Arts

chapter 5
FUNDAMENTAL PROPERTIES OF
HEXAGONAL FERRITES WITH
MAGNETOPLUMBITE
STRUCTURE
H. KOJIMA
Research Institute for Scientific Measurements
Tohoku University, 2-1-1 Katahira, Sendai
JAPAN
Ferromagnetic Materials, Vol. 3

Edited by E.P. Wohlfarth
North-Holland Publishing Company, 1982
305
CONTENTS
1. G e r e r a l
. . . . . . .
1.1. C h e m i c a l c o m p o s i t i o n
.
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1.2. P h a s e d i a g r a m
. . . . . . . . . . . . . . . . . . . . . .
1.2.1. B a O - F e 2 0 3 s y s t e m s
. . . . . . . . . . . . . . . . . .
1.2.2. S r O - F e 2 0 3 s y s t e m s
. . . . . . . . . . . . . . . . . .
1.2.3. P b O - F e 2 0 3 s } s t c m s
. . . . . . . . . . . . . . . . . .
1.3. P r e p m a t i o n
. . . . . . . . . . . . . . . . . . . . . . .
2. M c o m p o u n d
. . . . . . . . . . . . . . . . . . . . . . . .
2.1. BaFe1:.O19, SrFe12019 ~ n d Pb Fe1=O19 . . .
2.1.1. Crystal s t r u c t u r e
. . . . . . . .
2.1.2. M a g n e t i c ~,t~ u c t u r e
. . . . . .
2.1.3. S a t m atic n me gnet!2 a t i c n
. . . .
2.1.4. M a g n e t o c r ~ stalline a n i s o t r c py
. .
2.1.5. C o e r c i v e f o l c e
2.1.6.
2.1.7.
2.1.8.
2.1.9.
2.1.10.
2.1.11.
2.1.12.
2.1.13.
..
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2.1.14. M e c h a n i c a l proFertie s
.
.
F a r a m ~ g n e l i c proloert~e s
. . . . . . . . . . . . . . . .
Magnetic aftereffect
. . . . . . . . . . . . . . . . . .
FMR
. . . . . . . . . . . . . . . . . . . . . . .
NMR
. . . . . . . . . . . . . . . . . . . . . . .
M 6 s s b a u e r effe~ t
Domain observation
Optical pioperties
M a g n e l ostriction
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2.1.15. H e a t c a p a c i t y
. . . . . . . . . . . . . . . . . . . .
2.1.16. q h m m a l e x p a n s i c n
. . . . . . . . . . . . . . . . . . .
2.1.17. E l e c t r i c a n d dielectric IZrOl:erties
. . . . . . . . . . . . . .
2.2. Substitute d M c o m p o u n d
. . . . . . . . . . . . . . . . . . .
2.2.1. B a O - S r O - F b O - F e 2 0 3 s y s t e m s
. . . . . . . . . . . . . . .
2.2.2. G t h e r substitutions c f Ba:+ ions
. . . . . . . . . . . . . . .
2.2.3. Substitt t i c n c f Fe3+ l'ons
. . . . . . . . . . . . . . . . .
Sub~,titution with A l>, Ga3+ a n d C r3+ icn
. . . . . . . . . . .
Sub,~ tilution with Sc3+ a n d In 3+
. . . . . . . . . . . . . .
Substitution of Fe3+ with p a i r e d ions; C o - T i s y s t e m
. . . . . . .
C t h e r c c m b i n a t i o n s with I I - I V pairs
. . . . . . . . . . . .
2.2.4. Effect of substitutions on t h e t e m p e r a t u r e d e p e n d e n c e of m a g n e t i z a t i o n
2.2.5. Substitution with a n i c n s
. . . . . . . . . . . . . . . . .
References
. . . . . . . . . . . . . . . . . . . . . . . . . . .
306
307
307
308
308
312
313
315
317
318
318
323
325
329
334
342
344
345
347
351
354
358
360
361
361
362
364
367
367
368
368
368
375
378
379
38O
384
387
1. General
A group of ferrimagnetic oxides with hexagonal structures will be described in this

section'S. Most of these compounds have been developed over the past two
decades and it can be said that the first fundamental step of the investigations on the
properties of hexagonal ferrites, now seems to be nearly completed. Smit and Wijn
(1959) and Wijn (1970) collected comprehensive data on the compounds, and
moreover, many authors - such as Schieber (1967), Tebble and Craik (1969), Galasso
(1970), Standley (1972), and others-spent a few chapters to treat the magnetic
properties or crystal structures of the hexagonal iron oxides in their books.
1.1. Chemical composition

~fhe chemical compositions of the hexagonal compounds are shown in fig. 1" as
part of a ternary phase diagram and in table 1 for the BaO-MeO-Fe203 system.
Here, Me represents a divalent ion among the first transition elements, Zn, Mg, or
a combination of ions whose valency is two. S denotes a cubic spinel MeO.Fe203
and will be explained in detail in ch. 3 of this handbook by Krupi6ka, in vol. 2, ch.
3 by Slick (1979) and in vol. 2, ch. 4 by Nicolas (1979). However, we refer to it
here as to one of the major constituent blocks of the hexagonal compounds. M
compounds, which have the chemical formulae of BaO.6Fe203 (BaM),
SrO.6Fe203 (SrM) and PbO.6Fe203 (PbM) etc., were developed in the initial stage
by Went et al. (1952) and Fahlenbrach and Heister (1953) as a typical hexagonal
ferrimagnetic oxide for permanent magnet materials. They are isomorphous with
the mineral magnetoplumbite, the chemical composition of which is approximately PbzFe15Mny(A1Ti)O38.
Other interesting hexagonal compounds are potential industrial magnetic
materials in the systems: 2MeO-BaO.8Fe203 (Ba-Me-W), 2MeO-2BaO.6Fe203
(Ba-Me-Y), 2MeO.3BaO.12Fe203 (Ba-Me-Z), 2MeO.2BaO.14Fe203 (Ba-MeX), and 2MeO.4BaO.18Fe203 (Ba-Me-U); they have more complicated crystal
structures than BaM, and were originally investigated by Jonker et al. (1954) for
? CGS unit are used in this section. SI units are shown in brackets.
* More detailed diagrams of B a O - Z n O - F e 2 0 3 and SrO-ZnO--Fe203 systems were recently reported
by Slokar and Lucchini (1978a, b).
307
308
H. KOJIMA
,%\/\
\~
/ \\\/
E}00
Fig. 1. BaO-MeO-Fe203 system, showing the relationships of chemical compositions among ferrimagnetic hexagonal compounds (see table 1).
use at very high frequencies. They will be described in ch. 6 by Sugimoto, and in
vol. 2, ch. 3 (Slick 1979) and in vol. 2, ch. 4 of this handbook (Nicolas 1979). While
BaO.Fe203 (B) was reported as an antiferromagnetic hexagonal compound by
Okazaki et al. (1961a, b), here, it is rather important as an intermediate phase,
when BaM is prepared from Fe203 and BaO (Beretka and Ridge 1958, St~iblein
and May 1969, and Wullkopf 1975). In the BaO-Fe203 system, BaO-2Fe203 (T) does
not exist as a stable phase at room temperature (Okazaki et al. 1961a) but it is an
essential constituent block of Y, Z and U compounds. The constitutions and phase
relationships of each compound will be evident from fig. 1 and table 1.
1.2. Phase diagram

1.2.1. BaO-Fe203 systems
Numerous compounds have been found in the BaO-Fe203 system, for example,
7BaO.2Fe203 (Batti 1960), 5BaO-Fe203 (Bye and Howard 1971), 3BaO.Fe203
(Okazaki et al. 1961a, Bye and Howard 1971), 2BaO.Fe203 (Erchark et al. 1946),
BaO.Fe203 (Okazaki et al. 1955), 2BaO.3Fe203 (Okazaki et al. 1961a, Appendino
and Montorsi 1973), 5BaO-7Fe203 (Appendino and Montorsi 1973), BaO-2Fe203
(Okamoto et al. 1975), BaO-6Fe203 (Adelsk61d 1938, Went et al. 1952),
3BaO-4FeO-14Fe203 (Brady 1973), and in an oxidizing atmosphere BaFeO3-x
(Mori, 1970), and further in a reducing atmosphere, BaO-FeO.3Fe203 (Braun 1957),
BaO.FeO.7Fe203 (Braun 1957) and BaO.2FeO.8Fe203 (Wijn 1952, Neumann and
Wijn 1968).
Figure 2 is the phase diagram determined by Goto and Takada (1960) under the
oxygen partial pressure of Po2 = ~ arm [0.02 MPa] in the solid phase region and
FUNDAMENTAL PROPERTIES OF H E X A G O N A L FERRITES
t~
tt3
,,D
tt~
3
5 tt~
~o
~=~.
~ = ~
e~
0
tt3
d
o
e--
o66
<
d66666
~66666
Nmm
0
0
0
co
e-
ee"
309
310
H. K O J I M A
0.5
1,0
Fez03 / BoO
1.5 2.0
4.0 6.0
I
1600
"',~
1400
o0 1370
1565.
370
1330
O912oo
El.
E
(I)
O9
(2)
{3)
I000
800
I
~' 40
2BoO'Fe203
60
8o
Ioo
BoO'Fe203 BoO-6Fe203 Fee03

Mole %
Fig. 2. Phase diagram of a BaO-Fe203 system (Goto and Takada 1960). Poz = { atm [0.02 MPa] in the
solid phase region and Po2= 1 atm [0.1 MPa] in the liquid phase region. (1) 2BaO.Fe203 + BaO.Fe203;
(2) BaO-Fe203 + BaO.6Fe203; (3) BaO-6Fe203 + Fe203.
Po2 = 1 atm [0.1 MPa] above the eutectic temperature. Batti (1960) and Van H o o k
(1964) obtained somewhat different phase relations for the same system at
Po2 = atm [0.02 MPa] and Po2 = 1 arm [0.1 MPa], respectively, which are given in
fig. 3 and fig. 4. The main differences among these diagrams around the corn-
1500
/
1474
L
1420
p 1400
1380 / ~
O9
(3)
E
I. . . .
1300
BaO
,2,
20):2 2!, 40
,!, 60
Weight
8o,!6
Fe203
Fig. 3. Phase diagram of a BaO-Fe203 system (Batti 1960). Po2 = atm [0.02 MPa]. (1) 2BaO.Fe203 +
BaO.Fe203, (2) BaO.Fe203 + BaO-6Fe203, (3) BaO.6Fe203 + Fe203.
1600
311
.--%U
Liq
,9,
1500
//"
/
1400
/(I)
Q..
"'*,%
\
i5 (6)1(7) 1495
1330
1300
(5) !
(I) x
C2)
i /
1315
13)
80
6O
BoO 4 0
(4)
Fe203
Mole %
Fig. 4. Phase diagram of BaO-Fe203 (Van Hook 1964). Po2 = 1 atm [0.1 MPa]: (1) BaO-Fe203+ liq.,
(2) BaO-6Fe203 + liq., (3) BaO-6Fe203 + BaO-Fe203, (4) BaO-6Fe203 + Fe203, (5) BaO-6Fe203 +
Fe304, (6) 2FeO-2BaO-14Fe203 + liq., (7) 2FeO-2BaO-14Fe203 + Fe304, (8) 2FeO.BaO-8Fe2Oa + liq.,
(9) 2FeO-BaO.8Fe203 + Fe304, (10) Fe304 + liq.
1500
,~]) [
102
Temperature
1400
II
(C)
1500
I !
I0
13_
/
0
X
io-I
('4
io-Z
i,
Io-3
0.54
-~BaW
(3]
1.58
0.62
I/T
(10 -3 K-~ )
il
0.66
Fig. 5. P - T diagram of Fe304, BaO-6Fe203 (Van Hook 1964), 2FeO-BaO-8Fe~O3 (Neumann and
Wijn 1968) and 2FeO.SrO.8Fe203 (Goto et al. 1974).
312
H. K O J I M A
position of BaO.6Fe203 are the solubility limit into the B phase and the existence
of a phase transition at high temperatures. Though there is still some ambiguity,
the solid solution range is considered to be practically narrower than
Fe203/BaO = 5.0-6.0 as shown in fig. 2. According to Batti (1960) and Van Hook
(1964) it is within 5.%6.0, and 5.8--6.0 according to Stfiblein and May (1969).
Moreover, almost no solubility range is claimed by Reed and Fulrath (1973).
As for the liquidus line, it seems to be most probable that BaM dissociates into
a liquid phase and 2FeO-2BaO.14Fe203 (Ba-Fe-X) as shown in fig. 4, even when
it is heated in air (/o2 = arm [0.02 MPa]). In fact, an incongruent melting will
occur in the composition. Figure 5 is the equilibrium diagram of (1) BaO.6Fe203
(BaM) ~- FeO.BaO-7Fe203 (Ba-Fe-X) + liquid + 02 and (2) Fe203 ~- Fe304+x + 02
(Van Hook 1964), and also (3) the stable region of 2FeO.BaO.8Fe203 (Neumann
and Wijn, 1968). The latter authors obtained B a - F e - W under the condition of
/9o2 = 0.05-0.1atm [5-10x 103pa] at 1400C as a single phase. But Van Hook
(1964) found that BaM is congruently melted in Po2 = 40 atm [4 MPa] as shown in
fig. 6. Figure 7 is the phase diagram by Sloccari (1973), which shows the existence
of the peritectoid reaction, BaO.Fe203 (B)+ BaO.6Fe203 (BaM)~-2BaO-3Fe203,
at 11500-+ 10C.
1.2.2. SrO-Fe203 systems

The phase relations are quite similar to that of the BaO-Fe203 system. Figure 8 is
the equilibrium diagram in Po2 = atm [0.02MPa] given by Goto et al. (1971,
//
1600,
//
Liq
,j
/ /
z/
(5)
1 /
/ f/
(I)
1400
.......
',
,_2
,/"
.........
(3)
I1)
E
I1)
I-
(2)
(1)
(4)
1200
I
BaO
6o
8o
Fe203
Mole %
Fig. 6. Phase diagram of a BaO-Fe203 system (Van Hook 1964). P o 2 = 4 0 a t m [4MPa]: (1)
BaO'Fe203 + liq., (2) BaO.Fe203 + BaO.6Fe203, (3) BaO.6Fe203 + liq., (4) BaO.6Fe203 + Fe203, (5)
Fe203 + liq.
50
1200 ;
000, i
0000
a)
r~
(3)
0-00~.
0000
O.
iooo
F:
1-
Mole %
Fe=O 3
60
70
80 85.71
I[I
1
o,oo~ ?
I100=
313
oooe
9O0
(2)
i (I)
I
80C
Ili
//\\
ol
m
B(:]O/Fe203
Fig. 7. Phase diagram of a BaO-Fe203 system (Sloccari 1973). (1) BaO-Fe203+ 2BaO.3Fe203, (2)
2BaO.3Fe203 + BaO.6Fe203, (3) BaO-Fe203 + BaO-6Fe203, (0) one phase, ((3) two phase.
1974). They insisted from the results of ditterential thermal analysis that there
might exist some solubility range of SrM in 3SrO.2Fe203, as indicated with the
broken line in fig. 8. SrM is decomposed at 1435C to SrFe]sOz7 (Sr-Fe-W)+
liquid, and at 1465C, they change into Fe304 + liquid in air. The stable region of
Sr-Fe-W is also indicated by the region (4) in fig. 5 from the results of Goto et al.
(1974). Furthermore, they obtained Sr-Fe-X by heat treatment at 1420C for two
hours, but it is decomposed by prolonged heating to a mixed phase containing
Sr-Fe-W in air
1.2.3. PbO-Fe203 systems

The phase relations obtained by Mountvala and Ravitz (1962) and Berger and
Pawlek (1957) are considered as reasonable representations under normally
attainable equilibrium conditions. Figure 9 is the diagram by Mountvala and
Ravitz (1962). PbM is incongruently melted to Fe203 + liquid at 1315C (1255C) *,
and below 760C (810C) * it is decomposed to FezO3+ PbO.2Fe203. Mountvala
* Data by Berger and Powlek (1957).
314
H. KOJIMA
1500 ,,1480
\',,,
Liq
(2) X
1300
,,./ ~ " (I0)

