SMIT
H.P.J.WIJN
Z
I
>3?2i+tal3
FERRITES
PHILIPS' TECHNICAL LIBRARY
much
effort
has been
i.e.
on
ferrites,
ferromagnetic
their
has
many
interesting
and also
devices.
essentially
new applications
Due
to this research,
many
better
Smit and H.
P. J.
now
Research Physicists
Laboratories
in
of the
N.V.
in
Philips'
Gloeilampenfabrieken
Eindhoven,
engineering
degree
from
in
in in
explained
in
terms of intrinsic
in
properties.
physics from
Leiden University
turn
treated
relation
to
the
chemical
structures
composition
of
the
and
crystal
materials.
The
many
actual pro
and
his doctorate at
Leiden
in
1953.
various
processes
is
of
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
Kingdom and
Ltd.
Eire:
CLEAVERHUME PRESS
31, Wright's
FERRITES
PHYSICAL PROPERTIES OF FERRIMAGNETIC OXIDES
IN
J.
SMIT
J.
AND
H. P.
PHILIPS
WIJN
1959
PHILIPS'
TECHNICAL LIBRARY
2.720
&3
HARRIS
COLL GE
PRESTON
*H7
c
Translated by: G. E. Luton, Eindhoven
Publisher's note:
This
book
is
published in English,
editions
This
N.V.
Philips' Gloeilampenfabrieken,
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
rights
S.
L,
SNOEK
(19021950)
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
late J. L.
provement of the
Much
work of L. Neel has been of fundamental imporAt the present time many of the properties of magnetic oxides are better
The
new
field is
sible (it is to
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.
will
be used to refer to
all
book
The treatment
is
either the subject matter presented or the rigorousness of the theoretical devel
opment of
authors.
basic concepts.
The
selection of material
by the
special preferences
The reader
not a sufficient
justifirst
may
VIII
Foreword
these particular investigations
of especial importance
their exact chemical
The book
book
is
intended for
all
those
is
who
any member of
this large
specialization, to find
c.g.s.
The
practical
system of units
employed, that
is,
The authors
many
and suggestions,
in particular to Dr. E.
W.
Gorter
into English
by
gratefully
H. P.
J.
Wijn.
May
1959
CONTENTS
Part A. Theory
Page
Chapter
I.
1.
2.
3.
4
6 7
Spin moment
.... ....
9
11
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
.
18
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
....
34 34
38
Stretched configuration
Triangular configuration
10.
42
Chapter IV.
MAGNETIC ANISOTROPIES
46
46
cubic crystals
11.1. Magnetocrystalline anisotropy
in
...
50
X
12.
CONTENTS
Origin of Crystal Anisotropy
12.1. Dipoledipole interaction
52 52 54
55 55 57
Magnetostriction
13.1. 13.2.
Volume magnetostriction
Linear magnetostriction
Chapter V.
14. 15.
MAGNETIZATION PROCESSES
Weiss
Domain
Structure
wall)
.
60
64
.
16.
69 69
73
Coercive force
17.
X Chapter
VI.
18.
78
.
Resonance
in
78
18.2. Influence
of the
resonance conditions
18.3.
82 84 84
88
91
Magnetostatic modes
Ferrimagnetic Resonance
Spectroscopic Splitting Factor
Rotational Susceptibility
Wave
22.1.
92 92
95
97
100
.
. .
Damping
23.1. General Properties 23.2. 23.3.
100
102
103
Damping
106
wall)
Movement
107
Wall
inertia
107
108
24.2.
24.3.
110
CONTENTS
Part B. Measurements
Chapter VII.
XI
25.
Ill Ill
acting on a body in a
nonuniform 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
magnetic resonance
27.
Magnetostriction
27.1. Displacement 27.2. Strain 27.3. Stress
119
measurements
119
measurements measurements
Initial
120
121
28.
Permeability in
121
123
127
the
132
132 134
Eddy
current losses
30.
31.
Chemical Composition
Crystal Structure
31.1.
31.2.
Elementary
lattice
137 139
31.3. Distribution
tetrahedral sites
31.4. Ordering
phenomena
XII
32.
CONTENTS
Saturation Magnetization
32.1.
147
0K
32.2.
147
155
33.
34.
160
162
162
165
168
171 171
35. 36.
Linear Magnetostriction
Dynamic
36.2.
Domain
wall relaxation
175
Chapter IX.
177
Chemical compositions
177
179
180
37.5.
38.
Saturation Magnetization
38.1.
Predominant
superexchange
the
various structures
38.2. Saturation
191
magnetization
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
of crystal anisotropy
in
hexagonal oxides
210
CONTENTS
Chapter X.
XIII
GARNET STRUCTURE
40. 41. 42.
212
212
216 216
221
Phase diagrams
Mechanical properties
223
224
225
Chapter XII.
45. 46.
ELECTRICAL PROPERTIES
D.C. Resistivity 229 FrequencyDependence of Conductivity and Dielectric Constant 236
46.1.
Experimental results
236
241
46.2.
Phenomenological theory
Chapter XIII.
47.
243 243
247 250
....
250 257
260 260 on the 262
265
49.
External Influences
on the Permeability
a biased state
stress
49.2. Influence
initial
of unidirectional mechanical
permeability
49.3.
The
initial
of demagnetization
49.4. Stability
266
XIV
Chapter XIV.
CONTENTS
PERMEABILITY
50.
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.
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
55.
297
Chapter XV.
56.
57. 58. 59.
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.
61.
Hysteresis Losses
64.
Total Losses
346
348
REFERENCES INDEX
365
CHAPTER
1.
The Magnetic
Field
electric currents.
A magnetic field is
produced by
is
The magnetic
field inside
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
field at
by
A and
then applying
(1.2),
we see that
moment
per turn ^:
(1.3)
H=4n
where
V is
the
may occur. Their strength is characterM, which is the magnetic moment per cm3 Accor.
ding to
(1.3), then,
field
of
#mat
= 4irM.
(1.4)
is
One can
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
is
B = Ho + 4wM.
(1.6)
PROPERTIES
is
FIELDS
[CH.
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 crosssection (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
around
arrows)
it.
The
stray fields
and the
internal de
magnetizing
field (in
may
also be
(+ and
at the ends.
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
is
not zero;
we
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 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)
is
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.
= AM
(1.8)
1]
per
cm 2 where AMn is
,
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
For
Hidl
= 0.4imi
(1.10)
where
is
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
the major axis (a) as a function of the ratio of the length of this axis
to that of the
minor
axis
(c),
c,
and oblate
ellipsoids (a
b, disc).
PROPERTIES
It
FIELDS
is
[CH.
Hd
uniform
and equal to
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
(1.11)
and
will
satisfy
Nx + Ny + N = 4w.
z
(1.12)
Some examples
sphere
infinitely
long bar
NX = N = N = 4tt/3 Nx = Ny = 2TT N = Nx = Ny = N =
Z
z
4tt.
Fig. 1.2
shows for
ellipsoids
(a) plotted
(a/c) as derived
by Osborn [Os
1].
broken by
an
air
gap of width
which we assume to be
Bn
is
continuous, the
field in
the
narrow gap
is
tion
in the material. If
it
are present,
Hdl
(HD
+ 4nM)S = 0.
Fig. 1.3.
Ring interrupted
by an
air gap.
8/1
(8
<
/)
(1.13)
2.
gives rise to
an
e.m.f. in the
d$
At
108 V olt
'
(2.1)
{Bn
is
the normal
component of
on an element dA of a
surface through
the winding.)
2]
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
is i
by the
excites the
magnetic
Ho, and
it
may
easily
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
field is
W=^Hl
57T
(2.3)
present,
SB
consists of
SB
Since
SHo
+ SHD + 4ir&M.
i.e.
we
integrated
is
8Hn makes no
contribution. This
J
where the vector a
closed surface
is
abdV=0
i.e.
(2.4)
if
for each
J andA
= 0,
B field,
is
i.e. if
= 0. According
condition.
As a consequence,
Ho may be replaced by the total field H. In our case, Ho is the divergencefree vector (Ho = Bin the absence of matter) and Hd is the curlfree
vector (see
(1.9)).
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
work
S JFmat
= HSM  HD 8M,
(2.6)
PROPERTIES
FIELDS
[CH
where
upon the
material.
The
last
of the ellipsoid. This energy therefore represents extra work to be more general expression for the demagnetizing energy, which performed.
per
cm3
may
8(B Ho  Hd)
SHo
for
SM in
the last
make no
07T
which
is
comparable with
(2.3).
Equation
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
(2.3)
H.
shall
We
now
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
V = fiH
and
is
(2.9
at
of equilibrium
of the dipole.
3.
In
we
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]
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.
interest to us
come from
^ KH
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 semiclassical treatment
3.1
SPIN
MOMENT
After the existence of electron spin was postulated by Uhlenbeck and Goudsmit in 1925, in order to explain gasdischarge 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 Ethis is
2m
V=0
new equation
in which p also occurs an operator). This constant can
for
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
at
c). This
is
an
unexpected
result,
but
it
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
moment
/*.
and thus the an angular momentum / and associated with it a magnetic The magnitude of the angular momentum may be estimated
PROPERTIES
v
_
FIELDS
CH.
internal
motion of an
its
The electron
c,
moves
in
while
is
The
spin
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
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
v,
which
follows from
hv
= E E = 2mc
1 2
(3.1)
sec).
where h
is
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,
^"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
gamma quanta
may be
taken as
rsp in
=  = = 2x 10 11
w
2mc
Of
cm,
known
as the
Compton
wavelength.
Bohr
orbits in the
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
is
3]
9
so that the
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)
= e/mc
(3.4)
by the factor g in
y
= g e/2mc,
for the orbital motion.
Owing
is
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
is
eh
= 9.27
and
2mc
if
10 21 erg/gauss.
(3.6)
spin
orbital
may have an
arbitrary value.
3.2.
group of transition
electrons
Ni and
also
orbital
moment of the
that the orbital
much
moment
field).
"quenched". This
round in a
is
orbit with
momentum
states
utilized in
10
PROPERTIES
states as to
FIELDS
[CH.
two
of high potential
be avoided as
much
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
The
average charge distribution of the travelling waves is uniform, that of the standing wave is nonuniform. According to old quantum theory the electron
moving
in a
Bohr
orbit
is
associated with a
wave such
*
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.
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
momentum)
wave
field
3]
11
not removed. A Estate, however, is affected by such a field. The five fold energy
level is split
symmetry. If
this is
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 nonmagnetic and a combination of
of the
triplet states
momentum.
SPINORBIT INTERACTION
of electron velocity
will also
change
is
of a crystalline
field there
can
still
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
what
known as
spinorbit 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 fieldstrength prevails equal to (3.7),
which
states that in
if
H = (vxE)/9.W2,
if Eis
(3.8)
The
spin of the
moving
is
electron
E*.o.
= fi(vxE)/9.10U,
is
(3.9)
to
which a factor
i, the
electric field is
so that
a .o.
=2mc
r
(i(pXr)l9.WU
12
PROPERTIES
there
is
FIELDS
and
[CH.
and hence
in the
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
an energy
(1
upon
xlO
15
cm
1
).
TABLE
SPINORBIT
3.1
PARAMETER
ion
(cm 1 )
154
150 87 57
Ti
3d
3rf3
ym
Cri
CiiiMn 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
Cu"
The
effect
of an interaction (3.10)
is
of the crystalline
some
extent,
two
states acquire
slight orbital
h,
moment
again,
approximation to (X/AE)
where the
If,
original orbital
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 halffilled shells, the direction of the resultant spin is determined by that of the halffilled shell. These do not,
however, contribute to the orbital
momentum,
momentum
to
is
moment, corresponding
an
effective negative A.
3]
3.4.
13
It
was
c,
corres
ponding to an angular
find that only
momentum
of h/2.
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
be
c2
but 3c
2
.
In the
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
2S
spins in
SX
since,
(SX \
+ ^2 +
...)
Sxx
+ Sxz +
is
spins, the
also to
they
Sz 2
= Sz
increasing
For
similar reasons,
an expression analogous to
momenta:
x+a
UL +
1).
(3.12)
an
angular
momentum
an
vector
with
respect to
(z axis).
axis of quantization
/2
represents the
14
PROPERTIES
values of
1,
FIELDS
[CHI
The
(2L
Sz
or
Lz
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,
3.3).
alwaysintegers.
The
positions. In reality
were a zero point motion around them. Moreover, the whole figure should be thought of as arbitrarily rotating around the z axis.
there occurs as
CHAPTER
II
THEORY OF FERROMAGNETISM
4.
result
of a more or
less parallel
To produce
this
alignment
it
will
H. The magnetization M,
when
relatively small, is
//according to
M= ^
cm
3.
(4 1}
B=
The constant is Depending upon
/u.
(1
+ An 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
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
this change.
This
is
here expressed
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
lO 5
it is
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
paramagnetic materials, magnetic moments are also present, the difference being, however, that the spins of neighbouring ions are already more or
less parallel.
mean
is
necessarily
uniformly magnetized
soft iron is
no magnet),
16
for if
it
[CH.
II
would
to
more favourable energetically for the material subdivide itself magnetically into a large number of small regions, known
reason
it
is
usually
who
first
mm,
the magnetization
is
magnetization varies from one domain to another such that, in the absence
of an external
field,
there
is
no
overall magnetization
1
left.
The
to 100 oersteds
may
domain
structure
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
saturated in a strong
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
On
it is
due to
this
phenomenon
that after
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
of one electron (S
J):
parallel
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
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
More
(5.1)
given by
where
ration
<j>
is
the
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
rise
18
THEORY OF FERROMAGNETISM
the spins of neighbouring ions.
[CH.
II
don between
An
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
i.e.
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
and
Gd
and
Dy
are ferromagnetic.
It is
creasing temperature
ture, the
and vanishes
fairly
6. Statistical
6.1.
Theory of Magnetism
we
that a system
gEij kT
is
in
one of
its
possible states
equal to
where k
is
is
Boltzmann's constant {k
1.380
x lOw
erg/K)
and
T
all
sum
At
only the state with the lowest energy occurs, while at temperatures above
that point there
is
high temperatures
(total disorder).
states, parallel
According to
(2.9)
^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)
other:
l"**ahpBH/kT.
(6.2)
i6]
STATISTICAL
THEORY OF MAGNETISM
we may
tanh
19
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)
temperature.
The constant
C is
higher
1.5
H=
?
fields
approaches the saturation value Mo This saturation effect has been
fields
(H/T
large)
1^^+
by Henry [He
various paramagnetic
6.00
However,
SJOO
field
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).
As a moment
too
30
H/T*10~3 (0el)
Fig. 6.1.
magnetic
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
Brillouin
Henry
moment
is
given by
(6.5)
[He
1]).
m=
SgixB,
20
THEORY OF FERROMAGNETISM
5
g
is
is
[CH.
3.4).
II
where
factor
momentum
magnetic 
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
1)
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
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
1)
(6.10)
If
we keep
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
Weiss
Hw
It is
is
by
simply
neighbours. This
general
much
stronger
(=107
duced with
coils etc. The classical dipoledipole 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
constant,
assumed
to be independent of
M and T.
is
and
(5.1) the
energy change
AE due
AE = gix B WMo =
where
2zJS,
(6.12)
Mo
is
the saturation
moment
at
T=
0K.
The temperaturedependence 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
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.
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 soughtfor 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
With
rising
shifts
towards
B and C and
intersection has s decreases. For that temperature where the point of s is zero arrived at the origin, and has hence become a tangential point,
and remains so at still higher temperatures. This Curie temperature Tc given, for an arbitrary value of S, by
is
Tc
= Cs W = gMS +
l)WMo/3fc,
(6.13)
22
THEORY OF FERROMAGNETISM
we may
[CH.
II
Tc =
The Curie temperature,
action per spin (SJ or
2S(S
l)zJ/3k.
S for
is
W) and
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
may
is
maximum
thus larger at
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
for the
J;
this
the electrons inside one ion are in this case not coupled.
Fig. 6.3.
Spontaneous magnetiscales.
on reduced
field
The
solid lines
Weiss
= xh
and
and S
\.
The
ex
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
(6. 1 5)
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
1 it
amounts to 6x 10~4
at the
same tempe
The reason
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
is
practically
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)).
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
is
highest.
at
low temperatures.
At
T=
0,
dMs/dT =
0,
which
is
follows
we may
F of the magnetic
material
dF=SdT+HdM.
From
this
F the
free enthalpy
is
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
constant
T and
H, as was
(bSlbH)T
= (oM/oT)h.
(6.18)
24
THEORY OF FERROMAGNETISM
[CH.
II
According to Nernst, at
T=
0.
the entropy
is
at
T=
0,
and
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.
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
field,
so that
(6.19)
then
Hw =
The
susceptibility
TTc
H.
Tc, indicating that a spon
now becomes
infinite at
T=
(finite
M for H =
0).
The part
equal
T straight line is
W.
CRITICISM OF THE WEISS FIELD
field
6.4.
THEORY
its
In the Weiss
neighbour
the
field parallel to
we
still
way, such a
field will
At low temperatures, slowly varying from the rigorous region, which we shall discuss in more
reversed spin
is,
according to the
interferences
spinwave theory,
is
much
given by:
E*x
where a
2ir/\.
is
= 2JStfik\
(6.20)
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,
so that
all
very small;
therefore very
little
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
The theory
M= M
with
 (T/TB 3 2
)
'
],
(6.21)
Tb =
S=
\
it
21
S^J/k
is
(6.22)
T3 2
/
law.
For
follows
from
(6.14) that
TB =
from the temperaturedependence 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
at temperatures
theory
is
Fig. 6.4.
bility
Spontaneous magnetization
M,
suscepti
1/x as a function of temperature. The broken curves are in accordance with the Weiss field theory. Better approximations steadily reduce
the Curie point (cf
The
latter
full curve) and make the 1/x versus has as asymptote the Curie Weiss line.
.
T curve concave.
26
(in the region
THEORY OF FERROMAGNETISM
[CH.
II
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
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
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:
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
M=
is
in
) is
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
T curve will always be above the CurieWeiss 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
5=1
than with
It is therefore
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.
7.
Caloric Properties
7.1.
SPECIFIC
HEAT
Owing
to the decrease of
is
the temperature
accompanied by an extra contribution to the specific fields, is given in the Weiss approxi
mation by
cm
= iWd(M *)/dT.
s
(7.1)
cm
is
it
cm
is
zero,
jump
equal to
AcM
5S(S
+ 1) + (S + l) 2
'
(7.2)
finite
jump of
this
is characteristic
of what
is
called a second order transition. Transitions such as liquid state are first order transitions,
from the
solid to the
finite transition
infinitely small
temperature interval;
28
THEORY OF FERROMAGNETISM
jump
[CHII
is
in the
entropy (a different phase) but not in a second order transition. Fig. 7.1
shows the
specific
T=
Tc, in which
0.16
O.li
0.12
nm
250
500
*
1]).
750
1000
T(C)
of the Curie
temperature. (After
Moser [Mo
in fairly
is
is
theory
above
this
point,
as
is
entropy change
ASM = cM AT/T.
The
"tail" of the specific heat curve is thus a
(7.3)
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
increased
increased
(cf. (7.3))
by:
AS
c H ATjT,
7]
CALORIC PROPERTIES
specific
29
where ch is the
constant.
Making use of
we
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
effect.
[We
1]).
sign, since
bM/bT
<
0.
Owing
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
is
of the order of
and
0.1
at
T= 0.5
Tc
Using
(6.15)
field theory,
we can
express
T in
M:
.
AT =
so that
WM AM = AM W i
ch
ch
2
,
(7.5)
Experiments by Weiss
that
AT is
in fact
7.2).
CHAPTER
III
FERRIMAGNETISM
8. Origin of Ferrimagnetism
8.1.
In
many
be discussed, the
is
found
more or
less
separated by the
negatively charged antions, which, like the inert gases, have a closed shell
the
ions
IJ
is
ion
is
like that
wave functions
(orbitals) decreases
an
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
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
moment
the shell
was
(five
must occupy an
The
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.
many
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
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
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
exchange energy
to d^.
J.
In this case
to
we can again speak of an effecwe may therefore expect positive exnegative exchange energy
d1
d4 configuration and
One of
[An
1 ], is
and Hasegawa
is
transferred
energy. This
is
only possible
if
the
moments
exchange
(/<
0).
Which
states are
will
32
FERRIMAGNETISM
Fig.
8.2.
[CH.
orientation of the
Ill
2/>
orbit of the
which
is
and the
At
all
depedend depend
direct interaction
and
will rapidly
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
it
most favourably
lies
centrally
on the
line
connecting the
two metal
M1OM2
in the region
of 90, the interaction will be smaller. Such considerations are also frequently
some
cases of positive
SPIN
ORDER
would expect the
in Fig. 8.3.
spins of
moment.
ratios
is
shown
order depends not only upon the crystalline structure but also
will
with the lowest energy. In Fig. 8.3a), for example, the interaction between
the nearest neighbours
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.
bond AC
the strongest because of the 180 angle between the connecting lines, alis
greater.
The
MnO crystal
[Ya
is
example in Fig.
8.3.c) in the
twodimensional trigonal
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.
6/
cos 120
lower for
J<
0.
8.3,
up
into
are three.
If the sublattices are occupied
will
by
If
moment
as
be zero (antiferromagnetism).
tices differ in
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
rt+1
i
III f4H
*
i
i !
i
/
M
b
Fig.
8.3.
Twodemensional
representation of
some mofor
neJ. is
exchange energy
In a) the
stronger
it is
AB coupling
AC,
in
than
b)
\ /
34
FERRIMAGNETISM
Fig.
8.4.
[CH.
Ill
Antiferromagnetic
MnO
The
nearest neigh
(e.g.
two
and
magnetoplumsublattices
bite structure). In
it is
up these
STRETCHED CONFIGURATION
1 ]
Neel [Ne
field
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)
with that of an
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
field
from
(9.1).
In this
way we obsubstitut
unknown
found by
ing the Weiss fields from (9.1) for if in (5.7), which equation
now
holds for
TcMiQI,
WM=
i}
0,
(9.2)
i9]
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
the coefficients of
Mi
is
in
Tc with n
roots.
