SmitWijn Ferrites Text

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.

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.
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

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
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

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
_

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]

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

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]
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

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.

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,
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
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
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
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
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
[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
[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
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]

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]

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.
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]

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]
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
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 )
+ Kzaââ^
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
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]
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
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]

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
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 î 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.
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
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
Â 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
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 aâz + 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
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
[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.
[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 BaFeÔig 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
[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
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
[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
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
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
[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 - Eî. (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]
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
[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
ÊXx,
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]
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.

(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
JVêtt
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

#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

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'
= (Â/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

is
[CH. VI
^MBP + Â/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
yÊuEm/M2
corresponding to a susceptibility tensor of
92
Xxx
[CH. VI
<o 2 )
= y 2'22/(">r 2 = iwyM/(a) r 2 Xiw

the fact that
< 2 ) yM/(a> 2 = rÊuKair* 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
[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
[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
[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.

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
[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
tooiÂio
.
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
= VEÎ 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

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

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
= AHÂH/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
[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.
[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

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
[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

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
[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
/âpp
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
[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]

X
=
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
[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]

'

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
[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]

f
2

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
[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]

The
field inside

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
[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]
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

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

[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 MeFe24, 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
[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

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 MgFe24 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
[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

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
[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]
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
[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 Fe34 [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]
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
[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
[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]
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 MgFe24 these curves are highly dependent on the method of preparing
156
(T (gauss crrp/g)
I 120
[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

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]
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]
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 î2 +
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
[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.
[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
(êrg/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

,
,
[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
FeÔi
[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
[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
[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
[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.

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
[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
[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
[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]
181
S=
Me 2
E
Fe^ 0$
4$+2f
*
Fe ,Me
^2
^\
Fig. 37.3b. Cross-section
through a mirror plane of the spinel structure with the [111]
axis vertical,
drawn
for the ideal value of the parameter u.
The
of threefold symmetry. All ions not lying on one of these axes occur three times, as shown schematically by broken circles in the top layers. The small white and black circles represent respectively ions on octahedral and tetrahedral sites. The arrows indicate the
relative orientation
of the magnetic moments of the ions on these
sites.
182
FERRITES WITH
[CH. IX
M=
BaFe l2
19
4$
+2$\
^
Fig. 37.4. Cross-section
^\
M,
with the c axis vertical.
of the magnetoplumbite structure
The arrows
indicate the spin orientations.
The drawn
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]

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
[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]
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

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
[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]
187
W= flbMef Fe K
27
^
Fig. 37.7. Cross-section of the
^\
^\
^
The arrows
indicate
W structure with the c axis

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

41
[CH. IX
Z = Ba3 Me2 Fe2
4.
iê & 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]

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
[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]
191
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
â
Fig. 38.1.
^x
^\
^\
â^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

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]
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
BaFeÔio,
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
[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]
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
[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]
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
[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
[CH. IX
*-
N >
T3
as
P.
c til
H O
DO
cd
M
'
u,
en
""*
& o
r>
"5
38]
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

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.

39.1.
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

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)
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 BaFeÔig 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
[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
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

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-
êrg/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
^1S2ê
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

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
(î)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
The iron
ions
on the octahedral and
tetrahedral sites are coupled antiferro-
41]
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.
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 NiFe24 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
[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 MgFe24 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

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

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=îsin26.
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
BaFeÔig
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

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
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
[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,
[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
[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
[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
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
<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'
}'
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
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

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

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 ô 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

-?-.
[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.
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
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
[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]
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 ô 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
[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, ô 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
251
252
3000

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]
600
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 jô 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
[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]
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

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
[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]
39.1
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

/ô
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

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
[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]
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
[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]
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
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

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

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]

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

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]

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*->
rî
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
T)
Ov
^
<U
<SO
60 Hi
274

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]

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

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]

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

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
[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]
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

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]
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
[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]
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
[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

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 iû>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

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
[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
[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]

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]