1465
(8)
,~5 (7)11395(9)
I/
(5)
,,
(/
(3) ~
1195
"\
09
~- I 1 0 0
( I)
(4)
(6)
900
40
SrFeO3-x
60
Mole %
80
I00
Fe203
Fig. 8. Phase diagram of a SrO-Fe203 system (Ooto et al. 1971, 1974). Poz=atm [0.02MPa]: (1)
SrFeO3_x + 3SrO.2Fe203, (2) SrFeO3-x + liq., (3) 3SrO'2Fe203 + liq., (4) 3SrO'2Fe203 + SrO:6Fe203,
(5)
SrO'6Fe203 + liq.,
(6)
SrO'6Fe203 + Fe203,
(7)
SrO.6Fe203 + 2FeO-SrO-8Fe203 +
(2FeO-2SrO. 14Fe203), (8) 2FeO.SrO.8Fe203 + liq., (9) 2FeO.SrO.8Fe203 + Fe304, (10) Fe304 + liq.
2:1
14oo
1:2
2:5
1:5 1:6
/
1315
13oo
/
12oo
S
o II00
1
I
I
I
I
I
I
/iq
(9)
i
945
9oo ~-
! ,,/---I 9,ol
(8)
(4)
800
(2)
\\\2 /
7ooF.... 7~oq
I600 "
0
PbO
!"
'
20
1/
I I
L_~
(H)
i
i
i
I000
(61
, "
760
750
i (3)
(io)
650
60
40
Mole %
80
I00
Fe203
Fig. 9. Phase diagram of a PbO-Fe203 system (Mountvala and Ravitz 1962). (1) PbO + 2PbO.FezO3,
(2) PbO + liq., (3) 2PbO.Fe203 + Fe203, (4) 2PbO.Fe203 + PbO-2Fe203, (5) PbO.2Fe203, (6)
PbO-2Fe203 + PbO.6Fe203, (7) PbO-6Fe203, (8) PbO.2Fe203 + liq., (9) PbO.6Fe203 + liq., (10)
PbO-2Fe203 + Fe203, (11) PbO.6Fe203 + Fe203, (12) Fe203 + liq.
FUNDAMENTAL PROPERTIES OF HEXAGONAL FERRITES
315
and Ravitz (1962) also claimed that there is a rather wide solid solution range of
Fe203/PbO = 5.0-6.0 between 800-945C and proposed a crystal structure for the
end member of the solid solution, PbO.5Fe203. It would be reasonable to explain
the fact that the lattice parameters were found to be independent of composition
in this solid solution range, but the saturation magnetization of PbO.5Fe203 is
higher than that of PbO'6Fe203. There seems to be no investigation about the
hexagonal phase of P b - M e - W , P b - M e - X etc. in this system.
1.3. Preparation
The most typical way to obtain the ferrimagnetic hexagonal oxides as powder or
in a sintered polycrystalline state is the solid state reaction of heating the mixtures
of constituent oxides or of compounds which are easily changed to oxides by
heating. BaCO3, SrCO3, PbO and c~-Fe203 etc. are generally used as starting
materials, but oxalates, sulfates, chlorides, nitrates or hydroxides are also used for
specific purposes. Proper reaction temperature, atmosphere and cooling conditions should, of course, be chosen according to the phase diagrams. However,
single phase M type compounds, for example, can be usually obtained by heating
in air (PQ = ~ atm [0.02 MPa]) between 800 and 1200C, and just removing from
the furnace.
The formation processes of the reactions have been reported by many authors
from various points of view. Erchak Jr, et al. (1946), and Erchak Jr. and Ward
(1946) investigated the reaction between ferric oxide and barium carbonate and
found the formation of BaO.2Fe203 above 550C and BaO.6Fe203 above 750C
by X-ray diffraction. Sadler (1965) studied the reaction kinetics of BaM, and
obtained the activation energy of 73.2 kcal/mol [3.06 105 J/mol] above 735C.
Wullkopf (1972, 1975) observed the variations of the amount of reaction products,
length, weight and grain size for the mixed compact of BaCO3 and 5.5Fe203
during the sintering process and collected the data, as shown in fig. 10. Similar
results were also reported by Haberey et al. (1973). Furthermore, Haberey and
Kockel (1976) found that SrM is formed from a mixture of SrCO3 and 6Fe203
through the following two endothermal reactions:
SrCO3 + 6c~-Fe203 + (0.5 - x) 102 --~ SrFeO3-x + 5.5a-Fe202 + CO2
SrFeO3-x + 5.5ol-Fe203---> SrO-6Fe203 + (0.5 - x) 02.
Bowman et al. (1969) investigated the formation mechanism of PbM in the
PbO-Fe203 system and concluded that PbM is formed through the intermediate
compounds of 2PbO-Fe203 or PbO'2Fe203, depending upon the mixing method,
the time and temperature of heating. They used two kinds of co-precipitation
methods for mixing, in which the aqueous solution of ammonium bicarbonate was
added to the solutions containing lead nitrate and ferric nitrate, or lead nitrate
and ferric oxide.
The co-precipitation method was also used to obtain a high coercivity BaM or
316
H. KOJIMA
1.0
0.8
(b)
\\k\\\\\ M/
' ~
0.6
.o
\/,/,,
\/-
0.4
\/
!
!
!
I
/
'l
1.0
(0)
~ 0.8
(D
>, 0.6
P
"
0.2
0.4
//. w
"~ 0.2
rr
0
400
800
1200
i./411600
Temperoture (C)
Fig. 10. Changes of BaO-5.5Fe203 compact during heating (Wullkopf 1972, 1975): (a) variation of
reaction products, F: Fe203, Bc: BaCO3, B: BaO.Fe203, M: BaO.6Fe203, Y: 2FeO.2BaO.6FezO3, W:
2FeO-BaO-8Fe203, Z: 2FeO-3BaO.12Fe203; (b) variation of length L, weight G, grain size D and
saturation magnetization M.
SrM by Mee and Jeschke (1963), Haneda et al. (1974a), Roos et al. (1977) and Oh
et al. (1978). Furthermore, Shirk and Buessem (1970) obtained a high coercivity
BaM from a glass with the composition 0.265BzO3-0.405BaO-0.33Fe203 in mole
ratio. They reported that single domain particles can be crystallized in the
fast-quenched glass with this composition by the heat treatment under the
appropriate condition (see also table 10). A molten salt synthesis utilizing NaC1KC1 for BaM and "SrM submicron crystals with high magnetic quality was
proposed by Arendt (1973). Moreover, Okamoto et al. (1975) applied hydrothermal synthesis with ol-Fe203 suspension in barium hydroxide aqueous solution
and obtained BaO.2Fe203 crystals, whose space group was reported as P63/m
with the lattice parameter of a = 5.160 A and c = 13.811 A. Kiyama (1976) obtained
BaO.6Fe203, BaO.4.5Fe203 and BaO.2Fe203 with Fe(OH)3 or FeOOH and
Ba(OH)2 under the similar conditions in an autoclave and studied magnetic
properties.
Single crystals of M compounds were obtained by cooling a nearly eutectic melt
(Kooy 1958); under the high oxygen pressure (Van Hook 1964, Menashi et al.
1973); using various kinds of flux (Mones and Banks 1958, Brixner 1959, Linares
F U N D A M E N T A L P R O P E R T I E S OF H E X A G O N A L F E R R I T E S
317
1962, Suemune 1972, Aidelberg et al. 1974); or discontinuous grain growth

(Lacour and Paulus 1968, 1975). B a - Z n - Y , B a - Z n - W , B a - Z n - Z , B a - C o - Z n - W
and B a - C o - Z n - Z etc. were also grown by the flux method (Tauber et al. 1962,
1964, Savage and Tauber 1964, AuCoin et al. 1966, Suemune 1972). BaC12,
BaO-B203, BaO-B2Og-PbO, Na2CO3 and NaFeO2 were recommended as a flux
for these compounds. Takada et al. (1971) found that topotactic reactions among
a - F e O O H or ~-Fe203 and BaCO3 or SrCO3 are effective to obtain a grain
oriented specimen. The crystallographic relationships of the materials are
( 100 )~-F~OOH//(0001)~,_F~203//(0001)S~O.6Fe203,
[010],,-F~OOH//[11,201a -Fe203//[1010]SrO.6F~203
Hot press or hot forging processes are also useful to prepare a dense oriented
sintered body (St~iblein 1973, Haneda et al. 1974a).
2. M compound
A Ba 2+ ion in the M compound, BaO-6Fe203 (BaM), can be replaced partly or
completely by Sr 2+, Pb 2+ and a combination of, for instance, Agl++ La 3 or
Nal++ La 3+, without changing its crystal structure. Substitutions of Fe 3 and 02ion in the compound are also possible. In all cases, substituted ions would be
chosen to keep electrical neutrality and to have similar ionic radii with the original
ions (see table 2; a more comprehensive table of ionic radii can be seen, for
example, in the book of Galasso (1970)). BaM was at first the only main
constituent of M-type oxide magnet, produced on an industrial scale but
TABLE 2
Ionic radii of several related ions (Pauling 1960).
Element
valence
r (A)
Element
valence
r (A)
Element
valence
r (4)
Ag
AI
As
+1
+3
+3
+5
+2
+3
+2
- 1
+2
+3
+2
- 1
+2
+3
1.26
0.50
0.58?
0.46t
1.35
0.96?
0.99
1.88
0.72?
0.63?
0.72?
1.36
0.74t
0.64t
Ga
Ge
In
Ir
La
Li
Mg
Mn
+3
+4
+3
+4
+3
+1
+2
+2
+3
+4
+1
+5
+2
- 1
0.62
0.53?
0.81
0.68?
1.15
0.60
0.65
0.80?
0.66t
0.60?
0;95
0.70
0.69?
1.40
+3
+5
+2
+3
+5
+3
+4
+2
+5
+4
+3
+5
+2
+4
0.44t
0.35t
1.207
0.76?
0.62?
0.81
0.71
1.13
0.68t
0.68
0.95
0.59
0.74
0.80
Ba
Bi
Ca
C1
Co
Cr
Cu
F
Fe
? Ahrens (1952).
Na
Nb
Ni
O
Pb
Sb
Sc
Sn
Sr
Ta
Ti
T1
V
Zn
Zr
318
H. K O J I M A
SrO-6Fe203 (SrM) has more recently taken over some part of BaM. PbO.6Fe203
(PbM) is used only as an additional material for oxide magnet purposes at present
(see ch. 7 by Stfiblein for the applications). In the following section the fundamental properties of BaM, SrM and PbM are described. The properties of solid
solutions among BaM, SrM and PbM, and substituted M compounds are treated
separately in this chapter.
2.1. BaFele019, SrFe12019 and PbFea2019

2.1. i. Crystal struclure
Adelsk61d (1938) determined the crystal structures of BaM, SrM and PbM,
prepared by heating co-precipitated mixtures from the solutions of nitrates. Figure
11 is a perspective drawing of BaM. The 02 ions form a hexagonal close packed
lattice, so that its layer sequence perpendicular to the [001] direction is A B A B . . .
or A C A C . . . as is shown in the figure. Every five oxygen layers, one O 2 ion is
replaced with Ba 2+, Sr 2+ or Pb 2+ in BaM, SrM or PbM respectively and this occurs
due to the similarity of their ionic radii as given in table 2. Five oxygen layers
(15)
(12)
(11)
(10)
(9)
(8)
(7)
(6)
{5)
(4)
(3)
(2)
Fig. 11. Perspective illustration of BaO.6Fe203.
319
make one molecule and two molecules make one unit cell. Each molecule shows
180 rotational symmetry around the hexagonal c-axis against the lower or upper
molecule. The O z- layer containing Ba 2+ is a mirror plane, being perpendicular to
the c-axis. Fe 3+ ions occupy the interstitial positions of the oxygen lattice. The
space group of the compound is denoted as P63/mmc (D4h) using H e r m a n n Mauguin's (Sch6nflies') symbols.
Figure 12 illustrates more clearly the layer structure of BaM, where z means
the layer height along the [001] direction and the layer numbers are the same as
in fig. 11. Explanation of the symbols used in the figures are also given here.
Wyckoff's notations are adopted for every site in the crystal (Henry and Lonsdal
1952). The positions of each atom are tabulated in table 3 (Galasso 1970). Figure
~
(6) 0.45
C~) 0 -2
{12) 0,95
ion
(~) Be2+ ion
Fe3+(4f2)IOctahedral site
(5) 0.35
(11) 0,85
(~ Fe3+(2o)J
141 0.25
clot 0.75
(~ Fe3+ under the layer

Lt~ Fe3+ above the layer
T relative orientation
of magnetic moment
(5) 0.15
(9) 0.65
(2) 0.05
(8) 0.55
(I) Z=O
(7) 0.50
(13) 1.00
Fig. 12. The layer sequence of BaO.6Fe203.
320
H. KOJIMA
TABLE 3
Atomic positions of BaFe120~9 (see fig. 12) (Galasso 1970).
Ion
2Ba 2+
24Fe 3+
3802-
Site
Coordinate
0.028
0.189
-0.108
2d
2a
2b
4fl
4f/
12k
I, 2, 2; 2, ,
0,0,0;0,0,1
0,0,;0,0, 3
)l I
(, 2, Z; 2, 5,Z ~q_
1
___(1, 2, z ; 2, 3,1 ~+z)
+(x, 2x, z; 2x, x, Y.; x, 2, z; x, 2x, l - z; 2x, x, + z; , x, + z)
0.167
4e
+(0, 0, z; 0, 0, 1+ z)
1 2
2
(3, 3, z; ~, , + z)
(x, 2x, ; 2x, x, 3; x, g, )
--+(x, 2x, z ; 2x, x, 2 ; x, 2, z; x, 2x, ~1- z; 2x, x, ~+z; , x, 1+z)
1
1
1
(x, 2x, z ; 2 x , x, 2;x, 2, z ; x , 2 x , ~ - z ; 2 x , x , ~ + z ; x , x , ~ )
0.186
0.167
0.500
4f
6h
12k
--
0.150
-0.050
0.050
0.150
13, t h e (110) s e c t i o n of B a M , is a n o t h e r e x p r e s s i o n o f t h e c r y s t a l s t r u c t u r e ,
s h o w i n g a t o m s a n d s y m m e t r y e l e m e n t s in a m i r r o r p l a n e c o n t a i n i n g t h e c - a x i s
( B r a u n 1957). S a n d R a r e t h e b u i l d i n g b l o c k s of t h e crystal, a n d S* a n d R *
i n d i c a t e t h e b l o c k s , o b t a i n e d by r o t a t i n g S a n d R t h r o u g h 180 a r o u n d t h e c-axis,
as p r e v i o u s l y i l l u s t r a t e d . It can b e said, t h e r e f o r e , t h a t t h e u n i t cell of B a M is
21
63
6 C 6
63
++3++2,
R~
ooz
~'~hz ~U/~z iIz

[JTo]
Fig. 13. The (110) cross section of BaO-6Fe203.
321
expressed as RSR*S*. Moreover, Townes et al. (1967) refined the crystal structure
of BaM by X-ray investigation. They stated two points: o(i) The Fe 3 ion in the
trigonal bipyramidal site, 2b, is split into half atoms 0.156 A away from the mirror
plane, 4e. (ii) Some iron octahedra occur in pairs which share a common face to
form Fe209 coordination groups. The former is supported by some M6ssbauer
investigators (see ch. 2 section 4.2.1 M6ssbauer effect). Atomic coordinates,
interatomic distances and structure factors are tabulated in their paper which
gives more accurate results.
Figure 14 shows perspective drawing of the R (BaFe6Oll), S (Fe6Os) and T
(Ba2FesO14) blocks separately. The T block is related only with the Y, Z and U
I-
Fig. 14. Perspective drawings of building blocks in the hexagonal compounds, T(Ba2Fe8014), S(Fe6Os)
and R(BaFe6On).
322
H. KOJIMA
j
Qlf
j ~ J
Fig. 15. Unit cell of BaO.6Fe20), showing the crystal structure composed of spinel blocks and Ba
layers (Gorter I954).
TABLE 4
Lattice constants, molecular weights and X-ray densities of M-type compounds.
Lattice constant
Compound
Molecular
weight (g/mol)
a (,~)
c (,~)
c/a
X-ray density
(g/cm ~)
Ref.
23.i94
23.20
23.182
23.17
3.936
3.94
3.936
3.943
5.29
5.29
5.30
5.33
(a)
(b)
(c)
(d)
BaFe12019
1111.49
5.893
5.89
5.889
5.876
SrFe12019
1061.77
5.885
5.876
5.864
23.047
23.08
23.031
3.916
3.92s
3.928
5.10
5.11
5.14
(e)
(c)
(d)
PbFe12019
1181.35
5.877
5.889
23.02
23.07
3.917
3.917
5.70
5.66
(d)
(c)
(a) Tauber et al. (1963)

(b) Smit and Wijn (1959)
(c) Bertaut et al. (1959)
(d) Adelsk61d (1938)
(e) Routil and Barham (1974)
323
c o m p o u n d s but is shown here to illustrate the relationship a m o n g the blocks (see

ch. 2 sections 4.l and 4.3). S has the cubic spinel structure with the [ l l l ] axis
vertical. In other words, M is synthesized by piling up a Ba layer and a spinel
block, whose layer sequence is A B C A . . . . alternatively (see fig. 11). G o r t e r
(1954) showed this simply by fig. 15, where spinel block contains four oxygen
layers. Molecular weight, X-ray density and lattice constants reported by various
investigators are tabulated in table 4.
2. 1.2. Magnetic structure

M-type c o m p o u n d s have a typical ferrimagnetic structure, that is, the orientation
of the magnetic m o m e n t s of the ferric ions in the crystal are generally aligned
along the c-axis in antiparallel with each other. Ndel (1948) and A n d e r s o n (1950)
first considered from the theoretical view point that these alignments of magnetic
ions can be realized by superexchange interaction through oxygen ions and such a
structure has been proved from the experimental results of saturation magnetization, neutron diffraction, M6ssbauer effect and nuclear magnetic resonance
etc. Grill and H a b e r e y (1974) calculated the exchange parameters of Fe > ions in
BaM, as shown in table 5. H e r e it can be clearly seen that the closer the angle of
the F e - O - F e b o n d approaches 18(t, the larger the exchange p a r a m e t e r b e c o m e s
TABLE 5
Distances and angles of the Fe-O-Fe bonds and calculated exchange parameters in
BaFe12Ot,~ (Grill and Haberey 1974).
Distance
(A)
Angle
(degree)
Exchange
parameter
Calculated
value (K//z~)
'~ Fe(b')-OR2Fe(f2) {
]' Fe(b')-OR2-Fe(f:) ,~
1.886 + 2.060
1.886 + 2.060
142.41
132.95
Jbf2
35.96
{ Fe(f0-Os~-Fe(k) I"
,~Fe(f~)-Os2-Fe(k) ~"
1.897 + 2.092
1.907+ 2.107
126.55
121.00
Jkf~
19.63
]"Fe(a)-Osz-Fe(f~) +
1.997 + 1.907
124.93
Jaf~
18.15
{ Fe(f2)-OR3-Fe(k) ]"
1.975 + 1.928
127.88
Jf2k
4.08
]"Fe(b')-OR,-Fe(k) '['
'["Fe(b")-OR~-Fe(k) 1'
2.162+ 1.976
2.472 + 1.976
119.38
119.38
Jbk
3.69
]"Fe(k)-OR,-Fe(k) 1"
~"Fe(k)-Os,-Fe(k) ~"
I"Fe(k)-Os2-Fe(k) ~
'["Fe(k)-OR~-Fe(k) ~"
1.976 + 1.976
2.092 + 2.092
2.107+ 2.107
1.928 + 1.928
97.99
88.17
90.08
98.05
J~k
<0. I
"["Fe(a)-Os2-Fe(k) 1"
1.995 + 2.107
95.84
J~k
<0.1
{ Fe(f2~OR2-Fe(f2) $
2.060 + 2.060
84.64
Jf2f2
<0.1
Bond
324
H. K O J I M A
and when the angle is closer to 90 , the p a r a m e t e r becomes negligible small. Thus,
arrows in figs. 11 and 13 etc. are the orientation of the magnetic m o m e n t s of each
ferric ion as a result of superexchange interaction. One can see in these figures
that the S block contains four Fe 3+ of up-spin in octahedral sites and two Fe 3+ of
down-spin in tetrahedral sites. In the R block, there exist three Fe 3+ of up-spin in
octahedral sites, two Fe 3 of down-spin in octahedral sites and one Fe 3+ of up-spin
in a trigonal bipyramidal site. Considering the magnetization values of B a M with
the Andersons (1950) indirect exchange theory, the exchange scheme of the
compound is illustrated in fig. 16, proposed by Gorter (1957), and these relations
are tabulated in table 6. Notations of the sublattices commonly used for M6ssbauer or N M R investigations are also shown in the last column of the table.
[20 =l14f, ~
J4f2~ 2
14f2~ b[
[4f2//~12k [[[
I
14f2,2kHt
t20--lt4',
Fig. 16. Exchange interaction scheme in the unit cell of the magnetoplumbite structure. Each arrow
represents the magnetic moment of a Fe 3+ ion (Gorter 1957).
TABLE 6
Coordination number and direction of magnetic moment of Fe 3 ions in the unit cell of the
magnetoplumbite type crystal.
Coordination number
Number of
positions
Wyckof's
notation
Direction of magnetic
moment per mole
Remarks
6
(Octahedral site)
12
4
k
f2
I" I" I" I' '~ 1'

