in the

more

case that the electron orbits are not separated, it appears that the mutual spin orientation also partly determines the stationary states of a system in which there are several electrons. As a result of the electrostatic
realistic

interaction between the electrons the energy will

orientation of the spins.

The difference in energy of two


is

depend upon the mutual electrons in a system

with anti-parallel and parallel spins


generally, the interaction

called the exchange energy /.


is

More
(5.1)

between two spin vectors Si and S2


4,,

given by

where
ration

<j>

is

the

Eex. = -2/S1.S2 = -US1S2 cos angle between 5i and S2 For / >


.

the parallel configu-

the state with opposite spins more favourable and for /< has the lowest energy. The energy difference J can only differ from zero when the electrons come into each others' vicinity a great deal, that is to say when the orbits "overlap". Therefore we need only consider this effect for electrons belonging to the same or to neighbouring atoms.
is

Hund's

rule is

still

usually applicable where the elements occur as ions

in ionic crystals (as in the oxides). In itself this fact

would merely give

rise

to strong paramagnetism. However, there also occurs an exchange interac-

18

THEORY OF FERROMAGNETISM
the spins of neighbouring ions.

[CH.

II

don between

An

interaction of this nature

causes, for example, the formation of the hydrogen molecule


to binding between

and

gives rise

atoms of many other elements, both in the molecular form and in the solid state (valence bond). In this process the two interacting electrons always have opposite spins, corresponding to a negative exchange energy. In the ferromagnetic metals Fe, Co and Ni, on the other
hand, the exchange energy between the 3d electrons of neighbouring ions
is

apparently positive. The conduction electrons,

i.e.

the electrons in the 4s

orbits, presumably have no or only little part in this. Thus, for the ferromagnetism of the elements in the iron group, only the 3d electrons are of

importance. In the rare earth elements corresponding conditions hold for


the
4/" shell

and

Gd

and

Dy

are ferromagnetic.

It is

found that the spontaneous magnetization

decreases with in-

creasing temperature
ture, the

and vanishes

fairly

suddenly above a certain tempera-

Curie temperature 7c.

6. Statistical
6.1.

Theory of Magnetism

LANGEVIN'S THEORY OF PARAMAGNETISM

In order to explain the temperature-dependence of the spontaneous magnetization

we

shall first treat Langevin's theory

of paramagnetism, which was


statistical

put into a quantum mechanical form by Brillouin. According to

mechanics the probability


with energy Et
is

that a system
g-Eij kT

is

in

one of

its

possible states

equal to

where k
is

is

Boltzmann's constant {k

1.380

x lO-w

erg/K)

and

T
all

the absolute temperature. In (6.1) the

sum

of the probabilities over

states is equal to unity.

At

the absolute zero point of temperature, then,

only the state with the lowest energy occurs, while at temperatures above
that point there
is

a chance for states with a higher energy to occur. At very


all states

high temperatures
(total disorder).
states, parallel

have practically equal probability of occurring

For one spin in a magnetic field and antiparallel to the magnetic

H there are two possible


field.

According to

(2.9)

the energies (in this case potential energies) are


tively.
//.

^bH

and +{j,bH

respec-

The average magnetic moment in the direction of can then be found by multiplying the moments in the two directions by their probability
of occurrence
(6.1)

and subtracting one from the


gfglt/kT
-v-

other:

_ e B HSkT <*> = ^ e , HikT e-, H,kT = B + B

l"**ahpBH/kT.

(6.2)

i6]

STATISTICAL

THEORY OF MAGNETISM
we may
tanh

19

For a substance with


magnetization
is

N independent spins per cm3 such that the maximum


NfiB,

Mo =

therefore write

M/Mo =

^H/kT.

(6.3)

For high temperatures and weak fields the tanh in (6.3) can be replaced by its argument, and hence we may write for the paramagnetic susceptibility
/LIB

M/H= x =
This
is

Mo kT
_1
is

C T

(6.4)

Curie's law, which states that x

proportional to the absolute

temperature.

The constant

C is

the Curie constant. This law

many paramagnetic substances. For (6.4) is not valid (^bH = kT for


and

higher
1.5

H=
?

is satisfied by and low temperatures X 104 oersteds and 7*= 1 K)

fields

approaches the saturation value Mo- This saturation effect has been
fields

thoroughly investigated at low temperatures and high


7M}]
!

(H/T

large)

1^^+-|

by Henry [He

1] (see Fig. 6.1) for


salts.

various paramagnetic
6.00

From (1.7) we might expect that H


in (6.2)

would not be equal to the exit is

ternally applied field but equal to B.

However,
SJOO

not the average

field

that must be taken, but the field pro-

4.00

duced at the position of the ion by the other ions. For a cubic crystal this
is,

according to Lorentz,

H + 4wM/3.
K).

This correction can be neglected for


3.00

paramagnetic materials, except at

low temperatures (<


2.00

As a moment

general rule the magnetic

too

30
H/T*10~3 (0el)
Fig. 6.1.

magnetic

Magnetic moment of some parasalts as a function of H/T. The


the
theoretical

m of an ion will originate from more than one spin, which, according to Hund's rule, are parallel, while there can also be some orbital magnetism present; thus, where S is still a good quantum number (i.e. the value of S for an ion can still be measured without
changing the orbital motion) the magnetic

solid lines are

Brillouin

functions, according to (6.7). (After

Henry

moment

is

given by
(6.5)

[He

1]).

m=

SgixB,

20

THEORY OF FERROMAGNETISM
5
g
is
is

[CH.
3.4).

II

where
factor

the spin angular

momentum
magnetic -

of the ion (see

The Lande

then given by

g=2

total

moment
moment
is

(6.6)

spin magnetic

For pure spin magnetic moments, g = 2; deviations occur if there some orbital magnetism present, in which case g = 1 (see 3.1).

also

Where 5

> % the moment will then have,


field,

as discussed in 3.4, (25

1)

possible orientations in a magnetic

so that (6.2) must be generalized

and instead of
'

(6.3)

we

find

MlMo = Bs(a) =

25+1
25

cotanh

25+1
a

cotanh

25
and a
is

25

a 25

(6.7) v '

where Bs

is

the Brillouin function

given by
(6.8)

SgpBH/kT.

The measured points given in Fig. 6.1 are those of salts with 5= 3/2, 5/2 and 7/2 respectively, and fall on the Brillouin functions concerned. Here, too, Curie's law applies, with a Curie constant Cs which is equal to the initial slope of the Bs curve and is given by

Cs
where

= gn B (S +
**

l)M

/3k

(6.9)

is

the absolute magnitude of the


6.2.

HBg is(S moment.

1)

(6.10)

WEISS FIELD THEORY OF FERROMAGNETISM


all

If

we keep

the spins in a ferromagnetic substance in one direction

by means of a strong magnetic field, and we then try to turn one spin, or more generally the magnetic moment of one ion, out of that direction, this will be opposed not only by the external magnetic field but also by the exchange interaction with the spins of neighbouring
ions. It is as if there
field,

were
not a

an extra

field acting

on each

spin, the so-called

Weiss

Hw-

It is
is

true field, for that can be produced only

by

circular currents, but


its

simply

a measure of the strength of the spin's interaction with


field is in

neighbours. This

general

much

stronger

(=107

oersteds) than can normally be pro-

duced with

coils etc. The classical dipole-dipole magnetic interaction is of no consequence here, for this would only give fields of the order of AttM, which can be no more than ~2.104 oersteds. The Weiss field depends upon the magnitude of the average moment:

Hw=WM,

(6.11)

6]

STATISTICAL
field

THEORY OF MAGNETISM
is

21

where W, the Weiss


If the interaction is
(2.9)

constant,

assumed

to be independent of

M and T.
is

caused by the z nearest neighbours, then according to

and

(5.1) the

energy change

AE due

to the reversal of one spin

AE = gix B WMo =
where

2zJS,

(6.12)

Mo

is

the saturation

moment

at

T=

0K.

The temperature-dependence of the spontaneous magnetization can be in (6.8) found by applying the Langevin theory from 6.1. The field must then be replaced by + Hw, where Hw is given by (6.11). For the

calculation of the spontaneous magnetization

we have
at

to put

Equation

M which, a given temperature, H/T equal Thus, in can have a from M and HIT equal to T/W to WM/T. All points which the quotient of M
(6.7)

H = 0.

then becomes an equation in


s,

solution,

differing

zero.

Fig. 6.2,
is

is

for

on a straight line through the origin. The point where this intersects the drawn curve gives the sought-for value of the spontaneous magnetization. For low temperatures the straight line has a very small slope and in the point of intersection, for example A in Fig. 6.2, s /Mo is almost equal to 1.
lie

h/t
Fiig. 6.2.

this

Magnetic moment as a function of H/T. The points w tiere curve intersects the broken straight lines represent possible

spontaneous magnetizations at varous temperatures.

With

rising

temperature the point of intersection

shifts

towards

B and C and

intersection has s decreases. For that temperature where the point of s is zero arrived at the origin, and has hence become a tangential point,

and remains so at still higher temperatures. This Curie temperature Tc given, for an arbitrary value of S, by

is

Tc

= Cs W = gMS +

l)WMo/3fc,

(6.13)

22

THEORY OF FERROMAGNETISM
we may

[CH.

II

as follows from (6.4) and (6.9) if the Weiss field


(6.12)

Hw be inserted for H. Using


(6.14)

write for (6.13):

Tc =
The Curie temperature,
action per spin (SJ or

2S(S

l)zJ/3k.

then, increases with increasing

S for
is

constant interto say, if each

W) and

magnetization (Mo). That

ion has more than one uncompensated spin the Curie temperature is higher when these spins are coupled in one ion (following Hund's rule) than when
this is

not the case. This

may
is

be readily understood from the fact that in


greater (more possibilities for orientation)

the latter case, the entropy

with vanishing spontaneous magnetization than with coupled spins, where


the

maximum

disorder has not yet been reached.


is

the entropy) in the free energy

thus larger at

The term TS (S is here the same temperature, and

consequently the temperature (7c) at which this large entropy can occur
(corresponding to

0) will

be lower.

For the ferromagnetic metals of the iron group the Curie temperatures and the saturation magnetizations at absolute zero are:

Fe

Co
1131
18,150

Ni
358
6,394

Tc
AttMq

770
21,805
s

(Q
(gauss)
is

The curve

M /Mo can now be plotted as a function of temperature, and


The experimental curves
it

given in Fig. 6.3 for several values of S.

for the

metals iron and nickel are given, and

can be seen that they He with good


should indicate that the spins of

approximation on the curve S

-J;

this

the electrons inside one ion are in this case not coupled.

Fig. 6.3.

Spontaneous magnetiscales.

zation as a function of temperature

on reduced
field

The

solid lines

were found with the


theory for the cases

Weiss

= xh
and

and S

\.

The

ex-

perimental (dashed) curves for


iron
nickel agree with the

theoretical

curve
spins).

for

Va

(uncoupled

6]

STATISTICAL

THEORY OF MAGNETISM

23

Above the Curie point the Weiss field is zero and there should therefore no longer be any parallel alignment of neighbouring ions. For T > it is somewhat by an applied field; from the Weiss field possible to enlarge

theory

it

follows that

DM/bH = -(77 WM)bM/b T


According to the Weiss
field

(6. 1 5)

theory the magnetization decreases only

very slowly at low temperatures. For example, for S \ the relative decrease of where T/Tc 0.2, is only 2x 10~ 4 At higher values of S the s

decrease
rature).

is

faster (e.g. for

1 it

amounts to 6x 10~4

at the

same tempe-

The reason

for this faster decline of the magnetization at greater

values of

ion

S is that at low temperatures there occur only the state of the with Sz = S and to a slight extent the state with Sz = S 1. The energy
1

of this excited state

is

practically

gfisWMo. The deviation of the magneti-

zation from that in the total saturated state will then be proportional to:

AM
Mo
as follows
is (1

/S)e-"BWM lkT s

(6.16)

from

(6.7).

(Compare

6.1)).

The number of individual moments

proportional to 1/5. Irrespective of this factor the magnetization thus

same way for different values of S for increasing T. However, same value of the reduced temperature the decrease of M/Mo will then be greater for the higher value of S, for which according to (6.13)
decreases in the
at the

the Curie temperature

is

highest.

As this is manifest in the exponent of (6.16)


it

the l/S term in (6.16) can not compensate for

at

low temperatures.

At

T=

0,

dMs/dT =

0,

which

is

not merely a property of the model but


considerations. Using (2.5)

follows

from general thermodynamic

we may

write for the variation of the free energy

F of the magnetic

material

dF=-SdT+HdM.
From
this

F the

free enthalpy

is

found by adding a potential similar

to (2.9),

i.e.

G = F- HM,
so that

(6.17)

dG
In the state of equilibrium

= -SdT- MdH.
G
is

remarked

after (2.9).

By

differentiation

minimum for we get

constant

T and

H, as was

(bSlbH)T

= (oM/oT)h.

(6.18)

24

THEORY OF FERROMAGNETISM

[CH.

II

According to Nernst, at

T=
0.

the entropy

is

zero, irrespective of all

parameters and hence also of H; theiefore in (6.18), bS/i>H

at

T=

0,

and accordingly &M/oT'=


it

Curie's law, then, does not satisfy this,


that,

and

can be said with certainty


is

ments, Curie's law


ture
is

does not,

owing to the order of ihe magnetic moT= 0. How low the transition temperaof course, follow from such thermodynamic considerations.
not valid near

6.3.

PARAMAGNETISM ABOVE THE CURIE POINT

Although the spontaneous magnetization has vanished above the Curie point, the interaction between the magnetic moments is nevertheless still noticeable if a magnetic moment is induced by the external field. This induced moment, too, gives
rise to

added to the external

field,

so that

a Weiss field Hw of (6.11) which must be can now be found by substituting

H + WM in (6.4) for H. With the aid of (6.13) we may therefore write


T- Tc
The Weiss
field is

(6.19)

then

Hw =
The
susceptibility

T-Tc

H.
Tc, indicating that a spon-

now becomes

infinite at

T=

taneous magnetization sets in at this point

(finite

M for H =

0).

The part
equal

of the 1/x axis cut off by the extrapolated 1/x versus


to

T straight line is

-W.
CRITICISM OF THE WEISS FIELD
field

6.4.

THEORY
its

In the Weiss

theory the interaction of a single spin with

neighbour
the

was approximated by the interaction with a uniform


magnetization. In reality, at least
if

field parallel to

we

still

represent the interaction in this

way, such a

field will

vary from place to place in direction as well as in mag-

nitude, just as the magnetization does.

deviations in the spin orientation take place, as follows

spin-wave theory applicable in that


detail in 22.3.

At low temperatures, slowly varying from the rigorous region, which we shall discuss in more
reversed spin
is,

The exchange energy per

according to the
interferences

spin-wave theory,
is

much

smaller than 2zJS

and for long-wave

given by:

E*x
where a
2ir/\.
is

= 2JStfik\

(6.20)

the lattice constant

For k

it

costs

and k the magnitude of the wave vector k = no energy to reverse a spin. The entire uniform

6]

STATISTICAL
is

THEORY OF MAGNETISM

25

magnetization
field,

turned through a small angle out of the direction of the


spins remain mutually parallel.

so that

all

For a small value of k the


is

angle between the neighbouring spins (proportional to ak)


the exchange energy (5.1)
in
is

very small;

therefore very

little

increased, the increase being

first approximation proportional to the square of the angle of deviation (oca 2 & 2) in agreement with (6.20) (cos <=1 i^ 2). These low energy states can thus readily be excited at low temperatures (cf. (6.1)) so that the

magnetization decreases
theory (6.16).

much more

rapidly than follows from the Weiss

The theory

gives for this case:


[l

M= M
with

- (T/TB 3 2
)
'

],

(6.21)

Tb =
S=
\
it

21

S^J/k
is

(6.22)

for the b.c.c. lattice. Equation (6.21)

the so-called Bloch


1.7

T3 2
/

law.

For

follows

from

(6.14) that

TB =

from the temperature-dependence of s at low temperatures for Ni and Fe that Tb 4TC so that for T/Tc 0.2 the relative decrease in magnetization is 10 -2 as compared with 2 x 10 -4 according to the Weiss theory.

Tc

Experimentally

it

appears

A T3 2 dependence for the decrease in magnetization is found experimentally


'

at temperatures

below approximately 0.3 Tc, where only the spin-wave


field

theory can be applicable.

However, the Weiss

theory

is

also incorrect at high temperatures

Fig. 6.4.
bility

Spontaneous magnetization

M,

and the reciprocal

suscepti-

1/x as a function of temperature. The broken curves are in accordance with the Weiss field theory. Better approximations steadily reduce
the Curie point (cf

The

latter

full curve) and make the 1/x versus has as asymptote the Curie- Weiss line.
.

T curve concave.

26
(in the region

THEORY OF FERROMAGNETISM

[CH.

II

theory predicts that for

of the Curie point and higher). For example, the Weiss T Tc, in the absence of an external field,

>

the spin order will have vanished completely. This would mean that there would no longer be any correlation between the orientations of

two neighbouring spins. According to (5.1) and (6.1), however, there is an eJikT greater chance of the spins being parallel than antiparallel. At the
is ei~ 1.3 for a b.c.c. lattice. be noticeable over a short distance (short range order) so that the magnetization will nevertheless disappear above the Curie point, which can only exist if there is long range order. More rigorous theories which deal in an approximate way with this correlation

Curie point this factor, according to (6.14),


order, however, will only

The

also
is

above the Curie point all arrive at the result that the Curie temperature lower than that given by (6.14). At very high temperatures (T^> Tc ) the
is

correlation between the orientations of neighbouring spins

negligible

found as the asymptote of the However, the l/x versus T line is now curved (see Fig. 6.4), the slope always being smaller than that of the asymptote (6.19). An expression for this slope can be found from the differential of F:

and the Curie-Weiss


actual l/x versus

straight line (6.19) is

curve.

VoM/r
which can be written
as:

UtJm
oS
2
(6.23)

(i/x)

bT

d(M2)

This slope is therefore related to the decrease of the entropy as a result magnetization. Since in the

Weiss
2

field

approximation the state for

M=

is

in

complete disorder, &5'/6(M

) is

constant as a function of temperature, and

hence also d(l/x)/dr. In reality the entropy is smaller owing to the cluster formation and the change in it, caused by magnetization, will also be smaller (see Fig. 6.5). The orientation of the clusters is to some extent comparable
with the orientation of the spin moments with greater S. Thus, the l/x
versus

the Curie point will be lower.

T curve will always be above the Curie-Weiss line (6.19) and therefore From the Bloch T3 2 law, it also follows
/

that the experimentally found Curie temperature is lower than that given by (6.14). This curvature of the l/x versus T line is actually found, and is expressed as a difference between the ferromagnetic and the extrapolated

paramagnetic Curie temperature; this difference is, however, rather small in most cases (20 to 30 for nickel). According to the theory the difference
could amount to several tens per cent of the Curie temperature. In practice,

7]

CALORIC PROPERTIES

27

because the temperatures reached are not high enough, the true asymptote
will

probably not be drawn in most instances, but one with too low a slope.
with

In

fact, for nickel this slope agrees better

5=1

than with

It is therefore

dangerous to draw conclusions from the 1/x versus

S = \. T curve.

Entropy as a function of the square of the magnetiCurve (a) is according to Weiss field theory, whereas for curve (6) correlations between the spin directions of
Fig. 6.5.

zation.

neighbouring ions have been taken into account.

7.

Caloric Properties

7.1.

SPECIFIC

HEAT

Owing

to the decrease of
is

the change of the total exchange energy with

the temperature

heat which, in the absence of external

accompanied by an extra contribution to the specific fields, is given in the Weiss approxi-

mation by

cm

= iWd(M *)/dT.
s

(7.1)

Just below the Curie temperature,


i.e.

cm

is

maximum and above

it

cm

is

zero,

there occurs per spin a

jump

equal to

AcM

5S(S

+ 1) + (S + l) 2

'

(7.2)

finite

jump of

this

kind in the specific heat

is characteristic

of what

is

called a second order transition. Transitions such as liquid state are first order transitions,

from the

solid to the

where there occurs a

finite transition

heat which must be supplied in an

infinitely small

temperature interval;

28

THEORY OF FERROMAGNETISM
jump

[CHII

in other words this corresponds to an infinitely high value of specific heat


at the transition point. In a
first

order transition there

is

in the

entropy (a different phase) but not in a second order transition. Fig. 7.1

shows the

specific

heat curve of nickel in the region of

T=

Tc, in which

0.16

O.li

0.12

nm
250
500

-*
1]).

750

1000

T(C)
of the Curie

Fig. 7.1. Specific heat of nickel in the region

temperature. (After

Moser [Mo
in fairly

the magnetic contribution

is

good agreement with the theory.


field

The drop, however,

is

not so sudden as predicted by the Weiss

theory

according to which the magnetic contribution to the specific heat should be


zero above the Curie point. However,
all

order has not yet disappeared

above

this

point,

as

is

manifest in the magnetic contribution to the

entropy change

ASM = cM AT/T.
The
"tail" of the specific heat curve is thus a

(7.3)

measure of the short range

order above the Curie point.


7.2.

MAGNETOCALORIC EFFECT

In

all thermodynamic systems a change of temperature takes place during an adiabatic change of an intensive parameter (potential, field). In the magnetic case an increase of the field reduces the magnetic entropy according to

ASM

(i>S/i>H) T AH.
is

In order to keep the total entropy constant the temperature


(greater disorder), so that the entropy
is

increased

increased

(cf. (7.3))

by:

AS

c H ATjT,

7]

CALORIC PROPERTIES
specific

29

where ch is the
constant.

heat of the whole system, the external field remaining


(6.18)

Making use of

we

find for the temperature change:


(7.4)

AT = -(T/ch) (i>M/i>T) HAH,

10000

s
Ni

5000

,-""

V
T c
400

200
Fig. 7.2.

300

500

600

T(C)

Weiss

field

constant

W for

nickel, as

determined

from the magnetocaloric


Weiss et
al.

effect.

According to the simple

theory this should not be temperature-dependent. (After

[We

1]).

which has the correct

sign, since

bM/bT

<

0.

Owing

to the use of thermo-

dynamic only for reversible changes, i.e. for the change of the intrinsic magnetization and for those magnetization processes which take place without hysteresis. For AH 10,000 oersteds the
relations, equation (7.4) holds

temperature increase in the case of nickel and iron


at the Curie point,

is

of the order of

and

0.1

at

T= 0.5

Tc

Using

(6.15)

and applying the Weiss

field theory,

we can

express

T in

the accompanying change of

M:
.

AT =
so that

WM AM = AM W i
ch
ch

2
,

(7.5)

W can be calculated from the experimental values for AM and AT.


et al.

Experiments by Weiss

[We l]have demonstrated

that

AT is

in fact

proportional to the change of the square of the magnetization, but that

depends upon the temperature, especially in the region of Tc (see Fig.

7.2).

CHAPTER

III

FERRIMAGNETISM
8. Origin of Ferrimagnetism
8.1.

INDIRECT EXCHANGE INTERACTION


ionic crystals, as in the majority of oxides to

In

many

be discussed, the
is

exchange energy J between the spins of the neighbouring metal ions


these substances, however, the metal ions are

found

to be negative, so that antiparallel alignment gives the lowest energy. In

more or

less

separated by the

negatively charged antions, which, like the inert gases, have a closed shell

configuration in the ground state. For example, the electron structure of

the
ions

IJ
is

ion

is

like that

of neon (2s 2 2p 6 ). The distance between the metal

usually much too great for a direct exchange interaction to be possible,

since the extent of overlapping of the

wave functions

(orbitals) decreases

exponentially with distance.

Various magnetic interaction mechanisms


1 ]

have therefore been proposed [Va

in which the interlying anion plays

an

essential part (super exchange). In the


is

configuration the ion

rounding ions

will,

ground state with the inert gas and can produce no spin coupling. The surhowever, disturb this state somewhat, so that the extra
inert
this is expressed

electrons will for a small part of the time belong to the neighbouring ions. In

quantum mechanics

by the principle of the superposition of states. That is to say the state of the oxygen ion with the lowest energy 11 and (for a small amount) the is a superposition of the ground state O
state

O1 and possibly

that of the neutral

atom. In reality a whole variety

Jeff

Fig. 8.1. Ground state and excited state of two metal ions, Mi and Mi, with an oxygen ion between them. The spin configurations as drawn become intermingled, causing an extra reduction of ground state energy; this does not occur if Mi and Mz have

parallel spins.

8]

ORIGIN OF FERRIMAGNETISM

31

of excited states will be mixed together, but we shall consider only those which can be of use in explaining magnetic interaction. The electron separated from the oxygen will return to one of the surrounding metal ions from which it originally came (Mi in Fig. 8.1.). Within this metal ion there exists

a strong exchange interaction between the spins (Hund's rule). The electron can only be there if its spin has a given orientation with respect to the resultant spin moment of the ion, and that depends upon the orbit in which the electron in this excited state chooses to move. Where this (according to
Anderson)
if
it

is

the 3d orbit, the spin will be parallel to the resultant


less

moment

the shell

was

than half occupied

(five

or less 3d electrons); otherwise

must occupy an

orbit with antiparallel spin.

The

electron under consi-

deration has

has the highest energy. come from a 2/> oxygen According to the Pauli principle, an orbit can contain two electrons with
orbit since this

opposite spins.

The remaining, now unpaired,

electron can interact with

another metal ion. There are also


states will certainly

many

other possibilities, but these excited

be intermingled to a small extent. According to Ander-

son the second electron interacts with one of the metal ion electrons as in the covalent bond or hydrogen molecular bond, in which the two associated
electrons constantly

jump

tinually exchange their

and fro between the ions concerned and con(antiparallel) spins. The latter will now only take
to
will therefore

place to a

more

limited extent, since the spins at the position of the ions are

not free to orient themselves. In that case the energy gain


only be half as large.

Where these means that an

admixed and then cause a reduction of energy, it effective coupling has arisen between the spin moments of the two metal ions. For if the moments had been parallel there would have been no interrningling and hence no reduction of energy. This reduction of
states are

energy occurs because, owing to the intermingling of excited


charge distribution can adapt
itself

states, the total

with more economy of energy to the

potential occurring in the lattice. Accordingly


tive

exchange energy
to d^.

J.

In this case
to

we can again speak of an effecwe may therefore expect positive exnegative exchange energy

change energy for the


for
rfs

d1

d4 configuration and

One of
[An
1 ], is

the other possibilities, according to Anderson

and Hasegawa
is

that the equivalent state, in which the other electron

transferred

to the other metal ion, also occurs simultaneously, leading to a reduction in

energy. This

is

only possible

if

the

two metal ions have

their resultant spin

moments

antiparallel, so that in this case only a negative effective

exchange

energy can exist

(/<

0).

Which

states are

most strongly admixed

will

depend upon the distances

32

FERRIMAGNETISM
Fig.
8.2.

[CH.
orientation of the

Ill

Diagram showing the

2/>

orbit of the

oxygen ion with respect to the metal ions,

which

is

responsible for the indirect exchange.

and the

distribution of the surrounding ions.

At

all

events, this interaction

will also largely

depedend depend

direct interaction

upon the distance between the metal and oxygen

for the same reasons as in the case of


ions,

and

will rapidly

diminish with increasing distance. Apart from this depen-

dence upon distance, there is also dependence upon direction to be considered.

The orbits of the oxygen electrons in question are, as we have seen, the stretched
2/>orbits.

Since the interaction or the transition to the metal ions can take place

only

if there is

some overlap with the


if

orbits in these ions,

it

will take place

most favourably

the oxygen ion

lies

centrally

on the

line

connecting the

two metal

ions, so that the axis of the p orbit

under consideration can coinin Fig. 8.2.


is

cide exactly with this line. If the angle

M1-O-M2

in the region

of 90, the interaction will be smaller. Such considerations are also frequently

of importance for determining molecular configurations.


Experimentally, negative exchange energy
is

found in most cases, as in the

ferromagnetic oxides, although


8.2.

some

cases of positive

J have been reported.

SPIN

ORDER
would expect the
in Fig. 8.3.

In the case of negative exchange interaction one

spins of

neighbouring ions to be antiparallel, giving the sample a zero magnetic

moment.
ratios

simple two-dimensional model

is

shown

order depends not only upon the crystalline structure but also

The spin upon the


be that

of the magnitudes of the interactions. The order occurring

will

with the lowest energy. In Fig. 8.3a), for example, the interaction between
the nearest neighbours

A and B is stronger than that between the next nearest


Fig. 8.36) the converse is true.

neighbours
elementary

and C. In

The

latter

case%ill

be found, for example, when the joining antion lies in the centre of the square
cell.

Only the distances between cation and anion are important,


ions. In Fig. 8.3a), then, the

and not those between the metal


is

bond A-C

the strongest because of the 180 angle between the connecting lines, alis

though the distance between the metal ions

greater.

The

spin order in the

MnO crystal
[Ya

is

indicated in Fig. 8.4.

An antiferromagnetic order in which the elementary magnets are not purely


antiparallel occurs for
lattice
1 ].

example in Fig.

8.3.c) in the

two-dimensional trigonal

If a purely antiparallel order

were to appear, each spin would

H
8]
at the

ORIGIN OF FERRIMAGNETISM
most be surrounded by four
antiparallel neighbours, the other

33

two

The exchange energy would then be U. According to (5.1) the exchange energy in the situation as drawn, in which all spins make angles
being parallel.

of 120 with each other, will be

6/

cos 120

3J, this being

lower for

J<

0.

In the cases a) and b) in Fig.


lattices,

8.3,

the lattice can be split

up

into

two subc) there

each possessing uniform magnetization. In the case of

are three.
If the sublattices are occupied
will

by
If

identical ions, the resultant

moment
as

be zero (antiferromagnetism).

the magnetic moments of both sublatwill result.


1 ].

tices differ in

magnitude a net moment

This case

is

known

ferrimagnetism, a

name

given to

it

by Neel [Ne

we are concerned we can split the crystal lattice number of sublattices; these are not, however, crystallographically equivalent and moreover generally contain different numbers of ions
In the cases with which
into a

1
c
i

r--t--+-1
i

III f-4-H
*
i

i !

i
/

M
b

Fig.

8.3.

Two-demensional

representation of

some mofor

des of spin order


gative

neJ. is

exchange energy

In a) the
stronger
it is

A-B coupling
A-C,
in

than

b)

weaker. In the trigonal


order with

lattice c) the spin

three sublattices, the


tizations

magneof which make an

\ /

angle of 120 with each other

has the lowest energy.

34

FERRIMAGNETISM
Fig.
8.4.

[CH.

Ill

Antiferromagnetic

spin order in the cubic


crystal.

MnO

The

nearest neigh-

bours but one have antiparallel spins.

(e.g.

two

sublattices for the spinel structure

and

five for the

magnetoplumsublattices

bite structure). In

most such cases

it is

then possible for each of them to have


split

uniform magnetization, so that it is not necessary to


again for the magnetic spin order.

up these

9. Weiss Field Theory Applied to Ferrimagnetism


9.1.

STRETCHED CONFIGURATION
1 ]

Neel [Ne

has shown that the Weiss

field

theory can also be applied to

ferrimagnetism, albeit in a

somewhat more complicated form. An ion of surrounded by a number of neighbours, some of which a given sublattice is belong to the same sublattice and some to others, so that the Weiss field acting on this ion depends upon the magnetizations of all sublattices, according to

HW =
i

Wv

M,.

(9.1)

The Weiss field coefficients

W^ are a measure of the strength of the exchange


from the
ith sublattice

interaction between the spins of an ion

with that of an

ion from they'th sublattice. Thus, in the cases in which

we are interested these

Wji. Wtj values are negative. Since action is equal to reaction, Wis in (5.11) must be Formula (5.10) is now valid for each sublattice, and

augmented by the corresponding Weiss


tain n simultaneous equations, the

field

from

(9.1).

In this

way we obsubstitut-

unknown

quantities being the magnetiis

zations of the n sublattices. Here, too, the Curie point

found by

ing the Weiss fields from (9.1) for if in (5.7), which equation

now

holds for

each sublattice separately. For the

th sublattice this results in the equation:

TcMi-QI,

WM=
i}

0,

(9.2)

i9]

WEISS FIELD THEORY APPLIED TO FERRIMAGNETISM

35

where rhas been replaced by the Curie temperature Tc, since the equation applies to that only. These n linear, uniform equations in the magnetizations

Mj of the sublattices cannot all be independent and they only give a solution
differing

from zero for the

sublattice magnetizations if the determinant of

the coefficients of

Mi

is

zero. This gives

an equation of the nth degree

in

Tc with n

roots.

For example, where n

= 2:
=

0-

(9.3)

W21
This does not
that
is

(Wm--^)
its

mean
for

that every sublattice has

own

Curie temperature;

the

same

all

of them, for the one sublattice magnetization exists

solely

by

virtue of the others. It

means only

that there are n different

versus

T curves

for the resultant magnetization with n Curie points. Generwill

ally speaking,

a number of these roots of the determinant equation

be

negative or imaginary, so that in these cases there will be

magnetization.

Where

there

is

more than one

real,

no spontaneous positive root for Tc

only the state with the highest Curie temperature will occur; the others have

a higher free energy and are unstable. For n

= 2, we find according to (9.3)


C2W22) 2

Tc

= i [CiWn + CtWn + i(CiWu-

4CiCiW\.

(9.4)

For antiferromagnetism (both


follows that

sublattices identical

and W12

<

0)

it

then

Tn
ferred to as the Neel point.

= Ci(Wuis

Wu),

(9-5)

in which case the transition point

re-

In addition to the Weiss


cients

field

coeffi-

which indicate the interaction bedif-

tween the spins associated with two


ferent
sublattices,

equation

(9.1)

also

contains those for the interaction origi-

nating from spins in the same sublattice.


If this interaction is negative,

which

is

usually the case,

it

will try to

upset the
.
.

parallel alignment of the spins within this .. 1-, ... ., .. TT sublattice. However, if the interaction

fernmagnetic crystal. The ion in iU the


.

Fig. ,

9.1.

Ion configuration in a
..

_,

with the other sublattices


will

is

stronger this

centre

is

the

non . magnetic anion;

not happen. In Fig. 9.1 a schematic

a, B' and B" are metal ions.

36
representation
is

FERRIMAGNETISM
given of this situation, which
is

[CH

III

characteristic of ferri-

and the two metal and B" belong to the other lattice (n = 2). There is thus an unequal ions B' number of ions on the two lattices, so that in the case, for example, of occupation by identical ions a net moment can result. The ion A is separated from B' and B" by an oxygen ion, which is responsible for the negative interaction between A and B' and B" as well as between B' and B"
magnetism. The metal ion
belongs to the one
lattice,

mutually. If the latter interaction

is

relatively

weak, the A-B interaction

produces the antiparallel alignment of both B' and B" with A, so that B' and B" are parallel with each other. This applies as long as Jab is greater

than Ub'b", where Jab is the exchange energy between ion or B", and Jb'b" that between B' and B".

and B'

Proceeding from these principles, Neel developed his theory of ferrimagnetism for two sublattices and determined the various possible forms of
the

versus

T curves,

giving a very satisfactory explanation of the

magne-

tizations observed in ferrites with spinel structure, as well as of their para-

magnetic susceptibility above the Curie point. Depending upon the magnitude and the ratios of the magnitudes of the sublattice magnetizations at T

of the interactions, the

versus

T curve

can assume very

different forms.

Although in general the

sublattice magnetizations monotonically decrease

with increasing temperature, the form of the resultant magnetization curve

can be anomalous in view of the fact that it

is

obtained by subtraction of two

magnetizations. For example, the magnetization can pass through zero or

show a maximum as a function of temperature. The former case, which was first reported by Gorter and Schulkes [Go 1 ] (Fig. 9.2), is one of the most direct proofs of the existence of ferrimagnetism. Measurement of the saturation moment would reveal no reversal of sign; this takes place only in the measurement of the remanence established after the application and
return to zero of a strong
field.

The occurrence of magnetization curves of


of ferrimagnetism,
tive interaction

this kind,

which are typical

may

be understood in the following way. Let the negalattices

between the two

= -an Take first the case that Mbo > Mao, with
Waa
o.Wab
Weiss
field

= n, while WBb = PWab = -fin.*)


be

Wab

(9.6)

constant in the B lattice


in the

compared with that

j8 large and a small. The effective h(Mao/Mbo P) is then small at T = A lattice h(Mbo/Mao <*) The magnetization

*)

We

have chosen a and

JS

positive

where the exchange interaction

is

negative, in con-

trast to the practice in

most

existing literature.

9]

WEISS FIELD
20

THEORY APPLIED TO FERRIMAGNETISM

37

600PK
Fig.
9.2.

Magnetization versus temperature curve for

Lio.5Crj.25Fe1.25O4.

Curve II represents the remanence and

curve

the spontaneous magnetization.

in the

B lattice therefore A
lattice.

begins to decrease faster than that in the

lattice

(see Fig. 9.3a), as if the Curie point of the

lattice

were lower than that

At increasing temperatures both sublattice magnetizations vanish, but at the same Curie point. Consequently the Ma versus T curve is more convex than that for Mb, and it is possible that below the Curie
of the
point

Ma Mb will be

equal to zero. In order to explain a magnetization

curve with a

assume that

maximum, a curve which is also found experimentally, we must /? is small and a large. Then Ma decreases less rapidly than

Mb

(Fig. 9.3b).

M
n

o
Fig. 9.3.

In a)

/J

Examples of the cause of anomalous M, versus T curves. is greater than a and in b) a is greater than /J. The M

curves represent the resultant magnetization.

38

FERRIMAGNETISM

[CH.

Ill

in fact

The above theory for n = 2 is applicable to the spinel lattice, for which it was originally developed (see Chapter VIII). For more than two sublattices, such as occur in the hexagonal structures (Chapter IX) no such simple statements can be made about the form of the s versus T curves. antiparallel- oriented magnetizations has been demonThe existence of

strated in various cases


fact that these particles

matter; owing to their

by slow-neutron diffraction [Sh 1] Because of the carry no charge they are able readily to penetrate spin they undergo in matter an extra interaction
.

with the ion cores, from which conversely the magnetic

moment of the

latter

can be determined in magnitude and direction.


9.2.

TRIANGULAR CONFIGURATION

Where, in the case of Fig. 9. 1, Jab < 2Jb 'b", the parallel alignment of B' and = Jab/2Jb'b"becomes such that cos B" is perturbed and the angle This follows directly by minimizing the total exchange energy
<j> <f>

Eex

= 2JA b cos + Jb'b" cos


<j>

2</>.

An

extension of the Weiss field theory for triangular configurations, as

by Yafet and Kittel [Ya 1]. If, for example, Waa< (a > 0) then, where Wab = 0, an antiferromagnetic order will occur in the A lattice, e.g. with two antiparallel sublattices. Analogous to the case described above, this splitting into sublattices, depending upon
indicated above, has been developed

the relative magnitude of the interactions, will sometimes occur for

Wab^ 0,

but the two sublattice magnetizations


differing

will

make an

angle with each other

from 0 or

180.

The Weiss

fields are then:

Hwa = n [aiM/ + a 2 MA " + MB] = -[(<*i 2


'

a 2)MA

'

^MA + MB
2

(9.7)

HWA " = -n[a MA + aiMA " + MB = -[(ai- a )MA " + a MA +MB


] 2

Similar equations apply to the

B
'

lattice:

Hwb = - [MA +

jSiMb'

/S 2

MB = -n [MA + MB +
'

j8 2

(ft.

- ft)AfB
j8 2

']

(9.8)

Hwb" = -n[MA + faMB + ftMs "] =-n[MA + feMB + (ft'

)MB "]

splitting

up of this kind

will

only occur where a 2

> ai, or ft > ft. This is

also the reason for the angle formation: ions between which the greatest

negative interaction prevails are

no longer

in parallel alignment. It further

holds that

MA + MA
'

"

= MA

MB

'

+ MB " = MB

(9.9)

9]

WEISS FIELD THEORY APPLIED TO FERRIMAGNETISM


j8

39

and for a and

from

(9.6) that

= Ki + as)
(9.9) are

= Kfr +

&).

(9.10)

The equations

now

essentially vector equations, like those for

the Weiss fields (9.7)

and

(9.8). It is

evident that the magnetization of a


field

given sublattice must be parallel to the Weiss


also

concerned, as follows
the
first

from minimization of the energy [Ya


then that the vector (a 2
it

1 ].

(9.7) it follows

MA +

From Mb) is

equation of

parallel to

Ma,

and

from the second equation


to

would follow

that this vector

would be

parallel

Ma"- Thus,

if

angle formation occurs in the A

lattice, it necessarily

holds

that

a2

M^ +

AfB

=
we may
write

(9.11)

Likewise for angle formation in the

lattice

MA +
In general, a 2 /J 2 7^
1,

j8 2

AfB

= 0.
will

(9.12)

and therefore angle formation

only be able to

occur on one of the two sublattices at one time. In that case

we may

write

for the Weiss fields where, for example, angle formation occurs in the
lattice,

Hwa = n(P2
while

a)MA
',

(9.13)

HW B=n(p2-pi)MB
AT

(1

P2

(9.14)

In the
ing

A lattice, then, the Weiss field depends only upon Ma, so that accordto (9.14) the Ms versus T curve will have the same form as for normal
The angle
cf>

ferromagnetism.

(see Fig. 9.4)

between the magnetizations of

the sublattices B' or

B" and A
</>

follows
2

from
'

cos

= MA /2p MB < Ma/PsMb,


is

(9.15)

where

Ma

and

Mb

are determined by (9.13). If angle formation occurs,

then according to (9.12) the last term of (9.15) For fixed a 2 and fixed and (e.g. at T

equal to one.

Ma

Mb
j8 2 ,

angle formation) and variable


in Fig. 9.5.

configurations are obtained as


see

For

/? 2

< Ma/ Mb,

we

and calculated without shown from (9.12) that no angle forma-

40

FERRI MAGNETISM
tion can occur in the

[CH. Ill

B lattice. It does
(9.15)

occur for larger values of fa, whereby


the angle
n/l/Me'
<f>

from
(9.11)
is

becomes
it

steadily smaller.

Where

fa = 1/02,

follows

from

and

(9.12) that

angle formation
-n/J 2 Mfl"

possible in both

sublattices; in that case the configu-

ration becomes unstable and, at lar-

ger values of fa,


Fig. 9.4. Triangular configuration

it

changes discontizero).

of the

sublattice

magnetizations

(left)

together

nuously into an antiferromagnetic


configuration
(<f>

with that of the Weiss


lattice.

fields

on the B'

jumps to

Up

to the point fa
field

l/o 2 the Weiss

since a 2

>

a.

In Fig. 9.5

it

can be seen that l/a2

Hwa from (9.13) is still positive, is greater than Ma/Mb


we

but according

to (9.11) this is precisely the

condition with which

started,

namely that no angle formation should occur in the A lattice. With increasing temperature the configuration can change. For instance,
if at

T=

the parallel configuration appears, because, fa


faster with increasing temperature

<

Ma/Mb,

but

MA decreases

than

Mb,

a temperature

can be reached for which (9.12) is applicable, and therefore angle formation occurs. However, this configuration cannot go over into the pure paramagnetic

one when the temperature


respectively.
if

is

further increased, for (9.13) determines

separately the Curie point of the sublattices

Tcb or Tcb"
the ions

These
a

will

and B' or B", i.e. Tca and generally not be the same (they will

only be the same

fa'

fa

on both

sublattices). If

Tca

fa with equal Curie constants of > Tcb', then Mb would be zero


<f>

sooner than

Ma, but

in that case cos

from

(9.15)

would be greater than

0). one, so that at lower temperature the stretched configuration occurs (</> Curie point of the A lattice is the lower, the A On the other hand, if the

lattice will

become paramagnetic
(<

at this Curie point, while the

lattice

will

be antiferromagnetic

= 90).

This lattice does not become para-

Fig. 9.5. Spin configurations

Ma

for variable fc.

Mb

A>

9]

WEISS FIELD THEORY APPLIED TO FERRIMAGNETISM


is

41

magnetic until above the Neel point, which


equation of (9.13).
is

determined by the second

We

have here, then, the special circumstance that there

a Neel point above the Curie point. Thus, the case of both sublattices being antiferromagnetic occurs only when 02/82 1.

>

The

transition of the triangular configuration to the stretched one, or

vice versa,

with variable temperature

is

comparable with the ferromagneticIt is also

paramagnetic transition at the Curie point.


tion.

a second order transi-

The magnetization and entropy are continuous, but with increasing temperature dMs /dT shows a positive jump, accompanied by a jump in
the
specific

heat.

These jumps, however, have never yet been found


1 ]

experimentally.

An

example worked out by Lotgering [Lo

for the spinel lattice with

occupation by identical ions

(Mb

= 2Ma)

is

given in Fig. 9.6, which shows


p.

some possible forms of


ai

M
a.2

versus

T curves for variable a and

In this case
(9.16)

= 0,

= 2a

h=

kP,
is

//,

so that the boundary line for ferrimagnetism

given by a/J

=f

1-7.5

Fig. 9.6. Possible

forms of magnetization-temperature curves for variable v a l ues f a


1 ]).

and

/J

for the spinel lattice. (After Lotgering [Lo

42

FERRIMAGNETISM
Although some of the spins are
antiparallel in
0,

[CH.

Ill

a ferrimagnetic substance
field

without angle formation at


effect,
i.e.

T=

an applied

has nevertheless no

x(T

= 0) = 0,

because the exponents

n(H + Hw)/kT

of the

fields
if

exponentials (6.1) do not change (co), at least as long as the effective remain parallel to the sublattice magnetizations. That will be the case
the applied field
is

smaller than the Weiss

field.

Where angle formation


x

occurs, this angle will

be changed by an applied

field, resulting in

simple calculation shows in the case of angle formation in the


,

lattice

that

irrespective of the

magnitude of the angle. This

is

the

same

susceptibility

that

would be found for a purely antiferromagnetic B lattice. of x at low temperatures above saturation should show whether angle for-

Measurement

mation occurs.
10.

Paramagnetism above the Curie Point

The paramagnetic susceptibility above the Curie point can again be found by expanding the Brillouin functions for a small argument as in (9.2), so that in the absence of an applied field H we may write for each i:

TMiFrom
this

d }=i W fMj =
t

QH.
the 1/x versus

(10.1)

we can
line.

find

M=

Mj.For n

>

1,

T curve is

not

For T^> Tc the curve has an asymptote which can readily be found from (10.1) by first neglecting the Weiss field terms, so that Mt = dH/T, and then filling in these values in the Weiss field terms. For the
a straight asymptote

we then

find

lim l/ x

= I (r- Ta
^

),

(10.2)

T >oo

where

C=
and

S Ct
is

(10.3)

Ta

is

the asymptotic Curie temperature, which

given by
(10.4)

r=S j=i dWiiQ/C. S i=i


is

For antiferromagnetic interactions (Wtj < 0), Ta is negative. In general, Ta a measure of the average magnitude of the exchange interaction. For
it

antiferromagnetism

follows that

Ta = Ci(Wn +

1Z ),

(10.5)

10]

PARAMAGNETISM ABOVE THE CURIE POINT


may be compared
with
(9.5).

43
if

which

Therefore,

Ta = TN
(10.1).

only

W\\

= 0.
but

Formula

(10.2) holds for antiferromagnetism not only asymptotically

also strictly

above the Neel point, as follows from

Thus

for

T>

Tn

the 1/x versus


material.

curve

is

straight, as
is

it

is

in the case of a ferromagnetic

At

T=

Tn, then, x

not

infinite

but

is

given by

x(Tn)

= ~,
Wl2

(10.6)

which
lel

is

the

same value as that

resulting

from the

deflection of the antiparal-

magnetization vectors in (9.17). Below the transition point

TN

the sus-

ceptibility

depends upon the orientation of the sublattice magnetizations


field.

with respect to the applied


stalline

Roughly speaking
is

in a cubic or polycry-

substance two-thirds of the substance


third parallel. In the latter case a

perpendicularly oriented

and one

moment can

only result

if

the ab-

solute magnitude of the sublattice magnetizations changes

owing to the field.


apparently

At

T=

Tn, the susceptibility resulting from

this process is

equal to that in the perpendicular orientation, the latter being independent

of the temperature. At low temperature the parallel susceptibility be-

comes

zero, so that in this case the resulting

is

only two thirds of that at

T=

Tn. Thus, the

1/x T

curve shows a dip at

T=

Tn, which

is

also

found experimentally, although the from 2/3, except for MnO.

ratio x(0)/x(T#) differs in

most cases

For ferrimagnetism, Ta is also negative in most cases, but 1/x becomes zero at the Curie point; above the Curie point the 1/x versus T curve is therefore convex towards the T axis. As in the ferromagnetic case (compare
6.3) the

Weiss

fields
field.
is

immediately above the Curie point are large compared

with the applied

As a

result the ferrimagnetic state with antiparallel


field.

oriented sublattices

then restored by the application of the

With

increasing temperatures the magnetization of the antiparallel lattice decreases

and

at a given temperature

becomes zero. In the case of two


is

sublattices this

temperature, for which

Mi = 0, according to (10.1) T(M = 0) = Ci( Wu - W12).


2

equal to

In the case of an antiferromagnetic this temperature coincides, according


to (9.5), exactly with Tn,

which agrees with the fact that for

T > Tn
are

the sublattice
parallel.

magnetizations

in antiferromagnetic substances, too,

shows the various forms of the 1/x versus Tcurves for equal values of C. The curves, for anti ferromagnetism and ferrimagnetism (above the
Fig. 10.1

temperature of (10.7)) thus he above the curve for pure paramagnetism be-

44

FERRIMAGNETISM
Fig.
10.1.

[CH.
1/x
versus

Ill

>/x

>// //

curves for

(paramag(ferromagne-

netism),

>

tism)

ss
,'

,/ ' 0/
l< fields

Ys'
i

(antiferroand / < magnetism and ferrimagnetism).

f^^^

cause the Weiss

oppose the applied

field.
is

The curve for a ferrimagnetic

with a Neel point above the Curie point

given in Fig. 10.2.

The fact that the 1 /x versus T curves for ferrimagnetics are concave and for at least to the first approxiferromagnetics and antiferromagnetics straight mation follows also from more general thermodynamic considerations

with reference to

In this respect an antiferromagnetic does not differ from a ferromagnetic. In the Weiss field approximation there is complete disorder above the transition point. The establishment of a magnetization
(5.23).

caused by an applied
is

field is

then quite distinct, that

is

to say the

dS/d(M2)

independent of the temperature. In a ferrimagnetic, on the other hand,


is

the antiparallel order

restored just above


is

Tc when the field is applied. One


i.e.

of the sublattice magnetizations


zation.

then larger than the resultant magneti-

There arises, then, a


field

relatively large order,

dS/d(M2) is large, and


is

becomes smaller with increasing temperature where the Weiss fields decrease.

The Weiss
to the

approximation as applied to ferrimagnetism

subject

same criticism as when it is applied to ferromagnetism. For instance, Kaplan [Ka 1] has worked out that at low temperatures a Bloch T3 ' 2 law, analogous to (5.22), must also apply to the change of magnetization with temperature. In this approximation the spins of neighbouring A and B ions remain essentially antiparallel during thermal agitation and therefore the ratio Ma/Mb should remain constant. The resultant magnetization

p*

Fig.

10.2.

1/x

versus

curve

for

ferrimagnetic

substance which, at

T > Tc

becomes antiferromagnetic.

10]

PARAMAGNETISM ABOVE THE CURIE POINT

45

therefore can only decrease with increasing temperature, also in the case of
Fig. 9.3b.

The [Sm

influence of this

Moreover, above the Curie point, short range order will persist. on the susceptibility has been calculated by Smart

1] (Fig. 10.3). Here, again, the slope of the 1/x versus


field

T curve

is less

steep than the Weiss

approximation would have led one to expect. This

can again be explained with the aid of (5.23), for in consequence of the shortrange order, S will be smaller and hence diS/d(M 2 ) also. In this case, too,
the result will be a lowering of the Curie point.

Fig.

10.3.

1/x versus

curve for a

ferrimagnetic substance (a) in accor-

dance with the classic Weiss field approximation and (b) in accordance with more exact methods. (After Smart
[Sml].)

CHAPTER

IV

MAGNETIC ANISOTROPIES
11. Description of Magnetic Anisotropics
11.1

MAGNETOCRYSTALLINE ANISOTROPY
we have
discussed only the mutual orientation of the spins,

So

far

and have

regarded the orientation in the crystal of the resultant magnetization or of


the sublattice magnetizations as arbitrary.

ferromagnetic substance in

which this were the case would be perfectly soft, that is it could be magnetized by an infinitely small field. In reality the magnetization vector in a ferromagnetic specimen
finite field is
is

always bound to a certain preferred direction and a

required to turn

described by an anisotropy energy,


tion energy

HdM from

(2.5)

from that direction. This behaviour is i.e. by the value of the magnetizarequired to turn the vector from a preferred
it

direction into a so-called difficult direction. This anisotropy energy can have

various causes and hence can also appear in various forms.


It

has been found experimentally that the crystal anisotropy can be


first

described by the

two or three terms of an

infinite

power

series in the

direction cosines of the magnetization vector with respect to the crystal


axes. It
crystals

must have the symmetry of the

crystal lattice.

Thus, for cubic

we

have, for reasons of symmetry, the following expression to a

second approximation apart from a constant:

Fk

= Ki(ai

2 a.2 2

a.2 2 a.3 2

<X3 2 ai 2 )

+ Kza^a^a^

2 -\-

(11.1)

in which the coordinate axes coincide with the crystal axes. For the three
principal directions this energy
is

given in Table 11. 1.

TABLE

11.

Energy conditions for a preferred direction of magnetization and anisotropy


cubic crystals
[100]

field for

[110]

[Ill]

FK
(

J*
>0
t

Kl

+ Ti K*

Preferred direction if

Ki)

>
(

Ki

> - ^ K2
-(-Ki

(100):

HA

-2KxlMs

2Ki/M,
(

+ ^KMM,

(110):

(Ki+KMAf.

11]

DESCRIPTION OF MAGNETIC ANISOTROPIES

47

The conditions given

in this table for the appearance of a preferred di-

rection of magnetization are represented graphically in Fig. 11.1, in

which

K\ and Ki
axes.

are plotted along the

K\ 0, K2 > 0, i.e. on the boundary between the [100] and the [110] domains the

On

the semi-axis

magnetization vector
table in the

is

freely rotathis

cube planes in

approximation. Such planes can be


called preferred planes of magnetization.

An

important factor in magnetiis

zing processes

the stiffness with


is

which the magnetization

bound

to

the preferred directions, defined as

d02 ; e

= 0,

(11.2)
Fig. 11.1.

from the position of equilibrium. For the [100] and the [111] directions this stiffness is isotropic and equal to
where
6 is the angle of rotation

The

preferred directions of the

magnetization vector in a cubic crystal for


variable anisotropy contants JKi

and Kz

from

(11.1).

C[100]

= 2K!

c[lll]=--*l--#2.
is

(11.3)

For the [110]


the cube plane

direction the stiffness


find:
C(ioo)

anisotropic,

and for

deflections in

we

[HO]

= 2Ki,
2.

and

in the (1 10) plane:


C(iio)

[HO]

= Ki + K
equal to
0,

(11.4)

These

stiffnesses

may

be compared with that of the magnetic


is

moment

in a field

H, where the energy

E = HMs cos
and
(11.3)
is

the angle between


(11.4)

and

In this case, c = and s can also be expressed as anisotropy fields

M
s

HM
HA

S,

so that

H*
which are included in table

= (l/M )o2Fx /66>2

(11.5)

11. 1.

48

MAGNETIC ANISOTROPIES
The anisotropy energy
in hexagonal crystals

[CH. IV

must have

sixfold

sym-

metry around the c

with the same approximation as (11.1), we therefore write for the energy
axis;

may

FK =
and
<f>,

K-ism?e
is

+ K sm^0 + Ka'smW + K3 sm<>0 cos 6(< +


2

</,)

(1 1.6)

This energy

now

expressed, as

is

conventional, in the polar angles


axis, so that
<*3

where the c axis coincides with the z


ai

= sin
<f>

cos

4>,

a2

= sin

sin

<f>,

= cos

0.

The phase angle can be made zero for suitably chosen axes. The conK and K2 are not related to those in (11.1). Equation (11.6) can be understood only by starting from the direction cosines, in which it must
stants

be possible to express every analytical angular function (one might also proceed from spherical harmonics, which would give the same result).

The energy can contain only even powers of a*, so that cos and hence also sin appear in (11.6) with even powers only. The factor sin6 for the cos
6<f>

term

is
.

due to the

fact that cos

6<j>

is

a polynomial of the 6th degree in

ai

and a2

If the
|>fe

term with K\ is predominant,


case, the preferred

which is often the


direction for
axis (0o

K\ > is along the c it is 0) and for K\ <


i.e.

perpendicular thereto,

in the

e =o

basal plane (0 O = 90). in the latter case, K% = 0, the basal plane


If,

N.^ &o-90

if

is

a preferred plane of magnetiza-

tion.

Where Ki
are

is

not predominant,
as
follows

stable positions in arbitrary direct-

ions

possible,

by

minimizing (1 1 .6). For the case where


only K\ and
consideration,
Fig. 11.2.

K2
the

are

taken into
position

stable

The

preferred directions of the

follows as
O

magnetization vector in a hexagonal crystal for variable

and Ki from
basal plane
is

(11.6).

anisotropy constants K\ 90 the For 6

= 0, if Ki + K >0 and Ki > 0,


2

the preferred plane for the

whereas for

magnetization, while in the sector for which


sin
60

=
\

<
sin20 o

-JiTi

< 2K

2K2

all

directions

on the

shell

a stable position appears with

of a cone have the lowest energy (preferred


cone).

= -Ki/2 K2

11]

DESCRIPTION OF MAGNETIC ANISOTROPIES

49

having an energy
is

Ki z /4K2

lower than that for

=
is

which in the domain under consideration 90. In this case each generatrix or

of a cone of revolution
vector.

a preferred direction for the magnetization

For

all

other ratios of
is

K\ and

the basal plane

is

the preferred

plane of magnetization. This

indicated in Fig. 11.2. In the region

2K2

>

K\

>

metastable positions of

occur. According to measurements

by Sucksmith [Su 1] the preferred cone should occur in cobalt between about 200 and 300C.
For the anisotropy
0o
O

fields

we

find

= = 90
r

H*
9

= 2 Ki/Ms
2
S

HA = -2{Kr + 2K )/M
Hi

(11.7)

sin e

=l/ 2K
2

= THKilKfi

(/sTi

+ 2K2)/M

where

Hf

represents the effective field for rotations of the magnetic vector

in the direction in which only 6 changes, while

H, given by
(11.8)

H$
represents that for rotations
It

= 361*31 sin*0 o /Ms,


the surface of the cone.

on

appears from experiments that in most cases the crystal anisotropy

is

upon temperature. This can also be expressed in terms of dependence upon the spontaneous magnetization. The experiments
very strongly dependent
for iron, for example, then give

K\ccMs w and
,

for nickel even

KiccMt 20

Van Vleck's [Va 2]


ture.

theory indicates a less strong dependence

Zener [Ze

1 ],

however, has evolved a classical

upon temperatheory from which this


this,

strong temperature-dependence does follow. According to

the uniaxial

anisotropy constants K\ from (11.6) should vary


to

more slowly proportionally

3.

Zener's theory proceeds from the premise that

M changes with tems

perature as a result of

random

variations in direction in small regions; the


all

length of the vector remains constant,

that changes being the projec-

tion in the direction of the bulk magnetization. This will be approximately

true at low temperatures, at which only slowly variable spin deviations occur
(spin waves of large wavelength). Zener

equations (11.1) or (11.6)

assumed that the macroscopic remain valid for the direction variations due to
s is

thermal agitation. Since


in direction can occur,

proportional to cos

0, fairly

large variations

netization

and hence large changes in energy, without the magchanging appreciably. The change in crystal energy with tempera(1 1 . 1)

ture will also be greater the faster this energy changes with the angle, like

the

terms in

and

(11.6).

Zener assumed a diffusion process (random

walk) for the local variations of the magnetization vector in direction, and

50

MAGNETIC ANISOTROPIES
power term

[CH. IV
in the crystal energy

calculated for the variation of the n th


(really the

n th spherical harmonic)

K(n)ocMsn(n+1)
i.e.

'

2
,

with an exponent of
1]

3,

10 and 21 for n

2,

4 and 6 respectively. Keffer


better applicable at high

[Ke

has shown that

Van

Vleck's theory

is

temperatures.
11.2.

INDUCED UNIAXIAL ANISOTROPY IN CUBIC CRYSTALS


disordered alloys, and also in various ferrites with cubic crystal

In

many

structure, a uniaxial magnetic anisotropy

can be brought about by subjectfield.

ing the material to an annealing treatment in a magnetic


for the occurrence of the anisotopy
is

A condition

that the ions in the crystal should exhibit

no complete ordering and that the Curie point should be sufficiently high to allow the ion diffusion below that point to take place rapidly enough. The fact that the ion diffusion takes place appears from the curve of the treatment time plotted against temperature; from this curve an activation energy can be derived of the order of 1 to 2 eV. The applied magnetic field need
be no stronger than
value has
is

necessary to orient the magnetization at the temperais

ture at which the treatment

carried out; increasing the field above this


field to

no

effect.

Upon

slow cooling in the


is

room temperature
itself in

the high temperature state preferred


direction

then frozen-in, which manifests

of magnetization.
in cubic crystals can be represented

The induced anisotropy energy


the formula:

by

Em = -iWPl 2 +
where
a*

a2 2 |S2 2

a 3 2 j3 3 2 )

+
(H-9)

G(aia2i3i^2 +
ment and
tropy
is
j8i

aia-zPlfo

0203^2^3),

are the direction cosines of the magnetization during the measureare the direction cosines of the magnetization during the

mag-

netic annealing at elevated temperatures.

For

G = 2F the
field

induced anisowith respect to

independent of the direction of the annealing


i.e. it is

the crystal orientation,

of the form
(11.10)

Em = Ku sin2 (6-6u )
where

6 B u is the angle which the magnetization during the measurement makes with the annealing field. This equation applies to polycrystalline

specimens.

11]

DESCRIPTION OF MAGNETIC ANISOTROPIES


have seen that an anisotropy of the form sin 2

51
exist in

We

cannot

a cubic

crystal.

The contributions of the interactions of the neighbouring atoms around a given atom cancel each other out. This condition can be eliminated
by deformation of the
crystal, as occurs

Neel [Ne 2] and Taniguchi and


if anisotropy occurs in the

Yamamoto

with magnetostriction ( 13.2). [Ta 1] have pointed out that,


also cancelled in cubic alloys
similar atoms, for

as regards the bonds, this cubic symmetry

is

number of bonds between


lines

example when the connecting


in a diluted alloy are
direction. In that case
all,

between neighbouring atoms dissolved

or for the greater part, parallel to a particular

a magnetic anisotropy

may be

expected of the form


is

E= K

sin 2 6, in

which the sign of

K can

still

be arbitrary. In alloys,

the angle which the spin makes with the line connecting the atoms.

The

magnitude of K is proportional to the number of pairs of neighbours, which,


for a disordered alloy,
is

proportional to x z , where x is the (low) concentration


diffuse, as

of the foreign atoms. If the atoms are free to

they are at elevated

temperatures, a specific spin direction will conversely have a preference


for that orientation of the pairs which reduces the energy.

The

probability

of a pair occurring with an axis which makes an angle of the magnetization


is

a with the direction

then proportional to

P(0) oc exp.

-ea sin 2
an

/kT=

- e sin

6 a /kT

(11.11)

where
at

e a is

the magnitude of the anisotropy energy per


is

bond

(<^.kT).

If this configuration

frozen
is

in,

axial magnetic anisotropy will be


is

found
ea

low temperatures which

proportional to e ey, where et

the magnitude

of the anisotropy at the temperature of the measurement. In general

and e T have the same


direction
positive.
is

sign, so that, irrespective


i.e.

of the sign of e, a preferred

in fact always found,

F,
e

in (11.9)

and K in

(11.10) are

Neel brought the magnitude of


13.2).

into relation with the magnetose,

triction

of cubic material and showed that


This

converted per
10 8

cm3

is

of the
,

order of magnitude of XE (see

may amount to
It

10 9 erg/cm 3

corresponding to several
treatment

cm-1

per bond.

can happen, depending upon


field,
(s.c.)

the crystal structure, that for a given orientation of the field during the heat

bonds will have the same orientation with respect to the as for example for the bonds in a [111] direction in a simple cubic
all

lattice

or in the [100] direction in a b.c.c.


rise to anisotropy.

lattice.

In that case the annealing

does not give


for

field-cooling energy for

an

s.c. lattice

an

f.c.c. lattice

(11.8) will

The term with F in (11.8) represents the and that with G for a b.c.c. lattice; apply with G = 4 F. The above applies, then,
axis of the magnetic energy coincides

if it is

assumed that the anisotropy

with the line connecting similar neighbours.

52

MAGNETIC ANISOTROPIES
12. Origin of Crystal Anisotropy

[CH. IV

S
is

12.1

DIPOLE-DIPOLE INTERACTION
energy between two magnetic dipoles
fi\

The

classical interaction

and

fiz

given by
(1,2)

= 3
r

(12.1)

r5

in which r indicates the distance apart of the dipoles.


parallel or antiparallel, (12.1) reduces to

Where ^i and

fi2

are

(1,2)

= r

(1

- 3 cos2

0i2)

(12.2)

where

12 is

the angle between the direction of the dipoles

necting line.

The

sign applies to the parallel orientation

to the antiparallel.
pairs.

For a crystal, (12.2) Because of the relatively slow decrease with distance of (12.2) the
is

and the conand the sign must be summated over all dipole

interaction between

dipole energy

must be taken into consideration. The total therefore dependent upon the shape of the crystal. For a
all

pairs

uniformly magnetized sphere of a substance with a cubic crystalline structure,


(12.2) is exactly zero; this

Over each
dipole
/,

shell

of the sphere,

can readily be seen for a dipole in the centre point. < cos 2 6 > 1 / 3 The field hi acting on a

in the direction of the dipole

/ is

Ai

= -?-^(l-3cos0),

(12.3)

the potential (12.2) being of the

of the Lorentz
ellipsoid

form (2.9). The field hi of (12.3) is the sum and the demagnetizing field. In a general both are uniform. For the special case of a sphere these fields
field (see 5.2)
i.e.

exactly cancel each other out.

In non-cubic crystals, (12.1) will not be isotropic, even for a sphere,


it

will

depend upon
field is

the direction of magnetization. It can be said that the

Lorentz

then anisotropic. The dipoles within a sphere having a radius

of a few atomic diameters


dipole in the centre point.

now produce a

resultant field at the site of the

The contributions of

dipoles at large distances

apart again cancel each other out, as for the sphere of a cubic substance.

Consider therefore the dipoles in a spherical


with the radius. The spherical shell

shell the thickness


still

of which

is

at least equal to several times the lattice spacing, but

compared then contains per unit solid angle an


small

equal number of dipoles at every part, so that irrespective of the structure

12]

ORIGIN OF CRYSTAL ANISOTROPY


is

53

the contribution to the field in the centre point

zero.

The

dipole energy
1 ]).

can be calculated by a method reported by Kornfeld

(see Kittel [Ki

What
is

interests us is the

dependence of

this

energy upon the orientation of

the magnetization in a ferromagnetic material.

Owing

to the fact that (12.2)

a quadratic form in cos


thus

0,

the resultant energy will also be only a quadratic

form of the
is

direction cosines.

The most general form of this dipole energy

^dipole

= S

Ey

Ojcy

(12.4)
(11.6) in

This energy can


crystals,

make a

contribution to the

K\ of

hexagonal

in which then only 33 = 0, (c axis in the z direction); viz:

33

K\.
It

In the case of a cubic ferromagnetic crystal, (12.4) cannot, for reasons of

symmetry, be anisotropic.
magnetic
crystal.

can, however, in the case of a cubic antiferroslight

Apart from a

deformation, which

is

discussed in

the next section, the ion order has cubic symmetry, but not necessarily

the spin order. This


8.4) in

as

is

is the case for example in the MnO crystal (see Fig. which the spins in planes normal to the [111] direction are parallel, found by neutron diffraction. In the case of MnO the energy (12.4)

for the spin configuration as


-Edip

drawn

will

have the form:


ai<i3

2 I?i2(aia2
[1 1 1 ]

(X2C13),

(12.5)

which has an extreme value in the


the [111] axis).

direction (ellipsoid of revolution about

The

spin order in cubic ferrites with spinel structure also

has cubic symmetry, so that the dipole interaction cannot result in aniso-

tropy in these

either.

y&

So

far

we have

given a purely classical treatment of the dipole energy

on

effect to

Quantum mechanically there is yet another be considered, since in consequence of the general expression (12.1) for the dipole interaction some energy can be gained when the spins are not
the basis of equation (12.2).
in purely parallel alignment; this can

happen when mingling takes place

with a state in which the component of the spin

moment
h.

in the direction

of the total magnetization

is

smaller by an

amount
is

For S

= ^ this means
We
are

the state with opposite spin, so that the angular deviation


able.

may be considereffect.

For large values of S the angular deviation

relatively small.

concerned here then with a purely quantum mechanical

The

inter-

mingling will differ for different orientations of the magnetization vector


with respect to the crystal axes, resulting in anisotropy of the energy. Al-

though usually much smaller, this is of the same form as that due to spinorbit interaction, which we shall now consider.

54
12.2.

MAGNETIC ANISOTROPIES
SPIN-ORBIT INTERACTION

[CH. IV

As we have
with sin 2

seen in 12.1, the classical dipole energy can only give a term in (11.6). The occurrence of anisotropy in cubic materials and

the additional terms in (11.6) must therefore be explained by spin-orbit interaction, which was discussed in 3.3. The result of this spin-orbit inter-

[Va 2] that the total orbital angular momentum is no longer quenched and that the charge distribution will acquire an anisotropy depending upon the direction of spin. This can contribute to the magnetic
action
is

anisotropy in two distinct ways.


(a)

The

indirect exchange

depends upon the overlapping of the wave

functions (orbits) of the electrons of the anion and the metal ion. Thus,

ow-

ing to spin-orbit interaction, this overlapping can vary as

it

makes

spherical

charge clouds slightly ellipsoidal, and the extent to which it does so differs with differing spin orientations. The energy difference AE with a given excited
state (corresponding to the

jumping of an electron from the anion to the metal ion) can vary in a similar way. This mechanism is described as anisotropic exchange; for a substance with uniaxial anisotropy
,

it is

in the order

of magnitude per ion of J(X/AE) 2 where / is the effective exchange energy. It will be shown in 20 that X/AE is approximately equal to the deviation
0.1, so that J(g- 2) 2 Usually, g 2 of the g factor from 2, so that should be of the order of 1000 K the constant Ki from (11.5) for Tc 10 8 erg/cm 3 which is rather large. Higher approximations yield 10 7
.

K=

- ~

the next terms in the series expansion for the energy. It appears that subsequent terms should differ by a factor (X/AE) 2 which is quite small. In prac,

tice

a greater ratio

is

often observed. This

may be due to

the fact that

AE is a

fluctuating quantity in inhomogeneous media, which favours the higher terms.


(b)

One may
state

also consider only the interaction of the metal ion in the


field (see 3.2),

ground
ions
is

with the crystalline

having due regard to spin-

orbit interaction. In that case the exchange interaction

from the surrounding

taken only indirectly into consideration, in order to ensure that the magnetic moment of the ion is preferentially parallel to the bulk magnetization.

For the

rest,

the treatment

is

similar to that for a paramagnetic ion.

The mingling of states with an orbital angular


the energy,
crystal axes.

momentum

will

depend, like

upon

the orientation of the spin vector with respect to the

For the case that the ground state is non-degenerate, the result is of the same order of magnitude as under (a), where / is replaced by some energy splitting due to the crystalline field. Which of the mechanisms (a) or (b) is more important, or which mode of description is the correct
one,
is

in general difficult to say.

13]

MAGNETOSTRICTION

55

13. Magnetostriction
13.1.

VOLUME MAGNETOSTRICTION

The thermal expansion of a ferromagnetic substance shows a change in slope at the Curie point (see Fig. 13.1) and at low temperatures the dimensions of the body differ by a fraction 10 -3 from those which it would have if it had not become ferromagnetic; this appears from extrapolation of the curve above the Curie temperature (curve (a) in Fig. 13.1). For a ferromagnetic material with cubic crystal structure, this strain which we shall for the

moment assume

to be independent of the spin orientation


it is

can only be

isotropic, that is to say

purely a change of volume. In the case of hexaso, the strain

gonal ferromagnetics, for example, this need not be

then repre-

senting a change of volume plus a change of shape (e.g. greater strain along
the c axis). In cubic antiferromagnetics, in which the magnetic ordering
is

non-cubic

(e.g.

as in
is

MnO), a change of shape

(trigonal deformation)

also occurs,

which

likewise of the order of magnitude of 10~ 3 .

the exchange energy

The cause of the expansion anomaly is to be found in the dependence of upon interatomic spacing; this appears with metals,
1 3.2),

for example, in the so-called Slater curve (see Fig.

in which the exchange


shell

energy is plotted as a function of the ratio of inter-ionic distance to the


the iron group). This curve shows a

diameter of the electrons responsible for ferromagnetism (the 3d shell for

maximum;

for small distances the interlies

action

is

negative. In a material for

which the representative point

to

the left of the

maximum,

additional expansion will occur below the Curie

point, since in that case the exchange energy will increase (lowering of energy).
Fig. 12.1, then, applies to a material with relatively large interatomic spacing.

The change of exchange energy with interatomic


found by minimizing the
total energy:

distance d//da can be

d/ E=N (aaa
,

+ \c[

/a ad~
cio

Anomalous thermal expansion The broken curve of ferromagnetics.


Fig.
13.1.
is

J. Sa

^xS^W-Mo
*fb)

for the hypothetical paramagnetic sub-

stance, while (b) tization

would apply if the magnewere to remain equal to that at

T=

0,

(AT

Mo).