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

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)
[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 iô 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)
[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/ô 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

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
[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
sinô
(57.1)
<j>
and
Xrem
XO
1
sin
2<f>
(57.2)
2ô
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/ô 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
[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

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
[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
Qteâ^*
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
[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

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

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, /ô= 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
[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 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
[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'eÔ 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

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)îe 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 BaFeÔig 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

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 Hâx 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

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 ô
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(ô
+ 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
[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)
Oôc,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

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
[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
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
(/ô
> 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* <** aÂfJ^
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]
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/ô
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,
[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]

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
[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
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
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
341
COatFeosÔi
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 = 34.5 oersteds. The lower-amplitude pulses

first
give rise to correspondingly high voltage peaks within the
few tenths
of a microsecond after the application of the pulse.

63.2.
SWITCHING TIMES
is
The switching time of a core

drops
to, say,
ussually defined as the time needed for a

i.e.
complete reversal of the magnetization,
the time that elapses before
one tenth of
its
maximum
value (see Fig. 63.2). However,

is
according to this definition, the switching time of a material

the slowest reversal, which might lead to
governed by
wrong
interpretations.
Moreover,
for practical purposes the time that elapses between the
ing the field and the
moment
that
Vs
reaches
its
moment of applymaximum value is very

made
important.
From a more
physical point of view a comparison can be
with the definition of the coercive force c Instead of being defined as the field strength needed to obtain, say, 90% magnetization in the reversed direction
.
of a remanent magnetization,
annihilate
e is
defined as the field strength needed to

core. Accordingly
a remanent magnetization in the
we
shall
define the switching time as the time taken for the remanent magnetization to be annihilated, or, put
more
generally, the time that elapses
during a half reversal of the magnetization. After this time, the area
342
[CH.
XVI
its
between the
final value.
Vs
versus time curve
and the abscissa has reached half
From
plitude
Fig. 63.2
it
can be seen that the switching time depends on the amis
Hm of the applied pulse. For this ferrite the value of t_1 plotted versus Hm in Fig. 63.6. the reversal of the magnetization appears that
It if
takes place predominantly as a result of irreversible
domain wall
displace-
ments, the following relation exists:
(Hm Ho)r
where
= s microsecond oersteds,
a
ferrite.
(63.1)
Ho and
1].
s are constants for
This equation has been given by various authors, for instance [Ga 3]
and [Me
The threshold
field strength
Ho
is
usually slightly smaller than
The motion of a domain wall is governed by (24.11). The inertia is small and can be neglected compared with the viscous damping term. Moreover if we suppose that under the influence of a field m the walls come into uniform motion, the elastic term can also be neglected. The switching constant s is then proportional to the distance d between the domain walls and also proportional to the friction determined by the damping coefficient /3. Because the pressure on the wall is proportional to the amplitude of the vector difference between the magnetizations of the Weiss domains at each side of the domain wall, s will be
the coercive force of the
ferrite.
inversely proportional to
hence:
s oc
d/Ms
and
(63.2)
where
s is
the saturation magnetization.

5 are 0.9 oersted
For the
ferrite in Fig. 63.6 the
constants
Ho and
0.4 microsec.oersted respectively.
ffasecf'
M90AS^n0.5S^0.23 Fe 1.77 O4
/(Hm -0.9)Uo.9
2
it
s
Fig. 63.6.
The
reciprocal of the switch-
ing time, 1/t, as a function of the pulse
amplitude,
Fig.
63.2.
Hm
for
the
curves
of
63]
FERRITES