~ ~,
I (a)
III (d)
v (b)
4
(Tetrahedral site)
fl
$ ,~
II (c)
5
(Trigonal bipyramidal site)
I"
IV (e)
325
The total magnetization at temperature T, therefore, is expressed as

Ms(T) = 6O-k(T) -- 2o-f~(T) - 2o-~2(T) + O'b(T) + O'a(T),
(1)
where, Ok, O-fl, O'f2, O'b and O'a denote the magnetization of one Fe 3+ ion in each
sublattice. Because Fe 3+ has the magnetic moment of 5/~B at 0 K, eq. (1) is
calculated as
Md0 K) = 5 x (6 - 2 - 2 + 1 + 1) = 20/~B.
(2)
This value agrees well with the experimental result of BaM as described in the
next section.
The large magnetocrystalline anisotropy of compounds was explained by Smit
(1959) from the effect of Fe 3+ in the trigonal bipyramidal site, where a ferric ion is
surrounded by five oxygen ions. Fuchikami (1965) also showed theoretically the
contribution of Fe B+ in the trigonal site as principally responsible for the uniaxial
anisotropy. On the other hand, Van Wieringen (1967) stressed from the M6ssbauer investigations that the contributions to the anisotropy from all of five
sublattices should be more or less equally considered.
2.1.3. Saturation magnetization

The saturation magnetization per unit volume, Ms, per gram o-s, the number of
Bohr magnetons per mole Ns at room temperature or 0 K and the ferromagnetic
Curie temperature 0c for BaM, SrM and PbM reported by various authors are
collected in table 7. Values of NS at 0 K for these three compounds are about
20/-tB and agree well with the theoretically expected values from their magnetic
structures as given by eq. (1) or (2).
The temperature dependences of the saturation magnetization Ms near the
Curie points are shown for BaM and SrM by Shirk and Buessem (1969) in fig. 17.
Figure 18 illustrates the compariso n of Ms for BaM (Rathenau et al. 1952), SrM
(Jahn and Mfiller 1969) and PbM (Pauthenet and Rimet 1959a) in a wider
temperature range. In addition, fig. 19 and fig. 20 are other reported o-~T
relations for BaM and SrM (Shirk and Buessem 1969) and BaM (Tauber et al.
1963, Casimir et al. 1959) respectively. Belov et al. (1965) pointed out that the
spontaneous magnetization of BaM along the c-axis is somewhat greater than that
in the perpendicular direction to it, and found the difference of 0c between both
directions to be as shown in table 8. Similar facts are reported on the paramagnetic Curie points, as described later. Though the reported results are slightly
different from author to author, the magnetic characteristics of M-type compounds may be summarized as follows:
(i) The saturation magnetization becomes smaller according to the order to
SrM, BaM and PbM; (ii) The Curie temperatures also become smaller in the same
order; (iii) Saturation magnetization versus temperature curves are almost straight
or rather concave with a steep slope in the temperature range of 200 and
600 K.
326
H. KOJIMA
k~
s,
(-q
d
o.
+1
o';
+J
['---
8
+~
+1
t-,-
t'--
8
o'3
~
tt3
or-e0
+1
t~
tt3
t'q
,4~d
p-- ,,o
'4~ eq
r~
327
120
80
--(
'o_
6O
4 0
20
700
680
I T
720
740
760
Temperature (K)
780
Fig. 17. Saturation magnetization versus temperature near the Curie points of BaO.hFc_-(% and
SrO.6Fe203 (Shirk and Buessem 1969): (1) BaM, (2) SrM.
-200
600
-I00
TemperQture (C)
IO0
200
300
400
500
(I)
~.
400
300
,,
'-" 2 0 0
ioo
I'
0
0
200
----
400
Temperafure
600
__
800
(K)
Fig. 18. Saturation magnetization of BaO.6Fe203, SrO.6Fe203 and PbO.6Fe203 as a function of

temperature: (1) BaM (Rathenau et al. 1952), (2) SrM (Jahn and Mfiller 1969), (3) PbM (Pauthenet and
Rimer 1959a).
TABLE 8
Differences of ferromagnetic Curie temperature 0 of BaFe12Ot9
along and perpendicular to the c-axis (Belov et al. 1965).
Sample
0c//(C)
00~ (C)
0c/j-0ci
Single crystal
440.3
436.5
3.8
Polycrystal (oriented)
459.4
453.3
6.1
328
H. K O J I M A
I
\,
100
~g
<
E, 80
b
x 60
k
x
40
03
2O
200
400
600
Temperature (K)
800
Fig. 19. Plot of saturation magnetization per gram versus temperature for BaO-6Fe203 and
SrO.6Fe203 (Shirk and Buessem 1969): (1) BaM, (2) SrM.
Temperature (C)
2O0
200
400
100
,E
80
b-
'O
x 60
b
&
4O
ID
C 20
400
600
200
800
Temperature (K)
Fig. 20. Plot of saturation magnetization per gram versus temperature for BaO.6Fe203: (1) Tauber et
al. (1963), (2) Casimir et al. (1959).
329
2.1.4. Magnetocrystalline anisotropy

Villers (1959a) measured the specific magnetization of a PbM single crystal as a
function of the applied field. From his results along various measured directions
against the c-axis, as shown in fig. 21, a fairly large uniaxial anisotropy can be
estimated for the crystal. In fig. 22, magnetizing curves of B a M (Casimir et al.
1959) and P b M (Pauthenet and Rimet 1959a) perpendicular to the c-axis are
c o m p a r e d at various temperatures. Magnetocrystalline anisotropy constants K~ as
a function of t e m p e r a t u r e are plotted for B a M (Rathenau et al. 1952, Shirk and
Buessem 1969), SrM (Jahn and Mfiller 1969, Shirk and Buessem 1969) and PbM
(Pauthenet and Rimet 1959a, Villers 1959b) in figs. 23, 24 and 25 respectively.
When the direction of the spontaneous magnetization in a hexagonal crystal is
expressed by polar coordinates, 0 and ~b with respect to the crystal axis, assuming
the z-axis is the c hexagonal axis, then the magnetocrystalline energy E is given
by
E = K~ sin 2 0 + / ( 2 sin 4 0 + K3 sin 6 0 + / ( 4 sin 6 0 COS 6 (D q-
(3)
For M-type compounds,/2,/(3 . . . . are negligible in comparison with K1 and their

70
0=0
otOj,.e_e-e- -
60
/ - T
Fy
) 5o
y,
b 4o
H
,x 3 0
vl
__.t/#
20
,o/
0
I0
15
20
H (kOe) [ x l O 6 / ( 4 n -) A / m ]
Fig. 21. Magnetization per gram of PbO.6Fe203 single crystal as a function of the magnetic field
applied at various angles with respect to the c-axis (Villers 1959a).
330
H. K O J I M A
600
20.4
0 ~ C ' 0 4 2 ~ " 0 " .7 - - - ~ - - - 0 - 0
500
;.~,.
--0-
.77.4
K
-
,~ 2.3-4.2-9,5-15-20.4 K
400
b
//
~,l
,~ 300
eoo
7SI
JI
tOO
'
'
567 K
:4
t
,-----r - - 5
;
I0
I
15
I
20
H (kOe) E x l O e / ( 4 r r )
i
25
G-
30
A/m]
Fig. 22. Magnetization of BaO.6FezO3 and PbO.6Fe203 single crystals at various temperatures as a
function of the magnetic field applied perpendicular to the c-axis: ([]) B a M (Casimir et al. 1959), (O)
PbM (Pauthenet and Rimer 1959a).
-200
Temperofure (C)
0
I00 200 500
-I00
I
400
L !
500
I
L .........
~J5
!
L
ro
~L
~-o
i
i
200
400
Temperafure
600
800
(K)
Fig. 23. Magnetocrystalline anisotropy constant K~ of BaO-6Fe203 as a function of temperature: (C))

R a t h e n a u et al. (1952), (Q) Shirk and Buessem (1969).
331
~
5
tO
-3
%
,x, 3
.,
t,3
E
0
"" 2
--
"-- o
200
400
Temperafure
600
%800
(K)
Fig. 24. Magnetocrystalline anisotropy constant K~ of SrO.6Fe203 as a function of temperature: (O)

Jahn and Miiller (1969), (z~) Shirk and Buessem (1969).
t3
E4
s%
%s
X
t...a
,<
.-,%.
(2) K 2
2 ,n
E
O
\Xo ~'~.~
ID
x 0
0
200
400
Temperature
600
800
(K)
Fig. 25. Magnetocrystalline anisotropy constant KI and K2 of PbO.6Fe203 as a function of temperature: (O), (O), Kj K2, Pauthenet and Rimet (1959a); (A) K~ Villers (1959b).
values were reported only for PbM, as shown in fig. 25 and table 9. The order of
the values of Kj among the three compounds is again, the same as M~, i.e.,
SrM > BaM > PbM, though the difference between SrM and BaM is not clear in
s o m e cases.
Now, because HA defines the maximum coercivity as described in the next
section, we shall briefly compare HA values among these compounds. Since the
magnetocrystalline anisotropy field HA for uniaxial materials is given by
Ha = 2KI/Ms,
(4)
we can easily estimate the value of HA from the data of K1 and Ms, described
here. Figures 26 and 27 give curves of HA against temperature for BaM (Rathenau
et al. 1952, Shirk and Buessem 1969) and SrM (Jahn and M/iller 1969, Shirk and
332
H. KOJIMA
x~
~+~
~+
II
dddd
e.
II
dd
e-
e.
e-
-ff
d
+l
+1
tt~
t--
~.
+1
+i
Ca
e.
e)
xa
eqeq
q.
Me4
+1
t'q
m.
+1
+1
ff
o
~7
-200
,
20
T e m p e r e f u r e (C)
0
I00
200
300
i
I!
I
i
-I00
~
400
333
500
"..4
< i 5 - -
'~
o
I0
31
i!
260
400
Temper0ture
600
800
(K)
Fig. 26. Magnetocrystalline anisotropy field HA versus temperature for BaO.6Fe203: (C)) Rathenau et
al. (1952), (A) Shirk and Buessem (1969).
25
20
<
15
.........
(3)
" - . . ~
""\ \
10
o
'1-
0
0
200
400
Temperature
600
800
(K)
Fig. 27. Magnetocrystalline anisotropy field HA versus temperature for SrO.6Fe203 and PbO'6Fe203.
SrM: (1) Jahn and M/iller (1969), (2) Shirk and Buessem (1969). PbM: (3) calculated from the data of
Pauthenet and Rimet (1959a).
334
H. KOJIMA
Buessem 1969) respectively. The broken line in fig. 27 shows HA of PbM

calculated from the results of Pauthenet and Rimet (1959a). There are broad
maxima between 400 and 600 K, except Rathenau's results. Beside the data in figs.
23-27, the reported values of the magnetocrystalline anisotropy constant K~ and
anisotropy field Ha are tabulated in table 9. Above all, from these points of view,
SrM eventually shows the best properties as the permanent magnet material
among the three compounds.
2.1.5.
())ercive force
It can be generally said that the coercive force of ferrite magnets such as sintered
or bonded compacts of BaM, SrM or PbM powders, originates in the magnetic
behaviour of single domain particles with uniaxial magnetocrystalline anisotropy.
Now we shall briefly describe general considerations regarding the coercive force
of such materials. The critical diameter of a particle, where a single domain state
can be energetically realized, was obtained by Kittel (1946) and Ndel (1947) as
D = (9/2r)(O-w/m~),
(5)
cr,~ in the equation denotes the domain wall energy per unit area and approximately written by
O-w= 4(AK) '/2 .
(6)
Here, A expresses the exchange constant. In table I{L the values of D~, ow and
MHc are listed for M compounds.
Since only rotation of magnetization can be expected in a particle of smaller

diameter than D~, assuming its demagnetizing factor as N. we can write the
coercive force as
MHc = 2 K / M ~ - N M ~ .
(7)
For the magnetizing process of a powder assembly, Stoner and Wohlfarth (1948)
assumed the coherent rotation mode without any interaction effect, and concluded
that the coercivity factor obtained was 0.48 for the randomly oriented powders;
then MHc is given by
MHc
0.48(2K/Ms - NMs) .
(8)
For M compounds, crystals are usually easy to grow along the c plane, so that N
affects MHc more unfavourably than spherical particles. However, we still cannot
attain the MHc value of eq. (8) experimentally for practical hexagonal ferrite
powders. To explain this, various magnetization reversal mechanisms of incoherent
type have been proposed.
For example, by considering the interaction field of surrounding magnetic dipoles,
Eldridge (1961) simply estimated the effect of mutual interaction. Hence, we can
335
e~
io<
,=
!c
,
t3
;o
II
[,q
X
kD
kD
II
II
a
O
.o
0
,,=
'i
N
O
"a
ff
e~
D.
e~
o
6
L)
6
L)
~d
11
e~
~.~
..)
&-a
m.
uq
trl
~'~
O~
,4
o.
~D
tt3
t~q
o.
O0
e~
-
+1
t'4
e.
o
o
o,
~ E
g =N
336
H. K O J I M A
generally express MHc using his results:

MHc = MHc(0)- CpMs, with C = 1.7.
(9)
Here MHc(0) and p express the coercive force of ideal coherent rotation and the
volumetric packing factor of the powder assembly. Bottoni et al. (1972) deduced
the partial existence of chains of spheres with fanning mode from the rotational
hysteresis measurements for dry-milled BaM powders. Many researchers, for
example, Hoselitz and Nolan (1969), Ratnum and Buessem (1972), Haneda and
Kojima (1973a, 1974) besides others mentioned below, have been discussing the
causes for the reduction of domain nucleation field and they concluded that
domain wall movement should be also considered for the magnetizing process of
M compound powders, even though they are sufficiently small compared to Dc in
table 10. For instance, lattice defects (Heimke 1962, 1963), different phases
(Richter and Dietrich 1968), stacking faults or deformation twins (Rantnam and
Buessem 1970), local changes in anisotropy (Aharoni 1962), inhomogeneity of
magnetic field in the edge of plate like crystals (Holtz 1970) etc. can be given as
factors to be considered as possible causes.
Experimental results of packing effects on MHc are illustrated in fig. 28 for BaM
(1), (2) by Shimizu and Fukami (1972), BaM (3) by Luborsky (1966) and SrM (4)
by Hagner and Heinecke (1974). We can say from these results that the constant
C is rather smaller than the value of eq. (9) for BaM or SrM, and this may be
caused by their larger Ks and lower Ms values. The last authors especially stressed
the importance of the agglomeration effect to verify the dependence of MHc on
the packing density. To prevent the agglomeration, they used a soft ferrite to
dilute SrM powders and measured MHc above the Curie temperature of the soft
4000
<
3000
g
(4)
_o 2 0 0 0
x
o
o
"1"
I000
0.2
0.4
Packing
0.6
factor
0.8
1.0
Fig. 28. Effect of the packing factor on the coercive force of BaO.6Fe203 and SrO'6Fe203. (1), (2)
BaM (Shimizu and Fukami 1972), (3) BaM (Luborsky 1966), (4) SrM (Hagner and Heinecke 1974).
337
ferrite. But Tfmfisoiu et al. (1976) reported a very high MHc value of 6500 Oe
[5.17x 105A/m], obtained for SrM by the ordinary dispersion method in zirconium oxide powder or an epoxy resin, if the packing factor p ranges from 0.1 to
0.01.
Curve (1) in fig. 29 is an example of the change in MHc during the milling
process (after Haneda and Kojima (1974)). Though the shape of the curve
depends on the grinding conditions, MHc generally increases at first and then
decreases with milling time. The first rise is presumably caused by the approach to
the single domain behaviour and the following decrease may be explained b y
various causes introduced by the prolonged milling process, as mentioned before.
Curve (2) in the figure shows MHc obtained by annealing the specimenS of curve
(1) at 1000C for an hour. The remarkable increase may be mainly due to the
recovery of various defects. The MHc versus particle diameter relations of BaM
are compared in fig. 30. Shirk and Buessem (1971) determined the particle size by
X-ray (1) and electron microscope (2), while Sixtus et al. (1956) measured MHc
against thickness (3) and diameter (4) of the platelets. Powders larger than 10 .4 c m
seem to behave as multidomain particles and below 2 x 10 6cm by X-ray or
6 x 10-6cm by electron microscope, superparamagnetic effects are likely to be
predominant. Since superparamagnetic powders do not show a hysteresis loop,
MHc abruptly tends to zero in this region. If the particle has volume V and Sc
denotes the superparamagnetic critical size, the coercivity factor against V/Sc can
be expressed as in fig. 31, according to the calculated results of Shirk and Buessem
(1971) for the case of BaM. Hence, one can say the Stoner-Wohlfarth model is
valid only under the condition of V ~ 100So, that is roughly larger than 4 x 10-6 cm
in diameter for a BaM particle; the agreement of this estimation with the results
in fig. 30 is reasonably good.
II
1
~'
--e~e'--
50
100
Milling time (hr)
150
200
Fig. 29. Milling and annealing effect on the coercive force of BaO.6Fe203 (Haneda and Kojima 1974),
(1) as milled powder, (2) after annealing at 1000C for 1 h.
338
H. KOJIMA
104
<
I
i
I
i0 3
O
x
I)
(2)
x\
O
i0 2
I0
10-6
I I
II
10-5
I I
iO-4
Porficle
[ I
IO-3
diomefer
I
fO-Z
(cm)
Fig, 30. Relation of coercive force and particle size in BaO.6Fe203: (1) diameter as spheres determined by X-ray, (2) by electron microscope (Shirk and Buessem 1971), (3) thickness of platelets
determined by optical microscope, (4) diameter (Sixtus et al. 1956).
Figure 32 shows the changes of MHc with temperature; i.e., for SrM (1) and
BaM (2) by Mee and Jeschke (1963), BaM (3) by Sixtus et al. (1956), BaM (4) by
Rathenau (1953) and SrM (5) by Jahn and Mdller (1969). All results show maxima
between 200 and 300C. Rathenau tried to explain the maximum of MHc by
assuming a single domain state around 300C and a multidomain state at room
0.6
0.5
0.4
8
0.3
$ o.2
0.1
I0
10 2
03
V/Sc
Fig, 31. Coercivity factor against particle size for isotropic powder assemblies (Shirk and Buessem
1971). V: volume of a particle, So: super-paramagnetic critical size; dotted line: Stoner-Wohlfarth
model.
o~
.---o
'~
''
.-
339
?< 5~
~"
-200
200
Temperature
400
(C)
Fig. 32. Temperature dependence of the coercive force for BaO-6Fe2Os and SrO-6Fe203. (1) BaM, (2)
SrM (Mee and Jeschke 1963), (3) BaM (Sixtus et al. 1956), (4) BaM (Rathenau 1953), (5) SrM (Jahn
and M/iller 1969).
9
8
I
i
i
J
5
-200
200
Temperature (*C)
400
Fig. 33. Temperature dependence of ",/~/Ms, which is proportional to the critical diameter of single
domain particle (Rathenau 1953).
340
H. K O J I M A
temperature. He reported the temperature dependence of (KO1/2/Msas in fig. 33,