= 2:
=
0
(9.3)
W21
This does not
that
is
(Wm^)
its
mean
for
own
Curie temperature;
the
same
all
solely
by
means only
versus
T curves
ally speaking,
be
magnetization.
Where
there
is
real,
only the state with the highest Curie temperature will occur; the others have
Tc
4CiCiW\.
(9.4)
sublattices identical
and W12
<
0)
it
then
Tn
ferred to as the Neel point.
= Ci(Wuis
Wu),
(95)
re
field
coeffi
equation
(9.1)
also
which
is
it
will try to
upset the
.
.
parallel alignment of the spins within this .. 1, ... ., .. TT sublattice. However, if the interaction
Fig. ,
9.1.
Ion configuration in a
..
_,
is
stronger this
centre
is
the
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,
is
relatively
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,
magne
magnetic susceptibility above the Curie point. Depending upon the magnitude and the ratios of the magnitudes of the sublattice magnetizations at T
versus
T curve
different forms.
is
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.
this kind,
may
= an Take first the case that Mbo > Mao, with
Waa
o.Wab
Weiss
field
Wab
(9.6)
j8 large and a small. The effective h(Mao/Mbo P) is then small at T = A lattice h(Mbo/Mao <*) The magnetization
*)
We
JS
positive
is
negative, in con
most
existing literature.
9]
WEISS FIELD
20
37
600PK
Fig.
9.2.
Lio.5Crj.25Fe1.25O4.
curve
in the
B lattice therefore A
lattice.
lattice
lattice
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
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
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
by slowneutron diffraction [Sh 1] Because of the carry no charge they are able readily to penetrate spin they undergo in matter an extra interaction
.
moment of the
latter
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
2</>.
An
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
Wab^ 0,
will
make an
from 0 or
180.
The Weiss
a 2)MA
'
^MA + MB
2
(9.7)
B
'
lattice:
Hwb =  [MA +
jSiMb'
/S 2
MB = n [MA + MB +
'
j8 2
(ft.
 ft)AfB
j8 2
']
(9.8)
)MB "]
splitting
up of this kind
will
also the reason for the angle formation: ions between which the greatest
no longer
holds that
MA + MA
'
"
= MA
MB
'
+ MB " = MB
(9.9)
9]
39
from
(9.6) that
= Ki + as)
(9.9) are
= Kfr +
&).
(9.10)
The equations
now
and
(9.8). It is
concerned, as follows
the
first
1 ].
(9.7) it follows
MA +
From Mb) is
equation of
parallel to
Ma,
and
would follow
would be
parallel
Ma" Thus,
if
lattice, it necessarily
holds
that
a2
M^ +
AfB
=
we may
write
(9.11)
lattice
MA +
In general, a 2 /J 2 7^
1,
j8 2
AfB
= 0.
will
(9.12)
only be able to
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(p2pi)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.
B" and A
</>
follows
2
from
'
cos
(9.15)
where
Ma
and
Mb
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 ,
For
/? 2
we
40
FERRI MAGNETISM
tion can occur in the
[CH. Ill
B lattice. It does
(9.15)
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
it
changes discontizero).
of the
sublattice
magnetizations
(left)
together
fields
on the B'
jumps to
Up
to the point fa
field
since a 2
>
a.
In Fig. 9.5
it
but according
started,
namely that no angle formation should occur in the A lattice. With increasing temperature the configuration can change. For instance,
if at
T=
<
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
is
Tcb or Tcb"
the ions
These
a
will
and B' or B", i.e. Tca and generally not be the same (they will
fa'
fa
on both
sublattices). If
Tca
sooner than
Ma, but
from
(9.15)
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
(<
lattice
will
be antiferromagnetic
= 90).
Ma
Mb
A>
9]
41
We
a Neel point above the Curie point. Thus, the case of both sublattices being antiferromagnetic occurs only when 02/82 1.
>
The
vice versa,
is
The magnetization and entropy are continuous, but with increasing temperature dMs /dT shows a positive jump, accompanied by a jump in
the
specific
heat.
experimentally.
An
(Mb
= 2Ma)
is
M
a.2
versus
In this case
(9.16)
= 0,
= 2a
h=
kP,
is
//,
given by a/J
=f
17.5
and
/J
42
FERRIMAGNETISM
Although some of the spins are
antiparallel in
0,
[CH.
Ill
a ferrimagnetic substance
field
T=
an applied
has nevertheless no
x(T
= 0) = 0,
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
field.
be changed by an applied
field, resulting in
lattice
that
irrespective of the
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
given by
(10.4)
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]
43
if
which
Therefore,
Ta = TN
(10.1).
only
W\\
= 0.
but
Formula
also strictly
Thus
for
T>
Tn
curve
is
straight, as
is
it
is
At
T=
Tn, then, x
not
infinite
but
is
given by
x(Tn)
= ~,
Wl2
(10.6)
which
lel
is
the
resulting
from the
TN
the sus
ceptibility
Roughly speaking
is
in a cubic or polycry
perpendicularly oriented
and one
moment can
only result
if
the ab
At
T=
this process is
comes
is
T=
1/x T
T=
Tn, which
is
also
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
As a
oriented sublattices
With
and
at a given temperature
sublattices this
equal to
T > Tn
are
the sublattice
parallel.
magnetizations
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
f^^^
field.
is
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
is
to say the
dS/d(M2)
becomes smaller with increasing temperature where the Weiss fields decrease.
The Weiss
to the
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
T curve
is less
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
dance with the classic Weiss field approximation and (b) in accordance with more exact methods. (After Smart
[Sml].)
CHAPTER
IV
MAGNETIC ANISOTROPIES
11. Description of Magnetic Anisotropics
11.1
MAGNETOCRYSTALLINE ANISOTROPY
we have
discussed only the mutual orientation of the spins,
So
far
and have
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
required to turn
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 socalled difficult direction. This anisotropy energy can have
described by the
infinite
power
series in the
crystal lattice.
we
Fk
= Ki(ai
2 a.2 2
a.2 2 a.3 2
<X3 2 ai 2 )
+ Kza^a^a^
2 \
(11.1)
in which the coordinate axes coincide with the crystal axes. For the three
principal directions this energy
is
TABLE
11.
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]
47
which
K\ and Ki
axes.
K\ 0, K2 > 0, i.e. on the boundary between the [100] and the [110] domains the
On
the semiaxis
magnetization vector
table in the
is
freely rotathis
cube planes in
An
zing processes
bound
to
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
and Kz
from
(11.1).
C[100]
= 2K!
c[lll]=*l#2.
is
(11.3)
anisotropic,
and for
deflections in
we
[HO]
= 2Ki,
2.
and
[HO]
= Ki + K
equal to
0,
(11.4)
These
stiffnesses
may
moment
in a field
E = HMs cos
and
(11.3)
is
and
M
s
HM
HA
S,
so that
H*
which are included in table
(11.5)
11. 1.
48
MAGNETIC ANISOTROPIES
The anisotropy energy
in hexagonal crystals
[CH. IV
must have
sixfold
sym
with the same approximation as (11.1), we therefore write for the energy
axis;
may
FK =
and
<f>,
Kism?e
is
</,)
(1 1.6)
This energy
now
expressed, as
is
= 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
6<j>
is
ai
and a2
If the
>fe
perpendicular thereto,
in the
e =o
N.^ &o90
if
is
tion.
Where Ki
are
is
not predominant,
as
follows
ions
possible,
by
K2
the
are
taken into
position
stable
The
follows as
O
and Ki from
basal plane
is
(11.6).
whereas for
=
\
<
sin20 o
JiTi
< 2K
2K2
all
directions
on the
shell
= Ki/2 K2
11]
49
having an energy
is
Ki z /4K2
=
is
which in the domain under consideration 90. In this case each generatrix or
of a cone of revolution
vector.
For
all
other ratios of
is
K\ and
is
the preferred
2K2
>
K\
>
metastable positions of
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
H, given by
(11.8)
H$
represents that for rotations
It
on
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
,
KiccMt 20
Zener [Ze
1 ],
the uniaxial
3.
perature as a result of
random
true at low temperatures, at which only slowly variable spin deviations occur
(spin waves of large wavelength). Zener
assumed that the macroscopic remain valid for the direction variations due to
s is
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).
walk) for the local variations of the magnetization vector in direction, and
50
MAGNETIC ANISOTROPIES
power term
[CH. IV
in the crystal energy
n th spherical harmonic)
K(n)ocMsn(n+1)
i.e.
'
2
,
with an exponent of
1]
3,
10 and 21 for n
2,
[Ke
Van
Vleck's theory
is
temperatures.
11.2.
In
many
A condition
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
no
effect.
Upon
room temperature
itself in
of magnetization.
in cubic crystals can be represented
by
Em = iWPl 2 +
where
a*
a2 2 S2 2
a 3 2 j3 3 2 )
+
(H9)
G(aia2i3i^2 +
ment and
tropy
is
j8i
aiazPlfo
0203^2^3),
are the direction cosines of the magnetization during the measureare the direction cosines of the magnetization during the
mag
For
G = 2F the
field
of the form
(11.10)
Em = Ku sin2 (66u )
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]
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
Yamamoto
is
a magnetic anisotropy
may be
E= K
sin 2 6, in
K can
still
be arbitrary. In alloys,
the angle which the spin makes with the line connecting the atoms.
The
The
probability
then proportional to
P(0) oc exp.
ea sin 2
an
/kT=
 e sin
6 a /kT
(11.11)
where
at
e a is
bond
(<^.kT).
If this configuration
frozen
is
in,
found
ea
the magnitude
F,
e
in (11.9)
and K in
(11.10) are
triction
converted per
10 8
cm3
is
of the
,
may amount to
It
10 9 erg/cm 3
corresponding to several
treatment
cm1
per bond.
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
lattice.
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
52
MAGNETIC ANISOTROPIES
12. Origin of Crystal Anisotropy
[CH. IV
S
is
12.1
DIPOLEDIPOLE INTERACTION
energy between two magnetic dipoles
fi\
The
classical interaction
and
fiz
given by
(1,2)
= 3
r
(12.1)
r5
Where ^i and
fi2
are
(1,2)
= r
(1
 3 cos2
0i2)
(12.2)
where
12 is
necting line.
The
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
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
/ is
Ai
= ?^(l3cos0),
(12.3)
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.
will
depend upon
field is
Lorentz
now produce a
The contributions of
apart again cancel each other out, as for the sphere of a cubic substance.
of which
is
12]
53
zero.
The
dipole energy
1 ]).
What
is
interests us is the
dependence of
this
Owing
0,
form of the
is
direction cosines.
^dipole
= S
Ey
Ojcy
(12.4)
(11.6) in
make a
contribution to the
K\ of
hexagonal
33
K\.
It
symmetry, be anisotropic.
magnetic
crystal.
Apart from a
deformation, which
is
discussed in
the next section, the ion order has cubic symmetry, but not necessarily
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)
drawn
will
2 I?i2(aia2
[1 1 1 ]
(X2C13),
(12.5)
The
has cubic symmetry, so that the dipole interaction cannot result in aniso
tropy in these
either.
y&
So
far
we have
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
moment
h.
in the direction
is
smaller by an
amount
is
For S
= ^ this means
We
are
may be considereffect.
relatively small.
The
inter
though usually much smaller, this is of the same form as that due to spinorbit interaction, which we shall now consider.
54
12.2.
MAGNETIC ANISOTROPIES
SPINORBIT 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 spinorbit interaction, which was discussed in 3.3. The result of this spinorbit 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
The
indirect exchange
functions (orbits) of the electrons of the anion and the metal ion. Thus,
ow
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
may be due to
AE is a
One may
state
ground
ions
is
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
momentum
will
depend, like
upon
For the case that the ground state is nondegenerate, 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
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
can only 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
noncubic
(e.g.
as in
is
(trigonal deformation)
also occurs,
which
The cause of the expansion anomaly is to be found in the dependence of upon interatomic spacing; this appears with metals,
1 3.2),
maximum;
action
is
to
maximum,
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.
d/ E=N (aaa
,
+ \c[
/a ad~
cio
J. Sa
^xS^WMo
*fb)
T=
0,
(AT
Mo).
56
MAGNETIC ANISOTROPIES
Fig.
13.2.
[CH. IV
Dependence of
trons.
where
is
the
and
We then find
Nao dJ
c
a ao _ _
ao
da
For
ao
erg,
it
10 3 , a
= 3 X 108 cm, c =
d/^
10 12 dyne/cm 2 and
= 3 X 10~ 14
follows that
=~ da
/
3x108'
which
If
is
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 noncubic 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
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,
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
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
(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 nonmagnetized 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
then
^A 10o
2a 2 2
and
Am
respectively.
In an arbitrary direction
A(ai,a 2 ,a3)
we then have
a 2 2 a3 2
+ a3 2 ai 2
).
(13.2)
For a
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
room temperature
(for
Co
c axis) are
found to be:
Fe
Ni
Co
A//
<
'
The
deformed
total
it is
no longer
may
which
is
pro
The
of
this crystal
For a cubic
be written
as:
crystal the
F=
1) + eyyW  J) + ^(ag  \)\ + + eyzaiaz + ezsasai) + icii(exx + e yu2 + e +Ci2(e xx e yy + eyytzz + xx + iC4i(e X y + e yz + ezx
Bx
^(ai 2 a.\a.i
+ Bi{Xy
z2 )
+
(13.5)
zz
),
58
MAGNETIC ANISOTROPIES
it
[CH. IV
from which
follows
to ey
and using
(13.1):
Aioo
=
3
en
c\%
^lii
=same
(li.b)
i C44
The
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
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
ferrite,
however, Aioo
10 5
6
is
Ki
is
of the order of 3 x
erg/cm 3 which
erg/cm3 .
is
no longer
negligible as
K\ of 4x 10
An
stress
means of an external
analogous to the
due to the
Eatress

+pV term
<J
in thermodynamics
a potential
energy
stresses:
= ae = <*xxe xx
yye yy
zze zz
~\~
azxzx.
(13.7)
By minimizing
sist
This
deformation substituted in the energy gives, in addition to the cubic term in e, a noncubic term resulting from the deformation due to stresses:
stress
= 3 Aioo /a Am
/2 3
1 / 3)
\
/3
zz (3
/3 )
+
(13.8)
We
can interpret
(13.8)
13]
MAGNETOSTRICTION
stress.
59
For a
tensile stress
a in the z
axis,
we may
from
a constant, as:
(13.9)
^stress
=3
/2
A<rsin2 0,
which
is
(11.6).
One can
think of a rod
3 /aA,
loaded in the
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
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
(13.9)
(13.9) for
<t
is
approximately 10 4 to 105
erg/cm3
which
CHAPTER V
MAGNETIZATION PROCESSES
14. Weiss
Domain
Structure
it is
usually
more advantage
in
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
magnetization
vectors
side
Mi
of a
two
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 socalled 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
above requirement
Fig. 14.2.
by Neel [Ne 3 ] and later found by experiment. In Fig 1 4. 3a the Weiss domain structure is given around
dicted
is
if
there
is
14]
WEISS
DOMAIN STRUCTURE
As was
total
first
61
(Fig. 14.36).
the wall
energy.
are not parallel, and, because they are not aligned in the most favour
Fig. 14.3a)
inclu
able direction, this costs exchange energy and crystal anisotropy energy.
The
to
has a
finite
shall designate
aw This
.
will
we Owing
the
occurrence
of these
domains,
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
is
area is
if
the magnetostriction
for,
\f
ft
\w
\\\
\\t
ttt
ftt
W
H U
tf
\\\
Fig. 14.4.
in a thin plate.
62
MAGNETIZATION PROCESSES
[CH.
We
shall determine,
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,
d/D.
The
is
=1.7Af. +
^. d
d equal
to zero gives:
(14.1)
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
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
ment (cathode
rays),
is in agreement with who, with the aid of electron bombarddemonstrated fields of the order of 104 oersteds on a 1 ],
oc
14]
WEISS
DOMAIN STRUCTURE
The
derivation
is
63
D diminishes.
then no longer
valid. If
K<
plate at a thickness
DI0 <
t
6.8
M ^w
s
K
a
(14.4)
For every
finite
body
there
is
critical
exist. If
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
!),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
is
D is
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
Fig. 14.3
is
by
(14.5),
no extra Weiss
domains will appear here either. The Weiss domain structure can be made visible on a surface under the microscope with the aid of a Fe3C>4 powder colloidally suspended in a soap solution. This powder coagulates at the position where the strongest field
64
prevails.
MAGNETIZATION PROCESSES
[CH.
Even though the magnetizations in the Weiss domains are parallel to the surface, so that no stray fields can be expected, these nevertheless appear at the position of the wall, thereby making the walls visible. An example of a powder pattern on a crystal oriented sample of BaFe^Oig is given in Fig. 14.6. In the case of metals the surface must be thoroughly destressed, for example by electrolytic polishing and annealing, otherwise the Weiss domain structure appearing on the surface will not be representative of that inside the material. Owing to the occurrence of closure domains this pattern can differ from the simpler domain structure below the surface. Another way of making ferromagnetic domains visible is to analyse the light that has passed through a ferromagnetic body. As a result of the optical
Faraday
effect the
plane of polarization of planepolarized light will be rothe light passes a thin sample parallel to the
tated differently
when
maggives
and b
is
by Kooy [Ko
1 ]
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
field to
return
method is that which makes use of the magnetooptical 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.
wall)
The
to another does
much exchange
energy.
To
An
exact cal
by Landau and Lifshitz [La 1]. To estimate roughly the wall energy aw and the effective wall thickness
S w,
we
shall
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
cm2
= kTc/aS w
14)
WEISS
DOMAIN STRUCTURI
65
I'ig.
14.6.
66
M AG NETIZATION PROCESSES
[CH.
15]
67
where a
to
The exchange
is
make
opposed by the
which
will
OK
= \Ko w
Hence a
where
2kTc
S>
aK
cm 2
is
(15.1)
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
ponding to several hundreds of interatomic 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
Angle of deviation ^ as a function of position. The broken ration on which the calculation was based.
b)
68
MAGNETIZATION PROCESSES
[CH.
the preceding and the succeeding spin are equal and opposite, the same will hold for the torques acting on the central spin, so that owing to the exchange interaction the total torque acting on the spin is zero. This is not the case
is
by a
caused by
The
difference should be
smaller the nearer the spin approaches the preferred position (the crystal
anisotropy couple
is
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)
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,
general, a variation in
ever,
it
How
must be borne
mind
we have put
equal to kTc,
is
is
no longer valid
According to
2
,
smaller.
tional to
2
,
so that
As a function of temperature,
we
Dcr
In
oc
^K/Ms
(15.4)
many
cases
K decreases
(14.2)
it
(see 11.1)
critical
become
domains
in
and
From
this will
will
change in proportion to
fK/Ms
become
increas
16]
69
PERMEABILITY
An externally applied magnetic field will try to alter the Weiss domain structure and, if
it is
magnetic
field exerts
on a Bloch
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
= 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
bound with a
to a permeability
y.
which
is
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 crosssection, like a soap bubble, and will have a stiffness for displacement of <r42 v4/dx 2 , where A is the area of the crosssection. 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
would
stretch
much
70
MAGNETIZATION PROCESSES
that of the wall energy. This case
is
is
[CH.
comparable with
its
environment;
no
energy,
if
then, will be
is
more important
the inclusion
According to Neel
still
it is
netizing energy
further, or to eliminate
domains
Fig. 14.3, in
the inclusion.
Where
critical
the dimensions of the inclusion or the hole are smaller than the
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
The
wall
such as dislocations.
is
Where
imperfect the
will also
"*
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.
,
elusions,
16]
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,
be strongly
bound
to that line.
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
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
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
(K/NMS 2)
is
Ka /NM
applies
2
,
where
a demagneti
%NMS 2
<K. The
Kl/NM* per
cm 3
Fig. 16.2.
Owing
by a wall
to inclusions or internal
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).
or
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
by Neel, can
if
direct
>
NMs 2
Sw
.
(16.2)
72
MAGNETIZATION PROCESSES
[CH.
NM ~
S
10* erg/cm 3 ,
Ka =
2x 104
S,
= 5 X 106,
>
IO4 cm, as
is
In the foregoing case, the exchange energy was disregarded even though
the magnetization
is
So
that
far
plane wall.
is
stable only as
a whole,
and
in general a
move provided
If that
that
all
the others
or
at
case, poles
would
rise to large opposing fields. The magnetization movement should accordingly be regarded as being
is
movement
is
ging of a wall held at the edges. Kersten regards this as the most important
fields in
many alloys.
the difference vector of the magnetizations at each side of the wall does not
will
which
case,
Where
of the magnetizations
be the
stress
will
easy to
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
10~ 3
16]
73
can be estimated that the pole strength change by a factor K/2wMs 2 (< 1) and
It
which
will
of magnitude) will
now be
AEd ~K 2pV/M^D.
This energy
is still
AE,
>
p6V p ~ aw = 6K = ir/*rw =
,
H. The magne
Sw
V,
tic
cated.
since 8 W <z* D.
We
zing energy.
2HM .V,
S
so that by mini
mizing
we
H Where
that
if
/x.
~ 20 M\DIKM.
103 and
(16.4)
=
In
105
gaU ss 2
D = d=
K=
ios erg/cm 2 ,
is
it
follows
10.
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
shown
in a
minimum
in that
minimum. Upon a
move
until the
MH = AEw ldx.
no longer
possible
(16.5)
With
dEu>/dx
still
increasing
is
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
irreversibly to a position
It
dEw /dx
may
also
happen that a wall has already come from the other side, so i.e. the Weiss domain disappears.
is
now
74
MAGNETIZATION PROCESSES
minimum
field,
[CH.
for
H = 0,
now
let
after which,
E and
H approach
way a
hysteresis loop is
16.4Z>,
M of the
is
sample
is
(The loop in
this case is
turned 90 with respect to the normal representation.) The area of the loop
\HdM is
absorbed as heat, caused by for example eddy currents produced by the rapidly changing magnetization. In a nonconductive medium the retarding
of the wall by direct coupling of the spins with the
action)
is
The
of
determined by the
maximum
value
dEw /dx:
H = \M
c
(16.6)
It
can be calculated for the various mechanisms which hold the Bloch wall
in position
is
this
5.
Fig.