#0 do not have a
343
small value of s denotes a ferrite with a rapid pulse response. Materials
for
which
Hm
is
smaller than
rectangular hysteresis
loop. In these cases the contribution of the irreversible domain-wall dis-
placements to the reversal of the magnetization
is no longer predominant and t will be determined by the fast changes of the magnetization due to domain rotations. This explains the rise in the curve in Fig. 63.6 at field strengths below HoIn order to make a comparison between different rectangular-loop ferrites as regards their time response, the quantities Ho and s of (63.1) can be used.
Ho
is
a kind of threshold
field strength for wall
movement or
1
for wall nuc-
leation
[Go
10]
and
s can be considered as the additional field strength
required for a
full reversal
is
of the magnetization in
microsecond.
A survey
of these two quantities

ferrites
given in Table 63.1 for rectangular-hysteresis-loop

3]. It is
with widely varying chemical composition [He
noteworthy
that the switching coefficients for almost all these ferrites are of the order
of magnitude of unity, the only exceptions being two samples with a high
coercive force
58.4, for
and exhibiting the extreme rectangularity which s is much higher.

and in the magnetic anisotropies of the
resistivity
as
shown
in Fig.
Variation of the temperature of a core involves a change in the electrical

resistivity
ferrite.
Both
factors
might influence the switching time. The

Fe2C>4
is
of the
ferrite
Cuo.25Mno.75
only about 1500 ohm-cm, so that damping of wall motions by

investi-
micro eddy currents might be important. In the temperature range

gated
(i.e.
from 115
to
+250
C) the rectangularity of the hysteresis loop
TABLE
63.1
s
THE THRESHOLD FIELD H AND THE SWITCHING COEFFICIENT RECTANGULAR HYSTERESIS LOOPS
Ferrite
FOR SOME FERRITES WITH

s
Ho
oersted
microsec-oersted
0.4
0.4
1.1
Mgo.45Mno' 5B MnJ'| 3 Fei.7704 Cuo.25Mno.7oFe204

Mgo.6Nio.4Fea04
Lio.47Nio-oeFea.47O4
0.9
0.85
3.6
2
1]
0.5
0.5
1.6
MF1312B,
ref.
[Me
0.6
0.5
*) *) *) *) *)
MnFea04
(Mgo.6Nio.4)o.985COo.015Fe204
1.4
2.0
1.3
Nio.39Mg0.59COo.02Fe204
Nio.5FeJ? 4 Coo.iFe204
2.5
12
2.5
8
13
Mno.i8Feo?8Coo.o2Fe204
Coo.iFeJ? 9 Fe204
*)
50
These
ferrites
show the rectangular
hysteresis loop after a magnetic annealing process.
344
of this
is
[CH.
XVI
ferrite is such that by far the major part of the magnetization reversal brought about by domain-wall displacements. The switching time was
measured as a function of the applied field at various temperatures. For each temperature a straight line similar to the drawn line of Fig. 63.6
was obtained, and from these lines the threshold field-strength Ho and the switching coefficient s were calculated, the results being given as a function
of temperature in Fig. 63.7.
slightly
As can be
seen, the threshold field
Ho
decreases
is
with increasing temperature, which was to be expected since this
similar to
what
is
found for the coercive
force.
However, the switching coef2.
ficient s also varies
only slightly with temperature, the total change in s in the
temperature range investigated being not more than about a factor of
Eddy
currents cannot possibly, therefore, play any part in the
damping
it
process, since the resistivity changes according to
an exponential law with

will
temperature, and hence in the temperature range mentioned above
vary by several factors of
10, giving rise to a variation of s with temperature
in the opposite sense to that actually found.
The
ferrite
Coo.iFe 9 Fe204 of
(s
Table
63.1
shows an abnormally high switching

has a
resistivity
is
coefficient
50).
Although
this ferrite
of only about 5 ohm-cm, the long
switching time
not caused by eddy current damping, since, in this case
also, s increases
by about a factor of
3 in the
temperature range from
-130 C to +200 C. More information about
the origin of the magnitude of s
is
provided
by the curves in Fig. 63.8. This figure applies to the ferrite Mgo.eNio.4Fe204 to which 1.5% of cobalt is added. As a result the mixed ferrite shows a
Fig. 63.7.
The
quantities
Ho and
s,
see (63.1),
measured as a
function of temperature for the ferrite Cuo-asMno^sFeaOj of
Table
63.1.
63]
FERRITES