to which the critical particle diameter Do would be proportional. His explanation
is based on the increase of this quantity with temperature. However, this might
only be one reason, because many authors reported maxima of HA in the same
temperature range as MHc (see figs. 26 and 27).
Craik and Hill (1977) pointed out that the strong domain wall pinning could be
expected at grain boundaries of BaM powders without supposing any imperfections and so the role of grain boundaries is important in relation to the
coercivity mechanisms. Thus, the magnetization reversal process in hexagonal
oxide powders are still open to investigation for some details, even for the
particles of critical size. But we may now conclude that all the factors described
here should be considered, though the dominant magnetizing mechanism depends
perhaps on the preparation method.
When the magnetization reversal is achieved by the nucleation and growth of
reverse domain, the angular variation of coercive force, plotted as MHc versus
1/cos 0, shows a linear relation. Here, 0 expresses the angle between the applied
field and the easy axis of the oriented powder assembly. Ratnam and Buessem
(1972) obtained this relation with BaM particles of 100-200 Ixm as shown in fig.
34. However, if particles perfectly follow the Stoner-Wohlfarth model then MHc
can be drawn as the curve S-W in fig. 35; here the value of the effective
anisotropy field HA is assumed to be 12000 Oe [9.5 105 A/m], considering the
demagnetizing factor. For practical powders, magnetizing process takes place by
both of these mechanisms and thus curve (2) is observed as the angular dependence of ordinary ball-milled BaM powders. For the sample prepared under
relatively defect-free conditions, for instance by the chemical co-precipitation
240
o
E 200
<
F-
~O
-
160
120
O
IO
u
"r
40
o
.
0.2
0,4
0,6
0,8
1.0
cos 8
Fig. 34. A n g u l a r dependence of the coercive force for oriented BaO.6Fe203 powders (Ratnam and
B u e s s e m /972).
F U N D A M E N T A L PROPERTIES OF H E X A G O N A L FERRITES
12
341
/I
~lo
\
/
K//
tt
S-W
, ~ Q
O ~ Q ~ O
---''-tD'-''~"
~ ,
(2)
0
0
40
0 (degree}
60
80
Fig. 35. Analysis of magnetizing process in BaO.6Fe;O; powders from the angular variation of
coercivity (Haneda and Kojima 1973a): (1) co-precipitated powders, (2) ball-milled powders, (S-W)
calculated curve by the coherent rotation model, (K) calculated curve by the magnetizing process with
wall motion.
method, they may be magnetized mostly by coherent rotation, as proved by curve

(1) in fig. 35, where it completely agrees with curve S - W in the range 4 0 < 0 <
90 . To see the difference more clearly, magnetizing curves are compared with the
theoretical S - W curve in fig. 36. Demagnetizing curves of defect-less powders of
BaM (1) and SrM (3) agree well with the calculated curves for coherent rotation,
S-W, but ball-milled BaM powders (2) behave rather differently from the S - W
model (Haneda and Kojima 1973a, Tfinfisoiu et al. 1976). Ratnam and Buessem
i//
id " /'"'1
.g ,"
5 <koe~
--
,/i~
Fig. 36. Demagnetizing curves of unoriented powder assemblies: (1) co-precipitated BaM, (2) ballmilled BaM (Haneda and Kojima 1973a), (3) wet-milled and annealed SrM (Tfinfisoiu et al. 1976).
342
H. KOJIMA
(1972) and Haneda and Kojima (1973a) proposed methods to estimate the ratio of
the two magnetizing mechanisms in a powder assembly from the angular variation
of MHc. The highest MHc values obtained hitherto by special preparation methods
are listed, together with other experimental conditions, in table 10.
2.1.6. Paramagnetic properties

Borovik and Mamaluy (1963) measured the temperature dependence of the
susceptibility per gram above the Curie point for M compounds. Figure 37 shows
the 1/xg-r relations of BaM (1) (Gorter 1954), SrM (2) and PbM (3) (Borovik and
Mamaluy 1963). They also determined N6el's constants for the susceptibility per
atom XA; ~r, CA and X0,A in eq. (10) (N6el 1948) by a graphical method from the
results of fig. 37. Here,
1
1
T
~
XA Xo,A CA
oT-0'
(10)
and 0 can be given by

o = nCAA~
(2 + o~+/?),
(11)
where CA is the atomic Curie constant for Fe3+; A,/x are the numbers of the Fe 3+
ions in the A and B sublattice; n, a and /3 are the molecular field constants
connected with the exchange interactions of the AB, A A and BB types. If the
T (C)
600
8
800
iI
IO00
i ] ~ t , ~I
I
,~.
.o/e
{,9
~.
I
6
[/I/
..
~s
x
4
3
~o
x- 2
/
I
II00
1300
T{K)
Fig, 37. Temperature dependence of the specific susceptibility above the Curie temperature: (1) BaM
(Gorter 1954), (2) SrM, (3) PbM (Borovik and Mamaluy 1963).
700
900
343
m o l a r susceptibility XM is used i n s t e a d of XA in eq. (10), t h e n CM can b e o b t a i n e d

i n s t e a d of CA. T h e c o n s t a n t s are t a b u l a t e d in t a b l e 11. B o r o v i k a n d M a m a l u y
c o n c l u d e d that the c o n s t a n t s X0,A, Cr, CA, a n d t h e r e f o r e the m o l e c u l a r field
c o n s t a n t s are r o u g h l y the s a m e for h e x a g o n a l a n d cubic ferrites.
A l d o n a r d et al. (1966) m e a s u r e d XM of P b M a n d f o u n d different values for AiM
with a p p l i e d m a g n e t i c field parallel a n d p e r p e n d i c u l a r to the c-axis, as s h o w n in
fig. 38. T h e y also d e r i v e d t h e following f o r m u l a from the precise m e a s u r e m e n t of
the t e m p e r a t u r e c h a n g e in XM in cgs u n i t b e t w e e n 800 a n d 1200 K along the
c-axis:
1
XM
1
T
38.21 + 6 5
4367
T-655"
(12)
10
9
I
C aXiS
H II
H .L c oxis /
~7
.,//
fd-
J/"
Az
-~5
~3
"2_ I
///1
0 ////
710
720
7:30
T(K)
740
750
Fig. 38. Temperature dependence of the molar susceptibility of PbM along parallel and perpendicular
directions to the c-axis (Al6onard et al. 1966).
TABLE 11
N6el constants of M compounds according to eq. (10) (Borovik and Mamaluy 1963).
Compound
CA
cm3K/atom
CM
cm3K/mol
BaM
SrM
PbM
0.0515
0.0475
0.0526
58
51
61
CA: atomic Curie constant of Fe3+ ions,

CM: Curie constant obtained from molar susceptibility.
104 (emu/atom)
[1/(4zr) 10 4 S I / a t o m ]
o- x 105
K atom/cm3
5.1
5.8
6.8
26
27
31
l/X0, A X
344
H. K O J I M A
2.1.7. Magnetic aftereffect

Diilken et al. (1969) investigated the relaxation phenomena of polycrystal BaM.
They measured the complex permeability between 77 and 743 K in the frequency
range from 500 Hz to 100 kHz. The real p a r t / x ' and the imaginary part/x" of the
initial permeability as a function of temperature T, measured at i kHz for Fe 2+
free BaM, show linear relations with T, as shown in fig. 39(a). However, /x" of
BaM with 0.24wt% Fe 2+ measured at 10kHz shows three maxima at - 1 8 5 ,
- 1 4 5 and +60C, as shown in fig. 39(b). If k and Q denote Boltzmann's constant
and the appropriate activation energy, then the relaxation time ~- is expressed as,
"r=
exp(O/kT).
(13)
Diilken et al. (1969) determined O for the three maxima as (I) 0.1 eV, (II) 0.2 eV
and (III) 0.6 eV, and the relaxation frequency f = 1/2~-~-= as (I), (II) - 101 Hz and
( I I I ) ~ 1 0 1 3 Hz. These relaxation phenomena can be explained by the diffusion
process between Fe 2+ and Fe 3+, which is often observed in cubic ferrites.
t
h.
--o-c~-c. -o-o-oc - o - o F'
105
Io-) l
=._o_oj
F"
-%
I
t0 -2
(b)
I
!.c-.o--~ ~
"ov---o-c-~-.o~
I 15
F'
510-1l
(a)
lo-'
lo-2
5 o'o--c-~
-200
~c.o.o~5
-I00
0
Temperature
I00
(C)
Fig. 39. Temperature variation of the complex permeabi|ity for polycrystal BaO.6Fe203 (Dtinke] t al.
1969): (a) Fe z+ free B a M at i kHz, (b) B a M with 0.24 w t % Fe 2+ at 10 kHz.
345
2.1.8. F M R
Numerous experiments of ferromagnetic resonance absorption in BaM or SrM
have been reported, most of which aim to determine the anisotropy field H A and
the effective spectroscopic splitting factor gen against temperature. Several authors
also especially investigated the effects by the shape, size or surface roughness of
the samples, the existence of domain walls, or the angle between the applied d.c.
field and the easy axis, etc. Figure 40 shows the resonance absorption in BaM at
various temperatures. Smit and Beliers (1955) showed with a thin single crystal
that only the absorption peak excited by a parallel a.c. field is observed at lower
temperature, but the perpendicular field peak appears above room temperature
and splits into two at 200C (fig. 40(a)). Grosser (1970) investigated the resonance
absorption of an isotropic polycrystal between 21C (fres= 22.22 GHz) and 465C
@es = 22.03 GHz) as shown in fig. 40(b), where the resonance field at room
temperature moves to lower fields with increasing temperature near the Curie
2.5
\
\\
\
\
A
t3
(3
03
..Q
2.0
1.5
b)
\
\
I
450*
420*
1.0
Q.
o
J~
4ti~ .-
0.5
0o
8
H
50
~/
(kOe)
12
16
(a)
200"C
a~
o
40
IP
to
II
..a
30
g
"..7-.~
0
o~
t~
<
20
[xlOS/(4~-) A/m]
11
,/i
I
I/
20
'
IJ
I0
0
13
15
17
H (kOe) [x106/(4~) A/m]
19
Fig. 40. Ferromagnetic resonance absorption in BaO.6Fe203 versus applied d.c. field at various
temperatures: (a) single crystal (Smit and Beljers 1955), (b) isotropic polycrystal (Grosser 1970).
346
H. KOJIMA
points. The ordinate of the figure is illustrated in arbitrary scale but it is

proportional to/x".
Figure 41 is the relation of resonance frequency and applied d.c. field for a BaM
single-crystal, by Silber et al. (1967). The solid lines in the figure express the
calculated results for various angles 00 between the c-axis and the applied field,
using the following resonance conditions:
(o~/y)2 = [Ha(1 - 2 sin 2 0) + Hext cos(0o - 0)]Hext(sin 0o/sin 0),
(14)
sin 0 cos 0/sin(00- 0) = HexdHa.
(15)
and
Here, ~o, y and 0 represent the resonance frequency, gyromagnetic ratio and
angle between the c-axis and the magnetization vector, respectively. The effective
anisotropy field is generally given by Ha = HA--(NIl- N)M~. Thus, Silber et al.
determined y from the slope and HA from the intersection with the frequency axis
of the zero-degree curve in fig. 41. The "knees" in the experimental data
0o
44*
59*
ID
.o
.........---
. i'
rv
46
42
Applied
field
(k0e)
16
20
"xl06/(4=) A/m]
Fig. 41. Relation of resonance frequency and magnetic field applied at various angles to the c-axis of
BaO.6Fe203 single crystal (Silber et al. 1967).
347
represent the change from the single domain state at higher fields to the
multidomain state at lower fields. The resonance frequencies and absorption
intensities in BaM specimens with cylindrical domain structure have been calculated by Sigal (1977) and compared with the experimental results, changing the
direction of magnetic field with the easy axis. Typical experimental results are
summarized in table 12.
When the d.c. field is cycled between _-_25kOe [+_1.99 x 106A/m] for BaM
milled powder, Hempel and Kmitta (1971) found a microwave absorption peak at
about 2 kOe [1.59 x 105 A/m] with f - - 9.4 GHz, which shows a pronounced hysteresis apart from the F M R occurring at about 15 kOe [1.19 x 106 A/m]. They also
observed that the low field losses and the line width of the F M R decrease with
increasing annealing temperature of the sample. While Roos et al. (1977) found
microwave absorption of chemically co-precipitated, polycrystalline BaM at H
--HAl2, when the sample was previously saturated; however, no absorption peak
in negative fields was found for the conventionally prepared BaM. They obtained
three peaks at H = -6.6 kOe [-5.25 x 105 A/m], -8.8 kOe [-7.00 x 105 A/m] and
-15.3 kOe [-1.22 106 A/m] with f = 11.9 GHz, and concluded from these results
that the magnetization in most particles of the chemically precipitated sample is
reversed by coherent rotation.
Besides such basic investigations, several studies relevant to the applications to
microwave devices have been reported. For example, Dixon Jr. and Weiner (1970)
obtained H a = 17-5 kOe [13.5-4.0 x 105 A/m] over the frequency range of f =
23.2-37.6 GHz with BaZnxTixFe12 2xO19. De Bitetto (1964) also investigated the
F M R of BaO.x(TiCoO3)-(6-x)Fe203 and SrO-xA1203.(6-x)Fe203 systems and
determined HA as 17.5-6.6 kOe and 19.3--53.4 kOe [15.442.5 x 105 A/m] respectively.
2.1.9. N M R
Streever (1969) obtained the NMR line shapes of Fe 57 in single-crystal powders at
4.2K and resintered single-domain powder at 77 K for BaM, by plotting the
spin-echo amplitudes versus frequency as shown in figs. 42(a) and (b). Each line
can be assigned on the basis of the changes in relative intensities and shift in
external magnetic fields. M6ssbauer data are also useful to analyze the signals and
the reverse is naturally also true. The relations of the sublattices and the notations
in the figure are identical to those used in table 5. L/itgemeier et al. (1977)
measured relaxation rates of Fe 57 nuclei in BaM between 1.2 and 4.2K and
proved that the relaxation time is much shorter for the wall signals than for the
domain signals due to the influence of the wall excitations. The temperature
dependence of NMR frequencies is summarized in fig. 43, after the results of
Streever and Hareyama et al. (1970). Though the temperature changes of signal
III (sublattice d) and V (b) show some differences between the two papers, the
frequency changes of each signal are almost continuous over the whole temperature range. The temperature dependence of signal I (a) from Fe 3+ in octahedral a sites is more remarkable than those of signal II (c), III (d), IV (e) and V
(b), while signal IV (e) appears at a lower frequency than the others. These results
348
H. K O J I M A
T A B L E 12
Summarized results of F M R experiments for M-type compounds.
Compound
BaM
BaM
BaM
Experimental condition
fr~s(GHz)
T(C)
single cryst, disc, d = 1 m m ,

t = 40 tzm; disc _1_c-axis,
Hr~s and ha in basal plane,
angle between Hres and ha
is 45
23.93
23.98 '
23.98
23.98
23.98
-196
20
112
155
200
2.00 (assumed)
1.98
2.00
2.01
2.02
single cryst, disc, d = 0.083 cm,

t = 0.030 cm; Hr~s//disc,
58.2
58.4
58.6
58.8
59.0
R.T.
1.87
25
1.96
R.T.
1.91
1.91
20
2.05
Hre~//c-axis, hr~A_H ~
single cryst, sphere, d = 0.4 m m
53.0-55.3
ge~
Hresffc-axis, h~//c-axis
BaM
SrM
BaM
BaM
BaM
oriented polycrist, slab

single cryst, disc,
d = 2.60 cm, t = 0.01 cm
single cryst, sphere,
d = 0.036 cm
51-65
single cryst, sphere,

d = 0.05 cm
66.6, 120
66.6, 120
R.T.
2.02 0.01
4.2 (K)
20 (C)
1.99 - 0.03
single cryst, sphere, d = 0.038~.05 cm,
BaM
Hre~~~c-axis
I>52.0
22
BaM
* Spin wave line width