56

MAGNETIC ANISOTROPIES
Fig.
13.2.

[CH. IV

Dependence of

exchange energy upon the


ratio of the inter-ionic spa-

cing and the diameter of the


shell

of the magnetic elec-

trons.

where

is

the

number of atoms per cm3 a


,

the interatomic distance for

and

c the elastic constant.

We then find
Nao dJ
c

a ao _ _
ao

da

For
ao
erg,
it

10- 3 , a

= 3 X 10-8 cm, c =
d/^

10 12 dyne/cm 2 and

= 3 X 10~ 14

follows that

=~ da

/
3x10-8'

which
If

is

of the right order of magnitude.

K is subjected to a very strong a ferromagnetic substance at T field, a small change of volume occurs, which is known as volume magnetostriction. The strong field causes a slight increase in the intrinsic magnetization (cf. (6.15)), so that in Fig. 12.1 the curve sags in the direction of curve (b), which would apply if the spontaneous magnetization were to

>

remain constant as a function of temperature. However, the change of volume (and, in non-cubic ferromagnetics, also the change of shape) is relatively

owing to &M/5F being so small. There must therefore be a relation between the position on the Slater curve, the expansion anomaly and the volume magnetostriction [Sh 2j. This relation is satisfied in the case of the
small,

metals iron, cobalt and nickel. In gadolinium the magnetic 4/ shell lies well inside the atom, and therefore the point in question should lie to the right of
the

maximum on

the Slater curve. However, the expansion

anomaly has

the opposite sign, and an expansion occurs below the Curie point [Ba 4]. For alloys, too, this relation is not always satisfied. This may be due to the
fact that there are several interactions,

which do not always contribute in

the same ratio for variations in temperature and the application of a field. The indirect exchange energy, too, may be expected to be strongly depen-

dent upon distance. Here too, then, volume magnetostriction and expansion

anomalies

may be

expected.

13]
13.2.

MAGNETOSTRICTION
LINEAR MAGNETOSTRICTION

57

Experiments have shown that the deformation discussed in 13.1 depends


furthermore upon the direction of the magnetization. For a cubic crystal

magnetized in the direction given by the direction cosines

ai,

a 2 and a3

(defined with respect to the cube axes) this deformation, expressed in strain

components
e*

eq(i,j

= x,y,z)

becomes in
/2

first

approximation
),

=3

/2

Aioo(ai 2

- Va), *vv = 3

Aioo(a 2 2

- V3

H,

*xy

= 3/2 Aniaiag,

eyz

3/2 Am2as

= 3 h Aioo(<x32 - Vs), ezx 3 A1110301. /


a

(13.1)

The extra terms x /3 make the total change of volume nil (trace of the matrix is zero). The factors 3 / 2 ensure that the strain in the direction of magnetization with respect to the non-magnetized state (ai 2

a2 2

a3 2

/ 3)

is

A 10 o and

Am in the

[100]

and

[111
is

directions respectively.

The

strain in

direction perpendicular thereto

then

^A 10o
2a 2 2

and

Am

respectively.

In an arbitrary direction
A(ai,a 2 ,a3)

we then have

parallel to the magnetization

= A100 + 3(Am A100) (ai


A,

a 2 2 a3 2

+ a3 2 ai 2

).

(13.2)

For a

polycrystalline substance the average A will be:

2 /5

A100

+3

/5

m
,

(13.3)

ezz

For hexagonal crystals the A values of the deformation components and exz,yz will be different from those of exx yy and exy respectively. For

the ferromagnetic metals the values of A at


parallel

room temperature

(for

Co

and perpendicular to the

c axis) are

found to be:

Fe

Ni

Co
A//

= +25 X 10- Am = -19x 10-


A100

= -46 x 10-6 Am = -25x lO"6


A100
is is

= -60 X 10~ = +16x 10-

<

'

The

origin of linear magnetostriction

closely related to that of crystal

anisotropy. If a cubic crystal

deformed
total

it is

no longer

cubic, so that there

may

also be present a uniaxial crystal anisotropy as in (11.6),

which

is

pro-

portional to the deformation.


consists, then,

The

energy caused by the deformation


approximation,

of

this crystal

energy and the elastic energy.


first

For a cubic
be written
as:

crystal the

deformation energy may, in

F=

1) + eyyW - J) + ^(ag - \)\ + + eyzaiaz + ezsasai) + icii(exx + e yu2 + e +Ci2(e xx e yy + eyytzz + xx + iC4i(e X y + e yz + ezx

Bx

^(ai 2 a.\a.i

+ Bi{Xy

z2 )

+
(13.5)

zz

),

58

MAGNETIC ANISOTROPIES
it

[CH. IV

from which

follows

by minimizing with respect

to ey

and using

(13.1):

Aioo

=
3

en

c\%

^lii

=same

(li.b)

i C44

The

linear magnetostriction stands in the

relation to the crystal

anisotropy as the volume magnetostriction (or rather the expansion anomaly) to the exchange energy. The same mechanisms that give rise to crystal energy
will also

be able to produce magnetostriction. The temperature dependence of A or of B\ and B 2 in (13.5) will thus be as of K\ of uniaxial crystals, i.e. as Ms 3 according to Zener, provided the elastic constants do not change appreciably with temperature. Experimentally, A cc M 2 is found for nickel.
,

3 7 Since the B's are of the order of magnitude of Ki(l0 erg/cm ), A should

found experimentally. by minimizing (13.5), the equation expression in terms of the a's which has cubic symmetry, (13.5) gives an and thus is to be regarded as a cubic crystal anisotropy like the first term
,

be about 10 -5 as

is

Substituting the values of the e's found

in (11.1). This represents the difference in anisotropy energy between the


states

of constant stress and constant strain of the crystal. The order of


this contribution to
is

magnitude of
A

Ki
,

is

cA 2 ; for c
is

10 12 dyne/cm 2

and

10~ 5 , this

equal to 10 2 erg/cm 2

which

usually

much

smaller than

Ki. For cobalt


to

ferrite,

however, Aioo
10 5
6

is

540 X 10-6, so that this contribution


,

Ki

is

of the order of 3 x

erg/cm 3 which
erg/cm3 .

is

no longer

negligible as

against the observed

K\ of 4x 10

An
stress

extra deformation can be brought about by


<t.

means of an external

analogous to the
due to the
Eatress
-

This can be brought formally into the calculation by adding to (13.5)

+pV term
<J

in thermodynamics

a potential

energy

stresses:

= ae = <*xxe xx

yye yy

zze zz

~\~

axy exy ayze yz


we

azxzx.

(13.7)

By minimizing
sist

the total energy

find the deformations,

which now constress.

of the magnetostrictive deformation plus that due to the

This

deformation substituted in the energy gives, in addition to the cubic term in e, a non-cubic term resulting from the deformation due to stresses:

stress

= 3 Aioo /a Am
/2 3

~ ) + 3/y(a2 e xv aiaz + e yz a^az + e x^Z"-l


Oxxfal
2 1
r

1 / 3)
\

/3

zz (3

/3 )

+
(13.8)

We

can interpret

(13.8)

by saying that the magnetostrictive deformations

13]

MAGNETOSTRICTION
stress.

59

must perform extra work against the applied


<7zz

For a

tensile stress

a in the z

axis,

we may

write (13.8), apart

from

a constant, as:
(13.9)

^stress

=3

/2

A<rsin2 0,

which

is

of the same form as the Ki term in


(vertical)

(11.6).

One can

think of a rod
3 /aA,

loaded in the

z direction by a weight. If we change from transversal


so

to longitudinal magnetization, the length of the rod changes by


extra energy of z l%\a

must be supplied, in accordance with (13.9). that an If we insert Young's modulus E for <r in (13.9), corresponding to a doubling
of the length of the rod,

we have made

the material essentially non-cubic.

must then be of the same order of magnitude K\, which comes down to the as the quadratic term in (11.6), i.e. XE qualitative relation between A and K\ given above. The order of magnitude of

The anisotropy energy

(13.9)

(13.9) for

<t

1000 kg/cm 2 (10^ dyne/cm 2 )


is

is

approximately 10 4 to 105

erg/cm3

which

in the region of the energy of cubic crystalline anisotropy.

CHAPTER V

MAGNETIZATION PROCESSES
14. Weiss

Domain

Structure
it is

In consequence of the demagnetizing energy

usually

more advantage-

ous for a ferromagnetic body, rather than to be uniformly magnetized, to


divide itself into a

number of Weiss domains,


(2.8),

in

which the magnetization

vectors are parallel to a preferred direction such that the demagnetizing


fields,

and hence the energy

are as small as possible. These uniformly

magnetized domains are separated by a thin layer in which the direction


of the magnetization gradually changes from one orientation to another.
This transition boundary,

known

as a "Bloch

For the division into Weiss domains to be effective, no magnetic poles must form on the wall, that is to say the component of the magnetization perpendicular
wall", will be discussed in 15.
to the plane of the wall must, according to (1.8),

be equal at both
14.1.

sides,
is

i.e.

Mn = Mn
\

in Fig.
Fig. 14.1. Orientation of the

The requirement

that the wall should be

parallel to the difference vector

(Mi M2). With

magnetization

vectors
side

Mi
of a

two

directions of magnetization, then, there are

an infinite number of wall orientations. is not satisfied, demagnetizing fields will still appear and the Weiss domains will have lost, in part, their reason for existence. Fig. 14.2 gives some examples of Weiss domain structure with so-called 90 and 180 walls in which there is flux closure, that is to say no magnetic flux leaves the structure and hence there is no demagnetization. Weiss domains also occur in order to eliminate internal
associated
If the

and Mz at each Bloch wall.

above requirement

Fig. 14.2.

demagnetizing forces. This was pre-

by Neel [Ne 3 ] and later found by experiment. In Fig 1 4. 3a the Weiss domain structure is given around
dicted

a hole or non-magnetic inclusion in


a cubic material. Demagnetization
is

not entirely absent since there

is

always some charge present on the


walls that are not perfectly parallel.

Examples of Weiss domain configurations in which flux closure occurs.

This need not be the case

if

there

is

14]

WEISS

DOMAIN STRUCTURE
As was
total
first

61

a 180 wall near by


Lifshitz [La
1 ],

(Fig. 14.36).

the geometry of the Weiss

mined by the requirement that the


energy, this
also

remarked by Landau and domain structure is deterenergy must be minimum. In


Inside the wall the spins

addition to magnetostatic energy and crystal energy or other anisotropy


includes

the wall

energy.

are not parallel, and, because they are not aligned in the most favour-

Fig. 14.3a)

Formation of extra Weiss domains around an

inclu-

sion to avoid demagnetization energy. In b) there is a Bloch

wall near the inclusion.

able direction, this costs exchange energy and crystal anisotropy energy.

The
to

result is that the wall

has a

finite

energy per unit area, which


15.

shall designate

aw This
.

will

be dealt with more in detail in

we Owing

the

occurrence

of these

domains,

e.g. in Fig. 14.26, will

minimum of
will

the total

two kinds of energy, the width of the have a specific value, corresponding to a energy, and also the configuration in Fig. 14.36
if

change to that of Fig. 14.3a

the 180 wall

is

too far away. The wall

area is
if

reduced at the expense of some demagnetization energy. Furthermore,


is finite,

the magnetostriction

strain energy has to

be taken into account,

for,

except in the case of a 180 wall, the magnetostriction differs at each

side of the wall, giving rise to strains.

\f
ft

\w
\\\

\\t
ttt
ftt

W
H U

tf

\\\

Fig. 14.4.

Weiss domain formation

in a thin plate.

62

MAGNETIZATION PROCESSES

[CH.

We

shall determine,

by approximation, the thickness d of the Weiss do-

mains for the configuration of Fig. 14.4a, i.e. the same as Fig. 14.16, but without closure domains. The demagnetizing energy is proportional to the ratio d/D of the Weiss domains, where the values are not too large,

being the thickness of the specimen plate. Calculations show [Ki 2]

that the demagnetization energy per unit


netic material is 1.7

d/D.

The

wall energy per

volume of the plate of ferromagcm3 is ow /d, and hence

the total energy

is

=1.7Af.- +

^. d
d equal
to zero gives:

(14.1)

Putting the differential of

E with

respect to

(LZ^)i
crystal anisotropy.

(,4.3)

We have here
is

assumed a uniaxial

Where

K = K\ + Ki

from Fig. 14.2b will also be possible; some competition between the crystal energy and the wall D the wall energy. The crystal energy is Kd /ID per cm3 while for d energy is practically unchanged; in (14.1), then, the first term on the right hand side is replaced by Kd/2D. If the latter is smaller, the configuration from Fig. 14.26 will appear, that is if K < 3AMS 2 For cobalt at room tem2 = perature, 5 X 10 6 erg/cm 3 and s s = 1430 gauss; hence 3.4 6 3 The above calculation holds good for the case where the 7 X 10 erg/cm magnetization outside the walls cannot deviate from the preferred direction.
not too
large, the configuration

there will then be

K~

In reality this will not be the position of equilibrium, owing to the demagne-

no longer be mutually and will fan out slightly near the surface (Fig. 14.46). If the variation in direction is slow compared with that in a domain boundary, which is the case when the Weiss domains are thicker than the walls, the change in exchange energy is negligible. If the permeability due to rotations is /irot, the demagnetization energy is reduced by a factor (/urot + l)/2. It will be seen in 17 that jurot is equal to 1 + 2ttM$ z /K, so that the demagnetization energy for cobalt is reduced to about 3.1 x 10 6 erg/cm 3 for cobalt, therefore,
tizing fields arising. Consequently, the spins will

parallel

the configuration in Fig. 14.4 should appear. This

experiments by Germer [Ge

ment (cathode

rays),

is in agreement with who, with the aid of electron bombarddemonstrated fields of the order of 104 oersteds on a 1 ],

surface perpendicular to the c axis.

From (14.2) it follows that d/D

oc

D~i, so that the Weiss domains become

14]

WEISS

DOMAIN STRUCTURE
The
derivation
is

63

less slender as the thickness

D diminishes.

then no longer

valid. If

K<

2itM, 2 , the magnetization will rotate in the plane of the

plate at a thickness

DI0 <
t

6.8

M ^w
s

K
a

(14.4)

as follows by putting the energy (14.3) equal to K.

For every

finite

body

there

is

critical

dimension below which no

Weiss domains can

exist. If

the dimensions of a given configuration be re-

duced uniformly by a factor /, the demagnetizing energy will change by a factor/3 but the wall energy by/ 2 As regards a sphere one has to compare the configurations in Fig. 14.5a and b, in order to calculate the critical dia,
.

differ

meter in a material with uniaxial anisotropy. The demagnetizing energies 2 3 The loss by about a factor 2. The gain, then, is about (tt 2 /18) s Z>

in wall energy

is

ttD 2 ow /4, so that for the sphere

!),r=1.4(r,/Af,

(14.5)

In the next section we shall see that in most materials a w is of the 1000 gauss, then, the critical order of magnitude of 1 erg/cm 2 for s
;

dimension

is

D cr =
Where

10~ 6 cm. This

is

very small, being in most cases of the


thickness,

same order of magnitude as the wall


longer valid.

D is

smaller than the wall thickness, single

and the calculation is no domain be-

Fig. 14.5. Magnetization in

a small sphere without

and with Bloch

wall.

haviour

fairly large

some permanent magnetic oxides in which aw is -4 cm. and s small, D cr may be of the order of lO With the same assumptions for aw and s we can estimate the thickness of the Weiss domains. According to (14.2) where D = 0.1 cm, it follows
is

the result. In

that

x 10~4

cm. If the

size

of the non-magnetic inclusion or hole in

Fig. 14.3

is

several times smaller than that given

by

(14.5),

no extra Weiss

domains will appear here either. The Weiss domain structure can be made visible on a surface under the microscope with the aid of a Fe3C>4 powder colloidally suspended in a soap solution. This powder coagulates at the position where the strongest field

64
prevails.

MAGNETIZATION PROCESSES

[CH.

Even though the magnetizations in the Weiss domains are parallel to the surface, so that no stray fields can be expected, these nevertheless appear at the position of the wall, thereby making the walls visible. An example of a powder pattern on a crystal oriented sample of BaFe^Oig is given in Fig. 14.6. In the case of metals the surface must be thoroughly destressed, for example by electrolytic polishing and annealing, otherwise the Weiss domain structure appearing on the surface will not be representative of that inside the material. Owing to the occurrence of closure domains this pattern can differ from the simpler domain structure below the surface. Another way of making ferromagnetic domains visible is to analyse the light that has passed through a ferromagnetic body. As a result of the optical
Faraday
effect the

plane of polarization of plane-polarized light will be rothe light passes a thin sample parallel to the

tated differently

when

maggives

netization of oppositely oriented Weiss domains. Fig. 14.7a


pictures obtained

and b
is

by Kooy [Ko

1 ]

with the help of a polarizing microscope


a single

with not completely perpendicularly oriented nicols. The sample


crystal disc of

BaFei20i 9 with a thickness of about 1 micron. The magnetization of the domains is perpendicular to the surface of the disc. The light and dark regions are domains with oppositely oriented magnetizations. Fig.
14.7a applies to the demagnetized state, Fig. 14.76 to a state after complete

magnetization perpendicular to the plane and allowing the


to zero.

field to

return

method is that which makes use of the magneto-optical Kerr effect. The reflection of light on the surface of a magnetic material depends on the permeability. Results for the compound MnBi have been obtained by Roberts [Ro 1 ].
third
15.

The Domain Boundary (Bloch

wall)

The

transition of the spin direction

from one Weiss domain

to another does

not take place abruptly, since that would cost too


Instead, there
is

much exchange

energy.

a gradual rotation of the spin vectors, as shown schemati-

cally in Fig. 15.1.

To

prevent demagnetization the normal component of

the magnetization remains continuous inside the wall also.

An

exact cal-

culation of a 180 wall has been given

by Landau and Lifshitz [La 1]. To estimate roughly the wall energy aw and the effective wall thickness
S w,

we

shall

approximate the spin configuration inside the wall by assuming

the (small) angle Aj> between the spins in successive atomic layers parallel to the wall to be constant. According to (5.1) (with cos

</>

^
1

i(A<j>) )

and

(6.14), the

exchange energy per


ex

cm2

of the wall will be of the order of


,

= kTc/aS w

14)

WEISS

DOMAIN STRUCTURI-

65

I-'ig.

14.6.

Powder pattern of polycrystallinc BaFciaOis.

66

M AG NETIZATION PROCESSES

[CH.

15]

THE DOMAIN BOUNDARY (BLOCH WALL)


is

67

where a
to

the lattice constant.

The exchange
is

interaction will thus tend


crystal energy,

make

the wall as thick as possible. This

opposed by the

which

will

be of the order of magnitude of

OK

= \Ko w

Hence a

stable equilibrium will appear

where

2kTc

S>

aK
cm 2
is

(15.1)

and therefore the

total wall

energy per

a Wz

i/ 2kTc .K

K8

(15.2)

This wall energy, then, consists for one half of crystal energy and for the
other half of exchange energy. For

Tc
1

= 2x

10~ 8 cm, a w

is

of the order of

= 1000 K, K= 10 erg/cm and erg/cm and S w = 10~ cm, corres5

ponding to several hundreds of inter-atomic spacings. We see immediately that the assumed configuration cannot be the correct one if we consider the
equilibrium of one individual spin. If the angles

made by

this spin

with

<L

i>

\\
a

^JT\
IF

Fig. 15.1. a) Spin configuration inside a Bloch wall,

Angle of deviation ^ as a function of position. The broken ration on which the calculation was based.
b)

line indicates the configu-

68

MAGNETIZATION PROCESSES

[CH.

the preceding and the succeeding spin are equal and opposite, the same will hold for the torques acting on the central spin, so that owing to the exchange interaction the total torque acting on the spin is zero. This is not the case

with the crystal energy, since the spin

is

not in the easy direction. This crystal


difference in exchange couples

anisotropy couple must be cancelled

by a

caused by

the inequality of successive angles.

The

difference should be

smaller the nearer the spin approaches the preferred position (the crystal

anisotropy couple

is

then proportional to the angle of deviation from the


it

preferred direction)

from which
.

follows that
it is

<

oc

S^d^/dz,

so that for

>

8W ,

<f>

oc exp.

z/8w Actually
sin
<f>

found that
(15.3)

1/cosh (z/8 w).

is not much affected by this erroneous assumption of the conowing to the fact that we have minimized it. The term wall thickness, then, has a meaning similar to that of the skin depth of electromagnetic waves in conductors. From (15.2) we see that the wall energy is proportional to ^K. For two materials with approximately the same Curie temperature and lattice con-

The energy

figuration,

stant the wall energy will thus be greater for the material having the larger
crystal anisotropy,

whereas the thickness of the wall will be smaller. In

general, a variation in
ever,
it

K is also caused by a variation in temperature.


in

How-

must be borne

mind

in that case that the expression for the energy

of exchange interaction, which


at high temperatures,
(5.1) it

we have put

equal to kTc,
is

is

no longer valid
According to
2
,

where the exchange energy

smaller.

seems reasonable to put the exchange interaction energy as propor-

tional to

2
,

so that

kTc in (15.1) and (15.2) must be multiplied by Ms 2 /M


then,

where Mo is the saturation magnetization at the absolute zero of temperature.

As a function of temperature,

we

find according to (15.2) that o w cc

Msi/K, and according to (14.5)

Dcr
In

oc

^K/Ms

(15.4)

many

cases

K decreases
(14.2)
it

faster with increasing temperature than

(see 11.1)

and hence the

critical

diameter for wall formation, owing to

the relative cheapening of the walls, will


peratures.

become

smaller with higher tem-

domains
in

and

From

follows that also the dimensions of the Weiss

this will

apply to most other configurations too


,

will

change in proportion to

fK/Ms

exactly like the critical diameter. Thus,


will

most substances the subdivision into Weiss domains

become

increas-

ingly finer with higher temperature.

16]

MAGNETIZATION DUE TO DOMAIN BOUNDARY MOVEMENT


Domain Boundary Movement

69

16. Magnetization due to


16.1.

PERMEABILITY

An externally applied magnetic field will try to alter the Weiss domain structure and, if
it is

strong enough, will cause the Weiss domains to vanish.


pressure

magnetic

field exerts

on a Bloch

wall. Consider, for example,

a 180 wall and a

field parallel to the

magnetization. If the 180 wall has

moved by a slight amount Ax, then the total magnetic moment has increased by 2 s Ax per cm2 wall area. As a result, the potential energy has decreased by 2 e Ax. The same change of energy would occur if the wall were

HM

subjected to a pressure equal to

= 2HM

s.

(16.1)

This pressure pushes the wall in such a direction that the domain with the magnetization in the same sense as

H becomes larger.

Here 2M

is

under-

stood as the difference between the tangential components of the magnetization at either side of the wall. For other types of walls (e.g. 90 walls)

The pressure thus originates solely from The internal fields B Hot the Lorentz fields 4ttMs/3 are parallel to the local spin vectors and change with the movement of the wall, so that there is no change of energy. These internal fields therefore have no influence on the wall movement. As a general rule the wall will not be entirely free to move. In the foregoing sections we have seen that a particular configuration of the Weiss domain structure will establish itself in a crystal. That configuration corresthe pressure changes accordingly.
the field

H = H + HD (see

1.7)).

ponds to a minimum of
that the walls are

free energy, consisting of demagnetizing energy,

crystal energy, wall energy

and possibly magnetostrictive energy. This means


certain stiffness to their positions of equilifield this gives rise

bound with a

brium. For small amplitudes of the

to a permeability

y.

which

is

inversely proportional to that stiffness.

We

shall

demonstrate this

with a few examples. If the body is irregular in shape, for instance a grain with a constriction, then owing to the surface stress the wall will prefer to extend over the smallest cross-section, like a soap bubble, and will have a stiffness for displacement of <r42 v4/dx 2 , where A is the area of the cross-section. This tendency to reduce the wall area
is

also of importance

when non-

magnetic inclusions or holes are present, as is nical ferromagnetic substances. Attention was first drawn to

frequently the case in techthis by Kersten from hole to hole (Fig. However, it was shown
is

[Ke

1 ],

who assumed

that the walls

would

stretch

16.1a), resulting in the smallest possible wall area.

by Neel [Ne 4] that the reduction of the demagnetizing energy

much

70

MAGNETIZATION PROCESSES
that of the wall energy. This case
is
is

[CH.

more important than


that of Fig. 14.5,

comparable with
its

where the sphere


is

magnetized but not


is

environment;

although the reverse

true here, there

no

difference as regards energy.

The reduction of demagnetizing


than the reduction of wall energy
diameter
(14.5).

energy,
if

then, will be
is

more important

the inclusion

larger than the critical

According to Neel
still

it is

then possible to reduce the demagit,

netizing energy

further, or to eliminate

by the formation of extra


by

domains

(Fig. 16. lb). If the wall

moves, the situation arises as shown in


is

Fig. 14.3, in

which the wall area

larger, so that the wall is held firm

the inclusion.

Where
critical

the dimensions of the inclusion or the hole are smaller than the

diameter (14.5) or the wall thickness, no extra wall formation will


that the exchange energy
it,

take place, but the wall will nevertheless prefer to contain the inclusion.

The reason
in the wall

and the crystal energy are greater and therefore if the inclusion is inside the wall this extra energy will not be called for. The demagnetizing fields will try to turn the magnetization, causing the pole strength to decrease. For inclusions smaller then the wall thickness this will not occur to any appreciable extent since it would cost too much exchange energy. In effect, the dimensions may be compared with a wall thickness formula in which K is substituted by a demagnetizing energy, i.e. with approximately (y^r/Mg)S,. For a change of direction on this
is

than outside

scale the

exchange energy
with
the

is

com1]

parable

demagnetizing

energy. Dijkstra

and Wert [Di

have shown that the wall-immobilizing effect


is

greatest for inclusions

of Fe3C in iron with dimensions


equal to the wall thickness.

The

wall

movement is also hinder-

ed by physical imperfections in the


crystal,

such as dislocations.
is

Where

the atomic ordering

imperfect the
will also

exchange and crystal energy

be smaller. Inhomogeneities on an atomic scale, such as vacancies, and


deviations
j
j
it

"*

from periodicity

as in disFig- 16.1. a)
,
.

~
Wall formation between in' , whereby free poles can appear, b) Extra Weiss domains are formed; so that no or only very few poles appear.
,

ci _i ordered alloys, are of less importance r

elusions,

since the concentration fluctuations

over the distance of a wall thickness

16]

MAGNETIZATION BY DOMAIN BOUNDARY MOVEMENT

71

are small.

are important

The deviations from the periodic structure in a dislocation up to about ten lattice spacings from the centre. However,
one direction over a considerable distance, so
it will,

line dislocation extends in

that if a wall contains the whole line

according to Kersten [Ke 2],

be strongly

bound

to that line.

Finally, the wall

can also be bound by irregular internal mechanical stresses,

for if the magnetostriction A

^ 0, according to (13.8) there will be an extra

uniaxial magnetic anisotropy present,

energy. According to Becker

K in (15.2)

which is equivalent to the crystal and Kersten the wall energy changes because must be augmented by a term of the order of K8 = 3 /2A<r, which
either positive or negative, irrespective of the sign of the stress
stress).

can thus be

(compressive or tensile
the wall energy
is

The

wall will prefer to be at a position where

lowest. Neel [Ne

4] has pointed out that these stresses

cause the preferred direction of magnetization to vary from place to place. Consequently, the magnetization will not be uniform and poles and stray
fields will

appear. In the state so produced the total energy, consisting of

crystal energy, stress energy

mum. Due to
of

KJK =

and demagnetizing energy, will be at minimake an angle of the order with the original preferred direction for Ka < K. The angle
stresses the preferred direction will

of deviation of the magnetization will be of the order of

(K/NMS 2)
is

Ka /NM
applies

2
,

where

a demagneti-

zing factor of the order 4?r/3. This


to the case where

%NMS 2

<K. The

demagnetizing energy will

then be of the order of

Kl/NM* per

cm 3
Fig. 16.2.

This energy can now be reduced


since a 180 wall reverses

Owing

by a wall
to inclusions or internal

stresses, the material contains free poles (a).

the polarity of the charge (see Fig.


16.2).

If a

intersected
will

domain having a uniform polarity is by a wall, the sign of the poles reverse in the domain in which the
(b).

In a domain having a dimen/,

sion perpendicular to the wall of

being the correlation distance

or

magnetization has reversed, resulting in a


reductjon in magnetostatic energy

period of the internal stresses, the

energy is then changed by an amount

l/NMS 2 per cm 2 of the wall. This change in energy density (Kl/NMS 2) is thus much smaller than K itself, but since the former change of energy a takes place over a much larger volume than the latter, which occurs only
of
2

Ka

inside the wall, the effect of the magnetic poles, as suggested

by Neel, can
if

be more important than the

direct

change of the wall energy

>

NMs 2
Sw
.

(16.2)

72

MAGNETIZATION PROCESSES

[CH.

For example, where


then
ler
/

NM ~
S

10* erg/cm 3 ,

Ka =

2x 104

S,

= 5 X 10-6,

>

IO-4 cm, as

is

usually the case, although this distance must be smal-

than the linear dimension of a Weiss domain.

In the foregoing case, the exchange energy was disregarded even though
the magnetization

was not uniform. This

is

permissible if /^> 8 W , which was

the condition for the derivations given.

So
that

far

we have discussed the

factors that determine the position of a single


is

plane wall.
is

Weiss domain structure, however,

stable only as

a whole,

to say the walls are strongly coupled to each other,

and

in general a

particular wall will only be able to


least

a number of them move too.

move provided
If that

that

all

the others

or

at

were not the

case, poles

would

appear which would give


process caused by wall

rise to large opposing fields. The magnetization movement should accordingly be regarded as being
is

a cooperative phenomenon. This


ing the coercive force.

of particular importance for explain-

If the walls are strongly coupled to each other or to imperfections in the


crystal, individual wall

movement

is

nevertheless possible though the bul-

ging of a wall held at the edges. Kersten regards this as the most important

magnetization process in small

fields in

many alloys.

If in the bulging process

the difference vector of the magnetizations at each side of the wall does not

remain tangential to the surface of the wall, poles

will

appear on the wall


this will not

which
case,

will hinder the bulging.

Where

the walls are held by straight lines

parallel to the difference vector

of the magnetizations

be the
stress

and the opposing force

will

then be exerted only by the surface


it is

of the wall, as in the example of a soap bubble. In this case


calculate the permeability resulting

easy to

from a number of these walls

at a dis-

tance

apart,

and we

find

/*=4
in which

Ms*D 2

(16.3)

2 == 10 5 gauss 2 For example, where s 2 we find D d= cm and aw = 1 erg/cm 400. The temperature p, dependence for constant d is as S /^K, hence in most cases it rises sharply 2 with temperature. If d changes as D CT in (14.5), p would change as s /K. Where the wall is held on all sides, pole formation is unavoidable during the bulging process. Consider a ring of diameter D, in which the wall is spanned. If we approximate to the volume V through which the wall moves by an ellipsoid of revolution having major axes D and a minor axis p, the demagnetizing energy can be simply calculated (see Fig. 16.3); it is found to be about (20 p/D) S W, where V = (tt/6) pD*. Here again,
is

the span of the wall.

10~ 3

16]

MAGNETIZATION BY DOMAIN BOUNDARY MOVEMENT

73

the demagnetizing fields will slightly rotate the

magnetization vectors, so that fewer poles will


appear.
will

can be estimated that the pole strength change by a factor K/2wMs 2 (< 1) and
It

therefore the demagnetizing energy (including


crystal energy,

which

will

be of the same order

of magnitude) will

now be

AEd ~K 2pV/M^D.
This energy
is still

greater than that due to

Fig. 16.3. Bulging of a wall held in position at the edges,

the increase of the wall area

under the influence of an


external field
. .

AE,

>

p-6V p ~ aw = 6K = ir/*rw =
,

H. The magne-

Sw
V,

tic

poles appearing are indi-

cated.

since 8 W <z* D.

We

need therefore only take into account the demagnetiis

zing energy.

The magnetostatic energy

2HM .V,
S

so that by mini-

mizing

we

find for the permeability, at a wall spacing d,

H Where
that
if
/x.

~ 20 M\DIKM.
10-3 and

(16.4)

=
In

105

gaU ss 2

D = d=

K=

ios erg/cm 2 ,
is

it

follows

10.

this case the

temperature dependence
S 5

thus as

d remains
16.2.

constant, or as

M*/K z

/K

5 I 2 if

d also

varies.

COERCIVE FORCE
plot the energy of a wall,
its

If

we

no matter how an
is

it

may

be caused, as a

function of
as

coordinate of position, the result will be a fluctuating curve


external field the wall will be

shown

in Fig. 16.4a. In the absence of

in a

minimum

(A) and the susceptibility


field

then proportional to d 2Ew /dx 2

in that

minimum. Upon a

being applied the wall will

move

until the

pressure balances the opposing force:

MH = AEw ldx.
no longer
possible

(16.5)

With
dEu>/dx
still

increasing
is

reached (tangent point

H the wall goes on moving until the maximum value of B of the curve in Fig. 16.4a). If H increases
and the wall moves
where

further, a stable equilibrium is

irreversibly to a position
It

dEw /dx

does have a large enough value (C).

may

also

that the two walls eliminate each other,


If,

happen that a wall has already come from the other side, so i.e. the Weiss domain disappears.
is

the wall having arrived at C, the field

now

allowed to decrease, the

74

MAGNETIZATION PROCESSES
minimum
field,

[CH.

wall then returns reversibly to the

for

H = 0,
now
let

after which,

upon the application of an opposing


point

the wall goes to the tangent

E and

then moves irreversibly to point F. If we

H approach

zero again, the wall returns reversibly to A. In this

way a

hysteresis loop is

obtained as shown in Fig.

16.4Z>,

in which the magnetization


jc.

M of the
is

sample

is

put proportional to the change of

(The loop in

this case is

turned 90 with respect to the normal representation.) The area of the loop

\HdM is

the energy dissipated during the irreversible movements; this

absorbed as heat, caused by for example eddy currents produced by the rapidly changing magnetization. In a non-conductive medium the retarding
of the wall by direct coupling of the spins with the
action)
is

lattice (spin-orbit inter-

the most important mechanism.

The
of

critical field-strength, then, is

determined by the

maximum

value

dEw /dx:

H = \M
c

(dEw /dx) maK

(16.6)

It

can be calculated for the various mechanisms which hold the Bloch wall

in position

and which have been discussed

in 16.1. Statistical treatment

is

then necessary in order to obtain a representative


fluctuating quantity.

maximum value from

this

In most cases the process described reverses the resultant magnetization,

5.

Fig.

16.4.

a)

Schematic represen-

tation of the wall energy as a function of the position

x of
is

the wall.
either in

For

H=

0,

the wall

A
b)

or in D.

The change of magnetization

caused by the wall movement as a


function of the field H.

17]

MAGNETIZIATION DUE TO ROTATION OF THE MAGNETIZ. VECTOR 75

and accordingly

e is

to be identified with the so-called coercive force,

i.e.

the field strength for which

M = 0.

Neel has computed the coercive force

on the

basis of

minimum

demagnetizing energy for the case where an inter-

nal stress a prevails in a

volume

fraction v of the material.

H ~ (1.05 vXa/M
c

s)

[2.23
[1.79

+ ln(Af /yf Act]


g s

for

$ Act>

K
(16.7)

H ~
c

(0.191

v\W/KM

s)

+ ln(M /|/#)] for f Act < #.

in cubic crystals with

For the case of a volume fraction v consisting of non-magnetic material Ki > 0, Neel finds:
8|i|
277-M.2
(16.8)

H
For #i

0.39

4ttMs

+ iln2
/3

l*i

<

0,

Kx has

to be replaced

by

K\

in (16.8).

17. Magnetization due to Rotation of the Magnetization Vector


If there are

no Bloch walls present (almost complete


under the influence of the
in question.
rigid vector

saturation, or small

grains) or if the walls,

fields discussed,

are unable

to move, magnetizing will take place as a result of the uniform rotation

of

all

spins in the

zation of this

domain domain as a
field

We may
M. The

represent the magneti-

torque

exerted thereon

by a magnetic

is

given by

T=MxH,
I is
the
at right-angles to both
(this

(17.1)

where the vector product must be taken,

i.e.

moment is in the

M and H means plane of M and H) and has


6,

the magnitude

between
is

M and H. The equilibrium


by the
fields

HM sin

where 6

is

the angle

orientation

reached

when this torque is equal and

opposite

to that exerted
see
Fig.
17.1.

crystal anisotropy, etc.

We
H,

from

(17.1) that the effective field is again

Mutual
applied

orienta-

because the internal


exert

or 4ttMs /3

tions of the easy direction

(K),

the

field

and the magnetization vector

This

may

no torque on the magnetization vector. well be the case with an anisotropic


field,

M.

Lorentz

but

this

we

include in the crystal

76

MAGNETIZATION PROCESSES
it

[CH.

anisotropy. In general, then,

may be

said that in ferromagnetic substanis

ces the effective field for magnetization processes

equal to H.
is

The

position of equilibrium of the magnetization vector

found by

minimizing the total energy. For the case of uniaxial crystalline anisotropy

and a magnetic
energy per

field

H that makes an angle a with the easy direction, this


F=Ksw? 6 HMcos (a
0).

cm

3 (see Fig. 17.1) is:

(17.2)
is

For the position of equilibrium the condition is that dF/60 == 0, that the resultant couple must be zero. With this relation we can calculate which we shall do for two simple cases, o = 90. The position of equilibrium is then given by:
sin
O

0,

= HM/2K = H/HA
for

(17.3)

where

HA
;

is

the anisotropy field defined


(17.2)

in (11.5).

Equation

holds

H < HA
tibility is

for higher fields,

M remains

directed along H.

The

resultant suscep-

which
for all

is

= M/HA (17.4) A (Fig. constant for H < H


X
,

17.2a curve).

The value

(17.4)

holds

HA fields from (11.7).


.

180 In this case, a stable position a can appear only when sin0o = (6 =
or 180);the position with cos0
is

= H/HA

Fig. 17.2. Magnetization curves for a


crystal having uniaxial anisotropy with

always

labile.

In order to see readily

the field perpendicular (a) and parallel


(b) to the preferred direction

for

what

field

the magnetization vector

of mag'

will turn over,

we may

write in this

netization.

case for (17.2):


9 6 F=HM+2 sin2 - (2cos2 - - HM).

The

position will no longer be stable if, where between brackets becomes negative. This is the case

is

small, the factor

if

the field exceeds a

critical field strength

Ho

= HA

(17.5)

cess

With this field, then, there also occurs an irreversible magnetization proand a hysteresis loop is obtained which is perfectly rectangular (Fig.

17]

MAGNETIZATION DUE TO ROTATION OF THE MAGNETIZ. VECTOR


curve
b).

77

17.2,

This

is

contrary to the case for a

= 90, where there

is

always

equilibrium for every field strength and no hysteresis loop appears.

Where 90 < a < 180, the magnetization vector turns over for \HA < Hc < HA The value c = \HA appears for a 135. After turning over,
.

and in the case of a

<

90, the magnetization vector rotates gradually in

the direction of the field; this direction can only be reached, however, in

an
for

infinitely strong field.

This approach to saturation has been calculated an isotropic distribution of the preferred directions over a sphere, and
series

one finds for the

expansion in l/H:

am/Ms
'

K*

192
z

K3
h
(17.6) K
'
S

105

WM]

5005

IPM 3
is

The

fact that the

term with l/H does not occur

evident, since the total

energy difference, consisting of

HAM and the difference in crystal

energy,

must vanish with respect to the total saturated state for a very large field. Neel [Ne 5] has shown that for a polycrystalline specimen, for which must be substituted by (17.6) was derived,

4 H = H + -^.
t

(17.7)

This

is,

as

it

were, a macroscopic Lorentz


spherical, with

field.

The

grain concerned

is

assumed to be
in which

a preferred direction not parallel to H. The

surrounding material then induces in the direction of

Ha

field

4ttM/3,
field

is

practically equal to the saturation magnetization. This

can, therefore, exert a torque


its

own

demagnetizing

field,

on the magnetization in the sphere, whereas which commonly compensates the induced

field,

can not.

CHAPTER

VI

DYNAMICS OF MAGNETIZATION
PROCESSES
18. Ferromagnetic Resonance Conditions
18.1.

RESONANCE IN UNIFORMLY MAGNETIZED FERROMAGNETICS


we
dealt with the statics of magnetization processes

In the last chapter

and

calculated the energetically

most favourable configuration

after the appli-

cation of the

field.

We

shall

now

consider

how

the transition takes place

from the one state to the other. First of all we shall deal with the rotation processes and inquire into the resonance phenomena that can occur during
these processes.

Consider a static field in the z direction and a magnetic moment making an angle with it (Fig. 18.1). Owing to the field a torque (17.1) is exerted on M, which does not, however, rotate towards H. This is because of the gyroscopic properties of the magnetic moment. In 3.1 it was shown that the magnetic moment is associated with an angular mo-

mentum /

according to 5
is

w M = g(e/2mc)J =
.

yJ.

(18.1)

The equation of motion

}=T = MxH.
In very good approximation

(18.2)

we can

take for the

in (18.2) only the spin

angular

momentum

in (18.1), so that
(18.3)

M= yMxH.
from which
both
it

follows that the change of the


is

magnetization vector

always at right-angles to

itself

and

to

H. The

vector precesses

over the surface of a circular cone with an

angular frequency
cj

YH,

(18.4)

irrespective of the

magnitude of the precession


free electron
is

angle
Fig.
18.1.

0.

For the spin of a

the

Schematic repre-

resonance frequency
this

/ in

M c/s

according to

sentation of the precession of a magnetization vector


in a magnetic field

equation

H.

f=2.80H

Mc/s

(18.5)

18]

FERROMAGNETIC RESONANCE CONDITIONS


applied field

79
10 4

if the

His expressed in oersteds. As a rough estimate, HX =


is

oersteds cm, where A

the wavelength in free space.

By

substituting (18.1) into (18.2)

we

neglect the change with time of

the angular

momentum

of the electron in the directions at right-angles


this

to the spin axis.

The contribution of
is

change of angular

momentum

during the precession, which classically should give rise to nutation,


is

a fraction which at the most

of the order of the precession frequency

divided by the spin frequency of the angular


sion.

momentum due

to the preces-

Now

the frequency (18.5)

is

usually not greater than 10 11 c/s, while


is

the spin frequency according to (3.1)

of the order of

2x 10 20

c/s,

and so
c/s.

nutation can be neglected. If the angular


bital

momentum were due

only to or-

motion, the associated frequency would be of the order of 10 14


far

So

we have been

discussing the free vibration of the magnetization

vector. In reality the oscillation will be

damped, so that the magnetization

vector will
tion, in

move
be

in a spiral towards the equilibrium position in the z direc-

which process the magnetic energy (here only the potential energy
lost to the lattice.

HM) will

For every

free vibration there

must be at

least

two degrees of freedom.


a coordinate of

In the mechanical case these are the kinetic and the potential energy, described respectively by a coordinate of

momentum and
mean of

position which, during the vibration, alternately merge one into the other.

The

natural frequency

is

then the geometric


a> r

the

two

stiffnesses

y c /i,

(18.6)

where c

is

the normal stiffness (b 2 E/bx 2 )

kinetic stiffness (p 2 E/bp 2 ).

and 1/m can be regarded as the For ferromagnetic resonance there is only one

form of energy (magnetostatic HM) in the case discussed, but because the movement is in more than one dimension there are nevertheless two degrees of freedom: the deflection in the x direction, defined by the (small) angle
<f>

x,

and

that in the

direction,

<f>

We shall show that an expression similar to (18.6) exists for ferromagnetic


resonance.
tion of

To do so we motion (18.2):

shall start

from the most general form of the equa-

/,

bE/bfa
is

Jy

= -bE/b+s.

(18.7)

The minus
by

sign

is

important and

equation in (18.7)
90, hence

follows from the

connected with the fact that the second first owing to a rotation of the z axis

minimum

but y-> x. In the equilibrium position the energy is at and so the first derivatives are zero. Thus, according to Taylor,

x>y

80

DYNAMICS OF MAGNETIZATION PROCESSES

[CH. VI

one finds for small angles:

E = E + iW* 2 + EvfkJy + \EyyW +


where the second derivatives
position.
lar

...,

(18.8)

Ey

= b 2E/b<fnb<f>j

relate to the equilibrium

For a harmonic oscillation of the magnetization vector with angufrequency <o one then finds for (18.8), using the complex notation and
:

omitting the factor e i0>t

i(toM/y)<f> y = EXx4>x + EX i(wM/y)(f>x = Exyfyx + Eyyj>y.


y<f>y

(18.9)

These equations can be solved for


frequency
*> r

finite

4> x ,y

if o> is

equal to the resonance

= (y/M) (ExxEyy - E^i. (18.10) If the energy is on the principal axes {EX y = 0) then (18.10) is analogous to
where xx and yy are now the stiffnesses. The energy is found alternately in the deflections in the x and y directions. This expression holds
(18.6),

even

if

the energy

energy.

is formed by the crystal energy or the demagnetizing For the general case of the equilibrium position not coinciding with

the z axis,

we may

write (18.10) in spherical coordinates (0,

<f>),

hence
(18.11)

= (y/M sin 0) (Ege Eu -E*

)i,

where the second derivatives again relate to the equilibrium position, found by putting the first derivatives equal to zero (jbE/i>d bE/b^> 0).

The expression (18.1 1)

is

singular for sin

= 0, which points must therefore

be avoided as equilibrium positions in (18.11).

As an example we
which
is

shall take an ellipsoid in a uniform magnetic field x strong enough to orient the magnetization in the field direction.

The coordinate system


demagnetizing factors

coincides with the axes of the ellipsoid, which has

Nx Ny
,

and

z,

so

that

Hx >
2
<f>

(Nx
2

Ny>z)M

s.

The energy

is

then, according to (2.7):


)

E = -HMs sin 8cos$ + |MS 2


and the equilibrium position

JV^sin 2 6 cos 2

is

given by
first

+ JV^sin 9 sin <f>+Nzcos 2 0( = n/2, = 0. We then find for


<f>

the resonance frequency the formula

given by Kittel [Ki 3]

"r

yi\Hx

+ (Ny - Nx)Ms\

\HX

+ (N - NX)M
z
1 ]

S\

(18.12)

which, for a sphere, reduces to (18.4). The


for

first

ferromagnetic resonance

experiments were carried out by Griffith [Gr

on a

thin plate of nickel,


flat

which

Nx = N = 0, Ny =
z

4tt,

and hence for the

plate
(18.13)

a> r

yiBH.

18]

FERROMAGNETIC RESONANCE CONDITIONS

81

In (18.12)

from

x , while the terms

NxMs represents the static demagnetizing field to be subtracted NV M and NZ M are caused by the alternating
S

magnetization in the

y and

z directions respectively, which raise the

resonance frequency.

the

Where only crystal anisotropy is present, with a preferred direction along x axis such that F* = Kd 2 holds for small a deflection angle 0, it fol-

lows that

^ = yHA
where the anisotropy
11. 1.
field

B,

(18.14)

H$

is

given by (11.5). For cubic crystal anisofields

tropy (18.14) again holds with the relevant anisotropy


In

from Table

some

cases the application of a magnetic field can give rise to a


field coincides

lowering of the resonance frequency, as in the case where the

with the

difficult direction for the crystal energy.

sotropy, with the preferred direction


direction, the energy is

For uniaxial crystal anialong the z axis and the field in the x

= IsTsin2 9- HM sin 0cos


The and
field turns the

<f,.

magnetization vector out of the preferred direction,


is

the equilibrium position

reached

when

sine
as follows if the differential to zero.

= H/H*,
from

(H< W),
8 (or to sin 6)
is is

E with respect to

equated

When

H > Ha the magnetization vector


we
find
(to r / y

parallel to

H. For the

resonance frequency

Wry* = (my -m y = H(H-HA)


When

(h< m) (H>W),
is

K
'

'

(see Fig. 18.2).

H = HA

the resonance frequency


field in

zero. This ob-

vious, because with the application of the

the

direction the sym-

metry for the energy with respect to


fields it is

this axis

remains unchanged. For small

a direction of

maximum
precisely

energy, for large fields one of

energy. In between,

and
<o r is

when

the magnetization arrives in the

minimum x
stiffnesses

direction, the equilibrium position is neutral, so that


is

one of the

zero,

and hence

also zero. This

method can be used


at

to generate

ferromagnetic resonance in strongly anisotropic crystals at relatively low


frequencies [Su 2,
field strength.

Sm

2].

Resonance can then be found

more than one

In general, eq. (18.11) enables one to calculate the resonance conditions


for
all

cases in which combinations of field energy, crystal or stress aniso-

tropy and shape anisotropy occur. The equilibrium position is found first by equating to zero the first derivatives of the energy with respect to the

82

DYNAMICS OF MAGNETIZATION PROCESSES

[CH. VI

Fig. 18.2.
field

Resonance frequency as a function of the applied

H both parallel and perpendicular to the preferred axis


derivatives are then calculated at that point.

in a material having uniaxial anisotropy

angles,

and the second

As a

general rule the stiffnesses in directions at right-angles to each other will

not in that case be equal, and as a result the precession will no longer be
over the surface of a circular cone but over that of an
elliptical

cone, having

an

axial ratio y'E vv

^EXx,

as follows

from the constancy of the energy

(18.8) during the precession

(Exy

= 0).

18.2.

INFLUENCE OF THE WEISS DOMAIN STRUCTURE ON THE RESONANCE CONDITIONS


we have
fictitious
is

In 18.1

seen that a free oscillation of the magnetization vector

(resonance) can also occur in the absence of an externally applied magnetic


field.
field.

The

anisotropy field

HA then takes the place of the external


i.e.

Resonance

therefore also possible in a non-saturated specimen,

in a specimen

still

divided into Weiss domains, as was

first

recognized by

Snoek [Sn

1 ].

We shall now show that the Weiss domain structure can very
is

strongly influence the resonance conditions. Let us consider the simplest

case of an ellipsoid which

divided up into Weiss domains in the form

of thin slabs each oppositely magnetized to the next. The magnetization


vectors of the two kinds of domains can now be regarded as two systems coupled to each other by demagnetizing fields. The two vectors will precess
in opposite sense,

and consequently they cannot be in phase

in

two mutually

perpendicular directions. For the two modes of oscillation (natural reso-

18]

FERROMAGNETIC RESONANCE CONDITIONS

83

nance) of the system the alternating magnetization vectors are in phase


either in

a direction at right-angles to the domain boundaries or

parallel

thereto (cases (a)

and

(b)

of Fig. 18.3 respectively).

We

shall

now

calculate

the associated (natural) resonant frequencies. In case (a) the alternating

H~

Nf

ff

=Nx

ff ff Nf =0 N =0

ff Nf =6JT Nf ff=Ny

A//

ff

=0

(a)
Fig. 18.3.
field

Lb]
in unsaturated ellipsoids; (a) with the a.c.
a.c. field parallel

Resonance modes

perpendicular to the walls; (6) with the

to the walls.

magnetization in a direction at right-angles to the domain boundaries

is

continuous

(jc

direction),
ett

and so
,

for this case the boundaries have in

no

parti-

cular consequence:
ficient

Nx = Nx

which

Nx

is

the demagnetizing coef-

of the ellipsoid along the

x axis. In

the y direction, however, the alter-

nating poles at the edge of the e'lipsoid are oppositely oriented in adjacent

domains. At spacings greater than the thickness of the domains they will therefore cancel out each other's effect. For thin Weiss domains we can
ett 0. For the same reason, but then for static accordingly put y at that, summarizing, for case (a) 0, so Nz

fields,

NX = NX Ny = 0,
<**

<* {

JVz e

= 0.

(18.16)

These
to find

effective
.

demagnetizing factors must be inserted in (18.12) in order


in that formula
field

w r However, x and z
anisotropy

must be interchanged, and

Hx

now becomes an

HA

84 In case
phase.

DYNAMICS OF MAGNETIZATION PROCESSES


(b) the alternating

[CH. VI

magnetizations in the

direction are in anti-

On the boundaries there are then alternating poles which, if the thickdomains
is

ness of the Weiss


will give rise to

small compared with the other dimensions,


fields

demagnetizing alternating

at right-angles to the

boundaries of the order, of Airm, where


the magnetization.

is

the alternating

component of

Hence
ett

JVa;

eff

= 4n. N

In the
ett

direction the alternating

magnetizations are in phase, so that the domain structure has no special

consequence and

Ny = Ny
JV^ett

Again,

= 0,
,

so that for case (b)

4w,

Nju = Ny

ett

= 0.

(18.17)

Evidently, (1.12)

no longer holds
the inequality

for the effective demagnetizing factors;

what now holds

is

< NJ" + Ny*" + N


The extreme
limits are
z

<*<

<

8ir.

reached for an ellipsoid in the form of a

flat

plate

(Nx
the
8tt.

= Ny = 0, N 4n),

and therefore

in case (a), according to (18.16),

sum is zero, and in case (b), according to (18.17), the sum is equal The corresponding extreme resonance frequencies are, according

to to

(18.12),
(a):
cu r

= YHA

(h):

y(HA

4ttMs)

(18.18)

18.3.

MAGNETOSTATIC MODES
[Wa
1]

and experimentally there also exist resonance modes of a uniformly magnetized ellipsoid, whereby the alternating component of the magnetization is not uniform. For example, it can happen that the crystal is divided into parts in which the precession movements of the magIt

has been shown theoretically by Walker


et

by Solt

al

[Sol]

that

netization vectors are 180 out of phase. This gives rise to additional de-

magnetizing
fields

fields,

while in other directions the dynamic demagnetizing

are reduced.

As a

result the

resonance frequency will change and will

he in general between
precession.
rule,

and y(H + 2nM), as for the uniform The resultant alternating magnetization vector will, as a general be zero, and therefore these modes can only be excited with a non-

y(H AnM)

uniform alternating
19.

field.

Ferrimagnetic Resonance

In ferrimagnetic substances the magnetization vector is the sum of the various magnetization vectors of the sublattices. Generally speaking, these
sublattices. differ crystallographically

and are also occupied by

different

19]

FERRIMAGNETIC RESONANCE
Mi
and Afz
at ferromagnetic resoi

85

Fig. 19.1. Orientation of the sublattice magneti-

zation vectors

nance, for the case where

> Mi

and yi

The torques caused by

the Weiss fields

< yz. WM\ and

WM2

are then opposed to the torques exerted by

WM2

the field

H on the magnetization vectors.

ions.

The

intrinsic properties

of these ions, as manifested by the individual

factor of the ions in the crystalline field, will therefore vary accordingly.

In the foregoing

we have

seen that the magnetic properties of ionic crystals


latter

can be described in terms of the properties of individual ions. The


stalline fields.
yi.

are only modified with respect to the properties of the free ion by the cry-

Each

sublattice magnetization

Mi

is

given

its

own

factor

According to

(18.4), then, the

resonance frequency

differs for

each of

the subtattices.
lattices

Owing

to their strong mutual coupling, however, the subat the

and

in the

do not resonate individually but altogether same sense.

same frequency

Let us confine ourselves, for the convenience of the argument, to two


sublattice magnetizations

M\

each other. The difference in resonance conditions


fact that

and M2, which we assume to be opposite to is eliminated by the

H
is,

and Mi do not remain strictly antiparallel during precession (Fig. 19.1) and that M\ is subjected to the torque not only of the field but also of the Weiss field H21 WM%. For example, if yi < y%, the torque on Mi would have to be increased and on M2 decreased. This
however,
not possible.

Mi

From

Fig.

19.1

it

can be seen that both

torques are increased

or decreased simultaneously. However, since the

Weiss

field

torques are equal whereas the field torques differ (because


the relative changes of the torques are unequal,
still

Mi

7^

M2)

and hence

the resonance conditions can

be equal.

It

follows from this that

A 0/0 will be of A y = yi yi, A


resultant

the order

of magnitude of (Ay/y)

(H/WM), where

= Mi M2. For a relatively small and magnetization there can be relatively considerable differences
02,

= 0i

86

DYNAMICS OF MAGNETIZATION PROCESSES


#i

[CH. VI

between
yi

and

2.

In the situation as drawn,

for

Mi >
less

and

<

72, the torque acting

on

M\

is

reduced relatively

than that on
72.

2.

The

effective y, then, will in this case

be smaller than y\ or
6)

The

resonance conditions for each sublattice are (for small angles

given by
. ,

vMx 0i =
Wr

Me
2

ri

[HM& + WMiMtfi + WMiM^dxare

02)]

y 2 [HM2 6 2

6 2 )]

{
'

The vector equation reduces


tions in 61

in this case to a scalar, since all vectors are at

right-angles to the plane through

M and H. These
if
I

homogeneous equa-

and
Wr

2,

which have a solution only

\yi

-H- WM (-H + WMi) + WmiM \y


2)
I

= 0.

(19.2)

As we have assumed two sublattices we find here a quadratic equation with two roots for a> r By approximation the lower one can easily be found directly from (19.1). If we divide the first equation by y\ and the second
.

by

72,

and then subtract one from the

other, the Weiss field torques

drop

out and

we

find
co r

=
2 ),

M^! - M
as
is

(M1 /y 1)9 1 -(M2 /y 2)e 2


normally the case

H.

(19.3)

Where H<^.
and we then

W{M\

(WM~

10 6 oersteds)

then 6 1 and 6 2 will be practically equal and cancel each other out in (19.3),
find for the corresponding

value:

eH

M1-M2
(Mi/gd-Wifa)

= gi+gz
2

Since the absolute value of the factor


the value of gett never the foregoing.
lies

+ (M2 /g z 2 (Mi/g!) - (M 2 /g 2 after ^(gi g 2 is greater than unity


gig2

(Mi/gi)

) )

'

between g\ and g 2 as has already been argued in


,

The other root


instance, then,

for

a> r is

very high, and in this case the Weiss field torques


0i

predominate since the small angles

and

6 2 are quite different. In

first

we may

neglect the torque due to the external field,

i.e.

we

may

put

H=

in (19.2).

We

then find

o>r= W{y x

y 2 Mi),
0.1
is

(19.5)

which thus normally corresponds to a wavelength of about


in the infra-red region.

mm,
equal,

Now
,

the

form between brackets


is

in (19.5)

except for a factor y\y 2 to the denominator of (19.4); the minus sign indicates that the precession of (19.3)

in the opposite sense to that of (19.5).

19]

FERR1MAGNETIC RESONANCE
denominator becomes small,
analysis
it

87
decreases, so that

If this

a>i

increases

and wz

the resonance frequencies approach one another, as also appears

from a

more exact

[Wa

2].
e g "

From
merator

(19.4)

follows that

or

oo,

according to whether the nuis

(M =

0) or the

denominator (/
versus

= 0)

zero.

These phenomena
discussed in 9.1,
similar effect also

occur at different temperatures in the Li-Cr


resulting in hyperbolic

ferrites,

T curves

(Fig. 19.2).

ZOh

-3.0\Fig. 19.2.

Change of the g

factor as a function of temperature


1]).

for LiCr ferrite (after

van Wieringen [Wi

occurs in Ni-Al ferrites as a function of the composition [Gu

1 ],

while in

the vicinity of the compensation point even the second resonance (19.5)

has been observed.

The form of (19.5) might lead one to suppose that this second resonance would also occur if gi = g2 This is not so because, as appears from (19.1), the dynamic components of Mi and M% then compensate each other exactly, so that the resonance becomes unobservable and therefore physically meaningless. It also follows from the generally applicable equation (19.3) that
.

there

is

only one resonance frequency for gi

= gz.

Just as with ferromagnetic resonance, the influence of anisotropics can

As regards demagnetization no difference from the ferromagnetic case: the dynamic demagnetizing fields, caused by the total precessing magnetization vector, produce a torque that depends solely upon the orientation of the resultant magnetization
also be taken into account in ferrimagnetics.

there is

88j

DYNAMICS OF MAGNETIZATION PROCESSES


we have
the ferromagnetic case with

[CH. VI

vector. In other words,

= gett.
fields,

The

uniaxial crystalline anisotropy energies for each sublattice are given by the

constants K\ and A

respectively,
2

which are equivalent to the


(11.7).

fields

H = 2.Ki/Miand HA = 2K /M
2

2,

analogous to

These
fields

then,

are in opposite alignment (always in the


ions) hence if

same

direction as the magnetizat-

is

along the easy direction the effective

are

H + HA

and
ions

H H
now

A
.

differ

Apart from a difference in g factor, the resonance conditonce again for the two sublattices. The relative difference

between the precession angles for the low-frequency mode of resonance will now be of the order of A jWM, which again, generally speaking, is small.

If,

as before,

we

neglect this difference,

we can again speak of the

precession

K=

of one rigid magnetization vector in a crystal having an anisotropy of A A (HA Mx 2 )/(Mi 2 ). Once more we Ki 2 or

have g

M H = +HM +K = gett from (19.4). The second resonance frequency is again approx-

imately given by (19.5) for small

HA

All this follows again from equations analogous to (19.1) with the H's

changed in the manner described above. To conclude we can say that the resonance conditions for the low frequency mode of normal ferrimagnetic
substances

may be

calculated just as for ferromagnetic substances.

20. Spectroscopic Splitting Factor

For pure spin magnetism, the gyromagnetic ratio y governing ferromagnetic is equal to the y of (3.4), but where orbital magnetism is also present, it will differ, as we already assumed in 19. It cannot be said a priori that the corresponding g factors are equal to the Lande factors
resonance
introduced in
(6.6). Kittel

[Ki 4] has shown, however, that this

is

in fact

the case as regards the g factor in ferromagnetic resonance (called the spectroscopic splitting factor), but not as regards that g factor which governs

Haas effect. must calculate the frequency cd of the precession. According to quantum mechanics, ha> is equal to the difference in energy of the two states between which the transition takes place. In the present case this is the reversal of one spin. In a ferromagnetic material, in which the spins are very strongly coupled, there is no complete reversal of one specific spin
the Barnett experiment or the Einstein-de

We

but rather a slight

tilting

of

all

spins together, such that they remain in


is

mutually parallel alignment and the exchange energy


ferromagnetic substance in a
field

unchanged. For a

H we thus have the equation


AMovut).
(20.1)

hw

= H(AMBV m +

20]

SPECTROSCOPIC SPLITTING FACTOR G

89

We shall again, as in 3.3, consider the case in which, in first approximation,


the orbital angular

momentum

is

quenched,

this state

being only slightly

perturbed by the spin-orbit interaction.


that case remains unchanged in

As we

saw, the spin orientation in


it

first approximation, and therefore only be purely parallel or antiparallel to the magnetic field, i.e.

can

^1/spin

= h,
+ AMorbit
.

(20.2)

so that from (20.1)

we

obtain for y.

y
Since
all

^Mgpin

^/spin

composite vectors remain parallel to each other, we also obtain:

g
This

= 2 (M pin + Afortit)/M pi.


S S

(20.3)
susceptibility

is thus the same as (6.6), which governs the paramagnetic and the saturation moment.

In (20.1) the change in the mechanical energy of the


neglected owing to
its

lattice (rotation) is

large

moment of

inertia.

The change of angular

momentum
^/spin

of the

lattice (J/iattice)

need not necessarily be small (compare

with a ball bouncing from a rigid wall). Since evidently in this case

AJ

= h,

then ^/orbit

^/lattice
is

=0.

In

3.3

we saw
is

that /orbit

of the order of (\/AE)h, hence


0.2.

(g2)=

X/AE, which

of the order of 0.1 or

For more than

half-filled shells

the spin and orbital

momenta

are parallel so that

the magnitude of the orbital angular


direction of the spin
still

g is greater than 2. Since momentum will also depend on the


g can

momentum

with respect to the crystal axes,

be anisotropic.
is

There

another type of g factor, which also determines the ratio between

a magnetic and a mechanical

moment and which is known

as the magneto-

mechanical ratio
effect

Haas and the Barnett experiment, in which the change of angular momentum associated with a change of magnetization is measured by suspending a bar of ferromagnetic material from a thin wire. The bar is magnetized in
g'.

This

is

the governing factor in the Einstein-de

the long axis (which

is

also the direction of the wire)

by a surrounding

coil

The current
is

is

then reversed and this causes the bar to rotate. The g' factor

now

defined as follows:
(ejlmc)g'

= (^A/gpin + ^M rbit)/^/lattice,
momentum of momentum of the
the lattice,
bar, while

where
i.e.

J/iattice

is

the change in the angular

the observable change in the angular

90
in

DYNAMICS OF MAGNETIZATION PROCESSES


is

[CH. VI

^MBP + ^A/orbit

the change of

M.

Since the bar

is

suspended torsion-

free, it follows that

^/lattice

^/spln

^/orblt

= 0,

and

therefore, if again

we omit A,
*'

=2

Afgpin
:

Mspln
because the ratio between
tion

+ Morblt + 2M rblt
g of

(20.4)

M and /
1

is

smaller for orbital than for spin

mo-

by a

factor of 2. Evidently, then, there exists between the


relation
1 1.

(20.3)

and the g' of (20.4) the simple

(20.5)

Thus
(20.5) is

if

> 2,

then g'
g' are

which both g and

not entirely

and vice versa. With most substances, for known, this is indeed the case, but quantitatively satisfied, as appears from Table 20.1.
2,

<

TABLE
VALUES OF i AND
g"

20.1

FOR A NUMBER OF FERROMAGNETIC MATERIALS


g
g'

-+
g

Iron

2.12-2.17

1.93

0.980-0.990

Cobalt
Nickel

2.22
2.19
2.2
2.01

1.97

0.986 0.996
0.973 0.998
0.991-1.006

1.84
1.93

Magnetite Fes04
Heusler alloy

GwMnAl

2.00
1.91

Permalloy Ni78 Fe22

2.07-2.14

For the lowest resonance frequency of ferrimagnetics, (20.1) still holds moment, since the change of exchange energy can be neglected. This means that (20.3) also holds for the ferrimagnetic materials. In (19.1)
for the total

the yi's of the different sublattices were introduced phenomenologically.

We see that (19.4) and (20.3) are indentical if we also take for the g's of the
sublattices

gi

= 2-(Mi)spin + (Mf)orbit
(Mi)spln

(20.6)

For low-frequency resonance, then, we may take

in (19.4) the values for

gi and gz according to (20.6), but this has not been proved for the high-fre-

21]

ROTATIONAL SUSCEPTIBILITY
(19.5). It

91

would only be so if we were able to treat each sublattice quite separately, such that (20.2) would apply to each. In view of the strong coupling between sublattices, which is much stronger
quency case according to
than that with the external
field, it is

doubtful whether such a procedure

would be

possible.
is

Instead of (20.5) the relation usually given in the literature

g-2 = 2-g',
which
is

(20.7)
(20.5)

only equivalent to (20.5)

if A/orbit

<^ AfS pin. Thus

has a more
the spin

general validity; the only approximation

made

to

it is

(20.2),

i.e.

of the electron in an orbit


field.

is

always purely parallel or antiparallel to the


if

This

is

only true as regards normal ferromagnetics

the above resis

triction, A/orbit <^L Afspin is

obeyed, but as regards ferrimagnetics this


it is

not

necessary for the total

moment, provided
is

the case for the sublattice

magnetizations. This difference

particularly apparent with such nearly


spinels already discussed. In these

compensated ferrimagnetics as the Li-Cr


point. It

substances g can assume very high values in the vicinity of the compensation

can be seen that g'

to (20.3), A/gpin

>

0,

> 1, which is evident since then, according and therefore only orbital magnetism is present.

21. Rotational Susceptibility

In this section

we

shall

tization vector. Rotation


field

examine the off-resonance behaviour of the magnecan be caused by applying an alternating magnetic

at right-angles to the equilibrium position (z axis) of the magnetiza-

whose vector is at rightangles to the magnetization vector, the latter being, apart from a constant factor, equal to the angular momentum vector. The equation of motion (18.9), in the case of the energy (18.8) being on principal axes (Exy = 0),
tion vector. This produces

an

alternating torque

can be written for small angles


itoM<f> y

as:

= iaiM</> x =

yEn<f>x

+ yMh x yMhy, yEz2<f>y


the term

which follows by adding to


this

(18.8)

M(h x

<f>

h y y).
</>

From

we

obtain
... M* X =
E<t2h x

(ia>M/y)hy

(o, r

2-^)/y^
,

'

(ia>M/y)h x + Euh M^ = -(f^-^/yM

v
'

where

wr 2

y^EuEm/M2

corresponding to a susceptibility tensor of

92
Xxx

DYNAMICS OF MAGNETIZATION PROCESSES

[CH. VI
<o 2 )

= y 2'22/(">r 2 = iwyM/(a) r 2 Xiw


the fact that

< 2 ) <u 2 )

= io>yM/(a> 2 = r^EuKair* Xw
Xxy
r

to 2 )

The tensor is Hermitian and thus has real eigenvalues, in accordance with we have not taken damping into account. The off-diagonal elements are opposed. For elliptically polarized signals one finds from
combinations

(21.1) the

(<l>x/}'E22)

(^/V-Eii)

Oi^

(21.3)
(Of

It follows

from

this that

an

elliptically

polarized field with axial ratio

/Cn/^22
upon

excites

an

elliptical

rotation with exactly the opposite axial

ratios (the largest field being required in the stiffest direction). It

depends

the sense of rotation whether, at a specific frequency, resonance will

occur (x

oo) or not.

Resonance

will

always be excited in the case of a

linearly polarized signal, since

we may

look on
that

this as the superposition


(21.3).

of

two opposing
is

elliptical rotations, in
,

agreement with
all
is

polarized magnetic field h x practically

excited at

For a linearly low frequency

an

mx
is

in phase with h x
elliptically

At higher
still

frequencies the alternating magneti-

zation

polarized owing to the fact that one of the ellipses

becomes predominant,
of the
ellipses

mx

being in phase with h x At resonance, one


.

then being practically infinitely large,

m x goes

over into anti-

phase after which


cies the
field.

m x decreases faster than m y


is

so that at very high frequen-

magnetization
latter

linearly polarized in

a plane at right-angles to the

The

phenomenon can be

interpreted according to (21.3)

by

saying that at low frequencies the two oppositely rotating elliptical vibrations are in phase with the field, while at very high frequencies only

the

one of two has passed resonance and has rotated 180 in phase, so that super-

position

now
Wave

yields

a linear signal at right-angles to the

first.

22.
22.1.

Propagation in Magnetized Media

THE WAVE EQUATION

The consequences of the non-diagonal form of the susceptibility tensor (21.2) as regards wave propagation were first studied by Polder [Po 1]. The wave equation, as found from the Maxwell equations, can be written for an infinite medium having a dielectric constant e:

AH grad div H

5 25

=0.

c 2 bt 2

(22.1)

22]

WAVE PROPOGATION
is

IN MAGNETIZED MEDIA
not isotropic, div

93

Since the magnetic permeability

H=

does not hold.

In order to solve (22.1)

agreement with (21.2)

we must know the relation between B and H. In we assume for the alternating components of B and
letters):

H (indicated by small

\i K

(x

(22.2)

components of the

b and h are the alternating and therefore external demagand k. netization, for example, is left out of consideration in determining The solution we calculate for (22.1) has the form of a travelling wave and hence we assume that the time and place dependence of b and h can be represented by that of a factor exp /(At tot), in which k is the wave vector of magnitude 2ir/A. This is no restriction, because any function of place and time can be expanded in these waves with the aid of Fourier analysis. For the three components of h eq. (22.1) then becomes:
corresponding to

En =

22 in

(21.2).

In

(22.2),

internal field-strengths,

ju.

[- ky2 -k
kXky

2
\

hx

{kx ky-i^-\ h y
*

+ kxkjt =
z

K\ hX + lf ~ kx
j

<D 2

/C0 2 fl

-W
%
J

hy

+ kykzhz =

) (22.3)

kxkzh x

+ kykjiy + r k x 2 k y
I

hz

=
,
,

These are three homogeneous equations in h x h y and hz and thus they only yield a solution if the determinant of the coefficients is zero, which gives
a relation between k and
a>.

We

shall

now examine some

simple examples, taking

first

the case in

which the wave is propagated in the direction of the magnetization (kx k y .= 0, kz = k). We then find
fc

c
2

0*

k).

(22.4)

These two solutions correspond to circularly polarized waves with a rotation respectively equal and opposite to that of the natural precession of
the magnetization vector, as follows

from

substitution of (22.4) in (22.3).


fields,

The

quantity (^

) is

the permeability for circularly polarized

so

that (22.4) has the

We

shall

determine

same form as for a medium ft and k occurring in (22.4)

with isotropic

/x.

for the simple case in

94

DYNAMICS OF MAGNETIZATION PROCESSES

[CH. VI

static field is present in the z direction, possibly to be substituted by an anisotropy field A For a uniformly precessing magnetization vector we can then calculate /* and k from (21.2), in which En = 22 =

which a

HM

and

<o r

yH, hence

AtrM B wjy ^K=l+-=f.


4-

(22.5)

Owing to wave motion, however, the magnetization is no longer uniform, and a given spin will be subjected not only to the torque exerted by the magnectic field but also to a torque caused by exchange interaction. As a result the motion of the spin vector is changed, and with it the susceptibility.

We

shall

examine

this quantitatively for

slow variations of the spin orien-

tation (2ir/k being

much

larger than the lattice parameter).


1

The exchange

energy between two neighbouring spins


portional to the scalar product S1S2.

and 2

is

according to (5.1) pro-

The torque T which they exert on each

other will be proportional to the vector product of Si and S%:

ocSixSjj

The total torque acting on the magnetic moment of an atom follows from summation of the torques exerted by the moments of the surrounding atoms.
In the case of the neighbouring spin S2 at a distance

R we
...

can write for a

slow variation of the spin orientation

52

= 51 + {rv)s + XRvys +

where S is taken to be a continuous function of position in the lattice and where the derivatives at the position of the central atom must be taken.
In the summation of the torques the odd terms in
for

R cancel

each other out

lattice

with a centre of symmetry. For a cubic

lattice in particular the

torque,

now

expressed in terms of the magnetization, assumes the simple

form

T=AMxAM,
where A
is

(22.6)

again the Laplace operator, and


is

a constant. The torque for

the travelling waves considered here

T = Ak*Mxm,

(22.7)

where m is the variable part of the magnetization vector. The torque (22.7) would also be produced by a static magnetic field parallel to the magnetization of the magnitude

Hex = Ak*M.