s (psecOel 5
*
345
(Oe)
\
^s
^H
x\
\
("90.S %a)o.985 CoO.O!5 Fe2 i
\\
\
*'v
3
x
p..
<
_
^-x
2
"~+
1
-100
+ 100
+200
+300
-~T(C)
Fig. 63.8.
The The
quantities
Ho and
s,
see (63.1),
measured as a function of
temperature for the

annealing.
is
ferrite
(Mgo.eNio.4)o.985Coo.oi5Fe204 after magnetic

also given.
according to
coercive force He measured The dotted curve represents (16.8). Porosity p = 0.035.
the coercive force calculated
maximum
in the
versus
T curve
at
about
40 C
(see 48.1). It appears

critical field strength
that correspondingly both the coercive force
and the
Ho, derived from switching times at various temperatures according to (63.1), also show a characteristic behaviour as a function of frequency. The great
similarity of these curves indicates that the
related.
two
field strengths are closely
From the known trend
of
ju,o
versus
T and of Ms
versus
T a coercive
force of this ferrite can be calculated with the equations (16.8).
of 3.5% the dashed curve in Fig. 63.8
is
obtained, which in
For a porosity fact is found to

fact is
agree satisfactorily with the curve actually measured.
A remarkable
that the switching coefficient s as a function of temperature also shows the
same characteristic and (15.4) gives:
trend.
The combination of
the equations (63.1), (24.10)
s oc
Pd M
aM
cc
ydw
K8 W ~M?
M
1
OC
M?
et al. ( 23.3) the
(63.3)
According to the theory put forward by Clogston

ing coefficient a
is
dampis
proportional to the saturation magnetization; this
in
fact approximately the case as
found by experiments on
in the variation
single crystals.
This being so,

field,
it follows from (63.3) that which might explain the similarity
s is proportional to
an anisotropy
of 5 and
with
temperature.
346
[CH.
XVI
64. Total Losses
Total losses can be measured directly with a calorimeter in calories per
and imaginary part of the permeability as a function of frequency and induction by a coaxial line method or to measure directly the quality of a resonant circuit of which the self-inductance is formed by the ferrite core with coil [Bu 1] .In calculating the losses from these measurements it is assumed that the distortion of the signal by the ferromagnetic core can be neglected. The latter methods
cubic centimetre.
It is
also possible to
measure the
real
are therefore especially adapted for small inductions (up to about 100 gauss)
and high frequency
(0.1 to 10
Mc/s).
We
include the equation giving the
relation between the loss factor tanS
and the amount of energy dissipated
per cubic centimetre of ferrite per second:

Wtot
= (lO-V^^max/OanS)/^'
ferrite the loss factor
watt/cm^.
(64.1)
Data for the

in Fig. 64.1.
total losses
of the nickel-zinc ferrites of Fig. 50.1 are collected
For each
tanS
is
given as a function of
too
0.50
NifZn,. s Fe2 04
3 = 0.50
tan
S
0.20
6 = 0.36
Bmax'OJ SO gauss
0.10
bj cl
dl
25
10
0.05
/.>f
0.02 ^-.
~c~"'C.J--~"'Z^'''
0.01
0.1
0.2
0.5
20
50
f (Mc/s)
100
*
Fig. 64.1. Total losses (expressed as tanS) for nickel-zinc ferrites
NigZni-8Fe204
as a
function of frequency.
litudes
The four
loss-curves for each ferrite correspond to induction
amp-
of 60, 25, 10 and
gauss.
64]
TOTAL LOSSES
0.07
Fig. 64.2.
347
Comparison between the factor tan8 tot and the
tan So
total
loss
sum of the residual loss factor
and the hysteresis loss factor tan8 n for a sample of Nio.5Zno.5Fe204.
20
iO
>
60
80
no
Bmax (gauss)
frequency at
maximum
//.'
inductions
2?max
of 60, 25 and 10 gauss. The graph
also includes the curve for vanishingly small amplitude of the induction,
as derived
from the
and
yJ'
curves of Fig. 50.1.
One might
is
expect the total losses to consist of the