16.4.
a)
Schematic represen
x of
is
the wall.
either in
For
H=
0,
the wall
A
b)
or in D.
17]
and accordingly
e is
i.e.
M = 0.
on the
basis of
minimum
volume
H ~ (1.05 vXa/M
c
s)
[2.23
[1.79
for
$ Act>
K
(16.7)
H ~
c
(0.191
v\W/KM
s)
For the case of a volume fraction v consisting of nonmagnetic material Ki > 0, Neel finds:
8i
277M.2
(16.8)
H
For #i
0.39
4ttMs
+ iln2
/3
l*i
<
0,
Kx has
to be replaced
by
K\
in (16.8).
saturation, or small
fields discussed,
are unable
of
all
spins in the
zation of this
domain domain as a
field
We may
M. The
torque
exerted thereon
by a magnetic
is
given by
T=MxH,
I is
the
at rightangles to both
(this
(17.1)
i.e.
moment is in the
the magnitude
between
is
HM sin
where 6
is
the angle
orientation
reached
opposite
to that exerted
see
Fig.
17.1.
We
H,
from
Mutual
applied
orienta
or 4ttMs /3
(K),
the
field
This
may
M.
Lorentz
but
this
we
76
MAGNETIZATION PROCESSES
it
[CH.
may be
equal to H.
is
The
found by
minimizing the total energy. For the case of uniaxial crystalline anisotropy
and a magnetic
energy per
field
cm
(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
in (11.5).
Equation
holds
H < HA
tibility is
M remains
directed along H.
The
resultant suscep
which
for all
is
17.2a curve).
The value
(17.4)
holds
180 In this case, a stable position a can appear only when sin0o = (6 =
or 180);the position with cos0
is
= H/HA
always
labile.
for
what
field
of mag'
we may
write in this
netization.
The
position will no longer be stable if, where between brackets becomes negative. This is the case
is
if
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]
77
17.2,
This
is
is
always
Where 90 < a < 180, the magnetization vector turns over for \HA < Hc < HA The value c = \HA appears for a 135. After turning over,
.
<
the direction of the field; this direction can only be reached, however, in
an
for
This approach to saturation has been calculated an isotropic distribution of the preferred directions over a sphere, and
series
expansion in l/H:
am/Ms
'
K*
192
z
K3
h
(17.6) K
'
S
105
WM]
5005
IPM 3
is
The
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
field.
The
grain concerned
is
assumed to be
in which
Ha
field
4ttM/3,
field
is
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.
and
cation of the
field.
We
shall
now
consider
how
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)
}=T = MxH.
In very good approximation
(18.2)
we can
angular
momentum
in (18.1), so that
(18.3)
M= yMxH.
from which
both
it
magnetization vector
always at rightangles to
itself
and
to
H. The
vector precesses
angular frequency
cj
YH,
(18.4)
irrespective of the
angle
Fig.
18.1.
0.
the
Schematic repre
resonance frequency
this
/ in
M c/s
according to
equation
H.
f=2.80H
Mc/s
(18.5)
18]
79
10 4
if the
By
we
the angular
momentum
The contribution of
is
change of angular
momentum
momentum due
to the preces
Now
is
of the order of
2x 10 20
c/s,
and so
c/s.
only to or
So
we have been
vector will
tion, in
move
be
which process the magnetic energy (here only the potential energy
lost to the lattice.
HM) will
For every
must be at
least
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
the
two
stiffnesses
y c /i,
(18.6)
where c
is
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>
To do so we motion (18.2):
shall start
/,
bE/bfa
is
Jy
= bE/b+s.
(18.7)
The minus
by
sign
is
important and
equation in (18.7)
90, hence
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
...,
(18.8)
Ey
= b 2E/b<fnb<f>j
For a harmonic oscillation of the magnetization vector with angufrequency <o one then finds for (18.8), using the complex notation and
:
(18.9)
finite
4> x ,y
if o> is
= (y/M) (ExxEyy  E^i. (18.10) If the energy is on the principal axes {EX y = 0) then (18.10) is analogous to
where xx and yy are now the stiffnesses. The energy is found alternately in the deflections in the x and y directions. This expression holds
(18.6),
even
if
the energy
energy.
is formed by the crystal energy or the demagnetizing For the general case of the equilibrium position not coinciding with
the z axis,
we may
<f>),
hence
(18.11)
)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).
is
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.
Nx Ny
,
and
z,
so
that
Hx >
2
<f>
(Nx
2
Ny>z)M
s.
The energy
is
JV^sin 2 6 cos 2
is
given by
first
"r
yi\Hx
+ (Ny  Nx)Ms\
\HX
+ (N  NX)M
z
1 ]
S\
(18.12)
first
ferromagnetic resonance
on a
which
Nx = N = 0, Ny =
z
4tt,
plate
(18.13)
a> r
yiBH.
18]
81
In (18.12)
from
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
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
from Table
some
with the
For uniaxial crystal anialong the z axis and the field in the x
<f,.
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
parallel to
H. For the
resonance frequency
(h< m) (H>W),
is
K
'
'
H = HA
the
this axis
a direction of
maximum
precisely
energy. In between,
and
<o r is
when
minimum x
stiffnesses
one of the
zero,
and hence
to generate
Sm
2].
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
angles,
As a
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
^EXx,
as follows
(Exy
= 0).
18.2.
In 18.1
The
anisotropy field
Resonance
in a specimen
still
first
recognized by
Snoek [Sn
1 ].
We shall now show that the Weiss domain structure can very
is
in
two mutually
18]
83
parallel
and
(b)
We
shall
now
calculate
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
to the walls.
is
continuous
(jc
direction),
ett
and so
,
no
parti
cular consequence:
ficient
Nx = Nx
which
Nx
is
x axis. In
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
.
w r However, x and z
anisotropy
Hx
now becomes an
HA
84 In case
phase.
[CH. VI
magnetizations in the
On the boundaries there are then alternating poles which, if the thickdomains
is
demagnetizing alternating
at rightangles to the
is
the alternating
component of
Hence
ett
JVa;
eff
= 4n. N
In the
ett
consequence and
Ny = Ny
JV^ett
Again,
= 0,
,
4w,
Nju = Ny
ett
= 0.
(18.17)
Evidently, (1.12)
no longer holds
the inequality
is
<*<
<
8ir.
flat
plate
(Nx
the
8tt.
= Ny = 0, N 4n),
and therefore
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
by Solt
al
[Sol]
that
netization vectors are 180 out of phase. This gives rise to additional de
magnetizing
fields
fields,
are reduced.
As a
result the
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
different
19]
FERRIMAGNETIC RESONANCE
Mi
and Afz
at ferromagnetic resoi
85
zation vectors
> Mi
and yi
WM2
WM2
the field
ions.
The
intrinsic properties
factor of the ions in the crystalline field, will therefore vary accordingly.
In the foregoing
we have
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
resonance frequency
differs for
each of
the subtattices.
lattices
Owing
and
in the
same frequency
M\
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
Weiss
field
Mi
7^
M2)
and hence
be equal.
It
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
[CH. VI
between
yi
and
2.
for
Mi >
less
and
<
on
M\
is
reduced relatively
than that on
72.
2.
The
be smaller than y\ or
6)
The
given by
. ,
vMx 0i =
Wr
Me
2
ri
02)]
y 2 [HM2 6 2
6 2 )]
{
'
M and H. These
if
I
homogeneous equa
and
Wr
2,
\yi
= 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,
drop
out and
we
find
co r
=
2 ),
M^!  M
as
is
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
M1M2
(Mi/gdWifa)
= gi+gz
2
(Mi/gi)
) )
'
for
a> r is
and
first
we may
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)
mm,
equal,
Now
,
the
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)
19]
FERR1MAGNETIC RESONANCE
denominator becomes small,
analysis
it
87
decreases, so that
If this
a>i
increases
and wz
from a
more exact
[Wa
2].
e g "
From
merator
(19.4)
follows that
or
oo,
(M =
0) or the
denominator (/
versus
= 0)
zero.
These phenomena
discussed in 9.1,
similar effect also
ferrites,
T curves
(Fig. 19.2).
ZOh
3.0\Fig. 19.2.
Change of the g
1 ],
while in
the vicinity of the compensation point even the second resonance (19.5)
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
= gz.
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
[CH. VI
= gett.
fields,
The
uniaxial crystalline anisotropy energies for each sublattice are given by the
constants K\ and A
respectively,
2
fields
H = 2.Ki/Miand HA = 2K /M
2
2,
analogous to
These
fields
then,
same
is
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 lowfrequency mode of resonance will now be of the order of A jWM, which again, generally speaking, is small.
If,
as before,
we
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
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
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
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 Einsteinde
We
tilting
of
all
unchanged. For a
hw
= H(AMBV m +
20]
89
momentum
is
quenched,
this state
As we
first approximation, and therefore only be purely parallel or antiparallel to the magnetic field, i.e.
can
^1/spin
= h,
+ AMorbit
.
(20.2)
we
obtain for y.
y
Since
all
^Mgpin
^/spin
g
This
(20.3)
susceptibility
is thus the same as (6.6), which governs the paramagnetic and the saturation moment.
lattice (rotation) is
large
moment of
inertia.
momentum
^/spin
of the
lattice (J/iattice)
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
(g2)=
X/AE, which
halffilled shells
momenta
momentum
be anisotropic.
is
There
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
is
by a surrounding
coil
The current
is
is
then reversed and this causes the bar to rotate. The g' factor
now
defined as follows:
(ejlmc)g'
= (^A/gpin + ^M rbit)/^/lattice,
momentum of momentum of the
the lattice,
bar, while
where
i.e.
J/iattice
is
90
in
[CH. VI
^MBP + ^A/orbit
the change of
M.
is
suspended torsion
^/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
mo
by a
(20.3)
(20.5)
Thus
(20.5) is
if
> 2,
then g'
g' are
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
+
g
Iron
2.122.17
1.93
0.9800.990
Cobalt
Nickel
2.22
2.19
2.2
2.01
1.97
0.986 0.996
0.973 0.998
0.9911.006
1.84
1.93
Magnetite Fes04
Heusler alloy
GwMnAl
2.00
1.91
2.072.14
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
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)
gi and gz according to (20.6), but this has not been proved for the highfre
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
would be
possible.
is
g2 = 2g',
which
is
(20.7)
(20.5)
if A/orbit
has a more
the spin
made
to
it is
(20.2),
i.e.
is
This
is
not
moment, provided
is
substances g can assume very high values in the vicinity of the compensation
to (20.3), A/gpin
>
0,
> 1, which is evident since then, according and therefore only orbital magnetism is present.
In this section
we
shall
examine the offresonance behaviour of the magnecan be caused by applying an alternating magnetic
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
as:
= iaiM</> x =
yEn<f>x
(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^
,
'
v
'
where
wr 2
y^EuEm/M2
92
Xxx
[CH. VI
<o 2 )
< 2 ) <u 2 )
= io>yM/(a> 2 = r^EuKair* Xw
Xxy
r
to 2 )
The tensor is Hermitian and thus has real eigenvalues, in accordance with we have not taken damping into account. The offdiagonal elements are opposed. For elliptically polarized signals one finds from
combinations
(21.1) the
(<l>x/}'E22)
(^/VEii)
Oi^
(21.3)
(Of
It follows
from
this that
an
elliptically
/Cn/^22
upon
excites
an
elliptical
depends
occur (x
oo) or not.
Resonance
will
we may
look on
that
of
two opposing
is
elliptical rotations, in
,
agreement with
all
is
excited at
an
mx
is
in phase with h x
elliptically
At higher
still
zation
becomes predominant,
of the
ellipses
mx
m x goes
magnetization
latter
linearly polarized in
The
phenomenon can be
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
first.
22.
22.1.
The consequences of the nondiagonal 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
H=
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 fieldstrengths,
ju.
[ ky2 k
kXky
2
\
hx
{kx kyi^\ 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
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
The
quantity (^
) is
so
We
shall
determine
with isotropic
/x.
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
(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
much
The exchange
and 2
is
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
...
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
lattice
torque,
now
form
T=AMxAM,
where A
is
(22.6)
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
H + Hex for H.
done
I
in (22.5)
we
k2
which
is
= w*e
4irM 4ttM
c" V
H + AMk2
.
(22.8)
toly) a/yj
is
now a
equal to
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.
< 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 righthand 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 righthand 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
field.
w = yH which, m
is
of the order
least
of
10 7 .
>
good approxima
denominator
zero, hence
to
y(H
+ AMk 2
).
(22.9)
first
This
is
it
introduced by Bloch,
on k. For a> > yB the righthand 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
field,
We
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,
now propose
merge
22.2.
ELECTROMAGNETIC WAVES
in the z direction (22.8)
becomes
96
[CH. VI
Spin waves
Fig. 22.1.
(a)
(b)
as a function of the
wave number
(a).
k.
The
scale for
in (b)
is
at least a
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
negative.
Where
a>
<
yB
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
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
P/l
= W+k)
is
(22.11)
in the
22]
WAVE PROPAGATION
IN
MAGNETIZED MEDIA
(to
97
>
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.
ky
kt=
u
co 2 e
k2
co 2 e
C2
fi
C2
B 2 (o 2 /y 2 BHa> 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,
the
CottonMouton
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
equal to
y(H
wavelength
is
also
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
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
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
two de
the other.
is
wave
so that the
is
hco.
The energy
then
(22.15)
En
where n
= (n + i)hco,
n
^ 0.
The lowest
i.e.
state for
vibration of a crystal,
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
energy appears to be
cd.
/ito
From an
we saw in 3.4, the z component of the total angular momentum can only change by an integral multiple of h. The zeropoint vibration of spin waves
corresponds to the zeropoint motion of the individual spin moments, which
discussed in 3.4. Although spin waves have a zeropoint vibration, it makes no contribution to the energy since this, apart from the magnetostatic
is
22]
WAVE PROPAGATION
IN MAGNETIZED MEDIA
99
atoms:
Eex
(22.16)
= 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
energy
HM,
which
is
proportional to
HHS{ Z
The
En = nhu> = nhy{H +
The reduction of
wave
2/lib,
flex)
= Inyidfl + Hex
).
(22.17)
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
wave theory
M,
differs
but
little
at
T=
is
by the
is
and
given by
nic
J
1
.
(22. 18)
The reduction of
the magnetization
equal to
Mo Mg
The
possible values of
= 2 E njefiB
k
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
the wave
number
for
which
and
(22.18) is derived
the Bloch
3'2
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.
[CH. VI
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 phaseshifted 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
infinitely large.
Owing
to damping, this
a>
peak function
is
where
= 0,
i.e.
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
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 ()
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)
( X xy
Xvx)
= V ib".
b' is
a>
(23.5)
In
(23.3),
x"
is
In (23.5)
zero for
this is
u>
= 0.
= 0,
dW  = ^Re io>\xxx\hx\ + at
The
Xxyhx*h y
is
xyxhjiy*
Xyy\hy\ ]
(23.6)
a>Re(a"
If
 ib")h x *h y
is
(23.7)
b" =
for
to
= 0,
then (23.7)
The
losses
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
still
be dissipation in
fields in
positive definite).
is
For rotational
an
medium
AW =
dt
whW
k").
(23.8)
102
[CH. VI
first
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.
paper [La
as:
1 ],
Landau
and
motion
(23. 10)
equivalent to
(23. 1 1)
M=
y(l
in
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 BlochBloembergen equation is
applied by Bloembergen [Bl
(23.12)
1/ayH.
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
we
In the case of a noncubic medium, different values of a may occur in the x and y directions. For the susceptibility tensor we then find
Xxx
= yM
(a>ia>2
(o)l<o 2 
to 2 )o>2
tooi^Aio
.
2 J 2 )
+ +
<o a (J<o) 2
(oia.2.
a> 2 ) 2
+ o>2(J)) 2
(23.12)
Xxy
= iyM
(coia>2
co 2)a)
"> 2
J a) J
(coia.2
<*>
2 2
> 2 (Jo/) 2
(o)io) 2
to 2 ) 2
+ )2(Ja))2
aQd
< 2
and
Here
""i
= VE^I M
yEzzIM and
aifoi
a2&)2
= da>
(23.13)
which
line
is
to half the
the line width measured between the points where x" has dropped maximum value. This maximum value of xxx" is related to the
width according to
(X**"W A" = VM ]/
(23.14)
23.3
DAMPING THEORY
The microscopic theory on the damping of ferromagnetic precession was first put forward by Akhieser [Ak 1]. The deviation from the equilibrium
position
is
On the
atoms in the lattice is and thus they may both be regarded as the terms of a Fourier series of the nonperiodic 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
regarded as the
particles.
and
104
[CH. VI
somewhat
name "pseudo
dipolar interaction".
Owing
to the fact
on the
inter
will result in
As a consequence, the spin waves may waves be created, or conversely. The two most important
+ 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
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,
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
state of nonequilibrium to
return to the state of equilibrium, and in the process the magnetostatic and
For a return
This
is
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
this orientation.
The
relaxation time
5 ].
The
23]
DAMPING
state the
105
if
occupation of
all levels
differs
state,
[Po
1 ]
has pointed out that this does not correspond to the circumstances
One then
excites, as it were,
= 0,
so that in the
from the
state
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
from
lattice periodicity
ferrites in
can give
rise to tran
which two
different
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
when
= yH
e,
where
H
is
e is
the external
Owing
to the demagnetization in
The
fields
Ht, which
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
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
Once
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
when
106
[CH. VI
the magnetization
this
theory also
flat disc
on the shape of
field,
the specimen.
For the
which
field is
is
disc, the
resonance
sig
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
maximum
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
AH = 2aH (see
(23.13)).
From
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.
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
field. It
appears that
if
4ttJMz
= 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
field
hc
this condition is
= AH^AH/4nM
(23.16)
fields in
may
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]
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
field.
In
first
approximation
we may
hc
24.
24.1.
2ttM.
(23. 17)
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
by the
ex
order to
move
to
necessary in a plane
the
wall.
The angle of
movement from
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)
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.
attributed to
its results.
108
[CH. VI
The torque CO
M0
is
we have
zero.
Bz
must be equal to
As a consequence of
this,
a demagnetizing
arises
of the order of
H = 4nM = 4ttM
z z
0.
MHz at rightangles
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
<f>
Sw
(o^/oz)
l/cosh(z/8),
t
(24.3)
where 8 W
is
short time
is
= yH
If,
sin
<j>.
(24.4)
using (24.3),
we
component of the
total
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
According
z,
to (24.3)
and
(24.4), d</dz
and
(24.2)
and
t,
we
y*h w
H(W + 47rMs)t,
is
1
.
(24.6)
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.
some
23]
109
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
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
V
If
(yB/a)H.
(24.8)
we put
mw z +
where
that
fi
= 2MsH,
it
(24.9)
wz
fi
pw
= 2aMs
and
Y8 w
(24.10)
Where a
10~ 2 ,
H=
10 oersteds
Sw
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
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
For
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
wr
The
stiffness
fa/m w
(24.12)
is
related to the
a^
where
/ is
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 setup 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
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
is
nevertheless
still
Changes in
circuit.
The
specimen
A = S(Bwhere
H )dA,
Q
B=
The
field
H + HD + 4ttM.
o
HD
is
proportional to
M can be calculated
112
[CH. VII
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
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
field inside
It is
a known magnetization.
So
field
far
it
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
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.
during rapid
If the
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 airgap between the specimen and the polepiece 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 semicircular, uniformly wound coil. The total enclosed flux is then propor
25]
MEASUREMENT OF MAGNETIZATION
when placed on
13
the
is
its
two
ends of the
coil,
y/^///////////////////////^
is
uniformly
field out
wound around
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 crosssection of the yoke is large with respect to that of the specimen, the effect of the permeability of the yoke is
negligible.
circuit,
zation curves
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 xy recorder with the aid of an
integrating circuit [Br
sensitivity,
1 ].
This
calls for
If the magnetization
field is
its final
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
consequence of
this
114
falls
[CH. VII
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
BH loops. 5
search
coil;
inte
grating resistor;
Ga galvanometer; L Light
gasfilled
twin
phototube;
coil.
NO meter giving
1].
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%
this
makes the
Lx /R
time of
25.2.
component
in the
direction
is
equal to:
Fx = MbH/bx =
The magnetic moment
cally.
is
xHSHfix.
(25.1)
ballisti
However, the forces are soon large enough to be measured accurately. = 1000 Oe and bH/bx = 1000 For example where x = 104 /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
exists
is
made of
the field
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
direction.
maximum can
be
descibed as
H= Hoiax*.
The force/a
(25.2)
is
=
T2
1
1
aMV
47T2 /M
,
(25.3)
mB ^
TQ 2
116
[CH. VII
where
V is
and
the
is
In most cases
Fig. 25.6.
Pendulum device
for measur
Specimen
horizontal
p,
pole pieces
and
S,
pendulum P, cooling
vessel
V and
26.
26.1.
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
in 17 that
we have
only K\
difficult direction is
a straight
up
to saturation
26]
117
at
H = HA
If
with the
field
Kz
is
4K2
17*
1 ]
17 Mff +
Thus,
is
M* = Ms^,
(26 2)
'
if
HMs/Mh
is
plotted [Su
equal to
IKijMs, the slope being equal to 4KzjM2 s For cubic crystalline anisotropy the versus
from
as a function of
[110]
and [111]
field
directions.
magnetization versus
to
curves in the
K/3
+ Kz/27,
equal to K\/4.
26.2.
TORQUE METHOD
is is
field
H.
If this
much
For
fields
first
The torque
term
is
zero.
fields
we
T{9)
(sin
20
64
(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)
if
the applied
118
[CH. VII
field is
anisotropy
fields. If this is
netization can only be turned through a small angle out of the preferred
orientation,
in fact
is
measured
is
magnetization
bound
can more
26.3.
easily
An
ing the frequency of the torsional vibration of the specimen around the state
field.
The
stiffness c is
then given by
2 .F/oao0)d0/da
(W/d02)(d0/da) 2
is
(26.5)
stiffness
If the
moment
/ this magnetic
J(1/t 2)
= clAifll.
(26.6)
(26.5)
In
weak fields
HM COS (a2^1 cos 20 (H < H A the relation between c_1 and H1
S
0)
is
in first approxi
mation
linear:
1
cos 2a
HM
c,
COS a
2Ki COS 2 a
is:
(26.7)
=2ATicos2a.