22]

WAVE PROPAGATION
resultant permeability can be
If this is

IN

MAGNETIZED MEDIA

95

The

found quite simply, then, by substituting

H + Hex for H.

done
I

in (22.5)

we

obtain for (22.4) in this case:


\
,

k2
which
is

= w*e

4irM 4ttM

c" V

H + AMk2
.

(22.8)

toly) a/yj
is

now a

quadratic equation for k 2 If the half wave length


it

equal to

the lattice parameter,

then follows from an impermissible extrapolation

2 is of the order of the Weiss field that the field -9 oersteds cm 2 . If the denominator in 10

AMk

~ 10

7 oersteds,

hence

AM=
i.e.

(22.8) is not nearly zero,

< yH, the form between brackets in (22.8) is of the order For microwaves (at 10 u /sec), where e = 10, k 2 is of 10~7 oersteds, which the order of 10 2 so that the exchange field is only 3 oersteds). If to approaches yH, then is negligible compared to (=10 without the exchange field the right-hand side of (22.8) with the minus sign would be infinite, and with it k 2 The exchange field prevents this. If to > yH, the denominator in the right-hand side of (22.8), without exchange field, is negative for this resonance mode. In that case it can be made positive
for values of u>
2.

of magnitude

again by the exchange


larger than that for

field.

This happens for fairly large values of k 2 , according to (22.8),


that, in very
is

w = yH which, m
is

of the order
least

of

10 7 .

Consequently the factor between brackets in (22.8) must be at

of the order of 10 5 for


tion, the

>

yH. This means

good approxima-

denominator

zero, hence
to

y(H

+ AMk 2

).

(22.9)
first

This

is
it

the frequency of the so-called spin-waves,

introduced by Bloch,

on k. For a> > yB the right-hand side see (22.5) becomes positive again and therefore there is again a solution with small k2 in which the exchange field is negligible. For the oppositely precessing mode, (22.8) is always positive, i.e. k 2 is small and again of the order of ta 2 e/c 2 so that in this case,
and
thus depends quadratically

of (22.8), also without exchange

field,

too, the exchange field can be neglected.


gives

We

have shown, then, that (22.8)

namely electromagnetic waves, for which the exchange energy can be neglected, and spin waves, for which the electromagnetic energy is negligibly small and only magnetic and exchange energy enter into account. Both kinds of waves, which we
solution,

two kinds of waves as

now propose

to examine separately, gradually

merge

(see Fig. 22.1).

22.2.

ELECTROMAGNETIC WAVES
in the z direction (22.8)

For electromagnetic waves

becomes

96

DYNAMICS OF MAGNETIZATION PROCESSES

[CH. VI

Spin waves

Fig. 22.1.

Frequency of electromagnetic waves

(a)

and of spin waves

(b)

as a function of the

wave number
(a).

k.

The

scale for

in (b)

is

at least a

factor 106 smaller than in

kl

= ~<?e B i
a> 2

oj/y
(22.10)

Ha>/y
is

Above resonance (a> > yH), the magnetization field and therefore the rotational susceptibility is
this also results in

in antiphase with the

negative.

Where

a>

<

yB

a negative permeability and, apart from spin waves, no

wave propagation is possible, Where to = yB, according to (22.5) the permeability becomes zero (antiresonance). Above this point, wave propagation is again possible. The oppositely rotating mode exhibits no resonance and here, therefore, the magnetization is always in phase with the field.

The permeability

varies continuously

from

B/H at

low frequencies to unity

at high frequencies.

A linearly polarized electromagnetic field can be split up into two opposiFor propagation in a direction parcomponents will differ. Over a distance / the magnetization vector of the one component will thus have rotated through a different angle from that of the other. If, then, we again combine them into a linearly polarized signal, the polarization plane will have rotated through an angle ft which is given by
tely rotating circularly polarized fields.
allel

to the static magnetization vector, the wavelength of these two

P/l

= W+-k-)
is

(22.11)

Below resonance (w< yH) a rotation thus takes place which

in the

22]

WAVE PROPAGATION

IN

MAGNETIZED MEDIA
(to

97

opposite sense to that above antiresonance

>

yB). This so-called Fara-

day rotation (22.11) can be computed from (22.10) as a function of the frequency. For high frequencies (at ^> yB) we find

P/l= y
which
is

4tM

fe/c,

(22.12)

independent of the frequency and proportional to the magneFor many ferrites AitMs 4000 gauss and e 10, which means that in ferrites a Faraday rotation may occur of the order of 3607cm. Consider now the case of waves which propagate in a direction at righttization.

angles to the direction of magnetization, e.g.


find apart

ky

from a non-magnetic mode with kx 2

= k 0, kx = 0. We then = e/c a mode with


z
ai 2

kt=

u
co 2 e

k2

co 2 e

C2

fi

C2

B 2 (o 2 /y 2 BH-a> 2 /y2

(22.13) '

w = y^BH, which is a consequence of the fact owing to the wave motion in the x direction, is subjected to a demagnetizing field corresponding to a demagnetizing coefficient of Atr. Here, too, an electromagnetic wave at resonance goes over into a spin wave, with, for cubic materials, the same dependence on k 2
Resonance occurs here for
that the magnetization,

as in the case of spin waves in the z direction. Electromagnetic waves in

the

direction give rise to the

Cotton-Mouton

effect

[Du

1 ],

also familiar

in optics.

Up to now we have calculated the propagation only in an infinitely large medium, without taking account of boundary conditions. These are the normal boundary conditions of Maxwell's theory, namely that on any surface the tangential components of and E and the normal components of B and D are continuous. As was first shown by Van Trier [Tr 1 ], these conditions can radically modify the properties of wave propagation. For example, in the case of a thin rod, whose thickness is small compared with

the wavelength

and which

is

magnetized along

its

long

axis, the
is

resonance

frequency for waves propagating along the axis of the rod

equal to

y(H

2irM), corresponding to the frequency for ferromagnetic resonance. In the


latter case the

wavelength

is

also

assumed to be large in comparison with

the dimensions of the body.

22.3.

SPIN

WAVES

we saw that for small k a spin wave has a frequency between yH and y^RH, depending upon its direction of propagation. In this case the wavelength is much smaller than the dimensions of the body (k > 10 3)
In
22.1

98

DYNAMICS OF MAGNETIZATION PROCESSES

[CH. VI

and therefore the boundary conditions are unimportant. Nevertheless, we must take into account here that the fields used in Fig. 22.1 are the internal
static fields, Hi,
i.e.

Ht
where the external
field

=H

-N M,
z

(22.14)

always

lies

between Hi and | BiH{.

Spin waves describe the internal motion of the magnetic moments. In this respect they may be compared to sound waves (Debye waves) or to
lattice vibrations in solids. The sound waves form, as it were, a Fourier spectrum of the individual movements of the atoms. Owing to the mutual

coupling of the atoms, their movements are to some extent correlated. This
coupling, together with the mass properties, gives rise to

wave propagation.
is

In the case of spin waves the same coupling exists between neighbours, but
the

mass properties are


essentially

lacking. Instead, the

motion of the spin vectors


that there are
still

now
grees

is possible and hence also wave propagation. In the case of electromagnetic waves it are the electric and magnetic energies which, at each point, periodically go over one into

more dimensional (see 18), so of freedom, and therefore free oscillation

two de-

the other.

The lattice vibrations

are quantized, that

is

to say the amplitude of a


finite steps,

wave

with a certain frequency can only increase in certain

so that the
is

energy of the wave increases by equal amounts

hco.

The energy

then
(22.15)

En
where n

= (n + i)hco,
n

^ 0.

The lowest
i.e.

state for

corresponds to the zero-point

vibration of a crystal,

of the individual atoms, since, having regard to

atom cannot stand still (Ax = we assume no correlation with the movement of neighbouring atoms, an atom still moves in a potential well, i.e. it has positive energy with respect to the state with zero amplitude and velocity because
Heisenberg's uncertainty principle, an

Ap

= 0).

Even

if

the energy quadratically contains the coordinate

energy appears to be
cd.

/ito

for the Fourier

and the velocity. This component with angular frequency


it

From an

exact calculation of the spin waves


is

appears that a similar

quantization occurs for these also. This

connected with the fact that, as

we saw in 3.4, the z component of the total angular momentum can only change by an integral multiple of h. The zero-point vibration of spin waves
corresponds to the zero-point motion of the individual spin moments, which
discussed in 3.4. Although spin waves have a zero-point vibration, it makes no contribution to the energy since this, apart from the magnetostatic
is

energy, consists of the exchange energy between the spins of neighbouring

22]

WAVE PROPAGATION

IN MAGNETIZED MEDIA

99

atoms:
-Eex

= 2J(Si xS2x + SiySzy + SizSzz)

(22.16)

In the ground state the average value (expectation value) of S% z

= S22

is ^, while the expectation value of Sx and Sy for both spins is zero. Owing to the essential lack of correlation between the zero point motion of the

individual spins, the deviations

to (22.16), since this equation only contains products of the spin

from these values make no contribution compo-

nents of different electrons. Similar reasoning applies to the magnetostatic

energy

HM,

which

is

proportional to

HHS{ Z

The

energy with respect to the ground state then becomes

En = nhu> = nhy{H +
The reduction of
wave
2/lib,

flex)

= Inyidfl + Hex

).

(22.17)

the spontaneous magnetization with increasing tem-

perature can be described in terms of spin waves.


(increase of n

The creation of each

spin

by and therefore a spin wave can be thought of as a reversed spin moving through the crystal. Since a spin can be reversed once only, spin waves tend by
1

in (22.17)) causes the magnetization to change

to repel each other. In the given phenomenological derivation this interaction


far
is

neglected, so that the spin

wave theory

applies only to temperatures

below the Curie temperature, where the spontaneous magnetization


still

M,

differs

but

little

from the magnetization

at

T=
is

and there are


then governed

very few spin waves. The degree of spin-wave excitation

by the
is

so-called Bose-Einstein statistics, just as for lattice vibrations,

and

given by
nic

[exp (hu> k /kT)


is

J-

1
.

(22. 18)

The reduction of

the magnetization

equal to

Mo Mg
The
possible values of

= 2 E njefiB
k

are uniformly distributed over the

space.

Ac-

cording to (22.18), at low temperatures only those states are notably excited {i.e. where n is of the order of unity) for which haik^kT. The number of
excited spin waves, then,
is is

approximately proportional to ko 3 , where ko


heat

the wave

number

for

which

= kT. From this

and

(22.18) is derived

the Bloch

3'2

law (6.21) for the magnetization-temperature curve.

The

magnetic component of specific heat has also to obey a been found experimentally for magnetite by Kouvel [Ko

T3
2].

'2

law as has

100
23.
23.1.

DYNAMICS OF MAGNETIZATION PROCESSES


Damping

[CH. VI

GENERAL PROPERTIES OF COMPLEX SUSCEPTIBILITY


the applied alternating

Owing to the damping a phase shift occurs between field and the alternating magnetization to which it
the alternating magnetization
is is

gives rise. As a result not purely in phase or in antiphase and it possible, therefore, that an energy dissipation jh.m dV will occur. If the

complex notation is applied for the sinusoidally varying quantities, the damping and hence the phase shift find expression in the susceptibility becoming
complex:

X=x'~ix"

(23.1)

in which x' and x" are real functions of <o. Here x is proportional to the component of m which is in phase or in antiphase with h, while x" gives the 90 phase-shifted component of m. In principle, (23.1) holds for each component of the susceptibility tensor. For linearly polarized signals the energy

dissipation per

cm3

is:

dW =
If there is

ho>x"h\
all

(23.2)

no damping, x"

is

zero for

frequencies, except at resonance,

when x" becomes

infinitely large.

Owing

to damping, this
a>

peak function

is

widened and lowered. Further, x"

where

= 0,

i.e.

for very slow var-

iations the energy dissipation per cycle

is zero. This holds for those processes in which equilibrium always prevails throughout very slow variations, that is to say we exclude hysteresis, as we can do for small amplitudes. Before

discussing the

mechanism of damping, we

shall first consider

some pheno-

menological relations.

h varies arbitrarily with time the resultant m can be found by expanding h in a Fourier integral. For each Fourier component
If the applied field

the magnetization can then be found with (23.1), so that by integration over co the total magnetization follows as a function of time. If in particular we

apply a field which is zero for t 0, the same must also hold for m, irrespective of the further trend of h. This establishes a certain relation between

<

X and x" which can be represented by the Kramers-Kronig relations:


OO 00
.

X ()

2
o

fco lX "^l)
/

dcoi

x '\,o)

^^4 d
-2 f
/

cox'(co{)

<l

(23 - 3 >

b
is

Thus,

if either

x or x"

determined.

The

given as a function of frequency, x" or x is then relations (23.3) hold for each of the tensor elements of

23]

DAMPING

101

above considerations are equally valid if m and h are not in the same direction. The tensor element xxy in (22.2) is already imaginary without damping. If the stiffness is anisotropic and the x and v axes do not coincide with the principal axes of the energy, an equal, real
(22.2) separately, since the

part

added to xxy and xvx, so that these are then respectively of the form and a + ib. Where damping is present, a changes into a' ia" and b into b' ib". As a result the matrix is no longer Hermitian (it had already ceased to be Hermitian when (23. 1) was introduced for the diagonal elements)
is

a ib

and therefore the eigenvalues are complex, corresponding to signals decreasing exponentially with time and to energy dissipation. While (23.3) holds for a' and a", the relations for b' and b" are
oo

oo

b'(w)

=77"

cui^
U>*

dan

b"(a>)

= -IT

:
1

J OiV

; da>i <*

(23.4)

that

is

where
hixxy

Xvx)

= a' ia" and \

( X xy

Xvx)

= V ib".
b' is
a>

(23.5)

In

(23.3),

x"

is

automatically zero fora>

= 0, in agreement with the above.


automatically
as follows
for

In (23.5)
zero for

this is
u>

not the case for the damping term b"; here


Nevertheless, b"

= 0.

must also be zero

= 0,

from the more general formula


z

for the energy dissipation

dW - = ^Re io>\xxx\hx\ + at
The

Xxyhx*h y
is

xyxhjiy*

Xyy\hy\ ]-

(23.6)

cross term according to (23.5)

a>Re(a"
If

- ib")h x *h y
is

(23.7)

b" =

for

to

= 0,

then (23.7)

the only remaining term.

The

losses

for elliptically polarized signals are then proportional to b" (since h x *h y


is

imaginary for

this term).

By, for example, changing the sign of h y (oppothe energy dissipation into a generation

site

sense of rotation)

we change

this gen0. For w = of energy per cycle, so that b" must be zero for a> of energy as a result of the b" term is indeed possible, but in that eration

case the other terms in (23.6) ensure that there will


the total result (eq. (23.6)
isotropic
is

still

be dissipation in
fields in

positive definite).
is

For rotational

an

medium

the energy dissipation

AW =
dt

whW

k").

(23.8)

102

DYNAMICS OF MAGNETIZATION PROCESSES

[CH. VI

useful expression for the area of the absorption

peak follows from the

first

equation of (23.3) for


oo

co

= 0:
x '(0).
(23.9)

X"()d0n)=^

contribute

magnetization process that contributes by a given fraction to x'(0) will by the same fraction to the area of the absorption peak if the
is

frequency
23.2.

plotted logarithmically.

PHENOMENOLOGICAL DESCRIPTION OF DAMPING


their classical

In order to describe damping, various terms are proposed which must be

added to the equation of motion. In

paper [La
as:

1 ],

Landau

and

Lifshitz originally put the equation of

motion

M = y(Mx H) - (ay/M)Mx (MxH)


which, as can easily be seen,
is

(23. 10)

equivalent to
(23. 1 1)

M=

y(l

+ a2) (Mx H) - (a/M) (Afx M).

In (23.10) the damping term consists of a vector at right-angles to


the direction of the resultant magnetic field

in

H and proportional to the sine

of the deflection angle of the magnetization from the direction of H, so


that the magnetization vector
field.
is

forced back towards the direction of the

In (23.11) the viscous character of the damping term comes more to

damping terms leave the absolute magnitude of unchanged, as appears from the scalar multiplication of both sides of the equation by M. The correction to y in (23.11) is in the main unimportant, since a is of the order of 10 -2 The damping constant a can also be a function of the
the fore. Both
.

static field

Ho.

The damping terms from Bloch's theory of nuclear spin resonance were 1 ] to ferromagnetic resonance. The damping torque is put proportional to the deviation of from the equilibrium position. The Bloch-Bloembergen equation is
applied by Bloembergen [Bl

M = y{M xH)~ ay{MH- MH)


corresponding to a relaxation time t

(23.12)

1/ayH.

The damping term

in (23.10) can be written as

-ay

M HM MH M

23]

DAMPING

103

We

shall see in 24.2 that the damping terms discussed here only apply when the rotations of the magnetization vector are small; when they are large there can no longer be any question of a rigid magnetization vector. Without equal to HM, so that for small a loss of generality, then, we may put the damping terms of Landau and Lifshitz, the viscous damping term and

HM

that of Bloch-Bloembergen are all identical.


notation,
lected.

we

shall henceforth use only (23.11), in

For the sake of simplicity of which the a 2 tennis neg-

In the case of a non-cubic medium, different values of a may occur in the x and y directions. For the susceptibility tensor we then find

Xxx

= yM

(a>ia>2
(o)l<o 2 -

to 2 )o>2

tooi^Aio
.

2 J 2 )

+ +

<o a (J<o) 2

(oia.2.

a> 2 ) 2

+ o>2(J)) 2
(23.12)

Xxy

= iyM

(coia>2

co 2)a)

"> 2

J a) J

(coia.2-

<*>

2 2

> 2 (Jo/) 2

(o)io) 2

to 2 ) 2

+ )2(Ja))2
aQd
< 2

and

similar expressions for xvx an(i Xvv-

Here

""i

= VE^I M

yEzzIM and
aifoi

a2&)2

= da>

(23.13)

which
line

is

to half the

the line width measured between the points where x" has dropped maximum value. This maximum value of xxx" is related to the

width according to

(X**"W A" = VM ]/

(23.14)

23.3

DAMPING THEORY

The microscopic theory on the damping of ferromagnetic precession was first put forward by Akhieser [Ak 1]. The deviation from the equilibrium
position
is

described in terms of spin waves.

On the

other hand the thermal

atoms in the lattice is and thus they may both be regarded as the terms of a Fourier series of the non-periodic perturbations of the magnetization and of the atomic ordering, respectively. Quantization gives these waves the character of particles with an energy hw. These energies can be of the same order of magnitude, namely at maximum JcTc and kTD, where Tc is the Curie temperature and TD the Debye temperature. The wave numbers multiplied by h are to be
agitation of the

described in terms of lattice waves,

regarded as the

momenta of the The atomic magnetic moments

particles.

are coupled by exchange interaction

and

dipole-dipole interaction. Moreover, the spin-orbit interaction gives rise

104

DYNAMICS OF MAGNETIZATION PROCESSES


moments which
is

[CH. VI

to an effective coupling between the magnetic


similar to dipole-dipole
interaction,

somewhat

and to which Van Vleck [Va 2]

therefore gave the

name "pseudo

dipolar interaction".

Owing

to the fact

that the above-mentioned interactions are strongly dependent

on the

inter-

atomic spacing, interaction


vanish and

will result in

a deformed crystal between the

spin waves and the lattice waves.


lattice

As a consequence, the spin waves may waves be created, or conversely. The two most important

processes can be represented schematically as


s

+ s ^t /

and

s.

(23.15)

In the

first,

vice versa,

two spin waves are annihilated and one lattice wave is created, or and in the second a spin wave and a lattice wave together go over
be conserved, which implies a severe restriction of the processes. For this reason, to give an example, it is not

into another spin wave. In these processes the total energy as well as the total

momentum must

number of possible
the

possible for a single spin

wave number

is

wave to go over into a single lattice wave, since if the same the energy will be different and vice versa.

There must, then, always be at least three "particles" involved in the process. The magnitude of the interaction is connected with that of macroscopic phenomena. Thus, the dependence of the exchange energy on the interatomic
spacing gives rise to volume magnetostriction (see 13.1), and that of dipolar and pseudo dipolar energy gives rise to linear magnetostriction. Volume magnetostriction being essentially a much larger effect than linear magnetostriction, it was found by Akhieser to give the more important coupling

mechanism. In

fact,

Akhieser took only the true dipolar energy into account,

but multiplication by a factor of 50, which gives approximately the ratio between pseudo and true dipolar energy, leaves this conclusion unchanged.

The

interactions described

above can cause a

state of non-equilibrium to

return to the state of equilibrium, and in the process the magnetostatic and

exchange energies are converted into


to the state of equilibrium
it is

lattice vibration energy.

For a return

necessary that the spin waves should vanish.


process of (23.15).

This

is

only possible via the

first

The

variation of the

exchange energy with interatomic spacing cannot give rise to these processes, since the exchange energy depends solely on the mutual orientation of the
spins

and not on the orientation in space of the


change

resultant spin. Conversely,

therefore, the exchange cannot


is

this orientation.

The

relaxation time

accordingly governed via processes which are connected with linear

magnetostriction, as treated in the theory of Kittel

and Abrahams [Ki

5 ].

The

_1 calculated relaxation time r, which can be identified with (ay/f)

in a resonance experiment, appears to be of the correct order of magnitude

23]

DAMPING
state the

105

if

one assumes that in the non-equilibrium

occupation of

all levels

differs

from that in the equilibrium

state,

such as for example the distribution

pertaining to a temperature different

from the ambient temperature. Polder

[Po

1 ]

has pointed out that this does not correspond to the circumstances

in a resonance experiment performed


externally applied alternating field
is

on a small specimen within which the


uniform.
first

One then

excites, as it were,

spin waves with

= 0,

so that in the

instance only the distribution of

these spin waves will deviate

from the

state

of equilibrium. The interactions

described above cannot then occur, since to do so the wave

number as

well

as the energy of the other spin wave and the lattice vibration would have

The energy transfer would then have to take place in processes more than three particles, which is improbable. In such a case the relaxation time would become much longer. It has been pointed out by Clogston et al [CI 1 ] that, apart from dynamic
to be equal.

involving

perturbations, static deviations


sitions.

from

lattice periodicity
ferrites in

can give

rise to tran-

These are found, for example, in

which two

different

magnetic ions occur disordered at equivalent

lattice points, resulting in

non-periodic perturbing magnetic fields of appreciable magnitude. These

can change the wave number of a spin wave, but the energy remains constant thereby, comparable with the scattering of conduction electrons on an
impurity in a
co

solid.

For a

sphere, ferromagnetic resonance occurs


field.

when

= yH

e,

where

H
is

e is

the external

Owing

to the demagnetization in

the z direction, (22.14) applies.


fields
lies

The

fields

used in Fig. 22.1 are the internal

Ht, which

to say that the frequency for ferromagnetic resonance

to versus k curves extrapolated to k = 0, and the value to = yHe is degenerate with a large number of spin waves with a finite k value. This difference in behaviour between spin waves and the k = waves at ferromagnetic resonance is due to the fact that the ferromagnetic resonance frequency is increased by the dynamic poles arising at the edges of the specimen. These also arise in the case of spin waves pro-

between the values of the two

pagated in the z direction, but they then change sign with a wavelength
equal to that of the spin wave. The demagnetizing
length, so that in effect the frequency of the spin
fields

thus practically

cancel each other out at distances that are large with respect to the wave-

waves

is

not influenced

by the

finiteness of the crystal.

Once

these spin waves with the ferromagnetic resonance frequency are

excited, the excitation spreads out rapidly

by the normal Akhieser processes


lattice

over the entire spin wave spectrum, and interaction with the
place.

can take

The bottleneck

lies

in this

first

transition,

which

is

believed to deterfields

mine the relaxation time. Owing to the increase in perturbing

when

106

DYNAMICS OF MAGNETIZATION PROCESSES


is

[CH. VI

the magnetization

increased as a result of lowering the temperature, there

occurs an increase in 1/t and hence in line width.

Apart from a dependence upon the degree of ordering,


predicts a dependence of t

this

theory also
flat disc

on the shape of
field,

the specimen.

For the

which
field is

is

magnetized at right-angles to the plane of the


since the poles
this frequency coincides

disc, the

resonance
sig-

equal to the internal

on the edges are of no

nificance here. In other words,

with the lowest spin

wave frequency and no degeneracy occurs. With this shape of specimen, therefore, a longer relaxation time and hence a narrower line will be found.
23.4.

INSTABILITY AT

LARGE AMPLITUDES

The qualitative considerations discussed above were applicable to the damping mechanism described by (23.11), i.e. where the constant a is independent
of the amplitude of the
amplitudes, the
signal. If this

equation were also to apply to large

maximum

value of /' would then be independent of the

deviation from static equilibrium until the angle of deviation of the magnetization vector had reached 90. This is the case when the amplitude of the
alternating field
is

equal to the line width

AH = 2aH (see

(23.13)).

From

experiments by Bloembergen et al [B12]

it appears that non-linear phenomena

already occur at amplitudes of the alternating field of the order of l/50th of that value. The absorption curve then becomes lower and wider, as if a

had become

larger.

Suhl [Su 3] has shown that this

is

the consequence of a

stronger coupling of the ferromagnetic resonance mode with some of the spin waves having the same frequency, which coupling already existed owing

wave superimposed on the uniformly precessing magnetization vector, having the same frequency and being propagated along the z axis, becomes unstable and grows larger at a specific
to the Clogston mechanism. spin

amplitude of the alternating

field. It

appears that

if

4tt-JMz

= AH,

where

of the magnetization as a result of Z is the change in the z component the line width, standing waves are created, i.e. the precession and AH is the magnetization vector no longer remains stretched during precession.

AM

For the magnitude of the microwave


he
It further

field

hc

this condition is

= AH^AH/4nM

(23.16)

appears that these demagnetizing

fields in

the direction of pro-

pagation of a spin wave

may

also give rise to spin waves with a frequency

equal to half the frequency of the external field, if the alternating amplitude m+ of the still uniformly rotating magnetization vector satisfies

4nm+ sin

8 cos 6

>

AH,

23]

DYNAMICS OF DOMAIN BOUNDARY (BLOCH WALL) MOVEMENT


is

107

wave vector angle of the spin wave with the z axis. This is = 45. The instability, which manifests itself as an first satisfied for extra absorption peak, is noticeable with static fields that are some hundreds
where 6
the

of oersteds lower than the resonance

field.

In

first

approximation

we may

write for the critical value of the external field

hc
24.
24.1.

~ (o> - av) AHjy

2ttM.

(23. 17)

Dynamics of Domain Boundary (Bloch Wall) Movement

WALL INERTIA

The applied field, parallel to the magnetization on one side of a 180 wall, exerts a torque on the spin vectors inside the wall. This does not, however,
directly cause wall displacement, since

the spin vectors are turned

by the

ex-

ternal field in a direction at right-angles

to the plane of the wall, whereas in

order to

move
to

the wall a rotation of


is

the spin vectors


parallel

necessary in a plane

the

wall.

The angle of

movement from

the plane of the wall

obeys the relation

e=yHsm.<f>,
(see Fig. 24.1). This
rise to

(24.1)
Fig. 24.1.

Schematic representation

movement can

give

a torque, represented by a vector wall. in the plane of the wall, which may turn the magnetization vector in that plane and so cause the wall to move. This torque, for small values thereof, will be proportional to 0, hence

of a spin vector S, inside a moving wall, moving out of the plane of the

M<
where

= Af
dz

.v

C.O,

(24.2)

C is a constant of proportionality, which can still be a function of the


it is

position (z) in the wall. In (24.2)

assumed

that, apart

from

0,

the wall

moves undeformed. By diflFerentiating (24.2) with respect to time we find, with the aid of (24.1), that the acceleration (v) of the wall is proportional
to the applied pressure 2

HM.

This means that the wall has inertia [Do 1]


it.

and therefore mass can be


in detail,

attributed to

We shall not give the calculation

but simply explain

its results.

108

DYNAMICS OF MAGNETIZATION PROCESSES

[CH. VI

The torque CO

in (24.2) consists of three parts, due to exchange energy,

crystal energy and, as

an extra contribution, a torque caused by demagnetia magnetization

zation. In the z direction

M0

is

present only inside the wall.


too,
field

Outside the wall

we have
zero.

B = 0, and therefore inside the wall,


z

Bz

must be equal to

As a consequence of

this,

a demagnetizing

arises

of the order of

H = -4nM = -4ttM
z z

0.

This gives a torque

MHz at right-angles

to the magnetization vector at the

The torque of the exchange interaction is of the form 2 d 2 6/dz z of (22.6) which for the component considered here, becomes The crystal anisotropy torque is 2K cos 2 <. As explained in 15, we may
position of the wall.

AM

write for the exact 180 wall configuration in a uniaxial crystal


sin

<f>

Sw

(o^/oz)

l/cosh(z/8),
t

(24.3)

where 8 W

is

the wall thickness.

short time

after applying the field

the applicable expression, according to (24.1)

is

= yH
If,

sin

<j>.

(24.4)

using (24.3),

we

calculate with this value the

component of the

total

torque in the plane of the wall,

we
r

find
t l

T+

= (H* + 4i M + Hcm4>)M

.d.

(24.5)

The part A in the form between brackets originates from the exchange energy and the crystal energy together, while the term 4ttMs originates from
the demagnetizing field in the z direction.
external field
is

The term

originating

from the
so that

negligible for the calculation of the acceleration.

According
z,

to (24.3)

and

(24.4), d</dz

the notation in (24.2)


(24.5), then,

depend in the same way upon with a uniform v is permissible. From

and

(24.2)

and
t,

we

obtain for the velocity v of the wall, for short times

y*h w

H(W + 47rMs)t,
is
1
.

(24.6)

and therefore the mass per cm 2 of the wall

mw =

[277 y 2 8,(l

+ Ha /4ttM

s)

J-

(24.7)

The special point to be noted here is that the mass is inversely proportional
to the thickness of the wall.
24.2.

DAMPING OF THE WALL MOVEMENT


subject to damping, so that

The movement of the domain boundary is

some

23]

DYNAMICS OF DOMAIN BOUNDARY (BLOCH WALL) MOVEMENT


field

109

time after the application of the

which the wall moves

with constant velocity.

a stationary state will be reached, in We assume that the rotation

of the magnetization vectors inside the wall can be described by a damping term as in (23.1 1). However, it is not certain that a will have the same value
as for ferromagnetic resonance, since in the latter case the magnetization For wall movement the description with spin is practically uniform.

waves

is

no longer adequate, and

therefore the Akhieser theory cannot be

use the damping term from (23.11), then in applied here. If nonetheless the stationary state this torque must be neutralized by the torque exerted

we

by the external field H, as indicated in (24.5). The damping torque in direction becomes aMs dO/bt = aMs (&0/Bz) v, hence
.

this

Hcos<j>.0

= a(pe/Zz)v.

Now
and

in the stationary state, too, 6 is proportional to sin <j>, as in (24.4), therefore in the stationary state the relation between the velocity of
is

the wall and the applied field

V
If

(yB/a)H.

(24.8)

we put

for the equation of

motion of a 180 wall pwZ

mw z +
where
that
fi

= 2MsH,
it

(24.9)

wz

fi

wv represents the damping term,

then follows from (25.8)

pw

= 2aMs
and

Y8 w

(24.10)

Where a

10~ 2 ,

H=

10 oersteds

Sw

10-5 cni) the velocity of the

wall follows

is thus of the from Inside the wall the magnetization order of magnitude of the speed of sound. is not uniform and deformation will occur of the same kind as volume magnetostriction. The wall movement, then, will be associated with the

(24.8) as approximately 2000 m/s, which

propagation of a sound wave. Accordingly, the velocity of the wall will show a dispersion near the speed of sound in the material. The maximum value of the angle 6 in the centre of the wall is of the order

which, where

HA =

and 4ttMs

= 4000 gauss,

is

here of the order of 15.

For

larger fields the given derivation is thus

no longer valid and an increase

in $ w

may be

expected.

110
24.3.

DYNAMICS OF MAGNETIZATION PROCESSES

[CH. VI

WALL RESONANCE
that the wall is bound to its equilibrium position with a The equation of motion (24.9) then becomes

It

may be assumed

certain stiffness.

mw z +
For small damping
(/J

Pwz

az

= 2M H
S

(24. 1 1)

w2 <^ am w)

this

equation predicts the occurrence of

wall resonance with an angular frequency

wr
The
stiffness

fa/m w

(24.12)

is

related to the

low frequency permeability po by


\6ttMs * 11(^.0 \)
(24.13)

a^
where
/ is

the thickness of the domains.

CHAPTER VH

METHODS OF MEASURING
FERROMAGNETIC PROPERTIES
25. Measurement of Magnetization
25.1.

INDUCTIVE METHOD

For measuring magnetization several methods can be used which are based on the various physical laws. One of these is the induction law (2.1). The most common method of measuring magnetization is the ballistic method. The specimen takes the form of a prolate ellipsoid, since in that case, when the external field is uniform, the internal field is also uniform and hence the magnetization too. The experimental set-up is shown in Fig. 25.1. Inside the large coil which supplies the static field is mounted a short

Fig. 25.1.

Arrangement for

ballistically

measuring the magneti-

zation of a prolate ellipsoid.

which encloses the specimen as narrowly as possible and which is conballistic galvanometer. In series with this small coil is an identical but oppositely wound coil, which is set up at some distance
coil

nected to a

from the specimen but


this field

is

nevertheless

still

in the static field.

Changes in
circuit.

then produce no flux change in the galvanometer


is

The

specimen

now withdrawn from


of:

the coil so as to give rise to a flux

change per turn

A = S(Bwhere

H )dA,
Q

B=
The
field

H + HD + 4ttM.
o

HD

is

proportional to

(see Fig. 1.2) so that

M can be calculated

112

METHODS OF MEASURING FERROMAGNETIC PROPERTIES

[CH. VII

from the maximum

deflection of the galvanometer. If the measuring coil

does not tightly enclose the specimen, the measured flux will also include some stray field outside the specimen. When the diameter of the measuring
coil is small

compared with the length of the specimen, we may assume to

a good approximation that the external stray field inside the measuring coil is still practically equal to the demagnetizing field Hj> inside the ellipsoid
so that the correction can easily be applied.

This method can also be used for making an alternating current measurement by letting the specimen vibrate at the boundary between two oppositely wound measuring coils; this induces in the coils an alternating voltage which is proportional to the magnetization and the velocity of the specimen:

oc

(aM/az)u z

This method can be used [Oo 1 ] for measuring the magnetization of very small specimens. The magnetic moment can be treated as that of a point dipole,
in

which case the

field inside
It is

the measuring coils can easily be calculated

with the aid of (12.3).

also possible to calibrate with a specimen having

a known magnetization.

So
field

far

it

has been assumed that the magnetizing

can also be varied, for is then due not only to the change in the magnetization of the specimen, but also to the change in the primary field. If the measuring coil fits exactly around the specimen, the change of B in the specimen is
duced voltage

The The inexample stepwise by abrupt changes.


field is constant.

when the specimen cannot when measuring hard magnetic material be pulled out, as for example between the poles of an electromagnet. To prevent eddy currents appearing
measured
directly.

This method has to be used

during rapid
If the

field variations, the


is

specimen and the yoke must be laminated.

not perfectly in contact with the pole surfaces, the field in the specimen will not be equal to that in the gap when the specimen is not present. For example, with an air-gap between the specimen and the pole-piece equal to 1% of the thickness of the specimen, the value of

specimen

AttM being 10,000 gauss, the internal field is 100 oersteds smaller than the external. The internal field must therefore be measured separately. This can be done by making use of the continuity at a surface of the tangential component of the magnetic field. The field directly adjacent to the specimen is measured with a small coil. In this way, however, one measures the field at the distance equal to the radius of the coil around the specimen, which can differ appreciably from the internal field. In this case
it is

advantageous to use a magnetic potentiometer; see Fig. 25.2. This is a semi-circular, uniformly wound coil. The total enclosed flux is then propor-

25]

MEASUREMENT OF MAGNETIZATION
when placed on

13

tional to JTftd/ along the centre-line of the coil, which,

the

surface of the specimen,

is

equal to jHidl along

its

surface between the

two

ends of the

coil,

the field being measured exactly along the edge.

Fig. 25.2. Magnetic potentiometer orRogowskicoil.

y/^///////////////////////^

In the case of ring-shaped' specimens (principally suitable for soft magnetic


materials) the total induction
is

also measured. If the field coil


is

is

uniformly
field out-

wound around

the specimen, the internal field

uniform, and the

no correction whatsoever need be applied and the field is found directly from equation (1.1). In the case of straight rods, where the permeability would be too much restricted by the
side the ring is exactly zero; therefore
is closed with a yoke of magnetic material. If the cross-section of the yoke is large with respect to that of the specimen, the effect of the permeability of the yoke is

demagnetization, the magnetic circuit of the rod


soft

negligible.

With measurements on a closed magnetic


ferrite ring,

circuit,

such as for instance a


for instance

only changes in B can be measured. In order to measure magnetiit is

zation curves

necessary to start from a


is

known state, which is

obtained

if

the specimen

an

alternating field

demagnetized; this can be done by placing it in the amplitude of which is gradually reduced from a very

high value (sufficient to saturate the specimen) to zero. For measuring hysteresis loops the saturated state is taken as the starting point and measure-

ments are continued until the specimen is saturated in the opposite direction. Hysteresis loops can be recorded on an x-y recorder with the aid of an
integrating circuit [Br
sensitivity,
1 ].

This

calls for

the use of d.c. amplifiers of high


cells

galvanometers with photoelectric


25.3).

being suitable for the

purpose (see Fig.

If the magnetization
field is

does not reach

its final

value immediately after the

applied (which

present)
if

may be the case, for example, when eddy currents are wrong results may be obtained when measuring the hysteresis loop
[Sn 2].

demagnetization occurs

The

internal field

H = H NM
t

is

then temporarily too large at certain places, and therefore, as a result of


hysteresis, there will ultimately

be too great a change in the magnetization.

consequence of

this

can be that the virgin curve (commutation curve)

114
falls

METHODS OF MEASURING FERROMAGNETIC PROPERTIES


outside the hysteresis loop (Fig. 25.4).

[CH. VII

With non-conductive ferromag-

netic rings errors

can occur owing to the fact that, because of the presence of stray capacitances, oscillations appear in the field after interruption of the current. In measurements of the remanent magnetization, for example, can give rise to appreciable opposing fields, which result in an apparently lower value of the remanence. These oscillations can be adequately damped by applying a resistor R parallel to the primary winding Lx through which
this

Fig. 25.3. Basic

diagram of an integrator for measuring

B-H loops. 5

search

coil;

inte-

grating resistor;

Ga galvanometer; L Light

source for galvanometer;

gas-filled

twin

phototube;
coil.

NO meter giving
1].

a direct reading of the change of flux linked by the search

See [Br

1500

M
(gauss)

1000

500

-10
Fig. 25.4.

12

H (Oe)

ing

Main loop of a wire of carbonyl iron, as measured by switchon and off the current in the usual way. The virgin curve measured by the "step by step" method, in which the current is increased in small
steps, lies outside the loop. (After [Sn 2]).

25]

MEASUREMENT OF MAGNETIZATION
Fig, 25.5.

115

Damping of oscillations by a

resistance
coil of

parallel to

the primary

circuit for

measuring magneti-

zation ballistically.

about

10%

of the current flows (Fig. 25.5);

this

makes the

Lx /R

time of

the circuit sufficiently long.

25.2.

METHODS UTILIZING THE FORCE ACTING ON A BODY IN A NONUNIFORM FIELD


salts are generally

Magnetic moments of paramagnetic


the

mining the force on the specimen in a non-uniform magnetic

measured by deterfield, of which

component

in the

direction

is

equal to:

Fx = MbH/bx =
The magnetic moment
cally.
is

xHSHfix.

(25.1)

then generally too small to be measured

ballisti-

However, the forces are soon large enough to be measured accurately. = 1000 Oe and bH/bx = 1000 For example where x = 10-4 /cm3 and is still only 0.1 gauss. The Oe/cm, the force is 100 dyne per cm3 although compensated with, say, a spring balance. For ferromagforce is generally

netics the forces are very considerable.

method of measuring magnetization

exists

[Ral] in which use

is

made of
the field

the second derivative of the field with respect to position; the

first

derivative
is

may then be zero, i.e. the specimen is placed at a position where maximum in the x direction. For deflections in at least one directfield is

ion at right angles thereto the


is

then minimum. However, the specimen


it

suspended on a pendulum, (Fig. 25.6) so that

can only move in the x


of the

direction.

Suppose that the

field in the vicinity

maximum can

be

descibed as

H= Ho-iax*.
The force/a

(25.2)

= aMx acting on the specimen

is

thus a harmonic force. Hence

the period of oscillation will change according to:

=
T2

1
1

aMV
47T2 /M
,

(25.3)

mB ^

TQ 2

116

METHODS OF MEASURING FERROMAGNETIC PROPERTIES

[CH. VII

where

V is

the volume of the specimen


it is

and

the
is

mass of the pendulum.

In most cases

the weight of the sample that

determined, so that accor-

ding to (25.3) the magnetization a per

gramme is measured. This method is

used only for measuring the

moment in high fields. The demagnetizing fields

of the often irregularly shaped specimen are therefore unimportant.

Fig. 25.6.

Pendulum device

for measur-

ing the magnetization of a specimen


in a non-uniform field (after [Ra
1]).

Specimen
horizontal

p,

pole pieces

and

S,

pendulum P, cooling

vessel

V and

nitrogen current N2.

26.
26.1.

Measurements of Magnetocrystalline Anisotropy Energy

MEASUREMENT OF MAGNETIC ENERGY

The magnetocrystalline anisotropy energy can be measured from the different trend of the magnetization curves versus the field in the easy and difficult directions of magnetization in a crystal. The anisotropy is then equal to
the difference in magnetic energy:

FK = A fHdM.
It is

(26.1)

not possible from this relation alone to determine the different constants
(11.1) or (11.6).

from
the

M versus H curve
if

To do

this it is first necessary to analyse the

in the difficult direction.

form of For example, we have seen


line

in 17 that

we have

only K\

M versus H curve in the

in (11.6) for a hexagonal crystal, the

difficult direction is

a straight

up

to saturation

26]

MEASUREMENTS MAGNETOCRYSTALLINEANISOTROPY ENERGY


.

117

at

H = HA

If

with the

field

H in the basal plane the component Mh of M along H


2KX

Kz

is

also taken into consideration, for a preferred direction


satisfies:

4K2
17*
1 ]

17 Mff +
Thus,
is

M* = Ms^,

(26 2)
'

if

HMs/Mh

is

plotted [Su

as a function of Af|, astraight line


is

obtained whose point of intersection with the vertical axis


.

equal to

IKijMs, the slope being equal to 4KzjM2 s For cubic crystalline anisotropy the versus

H curves are always curved.


separately determined

The anisotropy constants Kx and K% can then be


measurements of
in the [100],

from

as a function of

H in different directions, for example


The area enclosed between the [111 ] and [100] directions is equal
[100] directions
is

[110]

and [111]
field

directions.

magnetization versus
to

curves in the

K/3

+ Kz/27,

and that between the [110] and

equal to K\/4.
26.2.

TORQUE METHOD
is is

In the torque method of magnetic anisotropy measurement the specimen

suspended on a torsion spring in a uniform magnetic

field

H.

If this

much

stronger than the anisotropy field

H A the magnetization vector will


H A the
(17.2),

be practically parallel to H. The torque acting on the specimen can then


be found simply by differentiation of the crystal anisotropy with respect
to the angle concerned.

For

fields

comparable to or smaller than


is

equilibrium position must

first

be calculated by, for example in


then

putting dF/d0 equal to zero.

The torque

T= dF/da = oF/Ba + (bF/i>0)dd/da,


where the
last

term

is

zero.

For cubic materials and for strong

fields

we

find in the (110) plane

T{9)

(2 sin 20+3 sin 40) +


8

(sin

20

64

+ 4 sin 40-3 sin 60),

(26.3)

where is the angle of the magnetization with the [100] direction. By harmonic analysis of the measured curve the constants K% and Kz can be determined. For rotation of the magnetization in a (111) plane, only Kz gives rise to anisotropy owing to the hexagonal symmetry in that plane:
r(0)

sin 60.

(26.4)

This method offers advantages and leads to simple results

if

the applied

118

METHODS OF MEASURING FERROMAGNETIC PROPERTIES


much larger than the
and what
is

[CH. VII

field is

anisotropy

fields. If this is

not the case the mag-

netization can only be turned through a small angle out of the preferred
orientation,

in fact

is

measured

is

the stiffness with which the

magnetization

bound

to the preferred direction. In this case the stiffness


26.3.

can more
26.3.

easily

be measured by the method described in

TORSION PENDULUM METHOD

An

analogon for the pendulum method of measuring magnetization also


determination of crystal anisotropy. This consists in determin-

exists for the

ing the frequency of the torsional vibration of the specimen around the state

of equilibrium in a uniform magnetic


(see Fig. 17.1):

field.

The

stiffness c is

then given by

= d F/d<x2 = o2F/oa + 2(o


2 2

2 .F/oao0)d0/da

(W/d02)(d0/da) 2
is

(26.5)
stiffness

If the

moment

of inertia of the torsion pendulum

/ this magnetic

changes the square of the reciprocal period of oscillation by an amount:

J(1/t 2)

= clAifll.

(26.6)

For uniaxial anisotropy described with a constant K\, equation


becomes:

(26.5)

In

weak fields

HM COS (a2^1 cos 20 (H < H A the relation between c_1 and H-1
S

0)

is

in first approxi-

mation

linear:
1

cos 2a

HM
c,

COS a

2Ki COS 2 a
is:

(26.7)

while for an infinitely strong field the limit value reached

=2ATicos2a.

(26.8)

At

< a<

45 the stiffness passes through a

differing

from zero can be obtained with a

stiff

maximum. These values of a torsion wire. At a = the

relation is linear for all fields:

-1

=mf

A = ^J H
a.

~1

+ iHA) - ^
1

(26 9)
-

The
it is

slope of the c _1 versus


generally equal to

H' 1

straight line is equal to

l/Ms

for a

\jMs cos

26]

MEASUREMENTS M AGNETOCRYSTALLINE ANISOTROPY ENERGY


NETIC RESONANCE

119

26.4.

DETERMINATION OF CRYSTAL ANISOTROPY FROM FERROMAG-

With the aid of the general expression (18.10) for the resonance frequency, an anisotropy energy can be determined by measuring the resonance frequency at different orientations of the static magnetic field with respect to the crystal axes. An example of this is given for uniaxial anisotropy in 18.1. For cubic anisotropy this method has been applied by Bickford [Bi 1], among others. The method determines not only the crystal energy but also the g factor. If for the same resonance frequency the field strengths Hi, Hz and Hs have to be applied in the [100], [111] and [110] directions respectively, then the resulting effective field strengths are given by:

[110]:

ett

=H
I

+ -^
Ms
3

[111]: Hett

4 = H -2

Ki Kz -- M M
4
9
s s I

(26.10)

2Ki\i

Ki

K2 \i
K\ and K% can be .STi and K% differ

From

the magnitudes of

eff

and

the quantities g,

determined. In the case of uniaxial crystals, in which both

from zero, the g factor can also be anisotropic. By measuring at only one frequency the crystal anisotropy cannot then be determined, and measurements must accordingly be made at more than one frequency.
27. Magnetostriction
27.1.

DISPLACEMENT MEASUREMENTS
the displacement of one

The magnetostriction of a rod can be measured by


of doing
this,

of the ends of the rod with respect to the other. There are various methods
nature. First of all there

which can also be used for displacements of a non-magnetic is the purely optical method, in which the displace-

ment

is first

increased mechanically

by

for instance a factor of 10 with the


is

aid of a lever, after which the translation


thin spindle

converted into the rotation of a


this

on which a mirror

is

mounted. In

way

displacements of

the order of 10~ 7

can be measured. The method has the advantage that the magnification factor depends only on mechanical quantities, determined by the construction. In principle the method can also be employed at tem-

cm

from room temperature. There are also several electrical methods that can be used, in which the displacement is converted into a
peratures differing

120

METHODS OF MEASURING FERROMAGNETIC PROPERTIES

[CH. VII

change in the capacitance of a condenser or into the change in the mutual


inductance between two coils (differential transformer). In the
circuit
first

case a

can be detuned so as to produce a different frequency. The beat


is

frequency produced with a signal of the original frequency

then a measure
device

of the displacement. In most cases a null method


nected in parallel. The disadvantage here

is

made of this

by

compensating the variation in capacitance with a variable condenser conis

that the

measurement cannot

be carried out quickly; quick measurements are usually necessary because of temperature variations.
rise to

An

increase in temperature of about 0.1 gives

The differential transformer can be made as a direct-reading instrument. With such small deflections several interfering effects can arise as for example a magneto-caloric effect when the field is switched on rapidly. This can produce temporary changes in temperature
.

a strain of 10~ 6

of 0.1 C.
27.2.

STRAIN MEASUREMENTS

In 1947

Goldman [Go

2] reported

how

strain gauges, at that time just in-

troduced, could be used for magnetostriction measurements.


wire,

A folded metal
is

which can have a resistance of the order of 100 ohms,

affixed to the

specimen. The magnetostrictive strain causes changes in the resistance of


the wire, which can be measured with the help of a Wheatstone bridge. Similar strain

gauges are in the other branches to compensate as far as

possible for temperature influences.

The measurement can be

carried out

with direct current or low-frequency alternating current


since the magnetic material to

(/<

100 c/s)

can give
-8 to 10

rise

which the current-carrying wires are affixed to an inductive effect which changes during magnetization.
also very sensitive, being capable of measuring strains

This method
.

is

up

The advantage is that no long rods or rings are needed, an important point in the measurement of single crystals. The minimum dimensions of
strain gauges are approximately

mm.

Additional errors that can occur


place by the magneto resistance
.

in this

measurement are caused in the

first

of the wire. At

room temperature
is

this is

not greater than 10 -7

When more
approxi-

than one strain gauge


mately eliminated
the
if

used in a Wheatstone
is

circuit this effect is


all

care

taken to ensure that

the strain gauges are in

same magnetic

field.

Strain gauges are not readily usable at

low temperatures. In the

first

place*

the temperature coefficient of the resistivity p has been


at

made

very small

This is only possible in a small range of temperatures, and at low temperature this coefficient can be a
.

room

temperature, (Ap/p)/C

~ 2.10-5

factor of 10 larger.

temperature coefficient as low as

this is

obtained

by

27]

METHODS OF MEASURING COMPLEX

INITIAL PERMEABILITY 121

using an alloy with a transition element (e.g. Cu-Ni alloy). Even though

become ferromagnetic at low temperatures, these alloys neverbecome strongly paramagnetic and exhibit a very considerable change in resistance (dp/p = 10 -3) in a magnetic field. The use of strain gauges at high temperatures imposes restrictions on the paper and the cement empthey do not
theless

loyed, so that the upper temperature limit for practical purposes

is

50 C.
then

To sum

up,

it

can be said that strain gauges provide a good method for


it

measuring magnetostriction on single crystals at room temperature,


applied voltage.
27.3.

being easy to vary the angle between the direction of measurement and the

STRESS

MEASUREMENT

In order to measure the dynamic magnetostriction in small alternating fields


(small enough to cause no heating) the rod of magnetic material can be clamped against a piece of piezo-electric material so that the total length remains constant. If the length of the piezo-electric material is small and the cross-section large with respect to the same dimensions of the magnetic

specimen, the length of the latter will also remain constant and the magnetostrictive stresses

of the magnetic specimen can be measured from the

polarization of the piezo-electric material.

28.

Methods of Measuring Complex

Initial

Permeability in Various Fre-

quency Ranges
28.1.

INFLUENCE OF DEMAGNETIZATION ON THE APPARENT PERMEABILITY


/*a pp

The relation between the apparent permeability


true permeability
p.

of an ellipsoid and the

of the material
/^app

is:
p.

i+_0i-i)
477-

(28.1)

where

is

the demagnetizing factor of the ellipsoid in the direction of


field,

the measuring

see

1.

High-permeability materials are preferably

measured in the shape of ring cores in order to avoid excessively large corrections for demagnetization.

The demagnetizing

factor of a sample can

be determined from the ideal magnetization curve, which is measured by superimposing an alternating magnetic field on a constant magnetic field

H in the core. The amplitude of the


from a high value to
zero.

alternating field

is

gradually reduced

magnetization obtained in this

The curve which gives the relation between the way and the intensity of the constant magnetic

122

METHODS OF MEASURING FERROMAGNETIC PROPERTIES

[CH. VII

field is called

the ideal magnetization curve. If no demagnetization

is

pre-

sent, the curve touches in the origin the magnetization axis,

(dH/dM)H=o = 0.
with the magneti-

Owing

to demagnetization the curve will

make an

angle

/?

zation axis determined by tan/J

= dH/dM = N,
sample,
exists

where

is

the effective

demagnetizing factor; see (1.11) and Fig. 28.1. Apart from the demagnetization caused

by the shape of the


demagnetization

internal

which is related to the presence


see
43.3.

of a second, non-magnetic phase or


pores;
ferrites,

With

sintered
j8

for instance,

the angle

gives

an impression of the magni-

tude of the porosity: the angle increases with the porosity. In this case

Ni

= tan

j8

is

called the internal

demagnetizing factor. For a


Fig. a)
28.1.

ring

Ideal

magnetization

curves:

with a small air gap, (1.13) gives the


relation

no demagnetization;

b) demagnetizing

between the

relative length

factor

N = tan

/3

of the gap and the corresponding


demagnetizing factor.

In 23.1 a complex susceptibility was introduced which describes the linear relationship between an alternating magnetic field and the alternating magit produces in a ferromagnetic core. The susceptibility complex owing to damping of the ferromagnetic rotator. Irrespective of the nature of the magnetization process and the nature of the damping,

netization which
is

we

write for the complex permeability

fJL

fj.

Ifl

(28.2)

The

the induction which changes in phase

and the imaginary part of the permeability determine respectively and that which changes 90 out of phase with the field. The phase angle S or the loss factor tan 8 is given by
real

tan 8

fi"/fi'.

(28.3)

The
and

influence of demagnetization

on
is:

the magnitude of tan 8 can easily be

calculated.

The

relation between the externally applied field strength

the internal field strength

H=H - NM.
e

(28.4)

Dividing (28.4) by

gives the general expression:

28]

METHODS OF MEASURING COMPLEX


X

INITIAL PERMEABILITY 123

=
Xapp

N,

(28.5)

where xapp from (28.5)

is

the apparent susceptibility of the magnetic core. If follows


//

that:
it

X app
IXappI
2

X
(28.6)
Ixl 2

Expressed in the permeability

this

becomes:
tan S

tan S app
/*'a

PP (1 - tan2

8 app )

'

(1 - tan*

S)

(28.7)
1

or in the case of high permeabilities and small loss angles:


tan S a pp
fiapp

tan 3
(28.8)

f
is

This equation states that

if

the permeability of a magnetic core

reduced

as a result of an air gap or as a result of internal demagnetization, then the


loss factor is
28.2.

reduced proportionally.

BRIDGE METHODS AT LOWER FREQUENCIES


soft

With

magnetic core materials


initial

it is

important to

know

the frequency-

dependence of the

For lower frequencies, up to about 50 Mc/s, this quantity is generally measured by winding a coil around a core of the material to be investigated. The properties of such lumped impedances
permeability.
dielectric constant

are determined with the aid of bridge or resonance circuits. In order to

measure the permeability and the


frequencies of about 50

of the material from

Mc/s up

to the centimetric

wave range, methods of

measurement have been developed in which the magnetic core is incorporated


in cavity resonators or transmission lines.

From

the resultant perturbations

the properties of the ferrites can be determined.

toroidal ferromagnetic core with permeability

/*,

cross-section

A and

average diameter D, provided with a winding of

N turns, can be treated as


Ls and
a resistance

an impedance
series:

consisting of a self-inductance

Rs

in

Z =R +jo)L r = w (N2A/D) j."-1(^ ohm


s s s
I

(28.9)

L8
With the aid of bridge

= (ATM/.DV-10-

henry.

circuits,

such as the Maxwell and Schering bridge

124

METHODS OF MEASURING FERROMAGNETIC PROPERTIES

[CH. VII

R s and Ls of the immeasured at low frequencies (below about 50 Mc/s) and and ju." calculated from the results. Measurements of the quantity /*' alone can be performed with great precision with an Owen bridge. A quick resonance method, which can be used at frequencies between about 50
or a mutual inductance bridge, the two components

pedance
ju.'

Z can be

kc/s

and

Mc/s in cases where the


[Bu
1 ].

loss angle is smaller

than approximately
high frequency, the

0.1 radian, is described in

When
high

measuring the permeability of

ferrite cores at

electric resistance

of these materials generally precludes the troublesome


to be kept small in order to avoid dimensional
is

skin effect found with metals. However, the cross-section of the ferrite core
to be measured

may have

resonance phenomena. The reason


stant of

that,

owing to the high

dielectric

con-

some

ferrites, it is

possible that at the measuring frequency the

wave

length in the ferrite will be of the order of magnitude of a linear dimension,

which can give

rise to

standing-wave phenomena in the core (see

29.1).

In the bridge measurements the ring core must be provided with a winding, which sets a limit to the measuring range. At low frequencies and low magnetic losses in the core the d.c. resistance of the

winding can so predominate


.

that there can be

no question of an accurate measurement of Rs


(b).

A method
made for To avoid

of eliminating
the d.c.

this d.c. resistance is that using the

mutual inductance bridge

described under

At higher
provided

frequencies a correction can be


it

resistance,

is

known

at this frequency.

an increase in resistance owing to skin effect, braided copper wire should be used at frequencies higher than 100 kc/s, the thickness of the separate wire strands being adapted to the measuring frequency; up to about 10 Mc/s
the rule of

thumb

is

that the wire thickness in

microns must be smaller than the wavelength in


metres.

Besides the earlier-mentioned self-inductance

Ls

and

resistance

Rs

the complete equivalent circuit

also contains

the stray parallel capacitance

Cv

Between the terminals P and Q apparent values R s and L s are thus measured,

shown in

Fig. 28.2.

'

'

which for small values of Cp are related to the true values R s and L s by the equations:
Rs'
Fig. 28.2. Equivalent circuit

Ls
tan

'

of a

coil

with

ferrite

S'

= Rs/(l - 2a>2L Cv = L L Cp) = (tan S)/(l - ofiL Cv


s ) s /(l

co 2

(28.10)
).

core.

The
is

stray capaci-

tance

indicated by

Cp

Consequently the values of

/*'

and

/*"

derived from

[28]

METHODS OF MEASURING COMPLEX


'

INITIAL PERMEABILITY 125


the

Ls and Rs
'

according to (28.9) will differ

all

more from

the real values

the larger the value of


frequencies, at
ible.

w 2Ls Cv
and

This

is

particularly the case at higher

which

Cp

Ls

must therefore be kept as small as poss-

To make Cp

small the ring can be provided with a special low-capacit-

ance winding, in the manner illustrated in Fig. 28.3. The number of sections

can be extended to more than two.


Moreover, in cases where the
ferrite

core has a high dielectric constant, the


stray capacitance can be reduced

by
e.

winding the

ferrite

core beforehand

Wi
Fig. 28.3. Low-capacitance
six turns

winding of

with an insulating material of low

on

ferrite core.

The

self-inductance

Ls cannot be

arbit-

rarily small, since otherwise the stray self-inductances

of the supply leads

would become
with metal

relatively important. In that case the core

can be wound

strip,

but

it is

even better to use a single coaxial winding, a

kind of box

fitting closely

around the

ferrite ring.

We
(a)

shall

now

outline

some commonly used methods of measurement

with lumped impedances.

Owen Bridge for Accurately Measuring p up


20 kcjs
as in Fig. 28.4

to

a Frequency of about

The Owen bridge

is

particularly suitable for the accurate


1 ].

measurement of self-inductances [Ow

The

conditions of balance are:

Lx

= R1R3C2
R1C2/C3.

Rx =
adjusting

(28.11)

Both these conditions can be satisfied by ^3 and Cz independently of each other, a facility which makes the bridge most
convenient to work with in practice. The value

of the self-inductance can be very accurately


ascertained if Cz
enser.
is

The

equivalent resistance

a well-calibrated condRx cannot

properly be measured with this bridge, since


Fig.
28.4.

Owen

diagram of bridge for measuring selfBasic


1].

closer analysis of the bridge reveals that the

inductances up to a frequency

of about 20 kc/s; see [Ow

adjustment of Cz is partly determined by the magnitude of Lx if Ri is not a pure resistance

and the loss factor of Cz is not zero. Conversely, the setting of R3 is not influenced by the magnitude of R x A difference measurement, carried out by short-circuiting points 4 and 5 and by inserting
.

126

METHODS OF MEASURING FERROMAGNETIC PROPERTIES

[CH. VII
set-

between them the unknown self-inductance, shows that there are two tings of R3 from which Lx immediately follows.
(b)

Hartshorn bridge for frequencies from about 30 to 2000 c/s


principle of the bridge
is

The

that the voltages induced in the secondary

windings (see Fig. 28.5) by the mutual inductances


core)

MF (with ferromagnetic
(with air core) cancel

and

Mo

each other out. The mutual inductance

Mo is variable,

and

if its

magis

nitude in the compensated state

M,
ring
osc

the
is

permeability of the ferrite

given by:

\0.4

MD
108,

N1N2A

(28.12)

where

is

the average diameter of

the ring

A its cross-section, and and N% are the numbers of primNi ary and secondary turns around the
and
respectively.

ring

voltages in
entirely
Fig. 28.5. Principle

Mf

The and

secondary

can never

of Hartshorn bridge.

compensate each other, since magnetic losses in the ferrite core

cause a phase shift. In order to compensate the resultant voltage component, which is 90 out of phase

with the secondary voltage of Mo, another voltage is introduced into the secondary circuit which is proportional to the current / in the primary
circuit.

The

resistances

and

r2

and
1 ])

R in

Fig. 28.5

can be replaced by an

equivalent resistance r (see [Kl


r

according to:

nr2 /(ri

+ r + R).
2
,

By making
ondary
core
is

R large with respect to n and r 2

the value of r can be

made

small

quite simply; hence the voltage Ir, used as compensation voltage in the seccircuit,

can also be arbitrarily small. The

loss angle

of the

ferrite

then given by
tan 3

r/coM,
is

(28.13)

where

to is

the angular frequency at which the measurement

performed.

The advantage of this method is that the d.c. the ferrite core plays no part.

resistance of the winding

around

28]

METHODS OF MEASURING COMPLEX


f
2

INITIAL PERMEABILITY 127


0.16

Example:

= 100 c/s Ni = 13, N = 57, D = 2.4 cm and A M = 16.5 /xH and r = 0.000,9 ohm = 91 and tan 8 = 0.09.
/i'

cm 2

(c)

Maxwell Bridge for Frequencies up

to

about 100 kc/s and Modified Schering

Bridge up to about 60 Mcjs

The conditions of balance of the Maxwell bridge shown

in Fig. 28.6 are:

Lx = RiR 2 C

Rx =
Resistances

R1R2/R4.

(28.13)

Ri and R2 with very small time


3 ]. All the connections and

constants have been described by Kohler

and Koops [Ko


low
all

switches of the bridge should have a very


resistance

parts

and reactance. Moreover, must be well screened, A conswith Wagner earth


is

truction

repres-

ented in [Ko4]. Self-inductances of 200

pH

and a loss factor tan 8 of about 0.22 can be measured by this bridge with an accuracy of 0.1% in the range from 0.5 to
100 kc/s.

Fig.

28.6.

Principle

of

Maxwell

bridge with

Wagner

earth.

For higher frequencies a modified Schering bridge has been developed by Sinclair (Radio-Frequency Bridge Type

916-A, General Radio Company), by

means of which reactances can


[Si 1
].

be measured in the frequency range between 300 kc/s and 60 Mc/s,


28.3.

WAVE METHODS AT HIGHER FREQUENCIES


to

(a)

Coaxial Resonator from 10 Mc/s


the accurate

2000 Mc/s

At higher frequencies
ed impedances
is

measurement of the properties of lump-

almost impossible owing to the self-inductance and stray

capacitances of the leads.

One of
is

the

commonly used

devices for measure-

ments at these frequencies


loop to an
oscillator.

a quarter-wavelength resonator.

coaxial

line of a certain length / (see Fig. 28.7) is magnetically

coupled via a small

The voltage appearing at the top of the resonator is measured with a crystal detector D mounted near the top of the inner conductor. The couplings between the coaxial resonator and the oscillator and between the detector and the resonator must be so weak as to make the
amplitude and the frequency of the oscillator independent of the tuning

128

METHODS OF MEASURING FERROMAGNETIC PROPERTIES

[CH. VII

of the resonator and also to prevent the detector from influencing the resonator. The principle of the measuring method is that a ferrite ring F is
inserted in the coaxial line at

a position where the magnetic field strength has a maximum and where the
electric field strength is

approximat-

ely zero.

For small disturbances of


the

the

line

displacement of the
is

resonance frequency
to
[i!

proportional

of the

ferrite.

Also the
of the

width of the resonance


loaded cavity
is

fine

broadend due to

the losses in the ferrite. This line

broadening

is

proportional to

p" of
while

the ferrite. In practice the resonance

~
<Z-

frequency

is

kept constant,
is

)g
<F()

ji. the length of the line


Fig. 28.8). In principle
all

varied (see

we now have

the information which, together

with a knowledge of the dimensions of the ring and the


1

fine, is

required

0^>
Coaxial line
(/

for calculating the

complex permegreatly

Fig.

28.7.

A/4)

for

ability.

The equations are


is

measuring p' and /*"

at high frequencies.

oscillator,

simplified if the displacement of the

detector coupled to

the electric

field,
1]).

F ferrite

ring (accord-

resonance frequency

also determ-

ing to [Bu

ined for the case where a copper ring

of the same dimensions

[Li

1] is

Ah

Fig. 28.8.

The changes
coaxial

$lF

and
a

S/c in the length /o

of
in-

tuned

quarter-

1L
*k

wave
ring

line as a result

of

troducing a ferrite or copper


respectively.
is

The

fre-

quency

kept constant.

28]

METHODS OF MEASURING COMPLEX


The
field inside

INITIAL PERMEABILITY 129


is

inserted in the line.

the copper

zero, so that the ring

can

be described as having ju. of the


UfJIo
line
is

= 0, which can be used for calibration. If the quality


high enough
1,

with

ferrite ring is

(> 10) and if the relative detuning


write:

small with respect to


ix!
'

we may

and

/"

l^ 8lF /Slc ^ (AlF - Al )/28lc

(28.14)

For the definitions of the symbols see Fig. 28.8. The measurements can also be carried out by varying the frequency and keeping k constant. The line can be terminated by a variable capacitance, so that the frequency range is
extended to lower values; see [Bu
small part of the line
it is
1 ].

Since the ferrite ring

fills

only a very

possible to measure ferrites with large loss angles,

the quality factor of the line remaining higher than about 10.

To

avoid the

presence of an electric

field in the ring,

the axial dimension of the ring

At very high frequencies care must be taken that the radius conductor remains smaller than 1/3 of the wavelength, since of the outer otherwise a wave guide mode can appear in the coaxial line in addition to
must be
small.

the principal mode, which would give rise to radiation losses and

make

accurate measurement impossible.


(b) Standing

Wave Method

A method of simultaneously measuring the complex dielectric constant and


magnetic permeability at centimetric waves has been developed by Roberts

and Von Hippel [R.o 2]. A coaxial line is terminated, as in Fig. 28.9, by a ferrite ring. The ring must fit closely into the coaxial tube. The line is first short-circuited immediately behind the ferrite ring (situation I), and

Fig. 28.9. A coaxial line terminated at one end by a ferrite ring. The waveform of the voltage in the line is given for situation I, in which the line is short-circuited by a plunger immediately behind the ferrite ring, and for situation II, in which the plunger is at a distance of A/4 behind

the

ferrite.

130

METHODS OF MEASURING FERROMAGNETIC PROPERTIES

[CH. VII

afterwards at a quarter-wave distance from the specimen (situation II).


is

What

now measured
first

for situation I as well as for situation II

is

the distance
respectively, respectively.

from the
(That
the
is

voltage

minimum

to the ferrite ring, xi

together with the voltage standing-wave ratios, E\ and


to say the ratio between the voltage in the

and xi E%

minimum and that in maximum.) The impedances Z\ and Z% in both cases can be computed as:
Zj/Z,

= {Ej

tan 2wxj/X )/(1

iE, tan 2nxj/X


line,

),

1,2

where

is the characteristic

impedance of the
is

which depends on the


1 ].

ratio of the diameters

Dz/Di, and A

the wavelength; see [SI


e

From

the

complex impedances Zi we can calculate


tions:

and

p.

with the help of the rela-

tan (2^d/X )f jue


yii/6

= ]/Zi/Z = (i/oyz7z2,
2

(28.15)

where d represents the height of the ring. For height of the ring should fulfil the condition d
losses are small;

maximum

accuracy the

A/8]/efi,

provided the

where the losses are larger the ring must be thinner. Con-

siderable errors can be


line.

made

if

the ring does not

fit

tightly into the coaxial

(c)

Cavity Resonator

At wavelengths smaller than about 30 cm the permeability of a ferrite can be measured on small rods in a cavity resonator, as shown in Fig. 28.10. With this method, as with the quarter-wave resonator, the detuning and the change
in quality caused

by the

ferrite

sufficiently thin to ensure that the electric field in the

rod are measured. The specimen should be rod will be small.

The theory of electromagnetic waves in resonant cavities is given in [Ca 1 ]. The permeability of ferrite spheres can also be measured with resonant

Fig.

28.10.

The

TE

Oil

cavity

resonator for measuring the permeability of ferrite rods at centi-

metre waves. The ferrite rod is mounted axially. The electric (0, ) and magnetic (broken curves) lines
of force are indicated.

28]

METHODS OF MEASURING COMPLEX

INITIAL PERMEABILITY
is difficult

131

cavities,

although at large permeabilities this

owing to demagjAapp is related


/*a P

netization. In the case of

a sphere the apparent permeability

to the true permeability of the material according to (28.1) as


2(ju

p =
1

+ 2). However, with small spheres ferromagnetic resonance experiments can readily be carried out in a cavity in the presence of an
l)/0
external magnetic field (see [Be

Such experiments also provide information on line widths (hence on the damping in the ferrite) and on g factors, (see 20). At resonance the resonant cavity is detuned and, above all,
1 ]).

damped.

The
theory

properties of the material, provided the sphere

is

small enough, can

be derived from the complex detuning, which according to perturbation


is

given by:
3cu/o)

= (H M + E P)/4W

(28.16)

where Ho and Eo are the field strengths at the position of the sphere in and P the energy content of the empty cavity and the empty cavity, the magnetic and electric dipole moments respectively of the sphere. For and P, although the constant /* and e these are therefore proportional to be taken into account. For demagnetizing and depolarizing effects must

example, with a small sphere of radius R,

we may

write:

M = ~ RWo and P = * R E +2 +2
3
fi

(28. 17)

For the general


8a./

susceptibility tensor (28.16)

becomes

=
the

X m|A.I

X=cyh x *h y

X yxhyhx *

X yy\h y \*]/4W, (28.18)

where

is

of these formulas
as well as the

H H and E thereby generated.


is
it

volume of the specimen. The condition for the validity and E should be uniform over the sphere, is that
This
is

the case

if

the wave-

length employed inside the specimen


sions. It is precisely at
fied.

large with respect to the dimenis

resonance that this condition

not always
s

satis-

From

(23.9)

then follows th at

hence for

ferrites

with

"

is

of tne order of

M jAH,
wave

300 gauss,
e is

/*" is

of the order of 100 when


10, so that the

AH =

50 gauss. Furthermore,

of the order of

length in the material can be roughly 30 times smaller than in vacuo. For A 3 cm, then, the diameter of the sphere must not be much larger than a few tenths of a millimetre and even less for shorter wave lengths ([Be 2] and [Ya 2]). This requirement of smallness need not be satisfied if the
material has the form of a disc

and is fixed against a wall. In that case the requirement need only be fulfilled by the thickness of the plate, which can

132

METHODS OF MEASURING FERROMAGNETIC PROPERTIES


be made small by grinding.
it is

[CH. VII

easily

A further requirement is

that the sphere


effect.

should not be placed too close to the wall, in view of the image
the platelet in question

With

also necessary to take into account the fields

produced in the wall by the precessing magnetization. The magnetic fines of force of the high-frequency field must remain parallel to the conductive
wall. Polder [Po 2] has pointed out that this

can be taken into account by

including the mirror image of the ferrite platelet in the considerations.

The

demagnetizing coefficients in the resonance condition (18.12) are then slightly


altered.

The

static

demagnetizing

field in

the

direction does not change,

and

is

put equal to

NM. The

demagnetizing

increase the resonance frequency, are

Ny and NZ M, which now no longer determined by the small


fields

demagnetizing factor

of the round platelet, but by the demagnitizing


its

factor of the platelet plus


parallel

mirror image; for the alternating magnetizing

and perpendicular to the wall they are

2N and 4n

respectively.

When

the applied static field


is

lies in

the plane of the disc, the resonance

frequency

given by:
o> r

= yi [H + (4?7 - N)M] [H + NM].


to the Dimensions of the Specimen

(28.18)

29. Loss
29.1.

Phenomena Related

SKIN EFFECTS

AND DIMENSIONAL RESONANCES


field

The propagation of an alternating magnetic is governed by Maxwell's equations:


curl

in a conducting dielectric

H = OAttoE + to( - ie")E/300c


e'

curl

E = -/<.(/*' -

z>")H.10- 8

>

In the following

we

replace e"

I20wcar/o)

by

e",

and we obtain for the

wave equation:

c*AH =
where
|e|

-a>2\e\\iJ.\e-

i(Se+Sm>

H,

(29.2)

and

|/*|

are the absolute values of the total dielectric constant


is

the permeability, respectively. Further S e

the total electric loss angle

and and

3m the magnetic

loss angle.