10 4 ohm-cm).
hysteresis losses (eddy current losses
sum of residual and can be neglected when the resistivity
losses
For Ni .5Zn .5Fe 2 O4 the residual and hysteresis losses, tanSs, were measured separately, and their sum compared with the measured total losses tanStot at 100 kc/s; see Fig. 64.2. The residual loss factor was measured at 100 kc/s and the hysteresis loss factor was calculated from ballistically measured hysteresis loops. It was found that the total losses measured were less than the sum of the separately measured hysteresis and residual losses. It looks as if very slow after-effects cause an increase in the ballistically measured hyshigher than about tan 8
teresis losses.
It
appears to be unjustified to derive total losses at high
frequency from the ballistically measured losses. The same holds of course
for the distortion (see 62).
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Ferromagnetic Resonance
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\\
]
INDEX
Activation energy
after-effect
172, 233, 235,
292
297
angle, loss or phase
122, 126
anisotropy,
crystal 46, 162, 202, 210, 214,
226
116
244, 252, 257, 307

,
energy
field
...
47, 81, 163, 204, 243, 269
stress
.
.
246
.
208 titanium M 154 Y 202, 210, 247, 257 Z 202, 204, 210, 223, 238, 247, 257, 278 281 zinc Z 280, 305, 310 341 damping 4 demagnetizing of expansion 247
,
cobaltites
,
.
204,
259,
coefficient,
,
anneal, magnetic
50,
166, 211,
312
55
coercive force
coil,
73,
301
113
anomaly, expansion
eddy-current
134 32
121
Rogowski Cole and Cole diagram
291
8
antiferromagnetism
Compton wavelength
conductivity
apparent permeability
145
approach to saturation Argand diagram

Avogadro's number
77
291
thermal
225
cone, preferred
constant, Boltzmann's
49
18
19,
144
BaFei 2 Oi9
ballistic
....
law
193,
283,
310,
321
Ill
method Barkhausen jump

Bloch,
340
25,
T 3 /2
44
99 69
9
18
Curie
dielectric
160
331
230, 238
hysteresis
lattice
145
8
Planck's
wall
60, 66,
constricted loop
310 232
144, 157, 163, 174, 289
Bohr magneton
Boltzmann's constant
Bose-Einstein statistics
controlled valency
copper
ferrite
99
66
126 127
125
boundary, domain
bridge, Hartshorn
manganese
ferrite
343
Y
zinc ferrite
effect
257
291, 297
Maxwell
Cotton-Mouton
critical
97
68,
Owen
Schering
diameter
321
127
dimension
63
141
Brillouin function
20 72
130 2
179 127
cross-section, scattering
crystal anisotropy 46, 162, 202, 210,
bulging of a wall
214, 226, 244, 252, 257, 307
Cavity resonator
charge, magnetic
crystalline field
9,
214
160
157,
Curie constant
19, 18, 21, 22, 34,
close-packed structure
coaxial resonator
temperature
155,
235,
250
19
cobalt ion
313
Curie's law
ferrite 144, 157, 163, 169, 174, 251,