(26.8)
At
< a<
differing
stiff
1
=mf
A = ^J H
a.
~1
+ iHA)  ^
1
(26 9)

The
it is
H' 1
l/Ms
for a
\jMs cos
26]
119
26.4.
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,
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
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 nonmagnetic is the purely optical method, in which the displace
ment
is first
increased mechanically
by
on which a mirror
is
mounted. In
way
displacements of
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
case a
then a measure
device
is
made of this
by
that the
measurement cannot
be carried out quickly; quick measurements are usually necessary because of temperature variations.
rise to
An
The differential transformer can be made as a directreading instrument. With such small deflections several interfering effects can arise as for example a magnetocaloric 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
A folded metal
is
affixed to the
carried out
(/<
100 c/s)
can give
8 to 10
rise
which the currentcarrying 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.
in this
first
of the wire. At
room temperature
is
this is
When more
approxi
used in a Wheatstone
is
care
same magnetic
field.
first
place*
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
~ 2.105
factor of 10 larger.
this is
obtained
by
27]
using an alloy with a transition element (e.g. CuNi 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
is
50 C.
then
To sum
up,
it
being easy to vary the angle between the direction of measurement and the
STRESS
MEASUREMENT
specimen, the length of the latter will also remain constant and the magnetostrictive stresses
28.
Initial
quency Ranges
28.1.
of the material
/^app
is:
p.
i+_0ii)
477
(28.1)
where
is
the measuring
see
1.
measured in the shape of ring cores in order to avoid excessively large corrections for demagnetization.
The demagnetizing
be determined from the ideal magnetization curve, which is measured by superimposing an alternating magnetic field on a constant magnetic field
alternating field
is
gradually reduced
The curve which gives the relation between the way and the intensity of the constant magnetic
122
[CH. VII
field is called
is
pre
(dH/dM)H=o = 0.
with the magneti
Owing
make an
angle
/?
= dH/dM = N,
sample,
exists
where
is
the effective
demagnetizing factor; see (1.11) and Fig. 28.1. Apart from the demagnetization caused
internal
With
sintered
j8
for instance,
the angle
gives
tude of the porosity: the angle increases with the porosity. In this case
Ni
= tan
j8
is
ring
Ideal
magnetization
curves:
no demagnetization;
b) demagnetizing
between the
relative length
factor
N = tan
/3
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
fJL
fj.
Ifl
(28.2)
The
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:
calculated.
The
H=H  NM.
e
(28.4)
Dividing (28.4) by
28]
=
Xapp
N,
(28.5)
is
that:
it
X app
IXappI
2
X
(28.6)
Ixl 2
this
becomes:
tan S
tan S app
/*'a
PP (1  tan2
8 app )
'
(1  tan*
S)
(28.7)
1
tan 3
(28.8)
f
is
if
reduced
reduced proportionally.
With
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
Mc/s up
to the centimetric
From
/*,
crosssection
A and
an impedance
series:
consisting of a selfinductance
Rs
in
(28.9)
L8
With the aid of bridge
= (ATM/.DV10
henry.
circuits,
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
than approximately
high frequency, the
When
high
ferrite cores at
electric resistance
skin effect found with metals. However, the crosssection of the ferrite core
to be measured
may have
that,
dielectric
con
some
ferrites, it is
wave
rise to
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
A method
made for To avoid
of eliminating
the d.c.
described under
At higher
provided
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
Ls
and
resistance
Rs
also contains
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'
co 2
(28.10)
).
core.
The
is
stray capaci
tance
indicated by
Cp
/*'
and
/*"
derived from
[28]
Ls and Rs
'
all
more from
w 2Ls Cv
and
This
is
which
Cp
Ls
To make Cp
ance winding, in the manner illustrated in Fig. 28.3. The number of sections
by
e.
winding the
ferrite
core beforehand
Wi
Fig. 28.3. Lowcapacitance
six turns
winding of
on
ferrite core.
The
selfinductance
Ls cannot be
arbit
would become
with metal
can be wound
strip,
but
it is
kind of box
fitting closely
around the
ferrite ring.
We
(a)
shall
now
outline
to
a Frequency of about
is
The
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
The
equivalent resistance
Owen
inductances up to a frequency
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 shortcircuiting points 4 and 5 and by inserting
.
126
[CH. VII
set
between them the unknown selfinductance, shows that there are two tings of R3 from which Lx immediately follows.
(b)
The
MF (with ferromagnetic
(with air core) cancel
and
Mo
Mo is variable,
and
if its
magis
M,
ring
osc
the
is
given by:
\0.4
MD
108,
N1N2A
(28.12)
where
is
the ring
A its crosssection, 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.
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
according to:
nr2 /(ri
+ r + R).
2
,
By making
ondary
core
is
made
small
quite simply; hence the voltage Ir, used as compensation voltage in the seccircuit,
loss angle
of the
ferrite
then given by
tan 3
r/coM,
is
(28.13)
where
to is
performed.
The advantage of this method is that the d.c. the ferrite core plays no part.
around
28]
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)
to
Lx = RiR 2 C
Rx =
Resistances
R1R2/R4.
(28.13)
parts
truction
repres
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 (RadioFrequency Bridge Type
(a)
2000 Mc/s
At higher frequencies
ed impedances
is
One of
is
the
commonly used
a quarterwavelength resonator.
coaxial
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.
the
line
displacement of the
is
resonance frequency
to
[i!
proportional
of the
ferrite.
Also the
of the
fine
broadend due to
broadening
is
proportional to
p" of
while
~
<Z
frequency
is
kept constant,
is
)g
<F()
varied (see
we now have
fine, is
required
0^>
Coaxial line
(/
complex permegreatly
Fig.
28.7.
A/4)
for
ability.
at high frequencies.
oscillator,
detector coupled to
the electric
field,
1]).
F ferrite
ring (accord
resonance frequency
also determ
ing to [Bu
[Li
1] is
Ah
Fig. 28.8.
The changes
coaxial
$lF
and
a
of
in
tuned
quarter
1L
*k
wave
ring
line as a result
of
The
fre
quency
kept constant.
28]
the copper
can
with
ferrite ring is
we may
and
/"
(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 ].
fills
only a very
the quality factor of the line remaining higher than about 10.
To
avoid the
presence of an electric
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
Wave Method
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 shortcircuited 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 shortcircuited 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
What
now measured
first
is
the distance
respectively, respectively.
from the
(That
the
is
voltage
minimum
and xi E%
minimum and that in maximum.) The impedances Z\ and Z% in both cases can be computed as:
Zj/Z,
= {Ej
),
1,2
where
is the characteristic
impedance of the
is
Dz/Di, and A
From
the
and
p.
= ]/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
made
if
fit
(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 quarterwave resonator, the detuning and the change
in quality caused
by the
ferrite
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
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,
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
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
we may
write:
M = ~ RWo and P = * R E +2 +2
3
fi
(28. 17)
becomes
=
the
X mA.I
X=cyh x *h y
X yxhyhx *
where
is
of these formulas
as well as the
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
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
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
[CH. VII
easily
A further requirement is
should not be placed too close to the wall, in view of the image
the platelet in question
With
produced in the wall by the precessing magnetization. The magnetic fines of force of the highfrequency field must remain parallel to the conductive
wall. Polder [Po 2] has pointed out that this
The
The
static
demagnetizing
field in
the
and
is
put equal to
NM. The
demagnetizing
demagnetizing factor
2N and 4n
respectively.
When
lies in
frequency
given by:
o> r
(28.18)
29. Loss
29.1.
Phenomena Related
SKIN EFFECTS
in a conducting dielectric
curl
E = /<.(/*' 
z>")H.10 8
>
In the following
we
replace e"
I20wcar/o)
by
e",
wave equation:
c*AH =
where
e
a>2\e\\iJ.\e
i(Se+Sm>
H,
(29.2)
and
/*
and and
3m the magnetic
loss angle.
When
direction),
with magnetic
Hy
falls
normally upon
we have
\
the solution:
(29.3)
Hy = Hy
giving for the skin depth d:
1
 x,dxl
jd
K8.
8),
(29.4)
29]
LOSS
133
= (o/cXM)icos i(Se +
S m).
(29.5)
The conditions
[e
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.
can be strongly
(29.5), is
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
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'
depend on the dimensions of the specimen, and are completely The frequencydependence of p' found
caused by the ferromagnetic resonance phenomenon
to be discussed in 50.1.
static
magnetic
field shifts
P'*r/ni
'eff/e;
5
f (Mc/s)
10
Fig. 29.1.
Dependence of the
drawn
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
[CH. VII
as a consequence of the
means of measuring
a high
initial
permeability, without
29.2.
effects.
EDDYCURRENT LOSSES
the skin depth
Where
d is
on
is
entirely
easily.
and the
losses
The amplitude of
axis of
Ex
is
at a distance
x from
the
Bmax
"
given by:
(29.7)
Ex =
tt/x
BmStX
10 8 VOlt/cm.
Fig.
29.2.
Rectangular
cylinder
in the
crosssection
through
with
radius
R.
Eddy current Ix
1
hollow cylinder
cm.
When
/>,
is:
W=
10i6 watt/cm",
(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 eddycurrent factor, a survey for some materials is given in Table 29.11.
29.1.
loss
It appears of that the amount of eddycurrent losses derived from loss measurements of ferromagnetic materials is always larger than is calculated from the resistivity. This discrepancy (eddycurrent anomaly) can
29]
LOSS
135
EDDYCURRENT LOSS FACTOR TAN BODIES CBmax EXPRESSED IN GAUSS, R IN CM, AND q IN OHM CM)
EDDYCURRENT LOSSES
Body
plate
W AND
W
10! watt/cm 3
tan & e
R
109
thickness
Q*mf*B*
m RVp
K 2 /P
(S^/3)(fR M V P)
2R
cylinder
nHfuK^lp)
(7r2/5)/2B2 m x
109
109
radius
sphere
(4^/5) (ffiRVp)
radius
TABLE
29.11
EDDYCURRENT LOSS FACTORS FOR SOME MAGNETIC CORES IN THE SHAPE OF PLATES AT A FREQUENCY/.
P
Material
/
kc/s
5
/i0
ohm cm
2105
Thickness
tan S e
Permalloy
Mno.4gZno.48Fe2.04O4
7000
1000
10
10 micron
10 2
102 105
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
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
same
as in the
homogeneous
W=
is
(l/p)
f2 dF=
(lip)
JdS /tfW,
Here AS
is
it.
homogeneous
case.
a surface element
For a
al.
special con
et
[Wi
2],
and
amounted to a
CHAPTER
VIII
30 Chemical Composition
The general chemical formula of ferrites possessing the structure of the mineral spinel, MgAl204, is MeFe2<I>4, where Me represents a divalent metal ion with an ionic radius approximately between 0.6 and lA. In the case of simple ferrites. Me is one of the divalent ions of the transition elements Mn, Fe, Co, Ni, Cu and Zn, or Mg and Cd. A combination of these ions is also possible; we then speak of a solid solution of two ferrites, of mixed crystals or, in general terms, of a mixed ferrite. Furthermore, the symbol Me can represent a combination of ions which have an average valency of two; for example Li1 and Fe 111 in lithium ferrite, Lio.5Fe2.5O4.
particular case is the ferrimagnetic yFe2C>3, which has the spinel structure and whose chemical formula can be written formally as l/sFes/sQi, the symbol representing a vacant lattice site ([Ve 1], [Ha 1]). In
this case
Me
and
trivalent iron
2.
The
mixed
also
ferrimagnetic at
room temperature
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.
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
exist,
compound can be
to 35
the structure.
is
replaced
shall
by sulphur [Lo
1 ].
and we
31]
CRYSTAL STRUCTURE
in ferrites can be determined
difficulty is that
137
by an analysis
one
is
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
( 33),
can
sum of the
a mixed
which means
is
crystal with
yFe203.
The
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
sites occur,
the tetrahedral
and the
64 tetrahedral
sites
and 32 octahedral
ions (called
A and B
sites respectively).
To
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
way
138
the
[CH. VIII
same way in
is
all octants.
Each octant contains four anions, which form shown in Fig. 31.2. The edge of the f.c.c.
oxygen lattice
\a.
As
common
are identical
(see Fig. 31.1). In Fig. 31.2 the positions of the ions are indicated in
two
Fig.
31.2.
Two
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.
The occupied tetrahedral sites of one of the octants are on four of the eight corners of the octant. In the adsite is
translation symmetry, half of the corner sites are again occupied. It can be
sites
{A
sites)
lattices
having an edge
a,
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.
lie
on four
interpenetrating
f.c.c. lattices
with
edge
a,
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
ions by other
31]
CRYSTAL STRUCTURE
The two cubes shown do not
in
lie
139
ions.
each
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
,*.
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
ions,
ions
on octahedral (B)
sites.
its
nearest
Each
A ion belongs
is
and each
B ion to
The
direction
O A
one of
the
directions
O B
cube edges.
31.2.
The statement
only in
first
form an
f.c.c.
structure is true
a metal
ion, if
we regard
consequence
Fig.
31.4.
The
nearest
neigh
Small
open
octahedral (B)
sites.
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
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
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
which
"id
.
of the parameter u found with the aid of Xray 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.
tb
=( u)a R
v
,
'
where Ro
31.3.
is
AND
TETRAHEDRAL
SITES
cell
We have
question
Now
the
may
It
be asked,
how
and
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.
many
cases this
is
is
MgAl2<I)4, which
therefore
known
[Ba
1 ]
this
simple assumption
is
correct in
all cases. By Xray 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
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
on the distribution of the ions over the available sites in magnetic compounds, namely, with the aid of Xray diffraction, neutron diffraction and from the
magnitude of the saturation magnetization at the absolute zero of temperature. The scattering crosssection of atoms for Xrays 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
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 Xray
examinations
it
[Ba
that aluminates
and
power
is
to
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 Xray scattering propern is quite different from that ties. The scattering of neutrons on magnetic Ni
ferrite is
1 ].
For a
referred to
Bacon [Ba
2].
The
and
saturation magnetization
is
MejFe^JMe^FeSalC^,
142
[CH. VIII
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 Xray 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)
(18)2
where the value of
'
1 *)
is
[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
ions will prefer to occupy the tetrahedral smaller than divalent ions (see Table 31.1)
structure.
(b)
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
their
to the favourable
field at
fit
an octahedral
([Sa
1 ],
[Ro
2],
[Du
2,3]).
31]
CRYSTAL STRUCTURE
TABLE
31.1
143
SPINELS,
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)
Another factor that can determine the distribution of the metal ions over the
available interstitial sites
is
thought to be
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
favourable.
will
From
com
plete lattice
made by Verwey
lattice
et al.
and
energy
when u
31.11
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
is
practically only
ne tr.
Mn11
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
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
Xray 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
dx
where
8M
Na3
g/cm3
N = 6.02
10 23
mol1
TABLE
<*
31. Ill
METAL ION DISTRIBUTION, LATTICE CONSTANT a. u PARAMETER, MOLECULAR WEIGHT Af AND XRAY 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
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
By quenching
room
tes,
temperature, however, the cubic structure can be maintained. Mixed copper ferrifor example copperzinc ferrites with not too high copper concentrations, retain
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
9.45
<(X)
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 nickelzinc
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
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
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
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
[CH. VIII
and the two lower ones Fein The drop in the conductivity on the octahedral sites from unity. The ordering
to
deviates
gives
rise
crystallographic
metry,
as
was
symdemonstrated by
Calhoun [Ab
ture of
point.
1 ]
by Xray
analysis.
The
in
Orthorhombic deformation of the cubic spinel structure of Fe304 below 119 K. The spontaneous magFig.
31.6.
netization
is
in
the
[001]
direction.
After [Bi
2].
parallel
The
face diagonal
BD
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.
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
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.
is
always present
from shortrange
32]
SATURATION MAGNETIZATION
low temperatures
at
147
which
this occurs in
Fe3C>4
by electron
diffusion.
ferrite
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
He found
that
The ordering
is
is
such that
alternate
struc
an
ferric
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
has been established experimentally that the predomior more than half
nating exchange energies between the magnetic ions in the ferrites are negative, as
filled
halffilled
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 MeOMe'; 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 GRAMION ACCORDING TO (6.9) IS GIVEN IN THE LAST COLUMN.
mo
/xjj
Ions
in
Spinonly
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
Cr"
Mn " Mn
1
Fe IV Fe Co IV
4
5
4
5
3.00
4.38
6 7
8
4
3
3.00
1.87
Co"
Nii
Ni"
2
1
1.00
0.37
10
32.1
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
exchange interactions
For the
of the two
AB
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>
one
may
spinel structure to
be two saturated and oppositely magnetized sublattices present. The resultant magnetization
32]
SATURATION MAGNETIZATION
149
BB
AA
T<=
125 9
Distances
125 2'
7938'
MeO
Distances
MeMe
r s
=a(l
a(iu
+ u)]/n + itfT

Fig. 32.1.
Some of the
make
and
tetrahedral
ion.
and octahedral
sites respectively.
The
large
open
circle represents
on an oxygen
The
3/8.
The
figure
is
drawn
for u
>
3/8.
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
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
moments
as determined
by various
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
by Hund's
There are at
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
may
occur (see
and octahefrom neutron diffraction 9.2), which has not yet been
the tetrahedral
proved experimentally. The antiparallel orientation of the magnetic moments of the A and B ions has been demonstrated for Fe3<I>4 [Sh 1 ], NiFe 2 4 [Ha 2] and MgFe204 [Ba 2] and [Co 1 ]. A problem is presented by the magnitude
of the saturation magnetization in the case of MnFe204. Neutron diffraction experiments on several specimens have shown [Ha 3] that at 4.2 K the average magnetic
moment of
ions
on the octahedral
sites is
twice as large
responds to 4.6
/tfl.
hard to explain.
An explanation for the resultant moment of 4.6 hb has been given by Harrison
et al.
Mnm and
Fe 11
ions.
An interesting
zinc ferrites in
by the mixed
ZnFeJE.[M^_ a
Since,
Fe>.a]04.
ions, the magnetization
ferrite,
of the tetrahedral
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 nonmagnetic ions can lead to an increase in the saturation magnetization. Apart from Znn and Cd11 [Ve 2], the nonmagnetic ions Ga [Ma 1 ] and In [Ma 2]
and
since the
,
32]
SATURATION MAGNETIZATION
pronounced for tetrahedral
sites
151
and
moment
/hjj
should
for 8
rise linearly
1,
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 BB exchange interaction, which remains unaffected.
9.2,
the
lattice will
then
that the ions within one sublattice interact less strongly with each other
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 magnesiumzinc 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
f.c.c. lattices
having an edge
a.
Owing
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
is
independent
B lattice with
A lattice
this is
immediately
clear.
The
Mbi
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
not affected
by a
re
moments
in
the
way
in
sublattices
an ex
pansion of
exerted
sublattices is necessary.
by the
sublattices
Fig. 32.3.
For constant
total magneti
zation
B the
sublattices Bj
can be com
Hbi,B
or more generally:
iiiMb + (2 i)Afej.
exchange energy in the B lattice is also indepen
From
If,
we put
and
j8 2 ,
stants
we get
2/8i,
has
an internal exchange
zation
is
interaction),
sublattices
find:
not
parallel.
According to
we then
32]
SATURATION MAGNETISATION
153
j8i
= j8andj3 a = ij8.
take
place
in
(32.1)
For the
the
lattice
the
two
interpenetrating
f.c.c. lattices,
lattice
do not
arise.
now:
ai
and a 2
= 2a.
(32.2)
Since
will
we may
expect the
A A
lattice;
no experimental indications of
On
B lattice angles
(32.3)
The
Mo =
The curves found experimentally
theory
(/8
(1
 3/4p)MA
two
(32.4)
for
by the
formation
explained by Neel
[Ne
7] as
and
ferric ions
i.e.
on
hedral
sites,
The
ferrite
ZnFe2C>4
paramagnetic.
From
the foregoing
it
might be
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 nonoccurrence 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 nonmagnetic ions on the octahedral
sites
?
K)
smallestconcentrations. Examples
are substitutions of Al m
[Go
3 ],
/
'
[Ma
2]),
Sc ni [Ma
2],
Ni"
be explained very
satisfactorily if
A negative exchange
20
also
40
60
80
*T(K)
Fig. 32.4. Specific heat in cal per
gram mole
cule for
ZnFe204
as a function of temperature.
Van
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
on
The
sub
ABO3. The
La
mMnin 03
m
Can Mnivo 3 ,Lara Mnni 03BaIIMnivo 3 LainMniiiOs  Srn Mnxv03 and in the
,
corresponding
Srn Co IV 03.
and
cobaltites.
all
At
sufficiently
low tempetri
ratures
valent
and
32]
SATURATION MAGNETIZATION
155
B (Fig.
32.4)
The
highest Curie
point
is
temperature (90 K)
(T (gauss cm3/g)
"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.
100
moment
moments
in the case
where
all
ionic
2].)
We
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
According to
may
magnetization
T for
ferrites
see for
and
9.6.
all
It
all
simple ferrites
32.7).
mixed zinc ferrites show a fairly normal s Normalized curves for simple ferrites as given
by Pauthenet [Pa 1 ] are reproduced in Fig. 32.8. In the case of CuFe2C>4 and MgFe2<I>4 these curves are highly dependent on the method of preparing
156
(T (gauss crrp/g)
I 120
[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,
of the
occur on both
lattice sites.
The form
versus
T curves in
theory. If
we assume
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
the sublattices).
As a
result the
M
be
versus
T curves
The
of the
lattice will
be
lattice will
convex.
total magnetization is
lattice
lattice,
will
1.0
0.8
V
Fig. 32.8.
Ms
M
0.6
1
Normalized curves
jt
NiFe 2
4
0.4
2 3 4 5
5^
>^
Co Fes O4 Fe3 O4
Mn Fe2
O4
0.2
0.2
0.4
0.6
0.8
1.0
T/Tc
32]
SATURATION MAGNETISATION
700
157
MetfZnFe2
600
/}
makes
lattice
Jc
(c)
\\^
500
e '
U0.5 + Feo.s
BOO
T c
will therefore
Nr>
positive value of a
makes the
lattice
Weiss
ler,
field in
the
400
(v
smal
300
600
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,
in porous substances.