When

a plane electromagnetic wave (propagatfield

ing in the positive

direction),

with magnetic

Hy

falls

normally upon

the plane surface of an isotropic medium,

we have
\

the solution:
(29.3)

Hy = Hy
giving for the skin depth d:
1

- x,d-xl

jd

(/cXIl Ml)* sin


I

K8.

8),

(29.4)

29]

LOSS

PHENOMENA RELATED TO THE DIMENSIONS

133

and for the wavelength A within the material:


2tt/A

= (o/cX||-M)icos i(Se +

S m).

(29.5)

The conditions
[e|

for magnetic metals with negligible magnetic losses are

120tic<t/(o; S e

it 12

and

Sm

= 0,
.

2tt/A

1/d

= (0.27TiJ.coa)i

so that 10- 4

(29.6)

Brockman

et al.

[Br 1] discovered that under certain conditions the


ferrites

apparent permeability and dielectric constant of

can be strongly

frequency-dependent. In these cases the wavelength of the electromagnetic

waves inside the material, see

(29.5), is

about twice the minimum dimension

of the core in which wave propagation takes place, so that these dimensional
resonances are already found at relatively low frequencies in ferrites showing
at the

same time a high value of e and of /*.

Fig. 29. 1 represents relative values

of the real part of and p as measured by Brockman et al for samples of manganese zinc ferrites with different dimensions. The dispersions found
for e

and

p'

absent for the very thin specimen.


in a laminated core
is

depend on the dimensions of the specimen, and are completely The frequency-dependence of p' found
caused by the ferromagnetic resonance phenomenon

to be discussed in 50.1.

static

magnetic

field shifts

the dimensional re-

P'*r/ni

'eff/e;

5
f (Mc/s)

10

Fig. 29.1.

Dependence of the

real part of the effective material constants

upon the dimen-

sions of the specimen (experimental). Specimen cross-sections

drawn

to scale for each

curve. Data given as the ratio of the effective constant to the real part of the corresponding constant at 1000 cycles. (A) Permeabilities. (B) Dielectric constant (according to [Br 2]).

134

METHODS OF MEASURING FERROMAGNETIC PROPERTIES


[Mo
1
]

[CH. VII

sonance phenomena to higher frequencies

as a consequence of the

resulting decrease in permeability. This provides a

means of measuring
a high
initial

at high frequencies the dielectric constant of ferrites having

permeability, without
29.2.

any interference from dimensional

effects.

EDDY-CURRENT LOSSES
the skin depth

Where

d is

very large compared with the thickness of the

sample, the influence of eddy currents


negligible,

on

the magnetic field

is

entirely
easily.

and the

losses

due to eddy currents can be calculated

The amplitude of
axis of

the electric field strength

Ex
is

at a distance

x from

the

a cylinder (see Fig. 29.2) in which a magnetic induction varies

sinusoidally in time with an amplitude

Bmax
"

given by:
(29.7)

Ex =

tt/x

BmStX

10 -8 VOlt/cm.

Fig.

29.2.

Rectangular
cylinder
in the

cross-section

through

with

radius

R.

Eddy current Ix
1

hollow cylinder

with radius x, thickness dx and length

cm.

When

the magnetic material has a resistivity

/>,

the energy dissipation in a

cylinder with radius

is:

W=

(7T2/2B2 ffiaxij2/ 4/?)


:

10-i6 watt/cm",

corresponding to a loss factor tan S e


tan S e

(jt^R 2 Ip)

10- 9

To

Analogous expressions for plates and spheres are given in Table give some idea of the order of magnitude of the eddy-current factor, a survey for some materials is given in Table 29.11.

29.1.

loss

It appears of that the amount of eddy-current losses derived from loss measurements of ferromagnetic materials is always larger than is calculated from the resistivity. This discrepancy (eddy-current anomaly) can

be ascribed to the inhomogeneity of the flux changes, due to Weiss-domain

29]

LOSS

PHENOMENA RELATED TO THE DIMENSIONS


TABLE
29.1
e

135

EDDY-CURRENT LOSS FACTOR TAN BODIES CBmax EXPRESSED IN GAUSS, R IN CM, AND q IN OHM CM)
EDDY-CURRENT LOSSES
Body
plate

W AND

FOR SOME SIMPLE

W
10-! watt/cm 3

tan & e

R
10-9
thickness

Q*mf*B*

m RVp
K 2 /P

(S^/3)(fR M V P)

2R

cylinder

nHfuK^lp)
(7r2/5)/2B2 m x

10-9
10-9

radius

sphere

(4^/5) (ffiRVp)

radius

TABLE

29.11

EDDY-CURRENT LOSS FACTORS FOR SOME MAGNETIC CORES IN THE SHAPE OF PLATES AT A FREQUENCY/.
P

Material

/
kc/s
5

/i0

ohm cm
2-10-5

Thickness

tan S e

Permalloy
Mno.4gZno.48Fe2.04O4

7000
1000
10

10 micron

10- 2
10-2 10-5

10 2
10

100
100,000

NiFe 2

cm 2 cm

by wall displacements) and the polycrystalline Wi 2]. Suppose that in the cylindrical rod the Weiss domains or grains are very small as compared with the outer dimensions of the sample. For the magnetically homogeneous material a varying axial
structure (magnetization
state of the

sample

[St 1,

magnetic

field will

produce the tangential

electric

field

according to

(29.7), which has at any instant of time a constant magnitude along a concentric circle perpendicular to the axis of the rod. In the real material the

contour integral
material, but
ly the

JTsjd/

along

this circle is the

same

as in the

homogeneous

E fluctuates both in magnitude and in orientation. Consequent-

energy dissipation W, obeying

W=
is

(l/p)

f2 dF=

(lip)

JdS /tfW,
Here AS
is
it.

greater than in the

homogeneous

case.

a surface element

perpendicular to the concentric circle going through


figuration this

For a
al.

special con-

anomaly was calculated by Williams


factor of about 3.

et

[Wi

2],

and

amounted to a

CHAPTER

VIII

INTRINSIC PROPERTIES OF FERRITES WITH SPINEL STRUCTURE

30 Chemical Composition

The general chemical formula of ferrites possessing the structure of the mineral spinel, MgAl204, is MeFe2<I>4, where Me represents a divalent metal ion with an ionic radius approximately between 0.6 and lA. In the case of simple ferrites. Me is one of the divalent ions of the transition elements Mn, Fe, Co, Ni, Cu and Zn, or Mg and Cd. A combination of these ions is also possible; we then speak of a solid solution of two ferrites, of mixed crystals or, in general terms, of a mixed ferrite. Furthermore, the symbol Me can represent a combination of ions which have an average valency of two; for example Li1 and Fe 111 in lithium ferrite, Lio.5Fe2.5O4.

particular case is the ferrimagnetic yFe2C>3, which has the spinel structure and whose chemical formula can be written formally as l/sFes/sQi, the symbol representing a vacant lattice site ([Ve 1], [Ha 1]). In
this case

Me

represents the combination of vacancies


1
:

and

trivalent iron

ions in the ratio

2.

The
mixed

trivalent iron ions (ferric ions) in

be replaced by another trivalent ion such as Al


crystals with aluminates

MeFe2C>4 can completely or partly or Cr In giving rise to

and chromites. These compounds are


if

also

ferrimagnetic at

room temperature

the non-magnetic ions are present in

not too large concentrations. If the ferric ions are partly replaced by one of the tetravalent ions Ti IV or Ge IV , the valency of an equal part of the ferric
ions
is

lowered by one.

great variety in the chemical composition of


is

ferirmagnetic oxides with spinel structure

possible

[Go

3 ].

Gorter [Go 4] has pointed out that solid solutions of spinels can occur with compounds which either do not exist themselves or possess a different
crystal structure: for

example (Nao.5Fe2.5O4) does not

exist,

but can give

a solid solution with Lio.5Fe2.5O4; up to 40

% of the lithium ions in the latter

compound can be
to 35

replaced by sodium ions.


1 ],

orthorhombic structure [De

The ferrite CaFe204 has an but in ZnFe20 4 at high temperatures up

of the zinc ions can be replaced by calcium ions without altering

the structure.

Certain ferrimagnetic spinels are known, where the oxygen

is

replaced
shall

by sulphur [Lo

1 ].

The Curie temperatures

are usually low

and we

not discuss these substances further.

31]

CRYSTAL STRUCTURE
in ferrites can be determined
difficulty is that

137

The valency of the metal ions


of the oxygen concentration.
different ions will

by an analysis

one

is

never certain that

not occur in more than one valency state. In the case of MnFea04, for example, an oxygen analysis does not reveal whether the formula is MnnFe 2 04 or Mn FenFe 04. The ferrite Cuo.5Fe2.5O4 constitutes an unsolved problem, since it is not known with certainty whether in this substance all iron ions are trivalent and the copper ion monovalent, or whether it is a mixed crystal of Cun Fe2C>4 and Fe n Fe2C>4 ( [Ko 5 ] and [Be 3 ]). For a discussion of this substance see [Go 5 ]. In many cases a

magnetic property, in this case the saturation magnetization


decide between the possible chemical formulas. If
analysis that the
it

( 33),

can

appears from oxygen


is

sum of the
a mixed

valencies of the metal ions per formula unit


sites,

greater than eight, this points to unoccupied metal ion

which means

that the ferrite

is

crystal with

yFe203.

31. Crystal Structure


31.1.

ELEMENTARY CELL OF THE SPINEL LATTICE


name from
the mineral MgAl2C>4, which crysthe cubic system. This crystal structure was

The

spinel structure takes its

first determined by Bragg [Br 3 ] and by Nishikawa [Ni 1 ]. The smallest cell of the spinel lattice that has cubic symmetry contains eight "molecules" of MeFe204. The relatively large oxygen ions form an f.c.c. lattice. In this cubic close-

tallizes in

packed structure two kinds of interstitial


In the above-mentioned cubic unit
sites
cell,

sites occur,

the tetrahedral

and the

octahedral sites which are surrounded by 4 and 6 oxygen ions respectively.

64 tetrahedral

sites

and 32 octahedral

are present, of which only 8 and 16 respectively are occupied by metal

ions (called

A and B

sites respectively).

To

describe the structure one

can best subdivide this elementary cube with edge a into eight octants with
edge \a, as shown in Fig. 31.1. The anions (oxygen ions) are positioned in

Fig. 3 1 . 1
cell

of the spinel

The cube represents symbolically the elementary lattice. The four shaded and the four

non-shaded octants are occupied by the metal ions in


the same

way

as indicated in Fig. 31.2.

138
the

INTRINSIC PROPERTIES OF SPINELS

[CH. VIII

same way in
is

all octants.

the corners of a tetrahedron as

Each octant contains four anions, which form shown in Fig. 31.2. The edge of the f.c.c.

oxygen lattice

\a.

As

regards the positions of the cations, the octants in

the elementary cube that have only one edge in

common

are identical

(see Fig. 31.1). In Fig. 31.2 the positions of the ions are indicated in

two

Fig.

31.2.

Two

octants of the spinel structure.

spheres represent the oxygen ions. spheres represent the metal ions

The large The small black and white on tetrahedral and octa-

hedral

sites, respectively.

adjacent octants.

thus in the centre and

The occupied tetrahedral sites of one of the octants are on four of the eight corners of the octant. In the adsite is

jacent octant the central

not occupied by a metal ion but, owing to

translation symmetry, half of the corner sites are again occupied. It can be

seen that the occupied tetrahedral


f.c.c.

sites

{A

sites)

form two interpenetrating

lattices

having an edge

a,

which are displaced with respect to each

other over a distance \a ]/3 in the direction of the body diagonal of a cube. The occupied octahedral sites (B sites) are found only in the other type of octant. The four metal ions are situated at sites analogous to those of the oxygen ions, i.e. on one quarter length of the diagonal from the other ends of the four body diagonals of the octant. Consequently the oxygen and
(octahedral) metal ions in this octant together span a cube with edge $a.

All octahedral ions together

lie

on four

interpenetrating

f.c.c. lattices

with

edge

a,

which are displaced with respect to each other over a distance

ia^2 in the directions of the face diagonals of the cube. The surrounding of a tetrahedral ion by the other ions has strictly cubic symmetry. This is not the case for an individual octahedral ion. The octahedral ions, of course, are cubically surrounded as far as concerns the oxygen
ions in the ideal lattice, but not as regards their environment by the neigh-

bouring metal ions. Fig. 31.3 shows the environment of

ions by other

31]

CRYSTAL STRUCTURE
The two cubes shown do not
in
lie

139

ions.

each

in one octant of Figs. 31.1 or 31.2: four

c?4=^?

one particular octant, the three other B ions belong to three different octants. It can be seen from this that the symmetry of the
ions
lie

environment of an octahedral
metal neighbours
is

site

by nearest
is

^=^T
i

lower than cubic, and that


(Jr
Fig.
31.3.

,*.

an axis only one of symmetry. However, in the whole lattice cell all [111] directions occur equally as symmetry axis, so that the overall symmetry
of the [111] directions
nevertheless remains cubic.

&^^
The
nearest neigh-

bours of a cation on an octahedral (S) site in the spinel structure.

Large spheres are oxygen


small spheres are metal

While Fig. 31.3 indicates the surrounding


of an octahedral ion, Fig. 31.4 gives the en-

ions,

ions

on octahedral (B)

sites.

vironment of an oxygen ion by


(metal) neighbours. These are one

its

nearest

A ion and three B ions.


lattice.
six.

This unit can be

regarded as the basic component of the spinel


to four of such units

Each

A ion belongs
is

and each

B ion to

The

direction

O A

one of

the

body diagonals of the cube, and the

directions

O B

are along the

cube edges.
31.2.

THE OXYGEN PARAMETER U


in 31.1 that the oxygen ions

The statement
only in
first

form an

f.c.c.

structure is true

approximation. In reality slight deviations are found owing to


sites, which are and many other oxidic

a deformation caused by the metal ions. The tetrahedral


smaller than the octahedral ones, are in ferrites
spinels too small to contain

a metal

ion, if

we regard

the metal ions as well


is

as the oxygen ions as solid spheres.


sites

consequence

that all tetrahedral

are expanded by an equal displacement of the four oxygen ions outwards

Fig.

31.4.

The

nearest

neigh-

bours of an oxygen ion in the


spinel
structure.

Small

open

spheres denote metal ions on

octahedral (B)

sites.

sphere denotes a metal ion


tetrahedral (A)
site.

The black on a The arrow


which
in the

indicates the direction in

the oxygen ion


case where

is

moved

>

3/8.

140

INTRINSIC PROPERTIES OF SPINELS

[CH. VIII

31.2). These four oxygen occupy the corners of an enlarged tetrahedron, so that the surrounding of each A ion retains cubic symmetry. However, the four oxygen ions of the "octahedral octants" in Fig. 31.2 are shifted in such a way that

along the body diagonals of the cube (see Fig.


still

ions thus

oxygen tetrahedron shrinks by the same amount as the first expands. is also the case as regards the oxygen ions indicated in Fig. 31.3. It can be seen that, as a result, the oxygen surrounding of each B ion no longer
this

This

has cubic symmetry, but a symmetry similar to that of the neighbouring

B ions.
tance

In Fig. 31.4 the oxygen ions move along the arrow. A quantitative measure of the displacement is the oxygen parameter u, given by the dis-

shown
is

in Fig. 31.2 between

an oxygen ion and a face of the cube,


f.c.c.

which

put equal to au. The ideal

parameters correspond to:

"id

|.

In the above-mentioned case therefore w

> wid. Table 31. Ill gives some values


make the tetrahedral
two
sites

of the parameter u found with the aid of X-ray or neutron diffraction. Whereas the displacements of the oxygen ions discussed above
sites larger,

the octahedral sites are reduced in size so that the sizes of the

interstitial sites

become more

equal.

simple calculation shows that for

small displacements the radii of the spheres in both types of interstitial


are given by:

tb

=(| u)a R

v
,

'

where Ro
31.3.

is

the radius of the oxygen ion.

DISTRIBUTION OF THE METAL IONS OVER OCTAHEDRAL

AND

TETRAHEDRAL

SITES
cell

We have
question

seen that in the elementary

of the spinel structure eight tetra-

hedral and sixteen octahedral sites are occupied by metal ions.

Now

the

may
It

be asked,

how

are the divalent

and

trivalent metal ions dis-

was thought to be no was believed that the eight divalent ions were in the eight available tetrahedral sites and the sixteen trivalent ions in the sixteen octahedral
problem.
In
sites.

tributed over the interstitial sites present? Initially this

many

cases this
is

is

in fact so, as for example in the mineral spinel,

MgAl2<I)4, which

therefore

known

as a normal spinel. Barth

[Ba

1 ]

have shown, however, that

this

simple assumption

is

and Posnjak by no means

correct in

all cases. By X-ray diffraction studies of a number of spinels in which the two kinds of metal ions show a sufficiently large difference in scattering power, they were able to demonstrate that spinels also occur with

31]

CRYSTAL STRUCTURE
sites,

141

the eight divalent ions in eight of the sixteen available octahedral

and

with the sixteen trivalent ions uniformly distributed over the remaining

sites.

The eight divalent and the eight trivalent ions are in this case distributed at random over the sixteen octahedral sites (for exceptions see 31.4). Spinels
having an ionic distribution of
this

nature are called inverse spinels.

Experimentally there are three different ways of acquiring information

on the distribution of the ions over the available sites in magnetic compounds, namely, with the aid of X-ray diffraction, neutron diffraction and from the
magnitude of the saturation magnetization at the absolute zero of temperature. The scattering cross-section of atoms for X-rays is determined by the

number of electrons

in the atom.

For

this

reason there

is

only a slight

diffe-

rence in the scattering power of the atoms of transition elements, and therefore the distribution of these ions

amongst the

spinel lattice cannot usually

be ascertained in this way. The scattering power for thermal neutrons is partly determined by the magnetic moment of the nucleus of the atom, due to interaction with the neutron spin. This often varies considerably for atoms
having roughly the same number of electrons, so that neutron diffraction is able to provide information on the occupation of the two spinel sites by
ions of the transition elements. It can also provide information

on

the value

of the oxygen parameter and on the magnitude and orientation of the magnetic

moments of
1 ]

the ions.

From X-ray

examinations

it

has been found

[Ba

that aluminates

and

chromites with spinel structure are normal. In

the case of ferrites the X-ray scattering


different for the various ions
distribution. Indirect derivations

power

is

often not sufficiently

to

provide any information on the ion

from lattice constants led to the conclusion normal and the other ferrites inverse. Neutron diffraction experiments have largely confirmed this conclusion. Shull et al. [Sh 1 ] found that Fe 3 4 is an inverse spinel. Hastings and Corliss [Ha 2 ] found that NiFe 2 C>4 is certainly inverse and ZnFe 2 4 normal.
[Ve 2] that zinc and

cadmium

ferrite are

It is interesting that
,

since Nin Fem and Zn11 have practically the same X-ray scattering propern is quite different from that ties. The scattering of neutrons on magnetic Ni

the X-ray diagrams of both these substances are identical,

on non-magnetic Zn11 Copper


.

ferrite is

completely inverse [Pr

1 ].

For a

treatment of the theory of neutron scattering by ferromagnetic media the


reader
is

referred to

Bacon [Ba

2].

The

relation between cation distribution

and

saturation magnetization

is

dealt with in 32.1.

A completely normal or completely inverse spinel represent extreme cases.


The
general cation distribution can be indicated as

MejFe^JMe^FeSalC^,

142

INTRINSIC PROPERTIES OF SPINELS


sites

[CH. VIII

where the ions on tetrahedral

are given in front of the square brackets

and the octahedral ions between the brackets. For a completely random distribution, 8 = ife, for a normal spinel 8 = 1 and for an inverse spinel 8 = 0. The quantity 8 is a measure of the inversion. In the case of some ferrites 8 depends upon the method of preparation. If these ferrites are quenched from a high temperature 8 has a value of about one third. A diffusion mechanism an energetically more favourable state causes to occur at lower temperatures. Depending on whether the diffusion rate is great enough compared to the cooling rate, an ion distribution will be retained at room temperature which is the equilibrium distribution at a temperature that varies from about 150 C to a much higher temperature. For samples of MgFe 2 04 and CuFe2C>4 quenched from various temperatures, the inversion has been determined by X-ray diffraction [Be 4] and by magnetic measurements, [Ne 6] and [Pa 1]. It was found that the results satisfy the Boltzmann distribution law:
8 (1

3)

(1-8)2
where the value of

'

1 -*)

is

approximately equal to 0.14 eV. Neutron diffrac-

tion examinations of MgFe2<I>4 have yielded a value of 8 approximately

[Co 1]). For MnFe 2 4 an ion distribution has been found [Ha 3 ] corresponding to the formula Mno.8Fe<j.2 [Mno.2Fei.8 ]04.
equal to 0.1 ([Ba 3] and

The following are some of the factors which can influence of the metal ions over the A and B sites:
(a)

the distribution

The Ionic Radius


is

Since the tetrahedral site

the smaller, one might expect that the smaller


sites.

ions will prefer to occupy the tetrahedral smaller than divalent ions (see Table 31.1)
structure.
(b)

Trivalent ions are usually


to favour the inverse

and this tends

The Electronic Configuration

Certain ions have a special preference for a certain environment. For example,
sites where form a covalent bond with the six 2/7 electrons of the oxygen ion. This produces four bonds oriented towards the corners of a tetrahedron. The marked preference of the ions Ni 11 and Cr for an octahedral environment can be explained as being due

Zn11 and Cd11 show

a marked preference for tetrahedral

their

4s,p or 5s,p electrons respectively can

to the favourable
field at

fit

of the charge distribution of these ions in the crystal


site

an octahedral

([Sa

1 ],

[Ro

2],

[Du

2,3]).

31]

CRYSTAL STRUCTURE
TABLE
31.1

143

SOME OF THE METAL IONS OCCURRING IN FERROMAGNETIC SCHMIDT RADIUS r IN A UNITS


Ion valency
I

SPINELS,

WITH THEIR GOLD-

II

III

IV
r

Ion
Li

Ion

Ion

Ion
Ti

0.78
0.98
1.13

Mg

0.78

Al
Sc

0.57
0.83

0.69

Na Ag

Cr

0.64 0.70

Mn
Fe

0.91

Mn
Fe

Mn
Ge

0.52 0.44

0.83

0.67

Co
Ni

0.82
0.78

Cu Zn Cd

0.70 0.82
1.03

(c)

The Electrostatic Energy

Another factor that can determine the distribution of the metal ions over the
available interstitial sites
is

the electrostatic energy of the spinel lattice


is

(denoted as "Madelung energy"). This


the ions, at
first

the electrostatic energy gained when

thought to be

infinitely far apart, are

brought together to

normal arrangement the metal ions with the are surrounded by 4 oxygen ions, and the metal ions smallest positive charge with higher positive charge by 6 oxygen ions, which is electrostatically most

form the

spinel lattice. In the

favourable.
will

With an oxygen parameter

larger than the ideal value, this state

be energetically even more favourable.

From

calculations for the


1 ], it

com-

plete lattice

made by Verwey
lattice

et al.

[Ve 2] and [Bo

follows that for the

spinels consisting of divalent

and

trivalent metal ions the inverse structure

has the lowest

energy in the case that u


lattice

structure has the lowest

energy

when u
31.11

< 0.379, whereas the normal > 0.379.

TABLE

CALCULATED RADII OF THE TETRAHEDRAL AND OCTAHEDRAL SITES, rtetr AND root RESPECTIVELY, FOR SOME FERRITES WITH SPINEL STRUCTURE, THE RADIUS OF THE OXYGEN IONS BEING ASSUMED TO BE 1.32 A. THE GOLDSCHMIDT RADII rMe OF THE DIVALENT METAL IONS HAVE BEEN ADDED FOR COMPARISON.
Tetrahedral
'tetr

site

Octahedral
roct

site

r Me

rMe 0.67;

MnFe204 ZnFe 2 04
FeFe204

0.67
0.65
0.55 0.58

0.91;

0.67

0.72 0.70
0.75

0.91

0.82 0.67
0.67;

0.67
0.83;

0.67
0.67

MgFe204

0.78

0.72

0.78;

144

INTRINSIC PROPERTIES OF SPINELS

[CH.

VIII

Table 31.11 gives the radii of the tetrahedral and octahedral sites (calculated with the aid of (31.1)) for those ferrites in Table 31. Ill whose u parameter
is fairly

accurately known. These are the normal ferrites MnFezQi and ZnFe204, and those with inverse structure FesOj and MgFe204. Apart from a large u parameter (0.385) the first two have a large lattice constant a.
It

can be seen from Table

31.11 that this large value of

is

practically only

used for the purpose of increasing of MnFe204, owing to the large

ne tr.

This appears most clearly in the case ion which


still

Mn11

partly occupies the

B sites. The radius of the octahedral site is larger when it is occupied by the large Fe n ion than by the Mgn ion. The tetrahedral sites are small in this
case, although for

MgFe2C>4 they are somewhat larger than for Fe3C>4,

possibly because of the partly normal structure of the former.

Table 31. Ill gives a summary of the metal ion distribution in a number of
ferromagnetic spinels as determined mainly by neutron diffraction.
table also gives the cell edges a, the u parameters, molecular weights
.

The and

X-ray densities dx For the molecular weight the formula MeFe204 is taken as
the molecular unit. Since an elementary cell contains eight of these molecules, the relation between the quantities in Table 31. Ill
is

given by the formula:


(31.3)

dx
where

8M
Na3

g/cm3

N = 6.02

10 23

mol-1

represents Avogadro's number.

TABLE
<*

31. Ill

METAL ION DISTRIBUTION, LATTICE CONSTANT a. u PARAMETER, MOLECULAR WEIGHT Af AND X-RAY DENSITY x FOR SIMPLE FERRITES WITH SPINEL STRUCTURE.
Metal ion
Ferrite

Reference
[
1

distribution

A
8.50
8.39

M
230.6 231.6 234.6 234.4 239.2
241.1

g/cm 3

MnFe2
Fe 3
4

Mno.sFeo.a

[Mno. 2 Fei. 8 ]

Ha

0.3846 0.0003
0.379 0.001

5.00 5.24
5.29
5.38 5.35 5.33

CoFe2
NiFe 2

4 4
4

Fe [Fe n Fe] Fe [CoFe] Fe [NiFe]


*

Shi, CI 2

Pr2

8.38 8.34

Ha 2
Prl,Ve2
<c

CuFe2
ZnFe 2

Fe [CuFe]

(a
4 4

= =

8.70 8.22

0.380 0.005
0.385

Zn

[Fe 2 ]
[Mgo.oFei.i]

Ha

8.44

0.002
0.001

MgFe2

Mgo.iFeo.o

Ba3,Col
Br 4

8.36
8.33

0.381

200.0
207.1

4.52
4.75
to

Lio.5Fe 2 .50 4

Fe

[Lio.5Fe1.5l

0.382

0.005
1].

Copper

ferrite

shows a tetragonal deformation below 760 C [Pr

By quenching

room
tes,

temperature, however, the cubic structure can be maintained. Mixed copper ferrifor example copper-zinc ferrites with not too high copper concentrations, retain

their cubic structure

even during slow cooling.

31]

CRYSTAL STRUCTURE

145

The lattice constants of mixed ferrites can mostly be found in good approximation by a linear interpolation of the lattice constants of the constituent
simple
ferrites,

as for instance

is

shown for

nickel-zinc ferrites in Fig. 31.5.

9.45

<(X)

NifZn 1 -. i Fe2 04.

8.40

8.35

8.30,

0.2

0.4

0.6

0.8

1.0

(T
Fig. 31.5. Cell edges

a in

for

mixed nickel-zinc

ferrites after

[Gu

4]

31.4.

ORDERING PHENOMENA

In the ferrites with inverse spinel arrangement, ions having different valencies occupy octahedral sites. Ordering of these ions gives rise to a gain in electrostatic energy.

Up

to now, ordering

in the case of two ferrites,


at tetrahedral sites if

on octahedral sites has been found and Lio.5Fe2.5O4. Ordering can also occur 4 these are occupied by ions of differing valencies. This
Fe3

has been found [Go 3] for the substance Feo.sLio.5[Cr2]04. Magnetite

Various experimental indications exist that Fe304 has a crystallographic transition point at 1 19 K, which can be related to an ordering phenomenon.

The

first

indication of a deviation

from cubic symmetry was found by Li

at

119 K, [Li 2]. Millar [Mi 1] and Ellefson and Taylor [El 1] discovered an anomaly in the specific heat of this substance at approximately the same

Verwey and Haaijman [Ve 4] studied the conductivity (see 45) and found that this dropped suddenly upon cooling below 119 K by a factor of about one hundred. This was ascribed to an electron ordering on the octahedral sites. They predicted an ordering such that successive n and Fe (001) layers of octahedral sites are occupied alternately by Fe
temperature.
ions, thus giving rise to
this order the

a crystal with uniaxial symmetry. According to 11 upper two octahedral ions in Fig. 31.2 are, for example, Fe

146

INTRINSIC PROPERTIES OF SPINELS


ions,
ions.

[CH. VIII

and the two lower ones Fein The drop in the conductivity on the octahedral sites from unity. The ordering
to

gradually vanishes as the ferrousferric ratio

deviates
gives

rise

crystallographic

structure with orthorhombic

metry,

as

was

symdemonstrated by

Bickford [Bi 2] with strain-gauge

measurements and by Abrahams and

Calhoun [Ab
ture of
point.

1 ]

by X-ray

analysis.

Fig. 31.6 gives a picture of the struc-

The

Fes04 below the transition transition from the cubic


is

to the orthorhombic structure

in-

Orthorhombic deformation of the cubic spinel structure of Fe304 below 119 K. The spontaneous magFig.
31.6.

dicated in this figure. According to

Bickford the changes during the transition are

netization

is

in

the

[001]

direction.

such that the c axis of


is

After [Bi

2].

the orthorhombic phase


to a cube edge,

parallel

smaller than the cube edge.

The

face diagonal

BD

and it is 0.03% becomes 0.07 % smaller

and the face diagonal AC becomes 0.06% longer. It appears that the edge of the cube along which the crystal is magnetized becomes the new c axis of the crystal below the transition point (see 34). According to De Boer et ah [Bo 1 ] the gain in electrostatic energy as a result of the ordering of divalent and trivalent ions at octahedral sites is approximately 1.7 eV, which is much higher than corresponds to the low transition temperature.

of the long range

Van Santen [Sa 2] supposes that this is the consequence of the Coulomb forces, unlike that of the exchange forces.
ordering (cluster formation) takes place also

As a

result, strong short-range

above the transition point. The difference in energy between the "ordered" and "disordered" state is then quite small, which could be the cause of the

low

transition temperature.

order, unlike
large

The transition apparently is one of the first what one would expect for an AB type of ordering. The

drop in conductivity indicates that the ordering is nearly perfect immediately below the transition point, showing that the ordering forces are much stronger than one would expect from this low transition temperature.

Romeyn [Ro 2] assumes


in
all ferrites

that a certain short-range order

is

always present

with spinel structure. In consequence of the low mobility of

the ions this transition

from short-range

to long-range order will not gene-

32]

SATURATION MAGNETIZATION
low temperatures
at

147

rally be able to take place at the

which

this occurs in

Fe3C>4

by electron

diffusion.
ferrite

Guillaud and Creveaux [Gu 3 ] observed in the case of cobalt


discontinuity in the conductivity between 85

and 90 K. At this temperature a fairly abrupt change in the magnetic anisotropy was also found, which could be derived from curves showing the magnetization of cobalt ferrite at various field strengths as a function of temperature. Measurements of crystal structure below this temperature have not been reported.
Lithium Ferrite

Braun[Br4]has shown thatUthiumferrite is aninverse spinel, Fe[Lio.5Fe2.5]04.

He found

that

an ordering of octahedral ions takes place below a tempe-

rature lying in the interval of 734 between 755C.

The ordering
is

is

such that
alternate
struc-

in rows of octahedral ions with the direction [110] there

an

arrangement of successively three


ture remains cubic.

ferric

ions and one lithium ion. The

As in Fe304 the ordering gradually vanishes for deviating


sites differs

compositions according as the ratio Li/Fe on the octahedral

from

a similar ordering in yFe20a are also found by Braun [Br 4]. A complete analysis of the structure of yFe20s is given by Van Oosterhout and Rooymans [Oo 2].
1/3. Superstructure lines indicating

32. Saturation Magnetization


32.1.

MAGNETIC ORDERING AND SATURATION MAGNETIZATION AT 0K


in ferrites
is

The exchange energy


described in 8.1.
It

of the indirect (superexchange) type,

has been established experimentally that the predomior more than half-

nating exchange energies between the magnetic ions in the ferrites are negative, as
filled

would follow from the theory for

half-filled

3d shells/These ions include the ferric ions, as well as the divalent metal ions of the first transition series which can be substituted in ferrites with
spinel structure (see Table 32.1, p. 157).

The magnitude of the negative exchange energies between two magnetic Me and Me' depends upon the distances from these ions to the oxygen ion O, via which the superexchange takes place, and on the angle Me-O-Me'; No quantitative relationship is we shall call these respectively /, /' and known between the exchange interactions and these quantities. In 8.1 it was shown that an angle of 180 will give rise to the greatest exchange energy, and that the exchange energy in general decreases very rapidly with for different configurations of increasing distance. The quantities /, /' and ion pairs in the spinel structure have been given by Gorter [Go 3]. Fig.
ions
<f>.
<j>

148

INTRINSIC PROPERTIES OF SPINELS

[CH. VIII

TABLE
NUMBER OF
3d

32.1

ELECTRONS AND RESULTING SPIN MOMENT OF IONS OF THE FIRST TRANSITION SERIES. THE CURIE CONSTANT Cs PER GRAM-ION ACCORDING TO (6.9) IS GIVEN IN THE LAST COLUMN.
mo-

/xjj

Ions

in
Spin-only

I"
*3!

magnetic

cs

ment

Sc" 1

Ti iv Ti in
Ti n Vii Cri v
1 1

0.37
1.00 1.87

2
3

2
3

Cr1 " Mniv

Cr"

Mn " Mn
1

Fe IV Fe Co IV

4
5

4
5

3.00
4.38

Fe" Co 111 Ni'v

6 7
8

4
3

3.00
1.87

Co"

Nii

Ni"

2
1

1.00

Cu" Cu1 Zn"

0.37

10

32.1

shows the configurations of ion pairs occurring in the spinel

lattice

which the distances and angles are most favourable for high exchange energy. The A and B ions shown in the figure refer to ions occupying tetrafor

hedral

and octahedral
first

sites respectively.
it

From

a comparison of the different

exchange interactions

follows that the

AB interaction is by far the greatest.


/

For the

of the two

AB

configurations drawn, the distances


<f>

and

/'

by p and q in the figure) are small and the angle is fairly large (^^125). The maximum BB exchange interaction corresponds to the first BB configuration drawn in Fig. 32.1 the angle however, is only 90. The weakest will be the AA exchange interaction for which the distance r 80). The is relatively large (^ 3.5 A) and the angle unfavourable (<f> magnitude of the exchange energies is affected by deviations in the oxygen parameter u from the value 3/8. If u> 3/8, which for most ferrites is the case (see Table 31. Ill), the oxygen ions are displaced in such a way that in the AB interaction the distance between the A and O ion is increased and that between the B ion and the O ion is decreased. Also the angle is decreased. The resultant influence upon the interaction is not known. The AA interaction is reduced, while the BB interaction increases owing to the reduc(indicated
; <f>,
</>

<f>

tion of the distance in p. Because of the relative magnitudes of the exchange


interactions

one

may

expect the spins of the

spinel structure to

be oppositely oriented, so that when


is

A and B ions in ferrites with T = there will

be two saturated and oppositely magnetized sublattices present. The resultant magnetization

thus the difference between the magnetization of the

32]

SATURATION MAGNETIZATION

149

BB

AA

T<=

125 9
Distances

125 2'

7938'

Me-O

Distances

Me-Me

r s

=a(l

a(iu

+ u)]/n + itfT
|

= (a/4)j/2 = (a/8)fll d = (a/4)p e = (3a/8)J/T / = (,a/4)Y6


b
c

Fig. 32.1.

Some of the

configurations of ion pairs which probably

make

the greatest con-

tributions to the exchange energy in the spinel lattice. Ions

and

are metal ions

tetrahedral
ion.

and octahedral

sites respectively.

The

large

open

circle represents

on an oxygen

The

distances between the ions are given in the Table below.

the ideal parameter u

3/8.

The

figure

is

drawn

for u

>

3/8.

The angles apply to The centre-to-centre dis<f>

tances of the ions, expressed in the lattice constant a and the oxygen parameter are given

below.

octahedral lattice (B) and that of the total tetrahedral lattice (A), whereby
the
first will

Neel [Ne
32.11

was first postulated by and is experimentally well confirmed, as appears from Table for a number of simple ferrites. In the last column of this table the
generally have the largest value. This
1 ],

TABLE

32.11

EXPERIMENTAL AND THEORETICAL VALUES OF THE SATURATION MAGNETIZATION OF SIMPLE FERRITES WITH SPINEL STRUCTURE IN BOHR MAGNETONS AT "K.
Postulated ion distribution
Ferrite

Magnetic

Magnetic

Magnetic moment
per

moment of moment of
tetrahedral

molecule

octahedral
ions

tetrahedral octahedral

MeFea0 4
theoretical

ions

ions
5 5 5 5 5 5

ions
5

experimental

MnFe204
Fe 3 04

FeJJI+MnJ'g

Fe" 1
Fe Fe 111 Fe 111 Fe Fe 111

CoFe2
NiFe a

4 4 4
4

CuFea

MgFe2

Mng.+FeSS Fe n +Fe m Co" + Fem Ni+Feni CuN+Fe1"

4
3

2
1

+ + + + + +

5.

4.6
4.1

5 5

4
3

3.7
2.3
1.3
1.1

2
1

+5
5

Mgn+Fe111
LiJ.s+FeJ
1

Lio.sFe2.50 4

7.5

2.5

2.6

150

INTRINSIC PROPERTIES OF SPINELS

[CH. VIII

average values are given of the magnetic


line specimens, after extrapolation to

moments

as determined

by various

authors from the magnitude of the saturation magnetization of polycrystal-

K ([Go 3], [Gu 3, 4, 5, 6], [Pa 1, moment is that of the divalent metal 2, 3 ]). For inverse ferrites the resultant ion. Use is made of Table 32.1, which gives the resultant spin moments of
the ions from the
first

transition series, determined

by Hund's

rule (see 5).

There are at

least three causes for the deviations

of the magnetic

moment

from the theoretical values. In the first place, the ion distribution may not be the same as that given in the table. As we have seen in 31.2, this is the case with MgFe2C>4 and CuFe 2 04. For these ferrites the saturation magnetization
is

greater after quenching than after slow cooling. In the second place the

ions

may have

in addition to a spin

moment an

orbital

moment, which

is

not completely quenched (see 3.2); this is particularly the case for cobalt ions. We shall return to this point in 34. The direction and the magnitude
of the average magnetic

moments of the ions on

dral sites can in principle be separately determined

experiments. Thirdly, angles

may

occur (see

and octahefrom neutron diffraction 9.2), which has not yet been
the tetrahedral

proved experimentally. The antiparallel orientation of the magnetic moments of the A and B ions has been demonstrated for Fe3<I>4 [Sh 1 ], NiFe 2 4 [Ha 2] and MgFe204 [Ba 2] and [Co 1 ]. A problem is presented by the magnitude
of the saturation magnetization in the case of MnFe204. Neutron diffraction experiments on several specimens have shown [Ha 3] that at 4.2 K the average magnetic

moment of

ions

on the octahedral

sites is

twice as large

as that of the ions

responds to 4.6

/tfl.

on For stoechiometric MnFe204


tetrahedral
sites,

and that the resultant moment corthis value is

hard to explain.

An explanation for the resultant moment of 4.6 hb has been given by Harrison
et al.

[Ha 4] based on the simultaneous occurrence of

Mnm and

Fe 11

ions.

An interesting
zinc ferrites in

aspect, typical of ferrimagnetism, is exhibited


is:

by the mixed

which the ion distribution

ZnFeJE.[M^_ a
Since,

Fe>.a]04.
ions, the magnetization
ferrite,

owing to the presence of (non-magnetic) zinc


lattice will

of the tetrahedral

be smaller than in the case of the simple

Fe111 ions have the largest moment, the saturation magnetization of a mixed ferrite at the absolute zero point would be expected to increase with rising zinc content. Thus the remarkable fact appears that the substitution of magnetic ions in a ferrimagnetic substance by non-magnetic ions can lead to an increase in the saturation magnetization. Apart from Znn and Cd11 [Ve 2], the non-magnetic ions Ga [Ma 1 ] and In [Ma 2]
and
since the
,

32]

SATURATION MAGNETIZATION
pronounced for tetrahedral
sites

151

also have a preference (although less

and

thus, with small concentrations, increase the saturation magnetization of

simple ferrimagnetic spinels at

K. Theoretically the saturation

moment
/hjj

should
for 8

rise linearly
1,

with the zinc content and should reach the value 10


divalent magnetic ions have been replaced

when

all

by

zinc ions.

For small concentrations, the linear rise with the theoretical slope has been found experimentally ( [Gu 3, 4, 5, 6 ] and [Go 3]), as appears from Fig. 32.2. For larger concentrations, however, deviations are found. The magnetic moments of the few remaining Fe111 ions on the A sites are no longer able to align all the moments of the B ions antiparallel to themselves, since this is opposed by the negative B-B exchange interaction, which remains unaffected.

According to the theory described in

9.2,

the

lattice will

then

divide itself into sublattices, the magnetizations of which

make an angle with


this subdivision

each other differing from 0 or 180. The criterion for


is

that the ions within one sublattice interact less strongly with each other

than with those in the other sublattices.

We

have seen in

31.1 that

the

1.0

ZnFe2 Oil
Fig. 32.2. Saturation
crystal series

moment in Bohr magnetons at K for various mixed For magnesium-zinc ferrites a region is indicated for the magnetization which is related to the ion distribution. After [Gu3, 4, 5, 6.]

152
octahedral
sites

INTRINSIC PROPERTIES OF SPINELS

[CH. VIII

form four interpenetrating

f.c.c. lattices

having an edge

a.

Owing

to the consideable distances between the ions in one sublattice

6 A) the exchange interaction inside a sublattice can be neglected (h a i 2 and therefore these sublattices satisfy the above criterion. But there are four B sublattices instead of the two for which the theory was evolved. Identical sublattices, however, can be combined to form two groups in which the
magnetizations are mutually parallel [Ya
division into

two

sublattices.

This

is

1 ], so that in fact we still have the due to the fact that for constant total

magnetization the exchange energy of identical sublattices

is

independent

of their mutual orientation. As regards the interaction of the


the

B lattice with

A lattice

this is

immediately

clear.

The

sublattices with magnetizations

Mbi

of equal magnitude but different directions, (see Fig. 32.3a), can be


field

combined to form two groups as indicated in Fig. 32.36. The Weiss exerted by the B sublattices on the magnetic moments of the A lattice

are:

Ha ,b = nEMm,
where Mbi
is

the magnetic

moment
this

of the Bi th sublattice. Evidently


field strength is

not affected

by a

re-

arrangement of the orientations of the


magnetic

moments

in

the

way

in-

dicated in Fig. 32.2. For the mutual interaction of the

sublattices

an ex-

pansion of
exerted

(9.8) for several identical

sublattices is necessary.

by the

sublattices

The Weiss field on the


sublattice

Fig. 32.3.

For constant

total magneti-

zation

B the

sublattices Bj

can be com-

magnetic moments of the


.Biis:

bined into two groups in which the


netizations are parallel.

Hbi,B
or more generally:

= Ml(AfB 2 + Mbz + MBi) + 2Mb1,


Hbub

iiiMb + (2 i)Afej.
exchange energy in the B lattice is also indepen-

From
If,

this it follows that the

dent of the re-orientation of the magnetic moments as indicated in Fig. 32.3.


then,
)8i

we put
and
j8 2 ,

the four sublattices parallel in pairs

and introduce the con(this

stants

we get

2/8i,

since each of the four sublattices interacts

with another sublattice having parallel magnetization

has

an internal exchange
zation
is

interaction),

and with two


(9.10)

sublattices
find:

now become whose magneti-

not

parallel.

According to

we then

32]

SATURATION MAGNETISATION

153

j8i

= |j8andj3 a = ij8.
take
place
in

(32.1)

For the
the

lattice

a division might possibly

the

two

interpenetrating

f.c.c. lattices,

so that the difficulties described above for


sublattice

lattice

do not

arise.

Here too the interaction within one

can be neglected, so that

now:
ai

and a 2

= 2a.

(32.2)

Since
will

we may

expect the

A A

exchange interaction to be small, angles

probably never form in the


the

lattice;

no experimental indications of

their the existence

have so far been encountered.


will occur

On

B lattice angles

with increasing zinc content, for com-

positions where, according to (9.12) and (32.1):


j8

> 3MA /4MB

(32.3)

The

saturation will then decrease with increasing zinc concentration and,

according to (9.14), will be equal to:

Mo =
The curves found experimentally
theory
(/8

(1

- 3/4p)MA
two

(32.4)

for

Mo as a function of the chemical comstraight lines predicted

position (Fig. 32.2) broadly follow the

by the

being assumed to be constant). According to the theory, angle


will

formation

occur at a certain zinc concentration. The gradual bend of


is

the saturation curves under the dashed lines

explained by Neel

[Ne

7] as

being due to the occurrence of fluctuations in the ratio of the numbers of


zinc

and

ferric ions
i.e.

on

the tetrahedral sites surrounding the various octa-

hedral

sites,

fluctuations in the tetrahedral-octahedral interaction.


is

The

ferrite

ZnFe2C>4

paramagnetic.

From

the foregoing

it

might be

expected to be anti-ferromagnetic, having the ordering described with a

Neel point of the order of 100 K or more. Paramagnetic measurements have never, however, revealed a Neel point for this substance. Moreover, neutron examinations at room temperature indicate that no ordering of the magnetic moments of the ferric ions exists [Ha 2], although a peak has been

found in the specific heat at about 9.5 K; see Fig. 32.4 [Gr 2]. It has been suggested by Anderson [An 2] that the non-occurrence of antiferromagnetism in zinc ferrite is due to the fact that the four sublattices on the B
sites
is

rapidly cooled
all

have to be formed, so that some degeneracy remains. When ZnFe204 from a high temperature, it becomes ferrimagnetic because
the zinc ions occupy tetrahedral
sites.

not

154

INTRINSIC PROPERTIES OF SPINELS

[CH. VIII

As maybeexpected, substitution
of non-magnetic ions on the octahedral
sites

?
K)

of the spinel strucZn Fe2 O4


1

ture causes a decrease in the satu-

ration magnetization, even at the

smallestconcentrations. Examples

are substitutions of Al m

[Go

3 ],

/
'

[Ma

2]),

Sc ni [Ma

2],

Ni"

Ti IV [Go 3] and also the substitution of

Cr111 for Fe on octahedral sites [Go 3]. The saturation magnetization


of the ferromagnetic spinels can

be explained very

satisfactorily if

one assumes a predominant negative exchange between the magnetic ions


sites.

on both kinds of lattice


is

A negative exchange

20
also

40

60

80

-*T(K)
Fig. 32.4. Specific heat in cal per

found in many oxides other than


the spinels.

gram mole-

The magnetic oxides

cule for

ZnFe204

as a function of temperature.

with perovskite structure, which

(After [Gr 2].)

have been studied by Jonker and

Van

Santen [Jo 2] are an exception in the

group of oxides. The perovskite structure is shown schematically in Fig. 32.5. Large divalent or trivalent ions A occupy
the corners of a cube and small trivalent or
tetravalent metal ions

B occupy the

centre

of the cube. The oxygen ions are situated


centrally

on

the faces of the cube.

The
sub-

general chemical formula of these


stances
is

ABO3. The

substances with inte-

resting ferromagnetic properties were found

in the mixed crystal series

La

mMnin 03
m

Can Mnivo 3 ,Lara Mnni 03-BaIIMnivo 3 LainMniiiOs - Srn Mnxv03 and in the
,

corresponding

Srn Co IV 03.

Lain Co C>3 These series of compounds


series

are designated respectively as manganites

and

cobaltites.
all

At

sufficiently

low tempetri-

Fig. 32.S. Idealized elementary cell

ratures

manganites containing both


tetravalent

of the perovskite structure.

valent

and

manganese ions are

32]

SATURATION MAGNETIZATION

155

ferromagnetic. In order to explain the saturation magnetization in these


oxides,
it

must be assumed that the magnetic moments of ions

B (Fig.

32.4)

separated by an oxygen ion have parallel orientation.

The

highest Curie

point

is

370 K. The magnitude of the saturation magnetization at low


is

temperature (90 K)
(T (gauss cm3/g)

given in Fig. 32.6 for mixed crystals of (La, Ca)

"120

_^*
100

La,. f CiifMn03

90

60

40
Fig. 32.6. Saturation magnetization

20

at

90

of

mixed

crystals

Lai- a Ca 8 Mn03.

The

calculated

broken
24
4.

line represents the saturation

100

moment
moments

in the case

where

all

ionic
2].)

are parallel. (After [Jo

MnOs. The broken

line in this figure

shows the magnitude of the saturation


all

magnetization assuming that the magnetic moments of

ions are parallel.

We

thus have here for a range of compositions a true ferromagnetism.


the curve in Fig. 32.6

From

between the

Mnm
is

and

Mn

it must be concluded that the exchange energy IV ions via the oxygen ion lying diametrically

between them

positive

and predominant.

corresponding situation

is

found with the


32.2.

cobaltites of the (La, Sr)CoC>3 series; see [Jo 3].

TEMPERATURE DEPENDENCE OF THE SATURATION MAGNETIZATION


9 various types of curves

According to

may

be expected for the saturation

magnetization

as a function of the temperature

T for

ferrites

see for

instance Figs. 9.3

and

9.6.
all

It

appears, however, that

all

simple ferrites

with spinel structure and


versus

T curve (see Fig.

32.7).

mixed zinc ferrites show a fairly normal s Normalized curves for simple ferrites as given

by Pauthenet [Pa 1 ] are reproduced in Fig. 32.8. In the case of CuFe2C>4 and MgFe2<I>4 these curves are highly dependent on the method of preparing

156
(T (gauss crrp/g)
I 120

INTRINSIC PROPERTIES OF SPINELS

[CH. VIII

.M e=Mn
Co

MeFe2Qi

no
80

IN.
60
L'o.5

^0.5
i

Ni

40

Mg

20

~Cu~
i i
i

\\
100

-273 -200

-100

200

300

400

500

600

700

T(C)
Fig. 32.7. Saturation magnetization per

gram,

a,

for simple ferrites

with spinel structure as a function of temperature T.

the specimen since

of the

Cu and Mg ions can


in
first

occur on both

lattice sites.

The form

versus

T curves in

Fig. 32.8 can be explained with the Weiss field

theory. If

we assume

approximation that the exchange interactions

between the magnetic moments in each sublattice are zero, a j8 0, see in the A lattice is approximately twice (9.6) then the Weiss field at T

= =

as large as in the

B lattice

(inversely proportional to the magnetizations of

the sublattices).

As a

result the

M
be

versus

T curves
The

of the

lattice will

be

much more convex than


the curve for the
that of the

those for a simple ferromagnetic substance, and


less

lattice will

convex.

total magnetization is

lattice

reduced by that of the

lattice,

and the curve

will

1.0

0.8

V
Fig. 32.8.

Ms

M
0.6
1

Normalized curves

j-t
NiFe 2
4

of the saturation magnetiza-

0.4

2 3 4 5

5^

>^

tion of simple ferrites with


spinel structure as a function

Co Fes O4 Fe3 O4

Mn Fe2

O4

of temperature, after [Pa 1]. For comparison the Langevin curve


is

0.2

given for the

case that elementary magne-

0.2

0.4

0.6

0.8

1.0

moments of two Bohr magnetons are present (/= !)


tic

T/Tc

32]

SATURATION MAGNETISATION
700

157

therefore be less convex than

that of a simple ferromagnetic.

Met-fZn-Fe2
600

A finite positive value of


the Weiss field in the

/}

makes
lattice

Jc
(c)

\\^
500

e '

U0.5 + Feo.s
BOO

T c

even smaller, and

will therefore

intensify the effect, while a finite

Nr>

positive value of a

makes the
lattice

Weiss
ler,

field in

the

400
(v

smal
300

and will counteract the effect.


saturation

600

Table 32.111 gives a survey of


the

magnetizations

Mn
200

and Curie
cates

points,

and also

indi-

the

magnetization

per
is

gram, a

s /d;

the latter

400
100

an

intrinsic quantity

terial,

of the mawhich is not the case with

in porous substances.

The
200
-100

relation

between a at

K and

the
tib

number of Bohr magnetons per molecule MeFe204 is

given by:

-200

TlB^
where

M
'

N-fis

a =-^^. 5585

cr,

Ki (32.5)

-27:

0.2

0.4

0.6

0.8

1.0
I

MeFe^3i

Zn ftaO
fc

is

the molecular weight


Fig. 32.9. Curie points of some mixed zincferrites Mei- 8 Zn 8 Fe204 ion of the zinc concentration.
32.111
series

of the substance corresponding


to one molecule MeFe2C>4, given in Table 31. III.

of

as a funct-

TABLE

THE SATURATION MAGNETIZATION Ms IN GAUSS AND a IN GAUSS CM3/G, TOGETHER WITH THE CURIE POINTS Tc OF SOME SIMPLE FERRITES WITH SPINEL STRUCTURE.

0K
Ferrite

20 C

a
gauss

M,
gauss

4itMs
gauss

a
gauss

M.
gauss

4irM,
gauss

cm
MnFez04
Fe 3
4

/g

cm

/g

112 98

560 510 475 300


160
140

7000
6400 6000 3800

80

400

5000 6000 5300


3400
1700 1500

300
585

92
80 50
25

480
425

CoFe 2 4 NiFe 2 4 CuFe 2 4 MgFez0 4


Lio.5Fez.50 4

90
56

270
135

520 585
455

30
31

2000
1800

27
65

120

440
670

69

330

4200

310

3900

158

INTRINSIC PROPERTIES OF SPINELS


to the reduced

[CH. VIII

Owing

A B

exchange interaction with increasing zinc

content in the case of mixed zinc ferrites with spinel structure, the Curie
point will drop as a result of the substitution of zinc. This was
first

found

by Forestier [Fo
32.9. Since the

1]

and

is

illustrated

by the experimental curves


K,
it

in Fig.

Curie point decreases with increasing zinc content and the

saturation magnetization increases at

cannot be predicted

how

the

saturation of a ferrite will change at an intermediate temperature, for in-

160

IT

(gauss crr>3/g)

Mn 1 .gZnsFe2 Qi.

120

80

40 s \aso\03S \ajZ\ao
-273 -200
-100

100

200

300

*~T(C)
Fig. 32.10. Saturation magnetization per

gram,

a,

as a function of temseries.

perature for

some

ferrites

of the

Mn1 - sZn g Fea04

120
(gauss crn^/g) >/s)

Ni 1 -sZnfFe2 i

100

80

SO

40

20

-o.6s\ o.so\
-273 -200
200
>
,

o.33\n!}\a!h*.
400
600

T (C)

Fig. 32.11.

The

saturation magnetization per gram, a, as a function of


ferrites

temperature for some

of the Ni 1 - g Zn 8 Fe204

series.

33]

SATURATION MAGNETIZATION
4-tlMs

159

(gauss)

Ni Fez-sAlg 4

T(K)

T vsS c

Fig. 32.12. Three-dimensional

graph showing 4irMs versus

r curves for different composi-

tions in the series of solid solutions

curves are
8

all

very slowly cooled. The shapes of the in (i.e., increasing those predicted by theory (see Fig. 9.3). Introduction of Al

NiFe 2 - gAl 8

4,

from

0) lowers

4wAf

at all temperatures. After

[Go

4].

stance at

room

temperature,
it

if

magnetic ions are substituted by zinc ions.


series

In Figs. 32.10 and 32.11

can be seen that in the

Mni_8Zn8Fe 2 04
increases with 8
8 is equal to 0.15

and
for

Nii-sZnsFe204 the saturation at low zinc concentrations

room temperature reaches a maximum when and

and 0.35 respectively. Although the form of the


so far
is still

versus

curves of the ferrites discussed

normal, other curves more characteristic of ferrimagnetism are also found, one example having been givenin Fig. 9.2. Curves of this kind also occur in the NiFe 2 -8Al80 4 system, a survey of which is given
in Fig. 32.12.

The curve

in the plane

T=

K indicates

the change in the

160

PARAMAGNETION ABOVE THE CURIE POINT


when
is

[CH. VIII

saturation magnetization of NiFe2C>4

part of

its

uted by Al ions. Since this substitution


sites

made

principally

Fe ions are substiton octahedral

and [Sm 3]), the total magnetization s decreases with and passes zero at 8 = 0.62; see [Go 3] and [Ma 1]. The substitution of non magnetic ions on octahedral sites, like the substitution on tetrahedral sites, causes a decrease in the Curie point, although relatively less, and the s versus T curves with increasing value of 3 have the forms
1]

[Ma

increasing

8,

as indicated in Fig. 9.3a

and

9.3b.

33. Paramagnetism above the Curie Point

The l/x
ples for
yields

versus

T curves
is

of

ferrites

with spinel structure are convex above

the Curie point; this

ExamFe3 4 and MnFe 2 4 are given in Fig. 33.1. The Weiss field theory for two sublattices the following relation, which can easily be derived
characteristic of ferrimagnetism (see 10).
1
-

from

(10.1):

l/x

Ta ~
,

Tb z Ta

'

(33.1)

the Curie constant being

constants of the

and

C = C\ + C 2 where C\ and C2 are the Curie B lattices and are related to the properties of the ions
gives the molar susceptibilities xmoi, so that the

according to
200

(6.9). Fig. 33.1

800
Fig. 33.1.

1000

1200

1400

T(K)

The

reciprocal value of the molar susceptibility, l/Xmol , as a function

of temperature for

MnFe20 4

(after [CI 3])

The asymptotes

for high temperature are

and Fe30 4 (after Kopp, see [Ne 1]). drawn in with the theoretical spin32.1.

only slope according to the Curie constants in Table

33]

PARAMAGNETISM ABOVE THE CURIE POINT

161

Cs values per gram-ion must be taken, as given in Table 32.1, and multiplied by the number of ions on the site in question, as occurring in the formula MeFe2 4 The equation (33.1) represents a hyperbola the asymptotes of
.

which

bisect the

T axis
C1

at

Ta

and

T' given by:

Ci*Wu + 2CiC2 ^i2 +

C#Wn

C2
Wii)

- a(aCi + 2CiC + /3C 2 C1 + C2


2

2 )

and

Ta =
'

(W11-2W12+
versus

= CiC

(2-a-j8)

C1

(33.3)

C2

The curvature of the l/\

T curve is

related to

r6

which

is

given by:
(33.4)

Tb = C1(Wii-Wi2) + C2(Wi2-W22) = n[C1 (l-a)-C2(l-mFor negative exchange interactions


only slope. Conversely
it

(a,j8

>

0)

we have \Ta

> Ta

'.

Figure

33.1 gives the asymptotes for high temperatures with the theoretical spin-

should be quite easy to determine the values of

from the measured l/x versus T curves. This has been done for a number of ferrites and the results are reproduced in Table 33.1. The result depends very much on the assumption of the ion distribution over tetrahedral and octahedral sites. A small percentage of zinc ions on octahedral sites
a and
j8

will influence the calculated

molecular

field

constants to a high degree.

TABLE

33.1

MOLECULAR FIELD COEFFICIENTS CALCULATED WITH THE WEISS FIELD THEORY FROM MEASURED l/x versus T CURVES.
Ferrite

a
0.82
0.51

P
0.28

Reference
CI. 3

MnFe 2 04
Fes0 4 NiFe 2
4

0.01

Ne

0.21

0.15

Ne8

Nio.8Zno.2Fez04 Nio.4Zno.6Fe204

0.48
1.16

0.16
0.15

Nio.aZno.7Fe204

3.08

0.14

moreover, very doubtful whether such detailed data can be obtained from an approximating theory, which the Weiss field theory is. In 6.4 and deviations from the Weiss 10 it was shown how short-range order causes
It is,

range order the quantity 1/x becomes larger, thereby causing a decrease in the Curie point, as illustrated in Fig. 10.3. This decrease can amount to several tens of percents. Highfield theory.

As a

result of the short

temperature behaviour

is

not influenced by

this,

and

Ta

will therefore

162

INTRINSIC PROPERTIES OF SPINELS

[CH. VIII

have the correct value, whereas the experimental value of

Ta

'

will

be too

low. This would accordingly result in a too large value /or a and/or $ when applying the eqs (33.2) and (33.3), although it cannot be ascertained from these equations whether especially a or f$ will be too large. It is seen from
Fig. 10.3, however, that
it is

just

above the Curie point that the slope of the


less.

1/x versus

curve will be too small, and hence the curvature


\

This

points to a too large value of \Tb in (33.4).


1

Now C2 is

approximately equal

to 2Ci, so that a large value of 7&| corresponds to a too large value of a or a

too small value of

This can be understood from the fact that immediately

above the Curie point the magnetizations of the A and B sublattices induced by an external field are still antiparallel. A too large value of x (high magnetization in external field)
is
is

obtained

when

the Weiss field in the


(|8

lattice

too small (a large) or in the


field theory,

lattice

too large

small). Thus,

when

applying the Weiss


for a,

we may
is

expect a too high value especially

which

is

the interaction within the sublattice with the smallest magneprecisely

tization.

This

is

what

found, as can be seen from Table 33.1.


in 32.1, one can scarcely assume that

Having regard to the

results

shown

a>
34. Crystal Anisotropy
34.1.

CUBIC CRYSTAL ANISOTROPY


of the crystal anisotropy
is

A review of some of the hitherto published values


constants

Ki and fa

(defined in (11.1)) for ferrites with spinel structure,

given in Table 34.1.

A striking fact is that all Ki values are negative, except


has been found that the anisotropy constants
( 26.1)
if

those for cobalt ferrite and for ferrites containing a large percentage of divalent cobalt ions. Bozorth [Bo 2] found that the ageing of cobalt ferrites

has an influence on K.
obtained by a
static

It

method of measurement

may

differ

from those

obtained with the help of microwaves ( 26.4)


ferrous ions as well as ferric ions.

the single crystal contains

Table 34.11 gives the results of measurements [Bo 3] carried out on 1 ohmcm (which points to a certainconcentration of ferrous ions) and on the ferrite MnFei. 9 4 , which is deNio.8Fe2.2O4 having a resistivity of only
ficient in

iron and thus probably contains no ferrous ions.

The authors

attribute the difference in the case of the nickel ferrite at -196 to rearrange-

ments of electrons on the iron ions when the orientation of the magnetization The values of t will then depend on whether the measurement has been carried out at a frequency which is much larger or much smaller than the reciprocal of the time constant which determines the electron
changes.

34]

CRYTAL ANISOTROPY
TABLE 34.1 AND K2 OF A NUMBER OF

163

CRYSTAL ANISOTROPY CONSTANTS STRUCTURE AT 20 C AND -1% C.


Composition

JSTi

FERRrTES WITH SPINEL

Temperature

K2
erg/cm 3
erg/cm 3
3

C
20

Reference

Fe 3

bK

20

110X10 28x103
187x103

280 x10s

Bi3

100X10 X 10 2X10
3
3

Bo 2

MnFe204

(
(

196

269
27

Mno.98Fe1.80O4

} 196
(
(

210x103 a 200X103 a

Di2
)) J

3 3

+
4-

28
0.9

10 3 a

90

CoFe 2 04

1 (
<

200 280

x10 s 66x103

Ta2

~0
+ 4.4X106 + 2.9X106 + 1.8 x10 s

196
20

Bo 2

Coo.8Fe2.2O4 *)
(

C01.1Fe1.9O4

20
^

Bo 2

196
20

NiFe 2

4
(
i

87 x 10 3

62 x 103

Gal Ga 1, Ya 2

196
20

206X103
3

CuFe 2 04

} (

400
20
20

MgFe 2 04

**)

Mno.45Zno.55Fe204
a

60X10 a 1x103 a 25X10 3.8xl0 a


3
3

Okl
J >

Ra2 Ga2

Obtained from microwave measurements; the values not denoted by a were found

from
b
*

static

measurements.

The

values denoted by a bracket apply to the

same specimen.
.

These values apply to a specimen aged for three days at 150 C. After quenching the specimen in air from 400 C the same authors found Ki = +3.9 x 10 s erg/cm 3

** Value extrapolated to zero ferrous content.

TABLE

34.11
2\Ki\IM>

THE CRYSTAL ANISOTROPY CONSTANT Ki AND THE ANISOTROPY FIELD DENT ON TEMPERATURE AND FREQUENCY ACCORDING TO [Bo 3].
Nio.sFe2.2O4

AS DEPEN-

MnFei.904
2\Kx\IM,

Temperature

Method of
measurement

Ki
erg/cm 3

21-STil/M,

oersted
3

erg/cm 3

oersted
3
3

static

39xl0

260
280

20 C

microwave
static

43 x 10s

34xl0 33 x 10

180
175

196 c[

42xl0

260
468

microwave

74x103

240 x10s 233 x 10s

840

812

164
transitions.

INTRINSIC PROPERTIES OF SPINELS

[CH. VIII

similar electron ordering

is

also proposed to explain

an

ex-

cessive width of the ferromagnetic resonance line

and

also as the cause of

relaxation losses occurring at entirely different temperatures


[CI 4]; see 36.1

and frequencies

and

54.3 respectively.

An

extensive investigation of Fe3C>4 has been carried out to determine

the change of the crystal anisotropy constants


Fig. 34.1 gives the result of the static

K\ and K% with temperature.


[Bi 3].

measurements by Bickford

Results obtained earlier by the

ments, are virtually


rature
this
is

same author, but from microwave measureno different from these. The variation of K\ with tempeis

quite anomalous: a change of sign takes place at 130 K: below


positive,

temperature K\

above

this

temperature

it is

negative. This

temperature does not coincide with the transition point for Fe304, discussed in
31.4,

which point

lies

at a temperature approximately 10 lower.


is

In the orthorhombic structure the c axis


netization.

the preferred direction of

mag-

Upon

cooling below the transition point of 119


is

the cube

edge along which the magnetization


(see

aligned

is

the orthorhombic axis

[Do

2]).

Bickford [Bi 3 ] has examined the change in the crystal anisotropy constants
of Fe304

when

small percentages of ferrous ions are replaced by cobalt ions.

In Fig. 34.2 and Fig. 34.3 the quantities K\ and


as a function of temperature for

respectively are plotted


ferrites

mixed cobalt ferrous

CoFe3- 8 04

where 8

= 0,

0.01 or 0.04.

The cobalt contribution


is

to the anisotropy for

these small concentrations

found to be proportional to the cobalt

content. For higher cobalt concentrations the anisotropy increases less


rapidly, [Pe
1 ].

By

the addition of cobalt ferrite the zero point in the crystal


is

anisotropy of magnetite

shifted

towards higher temperatures; for example

*3 0l
UO'erg/cm 3)
i

"'j/
-10

-15

"

_i"*H* j?~X "

Fig. 34. 1 .

Temperature varia-

tion
100

of crystal anisotropy

200

300

400

500 constants

K\

and

Kz

of

-+

T(K)

magnetite. (After [Bi

3]).

34]

CRYSTAL ANISOTROPY
in the case of the
it lies

165

<,

(JO^rg/cm 3)

compound

= 0.01
der

44

at

room

temperature.

Van

Burgt [Bu 2] has also found that the


crystal

anisotropy of mixed ferrites


ferrite
is

with cobalt
the value as

has generally not

derived simply from the

contributions of the compounds.

He

found moreover that for instance the


introduction of cobalt in
Nio.sZno.s
Fe2C>4 gives per cobalt ion a change in

the anisotropy which teenth of that

is

only one

six-

when the same amount of

cobalt

is

introduced in FesC>4. The co-

balt contribution to the anisotropy de-

pends of course on the

site

the cobalt

ions occupy in the structure


400
Fig. 34.2.

and

also

500 T(K)

on the kind of the surrounding ions. The cause of the crystal anisotropy
must be sought mainly
ions, since the ferric ions
filled shell,

The crystal anisotropy conKi versus temperature for magnetite and cobalt-substituted magnetite Co 8 Fe3-0 4 (After [Bi 3]).
stant
.

in the spin-

orbit interaction in the divalent metal

have a

half-

that

is

to say they have

no

orbital

moment
+;

in the ground state.

K2
(^erg/cm3)
-1

V
Ll

1,

SS-OAI

S-OM

Co^Fe->-t*

X
100

o/
200

so

2S0

300

350

- T(K)

Fig. 34.3.

The crystal anosotropy constant K%


3].

versus temperature

for

magnetite and cobalt-substituted magnetite CoaFe3-04.

After [Bi

166

INTRINSIC PROPERTIES OF SPINELS


,
,

[CH. VIII

With most ions (Mn11, Fe11 Ni11 Cu11) the orbital moment is quenched ( 3.2) and the spin-orbit interaction introduces only a relatively small anisotropy. In Co 11 however, the crystal field is not able to remove the orbital degeneracy, and the orbital moment is of the same order of magnitude as the spin moment. This must be regarded as the cause of the large aniso,

tropy of cobalt
(to

[SI 2],

which manifests

itself also in

the field-cooling effect

be dealt with in the following section), in magnetostriction and in the g factor. Yosida and Tachiki [Yo 1 ] examined theoretically the various mechanisms that can give rise to crystal anisotropy in the ferrites with spinel

and came to the conclusion that dipole energy, as treated at the end of 12.1, and mechanism (b) of 12.1, cannot explain the anisotropy observed in nickel ferrite; they can, however, explain the order of magnitude in FeaQi. Mechanism (a) of 12.2 was not, however, considered.
structure
34.2.

INDUCED UNIAXIAL ANISOTROPY


with cubic crystal structure a uniaxial anisotropy can be brought

In

ferrites

about by subjecting the material to an annealing treatment in a magnetic


field. If

a single crystal of a ferrite specimen has a sufficiently high Curie

point, for example above 250 C,

and if it is allowed to cool slowly from this temperature to room temperature, one finds in many cases that a uniaxial magnetic anisotropy is superimposed on the cubic anisotropy. The effect occurs particularly in ferrites containing cobalt. Bozorth et al. [Bo 2] found
for a single crystal, denoted direction of the magnetic
field

by the formula Coo.32Zno.24Fe2.i8O4, that the becomes the easy direction of magnetization
1

for the uniaxial anisotropy, irrespective of the direction of this field with

regard to the axis of the crystal. Penoyer and Bickford [Pe


single crystals of magnetite with

found that in

low cobalt concentrations (Co 8Fe3- g 04,

where

<

0.15) the direction of the induced uniaxial anisotropy does not

generally coincide with the direction of the magnetization during magnetic

annealing,

and moreover

that the magnitude of the uniaxial anisotropy


field

depends on the direction of the magnetic


results of their

during the magnetic annealing

process with respect to the crystallographic axes.

From an

analysis of the

measurements

it

appears that the coefficients

and

in-

troduced in (11.9) depend respectively quadratically and linearly upon the


cobalt concentration S (see Fig. 34.4).

The same
al.

figure indicates the results

of measurements performed by Bozorth et


axial anisotropy

[Bo 2] to determine the uni-

of polycrystalline specimens.

A maximum effect occurs in


and ferrous
ions.

compositions with larger concentrations of both cobalt

The
for

ferrous ion

promoting

diffusion.

and cation-vacancy concentration appear to be important The magnitude of the uniaxial anisotropy depends

(34]
Fig. 34.4.
crystalline

CRYSTAL ANISOTROPY
Drawn
curve

167

uniaxial
energy

K, (I0 e erg/cm3)

anisotropy

Ki

2.5

as a result of magnetic annealing

of specimens of CosFe3-a04, after

Cos
2.0

Fe^Oi

[Bo 2]. The broken curves represent


the coefficients

and

of eq.

(11.9), after [Pe 1].

7.5

G!
7.0

0.5
i
*

/
y
0.2
0.i

0.6
*"T

0.8

7.0

Fe3 Q{

CoFeaQ^
at

upon
which

the duration of the magnetic annealing


it is

and on the temperature

[Bo 2] have found the same activation energy of 0.94 eV for this process in the case of single crystals and a polycarried out. Bozorth et
al.

crystalline

specimen of different compositions. The greatest anisotropy

is

found when

the specimen has been aged for three days at the lowest temis

perature which, in their case,

150 C. For small cobalt concentrations


rapid; in the

the annealing process

is

much more

method adopted by Pe-

noyer and Bickford the annealing time was 5-10 minutes at 100 C. The phenomenon of magnetic annealing has long been familiar as far as
alloys are concerned,

and various

theories have been put forward to explain

it. It does not seem probable that the anisotropy arises from anisotropic magnetostriction, because the phenomenon is also found with single crystals

which can deform freely without the occurrence of stresses. The separation of a second phase in needle or disk form is a possible cause. In 11.2 a theory was given in which the ordering of ion pairs in a certain direction
under the influence of the magnetic
axial anisotropy.
field is

described as the cause of the uni-

When discussing the spinel structure in 31.2 it was pointed


site

out that the surrounding of a single octahedral


also

by the oxygen ions when u ^ becomes uniaxial with a symmetry axis along one of the [111] directions (see Fig. 31.3). The occurrence of crystal fields having this symmetry may
3/8, possesses

by the metal ions, and no cubic symmetry but

therefore be expected. According to


rise to

mechanism

(b) in 12.2, this

could give

a magnetic anisotropy with this particular [111] direction as the axis

168

INTRINSIC PROPERTIES OF SPINELS

[CH. vill

of symmetry. The total anisotropy, then, will depend on the occupation of


the four possible kinds of octahedral
sites

by foreign ions. With

this

mechaeffect this
,

nism Penoyer and Bickford [Pe


in
first

1 ]

explain the term


is

in (11.9)

which has

the appropriate symmetry. Since this

a property of a single ion the

approximation
fact found.

will

be proportional to the concentration, and

The term F, which was found to be proportional to S 2 is then to be explained by pair orientation. The connecting lines lie along the [110] directions which, in alloys, would give rise to an f.c.c. symmetry of the anisotropy (G = 4F) so that then G4F and not G would be proporwas in
tional to the concentration of cobalt ions. This
It
is not found experimentally. must therefore be assumed that pair orientation gives rise to a simple cubic

symmetry. This

is

plausible, since the exchange interaction


is

between two

cobalt neighbours

not direct but takes place via the two intermediate

oxygen ions (see Fig. 31.3). These four ions he in a cube face. For each exchange interaction we can therefore expect an anisotropy along the line
connecting the
for each

Co

ion and the oxygen ion. Since there are two such lines

Co

pair, there is
is

no anisotropy in the said cube

face,

but the easy

(or difficult) direction

perpendicular to the cube face determined by the

Hence we must in fact expect an anisotropy of the simple cubic type, corresponding to the F term in (11.9). This crystal anisotropy, then, is of the type (a) of 12.2. During cooling in the absence of a field a preferred direction will also arise owing to diffusion in each Weiss domain in the case of the mixed cobalt ferrites.
ions.
35. Linear Magnetostriction

two Co

The magnetostriction constants


crystals of ferrites with the aid

Aioo

and

Am have been measured on single


2].

of strain gauges [Go

The results

are given

in Table 35.1.