(a) Smit and Beliers (1955)
(b) W a n g et al. (1961)
(c) Mita (1963)
(d) D e Bitetto (1964)
(e) Burlier (1962)
(f)
(g)
(h)
(i)
Silber et al. (1967)

Kurtin (1969)
Dixon and Weiner (1970)
Grosser (1970)
R.T.
21
200
300
35O
40O
349
T A B L E 12 (continued)
Hr~ (kOe) [x 106/(4~-)A/ml
hrr//'Hres
14.3
15.05
15.40
15.40
15.35
hrr-l-Hres
-10
17.15
17.55
17.15
16.85
3.844
3.886
3.964
4.042
4.140
18.7-28.2
HA (kOe)
[X 106/(47r)A/m]
A H (Oe)
[x llY/(4~)A/m]
16.2
17.0
17.3
17.3
17.3
18.4
0-13
Ref.
47rMs = 6.67 (kG)

4.80
3.90
3.50
3.12
(a)
p = 5.13 (g/cm3)
3'4 = 2.62 (MHz/G)
(b)
17.55
<12
(c)
17.5
19.3
1600
1600
(d)
17.0
2.0-7.0
Remarks
3' = 2.87 (MHz/G)
16.2
16.1
17.1
(e)
(f)
~<10
46
4~'M~ = 5.2 (kO)

AHk* = 2 1.5 (Oe)
(g)
17.0
4~'Ms = 4.8 (kG)
(h)
17.0
17.0
15.1
13.1
10.5
Ms = 375 (G)
248
177
142
106
(i)
350
H. KOJIMA
I0
(b)
l
I
I
/,
4
i
m
o_
0
I0
:>
(a)
8
6
III
lI
2
0
58
/%
62
66
Frequency
70
74
78
(MHz)
Fig. 42. Plot of the spin-echo amplitudes versus resonance frequency for BaO.6Fe203 (Streever 1969):
(a) single-crystal powders at 4.2 K, (b) resintered single-domain powder at 77 K.
78
.........
~ _ ~ i__~__ .~
74
O. . . . . . .
I 70
2;
I
I
66
"7
'~ ~.,~
g62
b_
58
]7
54
0
I
I00
200
Temperofure ( K )
""~'
500
Fig. 43. Temperature dependence of NMR frequency: (O) Streever (1969); (O) Hareyama et al.
(1970).
351
can be understood from the differences of F e - O - F e bonds for each Fe 3+ ions (see
table 5).
2.1.10. M6ssbauer effect

Van Loef and Van Groenou (1964) investigated the M6ssbauer effect with BaM
single crystals and oriented crystallites enriched in Fe 57. Changing the y-ray
direction parallel or perpendicular to the c-axis and with or without the magnetic
field of 13 kOe [10.3 x 105 A/m], they observed spectra of I + V (sublattice a + b),
II (c), III (d) and IV (e); (note that different labelling methods are used by other
investigators). The temperature dependence of the sublattice magnetization,
anisotropy and dipole fields, and the exchange constant of the Bloch wall as a
function of relative magnetization are discussed in relation with the experimental
results. Furthermore, in contrast to other authors, an especially high hyperfine
field of the sublattice e was reported by Van Loef et al. (1964). Zinn et al. (1964)
also observed M6ssbauer spectra in BaM and explained the temperature dependence of the saturation magnetization by the temperature changes of internal
fields for each sublattice, although they considered only two kinds of sublattices as
a whole. Kreber et al. (1975) did further M6ssbauer study with BaM, an oriented
and enriched polycrystal between 4.2 and 200 K, and nonenriched fine powder at
300 and 870 K. They resolved the spectra as I (sublattice a), II + I I I + V (c + d + b)
and IV (e) at low temperature, and I (a), I I I + V (d + b), II (c) and IV (e) above
200 K, respectively. Based on the observed large quadrupole splitting of sublattice
e and its distinct change near 80 K, they proposed a model in which Fe 3+ occupies
randomly one of the two equivalent sites of Wyckhoff's notation 4e instead of 2b
at low temperature. Here, 4e sites are located on the trigonal axis and 0.156A
away from 2b site on the mirror plane (see also section 2.1.1 on crystal structure).
Using their model, they showed that the temperature dependence of the splitting
values, which they had observed, and also the anisotropy behaviour obtained by
the M6ssbauer data of Rensen and van Wieringen (1969) can be understood by
the molecular orbital calculation after Trautwein et al. (1975).
As for SrM, Van Wieringen and Rensen (1966) observed spectra for powders,
enriched in Fe 57 at room temperature. Four subspectra are assigned as I (sublattice a), II + V (c + b), III (d) and IV (e). Internal field Hi, quadrupole splitting
and isomer shift 6 of four subspectra as a function of temperature are illustrated
in figs. 44(a), (b), (c) and 45. Van Wieringen (1967) reviewed M6ssbauer data of M
compounds and derived the temperature dependence of saturation magnetization
from the values of Hi in fig. 44(a). Figure 44(d) shows the result together with
directly measured values, expressed with the open circles, which fit quite satisfactorily with the deduced curve. Comparing the results of BaM by Zinn et al.
(1964) or Van Loef and Franssen (1963) with the results by Van Wieringen and
Rensen (1966) it can be concluded that the M6ssbauer data of SrM are qualitatively the same as those of BaM, but the main quantitative difference concern
rather lower values of Hi and e in SrM. M6ssbauer effect measurements of PbM
single and polycrystals between 15 and 780 K were reported by Zinn et al. (1964).
Differing from BaM, an intense spectral line at v -- 0, arising from the paramag-
352
H. KOJIMA
120
E
'
"'---o
;'
iI
(d)
90
II
'~o 6 0 - -
~.~. 3o
o
I
(n
E
E
60
-I
(b)
-j
E
E
uo
6OO
(o)
,---1
500
400
....... ~---~r-- - - ~
.. "~"
3OO
o
200
I00
0
0
200
400
600
800
T (K)
Fig. 44. Variations of the internal field (a), quadrupole splitting (b), isomer shift (c) and saturation
magnetization (d) of SrO.6Fe203 against temperature (Van Wieringen and Rensen 1966, Van
Wieringen 1967).
353
f'
6 . 0 x 10 5
5.0
J
I[(c)
I
E(d)
IV(e)
I
I
-I0
V(b)
J
-5
I0
( mm/sec
Fig. 45. Assignment of the M6ssbauer spectrum of SrO.6Fe203 at room temperature (Van Wieringen
and Rensen 1966, Van Wieringen 1967).
netic phase was observed in PbO.xFe203 (x = 4-6) near the Curie temperature.
A signal corresponding to the paramagnetic phase of 30% was obtained at 700 K,
though further investigation regarding the effect of the PbO.2Fe203 paramagnetic
phase in the sample seems to be necessary to explain these phenomena.
As described hitherto, two kinds of labelling for the M/Sssbauer absorption
peaks of M compounds seem to be used. That is, Kreber and Gonser (1973)
considered one of the lines V (b) with III (d) as an unresolved one, while Van
Wieringen and Rensen (1966) recognized peak V (b) overlapped with peak II (c).
Since the N M R data at low temperature by Streever (1969) and at higher
temperature by Hareyama et al. (1970) proved that the hyperfine fields and their
temperature dependence of III (d) and V (b) are almost the same as shown in fig. 43,
the assignment of Kreber and Gonser is suggested to be reasonable. However, when
we compare the results of N M R and M6ssbauer measurements, we should, of course,
realize that the spectra observed by these two experimental procedures are based on
different physical origins. In conclusion, Van Wieringen (1967) summarized the
results of M6ssbauer studies with M compounds as follows:
(1) The iron ions are trivalent in all sublattices; (2) All five sublattices may be
expected to contribute to the crystal anisotropy; (3) The rapid drop in the
magnetization with increasing temperature is entirely due to Fe 3+ in sublattice a
(signal I).
The interest regarding the M6ssbauer studies with M compounds also concerns
the determination of ion distributions in the substituted compounds as discussed
in detail below. For example, Rensen et al. (1971) investigated A1, Cr, ZnTi,
354
H KOJIMA
ZnGe, ZnSn, ZnZr, CuTi, CoTi, CoCr and NiTi substituted M compounds and
found that AI firstly enters the 2a site (sublattice b) and then the 12k site (a); Cr
also starts by entering the 2a site. In addition, they concluded that there is no
indication of Fe 3+ ions in an asymmetric 4e site at low temperature, contrary to
the results of Towns et al. (1967) or Kreber et al. (1975). Kreber and Gonser
(1973, 1976) reported that As ions occupy preferentially the 2b site (sublattice e),
while Ti 4+ + Co 2+ firstly occupy 4fl (c) o r 4f 2 (d) sites and then randomly the 2a (b),
12k (a), and lastly 2b site (e). If Ba 2+ ion in BaM is replaced with a trivalent ion,
Fe 3+ may partly change its valency t o Fe z+ to keep the neutrality. LaFe12Oa9 was
investigated from this point of view by Drofenik et al. (1973) and also by Van
Diepen and Lotgering (1974). In both papers the authors described the difficulty
in observing the Fe z+ sublattice, but the latter authors discussed the preference of
Fe z+ ion from the intensity ratio of subspectra. Moreover, Drofenik et al. (1973)
determined the Curie point as 697 K from the appearance of the paramagnetic
Mrssbauer absorption peak. The hyperfine field at Fe 57 nuclei in different sublattices in LaFe12019 as a function of temperature are similar to BaM or SrM but the
change in the 12K sublattice (I) is found to be more convex than that of SrM as in
fig. 46. This agrees with the more convex o-s-T curve of LaM as compared to that
of SrM.
600
<
"~ 4 0 0
0
\\,,,
-~
200
\\ g
\\ g
\\ g
"7-
It
II
200
',
400
600
800
T (K)
F i g 46 Temperature dependence of hyperfine field in LaO 6Fe203 (Drofenik et al. 1973)
2.1.11. D o m a i n observation
In the earlier days, domain structures were mainly discussed qualitatively in
connection with the magnetic properties of the materials, magnetic anisotropy,
magnetizing process and so forth. However, as the sophistication of techniques in
domain observation and sample preparation improved, more quantitative investigations were attempted. Further, some of the results acquired in this research
F U N D A M E N T A L P R O P E R T I E S OF H E X A G O N A L FERR1TES
355
field have led to the development of the industrial application of bubble domains.
Kooy and Enz (1960), for example, observed the plate-like domains in thin layers
of BaM, which were peeled off from the surface of single crystals. They discussed
the results of the experimental domain period under the influence of magnetic
field and compared them with theoretically calculated results. Specific wall energy
and critical diameter of cylindrical domain were also reported in the paper as
~rw= 2.7erg/cm 2 [2.7x 10-3j/m 2] at 50C and Dc = 0.3 Ixm for a 3 Ixm platlet.
Figure 47 illustrates the domain period versus the magnetic field applied parallel
to the easy axis for (a) BaM (Kooy and Enz 1960), (b) SrO-4.5Fe203-1.5A1203 and
(c) SrO-4.2Fe203.1.8A1203 (Rosenberg et al. 1967). The curve for BaM is the
300
(c)
250
~o 150
x
c~ I 0 0
.4-
c~
_jl
200
(b)
ii
J
I
250
'~ 2 0 0
L
2
~5o
I00 ~
c:T
5O
0
50
0.5
1.0
1.5
H (kOe) [xlOS/(4"rr) A / m ]
200
400
H (Oe) [xlO3/(4rr) A/m]
12
I0
'-' 8
10
x
cE
1__
H (kOe) [x106/(4"n") A/m]

Fig. 47. Domain period as a function of the applied field: (a) BaM, thickness: 3 x 10 .4 cm (Kooy and
Enz 1960); (b) SrO'4.5Fe203'l.SA1203; (c) SrO-4.2Fe203.1.8A1203 (Rosenberg et al. 1967). D1 + D2:
width of antiparallel two domains.
356
H. KOJIMA
result of t h e t h e o r e t i c a l curve fitting. ( U n f o r t u n a t e l y , t h e crystal t h i c k n e s s is not

c l e a r for (b) o r (c), b u t t h e s a m e a u t h o r s (1966) r e p o r t e d s e p a r a t e l y t h e D - t
r e l a t i o n s of t h e s a m e c o m p o u n d s ; as d e s c r i b e d later.) F i g u r e 48 shows t h e c h a n g e s
of d o m a i n structures on t h e b a s a l p l a n e of B a M p l a t e l e t b y t h e F a r a d a y effect
( K o j i m a a n d GotO 1965). C y l i n d r i c a l d o m a i n s a r e c l e a r l y seen in t h e h i g h e r field,
just b e f o r e t h e s a t u r a t e d state, as s h o w n in (d) a n d (e).
Fig. 48. Changes of domain structures observed by Faraday effect on the basal plane of BaO-6Fe203
(Kojima and Got6 1965): (a) demagnetized state, (b), (c) H = 3600 Oe [2.86 105 A/m] parallel to the
c-axis, (d), (e) H = 3900 Oe [3.09 x 105 A/m] parallel to the c-axis. 0: set angle of the analyzer from the
crossed nicosol state.
357
Moreover, it was proved that maze, parallel or honeycomb domains can be

realized as a remanent structure for B a M (Kojima and G o t 6 1965) and for P b M
(Kacz6r and G e m p e r l e 1961, Palatnik et al. 1975) and for BaM, SrM and P b M
(Kojima and G o t 0 1970). H e n c e a specified domain structure among these three
can be brought into existence at will by choosing certain angle ranges of applied
magnetizing field direction against the c-axis before the remanent state is
produced in the crystal. Utilizing these facts, HA and K1 were determined for
small single platelets by Kojima and G o t 6 (1964) as shown in table 9(d). The
effects of various kinds of defects on the domain nucleation process were
discussed by Kojima and G o t 0 (1965), Wells and R a t n a m (1971) for BaM, and
Tfinfisoiu (1972) for A1 substituted SrM, Sr(Fe7.2A14.8)O19. Kojima and G o t 6 found
that the h o n e y c o m b domains are m o r e likely to appear in a defect-less crystal
which can easily be changed to a crystal showing maze remanent domains by
water quenching or pricking with a needle.
M o r e quantitative relations have been obtained on the variation of domain
width D with crystal thickness t. For simple slab domains, the relevant theoretical
equation is given by Kittel (1946) as,
D = (O-w/1.7Ms)l/2t m
(16)
For the domains with reverse spikes near the surface, Kaczdr (1964) modified the
relation as:
D = [0.3751/Ms)(O'wtX/Tr)l/212/3t2/3,
(17)
where
[,, = 1 + 8 r r 2 M d K 1 .
G o t 5 (1966) obtained an experimental formulae D = 0.392t 665 for B a M and

D = 0.441t 64 for SrM in the thickness range 2 t x m < t < 2 0 txm. On the other
hand, Kacz6r and G e m p e r l e (1960) reported D oc t 1/2 for t < 10 txm and D o c t 2/3
for t > 10 Ixm on the domains of PbM. Rosenberg et al. (1966), moreover,
obtained the relations for S r O - ( 6 - x)Fe2OyxA1203; D oc t 0.586 at x = 0, D oc t 0-616
at x = 1.0, D oct 0-665 at x = 1.5, D oct .418 at x = 1.8, D oct 0.ass at x = 1.9 and
D o c t 0.431 at x ~ 2.0. For thinner crystals observed by G o t 6 (1966), the results can
be rewritten as D = [0.386(t- 1.460)] 1/2 for B a M and D = [0.432(t- 1.1260)] 1/2 for
SrM respectively. H e n c e the one half Power law may be valid in this case, though
the physical meanings of the constants are not clear. However, if we consider the
existence of a surface layer where the Kittel model might b e c o m e unstable, giving
a kind of lattice distorted layer, and also the resolution limit in m e a s u r e m e n t s
with an optical microscope, the numerical values in these formulae seem to be
reasonable. For thicker crystals, the two third power law related to spike domains
seems to be valid. Some deviation from the law could be understood by the
complicated domain structures and the resulting ambiguity in the measured values
of domain widths.
358
H. KOJIMA
The temperature variation of the domain width D in BaM was studied by

Kojima and Goff) (1962). They obtained the temperature coefficient of D as
8.9 10-4/C and that of O'w as - 2 . 3 10 3/C. Gemperle et al. (1963) also
performed similar experiment with PbM and found the thermal hysteresis of the
domain width, as Shimada et al. (1973) observed with honeycomb domains.
Kacz6r (1972) discussed these results from a theoretical point of view and showed
the free energy decreases linearly to zero as T/Oc changes from 0.2 to 1.0, and the
domain width almost doubles in the same temperature range. Furthermore,
undulating Bloch walls, for which Goodenough (1956) first gave a theoretical
explanation, can be seen on the surface of crystals with medium thickness, for
instance, 10 fxm < t < 50 txm for BaM. Szymczak (1971) reported the temperature
dependence of domain width, wave amplitude and wave length in these domains.
The stability with temperature for honeycomb domains was investigated by
Gemperle et al. (1963) with PbM and by Shimada et al. (1973) with BaM. The
latter authors observed the increase of the nearest neighbour distance among the
cylindrical domains during the temperature rise. The honeycomb domains reversibly change to a mixture of honeycomb and stripe domains by the heat treatment
from 600 K to room temperature. It was pointed out that the equilibrium distance
theoretically predicted by Kaczdr and Gemperie (1961) would be realized only in
such a mixed domain structure. Regarding the same phenomenon, Kozlowski and
Zietek (1965) showed from a theoretical consideration that the deviation from
Kacz6r and Gemperle's equation in these experiments would rapidly increase for
thinner specimens.
Grundy (1965) observed Kittel type slab domains in PbM of 1000-2000
thickness by Lorentz microscopy and determined the Bloch wall thickness as
250 _+150 A. Grundy and Herd (1973) used the same technique and applied it in
an investigation of the nucleation mode of bubble domains. They gave the
material length l = Crw/(4~-M2) as 0.03-0.04 Ixm for BaM and PbM. Wall mobility
constant ,1 of 0.7 102cm/s/Oe for BaFe12019 and 1.6 102cm/s/Oe for
BaFeu.aA10.7019 were reported by Asti et al. (1968).
2.1.12. Optical properties