The
200
100
relation
between a at
K and
the
tib
given by:
200
TlB^
where
M
'
Nfis
a =^^. 5585
cr,
Ki (32.5)
27:
0.2
0.4
0.6
0.8
1.0
I
MeFe^3i
Zn ftaO
fc
is
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
7000
6400 6000 3800
80
400
300
585
92
80 50
25
480
425
90
56
270
135
520 585
455
30
31
2000
1800
27
65
120
440
670
69
330
4200
310
3900
158
[CH. VIII
Owing
A B
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
in Fig.
cannot be predicted
how
the
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
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
of the Ni 1  g Zn 8 Fe204
series.
33]
SATURATION MAGNETIZATION
4tlMs
159
(gauss)
Ni FezsAlg 4
T(K)
T vsS c
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
[Go
4].
stance at
room
temperature,
it
if
Mni_8Zn8Fe 2 04
increases with 8
8 is equal to 0.15
and
for
versus
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
160
[CH. VIII
part of
its
made
principally
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,
and
9.3b.
The l/x
ples for
yields
versus
T curves
is
of
ferrites
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)
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
800
Fig. 33.1.
1000
1200
1400
T(K)
The
of temperature for
MnFe20 4
The asymptotes
and Fe30 4 (after Kopp, see [Ne 1]). drawn in with the theoretical spin32.1.
33]
161
Cs values per gramion 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
C#Wn
C2
Wii)
2 )
and
Ta =
'
(W112W12+
versus
= CiC
(2aj8)
C1
(33.3)
C2
T curve is
related to
r6
which
is
given by:
(33.4)
(a,j8
>
0)
we have \Ta
> Ta
'.
Figure
33.1 gives the asymptotes for high temperatures with the theoretical spin
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
molecular
field
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 shortrange 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
temperature behaviour
is
not influenced by
this,
and
Ta
will therefore
162
[CH. VIII
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
1/x versus
This
Now C2 is
approximately equal
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
lattice
lattice
too large
small). Thus,
when
we may
is
which
is
tization.
This
is
what
results
shown
a>
34. Crystal Anisotropy
34.1.
Ki and fa
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
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
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
JSTi
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
Okl
J >
Ra2 Ga2
Obtained from microwave measurements; the values not denoted by a were found
from
b
*
static
measurements.
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
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
21STil/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
840
812
164
transitions.
[CH. VIII
is
an
ex
and
and frequencies
and
54.3 respectively.
An
measurements by Bickford
same author, but from microwave measureno different from these. The variation of K\ with tempeis
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
mag
Upon
the cube
aligned
is
[Do
2]).
Bickford [Bi 3 ] has examined the change in the crystal anisotropy constants
of Fe304
when
CoFe3 8 04
where 8
= 0,
0.01 or 0.04.
By
anisotropy of magnetite
shifted
*3 0l
UO'erg/cm 3)
i
"'j/
10
15
"
Fig. 34. 1 .
Temperature varia
tion
100
of crystal anisotropy
200
300
400
500 constants
K\
and
Kz
of
+
T(K)
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
with cobalt
the value as
He
is
only one
six
cobalt
is
site
the cobalt
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 cobaltsubstituted magnetite Co 8 Fe30 4 (After [Bi 3]).
stant
.
in the spin
have a
half
that
is
no
orbital
moment
+;
K2
(^erg/cm3)
1
V
Ll
1,
SSOAI
SOM
Co^Fe>t*
X
100
o/
200
so
2S0
300
350
 T(K)
Fig. 34.3.
versus temperature
for
After [Bi
166
[CH. VIII
With most ions (Mn11, Fe11 Ni11 Cu11) the orbital moment is quenched ( 3.2) and the spinorbit 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
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.
In
ferrites
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
found that in
where
<
annealing,
and moreover
From an
analysis of the
measurements
it
and
in
The same
al.
of polycrystalline specimens.
The
for
ferrous ion
promoting
diffusion.
and cationvacancy 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
Cos
2.0
Fe^Oi
and
of eq.
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
[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
is
found when
the specimen has been aged for three days at the lowest temis
is
much more
noyer and Bickford the annealing time was 510 minutes at 100 C. The phenomenon of magnetic annealing has long been familiar as far as
alloys are concerned,
and various
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
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
mechanism
could give
168
[CH. vill
this
mechaeffect this
,
1 ]
in (11.9)
which has
approximation
fact found.
will
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
between two
cobalt neighbours
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
face,
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
Aioo
and
The results
are given
in Table 35.1.
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.
and
according to Bickford
[Bi 4].
The
on poly
cristalline
specimens of simple
and on a
series
of nickelzinc ferrites
35]
LINEAR MAGNETOSTRICTION
169
10 e
T("K)
Fig. 35.1.
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
ferrite
with Fe3C>4
it
Nio.56Fe n o.44Fe2C>4.
H curves are
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
is
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
this process 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
predominates at
difficult directions
fields in polycristalline
specimens
we
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.
(After [W"i4]).
$36]
DYNAMIC PROPERTIES
is
171
The manga
much used
much
ferrous
all
field
.
strengths has
an absolute
10 6
36.
36.1.
Dynamic Properties
line
caused by ferromagnetic
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;
fine is
determined to a great
minimum
line
widths of approximately 50 Oersteds (see for example Fig. 36.1). The results of
on
ItlOU
fi[ro<?]
100
[1111
80
1 I
<
sonance
line
shapes measud.c.
magnetic
principal
60
along
the
660ei
40
\Le
crystallographic
SSOOe
46 Oe
directions.
20
mately
sec,
U mm
room
2]).
at 9.3
kMc/
at
temperature.
3000
3200
3400
3600
(After [Di
H(0e)
172
[CH. VIII
effect
A dimensional
is
occurs since
line
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
AH
(Oe)
goo
300
Fig.
36.2.
TM
350
Ferromagnetic resonance
line
width
AH
as
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]).
sec.
is
tivity
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
sonance
field
= AH/H.
36.3
it
(36.1)
is
From
ions
and
follows that a
of the order of
magnitude of a
no ferrous
and
rises to
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
width
MnZn
resistivity
unknown) amount of zinc and having a of about 104 ohmcm. (After Ta 3]).
= 2H/<oAH =
1/aw,
(36.2)
is
The shape of the narrow ferromagnetic resonance curves strongly resemwhich is to be expected from (23.12). The difference is that at equal halfvalue 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 highfrequency 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
An
phenomenon
as given
by Suhl was
moments
sites
given by
(Mtotal)B
(Afspin)B
(Aftotal)^l (Afspin).4
'
(36.3)
from which
value of gett
it
is
174
octahedral
site.
[CH. VIII
on
The fairly high value of the g factors for NiFe2C>4 and Co2Fe2C>4 can explain the difference between the spinonly value for
collected in Table 36.1.
1ST
Fig. 36.4.
The
value of y."
in arbitrary units as
a funct
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
lowfield
4000
H(0e)
the magnetic
moment
4 is
very satisfactory,
Mn11
TABLE
EXPERIMENTAL VALUES OF THE EFFECTIVE
Ferrite
g
36.1
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
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
halffilled
175
of which have a
3d
shell
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
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
is
necessary to
know
the
on
sites,
similar
been carried out by Smart [Sm 5] in the NiFe 2sAl8C>4 system. From susceptibility measurements on nickelaluminate Smart deduced a g
value gNi n (tetr)
36.2.
= 3.5
on
tetrahedral sites.
The movement of individual domain walls can be studied on socalled "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.
of a domain wall parallel to the surface of the crystal in the case of Fes04 and a
nickel ferrite having a composition (NiO)o75
(FeO)o.25Fe2C>3.
Oscillo
scopic observation of the secondary voltage across a coil shows that this voltage remains
Fig.
36.5.
Singlecrystal ferrite
and
that therefore
mw
then
(After
[Ga
3].)
176
8
[CH. VIII
T'201K
Nig 75 FenxFe*, 0,
(Kl
3cm/sec)
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 factor two.
TABLE
36.11
THE DAMPING COEFFICIENT a OF (23.10) DETERMINED FROM DOMAINWALL 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
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
BaFe2 04.
40,
S~Me2 Fe4_08
60
100
BaO
Fig. 37.1.
MeO
Composition diagram for the ferromagnetic
ferrites.
The symbol
Me represents
178
FERRITES WITH
firing at
[CH. IX
produced by
from mixtures of compounds, for example carbonates The method of preparation is analogous to that for ferro
magnetic
there
is
spinels.
On
BaO and
a point which represents the nonferromagnetic 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
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 MS and MY, ([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
O"
Ca11
Sr"
Ba" Pb 11
1.32
It is also possible
and
tetravalent ions.
by the trivalent amount of a combination of divalent For example, 28 ferric ions in the compound re
37]
179
placed by 8 cobalt ions and 8 titanium ions yield a formula: BaCo nTi8 IV Fei22sOi9 (see [Ca 2]).
8
<^Y)
37.2.
of the closepacked
struc
hexagonal structure
interstices in
(a)
are in the
ABAB etc.
to the
layer
do not
lie
ABCABC
new
triangles.
On
this layer
can
now be
placed a
shown in the diagram as A. These ions are also closely packed in a horizontal plane. With a hexagonal closepacked 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
The cubic closepacked 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.
oxygen
180
FERRITES WITH
[CH. IX
bottom ion
sufficient
information
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 crosssection through a mirror plane containing
of threefold symmetry. This
three times.
The
means
that
all
S=
Me^Fe4
Fig. 37.3a
Perspective
re
presentation
structure
axis
of the spinel
the
[111]
with
vertical.
The hatched
ions
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
some oxygen ions are replaced by barium ions, which are approxisize as oxygen ions (see Table 37.1). For a complete desis
37.3.
M
crystal
37]
181
S=
Me 2
E
Fe^ 0$
4$+2f
*
Fe ,Me
^2
^\
axis vertical,
drawn
The
of threefold symmetry. All ions not lying on one of these axes occur three times, as shown schematically by broken circles in the top layers. The small white and black circles represent respectively ions on octahedral and tetrahedral sites. The arrows indicate the
relative orientation
sites.
182
FERRITES WITH
[CH. IX
M=
BaFe l2
19
4$
+2$\
^
Fig. 37.4. Crosssection
^\
M,
with the c axis vertical.
The arrows
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 aHock by 180 about the c axis.
are mirror planes,
37]
183
eral
approximately PbFe7.5
of 10 oxygen
Mn3.5Alo.5Tio.5O19.
layers.
cell consists
is
the a axis
5.88 A.
in Fig. 37.4. In
an elementary
oxygen
The magnetoplumbite
(Fig. 37.4),
up from
oxygen layers
being blocks
S and
this
R (for a perspective
T
drawing of
Y structure.
The
latter
R* and S*
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
why
structure contains 10
and not 5
is
oxygen
layers.
In general
it
block
passed
in a structure the following blocks must be rotated over 180 around the
184
FERRITES WITH
[CH. IX
The
The
6],
would be possible of two more then obtained would not contain the but the block
It
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
sites in sites
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.
Ba 2 Me 2 Fei20 2 *
The
37.6.
compound Y,
consists
The
symmetry
If,
of
however, the
upright edges of the parallelepiped are not taken vertically but along the
it is
possible to find
an elementary
cell
through only
oxygen
layers.
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
4e*
+2*
4e*+2e +2
8e+2^ +*
O
^)
*
fia
"
Fig. 37.6.
Crosssection of the
Y structure
with the c axis vertical. The arrows indicate the spin orientations,
all
of threefold symme
^
The
structure
is is
^\
composed of
alternating
A
T
and
The rhombohedral
repeat distance
indicated.
186
FERRITES WITH
[CH. IX
in Fig. 37.3b,
in
which there are now, one above the other, two layers with barium ions;
for a perspective drawing of the
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 buildup 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 MY and MS 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 Xray 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 crosssections through mirror planes containing the c axis of
37]
187
W= flbMef Fe K
27
^
Fig. 37.7. Crosssection of the
^\
^\
^
The arrows
indicate
vertical.
The drawn
of threefold symmetry.
cross
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
188
FERRITES WITH
[CH. IX
4.
i^e & e o
*Ol
G e o
'4
;
lie
4i
+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. Crosssection of the
The arrows
indicate
The
of a block by
The
structure
M and the Y
and 37.6
respectively).
37]
189
Number of
Chemical
composition
Symbol
Crystallographic
layers per
c axis *) in
Molecular
weight
Xray**)
density
buildup
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
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
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 Xray densities of the most important of these compounds are given in Table 37.111.
TABLE
37.111
XRAY DENSITY dx AND MOLECULAR WEIGHT Af OF SOME OXIDES WITH HEXAGONAL CRYSTAL STRUCTURE.
Me
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
Co
Ni
1577
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
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 Xray
*)
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
have a
W.
Many
The
W compounds,
field
like
a powdered material
of force.
themselves in a
magnetic
crystallite will
be more or
glass plate,
on a small
field is
When the binder is left to dry and afterwards the magnetic field switched
of the
glass.
with a diffractometer
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 Xray diagrams. It appears from these diagrams of
for
M and W, and
these
specimens the
hexagonal axis
case with
magnetic
field; thus,
the spontaneous
As
is
the
this axis is a
preferred direction.
Y specimens,
means
axis lies perpendicular to the magnetic lines of force, the directions of the
of the
The
result
is
hko
reflections
*)
it is
38]
SATURATION MAGNETIZATION
191
38.1.
It is
ions in the
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
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
magis
chosen,
an upward direction
The
starting premise
Me
Y 6
^a
Fig. 38.1.
^x
^\
^\
^a^x^^^3k
moments with
respect to the crystal lattice
is
the
Schematic representation of the predominant superexchange interactions in and the Y structures. Each interaction is indicated by two connected heavy lines
*)
The
in 39.
of the ions.
192
FERRITES WITH
[CH. IX
again that the superexchange interactions between the magnetic ions take
place via the intermediate oxygen ions,
it is
this is
again a
d electrons
/
> =
lie
5) see 8.1.
As
for
the spinels (see 32.1) Gorter estimates the magnitude of the exchange
interactions
MeOMe and
the
angles
<f>
MeOMe
is
[We
2]).
which
is
containing barium, are directed downwards. The reason is that the loxygen2
large because the appertaining angle
<f>
large (approximately
moments of these
is
ions antiparallel,
is
smaller
basal plane
from the ion to the three surrounding oxygen ions in the and this promotes a high loxygen2 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
indicated
by the quantity
j8,
it is
relatively small
owing
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
it
(2.3 A).
it
(450 C)
From the fact that the Curie point of the compound is high may be deduced that the octahedraloctahedral interaction will
cell
of the
Y structure,
lies
[Go
7] is the octahedral
ion 2 which
If the
magnetic
moment of
right, the
left.
this
magnetic
moment of the
be oriented to the
In the
now
is
is
displaced in such a
way
More
over, according to
Braun [Br
6],
the ion 3
is
distance
from
this
(now comparable
block).
The loxygen4
interaction
now
important and
is
of the tetrahedral
38]
SATURATION MAGNETIZATION
lattice.
193
ion 3 is now oriented in accordance with the 3oxygen4 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
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.
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
unit
is
schematically
all
indicated
by
BaFe^Oio,
magnetic
+ 7  2  2) X 5 = 20
is
Bohr magne1].
Measurements on
hydrogen tem
up to 26,000
In Fig. 38.2 the saturation magnetization perature for BaFei 2 Oi9 (corresponding to 8
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.
T=
20 C one finds a
= 72
is
gauss
cm3 /g,
corresponding to
information
4wMs =
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 Fei22 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
.
8 equal to 1.2
and
'
38.3.
per
and mixed
W compounds
gram
for a
number of simple
is
38]
SATURATION MAGNETIZATION
195
case of these
lines are
compound BaFei20i9
structure. It appears
gives the highest saturation magnetization at low temperature; evidently in this case, just as with spinels, the zinc ion occupies tetrahedral sites
and
moment
sites.
ct 2 o,
Table
room
temperature,
and the
W compounds.
690
(C)
structure,
measured on polycrystal
specimens at a
field strength
of 6600 oersteds.
TABLE
SATURATION MAGNETIZATIONS AT
20 C
<T20
38.11
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
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
196
FERRITES WITH
[CH. IX
magnetization of a
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.
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
W structure in
Me
ions are
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
last
38]
SATURATION MAGNETIZATION
TABLE
38.IV
197
20 C
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
structure,
measured on polycrystalline
198
FERRITES WITH
[CH. IX
are seen to be
what
is
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
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
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
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 23 favours this orientation. The same holds for ions 3 and 4. Moreover, since each ion 3 interacts with six ions 4, and since the 34 interaction
is
strong, this will have the effect of favouring the parallel orientation
all
of the moments of
ions
4.
is
be
38.5.
points
20 C.
37]
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]
SATURATION MAGNETIZATION
80
201
s
MeZn
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
Tc
C
410 440
360
gauss
cm3 /g
50
46
58
structure
can be considered crystallographically as a superand Y, the experimentally found values for the
cell
of substances with
structure
is
for the
M structure
taken for
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
[CH. EX
M, and
Me ions
R blocks
of the
structure.
c AXIS
(11.6),
The
crystal anisotropy of
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 Xray 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 rightangles 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)
BaFeiaOig as
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
room temperature
all
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
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
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
room tem
20
(I0
3 0e)
204
the
FERRITES WITH
[CH. IX
method
it
K from (11.6)
will
single crystals
and on specimens
consisting of
whose
(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],
same
as found
by
direct (static)
magnetic
measurement.
TABLE
ANOSOTROPY CONSTANTS
JTi
t
,
39.1
ANISO
Compound
Symbol
10
Ms
gauss
Hi
oersted
erg/cm 3
*)
erg/cm 3
*)
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
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
C02Y C02Z
single crystals.
185
28,000
13,000
270
Fig. 39.4
4nMs
Hg and
ferrite
Ki
for
BaFei20i 9 as a function of
temperature.
The same
quantities for
C02Y
[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
The top angle O of the cone is represented Above 215 K the basal plane of
39]
CRYSTAL ANISOTROPY
205
Kl
(to
6erg/cm 3
100
200 300
400
500
600
700
**T(K)
Fig. 39.4. Saturation magnetization
Mi,
crystal anisotropy
K\ and
anisotropy field
H^
is
which
there
is is
characteristic
strength
H = 0,
As shown
compound C02Z
Above 480 K
the
between 220 K and 480 K the basal plane c axis is a is a preferred plane and below 220 K the material exhibits a preferred
preferred direction,
cone for the magnetization. Mixed hexagonal ferrites can be made which, at a specific temperature, possess an anisotropy that is found to he between the extremes of BaFe^Oig and
The anisotropy
C02Y. An example is the series of mixed crystals of the compounds Co aZn 2  8 Z constants at room temperature are given in Fig. 39.8 as a
206
FERRITES WITH
[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
jH* of
C02Y
as a function of
temperature.
200
Fig. 39.6.
300
400
+T(K)
Equilibrium orientation with respect to c axis
CoaY
as a function of tem
39]
CRYSTAL ANISOTROPY
207
(Oe)
30,000
20,000
10,000
K,+2K2
(Xfierg/cm3)
as
1.0
i.s
zo
Fig. 39.7. Saturation magnetization
Af
and anisotropy
field
H*
(nterg/cmJ)
K,+2Ka
Ki of
cobaltzinc
compounds
208
1
FERRITES WITH
[CH. IX
The compounds
at the ends of
the diagram,
and a
preferred plane for the spontaneous magnetization. For the mixed crystals
a gradual transition
sotropy to the other.
found as a function of
^erg/cm 3)
Ni Co 
Zn
Fig.
39.9.
Crystal
anisotropy
Kj.
of
several titaniumsubstituted
compounds
metal
ion)
with
M structure as
(or
a function of the
titanium
content.
divalent
K,+2K2
**
An
It
In the
compound M,
is
example of the
effect
on
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
of magnetization.
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,
39]
CRYSTAL ANISOTROPY
8000
209
c (erg/cm 3 )
A
f\
f\
i
/X
^1S2^e
0M^
j
14000
A
K
1
CK:
f\
'
>
,/
\J
\
4000
J
;in6p
J
\
.
,
1
360
tip/
K
1
e 30
8000.
c
/20
*3eK3 sir>ffj
ffiO
so
240
a
Fig. 39.10a.
300
The rotational
(/>).
stiffness
by
5000
d 2 Fg
= 36*3 sin 6 f
(39.1)
The Fourier
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
.
due to the
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.
some values
of the
stiffness
of #3
210
FERRITES WITH
[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
20
<6
<1
measured on various
the greater
is
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
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.
K\
^ 0.
The
2]
of a preferred plane.
made [Ca
(^i)dip
and
yields:
= (0.044
/*o
/*t
0.0006 im m>
+ 0.240 ^
).10 6
erg/cm3,
(39.2)
where
and
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
structure
In the
structure,
it is
all substantial. It is
makes a
39]
CRYSTAL ANISOTROPY
of the ions on the boundary plane of an
211
tive contribution
still
and S block
remains.
The
tion to
K\
is
negative
( 1.5 Xl06 erg/cm3) and therefore cannot explain K\ of about 4.5 x 106 erg/cm3 at T = K.
may
would have to be
is
it
K2
should
differ
by a
occur.
factor (X/AE) 2 ,
no
fluctuations in
is
AE
The
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
34.2
we saw
.
of the order of 50
cm1 From
structure
is
Table 39.1
it
about
It
2x 106
cm1
is
appears
such as to give
rise to consi
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
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
and
is
CHAPTER X
2]
MnsA^SisO^. By
Yra + Alm
made
Mnn +
Y3AI5O12. In
1956 Bertaut and Forret [Be 6] reported the preparation and magnetic
properties of Y3Fe 5 Oi2,
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 smal
sites just
as in
somewhat
According to
is
and Gilleo [Ge 3] the tetrahedraloxygen distance in yttrium garnet A and the octahedraloxygen 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,
octahedral
difference
occurring in the garnet structure are occupied by the metal ions. Perhaps
this fact contributes to the
respectively,
other hand, too small to be substituted for an oxygen ion, each of which
ions
surrounded by 12 oxygen ions. The closepacked structure of the oxygen is therefore not retained, but the yttrium or rareearth ions occupy sites which are rather irregularly surrounded by eight oxygen ions of which
cell,
A and four at 2.43 A. The edges of the cubic Y3 Fe 5 Oi2, are 12.37 A. The Xray
g/cm3
.
density of e.g.