On the manner in which the magnostriction constants change


TABLE
35.1

MAGNETOSTRICTION CONSTANTS OF FERRITES WITH SPINEL STRUCTURE AT


Ferrite
IO6.A100
IO8.A111

20 C.

Reference

Fe 3

Coo.8Feo.2Fe204
Nio.8Feo.2Fe204

20 590 36
little is

of Fe 3

+ + 120
78

Bi4 Bo 2 Bo 2
o,

with temperature

known.

Fig. 35.1 gives the constants Ai


4

and

Alio for a synthetic single crystal

according to Bickford

[Bi 4].

The

values of the saturation magnetostriction A measured


ferrites

on poly-

cristalline

specimens of simple

and on a

series

of nickel-zinc ferrites

are given in Table 35.11.

35]

LINEAR MAGNETOSTRICTION

169

10 e

T("K)
Fig. 35.1.

The magnetostriction constants


for
synthetic
4]).

Aioo,

Am
single

and Ano
crystal.

versus

temperature

magnetite

(After [Bi

TABLE

35.11

LINEAR SATURATION MAGNETOSTRICTION X a FOR SIMPLE FERRITES AND MIXED NICKELZINC FERRITES WITH SPINEL STRUCTURE AT 20 C.
Ferrite

A..10 6

Reference

MnFe204
Fe 3
4

5
+40 110

CoFea04 MgFe204
Lio.5Fe2.5O4

Nio.3eZno.64Fe204

6
8 5

Gu7 Sm4
En
1

Nio.5oZno.5oFez04
Nio. 64Zno. 3eFe204

Nio.8oZno.aoFe204

NiFe 2

11 16 21 26

Sm4

The magnetostriction at room temperature is positive only for the electrically conductive Fesd. This is because Am is relatively highly positive;
see (13.3). It

may

be expected that in the case of mixed crystals of a


ratio of

ferrite

with Fe3C>4

it

must be possible to have a

components such that the

saturation magnetostriction will be zero. In Fig. 35.2 the magnetostriction A


is

plotted as a function of the magnetic field

H for polycrystalline specimens


It

consisting of mixed crystals of Fe3C>4

and NiFe 2 04.

appears that the satu-

ration magnetostriction varies gradually with the composition

value of zero at about the composition


simple ferrites the A versus

Nio.56Fe n o.44Fe2C>4.

and has a For the

H curves are

monotonia For specimens with

170

INTRINSIC PROPERTIES OF SPINELS

[CH. VIII

a composition of approximately Ni2/3Fen i/3 Fe 2 04 the magnetostriction as a function of the field strength shows a reversal point, as found in
the case of the metal iron (Villari reversal point).
that the magnetostriction in small
fields,

The reason

for this

is

of the order of magnitude of

the coercive force,

is

mainly the result of irreversible wall displacements

which turn the magnetization towards a new preferred direction lying closer to the direction of the applied magnetic field. Where, for example, the

cube diagonal

is

the preferred direction of the magnetization,

this process is

connected with the magnetostriction constant


is

Am. For

all

superimposed on this magnetostriction a contribution caused by the rotation of the magnetization in each Weiss domain out of the preferred direction towards the direction of the applied magnetic field.
field strengths there

and compared with the coercive and Aioo have different signs, then one can force of the material. If A curves of the different types shown in Fig. 35.2. Conversely, such expect curves point to the magnetostriction having a different sign in the easy and
This magnetostriction
it

is

also determined

by

Aioo in the case considered,

predominates at

field strengths that are large

difficult directions

of the magnetization. Thus, from the trend of the A versus

curve for small

fields in polycristalline

specimens

we

can get an idea of the

magnitude of the magnetostriction in the crystallographic preferred direction of the magnetization. In the mixed crystal series of manganese ferrite and magnetite, compounds with very small values of magnetostriction have

nfi.X

750 *-

1000

1250

(Oe)

Fig. 35.2.

Magnetostriction versus magnetic field for polycrystalline


series.

specimens of mixed crystals of the NiFei-sFe204

(After [W"i4]).

$36]

DYNAMIC PROPERTIES
is

171

been found. Since the crystal anisotropy


nese-zinc ferrites,

also small, very high initial

permeabilities can be realized with thes ferrites (see 48.1).

The manga-

much used

in practice, always contain so


at
1

much

ferrous

ferrite that the magnetostriction

all

field
.

strengths has

an absolute

value lower than approximately

10 -6

36.
36.1.

Dynamic Properties

INDUCED FERROMAGNETIC RESONANCE


an example of the absorption
ferrite
2]).

Fig. 36.1 gives

line

caused by ferromagnetic

resonance in a single crystal of a

with spinel structure, in this case

Mno.98Fe1.86O4 (see [Di

measurement was made of the energy ab-

sorption in a cavity by a single-crystal sphere with a diameter of about

was determined from the result with the aid of (23.2). The orientawas such that, for each curve, one of the crystallography principal axes was parallel to the strong external magnetic field. The magnitude of the magnetic fields Hi, Hi and H3, which, at a given frequency/, are needed for resonance in the [100], [110] or [111] directions, is given by the eqs (26.10). From the magnitude of Ht and s the values of K\ and g are determined; the results are given in Tables 34.1 and 36.1. These tables include the g factors and anisotropics found in this way for
/a"

\ mm;

tion of the single crystal

several kinds of single crystals.

The width of the ferromagnetic resonance

fine is

determined to a great

extent by the ferrous concentration in the single crystal. Crystals of ferro-

magnetic spinels having a low ferrous content can yield


line-width measurements
120

minimum

line-

widths of approximately 50 Oersteds (see for example Fig. 36.1). The results of

on

nickel-ferrite single crystals containing ferrous

ItlOU

fi[ro<?]

100
[1111

Fig. 36.1. Ferrimagnetic re-

80
1 I
<

sonance

line

shapes measud.c.

red with the


field

magnetic
principal

60

along

the

660ei
40

\Le

crystallographic

SSOOe

46 Oe

directions.

Measurements were made on


a sphere of Mno.89Fe1.8eO4

20

with a diameter of approxi-

mately
sec,

U mm
room
2]).

at 9.3

kMc/

at

temperature.

3000

3200

3400

3600

(After [Di

-H(0e)

172

INTRINSIC PROPERTIES OF SPINELS

[CH. VIII
effect

ions are reproduced in Fig. 36.2 [Ya 4].

A dimensional
is

occurs since

the line width in the case of too large spheres


losses. It

increased by eddy current

can be seen from the figure that the

line

width increases with the

ferrous ion concentration.


at 160 K.

On

the basis

the authors arrive at a relaxation time Fe11 Fe ,kT From the t which depends upon the temperature according to t = t m e* -12 results of the measurement it follows that e = 0.022 eV and t =1.0x 10
electron transitions
.

^ m

As a function of temperature a maximum appears of a thermodynamic theory on the relaxation of

AH
(Oe)

goo

300
Fig.
36.2.

TM

350

Ferromagnetic resonance

line

width

AH

as

function of temperature for two single crystals containing


ferrous ions.
direction.

the

The d.c. magnetic field was in the [111] crystal The drawn curves apply to various diameters of ferrite sphere. The size effect is attributed to the eddy
4]).

current losses. (After [Ya

sec.

This activation energy

is

in agreement with that found for the conduc-

tivity

of crystals of the same kind.


crystals containing

no ferrous ions the line width depends upon the and it increases towards low temperatures (see Fig. 36.3). The magnitude of the damping parameter a in (23.10) is related, according to (23.13), with the line width AH and the re-

For

orientation of the crystal (see Fig. 36.1)

sonance

field

H in accordance with the equation:


2a

= AH/H.
36.3
it

(36.1)
is

From
ions

the results in Figs 36.1

and

follows that a

of the order of

magnitude of a

= (50/2) x 3000 = 0.008

for spinels containing

no ferrous

and

rises to

a value approximately 10 times higher in the spinels of

36]

DYNAMIC PROPERTIES

173

400

AH
300

200

23XXJ0Mc/s
100
f

9150 Mc/s

\5600Mcfi
100

200
line

300

tM
AH in
a

400

Fig. 36.3.
ferrite

Temperature dependence of the

width

Mn-Zn

containing a small (but

resistivity

unknown) amount of zinc and having a of about 104 ohm-cm. (After |Ta 3]).

higher ferrous content.


relaxation time t:

The damping can also be indicated by a characteristic


t

= 2H/<oAH =

1/aw,

(36.2)

which in these two cases


respectively.

is

of the order of magnitude of 10 -9 and 10 -10 sec

The shape of the narrow ferromagnetic resonance curves strongly resemwhich is to be expected from (23.12). The difference is that at equal half-value width and peak height the measured curve lies entirely
bles that

within the calculated curve (see, for example, [Ta 3 ]). If the amplitude of
the high-frequency waves in a ferromagnetic resonance experiment
creased, the shape of the resonance line changes
[Bl 2].
is

in-

The maximum
explanation of

value of

fi" is

decreased and a second absorption peak appears at lower

frequency for spheres of nickel-ferrite (see Fig. 36.4).


this

An

phenomenon

as given

by Suhl was

dealt with in 23.4.

In the case of the ferrimagnetic spinels in which the magnetic

moments

of the ions on tetrahedral and octahedral


factor according to (20.3)
is

sites

are mutually parallel, the

given by
(Mtotal)B
(Afspin)B

(Aftotal)^l (Afspin).4

'

(36.3)

from which
value of gett

it

follows that, for a completely inverse spinel, the measured

is

equal to the value of g for the divalent magnetic ion on the

174
octahedral
site.

INTRINSIC PROPERTIES OF SPINELS


Results of measurements carried out

[CH. VIII

on

polycrystalline specimens at different temperatures

on single crystals and and frequencies are

The fairly high value of the g factors for NiFe2C>4 and Co2Fe2C>4 can explain the difference between the spin-only value for
collected in Table 36.1.
1ST

Fig. 36.4.

The

value of y."

in arbitrary units as

a funct-

ion of the d.c. magnetic field

H at 300 K. At high microwave power level, indicated by the square of the microwave amplitude Ho, an anomalous absorption appears,
especially
at

the

low-field

side of the resonance. (Af-

4000

ter [Bl 2]).

H(0e)

the magnetic

moment

of these compounds and the measured saturation

magnetizations in Table 32.11.

since the carriers of the magnetic

The result for MnFe 2 moments here are

4 is

very satisfactory,

Mn11

and Fe111 both


,

TABLE
EXPERIMENTAL VALUES OF THE EFFECTIVE
Ferrite
g

36.1

FACTOR OF SIMPLE FERRITES

Temperature

Wavelength

cm
3.2

Sell

Reference

MnFea0 4

269 196
27

2.060
2.019

Di2

2.004

0.003

0.002

Fe 3

269 to 153 143


20

20

various
3.35 3.35
1.25

2.00

Ta3
Bi5
>)

2.06
2.08 2.09 2.17
2.13
2.7

3.35
1.25

"

CoFe204
NiFe 2
4

90
200

1.25 1.25
1.25 1.25

0.3

Ta2
J

2.27 2.19

20

CuFe 2

195
450
20 20

2.20
2.05 2.03

Ya3 Okl
,,

1.25

MgFe20 4
Lio.sFe2.50 4
*)

1.24

2.06
2.08

*)

Ya2
Be
5

3.18

From measurements on

polycrystalline samples

36]

DYNAMIC PROPERTIES
half-filled

175

of which have a

3d

shell

and are thus

in

S state.

In the case of

spinels for which the saturation magnetization as a function of temperature shows a zero point at a temperature below the Curie point, anomalies occur

in the value of the effective


If,

and Fig. 19.2). two other kinds of metal ions present in a ferrite, it is no longer possible to determine from the magnitude of the saturation magnetization alone how the ions are distributed over the two
apart from Fe

factor (see 19

there are

Gorter [Go 6] and Smart [Sm 5] have indicated that the ion distribution can nevertheless be determined from the measured value of gett and from known values of the g factors for the ions on both kinds of raTi5v 4 for which is site. This has been applied to the spinel Ni Fe
lattice sites.

lattice

u found an extrapolated value gett = 2.90 at K. Assuming that gm (oct) = = 2.00 irrespective of the lattice site, 2.3 on octahedral sites and thatgFe

then the ion distribution


this
it is

is

Feo.7Tio.3tNi1.5Feo.3Tio.2JO4. In order to apply

method tetrahedral and octahedral


analysis has

necessary to

know

the

factors of the different ions

on

sites,

except for the above example.

similar

been carried out by Smart [Sm 5] in the NiFe 2-sAl8C>4 system. From susceptibility measurements on nickel-aluminate Smart deduced a g
value gNi n (tetr)
36.2.

= 3.5

for nickel ions

on

tetrahedral sites.

DOMAIN WALL RELAXATION

The movement of individual domain walls can be studied on so-called "window frames", which are made from a single crystal and whose sides
are parallel to preferred directions of the magnetization. It
create in these specimens a simple pattern of
is

possible to

domain
36.5.

walls;

an example

is

given in Fig.

Gait [Ga 3] has observed the movement

of a domain wall parallel to the surface of the crystal in the case of Fes04 and a
nickel ferrite having a composition (NiO)o-75

(FeO)o.25Fe2C>3.

A typical example of a meamagfield.

sured curve is given in Fig. 36.6, where the wall


velocity
is

plotted as a function of the

nitude of an applied magnetic

Oscillo-

scopic observation of the secondary voltage across a coil shows that this voltage remains
Fig.
36.5.

Single-crystal ferrite

constant for a long time, indicating that the


wall has a uniform velocity the mass

sample used to study motion of

and

that therefore

mw

in the equation of motion (24.9)


is

domain The broken lines indicate positions of the domain walls.


individual ferromagnetic
walls.

can be neglected. Equation (24.9)

then

(After

[Ga

3].)

176
8

INTRINSIC PROPERTIES OF SPINELS

[CH. VIII

T'201K
Nig 75 Fen-xFe*, 0,
(Kl

3cm/sec)

V- 26,150 (H- 0.075)

0.1

02

0.3

-* H
Fig. 36.6. Typical plot of actual data for

IOe)

domain wall

velocity v as

a function of applied
satisfied if the applied

field.

(After [Ga

3]).

magnetic field is reduced by a critical field below which no wall movement takes place. This critical field corresponds in

good approximation to the coercive force of the crystal. From the slope of the straight line in Fig. 36.6 a damping coefficient /? for the domain wall displacement can be determined with (24.9) and from this coefficient, after making a correction for eddy current damping (see [Wi 2]) a damping coefficient a can be determined with (24.10) for the spin motion as given by (23.10). Some results of measurements on ferrous ferrites, in which the damping is probably caused by electron relaxation, are collected in Table 36.11. Compared with the damping coefficient a, as found from the width
of the ferromagnetic resonance
line, there exists

a difference of only about

a factor two.

TABLE

36.11

THE DAMPING COEFFICIENT a OF (23.10) DETERMINED FROM DOMAIN-WALL MOTION AND FROM THE WIDTH OF THE FERROMAGNETIC RESONANCE LINE ACCORDING TO [Ga 3].
Ferrite

a
wall

Domain
Fe 3
4

Ferromagnetic resonance
0.11

0.066 0.008

(NiO)o.75(FeO)o.25Fe20 3

0.018

CHAPTER
INTRINSIC PROPERTIES OF FERRITES WITH HEXAGONAL CRYSTAL

IX

STRUCTURE
37.
37.1.

Chemical Compositions and Crystal Structures

CHEMICAL COMPOSITIONS

crystal structures

group of ferromagnetic oxides exists possessing closely related hexagonal ([We 2], [Jo 4]). Fig. 37.1 shows a diagram in which the chemical compositions of the substances to be discussed can be indicated.

The corners of the diagram represent the oxides BaO, MeO and Fe2C>3. The symbol Me represents a divalent ion from the first transition series, 1 or it may represent Zn, Mg, or a combination of for instance Li and Fe just as can occur in the spinel structure. The compounds to be described are

Fe2 3
100 AO

M=BaFe 12
(BaO 2Fe2

19

W=BaMe2 Fef6

27

80

Y = Ba2 Me2Fe12 022

Z= Ba3 Me2 Fe^ 0^

BaFe2 04.
40,

S~Me2 Fe4_08
60

100

BaO
Fig. 37.1.

MeO
Composition diagram for the ferromagnetic
ferrites.

The symbol

Me represents

a divalent ion (or a combination of divalent ions)

178

FERRITES WITH
firing at

HEXAGONAL CRYSTAL STRUCTURE

[CH. IX

produced by

a temperature above 1000 C the appropriate mixture


It is

of the oxides represented by the corners of the composition diagram.


also possible to start

of the metal ions.

from mixtures of compounds, for example carbonates The method of preparation is analogous to that for ferro-

magnetic
there
is

spinels.

On

the line connecting

BaO and

Fe2C>3 in the diagram

a point which represents the non-ferromagnetic barium ferrite BaFe204. At an equivalent position is found the point S on the line between
the oxides

and Fe203, which represents Me2Fe4C>8 with the cubic Chapter VIII). The point represents the oxide with chemical composition BaFei 2 Oi 9 = Ba0.6Fe 2 3 ([Ad 1], [We 2]), which has a hexagonal crystal structure and which is one of the ferromagnetic oxides to be dealt with in this chapter. Another important compound is represented by point Y, having the chemical formula Ba2Me2Fei2022 = 2(BaO.Me0.3Fe20a). This compound possesses a hexagonal crystal structure differing from the structure [Jo 4]. In order to establish the position of Y, the diagram also indicates the hypothetical Ba0.2Fe 2 03. Twice the
spinel crystal structure (see

MeO

simplest chemical formula unit has been chosen for the composition of the

compounds S and Y. As we

shall see later, this

has the advantage that the

from which the different hexagonal structures can be built up, contain exactly the number of ions indicated by this chemical formula. Many chemical compounds are found on the lines M-S and M-Y, ([Wi 5], [Br 1], [Jo 4, 5]). However, the elementary cells of these crystal structures can be built up in a simple way from those of S, and Y. We shall therefore deal first with the crystal structures of the latter compounds. In most cases the Ba ion can partly or completely be substituted by a Ca, Sr or Pb ion, which have approximately the same ionic radii (see Table 37.1), or by a trivalent ion, such as La 111 In the latter case
simplest crystallographic blocks,

TABLE
Ion

37.1

GOLDSCHMIDT IONIC RADII


Radius in
1.32
1.06 1.27
1.43

O"
Ca11
Sr"

Ba" Pb 11

1.32

an equivalent amount of the ferric ions become ferrous ions.


ions of Al or Ga, or by an equivalent

It is also possible

in these crystal structures to replace the trivalent ferric ion

and

tetravalent ions.

by the trivalent amount of a combination of divalent For example, 28 ferric ions in the compound re-

37]

CHEMICAL COMPOSITIONS AND CRYSTAL STRUCTURES

179

placed by 8 cobalt ions and 8 titanium ions yield a formula: BaCo nTi8 IV Fei2-2sOi9 (see [Ca 2]).
8

compound with chemical

<^Y)

37.2.

HEXAGONAL CLOSE-PACKED STRUCTURE


structure
is

The hexagonal close-packed 37.2a. The centres of the ions

represented schematically in Fig.

B lie in a horizontal plane and form equilateral

Fig. 37.2. Schematic representation

of the close-packed
struc-

hexagonal structure
interstices in

(a)

and the close-packed cubic

ture (b) of identical ions. In (a) the ions

are in the

a plane both above and below the plane

containing the ions B, thus forming the sequence vertical

ABAB etc.
to the

In (b) the ions

A and C in the layers adjacent


vertically

layer

do not

lie

above each other,


etc.

resulting in the vertical sequence

ABCABC
new

triangles.

On

this layer

can

now be

placed a

layer of identical ions,

shown in the diagram as A. These ions are also closely packed in a horizontal plane. With a hexagonal close-packed structure there exists under the layer with B ions another layer of ions whose centres lie vertically below those of the ions in the A layer. Continuing in the vertical direction we thus obtain in a hexagonal structure the sequence of layers ABABA and so on. It is
evident that this produces a uniaxial hexagonal crystal structure in which the c axis
is

perpendicular to the oxygen layers.

The cubic close-packed structure is represented in a corresponding manner in Fig. 37.26. The sequence of layers, proceeding vertically, is here ABCABCA etc., where the ions A and B have positions similar to these in Figure a, and where the ions C lie closely packed in one plane at the same distance below
the plane of the drawing as the

ions

lie

above
set

it.

This cubic close-packed

oxygen

structure occurs in the spinels)(Fig. 37.3 gives

of the spinel structure, the [111] axis being

a perspective drawing out vertically. The top and

180

FERRITES WITH

HEXAGONAL CRYSTAL STRUCTURE

[CH. IX

bottom ion
sufficient

layers are identical, also as regards their environment, so that


is

information

present for continuing the structure in the vertical

direction.
tely

The distance between two successive oxygen layers is approxima2.30 A, and varies only in the third decimal place for the various metal
a cross-section through a mirror plane containing
of threefold symmetry. This
three times.

ions. Fig. 37.36 gives

the [111] axis.

The

vertical lines are axes

means

that

all

ions not lying

on one of these axes occur

S=

Me^Fe4

Fig. 37.3a

Perspective

re-

presentation
structure
axis

of the spinel
the
[111]

with

vertical.

The hatched

ions

and black circles represent on octahedral and tetrahedral sites respectively.

The ferromagnetic oxides to be discussed all consist of closely packed ions. The structures are built up from sections having alternately a cubic and a hexagonal structure. It is evident that in such a case the crystal
oxygen
structure will again have hexagonal symmetry. In certain layers in these

substances

mately of the same


of a

some oxygen ions are replaced by barium ions, which are approxisize as oxygen ions (see Table 37.1). For a complete desis

cription of the crystal structures the reader

referred to "Crystal Structures

New Group of Hexagonal Ferromagnetic Compounds" by Braun [Br 6].


THE MAGNETOPLUMBITE STRUCTURE
[Ad

37.3.

M
crystal

The compound M, with a chemical composition BaFei20i9, has a


structure which, according to Adelskold
1], is

equal to that of the min-

37]

CHEMICAL COMPOSITIONS AND CRYSTAL STRUCTURES

181

S=

Me 2

E
Fe^ 0$

4$+2f

*
Fe ,Me

^2

^\

Fig. 37.3b. Cross-section

through a mirror plane of the spinel structure with the [111]

axis vertical,

drawn

for the ideal value of the parameter u.

The

vertical lines are axes

of threefold symmetry. All ions not lying on one of these axes occur three times, as shown schematically by broken circles in the top layers. The small white and black circles represent respectively ions on octahedral and tetrahedral sites. The arrows indicate the
relative orientation

of the magnetic moments of the ions on these

sites.

182

FERRITES WITH

HEXAGONAL CRYSTAL STRUCTURE

[CH. IX

M=

BaFe l2

19

4$

+2$\

^
Fig. 37.4. Cross-section

^\
M,
with the c axis vertical.

of the magnetoplumbite structure

The arrows

indicate the spin orientations.

The drawn

vertical lines are axes

of three-

fold symmetry.

barium and are denoted by m. This structure consists of the same S blocks as in Fig. 37.3b separated by R blocks containing barium. The asterisk indicates a rotation of a-Hock by 180 about the c axis.
are mirror planes,

cross indicates a centre of symmetry. All layers containing

37]

CHEMICAL COMPOSITIONS AND CRYSTAL STRUCTURES


magnetoplumbite, the composition of which
is

183

eral

approximately PbFe7.5
of 10 oxygen

Mn3.5Alo.5Tio.5O19.
layers.

The hexagonal elementary

cell consists
is

The length of the c


is

axis corresponding to this

23.2A and that of

the a axis

5.88 A.

A schematic representation of the M structure is given


cell

in Fig. 37.4. In

an elementary

each layer contains four large ions. There

are in four successive layers always four

oxygen

ions, but each fifth layer

contains three oxygen ions and one barium ion.


structure can be built

The magnetoplumbite
(Fig. 37.4),

up from

spinel blocks of two

oxygen layers

being blocks

S and
this

S*, which are connected by a block

R (for a perspective
T

drawing of

block see Fig. 37.5a) containing the barium ion. Blocks

Fig. 37.5. Perspective drawings of the

block occurring in the

M structure and the T

block occurring in the

Y structure.

The

latter

block contains two adjacent barium layers.

R* and S*

are obtained from blocks

R and S, respectively, by rotation over

barium is hexagonally packed oxygen layers at each side. The four oxygen layers with respect to two between those containing barium are cubically packed. There is an overlap of cubically and hexagonally packed sections in the structure. The basal plane containing the barium ion is a mirror plane of the R block, and consequently the blocks preceding and succeeding the R block (S and S*)
180 around the c axis.

The

layer containing

must be rotated over 180 with respect to each


reason

other. This is also the

why

the elementary cell of the

structure contains 10

and not 5
is

oxygen

layers.

In general

it

can be said that when one

block

passed

in a structure the following blocks must be rotated over 180 around the

184

FERRITES WITH

HEXAGONAL CRYSTAL STRUCTURE

[CH. IX

c axis. Only after a second


again.

R block is passed is the original situation found


RSR*S*, and

The

crystallographic structure can thus be described as

the elementary cell contains a number of ions corresponding to 2(BaFei20i 9 ).

The

unit S, then, contains

to say that in the

oxygen layers [Br

6],

would be possible of two more then obtained would not contain the but the block
It

two molecules MeFe204.

structure the spinel block consists

metal and oxygen ions in the ratio 3

4.

For the ferric ions there are three different kinds of interstitial sites present. Along with octahedral and tetrahedral sites there exists a new type of interstitial site which is not found with spinels and which is surrounded by five oxygen ions constituting a triagonal bipyramid. These sites occur in the same layer as the barium ion, and they can be compared with tetrahedral sites. In the hexagonal structure two tetrahedral sites are adjacent to each other, and for these two only one metal ion is available. This metal ion now occupies a position halfway between them, amidst the three oxygen ions.
According to the ideal parameters the available space
also the case with the
is

extremely small.

This means that the three oxygen ions are certainly displaced outwards, as
it is

more spacious tetrahedral

sites in sites

the spinel lattice are occupied by

(see 31.2). In the


ferric

R block two

adjacent octahedral

ions. There are now, however, two ions available, so that in this
is

no abnormal environment. The fact that it is not the other two tetrahedral sites occupied and one ion available for the two octahedral sites together, is because an octahedral environment is energetically more favourable than a tetrahedral one (higher coordination number, compare with the situation in spinels). Moreover two ions in the octahedral sites lie further apart than they would do if they had occupied the two tetrahedral sites.
case there

way round,

i.e.

37.4.

THE CRYSTAL STRUCTURE OF THE COMPOUND Y =


by Braun
is

Ba 2 Me 2 Fei20 2 *

The
37.6.

crystal structure, as determined

[Bi 6], of the

compound Y,
consists

chemical composition Ba2Me2Fei2022,

represented schematically in Fig.

The

smallest elementary cell with hexagonal

symmetry
If,

of

18 oxygen layers, the length of the c axis being 43.56A.

however, the

upright edges of the parallelepiped are not taken vertically but along the

oblique lines indicated in the figure,


cell,

it is

possible to find

an elementary
cell

having rhombohedral symmetry, with a repeat distance extending


six

through only

oxygen

layers.

In the hexagonal elementary

each layer

again contains four large ions. There are four successive layers of four oxygen
ions, followed

by two layers each containing three oxygen ions and one barium ion. The Y structure can be built up from spinel blocks of two oxygen

37]

CHEMICAL COMPOSITIONS AND CRYSTAL STRUCTURES

185

K- Ba2 Me^Fe12022

4-e*-

+2*-

4e*+2e- +2-

8-e+2^- +*

O
^)

*
fia-

"

Fig. 37.6.

Cross-section of the

Y structure

with the c axis vertical. The arrows indicate the spin orientations,
all

perpendicular to the c axis.

which are here The drawn

vertical lines are axes


try.

of threefold symme-

-^
The
structure
is is

^\
composed of
alternating

A
T

cross indicates a centre of symmetry.


blocks.

and

The rhombohedral

repeat distance

indicated.

186

FERRITES WITH

HEXAGONAL CRYSTAL STRUCTURE

[CH. IX

layers: the blocks

in Fig. 37.3b,

which are connected by a block


37.56.

in

which there are now, one above the other, two layers with barium ions;
for a perspective drawing of the

T block see Fig.

The layers containing

barium are hexagonally packed with respect to their adjacent oxygen layers. These barium ions are somewhat larger than the oxygen ions (see Table 37.1). Therefore the distance between the layers with barium ions is greater than between the oxygen layers which contain no barium ions; the distances are 2.40 and 2.32 A respectively. The projection of the distance between the centres of the barium ions on to the c axis is 2.90 A, from which it follows that the centres of the barium ions
lie

at

a distance of 0.25

A out of the

plane of the nearest oxygen layer. The distance, too, between a layer with a

barium ion and the first following oxygen layer is slightly increased, namely up toj 2.35 A. In the Y structure, only tetrahedral and octahedral sites are occupied by the metal ions. Per formula unit Ba2Me2Fei2<I)22, four ions occupy tetrahedral sites and ten octahedral sites. The T block might be regarded as a combination of the innermost layers of two R blocks from Fig.

two octahedral ions lying one above the other a second pair is added from the adjacent barium layer, of which two of the octahedral ions coincide. In this way one obtains three octahedral ions one above the other. The two sites surrounded by five anions are no longer occupied either, because one of the tops of the adjacent tetrahedrons is now occupied by a Ba ion. The metal ion is pushed towards the centre of the other oxygen
37.5a.

To

the

The T block does not contain a mirror plane, so that now the preceding and succeeding S blocks are not rotated with respect to each other. The crystallographic build-up of the Y structure is thus represented by TS. It may be noted that the chemical composition of the T block is given by the hypothetical Ba0.2Fe 2 C>3 indicated in Fig. 37.1.
tetrahedron.
37.5.

MIXED COMPOUNDS

and Y, there also occur Apart from the three structures discussed, S, on the sides M-Y and M-S of the triangle formed by these three points in Fig. 37.1 a number of crystal structures whose elementary cells can be built

up from those of the compounds at the corners. The structure can again be given by the stacking of R, S and T blocks. For all these compounds the a axes are the same (= 5.88 A) and the c axes are approximately additive. The compounds listed in Table 37.11 have been prepared and identified by X-ray analysis. It is very remarkable that regularities of this order can occur in the sequence of R, S and T blocks. The most important of these and Z. By way of illustration the compounds are denoted by the letters and Z cross-sections through mirror planes containing the c axis of

37]

CHEMICAL COMPOSITIONS AND CRYSTAL STRUCTURES

187

W= flbMef Fe K

27

^
Fig. 37.7. Cross-section of the

^\

^\

^
The arrows
indicate

W structure with the c axis


vertical lines are axes

vertical.

the spin orientations.

The drawn

of threefold symmetry.

cross

indicates a centre of symmetry.

by 180 about the c axis. The structure can be thought to be the sum of the S and the structures (Figs. 37.3b and 37.4 respectively).

The

asterisk indicates a rotation of a block

188

FERRITES WITH

HEXAGONAL CRYSTAL STRUCTURE


41

[CH. IX

Z = Ba3 Me2 Fe2

4.

i^e & e o
*Ol

G e o
'4
;

lie

4-i

+2

4$+2$ + 2J

G e iQ eL O ~B U &
a G e% e e
vvi

4$

+2

<f>+39 + 2$

/n

^
^\ ^\
lines

jo!

o'

_Q e
Z
The drawn
vertical

%
^

on
*S\

I*
Fig. 37.8. Cross-section of the

structure with the c axis vertical.

The arrows

indicate

the spin orientations.

are axes of threefold symmetry.

cross indicates a centre of symmetry.

The

asterisk indicates a rotation

of a block by

180 about the c axis.


structure (Figs. 37.4

The

structure

can be thought to be the sum of the

M and the Y

and 37.6

respectively).

37]

CHEMICAL COMPOSITIONS AND CRYSTAL STRUCTURES


TABLE
37.11

189

FERROMAGNETIC OXIDES WITH HEXAGONAL CRYSTAL STRUCTURES

Number of
Chemical
composition

Symbol

Crystallographic

layers per

c axis *) in

Molecular
weight

X-ray**)
density

build-up

hexagonal
elementary cell

g/cm 8

BaFeiaOi9
Me2Fe.s08

M
S

RSR*S* S
(TS) 3

10

23.2

1112

5.28

232
1408 1575

5.24
5.39
5.31

Baa Me2Fei20a2

3x6
14

3x14.5
32.8

BaMeaFeieOa? Ba2Me2Fe28046 BaaMe2Fe2404i Ba4Me2Fe360eo

MS(W) RS2R*S2*
(RSR*S 2 *)3 MY(Z) RSTSR*S*T*S* RSR*S*TS* 2Y
2

MS

3x12
22
16

3x28.0
52.3
38.1

2686 2520 3622

5.29
5.33
5.31

are given in Figs. 37.7 and 37.8 respectively. For the metal ions

Me

about

the same variety of divalent ions can be taken as for the ferrites with spinel
structure.

Which these are will be indicated by short notation, as for example: C02Z, Ni1.5Zno.5W, Zn2Y, etc. The molecular weights and X-ray densities of the most important of these compounds are given in Table 37.111.

TABLE

37.111

X-RAY DENSITY dx AND MOLECULAR WEIGHT Af OF SOME OXIDES WITH HEXAGONAL CRYSTAL STRUCTURE.

Me

W = BaMe Fei 02 dx M g/cm


2

Z=
dx

Ba 3 Me 2 Fe240

Y=
dx

BazMe2Fei2022

g/cm 3
5.20
5.33 5.33

M
2457 2518

g/cm 3
5.14
5.38

M
1346 1406
1408

Mg Mn
Fe

5.10
5.31 5.31 5.31

1512
1573 1575

2520 2522 2526 2536 2539

5.39 5.40 5.40


5.45

Co
Ni

1577

5.35 5.35 5.37

1410 1414

5.32
5.36
5.37

1580 1590
1594

Cu
Zn
37.6.

1424
1428

5.37

5.46

IDENTIFICATION OF THE
by

HEXAGONAL OXIDES
mixtures of oxides for a certain

The

materials are prepared

firing specific

time at a temperature ranging between 1200 and 1400 C, so that a sintered ceramic product is obtained. Their crystal structures are determined by X-ray
*)

Independent of the type of

**) In the case


37.111.

where

Me ions in the approximation given here. Me represents a ferrous ion. For the other compositions

see Table

190
analysis.

FERRITES WITH

HEXAGONAL CRYSTAL STRUCTURE

[CH. IX

However, since the compounds

M and W, for example,


M,

have a

closely related structure, small quantities of

which can occur as by-

product in incomplete chemical reaction, are not easy to distinguish in the

X-ray powder diagrams from


following way.

W.

This difficulty can be circumvented in the

Many
The

W compounds,
field

like

M compounds, are ferromagnetic with a prewill therefore orient

ferred direction of magnetization parallel to the hexagonal axis (see 39).


crystallites in

a powdered material
of force.

themselves in a

magnetic

such that the hexagonal axis of each

crystallite will

be more or
glass plate,

less parallel to the lines

A few drops of a suspension of a powdered


now
applied

specimen in a solution of a binder are

on a small

and a strong magnetic


the crystallites are
left

field is

applied perpendicularly to the glass plate.


off,

When the binder is left to dry and afterwards the magnetic field switched
of the
glass.

with their hexagonal axes perpendicular to the surface


the X-ray reflections

In the X-ray diffraction diagram of such specimens, recorded


*),

with a diffractometer

from the planes perpendicular


whereas the other

to the hexagonal axis [ool],


reflections

appear

much

intensified,

have almost vanished. This greatly simplifies the diagram; see Fig. 37.9 (page 199). These simplified diagrams are characteristically different
this makes it easy to distinguish a small quantity of one of compounds from a large quantity of the other. Moreover, the powder diagrams of the other hexagonal compounds, for example Y and Z, also resemble those of and W, so that with powder diagrams alone it is not easy to ascertain in which composition of the oxide mixtures these compounds occur in a pure state. In these cases, too, the method of alignment in a magnetic field is employed, and here again one finds a characteristic simplification of the X-ray diagrams. It appears from these diagrams of

for

M and W, and

these

aligned specimens (Fig. 37.10 [page 200]) that in most

specimens the

hexagonal axis
case with

(c axis) is parallel to the


is

magnetic

field; thus,

the spontaneous

magnetization of these compounds

also parallel to the c axis.

As

is

the

M and with many representative oxides of the W group,


With
all

this axis is a

preferred direction.

Y specimens,
means

on the other hand, the hexagonal

axis lies perpendicular to the magnetic lines of force, the directions of the

other axes being arbitrary; this

that the spontaneous magnetization


axis.

of the

Y compounds lies in a plane at right angles to the c

The

result

is

that after a magnetic treatment as described above, only

hko

reflections

appear in the X-ray diagram.

*)

In diffraction experiments with a diffractometer


are used. See [Pa
1].

it is

precisely such flat specimens that

38]

SATURATION MAGNETIZATION

191

38. Saturation Magnetization

38.1.

THE PREDOMINANT SUPEREXCHANGE INTERACTIONS IN THE VARIOUS STRUCTURES


relative orientation of the

It is

assumed that the

magnetic moments of the

ions in the

with spinel structure. In each

S blocks of the hexagonal ferrites is the same as in the ferrites S block, then, there are four octahedral ions
moments;
this

and two
is

tetrahedral ions with oppositely oriented magnetic

by arrows in Figs 37.36, 37.4, 37.6, 37.7 and 37.8. To indicate the predominant superexchange interactions in the interlying blocks R and
indicated

T, these blocks are again reproduced schematically in Fig. 38.1, but now taking into account the correct parameters for the ions in the environment

of the

layers containing barium. In the

block (occurring for example in

the half elementary cell of the

structure) the direction of the


is

magis

neticmoment of the ion


parallel to the c axis in

in the layer containing barium


*).

chosen,

an upward direction

The

starting premise

Me

Y 6

^a
Fig. 38.1.

^x

^\

^\

^a^x^^^3k
moments with
respect to the crystal lattice
is

the

Schematic representation of the predominant superexchange interactions in and the Y structures. Each interaction is indicated by two connected heavy lines

with a dot included in the angle between them.


dealt with

*)

The

direction of the magnetic

in 39.

We are only concerned with the

mutual direction of the magnetic moments

of the ions.

192

FERRITES WITH

HEXAGONAL CRYSTAL STRUCTURE


and
assumed that

[CH. IX

again that the superexchange interactions between the magnetic ions take
place via the intermediate oxygen ions,
it is

this is

again a

negative exchange interaction (number of

d electrons
/

> =
lie

5) see 8.1.

As

for

the spinels (see 32.1) Gorter estimates the magnitude of the exchange
interactions

from the magnitude of the distances


(see

Me-O-Me and

the

angles

<f>

MeOMe
is

[We

2]).

This leads to the assumption that the


3,

magnetic moments of the metal ions 2 and


interaction
140),

which
is

closest to the layer

containing barium, are directed downwards. The reason is that the l-oxygen-2
large because the appertaining angle
<f>

large (approximately

whereas the other interaction, the 2-oxygen-3 interaction, which

attempts to align the magnetic


1

moments of these
is

ions antiparallel,

is

smaller

because the appertaining angle


over, the distances

unfavourable (approximately 80). More-

basal plane

from the ion to the three surrounding oxygen ions in the and this promotes a high l-oxygen-2 interaction. The coupling with the S block is brought about by the interaction between the magnetic moments of the octahedral ions 3 and 4. Interaction between octahedral ions also occurs in the spinel structure (its magnitude is
is

very small (1.3 A)

indicated

by the quantity

j8,

see 33), but there

it is

relatively small

owing

to the unfavourable angle (90).

The

distances here to the oxygen ions are

the same, but because of the different oxygen stacking in the

block, the

most important interaction between the R and the S blocks. The interaction between the ions 1 and 4 opposes the drawn spin configuration. This interaction will be small because of the considerable distance between ion 1 and the oxygen ion vertically above
angle
is

now

larger (130). This is the

it

(2.3 A).
it

(450 C)

From the fact that the Curie point of the compound is high may be deduced that the octahedral-octahedral interaction will

increase sharply with increasing angle.

In the case of the

block (occurring, for instance, in the elementary

cell

of the

Y structure,
lies

(see Fig. 37.6) the starting point

[Go

7] is the octahedral

ion 2 which

between the two layers containing barium.


ion
is

If the

magnetic

moment of
right, the
left.

this

oriented perpendicularly to the c axis towards the


tetrahedral ion
1 will

magnetic

moment of the

be oriented to the

In the

block the l-oxygen-3 interaction was equal to the l-oxygen-2

interaction. This is not the case

now
is

because the ion

is

displaced in such a

way

that the angle l-oxygen-2

larger than the angle l-oxygen-3.

More-

over, according to

Braun [Br

6],

the ion 3

is

shifted upwards, so that the

distance

from

this

ion to the oxygen ions in the layer containing barium


this reduces the l-oxygen-3 inter-

has become relatively large (2.33 A), and


action

(now comparable

to the l-oxygen-4 interaction in the


is

block).

The l-oxygen-4

interaction

now

important and

is

of the tetrahedral-

38]

SATURATION MAGNETIZATION
lattice.

193

octahedral type occurring in the spinel

The magnetic moment of the

ion 3 is now oriented in accordance with the 3-oxygen-4 interaction, which was also important in the R structure, and in this case would probably be

even stronger since the ion 3 is closer to the oxygen ion between ions 3 and 4. As a result, the moment of ion 3 is now antiparallel to that of ion 2. Consequently the
ing to the

T block contains as many ions (4) pointing to the right as point-

and therefore, if all these ions are of the same kind, there will be no net resultant moment. The T block may then be called "antiferrimagleft,

netic". It is

found experimentally, in agreement with the above, that the saturation magnetization of the Y crystals is relatively low, being about

survey of the relative directions of the half that of ferrimagnetic spinels. magnetic moments of the metal ions in the various blocks is given in Table
38.1.

TABLE

38.1

NUMBER OF METAL IONS ON THE VARIOUS SITES IN THE BLOCKS S. S AND T. THE RELATIVE DIRECTION OF THEIR MAGNETIC MOMENTS IS INDICATED BY ARROWS.
Tetrahedral ions

Octahedral ions

Ions with
fivefold

Block

(surrounded by 4

(surrounded by 6

oxygen

ions)

oxygen ions)
3

coordination

R
S

$
($

|)

* >i

,38.2.

SATURATION MAGNETIZATION OF COMPOUNDS WITH

M STRUC-

TURE
BaFei 2 Oi9 is equal to the sum of the moments of the seven octahedral ions and the ion in the layer containing barium, reduced by the moments of two octahedral and two

The

resultant magnetic

moment per formula

unit

tetrahedral ions, which are oppositely oriented to them; this

is

schematically
all

indicated

by

arrows in Fig. 37.4. In the case of


equal to
(1

BaFe^Oio,

magnetic

ions have a magnetic moment


tion per formula unit
tons.
is

of 5 Bohr magnetons, so that the magnetiza-

+ 7 - 2 - 2) X 5 = 20
is

Bohr magne1].

Measurements on

polycrystalline BaFei 2 Oi 9 at liquid

hydrogen tem-

perature and in fields

up to 26,000

oersteds result in exactly this value [St

In Fig. 38.2 the saturation magnetization perature for BaFei 2 Oi9 (corresponding to 8

given as a function of temin the figure).

The

satura-

194
too

FERRITES WITH

HEXAGONAL CRYSTAL STRUCTURE

[CH. IX

300

400

500

Fig. 38.2. Saturation magnetization as a function of temperature for a number of compounds with the magnetoplumbite structure M.

tion magnetization decreases approximately linearly with temperature in

a wide temperature range. At

T=

20 C one finds a

= 72
is

gauss

cm3 /g,

corresponding to
information

4wMs =

4775 gauss. The Curie point

450 C. Some

is available on how the saturation magnetization is affected by the substitution of other ions in the structure [Ca 2]. The curves in

where some of the by a combination of Co 11 and TiIV ions according to the formula BaCo 8 n Ti 6 IV Fei2-2 Oi 9 The measurements were carried out on polycrystalline specimens at the relatively low field strength of 6600 oersteds. It can be seen that both the Curie point and the saturation magnetization at low temperature decrease rapidly with increasing S. From measurements at liquid hydrogen temperature and in magnetic fields up to 25,000
Fig. 38.2 give the saturation magnetization for the case
ferric ions are replaced
.

oersteds a saturation magnetization has been found of approximately 14

and 12 Bohr magnetons per formula unit for values of


1.4 respectively.

8 equal to 1.2

and

'

38.3.

SATURATION MAGNETIZATION OF COMPOUNDS WITH STRUCTURE


cr

In Fig. 38.3 the saturation magnetization

per

and mixed

W compounds

gram

for a

number of simple

is

plotted as a function of temperature. In the

38]

SATURATION MAGNETIZATION

195

case of these

W compounds, too, almost straight


from the

lines are

found over a large

temperature range, as had already been found for the


with

compound BaFei20i9

structure. It appears

figure that the substitution of zinc

gives the highest saturation magnetization at low temperature; evidently in this case, just as with spinels, the zinc ion occupies tetrahedral sites

and

consequently lowers the average

moment

of the ions on these

sites.
ct 2 o,

Table

38.11 gives the saturation magnetization at

room

temperature,

and the

Curie points Tc of a number of

W compounds.

690

(C)

Fig. 38.3. Saturation magnetization as a function of temperature for a

number of compounds with


line

structure,

measured on polycrystal-

specimens at a

field strength

of 6600 oersteds.

TABLE
SATURATION MAGNETIZATIONS AT
20 C
<T20

38.11

AND CURIE POINTS Tc OF Ml&W COMPOUNDS.


4 it

Me2

Tc
C
415

gauss

cm3 /g

gauss

Mn2
Fe 2 n

59 78 52
,

3900

5220
3450

455

NiFe" ZnFe"

520

73 68

4800
4550

430
450

Nio.5Zno.5Fe 11

By

extrapolation to the absolute zero point of the a versus

T curves

in

K can be estimated. This value is Fig. 38.3 an approximate value of <ro at given in Table 38.111, together with the derived number of Bohr magnetons structure is built (b)W per molecule Me 2W. From the way in which the

up from double

spinel blocks

S and blocks R,

it

follows that the saturation

196

FERRITES WITH

HEXAGONAL CRYSTAL STRUCTURE

[CH. IX

magnetization of a

W compound should be simply related to the saturation


[(b)w,] theor

magnetization of BaFei20i9 (denoted by (b)m) and the corresponding spinel compound Me2S (denoted by (b)s); that is:

= (b)m + 2(b)s

(38.1)

compounds shown column of Table 38.111 are calculated from (38.1) assuming that (jib)m = 20 and that the values from Table 32.11 are applicable for (jib)sThe measured values are found to be in reasonably good agreement with the expected values. Deviations can be due to the fact that the Me ions also occupy sites in the R block, and they are certainly also partly due to the small fields with which the measurement was carried out, viz. about 6600 oersteds. For the compound Fe2W, the values are given in the table hold
values of the saturation magnetizations of the
in the last for a measuring field of 25.000 oersteds.

The

TABLE

38.111

SATURATION MAGNETIZATION ff OF Me2 W COMPOUNDS AT THE ABSOLUTE ZERO POINT, AND A COMPARISON OF THESE VALUES WITH THOSE OF THE COMPOUNDS M AND S ACCORDING TO (38.1), ASSUMING (ns)M = 20.

Me 2W
Me2
Mns;

CT0

[(fl)

w]theor =
s

gauss

cm3 /g

experi-

from
Table 32.11
4.6

mentally
27.4

20+2( B)
29.2

97 98
79
108

Fez 11

27.4
22.3

4.0
3.2 5.8

28
26.4
31.6

NiFe 11 ZnFe 11
Nio.5Zno.5Fe 11

30.7 29.5

104

4.6

29.2

38.4.

SATURATION MAGNETIZATION OF COMPOUNDS WITH Y STRUCTURE

Fig. 38.4 gives the saturation magnetization of a number of simple Y compounds as a function of temperature. In Table 38.IV a survey is given of the saturation magnetizations at room temperature and the Curie points of these Y compounds. It was seen in 38. 1 that the T block contains an equal number of oppositely oriented magnetic moments. If, then, we were to

assume, as in the case of the

W structure in

38.3, that the

Me

ions are

contained only in the spinel block, the magnetic


this

from column of Table 38. V and compared with the measured values, as found from the a versus T curves by extrapolation to T = 0. In this case the measured values
result

moment would

block alone. The corresponding values of ns are given in the

last

38]

SATURATION MAGNETIZATION
TABLE
38.IV

197

SATURATION MAGNETIZATIONS AT COMPOUNDS.

20 C

AND THE CURIE


4wAf,
gauss

POINTS OF SOME SIMPLE Me,Y

Me2Y Me

"20

TC
C
290
340 390
130

gauss

cm3 /g

Mn
Co
Ni

31

2100

34

2300
1600

24 42
23

Zn

2850
1500

Mg

280

TABLE

38.V

THE SATURATION MAGNETIZATION <7 OF COMPOUNDS McfcY AT THE ABSOLUTE ZERO. THE NUMBER OF BOHR MAGNETONS (nfl)Y PER UNIT CELL IS COMPARED WITH THE VALUE (nB)S OF THE CORRESPONDING FERRITES WITH SPINEL STRUCTURE.

MeaY

ffO

Me

gauss

cm3 /g

(b)y

2(b) s

from Table
9.2
7.4 4.6
2.6

32.11

Mn
Co
Ni

42
39 25 28

10.6
9.8
6.3
7.1

Cu

Mg
Zn

29 72

6.9

2.2
(20)

18.4

(gauss cmtyg)

**TpC)
Fig. 38.4. Saturation

magnetization as a function of temperature for a

number of compounds with

structure,

measured on polycrystalline

specimens at a fieldstrength of 11000 oersteds.

198

FERRITES WITH

HEXAGONAL CRYSTAL STRUCTURE

[CH. IX

are seen to be

somewhat higher than those of the

spinel block, contrary to

what

is

found in the case of W. This gives no cause to doubt the correctness

T block as postulated in 38.1, since any would result in much greater deviations in the number of Bohr magnetons. For example, if in Fig. 38.16 the spin moments of the ions 3 in the Y structure were to be reversed, this would give a resultant moment corresponding to Kb = 4 for each T block, which would have to be added to that of the S block, and therefore <ro would increase by a factor of three. It must rather be assumed that the divalent Me ions are also contained in the T block. If the cobalt or nickel ions, which have a moment
of the spin configuration of the
deviation from this

lower than that of the


Fig. 38.1Z>, the result

ferric ions, also


is

occupy the sites 3 in the T block of an increase in the magnetization. To explain the
still

moment

of the

C02Y compound,
then of the two

assuming the
ions 1.2 ions

moment

of the cobalt
sites

ion to be 3.7
in Fig. 38.16.

/*,

Co

For the

nickel ferrite this figure

must occupy the would be only 0.3.

The case of the Zn2Y compound is particularly interesting, because one must assume that the zinc ions in the Y structure too must occupy tetrahedral sites, the moments of which are all parallel. It is evident that the zinc
ions cannot
all

be contained in the spinel block, because otherwise the block

would become antiferromagnetic or paramagnetic. The lowering of the resultant moment in spinels with high Zn content is caused by the formation
of angles between the moments of the octahedral ions (see 32.1). This is due to the negative exchange interaction between the moments of these ions.

The measured value of the saturation magnetization suggests that this angle formation, without which hb would be equal to 20, is less pronounced in the Y structure. This is clear for the following reasons. The moments of the octahedral ions 2 and 3 in Fig. 38.16 are already antiparallel, so that the interaction 2-3 favours this orientation. The same holds for ions 3 and 4. Moreover, since each ion 3 interacts with six ions 4, and since the 3-4 interaction
is

strong, this will have the effect of favouring the parallel orientation
all

of the moments of

ions

4.

A further result of this

is

that the angle forwill

mation between the moments of the octahedral ions in the S block


opposed.

be

38.5.

SATURATION MAGNETIZATION OF COMPOUNDS WITH Z STRUCTURE


is

In Fig. 38.5 the saturation magnetization


ture for polycrystalline specimens of

plotted as a function of temperagives their Curie

Me2Z. Table 38.VI


at

points

and the saturation magnetization

20 C.

37]

C11HMICAL COMPOSITIONS AFD CRYSTAL STRUCTURES


s
',

199

W&~
m
ft

"V"'i'

^
U
o

l-*l

tn

S 1

.1

"t:

o
'

1
S

g ^~*

200

FERRITES WITH

HEXAGONAL CRYSTAL STRUCTURE

[CH. IX

*-

N >
T3

as

P.

c til

H O
DO
cd

M
'
u,

en

""*

& o

r>

"5

38]

SATURATION MAGNETIZATION
80

201

-s

Me-Zn

Me2 Z

eo
(gauss cm /o)

Cu
40
f

^""""N^"

20

k ^ \\
-100

n -273 -200

WO

200

300

^\
400

500

a function of temperature for measured on polycrystalline specimens at a fieldstrength of 11000 oersteds for C02Z and Zn2Z and of 18000 oersteds for CuaZ.
Fig. 38.5. Saturation magnetization as

compounds with

structure,

TABLE
Me2Z Me
Co Cu Zn
Since the
"20

38.VI

THE CURIE POINT AND THE MAGNETIZATION OF SOME COMPOUNDS Me2Z AT T = 20 C.


*
B0

Tc
C
410 440
360

gauss

cm3 /g

50

3350 3100 3900

46
58

structure

position of the structures

can be considered crystallographically as a superand Y, the experimentally found values for the

saturation magnetization per unit

cell

of substances with

structure

is

compared in Table 38.VII with the

sum of those found


The value hb
38. VI

for the

M structure
taken for

and the corresponding

structure.

20

is

TABLE

THE SATURATION MAGNETIZATION o OF COMPOUNDS Me2Z AT THE ABSOLUTE ZERO POINT. THE NUMBER OF BOHR MAGNETONS Olfi)Z PER UNIT CELL IS COMPARED WITH THE SUM OF THESE OF THE M COMPOUND, <bb)M - 20. AND THE CORRESPONDING Y COMPOUND, 38.V. OlB>Y. THE LATTER VALUES HAVE BEEN TAKEN FROM TABLE

Me 2 Z Me
Co
Ni

CO

gauss

cm3 /g

("b)z experimentally
31.2 24.6

[(njOzltheor

20

(hb) y

69 54 60
55

29.8
26.1 27.1

Cu

27.2

Mg

24

26.9

202

FERRITES WITH
the values for

HEXAGONAL CRYSTAL STRUCTURE


also occupying sites in the

[CH. EX

M, and

are obtained from Table 38.5. Deviations can

occur owing to the

Me ions

R blocks

of the

structure, as in the case of the

structure.

39. Crystal Anisotropy


39.1.

BINDING OF THE MAGNETIZATION TO THE

c AXIS
(11.6),

The

crystal anisotropy of

hexagonal crystals can be described with

Ki and Ki determine the direction of the magnetization as indicated in Fig. 11.2. The sign of the anisotropy can easily be determined by the method described in 37.6, that is by aligning powdered particles of the compound in a magnetic field and then determining their orientation by X-ray diffraction. The magnitude of the crystal anisotropy energy can be found by measuring the magnetization of a single crystal as a function of the field in both the direction of the hexagonal axis and at right-angles thereto. Results of measurements on BaFei20i 9 C02Y and Co 2Z are given in Figs. 39.1, 39.2 and 39.3 respectively. At room temwhere the values of the
coefficients
,

6000

r
BaFe 12 0js
20.4.kJ

4 T %77AK

4nM
(gauss)

4000

290.7K

/
to 15

2000

20

25

30

H
a function of an applied
field

(>0

0e)

Fig. 39.1. Magnetization curves for a single crystal of

BaFeiaOig as

perpendicular to the c axis at different

temperatures, after [Stl].

perature the

field parallel to

tively small

compound BaFeiaOig can be saturated with a relatively small the c axis, and the compounds Co 2 Y and C02Z with a relafield perpendicular to the c axis. The magnetization curves in
from which
at

the difficult direction of magnetization are almost straight lines,


it

would follow that

room temperature

all

higher order anisotropy con-

39]

CRYSTAL ANISOTROPY

203

(gauss)
IS00

Co2 Y

T=77K_
tooo

"7^215'K
soo

,s^

5000

tOftOO

1SJ00O

20000

25JD00

H(0)
Fig. 39.2. Magnetization curves for a single crystal

of C02Y

as a function of

an applied

field

along the c axis at different

temperatures, after [Ca2]

stents are small

in the difficult direction will differ


is

compared to K\. As stated in 26.1, the magnetization curve from a straight line if K% ^ 0. This case

found below room temperature for ferrites containing cobalt [Ca 2]. Anisotropy constants of hexagonal oxides have also been measured by

the torsion

pendulum method described in

26.3.

From

the description of

_l_c
3 1

^~ +

3000

(gauss)

2000

/
/
flic

Co2

WOO

Fig. 39.3.

Magnetization curves of a

/
/
10 75

single crystal of

C02Z

as a function of

an applied
perature.

field

both parallel and per-

pendicular to the c axis at

room tem-

20

(I0

3 0e)

204
the

FERRITES WITH

HEXAGONAL CRYSTAL STRUCTURE


is

[CH. IX

method

it

follows that where the c axis

a preferred direction of mag-

netization the quantity

K from (11.6)

will

of a preferred plane the combination K\

be measured, whereas in the case 2Kz is measured. Measurements

have been carried out on


crystals

single crystals

and on specimens

consisting of

whose

c axes were, to a fairly high degree, in parallel alignment

(for the preparation of these specimens see 44). Table 39.1 gives values

anisotropy

found at room temperature for the anisotropy constants together with the field strength Hg defined by (11.7). For BaFei20ig the value
of K\ was also determined by ferromagnetic resonance measurements

[Sm

2],

the results being the

same

as found

by

direct (static)

magnetic

measurement.

TABLE
ANOSOTROPY CONSTANTS
JTi
t
,

39.1

OR K + 2K2 SATURATION MAGNETIZATION Ms AND


Ki
Ki +2*2
106

ANISO-

Compound

Symbol

10

Ms
gauss

Hi
oersted

erg/cm 3
*)

erg/cm 3

*)

BaFei 2 Oi9 [We BaFei 8 2 7 [We

1]

M
Fe 2

+3.3

380
314 380 380

17,000 19,000

1]

W
W

+ 3.0
+2.4 +2.1

BaZnFei 7 Oa7
BaZm.5Fe17.5O27

FeZnW
Feo.5Zn1.5W

12,500 11,100
10,200 12,700

BaMnFeie027 BaNi 2 Fei6027


BaNio.5ZnFei6.5O27
BaCoo.75Zno.75Fei6.5O27

MnZnW
Ni 2
Feo.5Nio.5ZnW
Feo.5Coo.75Zno.75W

+ 1.9
+2.1

370 330
350

+ 1.6
0.4 0.6 0.9 1.0 0.9 2.6 1.8

9,100 2,200
10,000 14,000

360
119

BaaMgaFeiaOaa
Ba2Ni2Fei2022

Mg2Y Ni 2 Y
Zn 2Y
Feo.5Zm.5Y

127

Ba2ZnaFei20a2
*) *)
*) *)

227
191

9,000 9,500

Ba2Zn1.5Fe12.5O22

Ba2Co 2 Fei2022 Ba 3 Co 2 Fe2404i


Measurements on

C02Y C02Z
single crystals.

185

28,000
13,000

270

Fig. 39.4

shows the saturation magnetization

4nMs

the anisotropy field

Hg and
ferrite

the crystal anisotropy constant

Ki

for

BaFei20i 9 as a function of

temperature.

The same

quantities for

C02Y

are given in Fig. 39.5. For this

[Ca 2] a remarkable decrease in the anisotropy occurs near 215 K. The anisotropy field becomes here almost zero: what remains is perhaps due to inhomogeneities of the crystal. For temperatures below 215 K the
ferrite

C02Y has a

preferred cone for the magnetization with the c axis

as the axis of the cone (see 11.1).

as a function of temperature in Fig. 39.6.

The top angle O of the cone is represented Above 215 K the basal plane of

39]

CRYSTAL ANISOTROPY

205

Kl
(to

6erg/cm 3

100

200 300

400

500

600

700

**T(K)
Fig. 39.4. Saturation magnetization

Mi,

crystal anisotropy

K\ and

anisotropy field

H^

of BaFei20i9 as a function of temperature.

the hexagonal structure

is

a preferred plane of magnetization. The mag-

netization curves for various directions of the crystal also

which
there

is is

characteristic

show a trend of a preferred cone of the magnetization. At 77 K

already a magnetization in the direction of the c axis for a field

strength

H = 0,

(see Fig. 39.2).

As shown

in Fig. 39.7 the

compound C02Z

represents the remarkable


2].

case of having three types of crystal anisotropy [Ca

Above 480 K

the

between 220 K and 480 K the basal plane c axis is a is a preferred plane and below 220 K the material exhibits a preferred
preferred direction,

cone for the magnetization. Mixed hexagonal ferrites can be made which, at a specific temperature, possess an anisotropy that is found to he between the extremes of BaFe^Oig and

The anisotropy

C02Y. An example is the series of mixed crystals of the compounds Co aZn 2 - 8 Z constants at room temperature are given in Fig. 39.8 as a

206

FERRITES WITH

HEXAGONAL CRYSTAL STRUCTURE

[CH. IX

40,000

200

s (gauss)
(Oe)

30,000

20,000

10,000

K,+2K2 (K^rg/crn 3)

Fig.
(ATi

39.5.

Saturation

magnetization
field

s,

crystal

anisotropy

2Ki) and anisotropy

jH* of

C02Y

as a function of

temperature.

200
Fig. 39.6.

300

400

+-T(K)
Equilibrium orientation with respect to c axis

of the magnetization vector of


perature.

CoaY

as a function of tem-

39]

CRYSTAL ANISOTROPY

207

(Oe)

30,000

20,000

10,000

K,+2K2
(Xfierg/cm3)

-as
-1.0

-i.s

-zo
Fig. 39.7. Saturation magnetization

Af

crystal anisotropy (Ai+2)

and anisotropy

field

H*

of C02Z as a function of temperature.

(nterg/cmJ)

K,+2Ka

Fig. 39.8. Crystal anisotropy

Ki of

cobalt-zinc

compounds

as a function of the cobalt content.

208
1

FERRITES WITH

HEXAGONAL CRYSTAL STRUCTURE


8.

[CH. IX

unction of the composition parameter

The compounds

at the ends of

the diagram,

Zn2 Z and Co 2 Z, have


is

respectively a preferred direction

and a

preferred plane for the spontaneous magnetization. For the mixed crystals

a gradual transition
sotropy to the other.

found as a function of

from the one kind of ani-

^erg/cm 3)

BaMe% TiFFe,2 -2t0t9


T-20C
Mex
a

Ni Co -

Zn

Fig.

39.9.

Crystal

anisotropy

Kj.

of

several titanium-substituted

compounds
metal
ion)

with

M structure as
(or

a function of the

titanium
content.

divalent

K,+2K2

**
An
It

In the

compound M,
is

divalent ions can also be introduced, together

with the same number of tetravalent ions.


the crystal anisotropy quantities of Ti IV and

example of the

effect

on

given in Fig. 39.9.

appears that relatively small

tropy. In the case where

remains a preferred

Me11 ions can considerably reduce the crystal anisoMe represents the nickel or zinc ion the c axis direction. In the case where Me = Co the compounds
with 8

BaCo 8Ti s Fei2-2dOi9


39.2.

> 1.1 have a preferred plane

of magnetization.

ANISOTROPY IN THE BASAL PLANE

Where the spontaneous magnetization lies in the basal plane of the crystal with hexagonal structure, the anisotropy energy in the basal plane is determined by the magnitude of 3 from equation (11.6). It appears that 3 is

a factor of the order of magnitude 10 3 In Fig. 39.10a the stiffness c is plotted for a single crystal of Coi.9 2 Fe II o.o8Z as a function of the angle $ which a fixed direction in the preferred plane of the
least
.

smaller than

Ai by at

crystal platelet makes with the direction of the given by an equation analogous to (26.3):

field,

the stiffness c being

39]

CRYSTAL ANISOTROPY
8000

209

c (erg/cm 3 )

A
f\
f\
i

-/X

^1S2^e

0M^
j

14000

A
K
1

CK:

f\
'

>

,/

\J
\
-4000

J
;in6p

J
\
.
,

1
360

tip/

K
1

e 30
-8000.

c
/20

*-3eK3 sir>ffj
ffiO

so

240

a
Fig. 39.10a.

300

The rotational
(/>).

stiffness

of the magnetization vector in the basal

plane of C01.g2Feo.osZ as a function of the orientation in this plane


(indicated

by

5000

d 2 Fg

= 36*3 sin 6 f

(39.1)

The measurement was carried out in


a
field

strength of 3300 oersteds.


analysis of the curve

The Fourier

in Fig. 39.10a gives the spectrum

shown in Fig. 39.106. The sixth harmonic component has a strikingly high amplitude; this component corresponds to the term 3 in (11.6), erg/cm3 The and is equal to 120
.

appearance of the second harmonic


is

due to the

fact that the crystal

platelet is

not exactly parallel to the direction of the lines of force of the homogeneous magnetic field. Consequently a very small part of the
large anisotropy

K\

is

also measu-

Fig. 39.10b.

The Fourier spectrum


data of Fig. 37.10a.

red. Table 39.11 gives

some values

of the

stiffness

of #3

210

FERRITES WITH

HEXAGONAL CRYSTAL STRUCTURE


TABLE
39.11

[CH. IX

THE CRYSTAL ANISOTROPY CONSTANT K3 AND THE ANISOTROPY FIELD H# FOR SOME HEXAGONAL FERROMAGNETIC OXIDES.
Material

Temperature C
I

Ms
gauss

K3
erg/cm 3 2000
800
150 55
oersted

196
20
170

210
187
145

340
155

Co 2 Y
Coi. 5 Fe n o.sZ

1
(

37
7

(
'(

20
158

280
220 280 290
190

~9
120
25

~2
16
3

Coi.92FeII o.osZ

20 20

CoZn

.5Fe n o.5Z

Zni. 6 Fen o.5Y

20

<6

<1

measured on various
the greater
is

crystals at different temperatures, together with the


field

corresponding anisotropy

Hf

= 36 Kz/M
falls

s . It is

seen that

Kz

is

larger

the cobalt content in the material; for Zn1.5Feo.5Y a value possibly be present

of Kz which

may

within the measuring error.

The

most cobalt and has by far the field strengths H^ are small compared with the field strength of approximately 3000 oersteds at which the measurement is carried out, so that in these cases no great error is made if the extrapolation to an infinitely large measuring field is omitted.
relatively the
39.3.

compound C02Y contains largest Kz. The anisotropy

ORIGIN OF CRYSTAL ANISOTROPY IN HEXAGONAL OXIDES


which case only

In hexagonal crystals the characteristic dipole-dipole interaction can in


principle give rise to uniaxial anisotropy (see 12.1), in

K\

^ 0.

The
2]

spin configuration in the

structure favours the occurrence

of a preferred plane.

complete calculation of the dipole sums has been

made [Ca
(^i)dip

and

yields:

= -(0.044
/*o

/*t

0.0006 im m>

+ 0.240 ^

).10 6

erg/cm3,

(39.2)

where

and

are the averaged magnetic moments, expressed in

Bohr

magnetons, of the tetrahedral and octahedral ions respectively. Equation (39.2) yields values ranging from 5 to 7 x 10 6 erg/cm 3 for the various Y

compounds

(at

T=

K), so that

it is

probable that the negative crystal


is

anisotropy of compounds with the


dipole-dipole energy.

structure

caused by the magnetic

In the

structure,

on the other hand,

it is

not to be expected that the


true that the
parallel,
,

dipole-dipole energy will be at

all substantial. It is

one above the other in the

block (see Fig. 37.4) are


1

two ions and this


the nega-

makes a

positive contribution to Kj. of about

x 106 erg/cm 3 but

39]

CRYSTAL ANISOTROPY
of the ions on the boundary plane of an

211

tive contribution
still

and S block

remains.

The

calculation reveals indeed that the resultant contribu-

tion to

K\

is

negative

the observed positive value of


It is

( 1.5 Xl06 erg/cm3) and therefore cannot explain K\ of about 4.5 x 106 erg/cm3 at T = K.

possible that spin-orbit interaction


it

may

yet be able to explain the


spin-orbit interaction

anisotropy observed. In this case


in an excited state. Presumably

would have to be
is
it

K2

small because in this case the simple

theory of 12.2, which states that


is

should

differ

by a
occur.

factor (X/AE) 2 ,

applicable here, inasmuch

no

fluctuations in
is

AE

The anisotropy caused by

the cobalt ions

probably of the same kind

as that appearing in magnetic annealing.

The

sign of the anisotropy energy

was not apparent in these experiments. In the hexagonal oxides the sign of the anisotropy will depend on the sites which are occupied by the cobalt
ions, but

which are not precisely known. In


is

34.2

we saw
.

that the uniaxial

anisotropy per cobalt ion

of the order of 50

cm-1 From
structure
is

Table 39.1

it

follows that the contribution of cobalt in the

about
It

2x 106

erg/cm3 corresponding to approximately 3


,

cm-1
is

per cobalt ion.

appears

that the distribution over the available sites

such as to give

rise to consi-

derable cancelling of the anisotropy. In the

W structure, the contribution

is roughly twice as large. with spinel structure the cubic crystal anisotropy is positive for cobalt ions, that is to say the [111] direction is an abhorred direction. In the hexagonal structure this direction is equivalent to the c axis, which is

of each cobalt ion In


ferrites

an abhorred direction for the spins of the cobalt ions. These facts, however, are not directly connected, since the cubic Ki corresponds to the hexagonal K2. Thus, if the same mechanism is effective for the anisotropy energy of the cobalt ions in the cubic and in the hexagonal crystals, one
also

would expect

K<i in

agrees with the experimental finding in


tures, (see 39.1)

hexagonal crystals containing cobalt to be positive. This Co 2Y and in Co 2 Z at low tempera-

and

is

then the cause of the occurrence of a preferred

cone for the magnetization vector.

CHAPTER X

INTRINSIC PROPERTIES OF FERRITES

WITH GARNET STRUCTURE


40. Chemical Composition and Crystal Structure

Yoder and Keith [Yo


for

2]

showed in 1951 that

substitutions can be substituting

in the ideal mineral garnet

MnsA^SisO^. By

Yra + Alm

made

Mnn +

SiIV they obtained the first silicon-free garnet

Y3AI5O12. In

1956 Bertaut and Forret [Be 6] reported the preparation and magnetic
properties of Y3Fe 5 Oi2,

and Geller and Gilleo [Ge 2] preparedandinvestigated


is

GdsFe50i2, which compound

also ferromagnetic. It appeared [Be 6] that

the yttrium ion could be replaced by the rare-earth ions

Pm, Sm, Eu, Gd,

Tb, Dy, Ho, Er, Tm, Yb, or Lu, owing to their nearly equal ionic radius.

There are no other trivalent ions known with about the same ionic radius.

The crystal
lest radii, all

structure

is

quite complicated.

The iron ions, having


distorted.

the smal-

occupy tetrahedral (Fes) and octahedral (Fe2>

sites just

as in

the spinel structure, although they are


Geller

somewhat

According to

is

and Gilleo [Ge 3] the tetrahedral-oxygen distance in yttrium garnet A and the octahedral-oxygen distance is 2.00 A, which is about the same as in the spinel structure. Nevertheless the aluminium ions now pre1.88

ferentially

occupy tetrahedral
sites

sites,

whereas they occupy preferentially


2],

octahedral

in the spinel structure [Ge


is

difference

the spinel structure

also that all existing octahedral

compared with and tetrahedral sites

occurring in the garnet structure are occupied by the metal ions. Perhaps
this fact contributes to the

very great stability of the structure. The yttrium


sites,

or rare-earth ions are too large to occupy tetrahedral and octahedral

which are in 4-fold and 6-fold coordination


is

respectively,

but are, on the

other hand, too small to be substituted for an oxygen ion, each of which
ions

surrounded by 12 oxygen ions. The close-packed structure of the oxygen is therefore not retained, but the yttrium or rare-earth ions occupy sites which are rather irregularly surrounded by eight oxygen ions of which
cell,

four are at a distance of 2.37


unit

which contains 8 molecules

A and four at 2.43 A. The edges of the cubic Y3 Fe 5 Oi2, are 12.37 A. The X-ray
g/cm3
.

density of e.g.