The absorption coefficient a (=2~-K/nA) and Faraday rotation &F of BaM
measured at 300 K as a function of wavelength from 1 ~m to 8 p~m by Zanmarchi
and Bongers (1969) are shown in fig. 49. It is seen that &V changes sign between
2 ~m and 3 ~m. Drews and Jaumann (1969) measured the absorption coefficient K,
refractive index n, Faraday rotation &F, Faraday ellipticity ~/v and Kerr rotation
against air ~bw and against glass &KC for the same material in the shorter
wavelength region of 0.4 ~m-1.7 ~m. The results are illustrated in fig. 50. Kahn et
al. (1969) also added the data of the polar Kerr spectra for PbM, showing a
negative peak at 4.43eV (2799,~) and a positive peak at 5.5 eV (2254A).
According to their conclusion, charge transfer transitions occurring at about 4 eV
(3100 A) and 5 eV (2480 A), associated with Feoct and Fetet complexes, respectively, are responsible for the principal magnetooptical spectra. Blazey (1974)
reported on the wavelength-modulated reflectivity spectra of BaM with the
minima at 2.2eV (5636A) and 2.6eV (4769 A) corresponding to the internal
150
I00
'E
300
13
200
E
rj
50
I00
"o
LL
-g.
0
0
2
'-I00
I0
(Fm)
Fig. 49. Absorption coefficient a(=2~'K/nA) and Faraday rotation ~bF of BaO.6Fe203 in infrared
region at room temperature (Zanmarchi and Bongers 1969).
xlO 2
I0.0
7.5
1~F
o
o~
5.0
I--
xlO 2
"F]F
-2.0
LL 2.5
--I.0
o
E
g,
~,,
o
-
2.5
1.0
-8-
-5.0
2.0
I
r-
i o- 2
10.4
0.5
1.0
1.5
2.0
X (/~m)
Fig. 50. Optical properties of BaO-6Fe~O3 as a function of wavelength. K: absorption coefficient, n:
refractive index, OF: Faraday rotation, rTF: Faraday ellipticity, CbKL:Kerr rotation against air, ~bKo: Kerr
rotation against glass, t: 4.5 p~m, / 4 : 1 5 kOe [1.19 x 106 A/m].
359
360
H. K O J I M A
transition of Fetet and at 3.9 eV (3179 A), 4.3 eV (2883 A) and 4.8 eV (2583 A),
these being assumed to be charge transfers to Feoct.
2.1.13. Magnetostriction
The saturation magnetostriction in a hexagonal crystal is given by Mason (1954) in
the form,
a = /~A[(OZI~I q- a2~2) 2 -- (O/1]~ 1 q- O~2][~2)@3~3]q- ~.B[(I -- O~2)
x ( I - fl~) ~ - ( o ~ # , + o~=/?~)=] + a d o
- o d ) B 1 - (o~/3, + o~fl=),~,8~]
(18)
+ 4AD(alB1 + o12f12)a3B3,
where al, a2, O~3 and ill, fi2, r3 are the direction cosines of the magnetization
vector and measuring direction. Here, the direction cosines are taken with respect
to the Crystal axes, the z-axis coinciding the c-axis. Kuntsevich et al. (1968)
determined the constants AA, As, Ac and AD in eq. (18) for BaM in measurements
with the following geometry: A:O/1 =/31: 1, AB:OZl= /3== 1, Ac:OZl = J~3=
1, h D : a l = / 3 1 = a 3 = / 3 3 = l/X/2. Thus, they found the constants at room
temperature
as
AA = -- (15 --+0.5) X 10-6,
AB = + (16 + 0.5) X 10-6,
Ac =
+ (11 -+ 0.5) X 10-6 and AD = -- (13 --+0.5) X 10-6. For polycrystals, they also obtained
the longitudinal and transverse magnetostrictions, hi! = -(9-+ 0.5)x 10 6 and h~ =
+ (4.5 -+ 0.5) x 10-6. However, these values do not coincide with the values derived
by the simple averaging of the formula for a single crystal. The authors explained
these results from the effects of the defects in the crystals and the interference of
grains during deformation.
8.6
6.4
15.0
6.3
8.4
6.2
14.5
8.2
6.1
6.0
/
8.0
"14.0'
I00
200
T (K)
300
5.9
Fig. 51. Temperature dependence of Young's modulus E, rigidity modulus G and bulk modulus K
(x 1011 dyn/cm 2) [ 101 N/m 2] (B.P.N. Reddy and P.J. Reddy 1974a).
361
2.1.14. Mechanical properties

Fundamental studies of the mechanical properties of hexagonal ferrites are quite
few. Clark et al. (1976) referred to the following mechanical data for their BaM
specimen at room temperature. Density: 5g/cm 3, porosity: 5%, Young's
modulus: l a x 106kg/cm2 [1.38x 1011N/m2], Poisson's ratio: 0.28, compressive
strength: 4.5 x 103kg/cm2 [4.41x 108N/m2], tensile strength: 5.6x 102kg/cm2
[5.52x 107 N/m2]. Reddy and Reddy (1974a) measured the elastic modulus of
sintered BaM with a density of 4.8910 g/cm3. Figure 51 shows the relations of
Young's modulus E, rigidity modulus G and bulk modulus K versus temperature.
These moduli decrease with temperature, in contrast with those of Ni-Zn or
Mn-Zn cubic ferrites. Hodge et al. (1973) investigated the compressive deformation of sintered BaM with 18% porosity in creep and press forging modes in
the temperature range 1000 to 1200C. Figure 52 is the true strain rate against
l I T plot for an isotropic compact at 5% true strain. The activation energy for
creep was estimated from the experiments as 123-+6kcal/mol [(5.15-+0.25)x
105 J/moll.
-2
(x
13
--<..
..3
"
-6
6.8
7.0
7.2
I/T
7.4
7.6
7.8
( K -I x l O -4)
Fig. 52. Arrhenius plot of creep by compressive deformation of isotropic BaO.6Fe203 (Hodge et al.
1973). (1) 421.8 kg/cm 2 [4.14 x 104 N/m2], (2) 281.2 kg/cm 2 [2.76 104 N/m2], (3) 140.6 kg/cm 2 [1.38 x
104 N/mZ].
2.1.15. Heat capacity

Reddy and Reddy (1974b) determined the heat capacity of a BaM sintered rod in
the temperature range 80 to 303 K. Cp is plotted versus temperature in fig. 53,
giving values of 52.42 cal/mol deg [2.194 x 102 J/mol deg] and 107.56 cal/mol deg
[4.502 102J/mol deg] at 80 and 303K, respectively. Furthermore, the Debye
temperature was estimated from the calorimetric measurements at 166 K and
from the elastic measurements as 158 K, both of which are rather low compared
with the temperatures of Ni-Zn or Mn-Zn ferrites.
362
H. K O J I M A
10
O0
-8
E
'-"a
90
Cp
"-S
8 0 .x.
I0
"e 6
70
"o
"5
60
-6
u
50
:,.,"
I O0
200
300
T(K)
Fig. 53. Heat capacity and thermal expansion coefficient of sintered BaO-6Fe203. Cp: heat capacity
(Reddy and Reddy 1974b), (1) o~(Reddy and Reddy 1973), (2) a parallel to the magnetized direction, (3) a
perpendicular to the magnetized direction (Clark et al. 1976).
2.1.16. Thermal expansion

Reddy and Reddy (1973) also measured the thermal expansion coefficient o~ of
sintered B a M by a two terminal capacitance dilatometer. The result is illustrated
by curve (1) in fig. 53. They derived the following experimental equation in the
t e m p e r a t u r e range of 80 to 300 K:
a = 0.572
x 10 7 T -
1.437 x 101 T 2 + 0.175 x 1012 T 3 .
(19)
Clark et al. (1976) gave the values c~ of B a M parallel and perpendicular to the
magnetized direction, which are shown as curves (2) and (3) in fig. 53. They also
reported the thermal conductivity of their specimen having 5% porosity as
4 W / m deg at r o o m temperature. A b o v e r o o m temperature, Davis (1965) observed the change of lattice constants in B a M up to 1000C by X-ray diffraction, but
the value is fairly high and no noticeable change was found around the Curie
point. K 6 m o t o and Kojima (1976) showed the t e m p e r a t u r e variations of the a and
c-axis in B a M in fig. 54, where the sharp kinks can be seen at 450C for both axes,
but the value is rather low. In table 13, the expansion coefficients of B a M by
several authors are compared. The cause of the discrepancy in the list may be
explained by the difference of porosity, grain size, degree of crystal orientation,
chemical composition in the specimens, or accuracy of measuring methods.
FUNDAMENTAL
P R O P E R T I E S OF H E X A G O N A L
FERRITES
363
A5
o
X
--4
O
<l
O 3
1D
200
Temperature
400
(C)
600
Fig. 54. Variations of the lattice constants in BaO.6Fe203 with temperature (K6moto and Kojima
1976).
T A B L E 13
T h e r m a l e x p a n s i o n c o e f f i c i e n t o f B a M (x 10-6/deg).
T (C)
R.T.
27
R.T.
8.5 (a)
8.4 c)
8.8 ~)
11.1 (d)
T (C)
25-150
150-250
25-250
25-640
~(e)
9.5
T(C)
an (f)
ao (f)
10
10.5
100
5.7
10.8
6.8
11.0
200
9.8
250
8.2
12.1
10.5
13.8
10.2
300
18.6
17.2
350
450
20.7
17.2
* By X-ray diffraction
(a) H a b e r e y et al. (1973)
Co)R e d d y a n d R e d d y (1973)
(c>C l a r k et al. (1976)
(d/Davis* (1965)
(e) B u e s s e m a n d D o f f (1957)
If) K 6 m o t o * a n d K o j i m a (1976).
11.5
7.3
550
364
H. KOJIMA
2.1.17. Electric and dielectric properties
Zfiv&a (1963) observed the electrical conductivity of BaM and PbM single crystals
and found that the relations among the conductivities are approximately expressed by 100"BaM ~" OrpbM and 10or//~ o-1 for both compounds. Here, o-B~ and O-pbM
mean the values of the conductivities with each ferrite, and o-//and o-~ denote the
values measured along and perpendicular to the c-axis, respectively. Figure 55(a)
and (b) show the conductivities of BaM and PbM, rewritten from these results by
Wijn (1970). Z~veta also estimated the activation energy for the temperature
dependence of the conductivity and, moreover, reported on the thermoelectric
force for the same specimens. He finally concluded that an electron hopping
mechanism between Fe ions might reasonably be assumed and so the conductivity
TIE I0-I
T
b id z
io-3
/o)
TE
10-3
",,,.\
b 164
II C
id 5
I
2
I/T
(xlO-3/deg K)
Fig. 55. Temperature dependence of the electrical d.c. conductivity of the single crystals: (a)
BaFe12019, (b) PbFe12019. The different marks indicate the measuring points of different crystals
(Zfiveta 1963).
365
10-2
Ld ~
10-4
IE
0-5
10-6
to-T
io-e
j0-9
2
4
I/T
5
6
7
(xlO-3/deg K)
Fig. 56. Temperature dependence of the conductivity of BaFe12019 polycrystal containing 0.022% Fe 2+
by weight. The figures stand for the used frequency in Hz (Haberey and Wijn 1968).
104'
'
'
I0
.c,-''~"
I
!
IOM
'
---
i!
///
1
,o
-150
-I00
-50
50
I00
150
T (C)
Fig. 57. Temperature dependence of the real part of the dielectric constant for the same specimens in
fig. 56 (Haberey and Wijn 1968).
366
H. KOJIMA
is related to the presence of Fe 2+. D u l l e n k o p f and Wijn (1969) r e p o r t e d similar

experiments in the frequency range of 1 to 8 G H z and b e t w e e n - 5 5 and 100C.
T h e specimens were polycrystals containing Fe z+ up to 0.5% by weight. T h e
m o d e l of a thermally activated h o p p i n g process again received support in this
work. Figure 56 shows the t e m p e r a t u r e d e p e n d e n c e of the conductivity for the
p r o p o s e d composition of BaFe12.59019.39
3+
polycrystal, d e t e r m i n e d by chemical
analysis, at various frequencies r e p o r t e d by H a b e r e y and Wijn (1968). T h e y also
described the t e m p e r a t u r e d e p e n d e n c e of dielectric constants E' for the same
specimen, as shown in fig. 57.
TABLE 14
Properties of the magnetoplumbite type compounds substituted Ba ion.
Compound
a (A)
c (A,)
o's (Gcm3/g)
[x 4zr x 10-7 Wbm/kg]
NB (/xB/mol)
LaFe2Fe3+nOig*
65 (R.T.)
19.5 (0 K)
13 (300 K)
Na0.5La0.sFe12019
69 (R.T.)
113 (0 K)
21.5 (0 K)
Ca0.88La0.i4Fe12019*
5.877
22.91
Ag0.sLa0.sFe12Oi9
5.85
22.85
LaFea2019*
52 (R.T.)
73.4 (77 K)
96.2 (0 K)
19.2 (0 K)
LaFei2019*
LaFe12019*
Tl0.sLa0.sFea2019
(a)
(b)
(c)
(d)
Aharoni and Schiber (1961)

Summergrad and Banks (1957)
Ichinose and Kurihara (1963)
Laroria and Shinha (1963)
(e) Lotgering (1974)

(f) Van Diepen and Lotgering (1974)
(g) Drofenik et al, (1973)
367
2.2. Substituted M compound

2.2.1. BaO-SrO-PbO-Fe203 systems
As already discussed, replacement of Ba 2+ ion with Sr 2+, Pb 2+ or both of them is
possible with any mixing ratio without changing the crystal structure. For
example, Ba0.75Sr0.zsFea2019 (Borovik a n d Yakovleva 1962a, 1962b) and
Sr0.7sPb0.25Fe12019 (Borovik and Yakovleva 1963) attracted special interest owing to
the improved properties as permanent magnet materials. Hunty (1963) however,
found no improvement of these mixed ferrites. Kojima and Miyakawa (1965)
T A B L E 14 (continued)
KI (erg/cm 3)
[x 10 ~J/m 3]
2,5
10 6
/(2 (erg/cm 3)
[x 10-1J/m 3]
--
0c (K)
Composition
695
3.0 x 106
713 _+ 10
718
CaO
13.70
Fe203 82.78
La203 2.00
FeO
1.52
(mol %)
708
(10-13) x l0 s (0 K)
0 (293 K)
(5-10) x l0 s (77 K)
LaM
86.2
Fe304 10.3
LaFeO3 3.4
(wt %)
NB-T
G-La205
Ref.
(a)
o--T
o-j/, o - l - H
o-s-La203
(c)
Br = 1600 G
MHc = 2450 Oe
BHc = 1100 Oe
(d)
o-//,o--H
o--T
(e)
K1-T
M6ssbauer spect.
Hhf-T
(f)
Fe304
M6ssbauer spect.
(g)
removed by
10% H2804
e-T
8-T
Hi-T
Fe304 10
(wt %)
697 -+ 2
Other data
in the paper
M6ssbauer spect.
(g)
368
H. KOJIMA
investigated the changes of lattice constants, saturation magnetization and Curie

points for the Ba-Sr, B a - P b and Sr-Pb binary hexaferrites systems and found that
there are no sharp kinks on the curves relating the properties and the composition. These facts suggested that those systems form complete solid solutions
between both end m e m b e r s and no special c o m p o u n d can exist at any mixing
ratio. Therefore, it is m o r e plausible that the i m p r o v e m e n t s due to the substitutions in the Borovik's papers might be due to the acceleration of the solid
state reaction or sintering process etc., and not to the intrinsic properties of a
specific compound. Though such non-intrinsic but practically useful effects in the
p e r m a n e n t magnet properties of hard ferrites introduced by many kinds of
additives were once actively studied the results will n o t be mentioned further,
since the details will be discussed in ch. 7 by Stfiblein.
2.2.2. Other substitutions of B a 2+ ions
Ferrimagnetic properties of the magnetoplumbite type compounds are naturally
based on the superexchange interaction of F e - O - F e , so that no remarkable effect
on the magnetic properties would be expected by the replacement of a Ba ion.
However, the properties could be influenced to some extent by the changes in the
distance or the angle between F e - O - F e arising from the substitution, leading to
differences among BaM, SrM and PbM.
Table 14 shows the properties of several examples for Ba 2+ substituted ferrites.
In some cases m a r k e d * in the table, the partial coexistence of Fe 2+ may be
unavoidable in order to keep electrical neutrality?. The examples are so few that
no general tendency can be deduced from the table. As described before, when
discussing the M6ssbauer effect, Drofenik et al. (1973) concluded from the
t e m p e r a t u r e dependence of the hyperfine fields for L a M that a m o r e convex
magnetization against t e m p e r a t u r e curve than SrM comes from the difference of
the behaviour of the 12k sublattices. It is also pointed out in this p a p e r that in
LaFet2019 and T10.sLa0.sFe12019 no Fe 2+ sublattice was observed in the M6ssbauer
experiment and the averaged hyperfine fields could originate from a fast electron
exchange between Fe 2+ and Fe 3+, or in the process of electron sharing by the six
ions in the 12k sites of these compounds.
Van Diepen and Lotgering (1974) insisted from a similar study that the
substitution of Ba 2+ with La 3+ causes a valency change of Fe 3+ to Fe 2+ at the 2a or
4f2 site, although they also found no subspectrum of Fe 2+.
2.2.3. Substitution of Fe 3+ ions
Substitution with A13+, Ga 3+ and Cr 3+ ion. T h e replacement of Fe 3+ in B a M or
SrM with AP +, G a 3+ or Cr 3+ has been intensively investigated. Because of the
resemblance of their ionic radii with Fe 3+ (shown in table 2) especially the former
two ions are easily replaced at any substitution ratio without changing the crystal
structure. Figure 58(a) and (b) show the variations of the lattice constants a and c
t Replacements with combinations of a few ions are also cited in the next section.
369
23.2
22.8
o,=I
22.6
(j,
22.4
(b
22.2
i
22.0
6
X
I0
12
Fig. 58. (a) Lattice parameter a, and (b) c as a function of substituted ratio. (1) BaAlxFe12-,Om, (2)
BaGaxFe12-xOm,(3) BaCr, Fe12-xO19,(4) SrCrxFem-xO19(Bertaut et al. 1959), (5) SrAlxFe12-xOt9(Goto
and Takahashi 1973).
for (1) BaAlxFe12_x019, (2) BaGaxFe12-xO19, (3) BaCrxFe12-xO19, (4) SrCrxFelz-xO19
(Bertaut et al. 1959) and (5) SrAlxFem_xO19 (Goto and Takahashi 1973). Almost
the same results as given on line (1) for the Ba-A1-M system by Vinnik and
Zvereva (1969) and also on line (5) for SrAlxFe12-~O19 were reported by Florescu
et al. (1973). The parameters decrease linearly with the substitution ratio in all
cases. Numerical values for the end members were given by Adelsk61d (1938) and
Bertaut et al. (1959) as in table 15. This table also contains the results for
Ca/Sk112019 by Wisnyi (1967); Ca(AlFe)12019 by MacChesny et al. (1971);
BaGaa2019, SrGa~2Oa9 and LaMgGanO19 by Verstegen (1973).
370
H. KOJIMA
TABLE 15
Lattice parameters of some substituted M-type compounds with A1, Ga or Gr.
Formula
a (4)
c (4)
Ref.
BaA112019
5.577
5.66
22.67
22.285
Adelsk61d (1938)
Bertaut et al. (1959)
SrAl12019
5.557
21.945
Adelsk61d (1938)
CaA1~2OI9
5.566
22.010
Wisnyi (1967)
Ca(A1Fe)12019 5.792-+0.004
22.56_+0.04
MacChesneyet al. (1971)
BaGa12019
5.818
5.850 -+0.004
23.00
23.77 _+0.02