,
252 310
ferrous ferrite
167,
231,
253,
Damping
100, 108, 172, 176
366
INDEX
341
coefficient
exchange energy
deformation, tetragonal
demagnetization, internal
144
122, 223, 248, 309
superexpansion anomaly of
, ,
17
30,
147,
191,
213
55
coefficient
247
9,
demagnetizing coefficient
4
6
2
energy
field
Factor, g
173
Faraday
effect
diagram, Argand
,
291 291
221
15
68,
Cole and Cole

phase
diamagnetism
diameter, critical
dielectric constant
321
66 97
122,
rotation
factor, loss
,
239
333
88
11
quality-
spectroscopic splitting
Thomas
230, 238
38, 141
ferrimagnetic resonance
84
33
163, 169,
174,
diffraction,
neutron
ferrimagnetism
ferrite,
X-ray
critical
141,
190
63
cobalt
144,
157,
dimension,
dimensional resonance
dipole-dipole energy
52,
132
210
7 81
Dirac theory
direction, preferred
48,
disaccommodation
dislocation
distortion
255, 266
70
329
66
16,
domain boundary
Weiss domain wall displacement relaxation

, , ,
60,
82
285 245
175
cobalt ferrous 231, 253, 310 copper .... 289 copper-manganese 343 copper-zinc 291, 297 ferrous 292 lithium. .144, 174 Lithium-Chromium 87 lithium-zinc 253, 270 manganese. 251, 254 manganese-ferrous 254, 334 manganese-magnesium 339 manganese-zinc 217, 221, 234, 245,
, .
251, 252
167,
144, 157, 163, 174,
147, 157, 169,
37,
142, 150, 157, 161, 163, 169, 174,
163,
Earth,
Wagner
134,
127
eddy-current anomaly
134 172
loss
Einstein-de
Haas
effect
89
electromagnetic wave
electron spin
electrostatic energy
.
95
7
143,
146
energy, activation
anisotropy demagnetizing dipole-dipole exchange Madelung of the magnetic wall

,
,
172, 233, 235,
292
116
magnesium 169 .... 240, 251, 270, 272, 273, 297 magnesium-nickel 315 mixed zinc 157 nickel 245, ... 251, 270, 275, 299, 302, 310 nickel-aluminium 87 nickel-zinc 223, 230, 234, 239, 245,
,
252, 255, 267, 270, 292, 297, 303, 310, 330

142,
144,
157,
163,
174,
150,
144, 157, 161, 163, 169, 174,
161,
6 210
143,
252, 261, 269, 277, 288, 295, 298, 301, 310,
electrostatic
146
17
318, 336, 340 346

,
square-loop
zinc144,
153,
339
169
free
23
ferromagnetic resonance
78, 119, 171,214,
143
field
297
4
61,
67,
ferrous ion
244
23
W
,
252, 293
204,
234
enthalpy, free
field,
anisotropy
47, 81, 163, 204, 243, 269
entropy
24
INDEX
367
57
. .
crystalline
9,
214
linear magnetostriction
demagnetizing
energy of the magnetic
2
4
77
2
20, 24, 34, 85, 161
19, 52, 69, 75,
Lithium-Cromium
lithium ferrite
.
.
spinel
37, 87, 271
.144,147,157,169,174
144
253, 270
Lorentz
stray
magnesiumzinc ferrite
figure
Weiss of merit
Lorentz
loop, constricted
319
73,
.hysteresis
,
force, coercive
301
11
minor
field
310 .16,74,76,113,222,301 302
Lorentz,
frame,
window
175
free energy
,
23 23
enthalpy
19,52,69,75,77
11
force
loss
,
346
angle
126
134,
eddy-current
172
Garnet structure
gauges, strain
120,
212
168 143
.factor
,
122, 239
relaxation
289
143
142, 144, 157, 163, 169
Goldschmidt radius grain growth

Hartshorn bridge
heat, specific 27,
99,
227
126 145
Madelung energy magnesium ferrite

. .
.174, 240, 251, 270, 272, 273, 297
capacity
225
98
150
331
31,
nickel ferrite
315
204, 257, 279
Y
. .
Heisenberg's uncertainty principle 13,
magnet, permanent
magnetic annealing
,
319
50,
Hund
rule
17,
166, 211,
312
2
hysteresis, constant
loop
,
16,74,76,113,222,301
328
223
132 106
resistance
Ideal magnetization curve
122,
image
effect
instability
charge energy of the potentiometer magnetism, para,
field,
4
112 32
15
antiferro-
dia-
ferri
33
15,
24, 160
interaction, dipole-dipole
52
11,
magnetite 144, 157, 161, 163, 164, 166, 168