Y3 Fe5 Oi2 is

5.17

41. Saturation Magnetization

The iron

ions

on the octahedral and

tetrahedral sites are coupled antiferro-

41]

SATURATION MAGNETIZATION

213
ferrites.

magnetically by the superexchange mechanism as in the other

In this case the resultant magnetic


ions in tetrahedral coordination.

moment of

the iron ions

is

due to the

The rare-earth ions, which have a magnetic moment, are coupled antiferromagnetically to the net moment of the iron ions. This coupling usually is much weaker than that between the iron ions.

As a consequence the magnetization of the rare-earth ions drops very quickly


with increasing temperature, approximately asl/T. Because most of these ions

have a saturation moment which is much larger than the resultant magnetic

moment of the iron ions, (Table 41.1) the moment of the

rare-earth ions pre-

dominates at low temperatures and that of the iron ions at temperatures near
the Curie temperature. Therefore a compensation point of the magnetization
is

observed (Fig. 41.1), as in the case of LiCr observed in high


is

ferrite (see 9.1).

The intrinsic
not too

susceptibility,

fields, is

very high in these

ferrites at

low temperatures and


earth ions.
as

caused by the unsaturated magnetization of the rareis

The Curie point

determined by the superexchange interactions

30

t^
20
5Fe2t )33Me2 03

75

1e=Gd-Jb- Oy-Ho-Lu

i i

- Er-n -

'-7 n

10

V--V

ST~^-

U ''

''
i i

r*"^^
--=*-

30

*""
'-

w^

SS^
5

v
c

\/
%V
2C

4Cw

-'

6C

70

T(K)
as a function of temperature, after

Fig. 41.1.

Spontaneous magnetization of a number of rare-earth iron garnets and yttrium-

iron garnet, expressed in

number of Bohr magnetons

Bertaut [Be

7]).

214

FERRITES WITH GARNET STRUCTURE

[CH.

is almost the same for all rare-earth garnets The magnetic moments of the rare-earth ions is between that of pure spin and that of spin and orbit together, owing to partial quenching of the orbital angular momentum. This quenching is less complete than in

between the iron ions and


(560 K).

the ions of the iron


filled shell
fields,

group because the partly

filled

4/ shell

is

not the outer

of the ion, the 5s and 5p shells being are occupied. The crystalline which should cause such quenching, are therefore more screened off.
the reciprocal value of the susceptibility as a
is

The curve representing

function of temperature above the Curie point

hyperbolic, as should

hold for a ferrimagnetic substance. Aleonard


for

et al. [Al 1]

have determined

Y3Fe 5 Oi2 from


and
nf$ that

the 1/x curve the molecular field constants n, a


field

and

where na represents the molecular


lattice

constant within the octahedral sub-

within the sublattice containing the iron ions on tetra/8

hedral

sites.

The calculated values of a and


the ions

are 0.474

and 0.284 respectively.

This corresponds to fairly strong interactions between the spin magnetic

on equivalent lattice sites. The distance between the is, however, rather large (5.4 A) and moreover a superexchange interaction via one oxygen ion is scarcely possible. The interaction has to take
ions

moments of

place via at least two oxygen ions, and should therefore be very small. It

is

accordingly very likely, as in the case of the spinels ( 33), that the large values

of a and

jS

are erroneous, and are due to the fact that the molecular field
strictly apply. It

theory does not

was shown in 33 that in particular this gives


is

rise to excessive values

of the interaction constants inside the sublattice with


the interaction between

the smallest magnetization. In the present case this the ions

on the octahedral sites (here a), in agreement with the observed values.

42. Crystal Anisotropy

and Ferromagnetic Resonance Properties

The
line

great interest of ferrites with garnet structure,

and
is

chiefly of yttrium

garnet, resides in the small ferromagnetic resonance line width.

The

smallest

width on carefully polished spheres reported so far

0.6 oersted [Le 2]

at 3

cm

wavelength at

room

temperature. This
[CI
1],

is

presumably due, referring

to the theory of Clogston et

al.

to the fact that only trivalent magnetic

ions of one kind occur, having

no

orbital angular

fluctuating perturbing fields are present.


arises

momentum, so that no The high value of the resistivity also

from

this fact.

The

saturation magnetization at

room temperature

is

rather low (4itMs

1700 gauss) so that losses due to incomplete saturation

do not occur
interesting

ions invariably have broad resonance lines,

microwave frequencies. The garnets containing rare-earth and are therefore not very from a technical point of view.
at

42]

CRYSTAL ANISOTROPY AND FERROMAGNETIC RESONANCE


crystal anisotropy of yttrium garnet
is

215

rather low at room temOe, as has been measured by Dillon [Di 3] and can be quite well described with a single constant Below 100 K the x anisotropy strongly increases and varies approximately as l/T. At still
perature,

The

Ki/Mg = 40

lower temperatures, below 10 K, the situation becomes quite complex, anisotropy fields of the order of 3000 oersteds occur and the preferred direcis no longer along one of the simple crystallographic directions, so that anisotropy constants of higher order are necessary to describe such a behaviour. This is contrary to what one should expect from the simple theory developed, because the g factor is very close to 2, and therefore the

tion

anisotropy ought to be small and a power series expansion of the energy in the direction cosines should converge very rapidly. Moreover, since only

one type of magnetic ion


tend to

is

present, there are

no

fluctuations

which should

make

higher terms important.

TABLE

41.1

ELECTRONIC STRUCTURE AND ANGULAR MOMENTUM OF YTTRIUM AND RARE-EARTH IONS.

Y
At.
el. el.

Nd
4/Hs2
4/3
3/2

Pm
4/5 6j 2
4/*

Sm
4/6.s 2

Eu
4/'6i 2
4/8
3

Gd
4/?5rf6i 2

conf. conf.

4d5s 2

Ion

4p s

4/5
5/2

4/ 7
7/2
7

L
L + 2S

6 3
Tb

6
2

3
3

Dy
10 4f 6s*

Ho
4/"6j 2
4/10
2

Er

Tm
4/ l3 6s 2
4/12
1

Yb
4/ 14 6* 2
4/13
1/2
3

Lu
l 4f *5d6s*

At.

el.

codf.

4P5d6s 2
4/8
3 3

4/ 12 6j 2
4/ii

Ion

el.

conf.

4/9
5/2
5

4/14

3/2

L + 25

6
10

6 9

15

CHAPTER

XI

STRUCTURE OF POLYCRYSTALLINE
FERRITES
43. Isotropic Samples
43.1.

PREPARATION
by a
sintering proces as

Polycrystalline samples of ferrites are prepared

commonly used

in the ceramic industry. Broadly speaking this process

comprises the following operations. The metal oxides, carbonates or other

compounds which are to form the ferrite by a solid state reaction are mixed homogeneously and wet-milled, usually in a steel ball mill. The dried powder
which

may

or

may not have been pressed into

a particular shape,

is

prefired

at a temperature of about 1000 C in order to bring about the

initial

chem-

ical reaction between the constituents. In order to produce a chemically

homogeneous sample, the


quired shape, or
is

prefired

powder

is

again intensively milled and


is

mixed. This powder, after the addition of a binder,

pressed into the re-

extruded as a plastic mass in the form of tubes or rods.

The pressed or extruded products are sintered at a temperature between 1200 and 1400 C, the precise temperature depending upon the properties of the ferrite that are wanted, (see for example [Sn 3] and [Ec 1]). During this sintering process, a shrinkage of up to approximately 20 % can occur, a fact which has to be taken into account when dimensioning the
press mould. In the final sintering process the gas atmosphere in the furnace

plays

an

essential role, since


is

it

determines the degree of oxidation of the

product which

in

many

cases important for the magnetic properties (see

for instance 54.3).

produce an entirely dense material, but a product having a certain porosity. The porosity p of a ferrite is the relative volume of the pores it contains, and it is derived from a comparison of the
sintering process does not

The

X-ray density dx with the apparent density d of the


ferrite

ferrite. Fig. 43.1

shows a
that the

photomicrograph of the polished and etched surface of a manganese-zinc


with porosity

= 0.1.

The

firing

programme was such

maximum temperature of 1375 C. If the material is held for one minute at a maximum temperature of 1435 C
sample was held for
five

minutes at the

a denser product with larger crystals

which

is

obtained (p 0.05), a picture of shown in Fig. 43.2. The firing temperature necessary in order to
is

obtain a dense product depends

on

the chemical composition of the ferrite.

43]

ISOTROPIC SAMPLES

217

Fig. 4.1.1. Polished

and etched surface of a manganese-zinc


0.1.

ferrite,

sintered for

Ave

minutes

at

1175 'C. Porosity p

218

STRUCTURE OF POLYCRYSTALLINF

FF.RRt.TES

[CH. XI

Fig. 43.2.

Same

ferrite as in Fig. 43.1, hut

now

sinterett for

one minute

at a

tempera-

ture of 1435

X.

Porosity

0.05.

43)

ISOTROPIC SAMPLES

219

Fig. 43,3, Polished

and etched surface of

MnFcO

magnanese

ferrite

with a segregation

ofu second phase of aFeaOa.

220

STRUCTURE OF POLY CRYSTAL LINE FERRITIN

[CH. XI

mm
exaggerated case of a surface layer on a
the composition
the

Fig. 43.4.
feirite.

An

The core has approximately Co().r.FcJ I''C2Q,j. The surface of


J ., i

sample

has

been oxidised during cooling.

43]

ISOTROPIC SAMPLES

221

For instance a porosity of less than 0.1 is obtained for CuFe2C>4, MnFe2C>4 and NiFe2<I>4 if the sintering takes place at temperatures of about 1 100, 1200 and 1400 C respectively. These temperatures are related to the melting points, which are 1300, 1500 and 1650 C respectively. It seems that nickel ions in particular do not diffuse easily in ferrites. The addition of zinc lowers the firing temperature of most ferrites. If samples of Me sZni- 8Fe2C>4 with various values of S are sintered at the same temperature, the

sample with the highest zinc content

will

have the greatest density.

The temperature at which good sintering takes place depends to a large extent also on the grain size and grain shape of the starting material. A very fine-grained powder gives dense products at a lower firing temperature. For this reason the ball milling of the compounds or of the prefired ferrite is often replaced by a treatment of the powder in a vibration mill which
leads to a smaller particle size.
43.2.

PHASE DIAGRAMS
iron for example

Many ions can occur in a ferrite in different valency states;


can occur as a divalent or a trivalent
ical

ion.

In order to obtain a certain chemof the ions

composition of the

ferrite it

may be necessary for some types

to occur in different valencies. If either the gas atmosphere during firing


is

not sufficiently oxidizing, or the ratio of the quantities of metal ions in


is

the starting materials


obtained.

not correct, the wanted concentration cannot be

Where

the deviations are considerable a second phase segregates

from the ferrite. This can have an adverse effect on the magnetic properties. Under the microscope this second phase is often clearly visible on polished ferrite surfaces. Fig. 43.3 (see page 235) gives an example of a second phase of aFe2C>3. This is the result of an attempt to make a spinel from Fe2C>3 and MnO as basic materials having a molar ratio of 55 45. The lightcoloured segregations of the aFe2C>3 phase, clearly visible on the photograph,
:

result

from a

firing in

a too oxidizing atmosphere. The

light colour is

characteristic of aFe203. If the ferrite is fired in

a reducing atmosphere,
if there is

single-phase manganous-ferrous ferrite

may

be produced. Inhomogeneous

oxidation or reduction of the sample will take place

no equilibrium

between the sample and the atmosphere. Often a so-called surface layer will be the result; an exaggerated case is shown in Fig. 43.4 (see page 336). Phase
diagrams of the iron-oxygen and manganous-iron-oxygen systems have been
given by Darken [Da
1]

and by Gurry [Gu


are complicated

8] respectively.

Where the compositions

it is

important to study the com-

plete phase diagram. For instance in the case of Mn,Zn-ferrites the series of mixed crystals of MnFe2C>4 and ZnFe204 form only one single line of

222

STRUCTURE OF POLYCRYSTALLINE FERRITES

[CH. XI

compositions in the large spinel

field of the quaternary system Mn-Zn-Fe-O. The compositions Fe3C>4, M113O4 and ZnMn204 also belong to this system, and for a complete understanding at least a large part of the spinel region

has to be investigated. These investigations have only been carried out in

a few cases,

e.g.

in the system

Mg-Mn-Fe-O where

the

first

compositions
is

with rectangular hysteresis loops were found.

An

important point

to

represent phase diagrams in the appropriate way. In the quaternary system,

which can be represented as a tetrahedron,


to obtain a simple

all

so-called

stoichiometric

compositions (Mg,Mn,Fe)304 are found in one triangular plane. In order

diagram it is necessary to place equal amounts of compacompounds in the corners. This is done in Fig. 43.5, thoug in one corner of the triangle no spinel compound exists but rather a mixture 3MgO + ^02. In this method of representation, introduced by Jonker [Jo 6], the three different metal ions appear with equal weight and the simple compositions as MgFe2<I>4 MnFe2C>4, MgMn24 and MgMnFeC>4 are found on simple locations in the diagram. In the MgO-MnO-Fe2C>3 or MgO-Mn304-Fe2<]>3 diarable

grams, which are often used, spinel compounds, apart from the simple ones,

cannot be represented. The region of spinel compounds


(it

is

large in this system

covers the area within the drawn contour in Fig. 43.5). For different parts

methods of preparation are needed, for instance for Fe3C>4 a high MgMn204 a low temperature and a high oxygen pressure. The spinel compounds obtained by firing at
different

temperature and a reducing atmosphere, for

1350 C and slow cooling in air lie within the hatched area of Fig. 43.5. The compounds containing Fe11 and Mnlv ions are for the greater part not included and even MnFe2C>4 does not belong to this region. There are of course also non-stoichiometric compounds with an excess or a deficiency

*Q

MgFe2

t/

43.5. Example of a phase diagram of a ternary

Fig.

oxide system.

The

area be-

tween the solid


sents
crystals

lines repre-

with

spinel

structure.

The smaller shaded

region represents spinels obtained by firing at 1350 C


in air followed

by slow cool-

3MgO+'/202

Mg2Mn0i

MgMn2Qi

MnjOt

ing.

43]

ISOTROPIC SAMPLES

223

of oxygen. These compositions can only be represented in the three-dimensional diagram.


43.3.

INTERNAL DEMAGNETIZATION
owing to the porosity of the specimens. An impression is obtained by measuring the so-called

In the magnetization of polycrystalline ferrite specimens internal demagnetizing fields occur

of the demagnetization due to pores

ideal magnetization curve; see 28.1.

From

the slope of this curve an inter-

exists

It appears that a relationship between Nt and the porosity p which is fairly independent of the chemical composition of the spinel. For Nio.5Zno.5Fe20 4 this is represented

nal demagnetizing factor Ni can be derived.

by curve

a) in Fig. 43.6.

When, however, we determine

in the

same way the

relation between JV<

and

for various specimens of hexagonal ferrites for

which the basal plane is a preferred plane of magnetization (see 39.1), we then obtain an entirely different picture [St 3], as can be seen from curve b) in the same figure, which holds for C02Z. Even for very dense materials

fairly large value for the factor


is

Ni

is

obtained,

and

it

increases raleft

pidly with the porosity; curve b)

seen to be shifted towards the

with
re-

respect to curve a). This

anomalous behaviour can be understood by

ference to Fig. 43.7; a crystal lying crosswise affects the pattern of the
lines

of force in the same


is

way

as

an

air cavity

would. The demagnetizing


lines

influence

even greater: in the surrounding crystals the


i.e.

of force must

continue to run parallel to the preferred plane,

in the plane of the

0.20

11

0.15

bf
la
0.10

\t-Q
Fig.
1

43.6.

Internal demagnetizing coeffi-

A
1

c
1

cient

Ni as a function of porosity p;
ferrite

curve a) for the

with spinel structure


for
isotropic
cry-

X f'0.22
0.05

Nio.sZno.5Fe204,

curve b)

\f~0J50 f= 0.78 t

specimens of
stal

C02Z with a hexagonal


curve
c)

structure

and a preferred plane of


for

if = 0.91
0.2

magnetization,

anisotropic

specimens of C02Z having different degrees

OA

of orientation.

224

STRUCTURE OF POLYCRYSTALLINE FERRITES


by a wrongwhich the crys-

[CH. XI

Fig. 43.7. Demagnetization caused


ly oriented crystal in ferrites in
tals

(for instance the basal plane in the

have a preferred plane of magnetization hexagonal

crystal structure).

The

preferred plane of the

crystals lies in the plane of the drawing; that

of the hatched crystal


ing.

is

perpendicular to the

plane of the drawing and parallel to the hatch-

Magnetic lines of force have to bend round the sides of this crystal.

drawing. They can thus only bend around the wrongly oriented crystal

towards the
material

left

and

right

and not backwards and forewards.


ferrite

It is

under-

standable, therefore, that the internal magnetization of such a fairly dense


is

comparable to that of a cubic

having a porosity/? of about

one

third.

43.4.

MECHANICAL PROPERTIES

By

sintering ferrites at high temperatures the material gets mechanical


it

properties which greatly resemble those of earthenware. Thus, while

cannot be worked with a cutting tool,


grinding, the
als:

it

can be ground and lapped.

When

same precautions should be taken as with other ceramic materiis necessary with small feed and with suitable grinding discs. Very accurate dimensions and cleanly fitting surfaces are obtained by face-grinding and centreless rotary grinding. The ground surfaces can be
wet grinding
very well cemented together with adhesives such as plastics of the aethoxyline

group which harden

at

a temperature of about 180 C. The

air

gap need

not be greater than a few microns. In this way more complicated shapes can be built up from simple ferrite components. Although ferrites are not
sensitive to water or brine,
it is

advisable, if the ferrites are to be used in

high-quality circuits, to impregnate the components in order to prevent


dielectric losses

through absorption of moisture.


strength of sintered samples depends

The mechanical

on the

porosity.

In Fig. 43.8 the compressive strength for uniaxial pressure and the tensile
strength of nickel zinc ferrites with spinel structure are plotted as a function

of p [Bu
stress

2]. It is

well

known

that the ultimate unidirectional compressive

of ceramic materials exceeds their ultimate tensile stress by a factor of

43]
10 to 30.

CRYSTAL-ORIENTED SAMPLES

225

When using these data it must be taken into account that the tensile
is

strength of ceramic materials

a function of the cross-sectional area


200

or better, of the volume of the material, since


fracture in ceramic materials
is
is

essentially

a
<r
1

matter of

statistics.

Fracture

initiated at

the weakest point in the volume under load: the probability of there being a
increases as the

(kg/mm*) T 50

f
30

>"'

weak point
There are

volume

increases.

various indications that the tensile strength,


as given in Fig. 43.8, should be reduced

by a

-.
03
0.2

factor of 2 to 3 for very large cross-sections

in order to obtain the correct value.


0.3

0A

Young's modulus for sintered


all

ferrites

of
Fig.
43.8.
a\,
era,

+-P
strength, strength,

chemical compositions has the order of


10 12
.

magnitude

dyne/cm2 the porosity as shown by

It

depends on

The compressive and the tensile


as functions of the
refer to

Fig. 43.9.

The
vari-

temperature dependence of this quantity can

porosity p.

The curves

be influenced to a large extent by minor


Other properties which are
conductivity, about 1.5
0.2 cal/g-deg.
fairly

a cross-section of 2

mm

mm, and
same

they are roughly the

ations in the chemical composition, (see [Bu3]).

for the various types of

independent

ferrites, after

[Bu

2].

of the chemical compositions are the thermal

X 10 -2

cal/sec-cm-deg,

and the heat

capacity,

about

Fig. 43.9.

Young's modulus of

nickel-

(I0*dyne/cm*)

zinc ferrites with spinel structure as

dependent on the porosity p, [Bu 3].

after

44. Crystal-Oriented

Samples

Various methods of preparation are


material
is

known by means of which a magnetic


crystallites.

obtained with a textural alignment of the

In the cera-

mic materials use might be made, for instance, of the non-spherical shape of the powder particles of the hexagonal oxides. These crystals grow preferentially in the basal plane and much less in the direction of the c axis. By packing the powder in steel tubes sealed tightly at both ends and rolling these

226

STRUCTURE OF POLYCRYSTALLINE FERRITES


it

[CH. XI
slight

at high temperature,

has been found

[St 2] possible to

produce a

anisotropy.

A more elegant method [St 2] is to make use of the magnetic crystal anisotropy of the hexagonal oxides. Particles that can rotate freely, and for which
the c axis
is

the preferred direction of magnetization, will be aligned by an


externally applied magnetic field such that
their preferred axes of magnetization are
parallel (see Fig. 44.1).

The aligning torque


of Fig. 44.1
is:

exerted

on

the crystal

r=^isin26.
This torque
Fig. 44.1. Equilibrium orientation

(44.1)

135
18()
o
.

= 45 or is equal to Ki for and equal to zero for =0, 90 or


If for
.

for the magnetization

M.

in a fixed

o 9()
*>

particle with uniaxial magnetic ani-

sotropy
is

when an

external field
e

S reater thafl

1K^M
... ,.,

^
,.

fidd strength

is

the magnetization

....

applied at an angle

to the pre-

rotates in the direction of

H,

(0

90),

ferred direction.

while the orientation of the crystal axes

remains unchanged. The mechanical torque


is

then zero. The rotation of the magnetization is momentary, so that in general

the particle will not rotate with the magnetization

when

the field

is

applied.

Even when the


unoriented.
If,

field is further increased, the particle will therefore

remain
torque.

however,

H = y 2 Ki/M

s,

the sudden application of the


i.e.

field will give rise to

the state with

= 45,

with a

maximum
is

In that case the particle will be oriented. The conclusion

that the value

of a suddenly applied external magnetic

field

should be approximately
is

//=]/ 2 Ki/M;

in the case of

BaFe^Oig
is

for instance, this


effective if the

about equal

to 11,000 oersteds. This process

most
little

of separate particles which are unicrystalline.


particles

powder consists For an optimum result the

should hinder each other as

as possible in their orientation.

In this respect the platelet-shaped crystals of hexagonal oxides are unfavourable. The powder subjected to treatment with the magnetic field should thus not be too closely packed. After the particles have been oriented in the magnetic field, they must be fixed in this state without loosing the texture

obtained.

A simple method would be one in which the powder is first mixed

with warm, molten paraffin wax, the suspension then being placed in the magnetic field and the paraffin wax allowed to solidify. This method, however,
often not practicable, since the magnetic material in most cases must also have a high density. Fixation together with a high density can be obtained
is

with ceramic substances by compressing the powder suspension in a magnetic field

and by subsequent

sintering.

Although the forces arising during

44]

CRYSTAL-ORIENTED SAMPLES

227

the compression process are

much
is

greater than the orienting force of the

magnetic

field,

a good texture

nevertheless obtained.

must not be lost by a recrystallization process at the high temperature at which sintering is carried out and which is far above the Curie point. Surprisingly enough it has been found that the texture of the starting material is even improved by sintering at a temperature where crystal
Finally, the texture

growth occurs. This so-called


rial

foliate texture

of such a crystal-oriented mate-

can clearly be seen in Fig. 44.2a and b (see page 237), which shows photomicrographs of the faces of a cube of this material. In Fig. 44.2a the
direction of the magnetic field applied during compression
is

perpendicular

to the plane of the figure, whereas in Fig. 44.2b


It

it is

parallel to the figure.

appears that the greatest improvement


is

is

obtained in the texture

when

the density of the sintered material

about

90%

of the X-ray density.

The phenomenon of

the improvement of a preferred orientation by grain

growth has been extensively studied on metals, where it could more directly be followed with an electron emission microscope [Ra 2]. It is found that in a matrix of identically or almost identically oriented crystals, which contains
a differently oriented crystal, the latter crystal generally disappears while the

boundary planes between the identically oriented crystals remain unchanged. It also appears that the wrongly oriented crystal can only grow if it is large with respect to the crystals of the matrix. This behaviour can be understood

from surface energy considerations. In the hexagonal oxides, in which the basal plane is a preferred plane of magnetization, the foliate structure can be obtained [St 3] if a powder of a material of this kind, the particles of which are single crystals, is subjected to a magnetic field which varies in direction but remains parallel to

same plane. This may be, for example, a rotating magnetic field, obtainable by mechanical rotation of a yoke magnet. A rotating magnetic field can also be obtained with a stationary magnet, making use of for instance the three phases of the a.c. mains. Fig. 44.3 (see page 238) shows two electron
the

photomicrographs; the foliate texture of the samples

is

clearly visible. In Fig.

44.3a the preferred planes, which are also the basal planes of the crystals, lie parallel to the plane of the paper, while in Fig. 44.3ft they lie at right angles.

The magnetization curves of a specimen with foliate texture can be plotted for magnetization in a preferred direction and in a difficult direction. In
the case of an ideally oriented sample the area between both curves corresponds to the crystal anisotropy energy of the material. When the sample is

not ideally oriented the two curves


area which
is

lie

more

closely together

and include an

a fraction /of the area between the corresponding curves of crystal. We shall call this fraction the degree of orientation of the single

228

STRUCTURE OF POLYCRYSTALLINE FERRITES


The degree of

[CH. XI

the anisotropic material.

orientation of oriented specimens


is

of BaFei20i9 or of C02Z, for example,

found to have values up to over


Nt
c),

90%. Results of measurements of the


for crystal-oriented specimens of

internal demagnetizing factor

C02Z

are plotted in Fig. 43.6, curve


It is

showing the relevant degree of orientation/

seen that Nt drops sharply

with increasing degree of orientation, entirely as expected:

we thus approach
is

the ideally oriented state where, as in the case of the spinels, Nt


exclusively

determined

by the

porosity.

The
terials

orientation of crystals

by a magnetic
is

field

can only occur provided


is

the crystal anisotropy field

HA

not too weak. The result

poor for ma-

with a composition where

HA

is

in fact too weak, as for instance

in the case of certain

mixed

crystals

of C02W with other

Me2W compounds.

Substances of this kind can be oriented by a method developed by Lotgering

[Lo 2] in which the materials are prepared from a ferromagnetic oxide whose
crystals are oriented with help

of one of the above-mentioned methods.


is:

An

example of such a reaction

BaFei 2 Oi9

+ 0.8 CoO +

1.2

ZnO +

2 Fe 2 03-^BaCoo.8Zni.2Fei 6 027.

The
tals
is

starting materials are

placed in a uniform magnetic

mixed together and, during compression, are field, as a result of which the c axes of the crys-

of BaFei 2 0i9 are aligned mutually parallel. The reaction during sintering
that the c axes of the product Coo.sZn1.2W are also parallel,

now such
37.10.

as can clearly be seen

from X-ray diagrams

similar to those of Figs. 37.9


is

and

The

basal plane of the product Coo.sZn1.2W

a preferred plane

of magnetization, so that the specimen obtained has a magnetic anisotropy

corresponding to

this.

too weak for orienting in the


so-called topotactical

The anisotropy of this compound, however, is much more conventional way. Several of such reactions have been described by Lotgering [Lo 2].

CHAPTER

XII

ELECTRICAL PROPERTIES
45. D.C. Resistivity

The d.c. resistivity of oxide materials can be fairly reliably measured by means of a sonde method as illustrated schematically in Fig. 45.1. The same current is passed through a resistor R and the ferrite rod F. The voltage between points B\ across a part of the ferrite rod is compared with the vol-

known resistance JR. For an accurate measurement the internal resistance of the voltmeter V should be high as compared with the resistance of the ferrite rod and the resistances of the contacts B{. It is also possible to measure the resistance directly
tage between points B2 across the

between two electrodes on a

ferrite rod,

provided the contacts are properly


method
for measferrite

Fig. 45.1. Four-contact

uring the electrical

resistivity

of a

v/Mi//;M>M>*^

rod F. The voltage drop across the points B1B1 is compared with the voltage drop between the points B2B2 across a known
-TJinnrb-;
82

resistance R.

B2

applied.

Indium-amalgam contacts [Ui

1]

which are obtained by rubbing

indium, moistened with mercury, against a clean and preferably freshly ground surface, are very well suited for the purpose. Grinding is necessary

because
firing.

difficulties
is

may be
shown in

presented by a surface layer formed during


Fig. 43.4 for

This layer

an extreme

case;

it

can have either

a higher

than the bulk, owing to re-oxidation, particularly at the surface of the product during cooling, or a lower resistivity than the bulk, as found for example with mixed nickel-zinc ferrites of spinel structure
resistivity

[Ui

1].

In the latter case the explanation

is

that zinc has evaporated

from

the surface layer at the high sintering temperature


ions have formed.

and as a

result ferrous

For ferrites the resistivity at room temperature can vary, depending on the 11 chemical composition between about 10- 2 ohm-cm and higher than 10 ohm-cm. It has long been known [Ve 5] that low resistivities are caused in particular by the simultaneous presence of ferrous and ferric ions on equivalent lattice sites (octahedral sites). For example, Fe 3 4 at room tempera-3 ohm-cm, and NiFe2C>4 with ture has a resistivity of approximately 7.10

230

ELECTRICAL PROPERTIES

[CH. XII

TABLE
RESISTrvrTY p

45.1

AND DIELECTRIC CONSTANT e MEASURED AT A FREQUENCY OF 1 KC/S ON SPECIMENS OF Nio.4Zno.6Fe2 04, COOLED FROM THE SINTERING TEMPERATURE IN DIFFERENT WAYS (AFTER [KO 6]).
Sintering

Sintering
Ferrite

temp.

Method of
cooling

FeO

C
la lb

atmos.

%by
weight
0.10
0.38

ohm-cm
540,000
1,300

1300 1300 1300 1300

Oxygen Oxygen
Air

Slowly in oxygen

1,710

Rapidly in

air

28,200
4,300

2a 2b
3

Slowly in air

0.07

136,000
1,100

Air
Air

Rapidly in
Slowly in

air air

0.42

39,000
1,090

1280

<0.05

960,000

some

deficiency in iron

and

sintered in a sufficiently oxidizing atmosphere

so that the product contains

no ferrous

ions,

can have a

resistivity

higher

than 10 6 ohm-cm. Intermediate values of

resistivity

have been given by

Koops [Ko
low
tric

6]

among

others, for specimens of Nio.4Zno.6Fe2C>4 fired in

different gas atmospheres; the results are


resistivity is

shown

in Table 45.1.
ferrites

relatively

found to be associated in these

with a high dielec[Ve 6] and later


es-

constant.

An
[Ui,

extensive investigation into the origin of the electrical

conductivity of spinels has been carried out by

Verwey
7],

et al.

by Van Uitert

1,

2 and 3] and Jonker [Jo

who were concerned

pecially with obtaining ferrites of high resistivity. Specimens with

a varying

ferrous content can be obtained

by using

as starting materials mixtures

10"

P
(ohm cm)
A
10

Ni0JZn 0.7 Fe 2+S 4-+C

10

10*

10 2

p n
-0.2
0.2

-0.4
Fig. 45.2.

04

Nio.3Zno.7Fe2

The dependence of resistivity p upon iron content of the ferrites + &Oi-e fired at 1250 C in oxygen. The value of 8 is
e

determined by the starting material and the value of


conditions, after [Ui
3].

by the

firing

45]

D.C. RESISTIVITY

231

with different iron concentrations and by sintering all these in the same way. For the ferrites Nio.sZno.7Fe2+804+ Fig. 45.2 gives the resistivity in dependence on the surplus or deficiency 8 of iron ions for the case where the ferrites are sintered in an oxygen atmosphere at 1250 C. The value of 8 is determined by the starting material, the value of e by the sintering conditions. With ferrites of the series Coi_sFe2+8C>4, Jonker [Jo 7] has

obtained the results of Fig. 45.3a.

Two

regions

of conductivity are having

found; one region of compositions containing

Co11 and Co111 and

W7
1

ohm cm

%r

CoiSFe2 *s0i

K)

n*
'

-0.10

-0.05

0.05

0.10

a
7xK)~6

-<3

2BxKT 3
24
|C0;- sFei +3Q<
a-

1/

(ohmcmf
20
k
16

12

8
4

\/
-0.10
0.05

00

0.05

0.10

Fig. 45.3a.
ferrites
b.
is

The dependence of resistivity

upon iron content of the


45.3a.

Coi-8Fe2+04, after [Jo 7]. replot of the measuring points of Fig.


given

The conductivity a

now

on a

linear scale as a function of iron content of the

ferrites.

232 a high
resistivity,

ELECTRICAL PROPERTIES

[CH. XII

and having where there

and one region of compositions containing Fe11 and Fe low resistivity. Measurements of the thermo-e.m.f. show that is an excess of cobalt ions, hole conduction occurs (p type semia
1]. In Fig. 45.36 the results of Fig. 45.3a have been can be seen that the conductivity increases somewhat

conductor) and in the case of excess iron there is electron conduction (n-type

semiconductor) [Ui
replotted so that
it

more than
In the

linearly with the electron or hole concentration of the ferrite.

ferrites

of Figs. 45.2 and 45.3 the electron concentration can reach

a value of almost 10 22

semiconductors
results

cm-3 which is much higher than found in normal (about 10 19 10 20 cm -3). This figure combined with the
,

of the

resistivity

for electrons
respectively.

and holes

measurements leads to an abnormally low mobility in ferrites, namely about 10 -4 and 10 -8 cm 2 /V sec,

A
ions

low

resistivity

on

equivalent lattice

due to the simultaneous presence of ferrous and ferric sites can also be obtained in stoichiometric oxides

by applying the principle of controlled valency [Ve 6]. If small quantities, up to about 1 %, of foreign ions, can be incorporated in an oxide of very
high
resistivity,

and

if these

ions have a valency which differs from that of


it is

the ions already present, (for instance titanium ions in Fe2C>3), then
possible to force

some of the ions present into a different valency state. The result is that ions of the same atom are now again present in different valencies, so that the electrical resistivity of the oxide is reduced ([Ve 6] and
[He
2]).

It is

often important to
is

make

ferrite

samples with a high


it is

resistivity. It is

evident from what


there are

said

above that

then necessary to ensure that


it

no

ferrous ions in the stoichiometric ferrite. However,

appears

that stoichiometric

NiFegQi or

MgFe 2 C>4,

for example, has

resistivity

which
is

is

only slightly higher than 10 6 ohm-cm.

Van Uitert assumes that this


according to:

due to a

slight dissociation in the feirite, for instance

Nin

+ Fem ^> Nini +

Fe n

which in turn makes conductivity possible between Fe11 and Fe111 ions and between Ni11 and Ni ions. Van Uitert [Ui 1] obtained an appreciable

increase in the resistivity of the ferrite by adding to it small quantities of manganese or cobalt ions. Fig. 45.4 gives a picture of this improvement, which results in resistivities higher then 1011 ohm-cm. The explanation of
this substantial effect [Ui 3] is that in the case, for

example, of the addition

of

Mn

to NiFe2C>4 for the purpose of obtaining a stoichiometric ferrite


4,

with the formula NiFei.9Mn s

the concentration of

Fe 11 ions

is

kept

45]

D.C. RESISTIVITY

233

The increase of the resistivity of NiFe2C>4 samples as a result of additions of manganese or cobalt. Firing for 10 hours at 1250 C
Fig. 45.4. in Oa.

The value of e

is

determined by the firing conditions. After [Ui

3].

low by the

Mnm

ions, while the concentration

of any Ni

m that may be

present remains low owing to the presence of

Mn11 ions:

and
This
is

Fen _|_ Mnm Nini + Mn11

Fein + Mn11 Nin + Mnm

related to the increase in the third ionization potential for the ions

in the series Cr-Fe-Mn-Co-Ni. Since

in this series, small quantities of these

occur between Fe and Ni two kinds of ions have the same effect in opposing the formation of Fe11 and Ni 111 ions. If we use the method of raising the resistivity by adding small quantities of, say, Mn ions, then these ions will occur in two valencies and probably also on equivalent lattice sites. Nevertheless, this results in only a small contribution to the conductivity, owing to the low concentration of these
ions.

Mn and Co

Ferrites are semiconductors,

and

their resistivity decreases with increasing

temperature according to the relation

=
where

p~

*' JkT

(45.1)

E9 represents
jump

and De Boer [Ve


ion for a
tivity.

6] is the

an activation energy which, according to Verwey energy needed to release an electron from the
of the ions in the neigh-

to the neighbouring ion, so giving rise to electrical conduc-

Upon an electron jump, a displacement occurs


of the electron in question (see also

[He 2]). The mean free path bourhood is only about 3 A. It has been pointed out by Jonker [Jo 7] that in these non-

234

ELECTRICAL PROPERTIES

[CH. XII

/>

-0.40eV

/
/
I

/
J
/ZnF**W
Ep-0.22eV
O

p
(ohm cm)

0/

ySEp-aCBeV

y
Eg
-ft WeVj

/
f

'

^Ni .2i Zn0.U F'0.02 F 1t


0/

Ep

-O.BeV

0/

*
i

Mn0.2i Zn0.M F'*M Fe2i

/^

sZnos)t> 97

^DM Fe2

Ep.t).23tV
t -aos

W
'

/
1

AW
0.10

OI23iS6789IOIiaai*
Fig. 45.5.

Temperature dependence of

d.c. resistivity for several ferrites.

impurity

(intrinsic)

semiconductors the influence of temperature on the


is

concentration of the conduction carriers


the temperature influence

relatively small. This


is

means

that

on the conductivity

only a result of the change

of the mobility of the electrons or holes with temperature. Fig. 45.5 gives the relation between log p and 1/T for various ferrites. In most cases a
straight line is

found in a wide temperature range, with a slope corresponding

to

Ep

according to the relation:

= 0.198.10-3

d(log P)/d(l/T).

(45.2)

45]

D.C. RESISTIVITY

235

The

values for

Ep

lie

between

0.1

and 0.5 eV.

A high
is

activation energy
ferrite at

always goes hand in hand with a high


points to

resistivity

of the

room

temperature. In a few cases a change in slope

found in the curve, which

mechanisms with differing activation Similar changes have also been found at the Curie points of energies. MnFe204, NiFe2C>4 and CuFe2C>4; (see [Ko 7]). As regards the curve of
parallel conductivity
resistivity versus

two

temperature, a special case


is

among

the ferrites

is

pure

Fe3C>4

and Fe3C>4 which

not entirely stoichiometric or in which a small


4], shows log p plotted against IJT The jump in the resistivity at 119 K is

concentration of foreign ions has been substituted. Curve I in Fig. 45.6, as

found by Verwey and Haaijman [Ve


for highly stoichiometric FesQi.

caused by the electron ordering described in

31.4,

which

is

associated

with a transition from cubic to orthorhombic crystal structure below 119 K.


It

can be seen from the same figure that an excess of yFe2C>3 in Fe3C>4

reduces the

jump
1].

in resistivity

and

shifts it

towards lower temperatures.

The same

effect is

Zn

ions [Ep

found for minor substitutions of Ni, Co, Mg, Mn and Domenicali [Do 2] found on a single crystal of Fe 3 04

300
10*
1

T(K)
200
100

i >M
P

mem)

10 2

'^^
r~ET

m^
10

~2

r*

Z^j

i
4
t

EM
I1

-*- 10 3 /T(K- 1)
Fig. 45.6.

The

resistivity
I)

of sintered bars of Fe 3

composition (curve

and with small

quantities of

yFeaOs (increasing from

having a practically stoichiometric II to VI)

dissolved in the lattice, after [Ve 4].

236

ELECTRICAL PROPERTIES

[CH. XII

for the resistivity in the three principal crystallographic directions a similar

jump
45.7),

as indicated in Fig. 45.6.

Fe 3 C>4 does not continue to drop, but

Above room temperature the resistivity of shows a minimum at 80 C (see Fig.


4

above which the conductivity of Fe 3

shows a metallic behaviour.

W
P
+

UK

M
\

35
1

m
1

T(K)

m
1

(ohm cm)
7.05

FejOi

1.04

iO

80

160

-* T(C)
Fig. 45.7. Resistivity of a natural magnetite single crystal in the [100]

direction

above room temperature,

after

[Do

2].

46.

Frequency-Dependence of Conductivity and Dielectric Constant

46.1.

EXPERIMENTAL RESULTS
of about 100 kc/s measurements of the conductivity and

Up to a frequency
for

on a bridge, as described For much higher frequencies, resonance methods are used, such as described by Gevers [Ge 2]. An ideal
the dielectric constant of ferrites can be carried out

example by Kohler and Koops [Ko

4].

capacitor

Cp (with loss-free dielectric) in parallel with a resistor Rv is taken


The resistor

as the equivalent circuit of a capacitor with a dielectric having a certain


conductivity.
resistors,

Rv can be considered as built up from two parallel

finite ohmic resistance of the dielectric (ferrite) and the other representing an equivalent resistance of such a value that the

one representing the

energy dissipated in
It is

it

is

equal to the dielectric losses in the

dielectric.

not possible by a measurement at a single frequency to determine these


resistances separately,

and for this reason it is usual to apply the simple equivalent circuit of Fig. 46.1 for a capacitor with dielectric. For the impedance Z between points P and Q we can write:
two Z-i

=jwCv + Rp -K

(46.1)

Putting e' p as the real part of the dielectric constant and a as the conductivity

146]

FREQUENCY-DEPENDENCE

01

CONDUCTIVITY

237

(a)

(b)

Hg. The

44.2.

crystals with a preferred direction of magnetization


field.

Photomicrographs of sintered specimens of BaEcisOie with oriented crystals. have been oriented in a uniform
In (a) the hexagonal basal planes
1

magnetic

lie in

the plane of the paper; in (b) the

basal planes are perpendicular thereto.

cm

of the figure corresponds to 18 microns.

238

If

ECT R C A L PRO P E Rl
i

IIS

[CH. XII

to _y

lis
q
O. .a

g o'

J c.
-a

a
c
-

o o
=

2 U

H N

> 4*

5|

o
S c
r ->

J
i
4>
!=

a a
"<5

2
:J

a
-

'j

HI
"&=<=
2
to "5

i
-J

C / 5

M
i>

O,
ej

i
!

3 -E

n w o o U B

* | * ^ ^

46]

FREQUENCY-DEPENDENCE OF CONDUCTIVITY
we have

239
farad,

CP =

l.ll.lftj 12 ej,'j4/47rd

and
is

Rp
is

d/Ao ohm, where

expressed

in cm 2

the

area of the capacitor plates, and


Cp;
filled

d expressed
is

in

cm

the distance between the plates, which

entirely

with the dielectric under investigation. (The

plates are electrodes applied to the dielectric.)

The
e,

T
Fig. 46.1. Equivalent circuit

fact that the dielectric is

not loss-free can generally


dielectric

be denoted by a complex
hence:

constant

of a capacitor with

a lossy dielectric.

where

p"

e = ep p = 11.3xl012
le

(46.2)
<7/>.

(46.3)

The

dielectric loss factor is given by:

tan 8

= (cjCpRp)- 1 = 4iro/w<Ep'.

(46.4)

Brockman

et al. [Br 2]

conductivity at low frequencies (below about


dielectric constant (e

have discovered that sintered ferrites with a high 1 Mc/s) always have a high
5
).

^ 10

Koop's

results in

Table 45.1 give an impression

10 B (T 1 (ohrncm)'

f(&)
Fig. 46.2. Dielectric constant

and specific conductivity a of a ferrite sample No. 3 from Table 45.1. Measuring points Nio.4Zno.eFe204, is calafter [Ko 6]. Drawn curves according to (46.5). The c" p curve
e' p

culated according to (46.3) with correction for the d.c. conductivity.

240

ELECTRICAL PROPERTIES
<j

[CH. XII

of the relationship between


the measuring frequency, as

and c In general
a.

it is

found that

e is

roughly

inversely proportional to the square root of

may be

seen,
e

Both quantities depend on for example, from the measuring


<j

points in Fig. 46.2.

The

relaxation in

and

can be described in terms of

the relaxation formula:


go
1

<y + CuM
(46.5)

p
1

Oj2 T 2

where the indices

and

<s> indicate

the limiting values at very low

and
is

at

very high frequency respectively, and where the relaxation time t


characteristic time constant of the ferrite.

The

relaxation frequency (ocl/r)

for the different materials appears to be approximately proportional to the

low-frequency value of the dielectric constant. The true low-frequency


level for e

has never been reached according to the data recorded in literature;

measurements are needed at frequencies below 10 -1 c/s. Table 46.1 gives a survey of the quantities e and a as found for diverse subfor this purpose
stances.
ferrites

A constant high-frequency level for e has


mentioned in the
table,

not been reached for the

which have a high dispersion frequency.


of all
ferrites

At 9300 Mc/s the


which
It
is

dielectric constant

has decreased to about

10,
2].

a value corresponding to the polarizability for oxygen ions [Fa


field strengths

has been found that at

above
46.1

volt /cm

and

at

low frequency

TABLE

DATA CONCERNING DISPERSION IN THE DIELECTRIC CONSTANT AND THE CONDUCTIVITY a OF A NUMBER OF FERRITES WITH SPINEL STRUCTURE.
<f

Low-frequency
value *)
Ferrite
"0
eo

High-frequency
i

Relaxation

fre-

/alue
CToo

quency

(in

kc/s)

According

(ohm-cm) -1
0.510-6
2-

e<

(ohm-cm) -1
2.1-10-6

Measured
1.7

to (46.7) 2.0

No.

from Table 45.1

1,980
1,710

16
13.8

No

la

10-

14-10-6

4
200

15

No. 16
Hio.48Zno.48Fe Il: o.o4

28,200

0.810- 3
7.710" 3 0.510-s
0.3-10-s

~42
t)

2-10- 3

130

Fe 2 4 Ni .5Zn .5Fe2O4 MgFe204, after


[Fal]
*)

100,000

>lt)
2-10-6

2000
1

1.8

2,100

15

30,000

22

4.8- 10-6

11

0.3

t)

The figures represent the results of measurements at the lowest frequency, With this ferrite no constant level for e and a has yet been reached at 50 Mc/s.

46]

FREQUENCY-DEPENDENCE OF CONDUCTIVITY
the quantities e

241

and a' 1

(i.e.

the resistivity)

become
It

X J'
}'
Fig. 46.3. Equivalent circuit

smaller with increasing field strength, particularly


for
ferrites

with

a high

dielectric

constant.

appears that in sufficiently high measuring the low-frequency value of e does not differ

fields

much

from the high-frequency


46.2.

value.

PHENOMENOLOGICAL THEORY
be assumed that a polycrystalline sintered consists of large domains of fairly well

It

may

for

ferrite

core

ferrite

showing relaxation dispersions in e and a with


a single time constant.

conducting material (Ri and Ci in Fig. 46.3) which


are separated by thin layers of a relatively poorly

conducting substance
layers

(i? 2

and

C2).

These boundary
crystal

can have arisen by

superficial reduction or oxidation of the

in the porous material as a result of their direct contact with the firing atmosphere. In this case the relaxation time t is given by:

Ci
l/i?i

+ C2 + l/R 2

ei

4tt (a!

+ cz/a + ca/a)

(46.6)
'

9.10 11

where a(<^l)

is

the ratio between the thickness of the boundary layer

and

that of the large domain. Koops [Ko 6] has assumed that the intrinsic dielectric constant of the large domain has approximately the same value as that
e 2 ). This will be approximately equal to the e of the boundary layer (ei caused by the oxygen ions. If it is assumed, moreover, that i? 2 ;> Ri, we

then have,

if (Too is

expressed in (ohm-cm)" 1

Too 0

CTi

=*z/a

(46.7)

00

~ /a ^ 0.0855 X lO" 13
<r 2

eo/o-

In Fig. 46.2 the values of e and a of the ferrite No. 3 in Table 45.1 are plotted as a function of frequency. The crosses and the circles in the figure denote
the measuring results, while the curves are drawn in accordance with (46.5), 0.94 x 10" 4 sec. The thickness ratio*) is then it being assumed that t

a
(e

= 0.78 X lO- 2

(a

=e

2 /ro

foo

Ao).

In those cases where

e is

very high

^ 10

),

a becomes so small that the boundary layers can only be a few

*)

Koops [Ko

6]

did not disregard the high-frequency conductivity in (46.7) and there-

fore found a different value:

0.45T0" 2

242

ELECTRICAL PROPERTIES
is

[CH. XII

Angstroms thick. It this boundary layer

found then that where the ferrous content is high, will be only a few lattice spacings thick, whereas with
it

would be a factor of 100 thicker. Also plotted in Fig. 46.2 is the quantity e p ", which is calculated according to (46.3). The assumption is made that the direct current conductivity also makes a
a lower ferrous content
contribution to the losses at high frequencies, for which reason the values
inserted for
<r

in (46.3) are the differences


its

between a measured at a
<ro-

specific

frequency and

Kamiyoshi [Ka 2], Volger found the same activation energy [Vo 1] and Fairweather and Frost [Fa 1] Ep for the temperature-dependence of the d.c. conductivity (ocl/i?2) and for the relaxation time t. However, according to (46.3), the relaxation time
low-frequency value,
t
is

proportional to the high-frequency level of the resistivity (ocRi), so

that

we come

to the conclusion that the activation energies for the conduc-

tivity

of the boundary layers and the large domains are equal. Volger and Fairweather and Frost assume therefore that the grains make poor contact
with each other. The field-dependence of <j and e may, according to this model

be connected with

electrical

breakdown

in the layers.

CHAPTER XIH

STATIC INITIAL PERMEABILITY


47. Static
47.1.

Initial

Permeability at

Room

Temperature

FERRITES WITH ISOTROPIC ROTATIONAL PERMEABILITY


in Chapter V, the initial permeability of a ferromagnetic sub-

As explained
domain or
initial

stance can be due either to a simultaneous rotation of the spins in each Weiss
to a reversible displacement or bulging of
is

domain

walls.

The
dis-

permeability due to rotations

determined by the anisotropics

cussed in Chapter IV. For the general case that the binding of the magnetization to a preferred direction
is

described in terms of two anisotropy fields

H^ and Hj, we may

write according to (17.4) for the

components of the

rotational permeability in the three principal directions of a crystal with

the magnetization vector in the

direction (see Fig. 47.1):


l)/4*r

P*s

(f*w

l)/4^

= MslHf, fa -

= M./J3J

(47.1)

For a polycrystaUine specimen consisting of randomly oriented


without any magnetic interaction, the average value of the
ability
(xo is

crystallites

initial

perme-

given by the expression:

( -

1)/4tt

= (1/3)(M /Hf + M /Hi).


S

(47.2)

Fig. 47.1. Anisotropic rotational permeability.


is

The x

direction

rotation of the the preferred direction of magnetization. out of magnetization M, in the xy plane over a small angle
</>

the preferred direction


field

is

opposed by a

relatively small anisotropy


is

H$;

see figure a.

rotation in the xz plane

opposed

by the

larger anisotropy field

H^;

see figure b.

244

STATIC INITIAL PERMEABILITY


spinels,

[CH. XIII

For the ferrimagnetic

and

for the hexagonal ferrimagnetic oxides

having the c axis as the preferred direction of magnetization, we may write A A (=HA ); the rotational permeability is then isotropic, so that

H =H

(47.2) reduces to:

(mo-1)/4tt
If the crystal anisotropy
is

= (2/3)M /^.
s

(47.3)
field

predominant the anisotropy

HA

is

related

to the crystal anisotropy constants according to Table 11. 1

and

eq. (11.7).

In a polycrystalline material the crystals are not free to deform.


in their turn give rise to an anisotropy of the type (13.8).
this is [Ki 2] (see

As a

conse-

quence the rotation of the magnetization vector will induce stresses which

For cubic

crystals

page

58):

F*

=l

Kcii

- cia) A,*, - 2cu \ 2n

(47.4)

If the internal mechanical stresses in

a polycrystalline specimen are so

great that the stress anisotropy predominates, the situation for determining

the permeability due to rotations

is

complicated. Assuming for the sake of


is

simplicity that the magnetostriction

isotropic

and

positive, then according


stress value
\at\,

to [Be 8] the permeability


will

due to rotations, at an average be of the order of magnitude of:


0*0

1)/4t7

= (2/9)M 2/|A||
s

CTi |.

(47.5)

The reversible bulging of the domain wall does not change the Weiss domain pattern as a whole, and as stated in 16.1 the stiffness of the domain walls is determined by the energy increase due to the enlargement of the wall area. The permeability corresponding to this is given by (16.3). According to this formula the permeability depends not only on the anisotropics determining the magnitude of the specific wall energy, but also substantially

upon the span D of the wall. For simple spinels one can calculate an

initial

permeability for rotations

according to (47.3) with the aid of the crystal anisotropy and saturation magnetization data given in Tables 34.1 and 32.111. The result is always at
least

a factor of two lower than the value measured for polycrystalline specidepends closely on the method of preparing the specimen. The
effect size

mens. Naturally, the measured permeability varies within a wide range,


since
it

and

distribution of the pores, as well as the average size of the crystallites,

have a pronounced
tered specimens

on

ft

However, the permeability of the

sin-

is always appreciably higher than that which is to be expected from the magnitude of the anisotropy for the case of rotations alone.

This

may

be the consequence of a contribution from reversible wall

dis-

47]
10 3

STATIC INITIAL PERMEABILITY AT


,

ROOM TEMPERATURE

245
to be

,,,BOO*'
I.3

placements. Assuming the span

equal to the distance between the domain

-U.3-

-4~t

walls

and equal to

5 microns, which, in

125CP

ferrites fired at
&1200

high temperature, corres-

z 10
'

vV

itso

s,H50"C

ponds approximately to the distance between the pores, and assuming further 2 1 erg/cm , 300 gauss and a w s

M =

\ !V

which
wo\

is

an average value for the

ferrites

with spinel structure,

we

find according

10

NiFe 20i.

^ v
A,
\
SN
k

to (16.3) that /u.o= 200


(16.4) that
It

and according to

w=

60 for

K=
is

5104 erg/cm 3

appears from this that in the case of

xsso

ferrites

whose porosity

not too great and


finely distributed,

whose pores are not too


0.2
0.4-

the reversible bulging of domain walls can

Fig. 47.2.

The

initial

permeability

make a contribution to ^o which is greater than that originating from rotations. Fig.
47.2 gives the relation between initial per-

no of polycrystalline ferrite samples as a function of their porosity p.

The

was varied by varying the sintering temperature. The


porosity
sintering

temperature
indicated.

for

each

sample

is

and porosity p for specimens of nickel ferrite [Br 7] and nickel-zinc ferrite with spinel structure which have been fired the at different temperatures. For p = figure shows the result of a measurement
meability
fto

made on a
there
is

nickel ferrite single-crystal

by Gait [Ga
the

4]. It

can be seen that


with
increasing

an appreciable

increase

in

permeability

density of the material, which appears to be connected with an increase in

the contribution from

domain wall displacements.

An
firing

investigation of the influence of crystal size

on

the magnitude of

jx

has been carried out by Guillaud [Gu 9] on manganese-zinc

ferrites (the

composition in mol

was

52.5

Fe 2

3,

28.3

MnO
much

and

19.2

ZnO).

Care was taken to ensure that the pores occurred as

as possible only

on

grain boundaries, so that each crystallite

result is

considerable increase in

reproduced in curve a of Fig. 47.3. /xo when the average diameter of the

would be free of pores. The It can be seen that there is a


crystallite is

greater than about 5 microns. Guillaud assumes that

onwards the permeability

is

from this crystal size due not only to rotations of the magnetization

but also to wall displacements. In the preparation of samples with crystallites larger than 20 microns, pores also occur in the crystals, and these, according
to the author, limit the permeability.
for a nickel-zinc ferrite.

Curve b in

Fig. 47.3 gives similar results

246
6000

STATIC INITIAL PERMEABILITY


-?-.

[CH. XIII

**

4000

~7^
t

\
\
\ \,

/^~
2000

Is

y^
10

IS

20

'd

(10~3

mm)

Fig. 47.3.

Dependence of the

initial

permeability no on the diaferrites

meter d of the crystals in a) manganese-zinc


structure,

with spinel

made from

the oxide mixture 52

mol

Fe2C>3

28.3%

MnO
9].

and 19.2%

spinel structure: 50.3

ZnO and b) nickel-zinc ferrite with mol% Fe2 3 15% NiO and 34.7% ZnO.
,

After [Gu

For making
is

polycrystalline specimens with a high initial permeability

it

a prerequisite that the magnetic anisotropics, such as the crystal aniso-

tropy and the stress anisotropy, should be small. The crystal anisotropy and
the magnetostriction are determined by the chemical composition of the

With cubic crystals the internal stresses may be small, since these crystals have an isotropic coefficient of expansion. In order to obtain a high
ferrite.

permeability
as possible

it is also necessary that the specimen should have as few pores and that the crystallites should have a sufficiently large size. These conditions can be fulfilled by suitable technological procedure in the

preparation of the

ferrite.

A particular case is the ferrite with very small magnetic anisotropics,


may be

for

example a manganese-zinc-ferrous spinel, which has been sintered in such a way that it has only a small porosity consisting of a large number of
finely distributed cavities.

In this case the domain-wall thickness


is

of

the order of magnitude of the distance between the cavities. It

questionable

whether in such a case one can still speak of a Weiss domain structure, or whether one should speak of a gradual variation of the direction of magnetization throughout the entire specimen.

47] 47.2.

STATIC INITIAL PERMEABILITY AT

ROOM TEMPERATURE

247

FERRITES WITH ANISOTROPIC ROTATIONAL PERMEABILITY


ferrites

For the

with hexagonal crystal structure, whose basal plane

preferred plane of magnetization,

we have

Hf

is a ^> H^, so that the rotational

permeability of such crystals

is

anisotropic according to (47.1).

The

aniso-

tropy

field

H* is often a factor of 1000

smaller than

the magnetic interaction between the crystals,


talline

Hf, we can write for a

so that, neglecting
polycrys-

specimen in good approximaton:

(no-l)/4ir^(l/3)Ms /Hi.
Since

(47.6)
field in the

H^

is

of the same order of magnitude as the anisotropy

case of spinels, hexagonal ferrites with a preferred plane of magnetization


can, in principle, also

show appreciable values of


47.1.

permeability. Results of

measurements on polycrystalline isotropic specimens are represented in the


third

column of Table

The

initial

permeability of a sintered polycrys-

talline

sample of these

ferrites also

depends strongly on the method of


/to

preparation. It

is striking,

however, that the measured values for

are

appreciably smaller than those which

may

be deduced from the magnitude

of the crystal anisotropy in the basal plane (for the anisotropy energy see

Table

39.11).

Only in the case of C02Y is the crystal anisotropy comparatively

high, so that here this anisotropy probably determines the permeability.


It is

possible that, during the cooling of polycrystalline samples, appre-

ciable stresses arise in the hexagonal crystals in consequence of the aniso-

tropic coefficient of expansion.

Assuming these

internal stresses to be so

large that they approach the crushing strength of the ferrite (o-*^ 10 9

dyne/cm2),
(which of the
value
is

it

-5 follows that for a saturation magnetostriction value of 10


ferrites)

a quite normal value for hexagonal


permeability
/*o

the

maximum
10.

value

initial

will

be approximately equal to
it is

Such a

is

found experimentally in many cases, so that

not unlikely that

TABLE
INITIAL PERMEABILITY

47.1

OF SINTERED SPECIMENS OF HEXAGONAL OXIDES WITH A PREFERIsotropic specimen

RED PLANE OF MAGNETIZATION, AT 20 C.


Anisotropic specimen
Calculated

Ferrite

Calculated according
to (47.6)

Measured
12

Measured
29
55

C02Z
Coo.8Zn1.2Z Co1.0Zn1.0Z

75

~700 ~400

24

20
16
5

Zn 2Y C02Y

>

750
5

~ ~ > ~

x 75 X 700 3 / 2 x400 3 / 2 x750 3 5 /a x


s/a
3
/2

43
35
7

248

STATIC INITIAL PERMEABILITY

[CH. XIII

the stress anisotropy has a substantial influence

on the magnitude of no

for polycrystalline specimens of hexagonal ferrites with a preferred plane

of magnetization. There are no indications that domain wall displacements

make any
form walls

appreciable contribution in these ferrites.


parallel to the basal plane.

It is easy,

however, to
thicksmall.

ness large, since these

The energy will be low and the are both determined by Kz from (1 1.6), which is
is

Internal demagnetization due to pores

also appreciably larger in the case

of ferrites with a preferred plane of magnetization than in the case of spinels,

and

internal demagnetization exists even in the absence of pores,

owing to

crystal platelets

whose basal plane

is

at right angles to the magnetic flux;

see 43.6
is

and

Fig. 43.7.

A substantial reduction of internal demagnetization


The permeability
in these

obtained in specimens in which the crystallites are oriented with the basal

planes mutually parallel (curve c) in Fig. 43.6.

found to increase with the degree of orientation of the crystals; see Fig. 47.4. For these samples of C02Z and CoZnZ with foliate texture
specimens
is

44) the degree of orientation


field

is

varied by using different currents which


crystals. All

produce the rotating

used for orienting the

specimens have

approximately the same density. The figure clearly shows the considerable
gain in permeability obtained in particular at a high percentage of orien-

50
(&0

CoZnZ y
40

30

Co2 20

10

0.2

04

0.6

0.8

ID

Fig. 47.4. Initial permeability no of samples of C02Z and CoZnZ with different degrees of crystal orientation /.

47]

STATIC INITIAL PERMEABILITY AT

ROOM TEMPERATURE

249

tation. In
is

Table 47.1 the gain in permeability obtained by crystal orientation


parallel to the preferred planes.

given for several different compositions. For the measurement of the peris

meability the applied field strength

For a

measurement where the

field strength is

perpendicular to these planes, a


is

lower permeability than in the isotropic material

to be expected. In fact,
0.91,

by measuring
of only 2.5
is

in this

way
is

the

C02Z specimen

with/=

a permeability

found. For an ideally oriented sample the value derived from


1.3.

the uniaxial anisotropy

In Fig. 47.5 the


ferrites
is

initial

permeability at
S

room temperature

is

given for the

of the

series

Co 8 Zn2-Z. For

<

0.65 the c axis of these ferrites

a preferred direction of magnetization (see Fig. 39.8) and ^o is determined by the magnitude of K\. The susceptibility due to rotations is then extremely
small since

Ki

is

of the order of magnitude of 10 5 to 10 6 erg/cm 3 or higher.

In specimens with low porosity a further contribution to po

may be expected

from the domain wall displacements. That is why an initial permeability 4 may still be found for specimens corresponding to 8 < 0.65. The (xo compounds corresponding to 8 > 0.65 have a preferred plane of magnetization (see Fig. 39.8) and thus in principle have a greater value of /*<>, which is in fact found. The decrease in permeability when 8 increases from 0.65

to 2.0

is

related to the increase of anisotropy in the basal plane (A3) with

increasing cobalt content; see, for example, Table 39.11.

A curve

of permeability as a function of the composition, similar to that


is

of Fig. 47.5,

found for

all series

of mixed

ferrites

in the sign of the principal anisotropy constant K\, as for

which exhibit a change example the series

Co s Me2-sZ and Co 6 Me2-sW, where Me


that can occur in
30

represents one of the divalent ions

and

W compositions.

fi

\
20

Co$Zr>2-sZ
i

T-20C

10
'

'^
;

Fig. 47.5. Initial permeability

no at

room temfor

perature in dependence

on the cobalt content


OS

1.5

2J0

ferrites

of

the

series

CoxZn2-aZ.

250

STATIC INITIAL PERMEABILITY

[CH. XIII

48. Temperature Dependence of Initial Permeability


48.1.

FERRITES WITH SPINEL STRUCTURE

Simple Ferrites

The magnitude of the


of rotations
is

initial

permeability of a magnetic material as a result

proportional to the square of the saturation magnetization

and

inversely proportional to the magnetic anisotropy energy.


im>

Both quantities

vary with temperature, so that


ture.

can be a complicated function of tempera-

was pointed out that the anisotropy is related in general to the second or a higher power of s The permeability will thus, as a rule, increase up to the Curie point. For a number of simple ferrites with spinel structure the curves of f*o versus T are drawn in Fig. 48.1. The curves represent measurements on sintered samples, so that the same restrictions
In

1 1 it

concerning the reproducibility of the curves apply as in

47.

Since the density

of the sample

may

influence the permeability,

it is

mentioned in the figure

for each ferrite. In general, ^o increases with temperature

and shows a

maximum just below


This peak
34.1.
is

the Curie point.


at approximately 130 K.

For Fe3C>4 a second peak appears in the curve

related with a zero point in the crystal anisotropy; see Fig.

The

height of this

maximum may be limited not


by the shape and

only by some inhomostress

geneity of the specimen but also


present.

anisotropy

still

Mixed Zinc

Ferrites

Among

the technically important ferrites are the mixed zinc ferrites with a
1]

high initial permeability. After Forestier [Fo

had discovered

that the Curie

points of mixed crystals of ferrites with zinc ferrite are lower than those of the corresponding simple ferrite (see, for example, Fig. 32.9),

Snoek made

a broad investigation into the behaviour of the initial permeability of these


ferrites.

In doing so he was the

first

to prepare specimens with an initial

permeability well above 50 and even of the order of magnitude of 1000.

He found
shifts

not only that the maximum in the po versus T curves of Fig. 48.1 with the Curie point towards lower temperatures, and accordingly
at

may

lie

room temperature or immediately above it, but also


ferrites,
is

that, in

most

mixed zinc
the lower

appreciably higher values of po appear in this

maximum

the Curie point.

for the series of ferrites


is

Examples are given in Fig. 48.2 and Fig. 48.3 Mni_sZn 8 Fe 2 04 and Nii_ Zn s Fe 2 C>4. The effect
series (Li
is
.

less

pronounced for the

5 Feo.5)i-8Zn 8 Fe 2

04

(Fig. 48.4).

Also

in this case, however,

maximum

for the lowest possible Curie point.

48]

TEMPERATURE DEPENDENCE OF

INITIAL PERMEABILITY

251

252
3000

STATIC INITIAL PERMEABILITY


I I I I I I
I

[CH. XIII

Mni-sZnsFe2 0i.

S=0.50

2000

0.40

0.30

0.20

1000
0.0

\
-200
-100
100

t
V

200

300

T(C)
Fig. 48.2. Initial permeability
(to

as

a function of tempera-

ture for

mixed manganese-zinc ferrites with spinel structure Mni_8Zn 6 Fe204. These specimens also contain a small ferrous

ion content.

As examples

for the

manganese zinc

ferrites

experimental data are given

for specimens

which also contain a low concentration of ferrous ions; these

are ternary manganese-zinc-ferrous ferrites in which the

Fe30 4 content

can amount to 5%.

Mixed
Mixed

Cobalt Ferrites

crystals

between

ferrites

having a negative crystal anisotropy and the

cobalt ferrite having a positive crystal anisotropy can be

made

with such

proportions of the components that the crystal anisotropy of the mixed


crystal is zero at a desired temperature.

Owing

to the high anisotropy of


is

cobalt ferrite, only a small concentration of this ferrite


7400
1

needed.

Nii- s Zn s Fe2 0/,

1200

S = 0.70
"

/y
1

0.64

S'0.70
4000

WOO

/
800
600
400
,

2500

-/
SO

/
/,/
^0.50

-/TLJ

200 j

/ V^,
2C

V /

Fig.

48.3.

Initial

permeability

=
m
SVtf.5

0.36
lio

0.20

as a function of temperature

4 -A
40

for
PsJ

mixed nickel-zinc
spinel
structure,

ferrites

00

60
7 1 C)

with

Nii-gZn s Fe204.

'

48]

TEMPERATURE DEPENDENCE OF
600

INITIAL PERMEABILITY

253

(Li'os

e Feo.s)}-sZns F 24

n
400
\

o.sc

0.45

s=o. ss\

o.s \

200

*o/

K
-2 73-200 -100
100

200

300

400

500 600 *- T(C)

700

Fig. 48.4. Initial permeability no a as function of temperature for

mixed

lithium-zinc ferrites with spinel structure, (Lio.5Feo.5)i-sZn s Fe2C>4.

was shown that the zero point in the crystal anisotropy of magnetite (at 130 K) can be shifted towards higher temperatures by the formation of a mixed crystal with cobalt ferrite. For the compound Coo.oi
In 34.1
it

Fe2.99C>4 this zero point already lies near

room temperature. By

substituting

cobalt the

maximum
is

in the

juo

versus

T curve

for polycrystalline magnetite

specimens

also shifted towards a higher temperature (see Fig. 48.5).

The zero points in the crystal anisotropy for varying cobalt content are found at the same temperatures as the maxima in the ^ versus T curves. The peak value of j^o is found to decrease the more the composition differs from FesCU; this may be related to the fact that there are two anisotropics of
opposite sign, the absolute values of which are greater the higher
is

the

temperature of the zero point for the crystal anisotropy of the mixed

ferrite.

500

S=0
400
(to

(Fe3 Q()
i

CogFe3 -to*

s
=0.0025

k 300
S=0.005

200

7^
100

}
T150

A^ z-^

300

J' 0.01

S=0.02Fig. 48.5. Initial permeabili-

_--

^
5_
:

ty of cobalt-substituted
netite

mag-

Co s Fe3-s O4 measured
[Bi
4].

at a frequency of 10 kc/s,

700

200

250

350

400

after

-*- T(K)

254
In order to

STATIC INITIAL PERMEABILITY

[CH. XIII

make

certain that that the anisotropy in each part of the speciit is

men

is

zero at the same temperature,

necessary to ensure a uniform


ferrites, Fig.

distribution of the cobalt ions.

For equimolar lithium zinc

48.6 gives the initial

permeability as a function of temperature for various


2].

cobalt contents [Bu

pronounced second maximum is seen in these curves far below the Curie point, and the position of this maximum shifts with the cobalt content. In this case too, the relatively low value of no in the

maximum
to stress

will

be attributable to chemical inhomogeneities and possibly

and shape anisotropy. Similar results have been reported for lithium ferrites and nickel-zinc ferrites [Bu 2] and [Bu 3]. Van der Burgt found, however, that the effect of cobalt substitution on the permeability differs from one ferrite to another. In other words, one may find that the simple

Fig. 48.6.

Temperature
initial

dependence of the
permeability
v-o

of cobaltli-

substituted equimolar

thium-zinc

ferrites, after

[Bu
XX)

2].

300

relation JCi(8)

= (1

8)

Ki(8

= 0) +
Me

8 Ki(S

1)

does not hold at a given

temperature. For instance, where

stands for the divalent metal ions

Fe and
zero at

Mn

the cobalt content required to

make

the crystal anisotropy

room temperature appears

to be respectively

about

li

and 4

times the cobalt content predicted by the above relation [Bu

3].

Manganese-Ferrous Ferrites
Figure 48.7 shows the permeability versus temperature curves of some polycrystalline specimens of manganese-ferrous ferrites

too, a second

maximum
same

The

position of this

Mni- 8 FeFe204. Here, found besides the maximum at the Curie point. second maximum depends only slightly on the ferrous
is

content. In the

figure

a curve of similar shape (dashed)

is

shown

for a

48]

TEMPERATURE DEPENDENCE OF

INITIAL PERMEABILITY

255

1500

Fig. 48.7. Initial permeability of manganese-ferrous ferrites as

a function of temperature.

Fully drawn lines for polycrystalline specimens, the dashed curve for a single crystal,
after

[En

2].

single crystal with the single crystal


is

composition Mno.85Fe2.15O4. Measurements on this


2] indicate that the

by Enz [En

second

maximum

in the curve
It

not related to zero points in crystal anisotropy or magnetostriction.

was

found, however, that after demagnetization, the permeability of the single

The disaccommodation of this crystal is reAs a consequence of the disaccommodation the /* versus T'curve also depends on the measuring time. It is highly probable that the special form of the /io versus T curve, which was
crystal is very time-dependent.

presented for various temperatures in Fig. 48.8.

measured in a relatively short time, is connected with the increase in the disaccommodation rate at higher temperature. In the case of the polycrystalline specimens an appreciable disaccommodation is found also, but it is not yet certain whether this is sufficiently large to explain completely the
additional peak in the po versus

T curve.
fairly

The manganese-zinc

ferrites

have a

high

initial permeability,

which

can be further increased by making a ternary


48.9 the saturation magnetostriction A

ferrite

with

Fesd;

in Fig.

and the

initial

permeability pa of

such

ferrites

are plotted as a function of the ferrous concentration at


It

room

temperature.
ferrite,

As

is

a given composition of the ternary zero, and that for the same material the greatest value of ^0
can be seen
that, for

occurs. This result indicates that, in order to obtain very high permeabilities
in ferrites, the magnetostriction

maximum

in

/*o is

must also be made small. The fact that the found for a certain ferrous content does not necessarily
efiFect,

point to a magnetostriction

since

it is

known

[St 4] that

an excess of

256

STATIC INITIAL PERMEABILITY


no
T=-78C
80

[CH. XI11

T=-21C
SO

40

20

T-

0C

T-22C
500
1000
1500

-+*t.
Fig. 48.8.

crystal Mno.s5Fe2.15O4

Disaccommodation of the initial permeability for the single from Fig. 48.7 at different temperatures. The

permeabilities immediately after demagnetization have been normalized


to 100.

2500

A
'
\
:

1500

^3

J0 e /.,

^
Fig.
48.9.

Oxide mixtures

consisting:

of 18 FeaOa,

mol% ZnO, (50+8) mol% balance MnO, were fired for


at 1290

two hours

C in nitrogen

at-

mosphere. The three graphs from the

mo/%
FeO

bottom upwards give


ferrous

respectively the
in

content

expressed

mol%

FeO, the saturation magnetostriction A, and the initial permeability no or

s s

the samples, [Lo

3].

{j

48]

TEMPERATURE DEPENDENCE OF INITIAL PERMEABILITY

257

divalent oxides above the stoichiometric composition leads to better sintering,

which can also give

rise to

higher permeabilities.

48.2.

FERRITES WITH HEXAGONAL CRYSTAL STRUCTURE


and whose
c axis
is

Ferrites having a hexagonal crystal structure

a preferred

direction of magnetization will have an initial permeability of the order of


if the crystal anisotropy is large (Ki 106 erg/cm 3). For ferrites where the basal plane is a preferred plane such high values of K\ may be accompanied by higher values of permeability as a conse-

magnitude of unity

quence of rotations of the magnetization in the basal plane; Fig. 48.10 gives
the
juo

versus

curves for a

number of simple compounds of

this kind.