Y3 Fe5 Oi2 is
5.17
The iron
ions
41]
SATURATION MAGNETIZATION
213
ferrites.
moment of
is
due to the
The rareearth 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.
have a saturation moment which is much larger than the resultant magnetic
dominates at low temperatures and that of the iron ions at temperatures near
the Curie temperature. Therefore a compensation point of the magnetization
is
The intrinsic
not too
susceptibility,
fields, is
ferrites at
30
t^
20
5Fe2t )33Me2 03
75
1e=GdJb OyHoLu
i i
 Ern 
'7 n
10
VV
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.
Bertaut [Be
7]).
214
[CH.
is almost the same for all rareearth garnets The magnetic moments of the rareearth 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
filled
4/ shell
is
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
hyperbolic, as should
et al. [Al 1]
have determined
and
hedral
sites.
are 0.474
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
on the octahedral sites (here a), in agreement with the observed values.
The
line
and
is
chiefly of yttrium
The
smallest
at 3
cm
wavelength at
room
temperature. This
[CI
1],
is
al.
no
orbital angular
from
this fact.
The
saturation magnetization at
room temperature
is
do not occur
interesting
microwave frequencies. The garnets containing rareearth and are therefore not very from a technical point of view.
at
42]
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
is
no
fluctuations
which should
make
TABLE
41.1
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
commonly used
compounds which are to form the ferrite by a solid state reaction are mixed homogeneously and wetmilled, usually in a steel ball mill. The dried powder
which
may
or
a particular shape,
is
prefired
initial
chem
prefired
powder
is
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
it
product which
in
many
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
shows a
that the
= 0.1.
The
firing
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
which
is
obtained (p 0.05), a picture of shown in Fig. 43.2. The firing temperature necessary in order to
is
on
43]
ISOTROPIC SAMPLES
217
ferrite,
sintered for
Ave
minutes
at
218
STRUCTURE OF POLYCRYSTALLINF
FF.RRt.TES
[CH. XI
Fig. 43.2.
Same
now
sinterett for
one minute
at a
tempera
ture of 1435
X.
Porosity
0.05.
43)
ISOTROPIC SAMPLES
219
MnFcO
magnanese
ferrite
with a segregation
220
[CH. XI
mm
exaggerated case of a surface layer on a
the composition
the
Fig. 43.4.
feirite.
An
sample
has
43]
ISOTROPIC SAMPLES
221
For instance a porosity of less than 0.1 is obtained for CuFe2C>4, MnFe2C>4 and NiFe2<I>4 if the sintering takes place at temperatures of about 1 100, 1200 and 1400 C respectively. These temperatures are related to the melting points, which are 1300, 1500 and 1650 C respectively. It seems that nickel ions in particular do not diffuse easily in ferrites. The addition of zinc lowers the firing temperature of most ferrites. If samples of Me sZni 8Fe2C>4 with various values of S are sintered at the same temperature, the
will
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 finegrained 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
ion.
composition of the
ferrite it
Where
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
light colour is
a reducing atmosphere,
if there is
may
be produced. Inhomogeneous
no equilibrium
between the sample and the atmosphere. Often a socalled surface layer will be the result; an exaggerated case is shown in Fig. 43.4 (see page 336). Phase
diagrams of the ironoxygen and manganousironoxygen systems have been
given by Darken [Da
1]
8] respectively.
it is
plete phase diagram. For instance in the case of Mn,Znferrites the series of mixed crystals of MnFe2C>4 and ZnFe204 form only one single line of
222
[CH. XI
field of the quaternary system MnZnFeO. 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
a few cases,
e.g.
in the system
MgMnFeO where
the
first
compositions
is
An
important point
to
all
socalled
stoichiometric
diagram it is necessary to place equal amounts of compacompounds in the corners. This is done in Fig. 43.5, thoug in one corner of the triangle no spinel compound exists but rather a mixture 3MgO + ^02. In this method of representation, introduced by Jonker [Jo 6], the three different metal ions appear with equal weight and the simple compositions as MgFe2<I>4 MnFe2C>4, MgMn24 and MgMnFeC>4 are found on simple locations in the diagram. In the MgOMnOFe2C>3 or MgOMn304Fe2<]>3 diarable
grams, which are often used, spinel compounds, apart from the simple ones,
is
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
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 nonstoichiometric compounds with an excess or a deficiency
*Q
MgFe2
t/
Fig.
oxide system.
The
area be
lines repre
with
spinel
structure.
by slow cool
3MgO+'/202
Mg2Mn0i
MgMn2Qi
MnjOt
ing.
43]
ISOTROPIC SAMPLES
223
INTERNAL DEMAGNETIZATION
owing to the porosity of the specimens. An impression is obtained by measuring the socalled
From
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
by curve
a) in Fig. 43.6.
in the
and
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
Ni
is
obtained,
and
it
increases raleft
with
re
ference to Fig. 43.7; a crystal lying crosswise affects the pattern of the
lines
way
as
an
air cavity
influence
of force must
0.20
11
0.15
bf
la
0.10
\tQ
Fig.
1
43.6.
A
1
c
1
cient
Ni as a function of porosity p;
ferrite
X f'0.22
0.05
Nio.sZno.5Fe204,
curve b)
\f~0J50 f= 0.78 t
specimens of
stal
structure
if = 0.91
0.2
magnetization,
anisotropic
OA
of orientation.
224
[CH. XI
crystal structure).
The
is
perpendicular to the
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
It is
under
one
third.
43.4.
MECHANICAL PROPERTIES
By
it
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 facegrinding and centreless rotary grinding. The ground surfaces can be
wet grinding
very well cemented together with adhesives such as plastics of the aethoxyline
at
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
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
43]
10 to 30.
CRYSTALORIENTED SAMPLES
225
When using these data it must be taken into account that the tensile
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.
by a
.
03
0.2
0A
ferrites
of
Fig.
43.8.
a\,
era,
+P
strength, strength,
magnitude
It
depends on
Fig. 43.9.
The
vari
porosity p.
The curves
a crosssection of 2
mm
mm, and
same
independent
ferrites, after
[Bu
2].
X 10 2
cal/seccmdeg,
capacity,
about
Fig. 43.9.
Young's modulus of
nickel
(I0*dyne/cm*)
after
44. CrystalOriented
Samples
In the cera
mic materials use might be made, for instance, of the nonspherical 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
[CH. XI
slight
at high temperature,
[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
exerted
on
the crystal
r=^isin26.
This torque
Fig. 44.1. Equilibrium orientation
(44.1)
135
18()
o
.
M.
in a fixed
o 9()
*>
sotropy
is
when an
external field
e
S reater thafl
1K^M
... ,.,
^
,.
fidd strength
is
the magnetization
....
applied at an angle
to the pre
H,
(0
90),
ferred direction.
when
the field
is
applied.
remain
torque.
however,
H = y 2 Ki/M
s,
= 45,
with a
maximum
is
field
should be approximately
is
//=]/ 2 Ki/M;
in the case of
BaFe^Oig
is
about equal
most
little
In this respect the plateletshaped 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.
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
and by subsequent
sintering.
44]
CRYSTALORIENTED SAMPLES
227
much
is
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
foliate texture
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
it is
is
when
about
90%
The phenomenon of
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
is
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
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
[CH. XI
C02Z
we thus approach
is
determined
by the
porosity.
The
terials
orientation of crystals
by a magnetic
is
field
HA
HA
is
mixed
crystals
Me2W compounds.
[Lo 2] in which the materials are prepared from a ferromagnetic oxide whose
crystals are oriented with help
An
BaFei 2 Oi9
+ 0.8 CoO +
1.2
ZnO +
2 Fe 2 03^BaCoo.8Zni.2Fei 6 027.
The
tals
is
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.
and
The
a preferred plane
corresponding to
this.
The anisotropy of this compound, however, is much more conventional way. Several of such reactions have been described by Lotgering [Lo 2].
CHAPTER
XII
ELECTRICAL PROPERTIES
45. D.C. Resistivity
The d.c. resistivity of oxide materials can be fairly reliably measured by means of a sonde method as illustrated schematically in Fig. 45.1. The same current is passed through a resistor R and the ferrite rod F. The voltage between points B\ across a part of the ferrite rod is compared with the vol
known resistance JR. For an accurate measurement the internal resistance of the voltmeter V should be high as compared with the resistance of the ferrite rod and the resistances of the contacts B{. It is also possible to measure the resistance directly
tage between points B2 across the
ferrite rod,
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.
1]
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
This layer
an extreme
case;
it
a higher
than the bulk, owing to reoxidation, particularly at the surface of the product during cooling, or a lower resistivity than the bulk, as found for example with mixed nickelzinc ferrites of spinel structure
resistivity
[Ui
1].
is
from
and as a
result ferrous
For ferrites the resistivity at room temperature can vary, depending on the 11 chemical composition between about 10 2 ohmcm and higher than 10 ohmcm. 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 tempera3 ohmcm, and NiFe2C>4 with ture has a resistivity of approximately 7.10
230
ELECTRICAL PROPERTIES
[CH. XII
TABLE
RESISTrvrTY p
45.1
AND DIELECTRIC CONSTANT e MEASURED AT A FREQUENCY OF 1 KC/S ON SPECIMENS OF Nio.4Zno.6Fe2 04, COOLED FROM THE SINTERING TEMPERATURE IN DIFFERENT WAYS (AFTER [KO 6]).
Sintering
Sintering
Ferrite
temp.
Method of
cooling
FeO
C
la lb
atmos.
%by
weight
0.10
0.38
ohmcm
540,000
1,300
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
no ferrous
ions,
can have a
resistivity
higher
resistivity
Koops [Ko
low
tric
6]
among
shown
in Table 45.1.
ferrites
relatively
constant.
An
[Ui,
Verwey
7],
et al.
by Van Uitert
1,
a varying
by using
10"
P
(ohm cm)
A
10
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 + &Oie fired at 1250 C in oxygen. The value of 8 is
e
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
Two
regions
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 conductivity a
now
on a
ferrites.
232 a high
resistivity,
ELECTRICAL PROPERTIES
[CH. XII
and one region of compositions containing Fe11 and Fe low resistivity. Measurements of the thermoe.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 (ntype
semiconductor) [Ui
replotted so that
it
more than
In the
ferrites
a value of almost 10 22
semiconductors
results
cm3 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
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
resistivity. It is
said
above that
no
appears
that stoichiometric
NiFegQi or
MgFe 2 C>4,
resistivity
which
is
is
due to a
Nin
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 ohmcm. The explanation of
this substantial effect [Ui 3] is that in the case, for
of
Mn
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
3].
low by the
Mnm
of any Ni
m that may be
Mn11 ions:
and
This
is
related to the increase in the third ionization potential for the ions
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
and
=
where
p~
*' JkT
(45.1)
E9 represents
jump
6] is the
an activation energy which, according to Verwey energy needed to release an electron from the
of the ions in the neigh
[He 2]). The mean free path bourhood is only about 3 A. It has been pointed out by Jonker [Jo 7] that in these non
234
ELECTRICAL PROPERTIES
[CH. XII
/>
0.40eV
/
/
I
/
J
/ZnF**W
Ep0.22eV
O
p
(ohm cm)
0/
ySEpaCBeV
y
Eg
ft WeVj
/
f
'
Ep
O.BeV
0/
*
i
/^
sZnos)t> 97
^DM Fe2
Ep.t).23tV
t aos
W
'
/
1
AW
0.10
OI23iS6789IOIiaai*
Fig. 45.5.
Temperature dependence of
impurity
(intrinsic)
means
that
on the conductivity
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
to
Ep
= 0.198.103
d(log P)/d(l/T).
(45.2)
45]
D.C. RESISTIVITY
235
The
values for
Ep
lie
between
0.1
A high
is
activation energy
ferrite at
resistivity
of the
room
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
among
the ferrites
is
pure
Fe3C>4
31.4,
which
is
associated
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
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
quantities of
236
ELECTRICAL PROPERTIES
[CH. XII
jump
45.7),
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
after
[Do
2].
46.
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
4].
capacitor
finite ohmic resistance of the dielectric (ferrite) and the other representing an equivalent resistance of such a value that the
energy dissipated in
It is
it
is
dielectric.
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 Zi
=jwCv + Rp K
(46.1)
Putting e' p as the real part of the dielectric constant and a as the conductivity
146]
FREQUENCYDEPENDENCE
01
CONDUCTIVITY
237
(a)
(b)
Hg. The
44.2.
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
cm
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]
FREQUENCYDEPENDENCE OF CONDUCTIVITY
we have
239
farad,
CP =
l.ll.lftj 12 ej,'j4/47rd
and
is
Rp
is
expressed
in cm 2
the
d expressed
is
in
cm
entirely
The
e,
T
Fig. 46.1. Equivalent circuit
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
tan 8
= (cjCpRp) 1 = 4iro/w<Ep'.
(46.4)
Brockman
et al. [Br 2]
have discovered that sintered ferrites with a high 1 Mc/s) always have a high
5
).
^ 10
Koop's
results in
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
240
ELECTRICAL PROPERTIES
<j
[CH. XII
and c In general
a.
it is
found that
e is
roughly
may be
seen,
e
The
relaxation in
and
<y + CuM
(46.5)
p
1
Oj2 T 2
and
<s> indicate
and
is
at
The
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
dielectric constant
10,
2].
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
Lowfrequency
value *)
Ferrite
"0
eo
Highfrequency
i
Relaxation
fre
/alue
CToo
quency
(in
kc/s)
According
(ohmcm) 1
0.5106
2
e<
(ohmcm) 1
2.1106
Measured
1.7
to (46.7) 2.0
No.
1,980
1,710
16
13.8
No
la
10
14106
4
200
15
No. 16
Hio.48Zno.48Fe Il: o.o4
28,200
0.810 3
7.710" 3 0.510s
0.310s
~42
t)
210 3
130
100,000
>lt)
2106
2000
1
1.8
2,100
15
30,000
22
4.8 106
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]
FREQUENCYDEPENDENCE OF CONDUCTIVITY
the quantities e
241
and a' 1
(i.e.
the resistivity)
become
It
X J'
}'
Fig. 46.3. Equivalent circuit
with
a high
dielectric
constant.
appears that in sufficiently high measuring the lowfrequency value of e does not differ
fields
much
value.
PHENOMENOLOGICAL THEORY
be assumed that a polycrystalline sintered consists of large domains of fairly well
It
may
for
ferrite
core
ferrite
conducting substance
layers
(i? 2
and
C2).
These boundary
crystal
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
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 (ohmcm)" 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).
e is
very high
^ 10
),
*)
Koops [Ko
6]
0.45T0" 2
242
ELECTRICAL PROPERTIES
is
[CH. XII
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
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 temperaturedependence of the d.c. conductivity (ocl/i?2) and for the relaxation time t. However, according to (46.3), the relaxation time
lowfrequency value,
t
is
that
we come
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 fielddependence of <j and e may, according to this model
be connected with
electrical
breakdown
in the layers.
CHAPTER XIH
Initial
Permeability at
Room
Temperature
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
cussed in Chapter IV. For the general case that the binding of the magnetization to a preferred direction
is
components of the
P*s
(f*w
l)/4^
= MslHf, fa 
= M./J3J
(47.1)
crystallites
initial
perme
( 
1)/4tt
(47.2)
The x
direction
rotation of the the preferred direction of magnetization. out of magnetization M, in the xy plane over a small angle
</>
is
opposed by a
H$;
see figure a.
opposed
by the
H^;
see figure b.
244
[CH. XIII
and
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
(mo1)/4tt
If the crystal anisotropy
is
= (2/3)M /^.
s
(47.3)
field
HA
is
related
and
eq. (11.7).
As a
conse
quence the rotation of the magnetization vector will induce stresses which
For cubic
crystals
page
58):
F*
=l
Kcii
(47.4)
great that the stress anisotropy predominates, the situation for determining
is
isotropic
and
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
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
and
have a pronounced
tered specimens
on
ft
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
dis
47]
10 3
ROOM TEMPERATURE
245
to be
,,,BOO*'
I.3
U.3
4~t
walls
and equal to
5 microns, which, in
125CP
ferrites fired at
&1200
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
ferrites
we
find according
10
NiFe 20i.
^ v
A,
\
SN
k
and according to
w=
60 for
K=
is
5104 erg/cm 3
xsso
ferrites
whose porosity
Fig. 47.2.
The
initial
permeability
make a contribution to ^o which is greater than that originating from rotations. Fig.
47.2 gives the relation between initial per
The
temperature
indicated.
for
each
sample
is
and porosity p for specimens of nickel ferrite [Br 7] and nickelzinc 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
by Gait [Ga
the
4]. It
an appreciable
increase
in
permeability
An
firing
on
the magnitude of
jx
ferrites (the
composition in mol
was
52.5
Fe 2
3,
28.3
MnO
much
and
19.2
ZnO).
as possible only
on
result is
considerable increase in
reproduced in curve a of Fig. 47.3. /xo when the average diameter of the
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 nickelzinc ferrite.
Curve b in
246
6000
[CH. XIII
**
4000
~7^
t
\
\
\ \,
/^~
2000
Is
y^
10
IS
20
'd
(10~3
mm)
Fig. 47.3.
Dependence of the
initial
with spinel
made from
mol
Fe2C>3
28.3%
MnO
9].
and 19.2%
ZnO and b) nickelzinc ferrite with mol% Fe2 3 15% NiO and 34.7% ZnO.
,
After [Gu
For making
is
it
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.
for
example a manganesezincferrous 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.
of
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
For the
we have
Hf
is
The
aniso
tropy
field
smaller than
so that, neglecting
polycrys
(nol)/4ir^(l/3)Ms /Hi.
Since
(47.6)
field in the
H^
is
permeability. Results of
column of Table
The
initial
talline
sample of these
ferrites also
preparation. It
is striking,
are
may
of the crystal anisotropy in the basal plane (for the anisotropy energy see
Table
39.11).
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
the
maximum
10.
value
initial
will
be approximately equal to
it is
Such a
is
TABLE
INITIAL PERMEABILITY
47.1
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
~ ~ > ~
43
35
7
248
[CH. XIII
on the magnitude of no
make any
form walls
It is easy,
however, to
thicksmall.
The energy will be low and the are both determined by Kz from (1 1.6), which is
is
and
owing to
crystal platelets
is
see 43.6
is
and
Fig. 43.7.
obtained in specimens in which the crystallites are oriented with the basal
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
is
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
given for several different compositions. For the measurement of the peris
For a
field strength is
to be expected. In fact,
0.91,
by measuring
of only 2.5
is
in this
way
is
the
C02Z specimen
with/=
a permeability
initial
permeability at
S
room temperature
is
of the
series
Co 8 Zn2Z. For
<
a preferred direction of magnetization (see Fig. 39.8) and ^o is determined by the magnitude of K\. The susceptibility due to rotations is then extremely
small since
Ki
is
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
A curve
of Fig. 47.5,
found for
all series
of mixed
ferrites
and
W compositions.
fi
\
20
Co$Zr>2sZ
i
T20C
10
'
'^
;
no at
room temfor
perature in dependence
1.5
2J0
ferrites
of
the
series
CoxZn2aZ.
250
[CH. XIII
Simple Ferrites
initial
and
Both quantities
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
47.
of the sample
may
it is
and shows a
The
height of this
anisotropy
still
Mixed Zinc
Ferrites
Among
the technically important ferrites are the mixed zinc ferrites with a
1]
had discovered
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
first
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
that, in
most
mixed zinc
the lower
maximum
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
5 Feo.5)i8Zn 8 Fe 2
04
(Fig. 48.4).
Also
maximum
48]
TEMPERATURE DEPENDENCE OF
INITIAL PERMEABILITY
251
252
3000
[CH. XIII
MnisZnsFe2 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 manganesezinc ferrites with spinel structure Mni_8Zn 6 Fe204. These specimens also contain a small ferrous
ion content.
As examples
for the
manganese zinc
ferrites
for specimens
Fe30 4 content
Mixed
Mixed
Cobalt Ferrites
crystals
between
ferrites
made
with such
Owing
needed.
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 nickelzinc
spinel
structure,
ferrites
00
60
7 1 C)
with
NiigZn s Fe204.
'
48]
TEMPERATURE DEPENDENCE OF
600
INITIAL PERMEABILITY
253
(Li'os
e Feo.s)}sZns F 24
n
400
\
o.sc
0.45
s=o. ss\
o.s \
200
*o/
K
2 73200 100
100
200
300
400
700
mixed
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
room temperature. By
substituting
cobalt the
maximum
is
in the
juo
versus
T curve
specimens
The zero points in the crystal anisotropy for varying cobalt content are found at the same temperatures as the maxima in the ^ versus T curves. The peak value of j^o is found to decrease the more the composition differs from FesCU; this may be related to the fact that there are two anisotropics of
opposite sign, the absolute values of which are greater the higher
is
the
temperature of the zero point for the crystal anisotropy of the mixed
ferrite.
500
S=0
400
(to
(Fe3 Q()
i
CogFe3 to*
s
=0.0025
k 300
S=0.005
200
7^
100
}
T150
A^ z^
300
J' 0.01
_
^
5_
:
ty of cobaltsubstituted
netite
mag
Co s Fe3s 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
men
is
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
and shape anisotropy. Similar results have been reported for lithium ferrites and nickelzinc 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
vo
of cobaltli
substituted equimolar
thiumzinc
ferrites, after
[Bu
XX)
2].
300
relation JCi(8)
= (1
8)
Ki(8
= 0) +
Me
8 Ki(S
1)
Fe and
zero at
Mn
make
to be respectively
about
li
and 4
3].
ManganeseFerrous Ferrites
Figure 48.7 shows the permeability versus temperature curves of some polycrystalline specimens of manganeseferrous 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
is
shown
for a
48]
TEMPERATURE DEPENDENCE OF
INITIAL PERMEABILITY
255
1500
a function of temperature.