Verstegen (1973)
SrGa12Oa9
5.796 -+0.004
23.77 _+0.02
Verstegen (1973)
LaMgGa11019 5.799-+0.003
22.71 -+0.01
Verstegen (1973)
BaCrsFe4Oa9
SrCr6Fe6019
22.82
22.77

5.844
5.844
Van Uitert (1957), and Van Uitert and Swanekamp (1957) reported 4rMs of
BaAl~Fe12_xO19, (1) fired below 1400C and (2) fired above 1400C, and (3)
SrAlxFe12_xOi9 after Rodrigue (1963) as shown in fig. 59(a). Figure 59(b) illustrates
(1) BaAlxFe12_xO19; (2) BaGa~Fe12_~O~9 (Mones and Banks 1958); (3)
SrAlxFe,2_xO~9 (Rodrigue 1963) and (4) ditto (Gotto and Takahashi 1973). Lines
(3) and (4) agree quite well. In figs. 60(a) and (b), Bertaut et al. (1959)
summarized NB at 0 K per mole in Bohr magneton and 0c for (1) BaAl~Fe~2_xO~9,
(2) BaGa~Fe12_xO19, (3) BaCrxFe~2_xO~9; the m a r k A in (a) relates to
SrCrxFe12-~O19. Albanese et al. (1974) estimated 0c for BaAlxFe~2 xO,9 and
SrAlxFe~2-xO19 from the M6ssbauer experiments, as shown in table 16. The lines
D~ and D2 in fig. 60(a) were drawn on the hypotheses that AP + ions enter the 2a
and 12k sites, or G a 3+ the 4fl and 12k sites, respectively (after Bertaut et al.
(1959)). With these results, and in addition referring to the X-ray investigations,
they came to the conclusion that AI 3 and Cr 3+ first occupy 2a sites and then 12k
sites, while G a 3+ enters first 4fl and then 12k sites. These assumptions are
thoroughly supported by Rensen et al. (1971) by M6ssbauer studies, but in
contrast with these results, Suchet (1971) expressed a strong preference of AI 3 to
the 4f~ and 2a sites. Glasser et al. (1972) observed M6ssbauer and E S R spectra for
CaAl12-xFe~O~9 with x <~ 4.8, i.e., mainly on the A1 rich side. They recognized a
m a r k e d preference of Fe 3 for the tetrahedral 4fl sites from M6ssbauer investigations and interpreted the majority of E S R resonances by supposing Fe 3
ions in an axially distorted site.
T h e relations of a, Ms, 0c, K, MHc and the critical radius for a single-domain
800 1
.(3)
r...<-.,
60 O l ~ ' ~
[
i
371
Ib)
,.i
400
qb
(.3
200
121
5000
(0)
3)
4000
!
I
i
~', ,,,
~o 3 0 0 0
x.
2000
I==
1000
I
8
10
12
X
Fig. 59. (a) Saturation 4~rM~, and (b) Curie temperature 0c as a function of substituted ratio. (a) 4~-Ms:
(1) BaAlxFe12-xO19 fired below 1400C, (2) ditto fired above 1400C (Van Uitert and Swanekamp
1957), (3) SrAlxFelz-xO19 (Rodrigue 1963); (b) 0c: (1) BaAlxFelz-xO19, (2) BaGa~Fet2 xO19 (Mones and
Banks 1958), (3) SrAlxFel2-xOl9 (Rodrigue 1963), (4) ditto (Goto and Takahashi 1973).
particle Rc etc. versus x for BaCrxFel2 xO19; and BaAlxFel2-xOi9, BaGaxFe12-xO19

and BaCrxFe12_xOx9 were given by Haneda and Kojima (1971 and 1973b). In fig.
61, curves (3), (4) and (5) indicate H A for BaAlxFe12-xO19, BaGaxFei2-xO19 and
BaCrxFei2 xO19 (Haneda and Kojima 1973b) besides the marks and A illustrating HA for SrAlxFe~2_xO19, as obtained by De Bitetto (1964) and Rodrigue (1963).
Curves (1) and (2) are drawn with the calculated values of eqs. (20) and (21) by De
Bitetto who gave the experimental formulae:
372
H. K O J I M A
800
(b)
700
A
v" 6 0 0
0
500 --
400
300
25
(a)
20'~
\2a
D2
\\
D,,\ \
0
)--'~,X~L
6
I0
12
X
Fig. 60. (a) Saturation at 0 K and, (b) Curie temperature versus substitution ratio (Bertaut et al. 1959):
(1) BaAlxFe12-xO19, (2) BaGaxFeu-xO19, (3) BaCrxFeu-xO19, (A) SrCrxFelz-xO19, D1, D2: calculated
values.
T A B L E 16
Curie temperature for the compounds
BaAlxFe12-xO19 and SrAlxFelz_xOl9 (AIbanese et al. 1974).
BaAlxFei2-xO19
SrAlxFe12-xO19
Tc (K)
T~ (K)
0
2.5
4
723 -+ 5
595 ---5
518---5
0
1
2
723 -+ 5
658 -+ 5
590---5
7O
373
I
(2)
6O
// /(I)
,/
5O
/
z~
-g
/ /
//~e'~
40
131
I// /
~D
o
X
"1-
(51
I0
0
0
Fig. 61. Anisotropy field HA as a function of substitution ratio: (1) and (2) see text, (0) SrAlxFe12-xO19
(De Bitetto 1964), (A) ditto (Rodrigue 1963), (3) BaAlxFe12-xOxg, (4) BaGaxFex2-xO19, (5) BaCrxFe~z_xO19
(Haneda and Kojima 1973b).
HA(x)/H(o) = (12 - x)/612 - x/2 + (x/6)zss],
(20)
HA(x)/H(o) =
(21)
or
(12 - x ) / ( 1 2 - 3 x ) .
Since D e B i t e t t o e x p e r i m e n t a l l y o b t a i n e d a r e l a t i o n for K as a f u n c t i o n of x for

SrAlxFe~z-xO19 in t h e f o r m ,
K(x~/K(o) = 1 - x / 1 2 ,
(22)
w e can say that t h e m a g n e t o c r y s t a l l i n e e n e r g y m a y b e r o u g h l y a s s u m e d to h a v e

a b o u t t h e s a m e s t r e n g t h for all t h e five sublattices. A s s u m m a r i z e d in fig. 62, t h e
M s - x d e p e n d e n c e is r e l a t e d to t h e v a l i d i t y of eq. (20) o r eq. (21). D e B i t e t t o
c l a i m e d t h a t an e m p i r i c a l fitting f o r m u l a ,
374
H. KOJIMA
1.0
0.8
1~ O.6
0,4
0.2
Fig. 62. Variations of normalized saturation magnetization with composition in MAlxFe12-xO19(De

Bitetto 1964): (0) Ba (Bertaut et al. 1959), (A) Ba (Mones and Banks 1958), (V) Ba (Van Uitert and
Swanekamp 1957), (V) Pb (Bozorth and Kramer t959), (D) Ba, (C)) Sr (Du Pr6 et al. 1958), (&) Ba
(Vinnik and Zvereva 1970).
M(x)/M(o) = ~[2 - x/2 + (x/6)zss],
(23)
which is shown by curve (2) in fig. 62, is m o r e plausible than most other authors'
results given by curve (1), i.e. by
M(x)/M(o) = 1 - (x/4).
(24)
D a t a by Vinnik and Z v e r e v a (1970) for the B a - A 1 - M system m e a s u r e d at 4.2 K

were a d d e d to fig. 62. T h e y concluded that the preference of A13+ seems to agree
with the results of Bertaut et al. (1959) and the deviation at x = 3.3 m a y be due to
the differences of applied field. H o w e v e r , we would like to point out here that the
occupied site with a substituted ion might be different according to the preparation conditions, starting materials and various other factors, although the
substitution ratio m a y be perfectly identical.
HA was d e t e r m i n e d by D e Bitetto using F M R m e a s u r e m e n t s and the line width
A H was also given for the S r - A I - M system between x = 0-1.7. A l b a n e s e et al.
(1974) reported H i - T and Hi(T)/I-L(o)--T/Oc relations by M6ssbauer investigations
for A1 or G a substituted B a M and SrM. H e i n e c k e and Jahn (1972) studied the
angular variation of the nucleation field Hn for single d o m a i n particles of
SrA13.sFes.2019 and c o m p a r e d the Hn-O relation with the 1/cos 0 law or the
c o h e r e n t rotation model. Interesting investigations of the f o r m a t i o n m o d e of the
domain structures on the c-plane of PbA1Fel~O19 were r e p o r t e d by Williams and
S h e r w o o d (1958) using a motion picture technique. Tanasoiu (1972) o b s e r v e d
r e m a n e n t domain structures on the c-plane of SrAI4.8FeT.2OI9, the main magnetic
properties of which were previously d e t e r m i n e d as 4~rMs = 315 G [315 10 -4 T],
To= 5 1 8 K and Crw= 5 . 8 e r g / c m 2 [5.8 10-3j/m2]. H e f o u n d that the r e m a n e n t
375
structure after thermal demagnetization consists of a great number of domains

with irregular shape and are very unstable, while the remanent state by a.c.
demagnetization consists of only a few domains.
MacChesney et al. (1971) studied the ferrimagnetic phase of the CaO-A1203Fe203 system and, as for the hexagonal magnetic phase, they found the composition range extends from CaAI~20~4 to at least CaA14.2FetsOls.6. The lattice
constants of an idealized composition Ca(A1Fe)12019 were already referred to in
table 15. The magnetic moment at room temperature for the group varies from 1
to 10 emu/g [12.56 to 125.6 x 10-~ Wbm/kg] according to the Fe content, but they
show rather high anisotropy fields of about 60 kOe [4.78 x 10 6 A/m] regardless of
the composition.
1 / x - T relations up to 1000 K were determined by Florescu et al. (1973) for
SrAlxFe~2-xO19 from x = 2.0 to 9.0 and they estimated N6el's parameters by the
graphical method (N6el 1948) from these results. The photoluminescence of
BaGa~2019, SrGa120~9 and LaMgGauO~9 with and without Mn 2+ phosphors was
reported by Verstegen (1973) who found that the emission strongly resembles that
of Mn 2+ in MgGa204.
Substitution with Sc 3+ and In 3+. The partial replacement of Fe 3+ with Sc3+ or In 3+
ions in M-type compounds were investigated mainly by research groups in the
U S S R with an interest in their specific magnetic ordering. Perekalina and Cheparin (1967) measured the relations of a, c-x, ~rs-T and K ~ - T for BaScxFe~2 xO19
single crystals with x = 1.2-1.8, as shown in table 17 and figs. 63 and 64. Maxima
80
7O
.~,^
"" o
"~
6o
r
'~~4-O0~5_xS~=~~~
0~2,03~"
0~
C31
10
0
r
0
200
400
Temperature
I,o
600
(K)
Fig. 63. Temperature dependence of the specific magnetization BaScxFe12-xOa9single crystals (Perekalina and Cheparin 1967): (1) x = 1.2, (2) x = 1.4, (3) x = 1.8.
376
H. KOJIMA
o<
+1
o<
+1
tt3
t'3 t'e'j
"~"
'~" xl t'xl ('xl ~:7~ t'~ , ~ ,.~j

. . . . . .
~.,
tt3
0~
trq
tt3 "~" ,,..~

"
uS,.-~o~ ~ u E e 6
b,
,,~
t3 t ~
t'q
e3
r~
.=
.
3
~D
v
.=
~mmmm~m~
e~
FUNDAMENTAL
PROPERTIES
OF HEXAGONAL
FERRITES
377
(I).
8
/,
I
\_
7
6
E
5
o
X
4
tO
-2 3
03
%2
X
-I
-2
I
0
I
200
400
Temperature
600
(K)
Fig. 64. T e m p e r a t u r e d e p e n d e n c e of t h e a n i s o t r o p y c o n s t a n t K1 for BaScxFelz-xO19 ( P e r e k a l i n a a n d

C h e p a r i n 1967): x = 1.2, x = 1.4, x = 1.8.
in the O-s-T relations, which shift towards higher temperatures with increasing Sc
content, and the change of K1 for BaScl.sFe10.2019 to negative values between 125
and 355 K are in contrast with pure M-type compounds. It was suggested that the
t e m p e r a t u r e dependences of ~rs can be explained by N6el'S theory (N6el 1948).
Aleshko-Ozhevkii et al. (1968, 1969) determined the magnetic structure by
neutron diffraction studies at 77 K in magnetic fields up to 5 k O e [3.89 x 105 A/m]
for BaScxFe12-xO19 with x = 1.2-1.8. They showed conclusively that Sc 3+ ions
occupy 4fl and 2b sites, so that antiphase conical helixes were formed in certain
blocks of the crystal unit cell. In a later p a p e r these authors estimated (i) the
periods along the c-axis; (ii) the cone vertex half angle; and (iii) the phase angle of
the projection of theo total magnetic m o m e n t s in the basal
plane which were,
o
respectively: (i) 141A, (ii) 30 , (iii) 150 for x = 1.8; (i) 91 A, (ii) 20 , (iii) 135 for
x = 1.4; and (i) 70 A, (ii) 12 , (iii) 120 for x = 1.2. Alesko-Ozhevskii and Yamzin
(1969) added a detailed explanation of the intensity anomalies of the satellites in
the neutron diffraction patterns of BaScxFe12-xO19 on the basis of the superposition of ferro- and antiferromagnetic reflections. Koroleva and Mitian (1971)
378
H. KOJIMA
suggested the possibility of the appearance of these magnetic antiphase helical

structure based on Moriya's rule (Moriya 1960). The same behaviour of o-s-T and
K1-T plots for single crystals of BaInxFe12_xO19 for x > 1.9 and PbInl.gFemO~9
were observed by Perekalina et al. (1970). Their main data are added to table 17,
which can also be understood by the model of two magnetic sublattices with a
weak exchange interaction. Bashkirov et al. (1975) carried out M6ssbauer studies
for BaIn3FegO19 and showed the presence of an angular magnetic structure, which
was presumably caused by the almost full occupation of 2b and 4fi sites with In 3+.
Magnetic order-disorder transition of the compound was observed between 300
and 250 K with an external field of H = 16 k O e [1.28 x 10 6 A / m ] and below 100 K
in the absence of an external field. The difficulty of realizing the saturated state
even in 50 k O e [3.98 x 106 A/m] for BaInz4Fe9.6Oa9 was reported by Perekalina et
al. (1970). These anomalous magnetic properties are due to the fact that collinear
structures are not realized even at helium temperatures.
Substitution of Fe 3+ with paired ions; Co-Ti system