These curves show the normal behaviour of an increase in po with temperature up to the Curie point. An exception is C02Z, for which there is a sudden drop in /i at approximately 250 C, while the Curie point is much higher,
being approximately 400 C (see Fig. 38.5). The explanation
is that,

at

250 C, the
39.7).

first-order crystal anisotropy constant

changes sign (see Fig.

Below 250 C the compound C02Z has a preferred plane of magnetization, hence in principle a higher permeability owing to the possibility of
rotations of the magnetization in the basal planes of the crystals.

Above
The

250 C the material has a preferred direction of magnetization, and the

magnitude of

^10 is

determined by that of K, and


o-,

is

therefore small.

saturation magnetization

the crystal anisotropy and the initial permeability

of C02Z are plotted together as a function of temperature in Fig. 48.11 in


order to illustrate this relation.

r(c)

Fig. 48.10. Initial permeability versus temperature for a

number of polycrystalline

speci-

mens of simple hexagonal

oxides.

258

STATIC INITIAL PERMEABILITY

[CH. XIII

Po A
400

(gauss

cm 3 /g)

200

100

200

300

400/500 600

700

r(K)

/<,+2)<2
T

K,+2K2 0.5 a0%rg/cm3)


n
1.0

V
Fig. 48.11.
bility

-1.5

-2.0

netization a, the crystal anisotropy

Temperature dependence of the saturation magand the initial permea-

of a single crystal of C02Z.

300

T(C)

MX)

500

Fig. 48. 1 2. Initial permeability versus temperature curves for ferrites of the series Co a Zn2- aZ.

48]

TEMPERATURE DEPENDENCE OF
39.1

INITIAL PERMEABILITY

259

In

we saw

that,

at

plane of magnetization and


series

room Zn^L a

temperature,

C02Z has

a preferred

preferred direction and that in the

of mixed crystals

CogZ^-^Z a change of sign in the crystal anisotropy

occurs at a chemical composition corresponding to about S


Fig. 39.8).

= 0.6,

(see

For the other compositions

this

change of sign

will

occur at a

different temperature. In the po versus temperature curves of


ferrites

some of these
drops rapidly

one finds therefore a temperature range in which

/*o

with increasing temperature (Fig. 48.12). With


at

defined as the temperature

which m> has fallen to half of its peak value, Fig. 48.13 gives this temperature as a function of the composition parameter S. In the same figure the
500
I

CosZn 2 .$Z
400

300

T c

200

100
To

0.5

1.0

1.5

20

+-S
Fig. 48.13. at

The Curie temperature


initial

Tc

and the temperature To


its

which the

permeability has dropped to half

maxi-

mum

value (see Fig. 48.12) in dependence on the chemical


ferrites

composition of the

Co 8Zna-Z.

Curie point Tc
with S
rature

is

plotted for
it is

some of these compounds. For the mixed ferrites


/li

= 0.65 2.0
is

evident that the drop in

with increasing tempe-

not caused by the approach to the Curie point but, as in the case
first crystal

of C02Z, by the change in sign of the


the

anisotropy constant. For


/^o

two specimens

and

= 0.5 the sharp drop of

with increasing

temperature

is not found. This is in agreement with what is to be expected by extrapolation of the 7b versus S curve for these ferrites in Fig. 48.13. Moreover it can be deduced from this figure that, in the case of the specimen

with a composition corresponding to a value of 8 of approximately 0.5


to 0.6, the anisotropy changes sign at

room

temperature. This

is

the

same

composition, as follows from direct measurement of the crystal anisotropy;

260

STATIC INITIAL PERMEABILITY


CogMgs-$Z
/ff

[CH. XIII

S = 1.5
l

f\
~\&=2D

S=1J0/
ft-o

12

~fr

200

-too

100

200

300 *~T (C)

400

Fig. 48.14.

As

Fig. 48.12,

but

now

for

compounds Co g Mg2-Z.

see Fig. 39.7. In the


Fig. 48.12 a second

w versus T curves
maximum
initial

of some

Co s Zn2- 8 Z compounds

in

occurs, for which

no explanation has been

given.

In Fig. 48.14 the


zinc

permeability
series

is

plotted against temperature for a


in the series of cobalt-

number of specimens from the

Co 8Mg2 - 6 Z. As
juo

compounds, the sharp drop in

corresponds here to a transition

from preferred plane to preferred direction. It appears that Mg2Z (which contains no cobalt ions) also has a preferred plane at low temperature (below 95 C). The slight drop in no at high temperature takes place exactly at the Curie point. Properties corresponding to those mentioned above are compounds, since all also found in other mixed cobalt Z and cobalt compounds, apart from Co 2 Z and Co 2 W, have a preferred simple Z and

direction of magnetization at

room

temperature.

49. External Influences on the Permeability


49.1.

THE REVERSIBLE PERMEABILITY IN A BIASED STATE

The permeability of a magnetic core measured with a very small field strength
is

generally called the reversible (or differential) permeability


is

ju r ev.

When
/ire v

the core

in the demagnetized state, /^rev

no- In all other cases

depends on both the magnetic polarization (magnetization) of the core,


and, owing to hysteresis phenomena, on the sequence of applied biasing
fields

which have caused

this steady magnetization.

The

solid curves in

49]
Fig. 49.1

EXTERNAL INFLUENCES ON PERMEABILITY

261

show pTev in dependence on a polarizing field p in the case of Ni .36Zn .64Fe 2 O4, when the permeability is measured in a direction parallel to this field. The arrows indicate the cycle of the polarizing field after demagnetization of the core. The maximum value for fi iev is found when P is approximately equal to c this value differs but little from no- A magnetic field Pti perpendicular to the direction in which the
,

polycrystalline

reversible permeability

is

measured, reduces the

latter less

than a

field

Hp u

parallel to the direction

of measurement;
fields

this is indicated

by the

dashed curves in Fig.


sible permeability is

49.1.

In the case of

Hp which are large with res,l


.

pect to the internal anisotropy fields of the material, the transversal rever-

given by

jur ev,i

= 4ttM*IHp
1

The hyperbola

corresponding to

this is the

dotted curve in Fig. 49.1,

which approaches the


it is

measured curve at high strengths of the transversal polarizing field. To obtain


large variations of permeability with relatively small polarizing fields

necessary to polarize parallel to the direction of measurement. For small


variations of permeability, perpendicular biasing
is

more favourable

since

frev

Fig. 49.1.

The

reversible permeability of

polarizing field-strength

Hp

The

solid curves

asample ofNio.36Zno.54Fe2C>4 as a function of the and the broken curves apply to the cases
or perpendicular to each other respec-

where measuring and polarizing


tively.

fields are parallel

The arrows

indicate the cycle of the polarizing field.

The dotted curve


field

represents

the permeability to be expected in the case where the material has no magnetic anisotropics

and where the permeability


rection of measurement.

is

only determined by a biasing


inset

perpendicular to the discale.

The

shows a part of the curves on an enlarged

262

STATIC INITIAL PERMEABILITY

[CH. XIII

\<T= 0.36

\l\
frlrev

o.s\

Ni$Zn,-$Fe2 04

too

o.ei
*J
i

l.

^ ,>

^
/.<?

?-:

-.

....

^*

T' m '*;

,
70

- Wp

75

. ., (oersted)

Fig. 49.2.

The reversible permeability of ferrites Ni 8 Zm-Fe204


field are

as a function of the polarizing field strength. Measuring field

and polarizing
in that case there are

mutually

parallel.

no

difficulties

In Fig. 49.2,
case

[/. rev for ferrites

commonly

occurring in
jurev is

from coupling between the two circuits. of the series Ni 6 Zni- g Fe2C>4 is shown for the practice, where the field p is parallel to the

direction in which

measured. The demagnetized state was taken as

For p the curve must be parallel to the /Taxis, because the change in permeability does not depend on whether
the starting point of the measurement. the biasing field
49.2.
is

H =

parallel or antiparallel to the

measuring

field.

THE INFLUENCE OF UNIDIRECTIONAL MECHANICAL STRESS ON THE INITIAL PERMEABILITY


to the

Owing

phenomenon of magnetostriction,

internal stresses in a ferrite

can influence the permeability. The


will limit the permeability.

stress anisotropy, discussed in 13.2,

The influence of stress can be investigated quantitawith a negative saturation magnetostriction,

tively
ferrite.

by applying

external uniaxial tensile or compressive stresses to the


ferrites

In the case of

the magnetization will orient itself at right angles to the tensile stress, as
illustrated in Fig. 49.3a.

The
is

initial

permeability

/x

measured in the direction


anisotropy prevails over
is

of the

tensile stress

ae in the case where the


,

stress

the other anisotropics,

determined by domain rotations, and

related

to the magnitude of the tensile stress according to:


/*,

- = (477/3)^/^)1^1,
1

(large

ct)>

(49.1)

in

which A- 1

is

the average of the reciprocal values of the magnetostriction

49]

EXTERNAL INFLUENCES ON PERMEABILITY

263

u
Fig. 49.3. Orientation

k
is

T
ferrite

of the Weiss domains in a

bar with negative

magnetostriction; the bar

subjected to a uniaxial tensile stress (a) or a


(b).

uniaxial compressive stress

constants in the various crystal directions. Equation (49.1) was


for the case of nickel under tensile stress [Be
ferrites
8].

first

derived

In the case of the porous

a factor (dx/d) 1 / 3 must be added to the right-hand side, dx being the X-ray density and d the apparent density of the ferrite. Fig. 49.4 gives the
/*o of four ferrites as a function of the reciprocal tensile For Nio.36Zno.64Fe204 with a saturation magnetostriction 3.7 X 10- 6 it is found that, before the tensile strength of the ferrite is reached (this is reached at a tensile stress of approximately 4 kg/mm 2), a range of

initial

permeability
1/oe.

stress

BOO

Mn 0.4S Zn0.4B Fe0M Fe2 4


600

We
Hio.3G Zn
4-00

OM Fe2i

Ni0.50 Zn O.S0 Fe2t

200
Ni0.Si Zr'0.3B Fe24

_-x-x

x-

0.S

1.0

J.S

2J0
(3

2S
uniaxial

*"

e"'

{mm 3/kg)
homogeneous
ferrite bars.

Fig. 49.4. Initial permeability in the direction of a


tensile stress as

a function of that stress for four polycrystalline

264
stresses exists in

STATIC INITIAL PERMEABILITY

[CH. XIII

which po 1 is inversely proportional to ae in agreement with (49.1). From the slope of this straight line it follows that l/IA-ij 5.0 x 10- 6 , which is in reasonably good agreement with the earlier-mentioned
,

value of the saturation magnetostriction.


values
is,

The

difference between the

two

at least partly,

due to the

different values of the magnetostriction

constants for the various crystallographic directions, as for example indicated in Fig. 35.1 for magnetite. For the nickel-zinc ferrites with a low zinc

concentration (S

= 0.50

and 0.36) the

initial permeabilities

are small

and

the internal anisotropics large. It can be seen from the figure that in this case the stress anisotropy caused by the greatest tensile stress
is

not large

enough to predominate, so that a linear relationship between po and l/ae cannot be established. The values of the saturation magnetostriction are 11 X 10- 6 and 16 x 10~ 6 which is larger than in the case of the higher zinc content. It is evident that po in these ferrites is not determined by stresses. The ferrite Mno.48Zno.48Fe n o.o4Fe2C>4 has in fact a small internal anisotropy and therefore a high /xo, but no linear relationship is found to exist for this ferrite between po and l/o-e since the magnetostriction in this case is
,

exceptionally small,

|A,|

<

10~ 6

this

means

here, then, that tensile stresses

larger than the tensile strength are necessary in order to obtain a predomi-

nating homogeneous stress anisotropy.

When a uniaxial compressive stress


sive stress

is

exerted

on

ferrites

having a negative

magnetostriction, the magnetization will orient itself parallel to the compres-

and a Weiss-domain distribution will arise as in Fig. 49.3b. The change in the initial permeability of a polycrystalline specimen on which a small, homogeneous mechanical compressive or tensile stress is exerted, is given for the case where /*o is determined only by domain rotations, by
the expression:

/*-

= (poBr
Bel

1)[1

+ 0.072A

s Te

O*o-

1)/Af, a ], (small

<r,).

(49.2)

Hc

(oersted)

T
250

/%'

Fig. 49.5.
relative

Initial

permeability v^ e ,

"\
Br^

remanent induction

Br /Bcl

Bd
200
NL5

Hc

and coercive force He


crystalline

for a poly-

rod of Nio.5Zno.5Fe2C>4

as a function of externally applied


stress.

and

BT is the remanent induction Bcl is the induction at which


are
positive,

the hysteresis loop closes. Tensile


stresses
150
1 1

pressure

is

-8

-6

-t

-2

i
(><9/

negative.

&*

m m 2)

49]

EXTERNAL INFLUENCES ON PERMEABILITY

265

small In this expression, ae must be taken negative in the case of pressure. compressive stress raises the initial permeability of ferrites with negative magnetostriction. For greater compressive stresses the initial permeability again becomes smaller. In Fig. 49.5 the initial permeability of Nio.5Zno.5Fe 2 4
is

plotted as a function of an externally applied tensile or compressive stress [Ra 4]; it shows clearly the slight increase in /n with low pressures.

In the case of
is

ferrites

said above for tensile


49.3.

having positive saturation magnetostriction, what stress applies for compressive stress and vice versa.

THE INITIAL PERMEABILITY AS DEPENDENT ON THE METHOD OF DEMAGNETIZATION

ferromagnetic material can be demagnetized in two different ways. The ferromagnetic core can either be heated to a temperature above the

Curie point and then cooled slowly to


jected to

room

temperature, or

it

can be sub-

an

alternating magnetic field the amplitude of


latter

which decreases

monotonically to zero. Using the

method of demagnetization, the

direction of the demagnetizing field can also be varied with respect to the direction of the field with which the permeability is measured. Above the

broken line in Table 49.1 some results are given of investigations carried out by Rathenau and Fast [Ra 5] into the influence of the method of demagnetization on the magnitude of the initial permeability in the case of

Ni .5Zno.5Fe 2 04;

it is

probable that their results hold, at least qualitatively,

for other kinds of sintered ferrites also. the Curie point, the
initial

The

fact that, after cooling

from

permeability

is

greater than after demagnetizing

by an alternating field at room temperature may, according to (15.4), be due to the increase of the number of domain walls at higher temperature.

TABLE
THE
INITIAL PERMEABILITY

49.1

AT ROOM TEMPERATURE OF FERRITE BARS (Nio.,Zno.,Fe204) AFTER DIFFERENT METHODS OF DEMAGNETIZATION. DATA ON METALLIC NICKEL BARS ARE GIVEN FOR COMPARISON. VALUES AT ROOM TEMPERATURE, AFTER [Ra 5].
Sintering temperature

Metallic
nickel

Method of demagnetization

of the
1230 C

ferrite

1330 C

[Sn4]
600

a)

Heating above Curie point (265 C)


field

400

380

b) Alternating

with monotonically

decreasing amplitude. Measuring field


parallel to demagnetizing field.
c)

284

300

280

Demagnetization as under a) or b) followed by mechanical shocks until a


stable value
is

reached

252

258

220

266

STATIC INITIAL PERMEABILITY


these additional walls

[CH. XIII
6],

Some of

may

persist at

room temperature [Ra

so that the difference between the a and b values in Table 49.1 should be

made by reversible domain wall The influence of the direction of the demagnetizing field with respect to the measuring field on the magnitude of the initial permeability can be seen from Table 49.11. It appears that the largest values for the initial permeability are obtained when the measuring and demagnetizing directions are parallel. This is again explained by assumdisplacements to the
initial

regarded as a difference in the contribution


permeability.

ing that alternating current demagnetization gives rise to

domain

walls in

a particular direction, which can make a special contribution to the reversible magnetization in this direction.

TABLE

49.11

THE INITIAL PERMEABILITY OF A TUBE OF Nio. s Zno.jFe 2 04 IN DEPENDENCE ON THE DIRECTION OF MEASUREMENT WrTH RESPECT TO THE DEMAGNETIZING DIRECTION. SINCE IT IS DIFFICULT TO DETERMINE EXACTLY THE DEMAGNETIZING COEFFICIENT IN THE DIRECTION OF THE TUBE AXIS, THE VALUES (d) AND (a) HAVE BEEN EQUALIZED, AFTER [Ra 5].
After prior demagnetization along the

Measuring direction

circumference of
the tube
axis of the tube

Along the circumference Along the axis

185

(a)
(c)

167 (b)
185 (d)

167

49.4.

THE STABILITY OF THE INITIAL PERMEABILITY


important to

know whether the initial permeability of a ferrite core, having been demagnetized by an alternating field, remains constant for a long time, and what external perturbations can influence it. A change
It is

after

in the initial permeability with time, without

any external cause,

is

called

disaccommodation, as already mentioned (see Fig. 48.8). The initial permeability of a core can be permanently changed by the application of a transient mechanical deformation, for instance as a result of bending or dropping;
this is

known

as shock effect.

Disaccommodation

The phenomenon of disaccommodation in ferrites has been described by Snoek [Sn 3]. It is found particularly in manganese-zinc ferrites containing an excess of Fe203 and which are fired in an oxidizing atmosphere.
Fig. 49.6 gives

a result which
is

is

always found with

ferrites

of this kind,

but for which the explanation


exists

unknown. At each temperature there a kind of spectrum of relaxation times. The relaxation time becomes
as yet
(x

longer at lower temperature. After demagnetization the same variation of

49]
600

EXTERNAL INFLUENCES ON PERMEABILITY


tft
500

267

-60C

1400
300
j

"

200
TOO

town.
1

\lhour
i

Id
|

Iweek \lyear
i i

\lcent
i

XJ'

I0'

?"' /

O B2 C3

10* 10

10

K 7 8

K>

Fig. 49.6. Initial permeability no versus (the logarithm of) time

two different temperatures for a ferrite with and molar composition 23.5% MnO, 22.5%
at

spinel structure

ZnO and 54%

Fea03, after [Sn

3].

with time

is

always measured.

When

these ferrites are fired in a reducing

atmosphere, for example in nitrogen, mixed crystals of manganese-zincferrous ferrites are produced which often

show little or no disaccommodation.


absent at

In the case of manganese ferrite or manganese-zinc ferrite without excess


iron for example, disaccommodation
is

room

temperature, just

as in the case of nickel-zinc ferrites with a surplus or deficiency of Fe203.

An
at

indication of disaccommodation of

some

significance has

been found

196 C

in a nickel-zinc ferrite fired in


initial

an oxidizing atmosphere. In 15
to drop by about
in a single crystal of

minutes the

permeability at

196 C was found

5%. Exceptionally high disaccommodation occurs


Mno.g5Fe2.15O4; see Fig. 48.8.

Shock Effect
Sensitivity of the initial permeability to
ferrites

shock

is

found mainly in those

which combine a high magnetostriction with a high value of y.o, which case mechanical stresses can cause substantial changes in the Weiss domain structure of the ferrite core. Rathenau and Fast [Ra 5] found that, when nickel-zinc ferrites with spinel structure were subjected to shocks, the in itial permeability steadily decreased and reached a final value which was
in

independent of the method of demagnetization; see for instance Table 49.1 below the dashed line. The manganese-zinc ferrites are fairly insensitive to

shocks.

CHAPTER XIV

FREQUENCY-DEPENDENCE OF THE INITIAL PERMEABILITY


50.
50.1.

The Magnetic Spectrum of

Ferrites with Spinel Structure

DISPERSION FREQUENCY

Although, in

many applications
on

of ferrites, eddy currents are negligible up to


is

the highest frequencies, the initial permeability of these substances


nevertheless dependent

frequency.
left

The dispersion due

to dimensional

resonance (see

29.1) is

here

out of consideration.

By

the magnetic spectrum of a ferrite

we mean

the curves which give the

real part y!

and

the imaginary part

y" of the initial permeability as a function


is

of frequency for the case where the magnetization of the core


that hysteresis
If

so small

may be neglected. we know only one of the quantities y or y" in the whole frequency range we can determine the other quantities with the aid of the KramersKronig equations
range.
(23.3), so that in principle it is sufficient to

measure one

curve. In practice, both quantities are

measured in a limited frequency

The magnetic
Fe2C>4
is

spectra

up

to

/=

10,000

Mc/s of a number of
is

ferrites

with spinel structure from the series of chemical compositions Ni 8 Zni_ s


given in Fig. 50.1.

The general

characteristic of the spectra

that

remains constant in a certain frequency range, while at higher frequencies,


after a small rise,
exists
it

drops

fairly rapidly to

a very small value. There always


this initial rise

a frequency above which

<

1.

From

of y

with

frequency, and

from

the fact that the susceptibiUty


is

follows that the dispersion

caused,

it

least in part,

becomes negative, it by resonance pheno-

mena. Owing to the logarithmic


figure
is

scale, the

maximum

in the

y curves of the

not so striking, although on a linear scale

it is

in

pronounced. The losses indicated by the y" curves are


frequency at which

many cases very maximum at the

y has fallen to approximately half the static value. The y" curve is very asymmetrical with a large tail towards the high frequencies. For relaxation processes d log y"/d log/> 1. The peak of the loss curve appears at a lower frequency the higher is the static initial permeability yo, which means that high-permeability ferrites
can be used as cores in high-quality
coils

only in a small frequency range.


1]

This relationship was explained by Snoek [Sn

in 1948

by means of ferro-

50]

MAGNETIC SPECTRUM OF SPINELS


field

269

magnetic resonance in the anisotropy


magnetization in very small fields
is

HA

the result of

magnetization in each domain being bound to


effective anisotropy field

Snoek assumed that the domain rotations, the a preferred direction by an


.

HA

In order to calculate the resonance frequency

we

shall use the picture

of

18.1,

according to which the grains or other re-

10,000

- ~~~P" '"

4000 7000 f(Mc/s)


Fig. 50.1.

Frequency dependence of the real and the imaginary parts permeability, ft' and p" repsectively, for polycrystalline specimens of ferrites having chemical compositions which are determined by the different values of the parameter 8 in the formula Ni^Zm-sFeaOs. Note the scale shift by a factor of 10 between the y,'
of the
initial

and the

fi" scale.

gions with a regular Weiss

domain

structure are represented

by

ellipsoids.

In the case of high-permeability materials the demagnetization of these regions is not effective, and they are comparable with ellipsoids imbedded
in a material having a susceptibility xficients are

The

effective

demagnetization coef-

then

NM =
For small

,? AA +(4tt-N) x

(5(U)

N this expression reduces to iV/p which


this case that,

is

small at low frequencies.


fto is

We may

then assume in

according to (47.3),

given by:
(50.2)

/xo-

= (87r/3)Af,/fl*.

270

FREQUENCY-DEPENDENCE OF INITIAL PERMEABILITY


will occur,

[CH.

XIV

Under the same conditions ferromagnetic resonance


at

beginning

a frequency:

wr
for regions in to the

= yHA

(50.3)

which the alternating field has a component perpendicular domain boundaries. In that case practically no demagnetization occurs at the domain boundaries, but only at the edges of the ellipsoid which, according to (50.1), is again reduced by its surroundings. Thus, an important part of the material will resonate at a frequency given by (50.3), whereas
for the rest of the material the resonance frequency will be appreciably
raised, since the poles

on the domain boundaries are not

neutralized

by the

surroundings.

We may expect, then, a maximum in the losses whose frequency,


TABLE
50.1

THE RELATION BETWEEN THE MAGNITUDE OF THE INITIAL PERMEABILITY fo AND THE FREQUENCY </r)exp AT WHICH " IS AT MAXIMUM, FOR VARIOUS FERRITES WITH SPINEL STRUCTURE. THE LAST COLUMN BUT ONE GIVES THE RATIO BETWEEN THE MEASURED DISPERSION FREQUENCY AND THE RESONANCE FREQUENCY CALCULATED ACCORDING TO (50 4)
Porosity
Ferrite

M.
no

(/>0exp

(i)(/*0-l)(frlexp

Figure

P
0.10
0.08

gauss
182

Mc/s
0.5
5.5

yM
0.4
0.5

orRef
50.1
>

Nio. 3oZno- 7oFe2C>4

3800 640

Nio.36Zno.e4Fez04

292 332
321

Nio.5oZno.5oFe204
Nio.64Zno.36Fe2C>4 Nio.2oZno.8oFe2C>4

0.15

240
85

15

0.5
0.5 0.5

>

0.22 0.24
0.25

50 80

44
12
13
7.7

283
197

NiFe20 4 NiFe 2 4 NiFe 2 4 NiFe 2 4 NiFe 2 4 NiFe 2 4


MgFe2C>4
Mgo.5Zno-5Fe204 Mgo.97Fe \)3 Fe204 Mgo.8iFeoj 9 Fe2C>4 Mno.5Zno.4FeJ*! Fe204
Mno.48Zno.47Fejy 5Fe204
Mno.7Zno.2FeJ|i Fe204
Lio.5Fe2.5O4

250 200 450 700


1500

0.6
0.5

50.4

0.24
0.25

205
196
168 162 149

0.7

,,

0.36
0.38
0.43

4.5
2.3
1.7

0.6
0.5

>
>

2000
80

0.4 0.4
0.8

0.43
0.23

69 190
183 123

120
36
23

30

Ra2

0.06
0.21

20
50
1.0
1.5

0.2 0.4
0.5

0.10 0.04
0.06 0.08
0.1

4300 1760 800


33

350 266 407


285 293
9

0.4 0.4

50 20

0.2
0.7
0.8

Lio.2Zno.6Fe2.2O4
Lio.5Fe1.oCr1.5O4

250
1.35

0.2

500
18

Cuo.4Zno.eFe204
Nio.26Coo.ieZno.58Fe204

0.14
0.19
0.6

150
17
2.8

206 370
123

0.6
0.7

400
1200


B13

yFe203

0.4

50]

MAGNETIC SPECTRUM OF SPINELS


is

271

according to (50.2) and (50.3),


according to:

related with the static initial permeability

/r(/x

1)

=^yM

(50.4)

where

s is

the saturation magnetization per

cm3 measured
ferrites

for the porous

material. This equation applies very well to


ture, as

many

with spinel struc-

appears from Table

50.1.

The

last

but one column of this table gives


is

the ratio between the experimentally found frequency at which fi"

at

maximum
The

(/V)exp

relation

and the resonance frequency determined with (50.4). (50.4) can also be tested by measuring the spectrum of a ferrite

with a very different value of

which

8,

as for example Li0.5Fe1.0Cr1.5O4, for


9.2).

9 gauss (see for a similar material Fig.


given in Fig. 50.2.

The spectrum of
/*

this ferrite is

To an

initial

permeability

= 0.35
1

corresponds according to (50.4), a resonance frequency of 600 Mc/s, which


is

what

is

approximately found. In order to

make a

ferrite

with spinel struc-

ture having the highest possible initial permeability

up

to a high frequency,

the saturation magnetization according to this picture


possible.

For

spinels containing cobalt

it is

found [Sc

1]

must be as high as that (/ )e xp can be r

approximately a factor of 2 higher than for spinels with corresponding values

of

/*o

and

s,

but which contain no cobalt. The unsatisfactory aspect of


is

the situation, however,


ferrite is greater

that the initial permeability of, say, sintered nickel

than one might expect from the magnitude of the crystal

if ju is determined by domain rotations only. For single crystals of NiFe 2 4 it is found (see Table 34.1) that Ki = 62,000 erg/cm3 If we neglect mutual coupling between the magnetization in the different crystals and also demagnetizing effects, the magnitude of the initial permeability for the specimen from Fig. 50.1, in the case where this is due solely to simultaneous rotations of the spins, is found to be:

anisotropy constant Ki,

fio

- = 2w(d*/rf)il/ */|Ai| = 2tt(5.38/4.0)197


1
t

/62000

5.3.

w
1
1

llillll

u0S FeW CrU Qt


Fig.
50.2.

Magnetic spectrum of

Li0.sFe1.0Cr1.5O4.

The

dispersion

n
0.5
Hh;

frequency
is

is

appreciably lower than

S^N
\
N

P'~
+- ~v**

usually found at this low. value


initial

of the

permeability,

owing

to the exceptionally

low saturation
ferrite (o = = 4.0 g/cm3

magnetization of this
2.2 gauss

cm3 /g and d

).

;)

T m

[SJ
1>

+_--t5

1 too

;>

-^f(Mc/s)

272

FREQUENCY-DEPENDENCE OF INITIAL PERMEABILITY


susceptibility is thus

[CH.

XIV

The measured

a factor of 2 larger than


in the case of a

may be expected

for rotation processes alone.

This discrepancy

is

more

serious

still

number of magne-

sium-ferrites investigated by Rado et al. [Ra 2]. was measured on sintered specimens and the crystal anisotropy, K\, determined with the aid of torsion measurements on single crystals from the same range of compositions. An example of the nature of the spectra of these ferrites is reproduced in Fig. 50.3. In all cases, two dispersion regions are

The magnetic spectrum

26 r
24

22 20
18 16
14

\p-i

\
12
y

1
10

\
1

6
4

*M A
<

Fig. 50.3.

Magnetic spectrum of a
ferrite,

if

sintered ferrite consisting primarily

of magnesium

showing two

-2
1

P-1
2
5
X)

natural resonances at

room tem-

tP2

K)3

10*

perature, after

[Ra

2].

f (Mc/s)

found. The low-frequency dispersion for these


relation.

ferrites, too, satisfies

Snoek's
it

From

the measured crystal-anisotropy constants, however,


is

follows that a possible initial permeability due to rotations

approximately

a factor of six smaller than the value found by experiment for no. The resonance frequency /J?{ determined from the magnitude of K\ is higher by

an even larger factor than the experimentally found main dispersion frequency (see Table 50.11). Since the second dispersion region found by Rado et al. [Ra 7] in a large number of ferrites has a dispersion frequency (/r)exp in the microwave range,
which
is

of the same order of magnitude as the resonance frequency deterthis is attributed to ferromagnetic resonance.

mined from K\,

Consequently,

there remains as the cause of the low-frequency dispersion, according to


these authors, only the
sintered ferrites only

domain wall resonance. The


is

fact that in

many

one dispersion range

observed would then be due

<

'

50]

MAGNETIC SPECTRUM OF SPINELS


t/1

273

^s
a

vo

Ov

O 8 8 O m OS CS (S
C<1

'

* 8 OS m
-

r^ ^H

g *

8^
o.

*"

O 8 to

<N

V
*7 in
1
1

3
T>
"5 <n <s <M

m O CI
Ov] c->

u o

00

O r^ * O
f*>

m <

CO

V?

3
e

fO OO

rO
r*->

r^i

00

CS

W>

o
hi

^H
A,

VO

<N CN

3.

?*"
C9

f*>

g - O O _ g g O 8. g m rn r~ m <t
trt 11
1

*-H
I
1 I

|H

V
<u
*H

i
3
VO

?ll

to

VO (N

vo o\

vo <N

VO a\

ft

7
1

7
1

H
H*o
U.
<*)

70

*
eg

O
II

>T)

Ov
^

<U
<SO

60 Hi

274

FREQUENCY-DEPENDENCE OF INITIAL PERMEABILITY


is

[CH.

XIV

to the coincidence of both dispersion ranges. If this


walls,

a resonance of domain
ascertain whether the
ferrites is in agree-

we can apply

to

it

the theory

from

24.3

and

resonance frequency theoretically to be expected for these

ment with the value found by experiment. A combination of the equations (24.12) and (24.13) gives for the resonance frequency of domain walls:
0*o

1) -fr

ciS w /l)i Y

s,

(50.5)

where c

is

a constant of the order of magnitude of unity, depending on

the kind of walls. If


distance determined

we

take for the distance

between domain walls the

by (14.4), which is equal at maximum to 10 microns, find for the magnesium ferrites mentioned in Table 50.11 a domain-wall we resonance of approximately 100 Mc/s, to be compared with the experimental
value of 30 Mc/s. In the right-hand side of (50.5) there
is

also a variable

quantity (8 w /l)i, the dependence of which


to (15.1). Since

upon K\

is

as

K\~ z l* according
ju.
,

an increase of K\

will give rise to

a decrease in

one ought
,

to find in reality that for a series of ferrites the product

<

\, is

proportional to

r (no-l)

in

which

The

series

of NiZn

ferrites,
/Lt

however, are found

to satisfy nicely the equation (50.4), for a variation in

by a

factor of 300.

For a given chemical composition it is possible to vary the initial permeaby powdering the ferrite, so that each particle consists of one or only a few Weiss domains. The magnetization process in this case will only take place via domain rotation. Fig. 50.4 gives an illustration of the change in
bility

the magnetic spectrum

when samples with

various densities are

made

from the same


[Br
7].

powder of NiFe204, using different degrees of sintering


particles

Compressed powder consisting of

of 0.5 to
initial

micron and

fired at

960 C results in a sample having a very low

permeability:

ft 1 = 1.7. The higher the temperature to which the sample is fired the more this value rises, until for a firing temperature of 1327 C one obtains

(xo

=
1

13.

In Fig. 50.4

it

can be seen that the

rise in permeability is asso-

ciated with a lowering of the

main

dispersion frequency in the spectrum.

The

relation between the

measured dispersion frequency and the resonance


is

frequency to be expected according to (50.4)

given for these ferrites in

found as when varying the chemical composition. In a denser specimen (fired to a higher temperature) having a higher permeability, the dispersion extends towards a much lower frequency
Table
50.1.

The same agreement

is

than in a specimen that


dispersion there
is

is

very porous.

At

the high-frequency side of the

not

much difference between the spectra of the specimens;


Mc/s the
losses in all cases are very

for frequencies higher than about 10 4


small. If

we

take as our starting point that in the nickel-ferrite powder with

the smallest grains only

domain

rotations contribute to

juo,

and

that in the

50]

MAGNETIC SPECTRUM OF SPINELS


is

275

denser specimens a contribution


sion region. This, however,

also

made by

wall displacements, then

for this last magnetization process


is

we should expect an additional dispernot found. The dispersion frequency drops


It is

continuously with increasing density.


is

as if pa in the less porous specimen

larger because the rotation of the magnetiztation

becomes

easier:

lowered

porosity results in less internal shape anisotropy, and hence in higher


rotational permeability
If the density
is

and a lower ferromagnetic resonance frequency. very high, as in some examples reported [Kr 1], where

14

v
a
12
10

d = 4.18

4.02

3.44

3.32

3.06

-*- f (Mc/s)

Fig. 50.4. Permeability spectra

of incompletely sintered samples of nickel

ferrite NiFe2<34.

The five samples were sintered at progressively higher maximum temperatures in the range 960-1327 C. The densities d of the samples indicated in the figure should be compared
with an X-ray density

dx

5.38. After [Br 7].

276

FREQUENCY-DEPENDENCE OF INITIAL PERMEABILITY


wall displacements are presumably the
frequencies.

[CH.

XIV

= 0.02,
50.2.

main magnitization pro-

cess at

low

WIDTH OF THE DISPERSION REGION


the loss curves towards higher frequencies
is

The broadening of
the

due to the
parallel to

fact that the alternating

measuring

field possesses

component

domain

walls

and

also perpendicular to the saturation magnetization.

Consequently, in the case of resonance, as in Fig. 18.36, poles also appear

on

the walls, thereby appreciably increasing the effective demagnetizing

factors

a large part of the material

and hence the resonance frequency. Moreover, will be above resonance;


not be reduced according to
further.
(50.1).

at these frequencies
this

means

that the

permeability of the surrounding material will be small and therefore

Nx
be

and

y will

This increases the resonance

frequency

still

At very high
is

frequencies the ellipsoid of Fig. 18.36


field to

may

be regarded as isolated, so that the largest demagnetizing


that for a
flat plate, i.e.

expected in the v direction

AttMs The
.

highest re-

sonance frequency which, according to


tered specimen,
is

this description, will

occur in a sin-

given according to (18.186) by:

V,max

yiflA

AttMs).

(50.6)

Above

this

frequency there should be no magnetic losses. For

many mag4000 gauss,

netically soft spinels the demagnetizing field is

about AttMs

against which the small anisotropy fields


then, losses

HA are negligible. In these ferrites,


and AttMs

due to the Weiss domain structure may be expected up to a

frequency of the order of magnitude of 10 4 Mc/s. For NiFe204 the relevant


values are:
/r,max

2.19,

HA = 450

oersteds

3400 gauss, hence


is

7400 Mc/s, in reasonably good agreement with what


(see Fig. 50.4).

found
(50.6)

by experiment

The

fact that the losses are

low above the frequency determined by

has been illustrated by an experiment carried out by Beljers et al. [Be 9]. The losses were measured at 9300 Mc/s as a function of temperature on a
nickel-zinc ferrite with spinel structure (molar composition approximately

18% NiO, 32% ZnO and 50% Fe 2

3 ).

Fig. 50.5a gives for this ferrite the


is

quantity (y/2ir)4iTMs as a function of temperature (this

a frequency

which is proportional to the saturation magnetization s and which would fall to zero at the Curie point, that is at about 200 C). The same figure indicates the resonance width Af of a resonant cavity filled with a bar of this ferrite and measured at a frequency of 9300 Mc/s. It is found that Af
,

also

becomes smaller

at higher temperature,

and

at

about 60 C becomes

equal to

Af

for the case

where the bar

is

magnetically saturated and thus

50]

MAGNETIC SPECTRUM OF SPINELS


subject to losses

277

due to the Weiss domain structure. Below a temperature of 60 C, 4irMs is sufficiently large to be able to cause losses in the ferrite at 9300 Mc/s, according to (50.6); above 60 C, 4nM8 has become too small. The anisotropy field A is small with respect to 4nMs

no longer

iSflOO

Af"
(Mc/s) u

(tl2n)lnMs
(Mcjs)

150

T(C)

15

15,000

Af
(Mc/s)

(H/2n)4nMs
(7/2n)4nMs
to

(Mc/s)

10,000

9J00

Ni0.S Zn 0.S Fs2

*
/

A\
^

5,000

Af"
f = 9,300Mc/s

gt---^"
50

+T(t)

'

50

Fig. 50.5. High-frequency losses

Af" measured at a frequency of 9300 Mc/s

as a function of temperature for a ferrite in the demagnetized state (drawn


curve),

and

for the case that the ferrite is magnetically saturated, broken

curve.

The

saturation magnetization,

t , is

also given, expressed in the

quantity (y/2w)

4wMs
b)

The

figures a)

and

show

for

two

ferrites

of different chemical composis is

tions that the losses disappear if

(.y/2ir)

4nM

smaller than the measur-

ing frequency.

278

FREQUENCY-DEPENDENCE OF INITIAL PERMEABILITY


at different temperature is obtained for

[CH.

XIV

The same result, but


(see Fig. 50.56).

a specimen with

a molar composition of approximately 25

% NiO, 25 % ZnO and 50 % Fe2C>3

With

this ferrite

we

again find the losses vanishing at a

temperature at which 4ttMs has fallen to the same value as in the case of the
ferrite in Fig. 50.5a.

Since the losses in this frequency range are due to the


is

Weiss domain structure, they disappear when the material

magnetized.

51.

The Magnetic Spectrum of Hexagonal

Ferrites with the Basal Plane

as the Preferred Plane of Magnetization

The magnetic spectrum of

ferrites

with hexagonal crystal structure and


spinels.

having a preferred plane of magnetization resembles that of the

One

finds,

however, for the same value of

initial

permeability a higher dis-

persion frequency than in the case of spinels.

As an example,

Fig. 51.1

U
3 "i..

^V s
NiFe2 4
1
1

,.Co2

V
\
\
_i

-Ay

i
i
f

i
Jf.
>

_o
looo

^
2
s

100

-*- f (Mc/s)

The magnetic spectrum of a polycrystalline specimen of C02Z. For comparison, the spectrum of NiFe2C>4 with approximately the same
Fig. 51.1.

low-frequency permeability

is

given.

shows the
It

initial

permeability of the

compound C02Z

plotted as a function

of the frequency. This figure also gives the permeability of the spinel NiFe2C>4

can

clearly

be seen that, although the permeability at low frequency

is

approximately equal for both compounds, the dispersion in the case of

C02Z

is

substantially higher than in the case of the spinel. Corresponding

results are

found with many other ferrites with hexagonal crystal structure and a preferred plane of magnetization. The dispersion may be the result
of ferromagnetic resonance. In these materials the natural ferromagnetic
stiffness

resonance frequency will be determined by the rotational

of the

magnetization in the preferred plane as well as by the rotational

stiffness

51]

MAGNETIC SPECTRUM OF HEXAGONAL FERRITES


By analogy

279
it

of the magnetization out of the preferred plane.

to (18.14)

can be derived from (18.10) and

is

given by:

27T/ reB

=
is

yjHi H*.

(51.1)

According to (11.7) the


constants
39.1.
,

field

Hj

connected with the crystal anisotropy

K\ and K2 and can have very high values, as we have seen in The field H$ is connected with the crystal anisotropy constant K$,

which is a measure of the stiffness of the rotations in the preferred plane, or, if K% is small, then stress anisotropy and shape anisotropy can determine H*. Assuming that ft is due solely to rotations, H^ will be related to ^0
according to (47.6).

In Table 51.1 the values of the resonance frequency calculated according


to (51.1) are

compared with those found

directly
is

by experiment. The
/u."

reso-

nance frequency taken for the experiments


Contrary to the spinels (see
/*' is

that at which

is

maximum.

e.g. Fig. 50.1), at this

frequency the permeability

low frequency. The theoretically determined frequencies, for the case where the dispersion is due to ferromagnetic resonance, and the experimentally measured frequencies,
found to have
fallen to half of its value at
differ

by the same

factor 2 as

is

found for the

spinels.

The

fields

H$

in

Table

51.1, which are derived from the magnitude of the initial permeability

of the sintered polycrystalline specimens, are

much

greater than the equi-

TABLE

51.1

VALUES OF THE DISPERSION FREQUENCY OF HEXAGONAL OXIDES WITH A PREFERRED PLANE OF MAGNETIZATION, AS CALCULATED WITH (51.1) AND AS FOUND BY EXPERIMENT.
fio 1 at low
frequency

/res
4-irMs

in 103

Mc/S
measured

Ferrite

gauss

oersted

oersted

according to
(51.1)

C02Z

11

3350
1500

13,000
10,000

112

3.4

1.4
1.0

MgaY

62

2.2

valent crystal anisotropy fields

H* which are given in 39.2 for single crystals

of the same compounds. This indicates that the initial permeability in these
polycrystalline specimens
is

not primarily limited by the crystal anisotropy


stress anisotropy.

in the preferred plane, but

by shape or
be

Thus, in the crystal-

oriented samples

H^

will

much

smaller, causing a decrease of the reso-

nance frequency.

We

shall return to this subject at the

end of this

section.

The improvement as regards high-frequency behaviour which these ferrites with a preferred plane of magnetization offer as compared with the ferrites

280

FREQUENCY-DEPENDENCE OF INITIAL PERMEABILITY

[CH.

XIV

with spinel structure can be illustrated by combining equations (47.2) and


(51.1):

/re.G*o-

1)

(4/3)rMs HiHi/H*

+ HH*IHi].
is

(51.2)

For

ferrites

with spinel structure the factor between brackets

always equal

to unity, since

H*

= Hf, so that for a given value of the initial permeability


upon

the resonance frequency depends only

s.

In the case

Hj

H$,
fre-

the factor between square brackets

is

greater than unity.

At comparable

values of permeability this factor

is

equal to the ratio of the resonance

quency of a hexagonal
that of a spinel.

ferrite

with preferred plane of magnetization and

The

highest resonance frequency which, according to (18.18Z>), can occur

in a sintered

specimen

is:

>r,max

y^ 4ttMs (4ttMs

+ Hf),

(51.3)

analogous to

(50.6). For example, in the series of compositions denoted by the general formula Co s Zn 2 - s Z, the factor Hf/H^ can be continuously varied from a high value to the value 1 by changing the chemical composi-

tion.
series

Figure 51.2 shows the magnetic spectrum for some specimens of this

having a preferred plane of magnetization. The low-frequency value


initial

of the

permeability increases very little with thezinc content, indicatis

ing that
that

H^

substantially constant, whereas


8.

it

follows

from

Fig. 39.5

Hf

is

highly dependent on

The dispersion frequency, however, changes


\i"

considerably; the

maximum
at

Mc/s

for

C02Z and
20

found respectively at 1400 about 200 Mc/s for Coo.65Zn1.35Z, which represents
curve
is

of the

*\6=0.65

11

"

--""V^

0.72

CoiZn 2 4
j

\'-

10
~~~~

/
/
i -0 65/
0.72

w
/
'

>Oo

}
- Jizzz:k>

. b

i:

::S -'
10

//
/W
*
,<

fl\
/T"
,'2.0

s$p
100

Fig. 51.2.

f (Mc/s) series

Magnetic spectrum of some

ferrites

from the

Co*Zn2- g Z.

51]

MAGNETIC SPECTRUM OF HEXAGONAL FERRITES

281

a change by a factor 7. The saturation magnetizations 4nMs of these ferrites at room temperature are respectively 3350 and 3720 gauss. The considerable change in the dispersion frequency with the chemical composition does not appear to be related to variations in /i or 4ttMs but is presumably due to
,

0.65 the the change in the anisotropy field Hf. For the specimen 3 A is of the same order of magnitude as the anisotropy anisotropy field 6 fields determining no- The particular effect of a preferred plane is then no

longer present in the crystals of this specimen. The dispersion frequency is therefore equal to that which is found for a spinel with the same initial
permeability and approximately the same saturation magnetization (about

200 Mc/s for NiFe 2


Fig. 51.3

4).

shows the magnetic spectra of two specimens of the same comdiffers

pound C02Z. The preparation of the specimens

only in as

much

as

the basal planes of the crystals in the specimen with the highest permeability are oriented mutually parallel owing to the fact that during the pressing of the sample a rotating magnetic field
result of this crystal orientation
is

was applied, as described in 44. The an increase of (/x 1) from the value

11 for the isotropic fact revealed


initial

specimen to 27 for the crystal-oriented one.

striking

by the magnetic spectra is is accompanied by only a slight decrease of the dispersion frequency. A better comparison of the spectra is possible by dividing the measured values of /*' 1 and \x." by the low frequency value of /*' 1. The now "normalized" spectra for the same specimens are shown in Fig. 51.4, from
permeability

that this appreciable increase in

which

it

can

clearly

be seen that the dispersion frequency for the anisotropic

1000
f

(Mc/s)

Fig. 51.3.

Magnetic spectrum of two

Co aZ

samples.

The broken

lines

apply

to

an anisotropic and the

solid lines to

a crystal-oriented sample.

282

FREQUENCY-DEPENDENCE OF INITIAL PERMEABILITY


1.2

[CH.

XIV

p"/(r'-%oMc/s

-W-1)aoMC,s ae

-0.2
1000
2

10000

-* f (Mc/s)
Fig. 51.4. Comparison of the normalized spectra of the C02Z specimens of Fig. 51.3. The broken curves again apply to the isotropic sample, the solid curves to the crystaloriented sample. The measured values of fi' 1 and /*" of Fig. 51.3 have been normalized by dividing them by the low-frequency permeability. For this purpose the values of /j,' 1 at 80 Mc/s have been taken, being respectively 1 1 and 27.

specimen
slight

is only slightly lower than that for the isotropic specimen. This change can be explained on the basis of the theory of ferromagnetic

resonance. For

if the basal planes of all crystals are parallel one would have, according to (47.2) and (47.6), a gain in susceptibility by a factor of 1.5. (In that case the applied magnetic field-strength is parallel to the basal plane

one may expect 1.5x11 16.5. This increase in mo will not be associated with A*o 1 a change in the dispersion frequency. As explained in 47.2, owing to the orientation of the crystals the permeability increases more than by the said
in all crystals.) Accordingly, for the anisotropic specimen

factor of 1.5, because the stress anisotropy

are smaller in the case of oriented crystals.

and internal shape anisotropy The resultant gain obtained for

is an extra factor of 27/16.5. This lowering of anisotropy is accompanied by a lowering of the resonance frequency. The resonance

the permeability

frequency

is

determined by the two anisotropy

dance with

(51.1).

Of these, Hf

mines the preferred plane

the large

fields

Hf

and

H\

in accor-

crystal anisotropy

which deter-

will scarcely

be changed by the orientation

(although at relatively small values of Hf there

may be some influence from

51]

MAGNETIC SPECTRUM OF HEXAGONAL FERRITES

283

the changed shape-anisotropy due to the orientation of the crystals).


equivalent internal anisotropy field

The

H^

is

thus reduced owing to orientation


1 is

by a

factor of 16.5/27, assuming that /no

a measure of H*. Conse-

quently the dispersion should be lowered by a factor yi6.5/27

0.8,

which

is

in reasonable agreement with

what

is

found by experiment. This

unappreciable lowering of the dispersion frequency with a substantial increase in


juo

hexagonal

ferrites

due to the orientation of the crystals is found for all kinds of having a preferred plane of magnetization [St 3].

52.

The Magnetic Spectrum of Hexagonal

Ferrites with the c Axis

as the Preferred Direction of Magnetization

In the case of a polycrystalline specimen of a hexagonal


the c axis
is

ferrite,

where

the preferred direction of magnetization, the initial permeability


is

due to rotations
this is

generally small

(Ao

= 0.17.

and is given by (47.3). For BaFei20i9 However, owing to a contribution from reversible

domain-wall displacements the permeability becomes appreciably larger


if the

specimens are fired at higher temperatures (for instance above 1300 C),
size

which increases the

of the

crystallites
initial

This additional contribution to the

and hence reduces the porosity. permeability is found to be freand


c) respectively.

quency-dependent. In Fig. 52.1, the idealized textures of three ring-shaped

samples of BaFei20i9 are illustrated by

a), b)

In a) the

hexagonal axes of the


the basal planes of the crystallites are in

crystallites are parallel to the axis

of the ring; in b)
c)

all crystallites

pass through the axis of the ring, and in


orientation.

random

The

crystal-oriented samples
field,

were made by compressing the ring in the presence of a magnetic


case

as

discussed in 44. If the crystallites in the cores were ideally oriented, as in


a),

a tangential magnetic

zation by

field in the core would only produce a magnetidomain rotation and not by domain-wall displacements, whereas

Fig. 52.1. Illustration netic spectra

of the crystal orientation in three samples of BaFeiaOig; the magmeasured for these rings are reproduced in Fig. 52.2.

284

FREQUENCY-DEPENDENCE OF INITIAL PERMEABILITY

[CH.

XIV

in case b) a magnetization in a small field can only be brought about

by 180

domain-wall displacements. For a ring of type a) a permeability


/to

is

found of
were one

=
1

0.6,

which indicates that the texture

is

not ideal, for

if it

would expect a permeability originating from rotations: ^ 1 = 4nMs /HA = 0.28. For a ring of type c) without texture, 1 = 1.6, and for a ring of type b) whose texture is such that the initial permeability may be large if many
/u.

reversible domain-wall displacements contribute to

The magnetic

spectra of these rings

is

one finds po 1 = 5. given in Fig. 52.2. It can clearly be


it,

seen that there are two dispersion regions for the permeability, one being
in the frequency range

from 20 to 50 Mc/s and the other


is

in the frequency

range from 200 to 500 Mc/s. Above the highest dispersion frequency, the
permeability approaches a final value which

approximately equal to the


it is

permeability to be expected for each of the rings, provided

caused only

6.0
' 1

'
'

'

5.0

-^ F'-'^\
D
1

b)

pf-1

BaFe 12 0i9

II

4.0

3.0

_
-

_
2.0

[m \

ffB

-p'- 1
1.0

LA n\
**^wa|
a jm


Fig. 52.2.

Jr
0)
o

-/

Magnetic speca),

tra

of the rings
c)

b)

and

of Fig.

52.1.

The

rings

ill
10

\ l/

mical
1

have the same checomposition and


only in their crys-

100

1000

differ

tal texture.

f (Mc/s)

52]

MAGNETIC SPECTRUM OF HEXAGONAL FERRITES

285

by simultaneous rotations of the spins in the Weiss domains. This permeability will show a further dispersion as a result of the natural ferromagnetic
resonance at 50,000 Mc/s.

The high-frequency
ed for
((Jto 1).

dispersion at about 200-500

Mc/s

is

presumably assogiven by (24.12).

ciated with resonance of the

domain walls,

since negative values are measuris

The domain-wall resonance frequency

To

ascertain whether the value found experimentally for the resonance fre-

quency is in agreement with the value to be expected according to the theory, it is thus necessary to make an estimate of the equivalent mass m w and
stiffness

constant a introduced for the domain wall. The equivalent wall


is

mass

mw

given by (24.7). In this equation only the wall thickness S w

is

not accurately known for BaFeiaOis.

From

the Curie point,


ions,

Tc

= 450 C,

and the minimum distance between the magnetic

approximately

3xl0- 8 cm, we
imation
S,

arrive according to (15.1) at the very rough approx10~ 10 g/cm 2 . In this case the change 10 -6 cm, leading to w

in the crystal anisotropy for the

moving wall

is

more important than


constant a
is

the

change

in its

demagnetizing energy. The

stiffness

related to

the initial permeability

and

to the distance

configuration of Fig. 52.16

we have
figures

/ between parallel walls. For the 16ttMs 2 /((i 1)/. The distance /

can be determined from Bitter


finds 5

on polished
is

surfaces.

From these one


9

10~ 4 cm.

probable value for a

then a

^ 7 x 10

dyne/cm.

This leads, according to (24.12), to a resonance frequency for the domain


walls in these BaFei20ig specimens of about 1000 Mc/s, which, in view of

the rough approximation, particularly as regards the determination of 8 W


is

in reasonable agreement with the value found by experiment.

factory explanation has been given. If ring b)


state the permeability is

For the dispersion in the frequency range from 20 to 50 Mc/s no satisis measured in the remanent
found to be approximately half the permeability

in the demagnetized state. This

means that

in this ring with imperfect tex-

ture there are also

many

walls present in the remanent state, with the result

that in this state, too, the domain-wall displacements

make a

substantial

contribution to the permeability.

special feature, however, is that in the

spectrum of the

ferrite in the

vanished, whereas the high-frequency dispersion


that found in the demagnetized state.

remanent state the low-frequency dispersion has is scarcely different from


influence

The temperature of the specimen has


dispersion. Fig. 52.3

little

on

the low-frequency

shows for a specimen of BaFei20i9 without texture the low-frequency dispersion at 20 C and at 183 C. The temperature change is accompanied by a slight decrease of /x and an increase in the
dispersion frequency

by about a

factor of 2.

286

FREQUENCY-DEPENDENCE OF INITIAL PERMEABILITY

[CH.

XIV

Fig. 52.3.

The low-frequency
in

dispersion

an isotropic

specimen of BaFei20i9 at 20 C and -183 C.

The permeability of

finely

powdered materials subsequently


1.7,

fired at

low

temperature drops to the rather low value of


are to a great extent suppressed.

so that wall displacements


/j-q

The

dispersions in

occur at 200 and 900

Both dispersion frequencies are higher than was found and 52.2c. This may be in agreement with the lower value for po, which points to a stronger binding of the walls to their equilibrium position. For this material the losses expressed in tan 3 are given as a function of frequency in Fig. 52.4. In this curve both the abovementioned dispersions are conspicuous, and it is also striking that this material has low residual losses at audio frequencies. The loss angle at 20
respectively.

Mc/s

for the isotropic specimen of Fig. 52.1c

kc/s

is

only tan S

= 4x 10 -4

Magnetic spectra similar to those described for the compound BaFei20i9 are found for the other hexagonal oxides whose c axis is a preferred direction

As an example, Fig. 52.5 shows the spectra of two rings compound NiFen having a crystal anisotropy of about K 1 .8 X 10 6 erg/cm 3 The broken curves a) and the solid curves b) were measured on rings having a texture according to Fig. 52.1 a and b respectively. The
of magnetization.
of the

measuring

fields

were therefore respectively perpendicular and

parallel to

the c axes of the crystals.

The

rings were simultaneously sintered for

one

53]

EFFECT OF MECHANICAL STRESSES ON THE SPECTRUM


1
1

287

tanS
1

BaFtnPis

f.
3_

^n***

3_

<
0.01

1000
f (Mc/s)

Fig. 52.4. Loss factor tan 8 as a function of frequency for

which has been


temperature.

finely

powdered and subsequently

sintered at

BaFeiaOig low

Fig. 52.5.
tra

Magnetic spec-

of two rings of crys-

tal-oriented

NiFe"W.

The
on
f(Mc/s)

curves a) and the

curves b) were measured


rings having a crystal

texture as in Fig. 52.1a

and b

respectively.

hour

at 1360

C in an oxygen atmosphere. The spectra again show two

dispersions, entirely as given in Fig. 52.2 for BaFeigOig.

53. Effect of Mechanical Stresses on the Spectrum

An example

of a situation where either only rotations or only wall displace-

ments can contribute to the permeability in ferrites is obtained by applying an external mechanical stress to a ferrite rod as indicated in Fig. 49.3a.
If

tensile stress is applied to

a material having negative magnetostriction,

288

FREQUENCY-DEPENDENCE OF INITIAL PERMEABILITY


moments
will orient

[CH.

XIV

the magnetic
stress.

themselves perpendicular to the tensile


internal anisotropy is relatively small,
3

For Nio.3eZno.64Fe204 the


<je

lz\ s ve may be predominant, as described in 49.2 and as indicated in Fig. 49.4. The magnetic spectrum of this ferrite is given for two different tensile stresses in Fig.

so that for large tensile stresses

the stress anisotropy

53.1 and compared with the spectrum of the same ferrite without stress. The low-frequency level of the permeability is reduced by the tensile stress, while at the same time the frequency at which p" is at maximum becomes higher. The reduction of no from 640 to 320 is accompanied by an increase of the dispersion frequency from 5 Mc/s to about 15 Mc/s. This is more

than corresponds to the relation


fact that, at a stress ae

may be due to the most of the spins are perpendicular to the direction in which no is measured (see 49.2). In order to calculate the anisotropy field in this state from no it is therefore necessary to omit the factor 2/3 in (47.3), so that the same factor disappears in the
(50.4).

This difference

2.7

kg/mm 2

in this ferrite,

right-hand side of (50.4).

The n" versus frequency curve in the case of an applied tensile stress becomes broader; towards low frequencies the dispersion is particularly
broadened. If the magnetic moments are oriented perpendicularly to a
tensile stress,

then

all

directions in a plane perpendicular to that tensile

Fig. 53.1.

Magnetic spectra
different values
tensile stress

of a rod of Nio.36Zno.64Fe204

measured at
after

of a uniform
<r

e,

[Wi

6].

*~f(Mc/s)

54]
stress are equivalent,

RELAXATION LOSSES
and therefore rotation of the magnetization

289
in this

plane

not limited by the anisotropy due to the tensile stress. The ferromagnetic resonance frequency is in this case determined by the geois

stiffness of rotations in the plane and out of the plane, and since the anisotropics in this plane are smaller than the stress anisotropy that determines the magnitude of /*o, we may therefore expect dispersions at lower frequencies than would follow from the simple

metrical

mean of the
(51.1),

analogous to

relation (50.4). This

phenomenon may

also be the reason for the fact that

in ferrites with high internal stresses, substantial losses occur [Sn 1] far below the resonance frequency determined by (50.4).

54. Relaxation Losses


54.1.

IDENTIFICATION OF RELAXATION LOSSES


often finds in addition to the

In

many ferrites one


is

main dispersion described

probably due to ferromagnetic resonance, a second dispersion arising from a relaxation. In Fig. 54.1 an example is given of the

in 50, which

Fig. 54.1. Part

of the spectrum of a copper-containing

ferrite

with

spinel structure, Cuo.3Nio.69Co<j.oiFe204,

showing two dispersion

ranges.

spectrum of a spinel containing copper (Cu .3Nio.69Coo.oiFe204 ) measured fields of very small amplitude. In the /x" versus frequency curve the dispersion at about 200 Mc/s can be seen which is accompanied
with alternating

by a drop

in //; this dispersion

shows all the characteristics of the resonances

290

FREQUENCY-DEPENCE OF INITIAL PERMEABILITY

[CH.

XIV

discussed in the foregoing sections. In an extensive frequency range around

100 kc/s the value of p" is fairly high, whereas p becomes gradually smaller. This phenomenon, which seems to be connected with a relaxation, is discussed at greater length in this section. Losses of this kind are found to
occur in
all

copper-containing ferrites with spinel structure [Sn 3] and also

in those ferrites

which contain divalent iron

ions.

Such dispersions are


with hexagonal

also found in ferrites with garnet structure


crystal structure.
54.2.

and in

ferrites

PHENOMENOLOGICAL DESCRIPTION OF THE RELAXATION PROCESS


by postulating that
is

The

H the magnetization M does not immediately cation of a magnetic that the change equilibrium value Mx The simplest picture reach
field
its final
.

relaxation process can be described

after the appli-

of the magnetization
value:

is

proportional to

its

deviation from the equilibrium

M=(1/t)(Mm -M).
The change of
is

(54.1)

M with time then given by an exponential function: M = X - er*l*)H = - )MX


oo (1

(1

e-*l*

(54.2)

This function

is

plotted in Fig. 54.2.

The

relaxation time t

is

the time that

Fig. 54.2. Exponential increase of the

magnetization

M to

its final

value

with a relaxation time t according to


(54.2).

elapses after the application of a field

H before the
x
is

magnetization differs
defined by the relation

by

less

than 1/e from


If

its

equilibrium value, and

Ma,

= x<x>H-

an

alternating field
is:

H = Ho^""is applied,
XH
1

then the apper-

taining magnetization

M=
From
47TX*,

mt

(54.3)

this the permeability follows as:

AttX,
1

ix'=l

+
1

gj2 t 2

(54.4)
C0 2 T 2
!

54]

RELAXATION LOSSES
/*" as

291

Normalized curves of // and


54.3.

a function of frequency are given in Fig.


is

Another method of representation


between

the so-called
/*"

or Cole and Cole diagram, in which n' and


relation
(54.4),

are used as coordinates.


is

Argand diagram The


For a
ferrite

n'

and

y." for variable

frequencies

given, according to

by a

semi-circle, as in Fig. 54.4; see for instance [Br 8].

t{u>T)

Fig.

54.3.

Normalized curves ac-

cording to (54.4) of ft'

and

fi"

versus frequency for the case of a

relaxation dispersion with one time

constant

t.

2\ hours at 1000 C in an oxygen atmosphere 6x 105 ohm-cm) Figs. 54.5a and b show for different frequencies the real and the imaginary part of the permeability as a function of temperature. Measuring at various fixed frequencies as a funcCuo.5Zn .5Fe204,
fired for

(density 5

g/cm 3

resistivity

tion of temperature

is

much

simpler than measuring at various fixed tem-

peratures as a function of frequency.


is

The value of t
\x"

at

a certain temperature
a>,

equal to the reciprocal value of the angular frequency


versus

for

which the
of

curve at this temperathe envelope of

F
p^-MnXm

ture touches the broken curve


Fig. 54.56,

which

is

T curves. One can also and Cole diagram from the measuring results as shown in
the
fi" versus

plot a Cole

Fig. 54.6. This figure gives the rela1

and p" for various frequencies at a number of different temperatures. In the case of one retion between
/*'

tan i^u>r

laxation time t at each temperature

one would expect a number of semicircles.

2rO(a
*

The observed

deviations are

ft"

probably due to a spread in the


relaxation times.

The

distribution

Fig. 54.4.

The

relation between

fi'

and

fi"

in the case of

a relaxation dispersion with

laws governing relaxation times, and


their influence

one time constant t (so called Argand or Cole and Cole diagram).

on the Cole and Cole


been
extensively

diagrams,

have

292

FREQUENCY-DEPENDENCE OF INITIAL PERMEABILITY


too v

[CH.

XIV

20

-'soo

no
T('C)

Fig. 54.5.
ty, fi'

The real and imaginary part of the complex permeabilift" respectively,

and

measured

at various frequencies as

a function of temperature for a sample of Cuo.5Zno.sFe204 that

has been fired for 2 x lz hours at 1000 C in an oxygen atmosphere.

treated in publications

on

dielectric relaxation losses; see for

example [Br

8].

relaxation time r decreases with increasing temperature, and if we -1 against the plot for this ferrite, as is done in Fig. 54.7, the values of log t

The

reciprocal value of the temperature,

we

obtain a practically straight

line.

The

relation between these

two
r

quantities can therefore be described

by the
(54.5)

equation:

Too

e^l kT
The

where tm

is

the relaxation time at an infinite temperature

and Em is the acti-

vation energy controlling the process.

slope of the straight line for

Cuo.5Zno.5Fe2C>4 in Fig. 54.7 corresponds to an activation energy


0.32 eV.

Em

The

relaxations described here for a copper ferrite are

phenome-

logically entirely similar to the relaxation losses

found in carbonyl iron con-

taining a small percentage of carbon [Sc 2].


54.3.

RELAXATIONS IN FERROUS FERRITES


ferrites,

Considerable relaxation losses are found in ferrous

where the relax-

ation strength appears to be very closely connected with the ferrous content.

In Fig. 54.8 the loss factor tan S at frequencies of 25, 600 and 1000 kc/s
is

plotted as a function of temperature for a magnanese-zinc ferrous ferrite

having a chemical composition of approximately Mno.66Zno.28Feo.oeFe204


(at

room

temperature,

/lio

= 500,

d^5.0 g/cm3 and

^ 10

ohm-cm).

These

results are also typical

of a relaxation phenomenon. The relaxation

time as a function of temperature can be calculated from the straight line

54]

RELAXATION LOSSES
450

293

in Fig. 54.7, appertaining to this


ferrite

and

is

equal to .Em
small

=
Cu .sZn 5 Fea Oi
.

0.17 eV. This

activation
dif-

energy points to an electron


fusion process in this
ferrite.

400

For

a
at

ferrite

with a high

resistivity,

Nio.5Zno.5Fe204
1250 C,

(fired in

oxygen

resistivity

10<*

350

25

ohm-cm,
200),

d~ 5 g/cm3
results

and no

^
300

the

are given in

Fig. 54.9. It

can be seen that in


not show the high

the temperature range covered,

tan 8

does

values observed for the

manga250

/10C

nese zinc
is

ferrite.

However, tan 8

not a constant and the varia-

and frequency can again be ascribed to a relaxation process. Corretions with temperature

sponding values of the logarithm


of the frequency and the reciprocal

50 C

of the temperature at which


750

the tan 8 curves for this ferrite

have a

maximum
is

are therefore

also plotted in Fig. 54.7.

An actiof
100
100

vation energy

calculated

100

kc/s
"
"

0.40 eV. Refiring of this ferrite in


the

"C

x o

30 8
;

same atmosphere but


concentration

at a hig-

her temperature, 1525 C, causes

500 c/s

of

0.4

by
fer-

!2SC
50

200
a
a
100

weight of ferrous ions in the


rite,

45

leading to a decrease of the re-

sistivity

from 106 to 103 ohm-cm.


iL
50
100

As we
of

shall see in 62, the firing

150

this ferrite at

such a high temFig. 54.6.

perature causes tan 8 to increase

Argand or Cole and Cole diagram

with increasing
that hysteresis
this

field,
is

which means important. For


/j,"

for the copper-zinc ferrite of Fig. 54.3.

reason

of 5

p and and 2.5 mOe,

of this

ferrite

were measured at

field strengths

permitting an extrapolation to zero field strength.

294

FREQUENCY-DEPENDENCE OF INITIAL PERMEABILITY

[CH.

XIV

Fig. 54.7.

The

relation between relaxation time t

and temperature

T for

various ferrites

from Table
0.10

54.1.

0.08

tanS

0.06

0.04

0.02

Fig. 54.8.

The

loss factor tan<5

of Mno.eeZno.ssFeSosFeaC^ as

a function of temperature, measured for various frequencies


at

field strength

of about 5 millioersteds.

54]
0.02

RELAXATION LOSSES

295

tani

0.015

0.01

0.005

+ 100

t ec)
Fig. 54.9.

The

loss factor

tanS of a

ferrite

Nio.5Zno.sFe204

(fired for

two

hours at 1250 C in oxygen) as a function of temperature, measured at


a
field strength

of 2.5 millioersteds.

The

values of

p" measured

at these field strengths for 2, 8,

25,

and

100 kc/s are plotted as a function of temperature in Fig. 54.10. After a linear extrapolation to zero
tained.
field

strength,

the

drawn

lines

are ob-

The

variation of
it

p'

with the

field strength

proves to be less than one

per cent, so

suffices to give the values

of // measured at 2.5 mOe, neglect\i!

ing the extrapolation.

From

the values of

and the extrapolated values


is

of

/i"

a residual loss factor tan 8,- has been calculated: the result

given in

Fig. 54.11,

which shows the temperature dependence of tan8 r for various

can be seen that results are obtained similar to those for the manganese-zinc ferrite, which also contains both ferric and ferrous ions. Also the activation energies of the relaxation processes in both ferrites are
frequencies. It

about equal (see Fig. 54.7 and Table


rous
ferrites

54.1).

Relaxation times t are also given

in Fig. 54.7 as a function of temperature for a

Nii_8Fe"Fe204.

It

can be seen, as

54.1, that

Em

decreases with increasing


infinite

number of mixed nickel-feris also evident from Table ferrous content. The relaxation

frequency at an
c/s.

temperature

is

For the

nickel-zinc ferrite fired at

of the order of magnitude of 10 10 low temperature, which is porous


is

and

consists of small crystallites, this relaxation frequency

much

higher,

being about

10 13 c/s,

whereas for the nickel-zinc

ferrite fired at

high tern-

296

FREQUENCY-DEPENDENCE OF INITIAL PERMEABILITY

[CH.

XIV

Fig. 54. 1 0. The real and imaginary part of the complex permeability, ft and /j," respectively, measured at various frequencies as a function of temperature for the ferrite of Fig. 54.9.
'

This ferrite was fired additionally for two hours at 1525 C in oxygen, so as to introduce
ferrous ions.
0.75

Fig. 54.11.
results

The

residual loss factor tan 8 derived


figure.

from the measuring


represents the loss

of the preceding

The broken curve

factor at 100 kc/s of the

same

ferrite before the additional firing at

1525 C (compare Fig. 54.9).

55]

INDUCED FERROMAGNETIC RESONANCE


is

297

perature and consisting of large crystals, this frequency

on

the low side,

being about 3

10 8 c/s.

Table 54.1 gives a survey of the activation energies, Em , derived from the magnetic loss measurements on ferrous ferrites as well as the activation enercomparison of both activation energies gies Ep of their d.c. resistivities.

permits the conclusion that they are related to the same dissociation phe-

nomenon, and it is fairly probable that the magnetic after-effect found in ferrites in which atoms of the same element occur as ions of different valencies is due to an electron diffusion process. The activation energies found can be divided into two classes: for ferrites having a relatively high conductivity, Em is about 0.1 eV, and for ferrites that are almost insulators,^ is about
0.4 eV.

TABLE

54.1

THE ACTIVATION ENERGY Em OF THE MAGNETIC RELAXATION PHENOMENON COMPARED WITH THE ACTIVATION ENERGY E9 OF THE D.C. RESISTIVITY FOR SOME FERRITES. AN APPROXIMATE VALUE OF THE RELAXATION STRENGTH, TAN 8mttx IS ALSO GIVEN.
,

Resistivity at

Ferrite

room temp,
(ohm-cm)

Em
eV
0.40 0.10

p
eV
0.41

tan8 max

Figure

Nio.5oZno.5oFe204
Nio.49Zno.49Feo.ozFea04

10 6
103

0.02
0.13

54.9

0.10

54.10

NiFe204
Nio.99Fe II o.oiFea04

>10<>

*)

30

0.10
0.08

Nio.95Fe n o.05Fe204 Nio.86Fen o.i5Fe204

500
5

0.07


0.16 0.32 0.29

0.33

and 54.11

0.10 0.10 0.10


0.03
54.8

Mno. 6eZno.28Feo oeFe204


.

150
10"

0.17 0.37 0.32 0.20

MgFe 2 04
Cuo.5Zno.sFe204
Cuo.5Lio.25Fe2.25O4
*)

6xl05
500

0.30

54.5

0.40

No maxima found in the tan 8 versus temperature curves. The ferrite


low residual
losses:

shows abnormally

tan S

= 0.0017

at 100 kc/s at

room

temperature.

55. Induced Ferromagnetic Resonance

The ferromagnetic resonance


field

in a ferrite saturated in

differs

for

sintered

polycrystalline materials

an applied from that in

static

single

crystals.
field is

In the

first

place the peak in the losses as a function of the applied

seen to be very broad and asymmetrical (Fig. 55.1), and in the second yH place the mean resonance field does not satisfy the simple relation w when the frequency is varied. The latter phenomenon was first discovered

298
30

FREQUENCY-DEPENDENCY OF INITIAL PERMEABILITY


Fig. 55.1.

[CH.

XIV

Induced ferromagin

Ni0.8 Zn 0.2 Fe2 i

netic resonance
crystalline

a poly-

v
20
1

sphere

of

Nio.sZno.zFeaO^
of sphere 0.75
ing frequency/

Diameter
measur-

mm;
0.2.

= 9400 Mc/s,
The brothe
for the true

\
\

porosity

=
(a)

ii

ken

line

indicates

resonant
10
ii

field

factor

(g

2.02).

The

broken

line (6) is

through the

centre of gravity of the peak.


ii
ii

The
3500

losses are given

on an

ii

arbitrary scale.

2500

3000

4000

iSOO

H(Oe)

by Okamura [Ok assumed instead

2],

who, on the basis of the


<o

results

of his measurements,

y(H

+H

t ),

(55.1)
field

where Hi

is

a frequency-independent internal

(see Fig. 55.2). It is

always found that Hi


crease in the

>

0.

In practice this phenomenon appears as an inis

g For example, a
A

factor,
ferrite

which becomes larger the lower


with a "true"

the frequency.

factor according to (55.1) of 2.1 at

= 3 cm may have an apparent g factor of 2.4.


anomaly in
sintered

Snieder [Sn 5] has brought

this

Ni-Zn

ferrites into relation

with their porosity.