Fully drawn lines for polycrystalline specimens, the dashed curve for a single crystal,
after
[En
2].
by Enz [En
second
maximum
in the curve
It
was
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 timedependent.
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 manganesezinc
ferrites
have a
high
initial permeability,
which
ferrite
with
Fesd;
in Fig.
and the
initial
permeability pa of
such
ferrites
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
[CH. XI11
T=21C
SO
40
20
T
0C
T22C
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
2500
A
'
\
:
1500
^3
J0 e /.,
^
Fig.
48.9.
Oxide mixtures
consisting:
of 18 FeaOa,
two hours
C in nitrogen
at
mo/%
FeO
respectively the
in
content
expressed
mol%
s s
3].
{j
48]
257
rise to
higher permeabilities.
48.2.
a preferred
magnitude of unity
quence of rotations of the magnetization in the basal plane; Fig. 48.10 gives
the
juo
versus
curves for a
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).
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
magnitude of
^10 is
is
therefore small.
saturation magnetization
r(c)
number of polycrystalline
speci
oxides.
258
[CH. XIII
Po A
400
(gauss
cm 3 /g)
200
100
200
300
400/500 600
700
r(K)
/<,+2)<2
T
V
Fig. 48.11.
bility
1.5
2.0
300
T(C)
MX)
500
Fig. 48. 1 2. Initial permeability versus temperature curves for ferrites of the series Co a Zn2 aZ.
48]
TEMPERATURE DEPENDENCE OF
39.1
INITIAL PERMEABILITY
259
In
we saw
that,
at
room Zn^L a
temperature,
C02Z has
a preferred
of mixed crystals
= 0.6,
(see
this
change of sign
will
occur at a
some of these
drops rapidly
/*o
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
Tc
which the
maxi
mum
composition of the
Co 8ZnaZ.
Curie point Tc
with S
rature
is
plotted for
it is
= 0.65 2.0
is
not caused by the approach to the Curie point but, as in the case
first crystal
two specimens
and
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
room
temperature. This
is
the
same
260
[CH. XIII
S = 1.5
l
f\
~\&=2D
S=1J0/
fto
12
~fr
200
too
100
200
400
Fig. 48.14.
As
Fig. 48.12,
but
now
for
compounds Co g Mg2Z.
w versus T curves
maximum
initial
of some
Co s Zn2 8 Z compounds
in
given.
permeability
series
is
Co 8Mg2  6 Z. As
juo
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.
The permeability of a magnetic core measured with a very small field strength
is
ju r ev.
When
/ire v
the core
The
solid curves in
49]
Fig. 49.1
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
latter less
than a
field
Hp u
of measurement;
fields
this is indicated
by the
49.1.
In the case of
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
more favourable
since
frev
Fig. 49.1.
The
reversible permeability of
polarizing fieldstrength
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
The arrows
represents
the permeability to be expected in the case where the material has no magnetic anisotropics
is
The
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.
and polarizing
in that case there are
mutually
parallel.
no
difficulties
In Fig. 49.2,
case
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
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 =
measuring
field.
Owing
phenomenon of magnetostriction,
tively
ferrite.
by applying
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
of the
tensile stress
stress
related
 = (477/3)^/^)1^1,
1
(large
ct)>
(49.1)
in
which A 1
is
49]
263
u
Fig. 49.3. Orientation
k
is
T
ferrite
first
derived
a factor (dx/d) 1 / 3 must be added to the righthand side, dx being the Xray 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
We
Hio.3G Zn
400
OM Fe2i
200
Ni0.Si Zr'0.3B Fe24
_xx
x
0.S
1.0
J.S
2J0
(3
2S
uniaxial
*"
e"'
{mm 3/kg)
homogeneous
ferrite bars.
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/IAij 5.0 x 10 6 , which is in reasonably good agreement with the earliermentioned
,
The
two
at least partly,
due to the
constants for the various crystallographic directions, as for example indicated in Fig. 35.1 for magnetite. For the nickelzinc ferrites with a low zinc
concentration (S
= 0.50
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/oe since the magnetostriction in this case is
,
exceptionally small,
A,
<
10~ 6
this
means
larger than the tensile strength are necessary in order to obtain a predomi
is
exerted
on
ferrites
having a negative
and a Weissdomain 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
for a poly
rod of Nio.5Zno.5Fe2C>4
and
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
having positive saturation magnetostriction, what stress applies for compressive stress and vice versa.
ferromagnetic material can be demagnetized in two different ways. The ferromagnetic core can either be heated to a temperature above the
room
temperature, or
it
can be sub
an
which decreases
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
for other kinds of sintered ferrites also. the Curie point, the
initial
The
from
permeability
is
by an alternating field at room temperature may, according to (15.4), be due to the increase of the number of domain walls at higher temperature.
TABLE
THE
INITIAL PERMEABILITY
49.1
AT ROOM TEMPERATURE OF FERRITE BARS (Nio.,Zno.,Fe204) AFTER DIFFERENT METHODS OF DEMAGNETIZATION. DATA ON METALLIC NICKEL BARS ARE GIVEN FOR COMPARISON. VALUES AT ROOM TEMPERATURE, AFTER [Ra 5].
Sintering temperature
Metallic
nickel
Method of demagnetization
of the
1230 C
ferrite
1330 C
[Sn4]
600
a)
400
380
b) Alternating
with monotonically
284
300
280
reached
252
258
220
266
[CH. XIII
6],
Some of
may
persist at
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
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
185
(a)
(c)
167 (b)
185 (d)
167
49.4.
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
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 manganesezinc ferrites containing an excess of Fe203 and which are fired in an oxidizing atmosphere.
Fig. 49.6 gives
a result which
is
is
ferrites
of this kind,
unknown. At each temperature there a kind of spectrum of relaxation times. The relaxation time becomes
as yet
(x
49]
600
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>
two different temperatures for a ferrite with and molar composition 23.5% MnO, 22.5%
at
spinel structure
3].
with time
is
always measured.
When
atmosphere, for example in nitrogen, mixed crystals of manganesezincferrous ferrites are produced which often
room
temperature, just
An
at
indication of disaccommodation of
some
significance has
been found
196 C
an oxidizing atmosphere. In 15
to drop by about
in a single crystal of
minutes the
permeability at
Shock Effect
Sensitivity of the initial permeability to
ferrites
shock
is
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 nickelzinc 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 manganesezinc ferrites are fairly insensitive to
shocks.
CHAPTER XIV
DISPERSION FREQUENCY
Although, in
many applications
on
frequency.
left
to dimensional
resonance (see
29.1) is
here
out of consideration.
By
we mean
real part y!
and
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
The magnetic
Fe2C>4
is
spectra
up
to
/=
10,000
Mc/s of a number of
is
ferrites
The general
that
drops
fairly rapidly to
<
1.
From
of y
with
frequency, and
from
caused,
it
least in part,
scale, the
maximum
in the
y curves of the
it is
in
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 highpermeability ferrites
can be used as cores in highquality
coils
in 1948
by means of ferro
50]
269
HA
the result of
HA
we
of
18.1,
10,000
 ~~~P" '"
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^ZmsFeaOs. Note the scale shift by a factor of 10 between the y,'
of the
initial
and the
fi" scale.
domain
by
ellipsoids.
In the case of highpermeability 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 +(4ttN) x
(5(U)
is
We may
then assume in
according to (47.3),
given by:
(50.2)
/xo
= (87r/3)Af,/fl*.
270
[CH.
XIV
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
neutralized
by the
surroundings.
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)(/*0l)(frlexp
Figure
P
0.10
0.08
gauss
182
Mc/s
0.5
5.5
yM
0.4
0.5
orRef
50.1
>
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
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
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]
271
/r(/x
1)
=^yM
(50.4)
where
s is
cm3 measured
ferrites
many
50.1.
The
last
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
which
8,
The spectrum of
/*
this ferrite is
To an
initial
permeability
= 0.35
1
what
is
make a
ferrite
up
to a high frequency,
For
it is
found [Sc
1]
of
/*o
and
s,
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:
fio
/62000
5.3.
w
1
1
llillll
Magnetic spectrum of
Li0.sFe1.0Cr1.5O4.
The
dispersion
n
0.5
Hh;
frequency
is
is
S^N
\
N
P'~
+ ~v**
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
[CH.
XIV
The measured
may be expected
This discrepancy
is
more
serious
still
number of magne
siumferrites 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
26 r
24
22 20
18 16
14
\pi
\
12
y
1
10
\
1
6
4
*M A
<
Fig. 50.3.
Magnetic spectrum of a
ferrite,
if
of magnesium
showing two
2
1
P1
2
5
X)
natural resonances at
room tem
tP2
K)3
10*
perature, after
[Ra
2].
f (Mc/s)
Snoek's
it
From
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.
Consequently,
fact that in
many
<
'
50]
273
^s
a
vo
Ov
O 8 8 O m OS CS (S
C<1
'
* 8 OS m

r^ ^H
g *
8^
o.
*"
O 8 to
<N
V
*7 in
1
1
3
T>
"5 <n <s <M
m O CI
Ov] c>
u o
00
O r^ * O
f*>
m <
CO
V?
3
e
fO OO
rO
r*>
r^i
00
CS
W>
o
hi
^H
A,
VO
<N CN
3.
?*"
C9
f*>
g  O O _ g g O 8. g m rn r~ m <t
trt 11
1
*H
I
1 I
H
V
<u
*H
i
3
VO
?ll
to
VO (N
vo o\
vo <N
VO a\
ft
7
1
7
1
H
H*o
U.
<*)
70
*
eg
O
II
>T)
Ov
^
<U
<SO
60 Hi
274
[CH.
XIV
a resonance of domain
ascertain whether the
ferrites is in agree
we can apply
to
it
the theory
from
24.3
and
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
we
by (14.4), which is equal at maximum to 10 microns, find for the magnesium ferrites mentioned in Table 50.11 a domainwall we resonance of approximately 100 Mc/s, to be compared with the experimental
value of 30 Mc/s. In the righthand side of (50.5) there
is
also a variable
upon K\
is
as
K\~ z l* according
ju.
,
an increase of K\
a decrease in
one ought
,
<
\, is
proportional to
r (nol)
in
which
The
series
of NiZn
ferrites,
/Lt
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
made
of 0.5 to
initial
micron and
fired at
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
main
The
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.
is
is
very porous.
At
not
we
domain
rotations contribute to
juo,
and
that in the
50]
275
also
made by
becomes
easier:
lowered
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)
ferrite NiFe2<34.
The five samples were sintered at progressively higher maximum temperatures in the range 9601327 C. The densities d of the samples indicated in the figure should be compared
with an Xray density
dx
276
[CH.
XIV
= 0.02,
50.2.
cess at
low
The broadening of
the
due to the
parallel to
measuring
field possesses
component
domain
walls
and
on
factors
at these frequencies
this
means
that the
Nx
be
and
y will
frequency
still
At very high
is
may
AttMs The
.
highest re
occur in a sin
V,max
yiflA
AttMs).
(50.6)
Above
this
about AttMs
2.19,
HA = 450
oersteds
found
(50.6)
by experiment
The
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
nickelzinc ferrite with spinel structure (molar composition approximately
3 ).
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
is
50]
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
*
/
A\
^
5,000
Af"
f = 9,300Mc/s
gt^"
50
+T(t)
'
50
and
curve.
The
saturation magnetization,
t , is
quantity (y/2w)
4wMs
b)
The
figures a)
and
show
for
two
ferrites
(.y/2ir)
4nM
ing frequency.
278
[CH.
XIV
a specimen with
With
this ferrite
we
temperature at which 4ttMs has fallen to the same value as in the case of the
ferrite in Fig. 50.5a.
magnetized.
51.
ferrites
One
finds,
initial
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.
lowfrequency 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
is
C02Z
is
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
of the
stiffness
51]
279
it
to (18.14)
is
given by:
27T/ reB
=
is
yjHi H*.
(51.1)
field
Hj
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$,
which is a measure of the stiffness of the rotations in the preferred plane, or, if K% is small, then stress anisotropy and shape anisotropy can determine H*. Assuming that ft is due solely to rotations, H^ will be related to ^0
according to (47.6).
directly
is
by experiment. The
/u."
reso
that at which
is
maximum.
low frequency. The theoretically determined frequencies, for the case where the dispersion is due to ferromagnetic resonance, and the experimentally measured frequencies,
found to have
fallen to half of its value at
differ
by the same
factor 2 as
is
spinels.
The
fields
H$
in
Table
51.1, which are derived from the magnitude of the initial permeability
much
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
4irMs
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
of the same compounds. This indicates that the initial permeability in these
polycrystalline specimens
is
by shape or
be
oriented samples
H^
will
much
nance frequency.
We
end of this
section.
The improvement as regards highfrequency behaviour which these ferrites with a preferred plane of magnetization offer as compared with the ferrites
280
[CH.
XIV
/re.G*o
1)
(4/3)rMs HiHi/H*
+ HH*IHi].
is
(51.2)
For
ferrites
always equal
to unity, since
H*
s.
In the case
Hj
H$,
fre
is
At comparable
is
quency of a hexagonal
that of a spinel.
ferrite
The
in a sintered
specimen
is:
>r,max
y^ 4ttMs (4ttMs
+ Hf),
(51.3)
analogous to
(50.6). For example, in the series of compositions denoted by the general formula Co s Zn 2  s Z, the factor Hf/H^ can be continuously varied from a high value to the value 1 by changing the chemical composi
tion.
series
Figure 51.2 shows the magnetic spectrum for some specimens of this
of the
ing that
that
H^
it
follows
from
Fig. 39.5
Hf
is
highly dependent on
considerably; the
maximum
at
Mc/s
for
C02Z and
20
found respectively at 1400 about 200 Mc/s for Coo.65Zn1.35Z, which represents
curve
is
of the
*\6=0.65
11
"
""V^
0.72
CoiZn 2 4
j
\'
10
~~~~
/
/
i 0 65/
0.72
w
/
'
>Oo
}
 Jizzz:k>
. b
i:
::S '
10
//
/W
*
,<
fl\
/T"
,'2.0
s$p
100
Fig. 51.2.
f (Mc/s) series
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
4).
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
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
which
it
can
clearly
1000
f
(Mc/s)
Fig. 51.3.
Co aZ
samples.
The broken
lines
apply
to
solid lines to
a crystaloriented sample.
282
[CH.
XIV
p"/(r'%oMc/s
W1)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 lowfrequency 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 fieldstrength 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
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
dance with
(51.1).
Of these, Hf
the large
fields
Hf
and
H\
in accor
crystal anisotropy
which deter
will scarcely
51]
283
The
H^
is
by a
0.8,
which
is
what
is
hexagonal
ferrites
due to the orientation of the crystals is found for all kinds of having a preferred plane of magnetization [St 3].
52.
ferrite,
where
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
specimens are fired at higher temperatures (for instance above 1300 C),
size
of the
crystallites
initial
a), b)
In a) the
of the ring; in b)
c)
all crystallites
random
The
crystaloriented samples
field,
as
a tangential magnetic
zation by
field in the core would only produce a magnetidomain rotation and not by domainwall displacements, whereas
of the crystal orientation in three samples of BaFeiaOig; the magmeasured for these rings are reproduced in Fig. 52.2.
284
[CH.
XIV
by 180
is
found of
were one
=
1
0.6,
is
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.
The magnetic
is
seen that there are two dispersion regions for the permeability, one being
in the frequency range
in the frequency
range from 200 to 500 Mc/s. Above the highest dispersion frequency, the
permeability approaches a final value which
caused only
6.0
' 1
'
'
'
5.0
^ F''^\
D
1
b)
pf1
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
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 highfrequency
ed for
((Jto 1).
Mc/s
is
domain walls,
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
mass
mw
is
From
Tc
= 450 C,
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
moving wall
is
the
change
in its
stiffness
related to
and
to the distance
we have
figures
/ between parallel walls. For the 16ttMs 2 /((i 1)/. The distance /
on polished
is
surfaces.
10~ 4 cm.
then a
^ 7 x 10
dyne/cm.
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
means that
many
make a
substantial
spectrum of the
ferrite in the
little
on
the lowfrequency
shows for a specimen of BaFei20i9 without texture the lowfrequency 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 lowfrequency
in
dispersion
an isotropic
The permeability of
finely
fired at
low
The
dispersions in
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
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
parallel to
The
one
53]
287
tanS
1
BaFtnPis
f.
3_
^n***
3_
<
0.01
1000
f (Mc/s)
finely
sintered at
BaFeiaOig low
Fig. 52.5.
tra
Magnetic spec
taloriented
NiFe"W.
The
on
f(Mc/s)
and b
respectively.
hour
at 1360
An example
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
288
[CH.
XIV
the magnetic
stress.
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.
53.1 and compared with the spectrum of the same ferrite without stress. The lowfrequency 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
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,
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
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
phenomenon may
in ferrites with high internal stresses, substantial losses occur [Sn 1] far below the resonance frequency determined by (50.4).
In
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
ferrite
with
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
290
[CH.
XIV
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
in those ferrites
ions.
and in
ferrites
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
.
of the magnetization
value:
is
proportional to
its
M=(1/t)(Mm M).
The change of
is
(54.1)
(1
e*l*
(54.2)
This function
is
The
relaxation time t
is
magnetization
M to
its final
value
H before the
x
is
magnetization differs
defined by the relation
by
less
its
Ma,
= x<x>H
an
alternating field
is:
H = Ho^""is applied,
XH
1
taining magnetization
M=
From
47TX*,
mt
(54.3)
AttX,
1
ix'=l
+
1
gj2 t 2
(54.4)
C0 2 T 2
!
54]
RELAXATION LOSSES
/*" as
291
the socalled
/*"
n'
and
frequencies
given, according to
by a
t{u>T)
Fig.
54.3.
and
fi"
constant
t.
2\ hours at 1000 C in an oxygen atmosphere 6x 105 ohmcm) 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
The value of t
\x"
at
a certain temperature
a>,
for
which the
of
F
p^MnXm
which
is
T curves. One can also and Cole diagram from the measuring results as shown in
the
fi" versus
plot a Cole
and p" for various frequencies at a number of different temperatures. In the case of one retion between
/*'
tan i^u>r
2rO(a
*
The observed
deviations are
ft"
The
distribution
Fig. 54.4.
The
relation between
fi'
and
fi"
in the case of
one time constant t (so called Argand or Cole and Cole diagram).
diagrams,
have
292
[CH.
XIV
20
'soo
no
T('C)
Fig. 54.5.
ty, fi'
and
measured
at various frequencies as
treated in publications
on
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
we
line.
The
two
r
by the
(54.5)
equation:
Too
e^l kT
The
where tm
is
Em
The
phenome
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
room
temperature,
/lio
= 500,
^ 10
ohmcm).
These
54]
RELAXATION LOSSES
450
293
and
is
equal to .Em
small
=
Cu .sZn 5 Fea Oi
.
activation
dif
400
For
a
at
ferrite
with a high
resistivity,
Nio.5Zno.5Fe204
1250 C,
(fired in
oxygen
resistivity
10<*
350
25
ohmcm,
200),
d~ 5 g/cm3
results
and no
^
300
the
are given in
Fig. 54.9. It
tan 8
does
manga250
/10C
nese zinc
is
ferrite.
However, tan 8
and frequency can again be ascribed to a relaxation process. Corretions with temperature
50 C
have a
maximum
is
are therefore
An actiof
100
100
vation energy
calculated
100
kc/s
"
"
"C
x o
30 8
;
at a hig
500 c/s
of
0.4
by
fer
!2SC
50
200
a
a
100
45
sistivity
As we
of
150
this ferrite at
with increasing
that hysteresis
this
field,
is
reason
of 5
of this
ferrite
were measured at
field strengths
294
[CH.
XIV
Fig. 54.7.
The
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
of Mno.eeZno.ssFeSosFeaC^ as
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
of 2.5 millioersteds.
The
values of
p" measured
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
per cent, so
From
the values of
of
/i"
a residual loss factor tan 8, has been calculated: the result
given in
Fig. 54.11,
can be seen that results are obtained similar to those for the manganesezinc ferrite, which also contains both ferric and ferrous ions. Also the activation energies of the relaxation processes in both ferrites are
frequencies. It
54.1).
Nii_8Fe"Fe204.
It
can be seen, as
54.1, that
Em
number of mixed nickelferis also evident from Table ferrous content. The relaxation
frequency at an
c/s.
temperature
is
For the
and
much
higher,
being about
10 13 c/s,
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
of the preceding
same
55]
297
on
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 aftereffect 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,
(ohmcm)
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
500
5
0.07
0.16 0.32 0.29
0.33
and 54.11
150
10"
MgFe 2 04
Cuo.5Zno.sFe204
Cuo.5Lio.25Fe2.25O4
*)
6xl05
500
0.30
54.5
0.40
shows abnormally
tan S
= 0.0017
at 100 kc/s at
room
temperature.
in a ferrite saturated in
differs
for
sintered
polycrystalline materials
static
single
crystals.
field is
In the
first
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
[CH.
XIV
Induced ferromagin
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
The
3500
on an
ii
arbitrary scale.
2500
3000
4000
iSOO
H(Oe)
2],
results
of his measurements,
y(H
+H
t ),
(55.1)
field
where Hi
is
a frequencyindependent internal
>
0.
g For example, a
A
factor,
ferrite
the frequency.
this
NiZn
If
we
Okamura equation
we
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 NiZn 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
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
is:
Hi ^
0.5 p AttMs ,
(55.2)
55]
299
NiFe2 0t
40
1 (t0 9 c/s)
30
20
Fig. 55.2. Relation
between
ponding magnetic
of NiFe 2
4 , after
field
[Ok
2].
W
10
15
*
(kOe)
The
true
NiZn 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).
AH is
with high values of Hi the line width peak has a tail to5]
and
Schlomann[Sc
3]
Hi,
defined
by
(55.1)
and the
400 800
*. p 4ft
polycrystalline
specimens of NigZnisFezO^
Ms
1200 (gauss)
300
[CH.
XIV
of
different points
the material leaves the centre of gravity of the absorption peak unchanged.
If
we
maximum
if
absorption
occurs, as
is
t.