. .
spin-orbit internal demagnetization

,
54
71
169, 174, 175, 235, 238, 251, 292, 338
122, 223, 248, 309
magnetization, remanent
306
stress
saturation
.
inverse spinel
ion, cobalt
141,
173
22, 149, 157, 191, 193, 204, 212,

. . .
244
223 120
89
313
252, 293
142,
magnetization curve, ideal
122,
28,
.
.ferrous
ionic radius
magnetocaloric
effect
178
magneto-mechanical ratio
magnetostatic mode.
magnetostriction
g'
magnetoplumbite structure
Kerr effect Kramers-Kronig relations
64
.
180
84
100, 268
....
Langevin's theory of paramagnetism
lattice,
57, 119, 168, 244, 255, 262, 309
18
constant
3
145 103
volume manganese
,
55
ferrite 142, 150, 157, 161, 163,
,wave law, Bloch T Curie's Rayleigh's

,
169, 174, 251
/2
25,
'44
19
329
ferrous ferrite
254,
334 339
magnesium
oxide
ferrite
32
368
INDEX
204
ferrite 163, 217, 221, 234, 245,
W zinc
, ,
phase, angel S
252 330
154 108 127
122
221
8 3
diagram
255,
267,
270,
292,
297,
303,
310,
Planck's constant pole porosity
manganites
mass of wall Maxwell bridge

merit, figure of
216,245,298,310
112
potentiometer, magnetic
319
Ill
powder pattern
preferred, cone
66 49
48,
method,
ballistic
standing wave
129 117
118
torque
direction
81
plane
48
333
torsion pendulum minor loop mixed zinc ferrite

,
302
150,
Quality-factor
157
quenching of orbital angular
momentum
9,
mobility
232, 234
214
143
mode, magnetostatic modulus, Young's

molecular weight
84
225
144, 157, 189
Radius, Goldschmidt
radius, ionic 142,
178
Rayleigh's law
329 228
Natural resonance
82,
83
reaction, topotactical
Neel point
neutron diffraction
nickel-aluminium
ferrite
35
38,
relaxation
141
87
nickel ferrite 144, 157, 161, 163, 169, 174,
240
175
domain wall
loss
289
241, 290
time
ferrous W W Y zinc
, , , ,
175, 245, 251, 270, 271, 275, 299, 302,
310
287
resistance, hysteresis
resistivity
306
328
229,
204
204,
297
132
257
ferrite 161, 223, 230, 234, 239, 245,
resonance, dimensional
,
......
80,
ferromagnetic
78, 84, 119, 171, 214,
252, 261, 269, 277, 288, 295, 298, 301, 310,

318, 336, 340, 346
non-linear
phenomena
106 140
normal spinel
nutation
79
frequency natural wall resonator, cavity coaxial

, , , ,
297 285
83
269,
82,
110
130
127
Orbital angular
momentum
....
145,
214
235
146
125
ordering
rhombohedral symmetry Rogowski coil

rotation,
184
113
short-range
Faraday
97
278
91
Owen
bridge
rotational stiffness
oxide, manganese-
32
15,
susceptibility
Paramagnetism
24,
160
18
31
Langevin's theory of
17,
Saturation, approach to
,
77
magnetization
.
Pauli principle
.22, 149, 157, 191, 193, 204, 212, 244
powder permanent magnet

pattern,
66
scattering cross-section
141
319
69, 243, 250,
Schering bridge
shearing
127
permeability
267
121
309
apparent
shock
effect
267
146
perovskite structure
154
short-range ordering
INDEX
shrinkage
sintering process
369
228
117
118
38
216
216
124,
topotactical reaction
torque method
torsion
skin effect
Slater curve
specific heat
132 56
145
pendulum method
triangular configuration
27,
99,
spectroscopic splitting factor