(55.1)

If

we

substitute his experimental results in the

Okamura equation

we

find the values for

greai

and Hi as given

in Table 55.1.

TABLE

55.1

APPARENT g FACTORS AND VALUES OF THE REAL g FACTOR AS CALCULATED FROM THE OKAMURA EQUATION (55.1). TOGETHER WITH INTERNAL FIELDS Hi OF Ni-Zn FERRITES WITH SPINEL STRUCTURE AT ROOM TEMPERATURE.
Ferrite

porosity

g apparent

Ni 8 Zni_ s Fe2C>4
a

P
0.166
0.110 0.162
0.262
0.295

f=9320 Mc/s /=24000Mc/s


2.16
2.17 2.29 5

real

Hi
250 270

0.36
0.50 0.64 0.80
1.00

2.06 2.06
2.10=

2.01

2.00

2.00
2.02
2.13

430
600
500

2.46 5
2.47 5

2.17

2.22 5

In Fig. 55.3 the internal field Hi from Table 55.1 is plotted as a function of pAirMg, the magnetization taken being that of the dense material. A
linear relationship
is

found, which, for these materials,

is:

Hi ^

0.5 p AttMs ,

(55.2)

55]

INDUCED FERROMAGNETIC RESONANCE


50

299

NiFe2 0t

40
1 (t0 9 c/s)

30

20
Fig. 55.2. Relation

between

the ferromagnetic resonance


10

frequency/, and the corres-

ponding magnetic
of NiFe 2
4 , after

field

for a polycrystalline sphere

[Ok

2].

-W

10

15

-*-

(kOe)

The

true

factor for the

spin-only value; only for

Ni-Zn ferrites with high Zn content has almost the Ni ferrite is an essentially higher value found. This,
ferrites

however,
It is

is

smaller than that found for single crystals (see Table 36.1).

noteworthy that for


field side.

AH is

also large (see Fig. 55.1), whereas the absorption

with high values of Hi the line width peak has a tail to5]

wards the high

According to recent theories of Clogston [CI

and

Schlomann[Sc

3]

concerning the line width of polycrystalline samples, the


800

Fig. 55.3. Relation


field

between the internal

Hi,

defined

by

(55.1)

and the
400 800
*. p- 4ft

product p-AttM,, for

polycrystalline

specimens of NigZni-sFezO^

Ms

1200 (gauss)

300

FREQUENCE-DEPENDENCE OF INITIAL PERMEABILITY


moments of

[CH.

XIV
of

dipolar interaction between the magnetic

different points

the material leaves the centre of gravity of the absorption peak unchanged.
If

we

take for the resonance field the field at which


is

maximum
if

absorption

occurs, as

usually done, then the resonance field

is

too low, and should be


instead the

corrected by a field of the type


field

t.

It is

seen in Fig. 55.2 that

of the centre of gravity

is

taken, the resultant

Hi

is

very small. Such

a correction should be dependent on porosity, as the line width is stray fields near the pores. According to Clogston the line-width is A should be the mean order of magnitude (HA ) 2 /MS in which case root of the stray fields. According to (2.7) and (2.8) this (HA 2 is
,

due to
of the

square

of the

order of
pores.

4nNMs 2p,

where

N is

an averaged demagnetization factor of the

An expression for Hi of the type (55.2) is then plausible.

CHAPTER XV

STATIC HYSTERESIS LOOPS


56. The Coercive Force

As

described in 16 and 17 a ferromagnetic substance becomes magnetized

as a result of domain-wall displacements

and

rotations.

Both processes can

take place irreversibly, which

is

the cause of hysteresis. Rotation processes

are mainly associated with intrinsic properties of the material


fore fairly independent of the structure; this
is

and are

there-

not the case, however, as

regards the contribution of wall displacements to the magnetization. Con-

sequently the shape and width of the hysteresis loop of a ferrite depend

perties,

not only on the chemical composition, which determines the intrinsic probut also on various factors connected with the sintering process,
such as porosity, the size and shape of the pores and the size and shape

an example of the way in which the coercive depends on the porosity p in the case of sintered samples of Nio.5Zno.5Fe2C>4. The samples were obtained by compressing powder
of the
crystals. Fig. 56.1 gives
c

force

an average diameter of about 1 micron and by from 1100 to 1450 C. In this case c increases linearly with/?, as it should according to (16.8). The deviation from linearity at high values of p may be caused by the fact that in the very porous samples fewer domain walls are present. Some of the grains will consist
consisting of grains with
sintering at a temperature varying

of a single domain, which leads to greater coercive forces. The quantity KijMs from (16.8) becomes smaller with increasing zinc content in the

of nickel-zinc ferrites Ni 8 Zm- 8 Fe204, becomes larger (see Table 56.1). At


series

since the initial permeability

same time the coercive force becomes smaller, as appears from the column last but one in Table 56.1. The last column gives the
the
also

10

Ni0.S Zn 0.S Fe2i.

value of

calculated with (16.8),


9^. ""i

the anisotropy constant according to


(47.3) being derived

from the value


the calculated

of

ixq.

Here,

too,

values are probably

on the high side,

0.1

0.2

0.3

0.4

OS

since only pores with a diameter

Fig. 56.1. Relation

comparable with the thickness of


the

force

between the coercive and the porosity of sintered samples

domain wall make a contribution

of Nio.5Zno.5Fe204.

302
3000
(20"C)

STATIC HYSTERESIS LOOPS

[CH.

XV

4n M
J
|

-2000
.

20C__^

(ga JSS )

^Hg
NiFe2 4

WC

*^'
/?'
/

r^ "^'

J^r

ft // //
It

If

p = 025
(to= j.*

20

-10

10

20

30

40

50

60 H(0e)

70

Fig. 56.2. Virgin curve


line

and hysteresis loops of a polycrystalsample of NiFe204 at 20 C. The dashed curve is a

hysteresis loop at 100 C.

TABLE
.

56.1

RELATION BETWEEN INITIAL PERMEABILITY AND COERCIVE FORCE FOR FERRITES OF THE SERIES Ni8Zni-sFe204 THE LAST COLUMN GIVES THE VALUE OF He CALCULATED WITH THE AID OF (16.8), WHERE THE QUANTITY KilMs ACCORDING TO (47.3) IS DERIVED FROM [l
.

H
Ferrite

oersted

Ni g Zni_ s Fe204
8

gauss

/*o

measured

according to
(16.8)

0.25

196

17

13.7
6.8

16.1

0.80
0.67

0.24
0.22
0.15

283
321

45

10.4
6.2 2.0

90
230 650

4.0
1.4

0.50
0.33

332 292

0.09

0.4

0.4

to
all

H A
c.

better

comparison

is

complicated by the fact that, although

samples are fired at the same temperature, the average diameter of the

pores varies from sample to sample, as a consequence of the fact that a higher
zinc content promotes sintering.

The solid curves in Figs

56.2

and

56.3 represent the virgin curve, the

major

loop and two minor loops of NiFe2C>4 and Nio.5Zno.sFe204, respectively.

An
is
is

example of a magnetically really soft ferrite is Mno.65Zno.3sFe204, for which i^o 1500 and 0.2 oersteds. The hysteresis loop of this ferrite e

H ~

shown in

Fig. 56.4 In all these cases the relative

remanent magnetization

low, being

special

no more than half the saturation magnetization. By means of preparation techniques it is possible to make ferrites for which some

56]

THE COERCIVE FORCE


is

303

loops have a rectangular shape, as

shown

for example in Fig. 56.5 for

making ferrites with such Mgo.45MnJJ55 MnJ^3 Fei.7704. rectangular minor loops cannot be given. With many chemical compositions
general rule for
it is

possible to arrange the conditions during preparation so as to produce

4]. Even samples of the simple ferrites NiFe2C>4 and MnFe2C>4 have been made with rectangular minor loops [Ec 1]. It is

loops of this kind; see [Wi

5000
(no-cj

-4000

4nM
20"C
-3000

**

5S* *^

**^
-2000
,--'

^'
r s

y]
V

P-0.IS

[l,-29S

/
/ /

/
// 1/

/ 1
l

v ll
2
3
4
1

/ -2-10'<f/
//

II

10

15

25 H(Qe)

30

Fig. 56.3.

The same as Fig.

56.2,

but now for Nio.sZno.sFeaO^

Fig. 56.4.

The same

as Fig. 56.2, but

now

for Mno.65Zno.35 Fea04.

304
4000
(20"C)

STATIC HYSTERESIS LOOPS

[CH.

XV

-3000

4nM
'gauss)
ii

Mg

.4S

Mn 0.SS Mn 0.23 Fe 1.77 4 p=0.W

= 33

moo

/
-1

A
Fig. 56.2, but

10

15

20

25

30

H(0e)
Fig. 56.5. The same as some rectangular minor

now

for

Mg

.45Mno'55MnoI I 23Fei.770 4 showing


.
,

hysteresis loops.

probable that in order to obtain


permeability,

ferrites

with such loops, a small

initial

and hence a small permeability in the remanent state, must be associated with a low coercive force. It is also thought [Go 8] that the critical field strength needed to produce domain walls must be greater than
the field strength needed for the irreversible displacement of these walls.

Most polycrystalline
ferrites, for

sintered samples of ferrites with spinel structure have

a relatively low coercive force. Exceptions are the simple and mixed cobalt

which

can be larger than 1000 oersteds.

The
and
b,

ferrites

with hexagonal crystal structure and a preferred plane of

magnetization also have a low coercive force. See, for example, Fig. 56.6a

showing families of hysteresis loops for an isotropic and a

crystal-

oriented sample of Coo.sZn1.2Z.

The

crystal-oriented sample has the higher

remanence. In
loop the

this

sample the basal planes of the hexagonal crystals are as


44),

near as possible mutually parallel (see


field is parallel to these

and

for measuring the hysteresis

magnetically preferred planes of the crystals.

In the case of the hexagonal oxides with a preferred direction of magnetization the coercive force
is

generally very high, being of the order of

nitude of 100 oersteds and more.


possible to

By a

special

magmethod of preparation it is
these compositions (see

make permanent magnets

of

many of

60).

56]

THE COERCIVE FORCE


virgin curve determines the amplitude permeability
/*.

305
This
is
,

The

de-

fined as the ratio between the

maximum

value of the induction

Bma x

and
is

the corresponding value of the field strength /7ma x,


described:
ju.

when a minor loop

= Bmax /Hma,x- In Fig. 56.7 the relation between the normalized


(/i/w>)

amplitude permeability
56.2 to 56.6.

and

Hma K
,

is

given for the ferrites of Figs

At a

field strength slightly

reaches a

maximum

value,

/x

max and at a
,

higher than the coercive force, p much higher value of ma K it

approaches asymptotically the value

1.

If the ratio /tmax/^o as a function

4000

ArMstXftj

inM
(gauss)
,

a, 0.Q^n J.2

p'O.H)

(tc-2 S
2000

20

30

-H(Ot)

X
-

40

(Oe)

Fig. 56.6. Hysteresis

loops and virgin curve of polycrystalline

samples of Coo.8Zm.2Z.
a) isotropic sample, b) crystal-oriented sample.

306
25

STATIC HYSTERESIS LOOPS


Fig.
56.7.

[CH.

XV

The normalized

X
K P
fto

values of the amplitude per-

Uo-59

meability of the ferrites of


Figs.

56.2

to

56.6

as

function
10

of the amplitude

1
i.0

Hmax f tne measuring fieldstrength. The value of fia of


each
ferrite is

marked beside

the curve.

/'N \
;
i

\
N

-.

Nif

/ l
i

/ /
^-n/

^^^
Ni0s Znas Fe3 O4

1
1

/\s

CoojZnjfZ

v^Bo-^

1.0

fo58

Mnoss Zn
J

Po-W0
20

x Fe2 (k
30
40 SO

to

-HnJOe)

of

H differs

little

from

unity, this
little

means

that

when such

ferrites are

used as

cores in a circuit they cause

distortion.

In Figs. 56.2 to 56.4 the broken curves indicate the hysteresis loops at 100 C. It is known that, in general, the initial permeability increases ( 48.1)

and the saturation magnetization decreases


field strength

( 32.2)

with increasing tempe-

rature, so that the virgin curves for different temperatures intersect.

At the

caused by
strength.

this field is

corresponding to this point of intersection the magnetization almost independent of temperature. This also applies
/*rev,

to the reversible permeability,

at

a particular value of the biasing

field

57. Remanent Magnetization

In the process of demagnetization the material divides itself into Weiss domains, such that the average magnetization over all domains is zero.

The
If,

preferred direction of the magnetization vector in each


the three anisotropics: crystal, stress

termined by

domain is deand shape anisotropy.


the field
is

after saturation of the material in

a very strong

field,

allowed

57]

REMANENT MAGNETIZATION

307

to return slowly to zero, the magnetization vectors rotate out of the field
direction towards the nearest preferred direction, which
is

determined by

one or a combination of the above-mentioned anisotropics. For a field = 0a. remanent magnetization Mfem is left. In this state the susceptibility in the case of small fields is xrem. We shall now examine in turn what the magnitude of the ratios iem /M8 and xrem/xo will be when one of the three

types of anisotropy

is

predominant.

(a) Crystal Anisotropy


If

a crystal

is

subjected to a strong magnetic

field,

which

is

subsequently

reduced to zero, the magnetization vector will stick in that preferred direction

which

is

nearest to that of the applied

field.

This will also occur in a poly-

crystalline material, provided the

magnetic coupling between the individual

crystals

can be neglected. In the case of a cube whose edges are preferred

directions of magnetization, there are six preferred directions in each crystal.

In the remanent state the magnetization vectors then distribute themselves

over a solid angle of 2ir/3 steradians.

Where
is

the eight body-diagonals are

the preferred directions, the solid angle


will

In Table 57.1 be found the relative values of the remanent magnetization and the
tt/2 steradians.

rotational susceptibility in the remanent state as calculated for these cases

by Gans [Ga

5].

TABLE

57.1

RELATIVE REMANENT MAGNETIZATION T emlMs AND SUSCEPTIBILITY Xrem/xo FOR ISOTROPIC POLYCRYSTALLINE SPECIMENS WITH VARIOUS CRYSTAL-STRUCTURES AND CRYSTAL ANISOTROPIES. THE INTERACTION BETWEEN THE CRYSTALS IS NEGLECTED.
Crystal anisotropy,

Crystal structure

preferred direction

Mrem/Ms
0.83

Xrem/X0

cubic cubic

cube edge

0.45

body diagonal
c axis

0.87
0.5

0.36
1

hexagonal
hexagonal

basal plane
a.

uniaxial anisotropy in

basal plane
b.

0.5

0.33

hexagonal symmetry in
basal plane
0.75

0.06

In the case of hexagonal crystal structure and a preferred direction of

magnetization (c axis) the magnetization vectors in the remanent state are


distributed (again neglecting interaction) in a solid angle of
2-n-

steradians

and the remanent magnetization


this state xrem/xo

is

half the saturation magnetization. In


is

1.

Where

the plane at right-angles to the c axis

308

STATIC HYSTERESIS LOOPS

[CH.

XV

preferred plane, the anisotropy in this basal plane determines the remanent

magnetization. If 2<f>o

is

the angle between

two

successive preferred directions

of magnetization in the basal plane, the relative remanent magnetization

and the

relative susceptibility are given by:

MIem M
s

tt

sin^o
(57.1)
<j>

and
Xrem
XO
1

sin

2<f>

(57.2)

2^o

In the case of anisotropic samples with oriented crystals the above-mentioned quantities depend on the direction of the applied magnetic
field

with

respect to the anisotropy directions in the samples. If the preferred directions of magnetization of
tion, the relative
all crystallites

in a sample are in parallel orientawill

remanent magnetization, neglecting interaction,


it

be

equal to unity in the preferred direction; at right-angles thereto

would

be equal to zero. In the case of hexagonal crystals with a preferred plane of


magnetization and hexagonal anisotropy in the basal plane, the relative remanent magnetization for a sample consisting of crystals with mutually
parallel c axes, will

be equal to

3/7r for all directions in the basal

plane and

equal to zero in the direction of the c axis.


(b) Stress Anisotropy

When

stresses

due to

elastic

deformation aie

present

in

a magnetic

material with magnetostriction, the magnetization tries to orient itself such


that the

accompanying changes in length eliminate these

stresses as far as

possible. If stress anisotropy predominates, then in the case of positive

magnetostriction, a plane at right-angles to a compressive stress

is
is

a preferred

plane of magnetization, and the direction of a tensile stress


direction.
after

a preferred

With negative magnetostriction the


field is

reverse

is

the case.

Once again,
will arise

a strong

switched

off,

a Weiss domain distribution

in such a

way

that the magnetization vectors rotate out of the direction of

the field back to the nearest preferred direction.


distribution in the material
it is

With a random

stress-

not possible to determine the remanent

magnetization by simple means.

no mechanical stresses present in the material after preparaand demagnetization by cooling from a temperature above the Curie point, the direction of the magnetization vector in each Weiss domain is determined by the crystal anisotropy (shape anisotropy, which is dealt with
If there are

tion

under (c), is disregarded here).

When the material is brought into the remanent

57]

REMANENT MAGNETIZATION
means
that

309

state this

most magnetization vectors are turned out of a mag-

netically

preferred crystallographic direction towards another preferred

direction

isolated crystal this


crystal,
stresses.

which makes a smaller angle with the direction of the field. In an would be accompanied by a change in the shape of the but a crystal in an agglomerate polycrystalline sample will suffer
In the remanent state no stresses will arise
if

the magnetostriction

in the preferred direction

(Am

or Aioo for a cubic

ferrite) is zero.

Only

in

that case can

we

expect a remanent magnetization as given in Table 57.1;

otherwise
(c)

it

will

be lower.

Shape Anisotropy
is

Although, seen macroscopically, the hysteresis loop


magnetically closed circuit of the material, there
is

nevertheless

measured on a an appreci-

able degree of internal demagnetization due to shape anisotropy arising

from the more or

less

porous structure of the sintered

ferrite (see 43.3).

M
\

*
1

/
>'

Fig. 57.1. Effect of demagnetiza-

on the shape of a hysteresis loop. The internal demagnetition

[
1 1

/
/

'

(
1

''

zing factor Nt

tan

a.

(/

a./

1/

In Fig. 57. 1 the magnetization


plied magnetic field
field

is

plotted against both the externally ap-

(broken curve) and the average internal magnetic

Ht

(solid curve). It is

assumed

that:

H -Hi = NiM,
where Ni denotes the internal demagnetizing factor
be seen from the figure that the ratio
demagnetizing
smaller
is

(57.3)

(see 43.3). It

can

re

m/M

is

greatly reduced

by the

demagnetization, and also that the ratio /xrem/^o approaches unity. This
field will

have a greater influence on the hysteresis loop the

the coercive force of the ferrite.

For the ferrites of Figs. 56.2 to 56.6 the relative remanent magnetization and the relative permeability in the remanent state are given in Table 57.11. The table also indicates the properties of the isotropic and crystaloriented samples of BaFei20i9 to be discussed in 60.

The
the

values of the remanent magnetizations are

much
is

lower than those

that might be expected according to Table 57.1, which

probably due to

phenomenon of "shearing"

as a result of internal demagnetization.

310

STATIC HYSTERESIS LOOPS

[CH.

XV
AND

TABLE

57.11
,

RELATIVE REMANENT MAGNETIZATION, Tem /M3 RELATIVE PERMEABILITY, POROSITY p OF THE FERRITES IN FIGS. 56.2 TO 56.6.
Ferrite

HvemllMs,

P
0.25 0.15

no 13

V-reml 1*0

Wrem/Afs
0.5

Figure
56.2
56.3

NiFe 2 04
Nio.5Zno.5Fe204

1.0

300
1500
55

0.80

0.33 0.33

Mno.65Zno.35Fe204

Mgo.45Mnn o.55Mn
Coo.8Zn1.2Z
isotropic

mo.23Fei.7704

0.05

0.84
0.32

56.4
56.5

0.10

0.67

0.10 0.10

26
58

0.64 0.52

0.38
0.65

56.6a 56.66

crystal-oriented

BaFei20i9
isotropic
crystal-oriented

~1.5

S2
when high
is


is

0.46
0.94

60.5a 60.56

This

is

particularly important

porosity

combined with low

coercive force (the coercive force

generally inversely proportional to po).

In the case of the isotropic samples of Coo.sZni. 2 Z the effective internal de-

magnetization
lite

is

high owing to the anisotropic permeability of each crystalferrites

(see 43).

Accordingly isotropic samples of these hexagonal

with

a preferred plane of magnetization always have a low remanence, even when the porosity is small. For anisotropic (i.e. crystal-oriented) specimens
the remanence
is

appreciably higher in a direction parallel to that of the

preferred plane. Nevertheless their remanence values

by no means reach
to the fact that the
forces

the high values given in Table 57.1. This


crystallites are far

may be due

from

ideally oriented,

and for the small coercive

in question

it

will also be due to the porosity.

The remanent magnetization of the


uniaxial anisotropy,
theoretically to
is

isotropic polycrystalline sample of


crystallites

BaFei20i9 with a high coercive force and whose


only slightly
less

show a

large
is

than half the saturation value, as

be expected. For the crystal -oriented sample the remanence


crystals differs little

measured in the preferred direction of the


saturation magnetization.
the crystals has
that
little effect

from the

The mutual

interaction of the magnetizations of

since the crystallites of

both samples are so small

most of them are single-domain

particles (see also 60).

58. Constricted Hysteresis Loops and Magnetic Annealing

special shape of the hysteresis loop

is

often found in polycrystalline samif

ples of

mixed
cobalt

crystals
ferrite.

of

ferrites

with spinel structure


Fig. 58.1

one of the compo-

nents

is

As an example,

shows loops as found for a

number of rings of cobalt-ferrous ferrites Co s Fe"_ 8 Fe2C>4, which were slowly

58]

CONSTRICTED HYSTERESIS LOOPS AND MAGNETIC ANNEALING

311

CW F,M F*lt

c%s ff'V,
Fig. 58.1. Major and minor hysteresis loops for ferrites been cooled slowly in the absence of a magnetic field.

Co sFei-Fe204 which have

cooled to
of

room temperature from above the Curie point (for the whole
temperature
lies

series

ferrites this

between 500 and 600 C). In most samples


is

the minor loops

show a
is

constriction near the origin. This


tips

not found in
fall

the major loops. It

remarkable that the


is

of the minor loop

outside

the major loop, which

equivalent to the fact that the virgin curve runs

mainly outside the major loop, as indicated by the dotted curve in Fig.
58.1c. In these ferrites the virgin state is very stable.
teresis is

found; at somewhat larger


field

fields hysteresis

At small fields no hysphenomena appear,


is

but when the


restored.

drops again to zero the virgin state

approximately
is

The

difference as

compared with
i.e.

ferrites

containing no cobalt

probably

that,

during slow cooling, a very stable domain pattern arises


diffusion.

owing to ionic

Rapid cooling,
also

quenching, gives rise to normal

loops; the time for diffusion seems in that case to have been too short.

The

Curie point of the

compound must

be sufficiently high (higher than 150

to 200 C) in order for the diffusion to be influenced

by the magnetization.
at

The family of
point
is

hysteresis loops

measured

after

slow cooling from the Curie

in practice not influenced

by demagnetization

room temperature

The shape of the minor by a field seen in Fig. 58.2. Above room loop changes with temperature, as can be temperature the constriction in the loop is generally somewhat more prowhose amplitude
is

gradually decreased.

312

STATIC HYSTERESIS LOOPS

[CH.

XV

tures

nounced, but disappears at a temperature higher than 100 C. At temperabelow 20 C the constriction rapidly becomes smaller and vanishes at
It is

liquid-air temperature.

generally found that ferrites with constrictions in their hysteresis


is

loops are sensitive to so-called magnetic annealing, that

to say the shape

of the hysteresis loop changes

when

the ferrite, placed in a sufficiently strong

magnetic

field (a.c.

or

d.c.), is

slowly cooled to

room temperature from


fields

the

Curie point. If one measures the hysteresis loop in

which are

parallel

to the field present during cooling, one finds rectangular loops, both for a

minor and for the major loop.

Fig. 58.3 gives the loops


a.c. field

found

after the

process of magnetic annealing in an

has been applied to the samples


is

of Fig. 58.1. In some samples the rectangularity

so

marked

that a

minor loop
to the

exists consisting

of two lines which are approximately parallel

H axis.

the other level

The magnetization jumps discontinuously from the one to when the magnetic field is gradually made only very little
0.5%) than a certain
critical

larger (less than


Fig. 58.4).

value (see the solid curve in

A particular feature of these ferrites is that asymmetry with resB axis


The
(and sometimes also with respect to the

pect to the

H axis)

is

caused

by annealing
Fig. 58.4.

in a d.c.

magnetic

field; this is

shown by

the broken curve in

fact that this heat treatment of cobalt-ferrous ferrites

the hysteresis loop

makes more rectangular was discovered by Kato and Takei

4JTM(gauss)

\
3000

Qfc, *,<!,

Fig. 58.2.

Minor

hysteresis loops of Coo.6Feo.4Fe204,

measured

at various temperatures.

58]

CONSTRICTED HYSTERESIS LOOPS AND MAGNETIC ANNEALING 313


4-7TM(gauss)

3000

3000

\-2000

1000 H(oersted)

500
-1000

500

2000
3000

G%,^g/V%

Co0A Fe0S^20i

Qte^a^*
Fig. 58.3.

C0S F43 Fe20i

Major and minor

hysteresis loops for the


after

same samples as

those of Figs. 58.1, but


the samples.

now measured

magnetic annealing of

[Ka

3]

and led

to the development of a

permanent magnetic material known

as "Vectolite".

point,

other ferrites having spinel structure, and a sufficiently high Curie and containing a small concentration of cobalt ions show a constricted hysteresis loop and are sensitive to magnetic annealing. Examples are ferrous-

Many

314

STATIC HYSTERESIS LOOPS

[CH.

XV
fer-

manganese, ferrous nickel, ferrous magnesium and nickel-magnesium


rites

[Go

9] (see Fig. 58.5),

magnesium-zinc

ferrites

[Ko

8]

and

nickel-zinc

ferrites

[Ec 2] which contain a small percentage of divalent cobalt. Bozorth


effects
still

[Bo 2] and Eckert [Ec 2] found that at 150 C annealing


place.

take

The magnitude of the

effects

depends both on the temperature and


constriction of the loop

on the duration of the treatment. The

and the phe-

nomenon of magnetic annealing


ferrites

are both related to the uniaxial anisotropy

discussed in 43.2, which arises in the field-cooling of single crystals of

containing cobalt and which is the result of a directional ordering of cobalt ions under the influence of the magnetization. If no external magnetic field
is

present, this ordering will

still

take place along the direction

of the spontaneous magnetization in each domain.


then be bound more rigidly to
is
its

non-180

wall will

equilibrium position since the ion ordering

along different directions in the adjacent Weiss domains (see [Ta 4]). In Fig. 58.6 the potential energy per cm 2 of a 90 wall is plotted as a function

of

its

position for the case where a uniaxial anisotropy

is

present in the

adjacent domains in the direction of the magnetization.

The ion ordering


is

in the wall itself has also taken place along the direction of the spins in the
wall.

Normalized coordinates are used. The potential energy

expressed in

K8 W units, where 8 W is the wall thickness, and the displacement z is measured

Fig. 58.4. The solid curve describes a rectangular minor hysteresis loop of Coo.iFeo.9Fe204 after magnetic annealing in an a.c. field. A single

large Barkhausen jump causes the magnetization to change sign. The broken curve shows the asymmetric curve obtained for the same ferrite
after

magnetic annealing in a

d.c. field.

58]

CONSTRICTED HYSTERESIS LOOPS AND MAGNETIC ANNEALING 315

For the directional distribution of the spins in the wall we assume for the sake of simplicity a linear relationship between 4> and z instead of (15.3). It can be seen that no hysteresis occurs; as a result of this phenomenon the wall returns reversibly to the position of equilibrium. The broken curve
in S w units. in the figure shows the potential energy assuming that the ions have oriented themselves at the position of the wall at a higher temperature than the

temperature at which the measurement was performed. It is assumed that the ion orientation in and near the wall corresponds to a wall thickness

28 w For the case of a 180 wall the additional potential energy is represented in Fig. 58.7. The most important anisotropy effect caused by the directional ordering of the ions is now to be found in the wall itself. For wall-displace.

ments over a distance which is small compared with the wall thickness the permeability will thus be small. If the wall has once been displaced by a large field over a distance equal to the thickness of a wall, it will be able, under the influence of this
field,

to cover a

much

greater distance.

The

coer-

cive force for this irreversible

wall-movement

is

determined by the maxi-

mum slope of the curve in Fig. 58.7. In order of magnitude this is equal to K/M In the case of the sample in Fig. 58.1c the value of K can be derived
t.

from

Fig. 34.4.

From

this

one

finds

H ~
c

10 4 oersteds, which

is

much

by experiment (the abnormal increase in the amplitude takes place at about 500 oersteds). The phenomenon despermeability
greater than found

B (gauss)
k 2000r

H(0e)

Fig. 58.5.

family of hysteresis loops of a ferrite Mgo.59Nio.39Coo.o2Fe 2 04


field.

which has been annealed in a magnetic

316

STATIC HYSTERESIS LOOPS


IT/
i
1

[CH. 90

XV

4?
Xfe.
^
>

2/Sw
The additional potential energy of a 90 wall as a result of a directional ordering of ions in the wall itself and in the adjacent domains where it causes a uniaxial anisotropy along the direction of the magnetization. The potential energy and the position of the
Fig. 58.6.

KB W and S, respectively, where S a is the wall thickness. The and the broken curve apply respectively to an ordering of the ions in the wall corresponding to the directional distribution of the magnetic moments and to the case where
wall are expressed in units
solid

the ionic ordering in

and near the wall corresponds to the directional distribution of the magnetic moments in a wall with thickness 2S W
,

on an atomic scale and hence must influence all walls equally. Since the walls are only in the deep potential wells in the demagnetized state, this wall pattern will be particularly stable, and this is reflected
cribed occurs
in the constriction in the hysteresis loop at a field

H=

after this ferrite

has only been partly magnetized. If the material is magnetized by such a strong field that the domain walls disappear, then it will be purely
coincidental
if

the walls which

form while

this field returns to zero

resume

<r/>
i

180

""*

\
/

"

5
Fig. 58.7.

J
5
Z/tfu
1

The same

as Fig. 58.6, but

now

for a 180 wall.

59]

EFFECT OF UNIFORM MECHANICAL STRESSES


former positions. The new domain pattern
will generally

317

their

be quite

different

from that

originally obtained after demagnetization.

A minor loop

can thus have a constriction, the major loop cannot. At low temperatures the domain walls are thinner than at the temperature
at

which the directional ordering of the ions took place as a

result of diffu-

sion, so that the ion ordering in the

directions.

On

match the spin the other hand the other anisotropics which determine the
wall does not

domain

hysteresis are usually larger at lower temperature. This

may

be the reason

for the disappearance of the constriction in the loop at

low temperatures.

At high temperature,
in this case too.

far

above room temperature, the ordering changes


at

during the measurement, as a result of which the constriction disappears

For a sample

a temperature of about 200 C the change

in the hysteresis loop with time can be followed

on an

oscilloscope,

and a

constriction originally present can be seen to disappear gradually. If the


field is

switched off for a while, the constriction reappears in about the same
it

relaxation time as

took to disappear.

59. Effect of Uniform Mechanical Stresses on the


Hysteresis

Form of

the

Loop
and
illustrated in Fig. 49.3,

As described in
mechanical

49.1

a sufficiently large uniform

stress, either tensile

or compressive, can bring about a special


ferrites.

Weiss-domain configuration in
hysteresis loop in
(fxo

This influences the form of the

a manner as illustrated in Fig. 59.1 for Nio.5Zno.sFe204

Without external stress (ae = 0) a loop of normal shape is measured (the demagnetization measured on a rod is kept small by, for example, closing the magnetic flux with a yoke of a material
As
).

~ 220 and

= 8 x 10- 6

having a high permeability). In the presence of a compressive


see the curves for compressive stresses ae
If the

stress the

loop changes in such a way that the remanent magnetization increases;

from 2.5 to

kg/mm2 in the
is

Figure.

compressive

stress is so

high that the stress anisotropy

predominant,

the remanent magnetization measured in the direction of the rod axis will

be equal to the saturation magnetization.

remanence smaller

see the broken curve in Fig.

compressive
59.1.

stress makes the The reason is that


is

during the measurement of the hysteresis loop the magnetization

turned

out of the preferred direction determined by the stress anisotropy, towards a direction at right angles thereto. In the extreme case where the tensile
stress is so large that the stress

anisotropy

is

predominant, a linear relationfield

ship without hysteresis


strength.

would be found between magnetization and

For

field

strengths of the order of magnitude of the coercive force

318

STATIC HYSTERESIS LOOPS


ferrite

[CH.

XV

of the

posite influence

and larger, tensile and compressive stresses thus have an opon the amplitude permeability /*. At smaller field strengths

and tensile or compressive stress is somewhat more complicated, as described in 49.2. The variation in the coercive force the low amplitude permeability and the relative remanent e

the relation between permeability

magnetization
Fig. 49.5 for

xe

mlMcl

with tensile and compressive stresses

is

shown

in

a polycrystalline sample of Ni .sZn .5Fe2O4. The quantity

Mci denotes the magnetization at a field strength above which hysteresis phenomena no longer occur in the ferrite. In the case of ferrites with positive
magnetostriction what
tensile stresses
is

said

above for compressive


extent to which the

stresses applies to

and

vice versa.

The The

form of the

hysteresis

loop of a

ferrite

can be influenced by external


Fig. 59.2.

stresses is further illustrated

by the curves in

polycrystalline ferrite ring (composition

Nio.34Zno.6eFe204, /^o= 650 and A s

= 4x 10~

) is

surrounded by a ring
fer-

of glass with a somewhat higher thermal expansion coefficient than the


rite.

When the glass ring is fitted around the ferrite ring at a high temperature,
room
temperature will be subjected to a

the ferrite after being cooled to

uniaxial tangential compressive stress.

The

figure
4].

shows that the hysteresis

loops consequently become rectangular [Ra


5000

4jiM
(gauss)

4000

3000

2000
Fig. 59.1.
resis

The change

in the hyste-

loop of a polycrystalline sample

of Nio.5Zno.sFe204 with negative


1000

magnetostriction
to

when
stress.

subjected

an external

The

solid

curves apply to different values of

a compressive stress curve applies


75

oe.

The broken
stress

to
.

tensile

20
HlOersted)

25

^=

2.5

kg/mm 2

60]

PERMANENT MAGNETS

319

Fig. 59.2.
ring.

The

Family of hysteresis loops for a glass-covered ferrite ferrite, with negative magnetostriction, is under a

tangential compressive stress.

represents a

For comparison the dotted curve minor loop for the unstressed ferrite. The inset
ferrite ring F,

shows a cross-section of the glass-covered


glass G.

with

60. Permanent Magnets


60.1.

FIGURES OF MERIT FOR PERMANENT MAGNETS


the spinel ferrites containing cobalt,

Among

and

in the series of ferromag-

netic oxides with hexagonal crystal structure having the c axis as the pre-

found a number of compounds from which permanent magnets can be made. In order to make a comparison of various permanent magnetic materials, we shall first consider what characteristics in quantitative form are important for various applications.
ferred direction of magnetization, are
(a) Generation of

Magnetic Fields by Magnets


(2.4)

Making use of equation


systems in which the

field is

and b B, we may write for with a due to permanent magnets alone:


(60.1)

=H

SHBdV=0,
where integration
is

carried out over the total volume.

Assuming that the

320

STATIC HYSTERESIS LOOPS

[CH.
air,

XV
the

system consists of magnets plus "magnetically soft" materials and


integral (60.1)

can be

split into

the following parts:


2

fHBdV = $HB dV + J*# dV = 0,


magnet
air

since the contribution of the magnetically soft material

(i7=0) can be
it

neglected. For a given value of the volume integral over the air

follows

that the required volume of magnetic material will be inversely proportional


to the value of the product

BH. The maximum

value of this product can be

taken as the figure of merit of the magnetic material for this type of application. In practice, at smaller values of (Bi/)max the required magnetic

volume
be
filled

will increase relatively

extensiveness in space increases and therefore

more than (BH) ma,x more

decreases, since the


ineffective space will

by

stray fields.

(b) Attractive Forces

of Magnets

For the magnitude of the forces which various magnetic systems exert on each other, as for example in sticking magnets, a different figure of merit should be used. This can be derived by calculating the work which must be done in order to bring about a small change in the configuration, as would
be caused by the magnetic force. This energy consists
of:

SA

=
1

4ir

HSBdV +

877

f J
air

dV,

(60.2)

magnet

where SB is the change in B in a fixed point of the magnet, while the last term is the change in the total integral. Let us now eliminate the contribution from air, so that SA is expressed only in quantities which refer to the magnet. For this purpose we make use of (60.1), remembering that the change
in this integral due to the change in the configuration

must then

also be zero.

This gives:
J"

{HSB

+ B8H) dV +

8J
air

H *dV = 0.

(60.3)

magnet

Combining

(60.2)

and

(60.3) gives
8.4

=J
077"

(HSB - B8H) dV.

(60.4)

magnet

Assuming that the

relation

between

and

H
,

is linear,

the magnitude of

SA, except for the factor

%ir, is

given by the hatched area in Fig. 60.1. The

maximum

value of SA, which


is

is

a linear measure of the work that can be


,

done by a magnet,

equal to

BrHm

where

Hm

is

the

maximum permissible

60]

PERMANENT MAGNETS
is still

321

value of the field at which the magnet


reversible.

This product which, except for a


represents the work to be performed

factor

877,

open a short-circuited magnetic system, we shall use as a figure of merit for magnets for these applications.
in order to
60.2.

PERMANENT MAGNETIC PROPERTIES OF HEXAGONAL OXIDES


Fig.
60.1.

The

origin of the permanent magnetic pro-

perties of

some hexagonal oxides

is

to be

represents

The hatched area 8w times the work

found in the high value of the uniaxial anisoA In 17 it was calculated that tropy field a field of the order of A is needed in order to cause an appreciable rotation of the

cm3 of magnetic material needed for changing the confiper


guration of a magnetic system so as to cause the working point
to go

from

to

2.

magnetization vector in a Weiss domain. If


the crystal
is

large

enough

to contain several Weiss domains, the

movement

of the walls will usually require a substantially lower field.


force can therefore be expected in these substances only
consist of single Weiss domains. It
is

A high coercive
the crystallites

when

For single which follows from (14.4). In the case of BaFei20i9 the wall energy is large because Ki is large. Assuming a to be 3.10" 8 cm, the wall energy is found according to (15.2) to be of the order of <jw 5 erg/cm 2 It then follows from (14.5) that the critical thickness of the platelets for single domain behaviour is D CI 0.5 x 10~ 4 cm; this is much larger than the wall thickness, which is approximately 2 x 10~ 6 cm. Samples having grains of about 1 micron or smaller consequently have a large coercive force, whereas a material having grains of about 10 micron in diameter or more have a low coercive force (Fig. 60.2). Since the quantities that determine the critical diameter (14.5) depend on the temperature, the critical diameter
the shape of platelets.
fore be smaller than that

found that the crystals are mainly in domain behaviour the thickness must there-

will

also be temperature-dependent.

One

finds
(60.5)

Dcr
it

OC

^Ki/Ms,

being assumed that the exchange energy, in agreement with the Weisstheory of ferromagnetism, varies with temperature as

field

M 2

does.

The

quantity

^K\\MS

for BaFei20i9

is

shown

as a function of temperature

As can be seen, it increases by almost a factor of 2 going from low to high temperatures. This is in agreement with the variation of the coercive force as a function of temperature (Fig. 60.4); at low temperature
in Fig. 60.3.

322

STATIC HYSTERESIS LOOPS

[CH.

XV

3000

4XM
(gauss)

__

--"
~<*

2^ ^S&

2000

WOO
BaFei2 0i9

^
-2000

/
2000
4000 6000
-

8000
(Oe)

3000

4nM
(gauss)

2000

"/ &*\
s

-S^

s*3

1000

f
2000

BaF'e^O 19

}
I
2000
4000 S000
(Oe)

8000

*W
Fig. 60.2. Hysteresis loops at

room temperature of BaFei20i9


1

with

random
[Ra
7].

crystal orientation, sintered at 1350

and 1400 C, so that the

average grain sizes are about 10 and

microns, respectively. After

Dashed: demagnetization curves for pure rotation.

some wall formation still occurs, which reduces the coercive force. Stoner and Wohlfahrth [St 5] have calculated the magnetization curves for pure rotational processes, neglecting the interaction between the grains. The demagnetization curves according to this model are given by the broken lines in the Figures 60.2. The corresponding coercive force (in this case the = 0) is 0.96 K\\M for random orientation of the field strength at which crystals. In the case of BaFei20i9 at room temperature, this would be approximately 8000 oersteds. The fact that the coercive force found by

experiment

is

smaller

is

probably attributable to the formation of walls in


found, however, that in that case the

a negative

field. It

seems therefore desirable to make the grains even smaller


It is

(by longer milling of the powder).

60]

PERMANENT MAGNETS

323

coercive force again decreases, probably owing to plastic deformation of


the grains; this can be eliminated

by annealing

at 1000 C, at
60.1).

which tem-

perature no noticeable sintering takes place (see Table

TABLE

60.1

DEPENDENCE OF THE COERCIVE FORCE OF A POWDER OF AND HEAT TREATMENT.


Milling time
in hours

BaFe 12 Oi 9

ON THE MILLING TIME

mHc
oersteds

100 2

500

4
8

700
1000 1570

18

38

1600
1

Additional heat treatment of


at various temperatures

hour

in air

Temperature

M^c
oersteds

C
200 700
1000

1600

1900

3400

1100
1200

3900
3440

The high coercive

force in Table 60.1 can occur only in loose powders.

In denser materials the tiny grains have grown as a result of the sintering
process into bigger units, in which walls are formed. Moreover in dense
terials the interaction

ma-

between neighbouring grains cannot be neglected, so

that a correlation between the Weiss

domain

patterns occurs (e.g. walls

do not stop
8r

at the

boundary between two

grains).

Thus with the formation'

^-^*^
ffi

Fig. 60.3. The quantity YKi/Ms of BaFei 2 Oi9 as a

BaFe 12 Q m

function of temperature. This


quantity
the
is

proportional to

critical

diameter

for

single-domain behaviour.
-200
-100

100

200

300
-*~

400

500

After [Ra

6].

T(C)

..y

324
10.000

STATIC HYSTERESIS LOOPS


Fig. 60.4.
f

[CH.

XV

The

intrinsic coerc

"

OMKi/M
7

cive force

mH

as

measured

7500
(Oe)

for

fine-grained

BaFei20i9

as a function of temperature,

compared with the quantity


5000
0.96 Ki/Ms.

^M^c
2500

-200

100

100

200

300

400

500

+
of a wall more energy
tain degree of porosity
(
is is is

T(C)

gained than without this interaction, and conseIt

quently walls will already occur in smaller grains.


is

can be seen that a

cer-

indispensable.

For

practical purposes ^he

B-H

curve of permanent magnetic, material

of prime importance?YmTthe case of high-coercive materialju where c (for example the hexagonal comat least of the order ormagnitude qf Br
(

pounds with uniaxial anisotropy)^ie B-H curve differs essentially from the 4ttM-H curve. For instance, bH' can never be larger thanBr As shown c
.

in Table 57.1,

M /M
r

/z

for the polycrystalline material with

random
r
s.

crystal orientation.

The

quantities

(BH)m&x or

BT Hm

=BH
T

can thus be

increased by orienting the crystallites, resulting approximately in

M =M

The figures of merit mentioned can then rise by a


This orientation in a magnetic
in 44.
field

maximum

factor of 4.
is

during the pressing process

described

A drawback to this orientation is that it promotes the formation of


same
orientation,

Weiss domains, owing to the fact that the preferred direction of magnetization (c axis) in adjacent grains has approximately the so that Weiss domains can easily continue

from one
will

crystal to the other

and
is

there

is

thus a danger that the graininess of the material, which should

be the reason for the absence of domain walls,


thus associated with a low coercive force.

be lost. A high remanence microphotograph of a cross-

section parallel to the c axes of the crystals of a sample having large crystals

shown in Fig. 14.6. A deposition of a colloidal solution of Fe3C>4 powder marks the position of the domain walls. Examples of the 4-n-M-H curves and demagnetization curves for both an isotropic and a crystal-oriented sample of BaFe^Oig are given in Figs. 60.5 and 60.6. The corresponding figures of merit are given in Table 60.11. Comparable results can be obtained with compounds of the structure; for example an isotropic permanent magnet of Fe can have a value of (Sff) max = 10 6 gauss oersted. The
is

60]

PERMANENT MAGNETS
5000

325

4rtMtfrot)

{4000
1

^b
BaFeaOs

inM

(*luss)

3000
t

20001

/
/
-5000

-2500

2500

S000

7500

I0OO0

H(Ot)
Fig. 60.5. Hysteresis curves of

crystal-oriented

BaFei20i9 for magnets of BaFei20i9.

a) isotropic

and

b)

TABLE
Polycrystalline

60.11

SOME FIGURES OF MERIT OF PERMANENT MAGNETS OF


sample
isotropic
crystal-oriented

BaFei 2 Oi 9

BrHm
gauss
oersted oersted

gauss oersted

gauss oersted
3.3-10 8

2000

3000
1450

1650 1360

0.8106
3.0106

4080

510

saturation magnetization at

room temperature

of

this

compound
optimum

is

about

8%
is

higher than
for

that

of BaFei20i9,

which

important

obtaining

properties.

The

highest value of (2?.ff)max theoretically

to be expected for a material corresponds to

a remanence

and an

infinite coer-

cive force. This

can only occur

in the impossible

case of ideally oriented crystals without mutual


interaction,

and

having no porosity.
case,
-2000

moreover with a sample For BaFei20ig in this


2

(5if) ma x

= V^M,) =
is

6.10 6

gauss

oersted.
-WOO

H (Oe)
Fig.
60.6.

useful property of these oxide

magnets

is

Demagnetization

that the coercive force

comparable with the

curves

of the magnets in

remanence.

This

allows a considerable free-

Fig. 60.5.

326

STATIC HYSTERESIS LOOPS


in the shape of the magnets,

[CH.

XV

dom

since demagnetizing fields will not

irreversibly

demagnetize the magnet. This applies particularly to the

unoriented material, where


large crystal anisotropy
is

mHc > bH A
c.

further consequence of the


is

that the susceptibility

small both perpen-

dicular

and

parallel to the c axis (about 1.4).

CHAPTER XVI

DYNAMIC PROPERTIES AT HIGH FIELD STRENGTHS


61. Hysteresis Losses
61.1.

and Distortion in the Rayleigh Region

HYSTERESIS RESISTANCE

AND DISTORTION
coil containing

The
core

distortion caused in
is

a network by a

a ferromagnetic

and the

a consequence of the non-linear relation between the induction B field strength Hin the core. This non-linearity can have two reasons:

(a) The induction

is

a single-valued non-linear function of

H
sym-

The function B(H), then, has the origin (H = 0, B = metry, so that B{H) = B(H). For small values of
can be expanded into a
series:

0) as point of

H the function B{H)


(61.1)

B(H)
from which
tively the
it

ixqH

+ vm + XH5 +

follows that for a sinusoidal field

(H =

//maxcos wi) the

distortion D =

V%\V\ is proportional to H^ax fundamental and third harmonics of the voltage across a coil with ferromagnetic core when a sinusoidal current passes through the coil).
(where V\ and V% are respec(b) Hysteresis

When
teresis

the induction in the core

not a single-valued function of H, hysphenomena will occur. The simplest representation of the lower
is

branch

(1)

of the hysteresis loop of Fig. 61.1


b(h)

is

given by the equation:


(61.2)

/x

vh\

Fig. 61.1. Hysteresis loop at

low induct-

ion consisting of two quadratic curves.

328

DYNAMIC PROPERTIES AT HIGH FIELD STRENGTHS


an analogous equation

[CH.

XVI

the point 0' being the origin of the coordinates b


(2)

and h. To the upper branch


a coordinate system

applies, with reference to

having

O"

as

its origin.

After a simple transposition to coordinates

and

H with

as origin, both branches are represented

by the expression:

B(H)

= vH^ + (/xo + 2vHm*x)H T

vH\

(61.3)
It

the upper signs referring to the upper branch of the hysteresis loop.

should be noted in

this

connection that, in principle, the coefficients ^o

and
as

v can be a function of //max- In the case of

a sinusoidal

field

H=
(in

/Tmaxcosarf, the distortion

D=

F3/F1

will

be proportional to flmax

do not depend on iTmax). In ferromagnetic materials there is practically always some hysteresis, so that where the field strengths are sufficiently small the distortion is entirely caused by this hysteresis and not by the non-linear character of the B-H curves [Pe 2]. The energy dissipated per cycle and per unit of volume is according to (2.2) proportional
as po
v

much

and

to the area of the hysteresis loop:

W=(l/4w)fHdB

erg.

(61.4)

Integration of the two series (61.3) yields for (61.4) the result:

W=(2/3^vH^ +
It

...

(61-5)

appears, then, that the hysteresis losses per period and per
first

cm3

of material

are proportional in

approximation to the third power of the amplitude


total heat per

of the

field strength.
is:

The

second generated in a core by

hysteresis

W = (2/3ir)vHUV erg,
where / is the frequency of the applied
in
field

(61.6)

and

V the

volume of the core

cm3 We
.

can

now

define a hysteresis resistance

Rh by

W = IlBRn,
(61.7)

hence according to (61.4)

Rh =

(4j/2/3n-)w 1 37eff/r 10-7

hm,

where the geometric factor a denotes the relation between coil current and the magnetic field strength in the core: m&x = cilmax For a toroidal core with cross-section A and mean diameter dm and provided with turns, one

finds:

ci

= (0.4 N)/dm

and

V=

ttA

dm

Rh =
The
distortion caused

(1.21 /d^WAflett v

10-8

ohm.

-8)

by the core can be brought into

relation with the

hysteresis resistance given in (61.7). In the case of sinusoidal fields

(H =

61]

HYSTERESIS LOSSES
cat)

AND DISTORTION

329

//max cos

of small amplitude, equation (61.3) becomes:

Bit)

= (/no + 2r.ffmax)#max cos cat vH max sin


2

wt

=(juo

+ 2v.ffmax)flmax COS cat +


/sin cof

+(8/^max (nrr - T3^ - T3^y ~


The induction
is

sin 3cot

sin 5tf

'

).

directly related to the voltage across the coil:

10 8 E\C%

= dB(t)/dt = (ixo + 2vf/max)<>flmax sin oat + - (8/7T>co ff2 max(l cos cat -I cos 3<^
J

),

(61.9)

where

cz is again

The

loss factor

a constant depending on the core and coil dimensions. tan8 A that determines the hysteresis losses in the coil is

defined as:

3t7(^o

+ 2r//max)
(6i.il)

and

the distortion Z)

is:

a-k^-- ^fr +
37r(/i0

Zvlima-x.)

From

(61.9)

and

(61. 10) follows the

simple relation:
ft

D = 0.6 tanS =
in which

0.6

R h /a>L,

(61.12)

is

the self-inductance of the coil with core.

relation between the reactance of the coil with core


hysteresis resistance

From (61.9) (X=coL) and

the the

Rh

is

found to be
cav-ocicz

X=
The
resistance of

+ (3W4)-Rft.
is

(61.13)

coil containing

a ferromagnetic core

often plotted

as a function of the appertaining hysteresis resistance

Rh for diflFerent values

of jffmax; this is done in Fig. 61.2. If fi is independent of ifmax, the relation between both quantities (each measured as a function of the coil current) is given by a straight line which makes an angle j8 of 23 with the ordinate. If the relation (61.13) applies, it is then said that the material satisfies Rayleigh's law.

Lord Rayleigh found

that

/j.

and

v in several iron samples are


1

independent of Hm&z.
apply.

when

the samples are magnetized to about


ferrites,

of the

saturation magnetization. In the case of

equation (61.13) does not

The angle

j8

crystalline ferrite

always smaller than the Rayleigh value. For a poly1090) the loss factor tan8 and Mno. 5 Zno.5Fe20 4 (ho
is

330

DYNAMIC PROPERTIES AT HIGH FIELD STRENGTHS

[CH.

XVI

the selectively measured distortion F3/F1


(see

62) are given in Fig.


,

61.3

as a

function of the amplitude

Hma K of a sinufield strength

soidal measuring-field having a frequency

of 2 kc/s. Both quantities are seen to be


linearly

dependent on the
to
(61.10)

O^oc,c2

up

to about 30 millioersteds, as expected

according

and

(61.11).

The

relation (61.12) holds fairly well, especially

*h
Fig.
61.2.

for low values of

Hma K
,

as can be seen
curve,

The reactance

as a

from the comparison of the dashed


giving 0.6 tanS ft , with the curve for

function of the hysteresis resistance

Kh

in the case

where the core ma-

V3 /Vi.
the

terial

obeys Rayleigh's law. The

At higher

field

strengths, however,

straight line carries a linear

magne-

field-dependent contribution to the loss


factor, (tanS

tizing-force scale.

tanS r), seems to be not


generally found to
it is

only the consequence of hysteresis. The


discrepancy between distortion and hysteresis losses
is

be larger the higher

is

the measuring frequency. In Figs. 62.1 and 62.2

shown

that in the case of a ferrite with high initial permeability, the

mag-

netization curves and the distortion depend on the frequency. The selectively measured distortion becomes smaller at higher frequencies, but the fielddependent part of the loss factor generally becomes larger [Sm 4].
61.2.

HYSTERESIS CONSTANTS
the foregoing, in order to calculate the hysteresis resistance

As appears from

7.2-2 r

ta/itf

V)/v,

2i 26 32 ?-* * Umax (oersted)


Fig. 61.3.

The

loss factor

tanS and the selectively measured

distortion Vzl Vi as a function of the amplitude

Hmax of a sinusoiindicates the

dally varying measuring-field.

The broken curve


from the

distortion calculated with (61.12)

hysteresis losses.

61]

HYSTERESIS LOSSES

AND DISTORTION
it is

331
necessary

or the distortion of a coil containing a ferromagnetic core


to

know

the quantities

/*o

and

v of the core material as a function of //max,

together with the dimensions of the core


the coil, comprised in the constants

and the number of turns around and ci. Where the core material a obeys Rayleigh's law, that is where /*o and v are independent of //max, a hysteresis constant of the core material can be given by means of which the hysteresis resistance and the distortion of the coil with core can be
determined as a function of the
tance. This simplifies the
coil current at

a given value of self-induc-

comparison of various core materials to be used


it

for the

same purpose, and

also simplifies the calculation of hysteresis

losses or distortion

when

cores with air gaps are used. In the latter case

the relations (61.6) or (61.11) are complicated, since //max then refers to the internal magnetic
fields.

Hysteresis constant a

Legg [Le

1]

introduced a hysteresis constant a according to the equation*):


(tan8 ft)/|Lio

= a B^lir,
From (61.10)
it

(61.18)

where Umax is the maximum induction in the core for a sinusoidal magnetic
field in

the core with amplitude //max.

follows that for small

field-strengths

(vHm&x <^

/x )

and

at constant frequency, the hysteresis loss

factor tanSft

(=

Rh/2ttJL)

is

proportional to the induction in the core.


first

Since the quantity (tanS)//*. undergoes, to the

approximation, no change

when an

air

gap

is

introduced in the core, see (28.8), the hysteresis constant

a in (61.18)

will also

not depend on air gaps, and

it is

related to

ja

and

v.

= -~j
Bm&7i
only

16

(61.19)

It will

be clear that the hysteresis constant according to (61.18) cannot


it is

reasonably be introduced unless

independent of
is fulfilled

very special case, however, this condition

if

Apart from a v and /xo are


can only

independent of

jB max ,

which means that the

hysteresis constant

be introduced for those substances that obey Rayleigh's law; only in those
cases
is

a a material constant.
find the relation between the distortion F3/F1

One can

and the

hysteresis

constant a for a ring-shaped core of constant cross-section, in which an air

*)

The symbols

and Cn are

also used, being defined as:

Ch
Cji

=a = 10.a

332

DYNAMIC PROPERTIES AT HIGH FIELD STRENGTHS


is

[CH.

XVI

gap

introduced at right-angles to the magnetic lines of force.


is

It is

assumed

that the air gap

small enough to allow the stray magnetic flux to be neis

glected, so that the induction in the core


is

homogeneous and the core volume


Let
/i a pp

given in good approximation by

vA Jmean.

be the apparent
get:

permeability of the core with air gap, then from (61.18)


J?ft

we

=
as:

ai//A 2 appCi/max

ohm,

which can also be written

Rh =

0.2

yiO^ a

^t ./. ^/2

/max

104

ohm.

(61.21)

This in combination with (61.12) yields:

D=

600 |/T0^

yZ/F a tf* /max

(61 .22)
is

This equation can be read in the following way.


small volume Vis a large self-inductance angle 8
is

What

wanted in a
selected

L with low losses,

such that the loss


is

small.
is

For

this

purpose a particular core material

and

an

air

gap

introduced such that the loss factor (tanS) app of the coil with

core

is sufficiently

low

at

a given frequency or in a given frequency band.

From

the apparent value of the permeability and the values

L and V one
harmonic

can now, with the aid of

(61.22), calculate the expected third

components in the voltage as a function of the coil current, given the hysteresis constant a of the core material. Equation (61.22) indicates that the hysteresis constant a is a particularly good measure for comparing core
materials as regards the distortion which they will cause in circuits. In cores

of various magnetic materials but of the same dimensions (same value of V),
ju app will be the same for all The quantity a then gives directly the ratio between the amounts of distortion caused by the various cores for equal coils and coil currents. The hysteresis constant a can best be measured on an a.c. bridge {e.g. Maxwell bridge, see 28.2) on which L and Rn of a coil with core can be determined as a function of the current 7max The core should then preferably have no air gap, so that ju app will be equal to the known true initial perme-

air

gaps can be introduced in such a way that

cores.

ability

of the material.
q?.

Hysteresis Constants h and

Another method of introducing a hysteresis constant has been worked out by Jordan [Jo 8]. He introduced the quantity h, which represents the
ratio of the equivalent hysteresis loss-resistance

Rn

to the self-inductance

of a coil containing a ferromagnetic core,

if

both are measured at a frequency

62]

FREQUENCY-DEPENDENCE OF THE MAGNETIZATION CURVE


1

333

of 800 c/s and at a magnetic field-strength corresponding to per

ampere turn

cm

core length:

RnjL

= h, when/=
it

800 c/s and (N/1)

hit

A/cm.

(61.23)

According to (61.7)

follows from this, for

an

arbitrary

frequency/and an

arbitrary field strength, corresponding to a current Je that:

RnIL

= /z(iV//)/eff//800.
this gives for the hysteresis constant

Brought into relation with (61.10)


the expression:

= 750 v/no.

( 61 - 24)

A reference frequency of 1000 c/s is also

often used, resulting in a different

value for the hysteresis constant h of a magnetic core. For loading coils for telephony applications the quality-factor q 2 is used for determining the amount of distortion. In conformity with the require-

ments of the C.C.I.F. [Co 2], qz is defined as the increase of the resistance of a coil with core, having a self-inductance of 1 henry, when the coil current of is increased from 1 to 2 mA. This increase is measured at a frequency Table 61.1 gives the relation between the various hysteresis con800 c/s.
stants in use for magnetic cores,
/no

and

also their connection with the quantities


is

and

v.

The

indices of 92 indicate that this quality factor


3

given for a

core with a uniform cross-section having a volume of 24 cm and an apparent permeability of 100 (these were once the usual figures for loading coils).

The

lowest values of hysteresis constants can be achieved in the case of magnetically very soft manganese-zinc ferrites with spinel structure, where 0.5- 10~ 6 (or 2.800 1)for instance a

<

<

24.100

TABLE
a h

61.1

RELATION BETWEEN THE VARIOUS HYSTERESIS CONSTANTS USED IN LITERATURE.

= =

(16/3)v//*o 3

= = =

0.71.10 3 /i//"o 2
1.4-10 3 /to a a

0.39-1CT 6
-3

<72.soo

24.100

750

villa

= 0.54.10
=

2 /*o tf2.80o

24.100

92.800

13.8-10* v//*o 3

2.6-106 a

1.85-10 3

AW

24.100

62. Frequency-Dependence of the Magnetization Curve

The single-valued function which gives the relation between the amplitude #max of a sinusoidal magnetic field and the maximum value 5max of the
induction in a ferrite core will be called the alternating current magnetiza-

334

DYNAMIC PROPERTIES AT HIGH FIELD STRENGTHS

[CH.

XVI
is

tion curve of the ferrite at a fixed frequency of the field H. This definition

only useful for materials having a high

resistivity, as

the a.c. magnetization

curve

is

otherwise highly influenced by eddy currents, depending on the

dimensions of the sample. Measurements at high inductions and under continuous-wave conditions have been made on
to a frequency of 1.5 Mc/s.
It is

ferrites

with spinel structure

found [Wi

7] that ferrites with high initial

permeability

have frequency-dependent magnetization curves in a frequency range below that of the ferromagnetic resonance. As an example Fig. 62.1 shows the data for a manganese ferrite with spinel structure
(/^o

> 400)

(43.5

mol % MnO, balance Fe20 3

+ FeO;

initial

permeability

/xo

860;

ferromagnetic resonance frequency about 5 Mc/s). The inset shows the change

with frequency for the amplitude permeability

ft

at

Hmax = 0.6 oersted.


two magneti-

An

obvious interpretation of

this

behaviour

is

that there are

zation processes. One process which gives rise to /*o is frequency-independent up to at least 626 kc/s, and a second process makes an important contribution to the magnetization at field strengths of about the coercive force. This second process is already very frequency-dependent from 100
kc/s onwards.

2000
ft

~\

(H-0.BOe)

r
S0.5kc/s

2500

1750 2000

^
-("0=860

Bmax(9 uss)
i
1500

1500 1000

/t
200 iOO
600
S00

sSOkc/s

500

Pl60kc/s

1250
0.

f (kc/s)

A
/:

//"
t?\

$215kc/s 217kc/s
itOOkc/s

1000

750
500

S&6kqk.
--860

J/y* <** a^AfJ^

250

0.1

0.2

0.3

0A

OS

0.6 *-

0.7

0.8

0.9

1.0

Hmax (oersfed)

Fig. 62.1. Magnetization curves of a manganese-ferrous ferrite with

spinel structure (43.5

mol

% MnO

balance FezOs
.

FeO). Inset:

the amplitude permeability n for

Hma K = 0.6 oersted as a function

of frequency.

62]

FREQUENCY-DEPENDENCE OF THE MAGNETIZATION CURVE

335

250

300

350

Fig. 62.2.

tOO i50 &max<gauss>

500

The

distortion V2I Vi versus the

maximum value

of the

induction

Smax

caused by a sinusoidally varying

field strength

in a core of the ferrite of Fig. 62.1.

The encircled crosses represent

the distortion calculated according to (61.12) from the hysteresis


resistance at a frequency of 2 kc/s.

We shall define the distortion of a core material as the ratio of the amplitudes of the third harmonic Vz and the fundamental V\ of the secondary
voltage of an open transformer completely
filled

with

this

core material,

when the primary current is sinusoidal. The distortion measurement provides


information on the loop that gives the relation between the
field strength

one period of the sinusoidal field H. It is to be expected that this loop will also depend on frequency when the magnetization curve does. Fig. 62.2 gives for the manganese ferrite of Fig.

and the induction

in the core during

62.1 the results of the distortion

measurements

at four frequencies. It is

much on frequency, being almost abThus the shape of the hysteresis loop for this ferrite must likewise change with frequency: at low frequency it is the well-known loop and with sharp tips, whereas at high frequency B is a linear function of only a phase shift between the two can occur, giving rise to an elliptical loop.
seen that this quantity depends very
sent at 700 kc/s.

In
little

ferrites for

which the

initial

permeability

is

lower than about 400,


is

or no dispersion in the

a.c.

magnetization curve

found in

this

range

of frequencies and

field strengths, if they are sintered at the relatively

low

temperature of 1250 C.
material
is

When
much

fired at

lower and a

larger ratio /xmax/^o

about 1450 C the porosity of the is found; compare, for

instance, the low-frequency curves in Fig. 62.3a

and

b.

This additional

contribution to the magnetization at field-strengths of the order of magni-

tude of the coercive force appears to have a frequency dependence similar to that shown in Fig. 62.1. The distortion curves for these ferrites are given
in Fig. 62.4a
ferrite

and

b.

The

three curves in Fig. 62.4b are similar to those for a

having a high

initial

permeability, but with one exception, namely

336
1750,

DYNAMIC PROPERTIES AT HIGH FIELD STRENGTHS

[CH.
1750

XVI

1500

Bmax(9auss)
)

fi/noxfsouss)

1250

a
1000

750

500
S70kcfc

250

0.75

125

075

HmaK (oersted)

1.25

Wmax(oerstedJ

Fig. 62.3. a) Magnetization curves of Nio.sZno.sFeaCU fired at 1250


b)

C in oxygen.
1450 C in oxygen-

Magnetization curve of the same

ferrite after additional firing at

that, besides the

frequency-dependent distortion, a frequency-independent

low inductions. At 590 kc/s the distortion curve is easily by the curves OA and ODE. Subtracting the distortion given by the curve ODE from the measured curves at 80 and 360 kc/s we get the dotted lines OA' and OA" in the figure. It is to be concluded that the distortion caused by ferrites sintered at relatively high temperature (e.g. 1450 C) is brought about by two magnetization processes. The exceptionally high distortion at low inductions seems to be caused by the fact that the high-temperature firing is done in a reducing atmosphere. A large distortion is also found [Sm 4] for a nickel ferrite fired at the relatively low temperature of 1050 C but in an atmosphere of CO2, which should be considered as a reducing atmosphere for the ferrite at this temperature. It seems that the distortion caused by a ferrite core at low inductions dedistortion arises at

divided into two parts, given

pends to a great extent on the presence of ferrous ions. Microscopic eddy-currents might be the cause of the damping.
that the high-frequency level of the resistivity of ferrites
is

It is

often

known much

smaller than the d.c. resistivity (see 46.1). However,

it

appears that the

dispersion in the magnetization curve takes place in the


factor of 10 6
sults in

region for ferrites for which the high-frequency resistivity


.

same frequency is varied by a


effect re-

Moreover a calculation of

this

micro eddy-current
is

much

higher relaxation frequency than

found experimentally.

62]

FREQUENCY-DEPENDENCE OF THE MAGNETIZATION CURVE


irreversible

337

damping of the

domain-wall displacements by eddy currents


the frequency range considered.

will

not take place in these

ferrites in

The relaxation of the a moving wall suffers a

irreversible

friction

domain-wall displacements means that which prevents it from covering the same

it would at the same low frequency. In these samples the walls move under the influence of an applied field of about 1 oersted, at a frequency of about 0.5 Mc/s. If the wall displacement is equal to the domain width, which is of the order of magnitude of 10~4 or 10 -3 cm, their velocity would

distance in the short time available at high frequency as

maximum

field-strength at

'(%)

x 90 kc/s
o eoo kc/s

X
JX.'

^
100

200

300
(gauss)

100

150

200

250

300

350
+-

i,00

iSO

500

Bma)t (gauss)
of Fig. 62.3a.

D
Fig. 62.4. a) b)

Frequency-independent distortion curves for the

ferrite

Frequency-dependent distortion curves for the ferrite of Fig. 62.36. The encircled crosses
denote the distortion calculated according to (61.12) from the hysteresis
resis-

in the inset

tance at a frequency of 2 kc/s.

338

DYNAMIC PROPERTIES AT HIGH FIELD STRENGTHS

[CH.

XVI

be about 10 2 or 10 3 cm/sec, respectively. Accordingly, the damping coefficient /8 from (24.10) has to be smaller than unity. For Fe 3 C>4 Gait [Ga 3]
has found that $

0.4,

whereas for nickel-ferrous

ferrite

/3

= 0.02.

Thus

it is possible that the same unknown wall-damping mechanism applies to the experiments with polycrystalline samples as to experiments with single

crystals.

63. Ferrites under Pulse Conditions


63.1.

THE SHAPE OF THE PULSE RESPONSE CURVES

current pulse applied to the primary winding of a transformer with a ferrite core will cause a voltage Vs to appear across the terminals of a se-

condary winding

(see Fig. 63.1).

The length of the voltage pulse is short compared with the duration of the current pulse. The voltage Vs varies with time in a way that depends on the changes with time of the magnetization in the core. The pulse
response curves, which give

Vs as

a function

of time, are measured with an oscilloscope;


see for instance

[He

3].

1
-1
Fig. 63.1. Ferrite core (a) with

The shape of
a
ferrite

the pulse-response curve of

depends on the amplitude m of the applied pulse. For the ferrite with hysteresis loops as reproduced in Fig. 56.5, pulseresponse curves at various values of m are

given in Fig. 63.2. In the case of low pulse

amplitudes

{Hm

<

oersted) only

one maxithe start

two windings.
(6) in

current pulse

mum

occurs

very

shortly
jusec).

after

the primary gives rise to


(c)

a voltage pulse
condary.

in the se-

of the pulse (0.1

At higher pulse
in the curve

amplitudes a second

maximum

appears. This second peak shifts to shorter

times

when

Hm

is

increased,

and

for a sufficiently large value of

Hm

the second peak merges into the


in Fig. 63.2 for

first.

This situation

is

almost obtained

Hm =

2.6 oersteds.

The area of the voltage-response

curve is proportional to the total change of flux in the ferrite core caused by the switching field. When all dimensions are known, it is possible
to calculate the corresponding change of the magnetization of the core (or of the induction B, since m <^ B). The integration, carried out electron-

ically, yields

the result reproduced in Fig. 63.3.


is

For

this ferrite,

where the

remanent magnetization

approximately equal to the magnetization in a

63]
Kfyolt)
\

FERRITES
^,=2.6 Oe

UNDER PULSE CONDITIONS


Fig.
63.2.

339
Family
of pulse-

response curves for the ferrite


St JL Mgo.iS Mn O.S5 Mn0.23 Fe 1.77

Mgo.45Mn" 55 MnJ" 3 Fei.770 4


of Fig. 56.5. The amplitudes
of the various pulses corre-

spond to the maximum field strengths for which the hysteresis loops of that figure were
obtained.

0.5

10

7.5

2.5

3-0

-t(fiac)

field

Hm

the curve giving the total change of the induction

{i.e.

AB in

Fig.

63.3 for infinite time) as a function of

Hm corresponds to the virgin magneti-

zation curve.

The two maxima in some of the curves in Fig. 63.2 might be related to two different types of magnetization processes, each of which gives rise to a time-dependent secondary voltage as indicated for one case by the dashed curves. A relatively small change of the magnetization occurs fairly rapidly in this square-loop ferrite, and the major part of the magnetization
reverses

only slowly.

It

seems possible to associate these changes of

magnetization with reversible rotation processes and with irreversible domain-wall displacements respectively. Suppose that the permeability of
the ferrite in the remanent state,
/ire

m,

is

the result of simultaneous rotat-

ions of the magnetizations in each Weiss domain.

field

Hm

will

then

Fig. 63.3.

The

reversal of

the magnetization of the


ferrite as

a function of
the
applied

0.9

time, for various ampli-

tudes
pulses.

of

16

IS

2.0

22

2,4.

26

340

DYNAMIC PROPERTIES AT HIGH FIELD STRENGTHS

CH. XVI

cause in the

which

^ H = 22, so that AB ^ 40, for Hm = Mrem


is

ferrite a change of induction as a result of rotations, AB, about equal to em m For the ferrite under consideration
.

1.85 oersteds. This induction

change

is

in fairly

good agreement with

that corresponding to the smaller area

below the dotted curves in Fig. 63.2. Pulse-response curves of a ferrite Nio.36Zno.64Fe204 having a hysteresis loop similar to those in Figs 56.2

and

56.3

and an

initial

permeability

/u

= 600,

see for instance the curve


1.5 oersteds.

marked
will

in Fig. 63.4, which


is

do not show two maxima; is found for m=

However,

if

a tangential pressure

applied to the ring, the

shape of the hysteresis loop

change as a consequence of magnetostricis

tion (see 59). This behaviour

reflected in the voltage-response curve.

Y,

(yolt)

!
76
-

Fig. 63.4. Voltage-response curves

Ni036 Zn 0S4 Fe2 4

for a nickel-zinc ferrite


Nio.36Zno.64Fe2C>4.

Curve

is

ob-

tained in the absence of pressure.

Curves

1,

2 and 3 are obtained at


values

increasing

of an

applied

tangential pressure,

which corresrectangularity

pond

to

increased

of the hysteresis loop.

The curves denoted by 1, 2 and 3 in Fig. 63.4 are obtained at increasing values of an applied pressure. It is seen that in the case of the largest pressure, when the flux reversal is mainly brought about by domain-wall displacements,
a second

maximum
may

apears.
distinction

more pronounced

between the two maxima in the pulse-

response curves

be found with a magnetically annealed sample of the ferrite Co .iFen o.9Fe 2 04; see 58. In the remanent state the permeability of this ferrite is very small, i.e. ^rem 2. The reversal of the magnetization is

brought about by a single Barkhausen jump. The pulse-response curves are reproduced in Fig. 63.5. There is a clear distinction between the first narrow
peak, corresponding to the small change of the magnetization caused by

63]

FERRITES

UNDER PULSE CONDITIONS

341

COatFeos^Oi

10

12

t((isec)

Fig. 63.5. Coo.iFe^9Fe204 annealed in a magnetic field: pulse response curves recorded for various amplitudes ffmK of the field pulse.

rotations,

and the following broad curve, corresponding to the bulk change


first

of the magnetization caused by the Barkhausen jump (which is a domain-wal


displacement). In the figure the
for the pulses of amplitude

peak in the response curve

is

given only

Hm = 34