It is
is
Hi
is
a correction should be dependent on porosity, as the line width is stray fields near the pores. According to Clogston the linewidth 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
CHAPTER XV
As
and
rotations.
is
and are
there
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
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
value of
of
ixq.
Here,
too,
0.1
0.2
0.3
0.4
OS
force
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
TABLE
.
56.1
RELATION BETWEEN INITIAL PERMEABILITY AND COERCIVE FORCE FOR FERRITES OF THE SERIES Ni8ZnisFe204 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
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.
56.2
and
major
An
is
is
example of a magnetically really soft ferrite is Mno.65Zno.3sFe204, for which i^o 1500 and 0.2 oersteds. The hysteresis loop of this ferrite e
H ~
shown in
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]
303
shown
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
4]. Even samples of the simple ferrites NiFe2C>4 and MnFe2C>4 have been made with rectangular minor loops [Ec 1]. It is
5000
(nocj
4000
4nM
20"C
3000
**
5S* *^
**^
2000
,'
^'
r s
y]
V
P0.IS
[l,29S
/
/ /
/
// 1/
/ 1
l
v ll
2
3
4
1
/ 210'<f/
//
II
10
15
25 H(Qe)
30
Fig. 56.3.
56.2,
Fig. 56.4.
The same
now
304
4000
(20"C)
[CH.
XV
3000
4nM
'gauss)
ii
Mg
.4S
= 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
hysteresis loops.
ferrites
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
a relatively low coercive force. Exceptions are the simple and mixed cobalt
which
The
and
b,
ferrites
magnetization also have a low coercive force. See, for example, Fig. 56.6a
crystal
The
remanence. In
loop the
this
and
In the case of the hexagonal oxides with a preferred direction of magnetization the coercive force
is
By a
special
magmethod of preparation it is
these compositions (see
of
many of
60).
56]
305
This
is
,
The
de
maximum
Bma x
and
is
amplitude permeability
56.2 to 56.6.
and
Hma K
,
is
At a
reaches a
maximum
value,
/x
max and at a
,
1.
4000
ArMstXftj
inM
(gauss)
,
a, 0.Q^n J.2
p'O.H)
(tc2 S
2000
20
30
H(Ot)
X

40
(Oe)
samples of Coo.8Zm.2Z.
a) isotropic sample, b) crystaloriented sample.
306
25
[CH.
XV
The normalized
X
K P
fto
Uo59
56.2
to
56.6
as
function
10
of the amplitude
1
i.0
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
PoW0
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
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)
( 32.2)
At the
caused by
strength.
this field is
corresponding to this point of intersection the magnetization almost independent of temperature. This also applies
/*rev,
at
field
In the process of demagnetization the material divides itself into Weiss domains, such that the average magnetization over all domains is zero.
The
If,
termined by
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 abovementioned 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
is
field,
which
is
subsequently
reduced to zero, the magnetization vector will stick in that preferred direction
which
is
field.
crystals
Where
is
In Table 57.1 be found the relative values of the remanent magnetization and the
tt/2 steradians.
by Gans [Ga
5].
TABLE
57.1
RELATIVE REMANENT MAGNETIZATION T emlMs AND SUSCEPTIBILITY Xrem/xo FOR ISOTROPIC POLYCRYSTALLINE SPECIMENS WITH VARIOUS CRYSTALSTRUCTURES 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
steradians
is
1.
Where
308
[CH.
XV
preferred plane, the anisotropy in this basal plane determines the remanent
magnetization. If 2<f>o
is
two
and the
MIem M
s
tt
sin^o
(57.1)
<j>
and
Xrem
XO
1
sin
2<f>
(57.2)
2^o
In the case of anisotropic samples with oriented crystals the abovementioned 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
be
would
be equal to
plane and
When
stresses
due to
elastic
deformation aie
present
in
a magnetic
stresses as far as
is
is
a preferred
a preferred
reverse
is
the case.
Once again,
will arise
a strong
switched
off,
in such a
way
With a random
stress
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
57]
REMANENT MAGNETIZATION
means
that
309
state this
netically
direction
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
(Am
ferrite) is zero.
Only
in
we
otherwise
(c)
it
will
be lower.
Shape Anisotropy
is
nevertheless
measured on a an appreci
less
M
\
*
1
/
>'
[
1 1
/
/
'
(
1
''
zing factor Nt
tan
a.
(/
a./
1/
is
Ht
(solid curve). It is
assumed
that:
H Hi = NiM,
where Ni denotes the internal demagnetizing factor
be seen from the figure that the ratio
demagnetizing
smaller
is
(57.3)
(see 43.3). It
can
re
m/M
is
greatly reduced
by the
demagnetization, and also that the ratio /xrem/^o approaches unity. This
field will
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
much
is
probably due to
phenomenon of "shearing"
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
Vreml 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
crystaloriented
BaFei20i9
isotropic
crystaloriented
~1.5
S2
when high
is
is
0.46
0.94
60.5a 60.56
This
is
particularly important
porosity
In the case of the isotropic samples of Coo.sZni. 2 Z the effective internal de
magnetization
lite
is
(see 43).
with
a preferred plane of magnetization always have a low remanence, even when the porosity is small. For anisotropic (i.e. crystaloriented) specimens
the remanence
is
by no means reach
to the fact that the
forces
may be due
from
ideally oriented,
in question
it
show a
large
is
from the
The mutual
is
ples of
mixed
cobalt
crystals
ferrite.
of
ferrites
nents
is
As an example,
58]
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.
cooled to
of
room temperature from above the Curie point (for the whole
temperature
lies
series
ferrites this
show a
is
not found in
fall
outside
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
fields hysteresis
approximately
is
The
difference as
compared with
i.e.
ferrites
containing no cobalt
probably
that,
owing to ionic
Rapid cooling,
also
loops; the time for diffusion seems in that case to have been too short.
The
compound must
by the magnetization.
at
The family of
point
is
hysteresis loops
measured
after
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
liquidair temperature.
when
magnetic
field (a.c.
or
d.c.), is
slowly cooled to
the
which are
parallel
to the field present during cooling, one finds rectangular loops, both for a
found
after the
so
marked
that a
minor loop
to the
exists consisting
H axis.
The magnetization jumps discontinuously from the one to when the magnetic field is gradually made only very little
0.5%) than a certain
critical
pect to the
H axis)
is
caused
by annealing
Fig. 58.4.
in a d.c.
magnetic
field; this is
shown by
4JTM(gauss)
\
3000
Qfc, *,<!,
Fig. 58.2.
Minor
measured
at various temperatures.
58]
3000
3000
\2000
1000 H(oersted)
500
1000
500
2000
3000
G%,^g/V%
Co0A Fe0S^20i
Qte^a^*
Fig. 58.3.
same samples as
now measured
magnetic annealing of
[Ka
3]
and led
to the development of a
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
[Go
magnesiumzinc
ferrites
[Ko
8]
and
nickelzinc
ferrites
take
effects
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
still
non180
wall will
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
is
present in the
in the wall itself has also taken place along the direction of the spins in the
wall.
expressed in
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]
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 walldisplace.
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
wallmovement
is
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.
316
[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
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=
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
form while
resume
<r/>
i
180
""*
\
/
"
5
Fig. 58.7.
J
5
Z/tfu
1
The same
now
59]
317
their
be quite
different
from that
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
result of diffu
directions.
On
match the spin the other hand the other anisotropics which determine the
wall does not
domain
may
be the reason
low temperatures.
At high temperature,
in this case too.
far
For a sample
on an
oscilloscope,
and a
switched off for a while, the constriction reappears in about the same
it
relaxation time as
took to disappear.
Form of
the
Loop
and
illustrated in Fig. 49.3,
As described in
mechanical
49.1
Weissdomain configuration in
hysteresis loop in
(fxo
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
stress the
from 2.5 to
kg/mm2 in the
is
Figure.
compressive
stress is so
predominant,
the remanent magnetization measured in the direction of the rod axis will
remanence smaller
compressive
59.1.
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
For
field
318
[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
magnetization
Fig. 49.5 for
xe
mlMcl
is
shown
in
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
stresses applies to
and
vice versa.
The The
form of the
hysteresis
loop of a
ferrite
by the curves in
= 4x 10~
) is
surrounded by a ring
fer
When the glass ring is fitted around the ferrite ring at a high temperature,
room
temperature will be subjected to a
The
figure
4].
4jiM
(gauss)
4000
3000
2000
Fig. 59.1.
resis
The change
in the hyste
magnetostriction
to
when
stress.
subjected
an external
The
solid
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 glasscovered ferrite ferrite, with negative magnetostriction, is under a
represents a
For comparison the dotted curve minor loop for the unstressed ferrite. The inset
ferrite ring F,
with
Among
and
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
field is
=H
SHBdV=0,
where integration
is
320
[CH.
air,
XV
the
can be
split into
(i7=0) can be
it
neglected. For a given value of the volume integral over the air
follows
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
by
stray fields.
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"
(60.4)
magnet
relation
between
and
H
,
is linear,
the magnitude of
%ir, is
maximum
is
done by a magnet,
equal to
BrHm
where
Hm
is
the
maximum permissible
60]
PERMANENT MAGNETS
is still
321
factor
877,
open a shortcircuited magnetic system, we shall use as a figure of merit for magnets for these applications.
in order to
60.2.
The
perties of
is
to be
represents
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
from
to
2.
large
enough
movement
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 temperaturedependent.
One
finds
(60.5)
Dcr
it
OC
^Ki/Ms,
being assumed that the exchange energy, in agreement with the Weisstheory of ferromagnetism, varies with temperature as
field
M 2
does.
The
quantity
^K\\MS
for BaFei20i9
is
shown
as a function of temperature
As can be seen, it increases by almost a factor of 2 going from low to high temperatures. This is in agreement with the variation of the coercive force as a function of temperature (Fig. 60.4); at low temperature
in Fig. 60.3.
322
[CH.
XV
3000
4XM
(gauss)
__
"
~<*
2^ ^S&
2000
WOO
BaFei2 0i9
^
2000
/
2000
4000 6000

8000
(Oe)
3000
4nM
(gauss)
2000
"/ &*\
s
S^
s*3
1000
f
2000
BaF'e^O 19
}
I
2000
4000 S000
(Oe)
8000
*W
Fig. 60.2. Hysteresis loops at
with
random
[Ra
7].
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
a negative
field. It
60]
PERMANENT MAGNETS
323
by annealing
at 1000 C, at
60.1).
which tem
TABLE
60.1
BaFe 12 Oi 9
mHc
oersteds
100 2
500
4
8
700
1000 1570
18
38
1600
1
hour
in air
Temperature
M^c
oersteds
C
200 700
1000
1600
1900
3400
1100
1200
3900
3440
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
domain
do not stop
8r
at the
grains).
^^*^
ffi
BaFe 12 Q m
proportional to
critical
diameter
for
singledomain behaviour.
200
100
100
200
300
*~
400
500
After [Ra
6].
T(C)
..y
324
10.000
[CH.
XV
The
intrinsic coerc
"
OMKi/M
7
cive force
mH
as
measured
7500
(Oe)
for
finegrained
BaFei20i9
as a function of temperature,
^M^c
2500
200
100
100
200
300
400
500
+
of a wall more energy
tain degree of porosity
(
is is is
T(C)
cer
indispensable.
For
BH
of prime importance?YmTthe case of highcoercive materialju where c (for example the hexagonal comat least of the order ormagnitude qf Br
(
pounds with uniaxial anisotropy)^ie BH curve differs essentially from the 4ttMH curve. For instance, bH' can never be larger thanBr As shown c
.
in Table 57.1,
M /M
r
/z
random
r
s.
crystal orientation.
The
quantities
(BH)m&x or
BT Hm
=BH
T
can thus be
M =M
maximum
factor of 4.
is
described
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
and
is
there
is
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 4nMH curves and demagnetization curves for both an isotropic and a crystaloriented sample of BaFe^Oig are given in Figs. 60.5 and 60.6. The corresponding figures of merit are given in Table 60.11. Comparable results can be obtained with compounds of the structure; for example an isotropic permanent magnet of Fe can have a value of (Sff) max = 10 6 gauss oersted. The
is
60]
PERMANENT MAGNETS
5000
325
4rtMtfrot)
{4000
1
^b
BaFeaOs
inM
(*luss)
3000
t
20001
/
/
5000
2500
2500
S000
7500
I0OO0
H(Ot)
Fig. 60.5. Hysteresis curves of
crystaloriented
a) isotropic
and
b)
TABLE
Polycrystalline
60.11
BaFei 2 Oi 9
BrHm
gauss
oersted oersted
gauss oersted
gauss oersted
3.310 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
a remanence
and an
infinite coer
in the impossible
and
having no porosity.
case,
2000
(5if) ma x
= V^M,) =
is
6.10 6
gauss
oersted.
WOO
H (Oe)
Fig.
60.6.
magnets
is
Demagnetization
curves
of the magnets in
remanence.
This
Fig. 60.5.
326
[CH.
XV
dom
irreversibly
mHc > bH A
c.
dicular
and
CHAPTER XVI
HYSTERESIS RESISTANCE
AND DISTORTION
coil containing
The
core
distortion caused in
is
a network by a
a ferromagnetic
and the
a consequence of the nonlinear relation between the induction B field strength Hin the core. This nonlinearity can have two reasons:
is
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
B(H)
from which
tively the
it
ixqH
+ vm + XH5 +
(H =
distortion D =
V%\V\ is proportional to H^ax fundamental and third harmonics of the voltage across a coil with ferromagnetic core when a sinusoidal current passes through the coil).
(where V\ and V% are respec(b) Hysteresis
When
teresis
not a singlevalued function of H, hysphenomena will occur. The simplest representation of the lower
is
branch
(1)
is
/x
vh\
low induct
328
[CH.
XVI
having
O"
as
its origin.
and
H with
by the expression:
B(H)
vH\
(61.3)
It
the upper signs referring to the upper branch of the hysteresis loop.
should be noted in
this
and
as
a sinusoidal
field
H=
(in
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 nonlinear character of the BH curves [Pe 2]. The energy dissipated per cycle and per unit of volume is according to (2.2) proportional
as po
v
much
and
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
...
(615)
appears, then, that the hysteresis losses per period and per
first
cm3
of material
are proportional in
of the
field strength.
is:
The
hysteresis
W = (2/3ir)vHUV erg,
where / is the frequency of the applied
in
field
(61.6)
and
V the
cm3 We
.
can
now
Rh by
W = IlBRn,
(61.7)
Rh =
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 crosssection 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
108
ohm.
8)
(H =
61]
HYSTERESIS LOSSES
cat)
AND DISTORTION
329
//max cos
Bit)
wt
=(juo
sin 3cot
sin 5tf
'
).
10 8 E\C%
= dB(t)/dt = (ixo + 2vf/max)<>flmax sin oat +  (8/7T>co ff2 max(l cos cat I cos 3<^
J
),
(61.9)
where
cz is again
The
loss factor
a constant depending on the core and coil dimensions. tan8 A that determines the hysteresis losses in the coil is
defined as:
3t7(^o
+ 2r//max)
(6i.il)
and
the distortion Z)
is:
ak^ ^fr +
37r(/i0
Zvlimax.)
From
(61.9)
and
simple relation:
ft
D = 0.6 tanS =
in which
0.6
R h /a>L,
(61.12)
is
the the
Rh
is
found to be
cavocicz
X=
The
resistance of
+ (3W4)Rft.
is
(61.13)
coil containing
a ferromagnetic core
often plotted
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.
that
/j.
and
independent of Hm&z.
apply.
when
of the
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
61.3
as a
dependent on the
to
(61.10)
O^oc,c2
up
according
and
(61.11).
The
*h
Fig.
61.2.
Hma K
,
as can be seen
curve,
The reactance
as a
Kh
in the case
V3 /Vi.
the
terial
At higher
field
strengths, however,
magne
tizingforce scale.
is
shown
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
7.22 r
ta/itf
V)/v,
The
loss factor
hysteresis losses.
61]
HYSTERESIS LOSSES
AND DISTORTION
it is
331
necessary
know
the quantities
/*o
and
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
for the
losses or distortion
when
the relations (61.6) or (61.11) are complicated, since //max then refers to the internal magnetic
fields.
Hysteresis constant a
Legg [Le
1]
= a B^lir,
From (61.10)
it
(61.18)
where Umax is the maximum induction in the core for a sinusoidal magnetic
field in
fieldstrengths
(vHm&x <^
/x )
and
factor tanSft
(=
Rh/2ttJL)
is
approximation, no change
when an
air
gap
is
a in (61.18)
will also
it is
related to
ja
and
v.
= ~j
Bm&7i
only
16
(61.19)
It will
independent of
is fulfilled
if
independent of
jB max ,
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
*)
The symbols
and Cn are
Ch
Cji
=a = 10.a
332
[CH.
XVI
gap
It is
assumed
vA Jmean.
be the apparent
get:
we
=
as:
ai//A 2 appCi/max
ohm,
Rh =
0.2
yiO^ a
^t ./. ^/2
/max
104
ohm.
(61.21)
D=
600 /T0^
(61 .22)
is
What
wanted in a
selected
small.
is
For
this
and
an
air
gap
introduced such that the loss factor (tanS) app of the coil with
core
is sufficiently
low
at
From
L and V one
harmonic
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
cores.
ability
of the material.
q?.
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 lossresistance
Rn
to the selfinductance
if
62]
333
ampere turn
cm
core length:
RnjL
= h, when/=
it
hit
A/cm.
(61.23)
According to (61.7)
an
arbitrary
frequency/and an
RnIL
= /z(iV//)/eff//800.
this gives for the hysteresis constant
= 750 v/no.
( 61  24)
value for the hysteresis constant h of a magnetic core. For loading coils for telephony applications the qualityfactor 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 selfinductance 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
and
v.
The
given for a
core with a uniform crosssection 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 manganesezinc ferrites with spinel structure, where 0.5 10~ 6 (or 2.800 1)for instance a
<
<
24.100
TABLE
a h
61.1
= =
(16/3)v//*o 3
= = =
0.71.10 3 /i//"o 2
1.410 3 /to a a
0.391CT 6
3
<72.soo
24.100
750
villa
= 0.54.10
=
2 /*o tf2.80o
24.100
92.800
13.810* v//*o 3
2.6106 a
1.8510 3
AW
24.100
The singlevalued 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
resistivity, as
curve
is
dimensions of the sample. Measurements at high inductions and under continuouswave conditions have been made on
to a frequency of 1.5 Mc/s.
It is
ferrites
found [Wi
permeability
have frequencydependent magnetization curves in a frequency range below that of the ferromagnetic resonance. As an example Fig. 62.1 shows the data for a manganese ferrite with spinel structure
(/^o
> 400)
(43.5
+ FeO;
initial
permeability
/xo
860;
ferromagnetic resonance frequency about 5 Mc/s). The inset shows the change
ft
at
An
obvious interpretation of
this
behaviour
is
zation processes. One process which gives rise to /*o is frequencyindependent 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 frequencydependent from 100
kc/s onwards.
2000
ft
~\
(H0.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
250
0.1
0.2
0.3
0A
OS
0.6 *
0.7
0.8
0.9
1.0
Hmax (oersfed)
mol
% MnO
balance FezOs
.
FeO). Inset:
of frequency.
62]
335
250
300
350
Fig. 62.2.
500
The
maximum value
of the
induction
Smax
field strength
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,
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.
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 wellknown 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
or no dispersion in the
a.c.
magnetization curve
found in
this
range
of frequencies and
low
temperature of 1250 C.
material
is
When
much
fired at
lower and a
and
b.
This additional
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
having a high
initial
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
C in oxygen.
1450 C in oxygen
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 hightemperature 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
pends to a great extent on the presence of ferrous ions. Microscopic eddycurrents might be the cause of the damping.
that the highfrequency level of the resistivity of ferrites
is
It is
often
known much
it
Moreover a calculation of
this
micro eddycurrent
is
much
found experimentally.
62]
337
damping of the
will
ferrites in
irreversible
friction
domainwall 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
maximum
fieldstrength 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)
ferrite
Frequencydependent 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
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,
ferrite
/3
= 0.02.
Thus
it is possible that the same unknown walldamping mechanism applies to the experiments with polycrystalline samples as to experiments with single
crystals.
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
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
[He
3].
1
1
Fig. 63.1. Ferrite core (a) with
The shape of
a
ferrite
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
amplitudes
{Hm
<
oersted) only
two windings.
(6) in
current pulse
mum
occurs
very
shortly
jusec).
after
a voltage pulse
condary.
in the se
At higher pulse
in the curve
amplitudes a second
maximum
times
when
Hm
is
increased,
and
Hm
first.
This situation
is
almost obtained
Hm =
2.6 oersteds.
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
For
this ferrite,
where the
remanent magnetization
63]
Kfyolt)
\
FERRITES
^,=2.6 Oe
339
Family
of pulse
spond to the maximum field strengths for which the hysteresis loops of that figure were
obtained.
0.5
10
7.5
2.5
30
t(fiac)
field
Hm
{i.e.
AB in
Fig.
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 timedependent secondary voltage as indicated for one case by the dashed curves. A relatively small change of the magnetization occurs fairly rapidly in this squareloop ferrite, and the major part of the magnetization
reverses
only slowly.
It
magnetization with reversible rotation processes and with irreversible domainwall displacements respectively. Suppose that the permeability of
the ferrite in the remanent state,
/ire
m,
is
field
Hm
will
then
Fig. 63.3.
The
reversal of
a function of
the
applied
0.9
tudes
pulses.
of
16
IS
2.0
22
2,4.
26
340
CH. XVI
cause in the
which
ferrite a change of induction as a result of rotations, AB, about equal to em m For the ferrite under consideration
.
change
is
in fairly
below the dotted curves in Fig. 63.2. Pulseresponse 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,
marked
will
However,
if
a tangential pressure
Y,
(yolt)
!
76

Curve
is
ob
Curves
1,
increasing
of an
applied
tangential pressure,
which corresrectangularity
pond
to
increased
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 domainwall displacements,
a second
maximum
may
apears.
distinction
more pronounced
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 pulseresponse 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
COatFeos^Oi
10
12
t((isec)
Fig. 63.5. Coo.iFe^9Fe204 annealed in a magnetic field: pulse response curves recorded for various amplitudes ffmK of the field pulse.
rotations,
is
given only