spin, electron
....
11,
88
7
Uncertainty principle, Heisenberg's

13,
98
75 144
18
orbit interaction
54
wave
49, 95, 97, 103, 106

141,
uniform rotation u parameter

Valence bond
valency, controlled
Villari point
139,
spinel, inverse
,
173
Lithium-Cromium normal
structure
...
37, 87, 271
140
137,
232
170
.........
179
splitting factor, spectroscopic
...
88
virgin curve
302
55
square-loop ferrite
standing
339
129
volume magnetostriction
wave method
120,
stiffness, rotational
278
168
W
Wagner
wall,
187, 194
strain gauges
earth
60, 66,
127
stray field
strength, tensile
stress
2 225
Bloch
69 72
anisotropy
246
71
internal
structure, close-packed
179
garnet magnetoplumbite perovskite spinel W Z

,
, , ,
212
180 154
137, 187,
.-'.
179
194
188
domain energy mass of resonance thickness wave, electromagnetic equation spin

,
bulging of a
285
61,
67,
244
108
110
66 95
92
103
lattice
49,95,97,103,106
8
144, 157, 189
16, 60,
superexchange
....
30,
147, 191, 213
wavelength,
Compton
susceptibility, rotational
91 91
weight, molecular
tensor
Weiss domain
82
175
switching time
341
field
20, 24, 34, 85, 161
window frame
Temperature, Curie
18, 34, 155, 235,
250
35
Neel
stress
X-ray diffraction
141,
190
tensile, strenght
,
225 288
91
Y
Young's modulus
178, 184, 196
tensor, susceptibility
225
198
8,
tetragonal deformation
144 55 225
thermal, expansion
Z
zero point motion
zinc ferrite
conductivity
98
157
thermo-e.m.f.
thickness, wall
232
66
11
144, 153, 169 150,
Thomas
factor
time, relaxation
241, 290
W Y
,
,
ferrite,
mixed
204
204, 210, 247, 257
switching
341
_, Z
208
188
titanium
M,
cobalt-
208
structure
PHILIPS
TECHNICAL LIBRARY
S
53S-&+UI-3I*

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J.

About the book

put into research

oxides with iron as

main metallic component. This

About ihe authors

of magnetic materials to electrical

Wijn are both

properties of ferrites are

understood than corresponding properties of metallic ferromagnetics.

Netherlands. Dr. Smit received his

purposes are presented

and discussed and, whenever possible,

1948 and his doctorate

These properties are

1956. Dr. Wijn took his degree

physics in 1948 at Utrecht University

authors deal with

blems of the theory of phenomena

magnetization. The subject

Distributors for United

Lane, Kensington, London, W.8.

RELATION TO THEIR TECHNICAL APPLICATIONS

RESEARCH LABORATORIES GLOEILAMPENFABRIEKEN EINDHOVEN - THE NETHERLANDS

German and French

U.D.C. Nr. 538.221:621.318.124

book contains 384

pages, 244 illustrations

Eindhoven (Holland). 1959

book does not imply freedom from patent

by the work of the

Snoek. The rapid

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

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

characteristics of these materials has

refined applications possible.

progress has been

made increasingly made towards the

development of a theoretical description of the magnetic properties of these

understood than the corresponding properties of metallic ferromagnetics.

For example the magnitude of the saturation magnetization of an oxide

original literature in this

voluminous and readily acces-

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

The term ferrites

magnetic oxides containing

iron as major metallic component. This

represents an attempt to meet

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

the basic properties of ferrites.

not exhaustive as regards

and manner of presenand viewpoint of the

tation have been governed

will perceive that

some emphasis has been placed on work

carried out in the Philips Laboratories. If history

be recognized that the authors have

band information about

and thus should be

in a position to undertake a lively

and penetrating discussion of them.

thorough familiarity with the experimental

many properties of the ferrites strongly depend on