Smit et al. (1960) measured the torque curves of BaCox/zTix/2Felz-x019 for x = 0.9,
1.0 and 1.5 at T = 90 K and H = 32 k O e [2.55 x 10 6 A/m] after thermal demagnetization and suggested from the results that the characteristic details of these
curves were due to the effects of incomplete alignment, both on a microscopic and
an atomic scale. Rodrigue (1963) pointed out that the effective internal anisotropy
fields of B a M could be varied from virtually zero to 17.5 k O e [1.39 106 A/m] by
substituting with Co-Ti, and this is quite advantageous for applications to
microwave devices. In fig. 65, the data in this p a p e r were cited in (a), (b) and (d).
De Bitetto (1964) determined the relation of H A with x by r o o m t e m p e r a t u r e
microwave ferrimagnetic resonance measurements. The line widths A H of these
oriented polycrystalline compounds were all about 2 k O e [1.6 105A/m]. His
results are also plotted in figs. 65 (a), (b) and (c). Lines (1) and (2) in (a) are drawn
based on G o r t e r ' s assumption (Casimir et al. 1959): (i) a random distribution of
both Co and Ti ions among only the nine octahedral sites (12k, 2a and 4f2), or (ii)
both ions are substituted preferentially for some Fe 3+ ions with only the eight
favourably oriented moments (12k, 2a, 2b). It seems that D e Bitetto's data are
situated on line (1), G o r t e r ' s results on line (2), but that Smit and Wijn's and
Rodrigue's data are just between the two lines. The microscopic structure of
C o - T i substituted samples were reported by Bonnenberg and Wijn (1968) using
an electron microprobe analyser. They found, for instance, that in the composition BaComTimFe~2019, the concentration of Fe, Co and Ba, Ti showed the
same distribution tendency in pairs but the opposite tendency in the sintered
grains. Investigations of the cation distribution on an atomic scale were reported
by K r e b e r and Gonser (1976). They compared the electric quadrupole splitting E
and the area of the M6ssbauer spectra for BaCox/2Tix/2Fe12-xO19 sublattices from
x = 0 up to x = 11 at temperatures above the corresponding Curie points of each
compositions. Their conclusions are as follows: The Fe 3+ ions in 4fl and 4f2 sites
are replaced for x ~<4 and the remaining octahedral 2a and 12k sites are
substituted randomly for 4 < x < 8. Finally, for x > 8, a weak substitution in the
800
, _,
%
x
400"
379
Idl
i
(c)
~,0<
.2 z.0
%
1.0
~g
18~
(b)
12
0
X
o
I
r.o~ ~ ~ _
o.8
0.6
(a)
- ...... --~
2
x
Fig. 65. Normalized magnetic saturation at room temperature, anisotropy field, anisotropy constant
and Curie temperature against composition in Ba(TiCo)xFe12-xO19. (a) M(x)/M(01: () De Bitetto (1964)
at room temperature, (11) Gorter (Casimir et al. 1959) at 77 K, (A) Smit and Wijn (1959 at 20 K, (3)
Rodrigue (1963) at room temperature, (1) and (2) calculated values (see text); (b) Ha: ((2)) De Bitetto
(1964), ( 0 ) Rodrigue (1963); (c) KI: De Bitetto (1964); (d) 0o: Rodrigue (1963).
2b site occurs. When comparing these conclusions with the above mentioned
results in fig. 65, it should be noticed that the latter observations correspond to
the paramagnetic region.
Other combinations with H-IVpairs. D u e to the interest in the effect of substituting ions on the magnetic properties of M compounds, attempts to replace Fe 3+ by
non-magnetic ions are still being reported occasionally. Since equal amounts of
380
H. KOJIMA
M2++ M 4+ are simplest for electrical neutrality in these substituted compounds, a

number of papers has been published regarding such a substitution. For instance,
Tauber et al. (1963) investigated BaZnx/2Irx/zFe~2 xOi9 single crystals with x = 0-0.6
and found that the lattice constant a increased from 5.893-+0.001 A to 5.920-+
0.001A but that c remained constant at 23.194_+0.002A with increasing I r
content. The o-~-T relations for x = 0, 0.32, 1.04 and 1.2, determined by the
chemical analysis of total Ir, were given in their paper. Other main results
obtained using FMR are summarized in table 18. They showed that the substitution of Ir 4+ causes the spin system in the compound to be pulled down toward
the basal plane. Similar FMR measurements have been done by Dixon et al.
(1971) with single crystals of BaZnx/zTix/zFelz-x019 for nominal compositions,
x = 2.0-5.0. They succeeded in decreasing the resonance line width A H to 36 Oe
[2865 A/m] with x = 3.0. The variation of A H versus x at 37.6 G H z was illustrated
in their paper. A summary of their results is given in table 18.
Rensen et al. (1971) discussed ZnTi, ZnGe, ZnSn, ZnZr, CuTi, CoZr or NiTi
substitution pairs. They referred briefly to the cation distributions for each
compound from M6ssbauer effect results. Magnetization, anisotropy field and
M6ssbauer spectra of BaZnxTiyMnzFe12_x_y_z019 were investigated between 4.2
and 300 K by Mahoney et al. (1972). The o-~-T curves for various nominal x
values, H~-x and e - x diagrams and tables of magnetic moments at 0 K and cation
distributions were given in their paper. They concluded that Ti 4+ mainly, and
Mn 3+ completely occupied 12k and 2a sites, and Z n 2+ w a s primarily assigned to 4fi
sites on crystal chemical grounds, but partly distributed on to 12k or 2a sites to fit
with the observed magnetic moment. Haneda and Kojima (1973b) measured HA,
MHc and Rc as a function of x for BaZnx/zGex/zFe12-x019 and BaZnzx/3Vx/3Felz-x019,
BaZn2x/3Tax/3Fe12-~019 and BaZn2x/3Nbx/3Fe12-~O19, also involving M2++ M 5+ pairs.
The main problem concerned the changes of MHc with x for these compounds and
this was also considered in connection with the changes of H A and also Rc for
sintered specimens.
o
2.2.4. Effect of substitutions on the temperature dependence of magnetization

An attempt to improve the temperature dependence of the magnetization of the
magnetoplumbite structure, which is inferior by one order than for Alnico
magnets, was perhaps reported f o r the first time by Heimke (1960). H e showed
that the Ms-T relation could be changed for the M-type compound
BaTiO3"5Fe203+ 1.5% CaSiO3, that is, its magnetization varies almost parallel
relative to the temperature axis below 0C, as illustrated by line (1) in fig. 66(a)
(using the scale of the right-hand axis). For an explanation of this result, he
proposed two kinds of exchange schemes other than the one reported by Gorter
(1957). Esper and Kaiser (1972) continued this analysis and obtained interesting
results on the changes in the temperature dependence of O-s for M compounds.
Their o-s- T relations are shown in fig. 66(b) as curves (2) and (3), with (1) as the
normal relation of BaM. Their typical substituted compound has the composition
Ba(Sb203)0.25(Fe203)5.75 and the sample of curve (2), having almost the same
temperature coefficient a(o-s)= 0.2% per degree and about ~O-s of BaM, was
FUNDAMENTAL
PROPERTIES
OF HEXAGONAL
FERRITES
-g
T
X
o X ~
rO
{IN]{[{
{{
r
eq
tt3
1
k~) tt~ ~
ee)
tt3
0J
~2
t--
e~
e5
,<1
e'~
t~, ,,o
O
r.)
X
cq ~ ,~1- tt3
.+
N
+
~z
rqrd
i--.
381
382
H. K O J I M A
I00
..L,~
(c)
80
60
40
i
20
0
E
I
..Q
b--
I0
I00
--.
b~
(b )
-4) 1
Bo
--.<\-..~
~.
20
5000
I00
8O
i~)-~ I
~_,p~.~,-~-~-~.
(5) _
60
(0 ) -
4000
~ . ,
5000
~o
2000
4O
2O
i
I
0
0
200
400
Temperature
600
I000
800
(K)
Fig. 66. Temperature dependence of the saturation magnetization o's for some substituted M compounds. (a): (1) 4~rMs of BaTiO3'5Fe203 with the scale of the right ordinate (Heimke 1960), (2)
"4+
2+
3+
5+
2+
3+
BaTlo.6Feo.6Felo.8Ol9,
(3) BaSbo.sFel.oFelo.5019
(Lotgering 1974); (b): (1) BaM, (2) and (3) Sb-substituted
BaM (Esper and Kaiser 1972); (c): (1) SrM, (2) As-substituted SrM (Esper and Kaiser 1972).
383
p r e p a r e d through the heat treatment in air and below 1300C. The sample of
curve (3) received a secondary heat treatment above 1200 in N2 or above 1300C
in air, after the normal solid state reaction. Sb205, i.e., Sb 5+ was used as a starting
material in both cases. It was claimed that the anomalous t e m p e r a t u r e dependence of curve (3) was caused by the partial replacement of Fe 3 in 4f2 sites with
non-magnetic trivalent ions having ionic radius smaller than Fe 3. In this case, the
crystal structure or the magnetic coupling scheme gradually turns to the Wstructure from M-type, though the sample of curve (2) still has a distorted M
structure. In conclusion As and P were r e c o m m e n d e d as the most suitable
replacing ions to realize a low t e m p e r a t u r e coefficient around room temperature.
A valve c~(o-s)= 0.1% per degree was obtained with As substituted SrM as
illustrated with curve (2) in fig. 66(c), in contrast to curve (1) for the normal SrM.
On the other hand, Kreber and Gonser (1973) concluded from the M6ssbauer
experiments at r o o m t e m p e r a t u r e and 77 K for the same composition, that As
ions occupy preferentially 2b sites, although they did not describe the preparation
conditions. Lotgering (1974) showed in curve (2) in fig. 66(a) the saturation
magnetization measured parallel to the easy direction, o-//, of oriented polycrystalline BaFe2+0.6Ti4+0.6Fe10.8019 and curve (3) for or// of BaFe2+1.0SbS+0.sFe10.sO19,
both of which behave very similarly with t e m p e r a t u r e as curve (1) obtained by
H e i m k e (1960). Lotgering reported Ti 4+ and Sb s+ to occupy 4f2 sites, which was
supported by the X-ray and neutron diffraction investigations. H e stressed the
effect of Fe 2+ on a 4f2 site on the t e m p e r a t u r e dependence of the magnetic
anisotropy for the substituted compounds, which would be caused by the effect of
an Fe 3+, Ti 4+ or Sb 5+ ion on the neighbouring 4f2 site.
As described before, Grill and H a b e r y (1974) calculated the exchange
parameters of BaM (see table 5) and mentioned that the t e m p e r a t u r e coefficient
of the magnetization at room temperature cannot be decreased without decreasing the magnetization, and moreover, the saturation magnetization would only be
increased with a diamagnetic substitution on 4f2 sites, measuring the magnetic
properties of Bal-xDxPxFe12-x019 with D = K ~+, Bi 3 and P = Cu 2+, Ni 2+, Mn 4+ between 180 and 770 K, Grill (1974) practically proved that all the compounds have
lower ~r~, 0c and almost the same c~(o-s) values as those of pure BaM. On the other
hand, H a n e d a et al. (1974b) studied the effect of replacements of Fe 3+ in M type
compounds with (Cu 2+ + Ge4+), (Cu 2+ + Si4+) and moreover with (Cu 2+ + Vs+),
(Cu 2+ + Nb 5+) or (Cu 2+ + TaS+). They obtained ~(Br) = 0.1% per degree without
reducing other p e r m a n e n t magnetic properties and insisted that ce(Br) can be
improved by changing the temperature coefficient a(MHc) or C~(BHC) by such
substitutions, instead of improving or(O-s), as proposed by most other investigators.
Esper and Kaiser (1975) found that the anisotropy field HA, and accordingly MHc,
and also their temperature coefficients can be varied with Sb-substituted BaM by
different heat treatments. HA can be changed from 6.3 to 12.6kOe [5001000 kA/m] by varying the preparation conditions, and c~(MHC) was determined to
be negative for HA = 6 . 3 k O e [500kA/m] and positive for HA = 12.6kOe
[1000 kA/m]?. The results of the studies on the mechanisms of the i m p r o v e m e n t
t o~(MHc)=+ 0.28%/C and o~(BHc)- -0.09%/C near room temperature for the normal BaM were
estimated by Haneda et al. (1974b).
384
H. KOJIMA
of these t e m p e r a t u r e coefficients are fairly confused, but Lotgering's consideration

(Lotgering 1974) seems to be most reasonable. H e proposed that the effects of
partially existing reduced Fe 2+ ions could be considered to contribute to the
temperature change of the anisotropy with any combinations of substituted ions.
2.2.5. Substitution with anions

Q u i t e a few researches have been published on the substitution with anions in Mtype compounds. It is presumably more difficult to obtain the specimens with
definite concentration of substituted anions than in the case of cations. Moreover,
if it is possible to replace O 2- with only anions, this will dilute the ferromagnetic
ions, so that the magnetic properties would be unfavourable for most industrial
purposes. H e n c e some examples described here concern the substitution of 02with F 1- and some other kinds of cations for the purpose of valency compensation. Because of the resemblance in their ionic radii, F 1- seems to be the only
suitable anion (see table 2). Frei et al. (1960) obtained an M-type c o m p o u n d
BaFz.2FeO-5Fe203, showing specific gravity p = 5.25 g/cm 3 and saturation magnetization at r o o m temperature o-s = 72 emu/g [9 x 10 -3 Wbm/kg] in comparison
with p = 5.25 g/cm 3 and O-s= 67 emu/g [8.4 x 10 -3 Wbm/kg] for BaM. F r o m these
experiments, they suggested that the Fe e+ ions are on 4f2 sites and F 1- ions near
Ba 2+ ions. C o m p o u n d s intended to give the formula BaCoxFe12-xO19-xFx with
x = 0, 0.3, 0.4, 0.45, 0.47, 0.5, 1.0 and 2.0 were prepared by Robbins and Banks
(1963) and recognized as single phase magnetoplumbite type by X-ray diffraction
for the compositions x <~ 0.47. The estimated magnetization values for randomly
oriented powders at 0 K and H = 6 k O e [4.8 x 105 A/m] were: 76, 76.5, 85, 95.2
and 100 emu/g [9.55, 9.61, 10.68, 11.96, 12.57 x 10 -5 Wbm/kg] for x = 0, 0.3, 0.4,
0.45, 0.47 respectively. They also confirmed from torque m e a s u r e m e n t s that the
cone angle of the easy magnetization was 10 at 77 K for x = 0.3; and 40 at r o o m
t e m p e r a t u r e and 58 between 200 and 77 K for x = 0.47.
Robbins (1962) investigated the preferential site of Co 2+, Ni 2+ and Cu 2+ in the
hexagonal compounds BaAla2019, BaGa12Oa9 and BaFe12019. Ba 2+ was replaced by
La 3+ or O 2- by F ~-, for the charge compensation in these compounds. Referring to
the results of Banks et al. (1962) regarding the same compounds we can deduce
the following tendency for the preference of bivalent ions: In the
BaMZ+Al12_xO~9_xFx system, the order of the tetrahedral preference is Co2+>
Zn2+> Ni 2+, while in the BaM2+Galz_xO19_xFx system, it is Co2+> G a 3+ > N i 2+.
These results were derived from X-ray investigations and diffuse reflectance
measurements for powder compacts. Tables 19 and 20 give lists of the lattice
parameters after Robbins (1962) for the BaA112019 and BaFe12019 systems, respectively. Examples of reflectance measurements are illustrated in fig. 67, with
curve (1) for BaNi0sGa1150185F0s, curve (2) for BaCo0.sGalLsO18sF05 and curve (3)
for BaNi1.sAl10.50175Fls. Assignments of the absorption peaks shown as T or O in
the figure have been obtained from the literature values. As for
BaM2+xFe~2_,O~9_~F~, Robbins obtained M phase single crystals with a flux of a
Fe203 and NazCO3 mixture for the composition x ~< 0.5 for Ni 2+ and Co 2+, and the
concentration x = 0-2 for Cu 2+. The bivalent cations in these substituted systems

T A B L E 19
Lattice parameters of substituted Bamll2019 with M 2+ and
F 1- (Robbins 1962).
Formula
BaAl12019
BaNixAla2-xO19-xFx
B aNio.sZn2A19.sO16.sF2.5
BaCox Al12- x O19-xF x
BaCoZnAlloO17F2
BaCoo.sZn2A19.5Ox6.~F2.5
a (A)
c (A)
5.577
22.66
0.1
0.4
0.6
5.585
5.597
5.607
22.64
22.64
22.64
0.8
5.610
22.64
5.617
22.76
0.1
0.4
1.0
2.0
2.5
5.586
5.598
5.603
5.616
5.622
22.63
22.63
22.63
22.70
22.81
5.613
5.616
22.63
22.70
T A B L E 20
Lattice constants of M 2+ and F 1" substituted M compounds
(Robbins 1962).
Formula
a (,~)
c (A)
0.5
0.6
1.0
2.0
5.888
5.892
5.891
5.896
23.15
23.14
23.19
23.21
5.882
32.83
BaCuxFe12-xO19-xFx
0.35
0.63
1.14
5.883
5.884
5.885
23.15
23.16
23.19
BaCoxFe12-xO19-xFx
0.3
0.4
0.45
0.47
5.883
5.886
5.886
5.887
23.12
23.12
23.13
23.15
BaNixFe12-xO19-xFx
BaFe22+Nio.ssFels.4201s.42Fo.ss
385
386
H. K O J I M A
8O
7o
/s)
6O
r~i_
/ /~IT~-
(21
50
t j...
I//
iX
. . . .
1~
.//,"
(_./
200
g
I
/i
i~ V1,
,~ '
Io
r,J
+%,.,d;
400
600
.X. ( m,u.m )
800
I000
Fig. 67. Examples of the reflectance spectra for the pellets with some anion substituted M compounds
(Robbins 1962). (1) BaNi0.sGall.5Ois.sF0.5, (2) BaCo0.sGall.sO1s.sF0.5, (3) BaNii.sAl10.5017.sF1.5. T and O
are absorption peaks from relevant ions in tetrahedral or octahedral site.
also exhibited a preference for 4fl sites, as was confirmed from the results of
magnetic measurements. The magnetic properties at 0 K are listed in table 21,
where the saturation values were estimated from the o-s-T relations in a rather
higher temperature range compared with the literature value o f BaFei2019 as a
standard. Though the Curie temperatures seem to be higher than the other
reported values by about 50C, the increase of O-s and the decrease of 0 with
increasing substitution ratio are clearly seen. For the higher substitution ratio of
Co 2+, x > 0 . 5 , the compound changes to a mixture of M and W phases, then
rapidly becomes single W phase with increasing x values, which was confirmed by
X-ray and magnetic torque measurements in this paper.
T A B L E 21
Magnetic properties of M 2+ and F 1- substituted M compounds (Robbins 1962).

KI at R.T. (x 10 6 erg/cm 3)
[x 105 J / m 3]
0% at 0 K (emu/g)
[x 4~- x 10-7 Wbm/kg]
NB at 0 K
(/xB)
0c
(C)
100
20
500
3.3
BaNixFe12-xOm-xFx
0.6
113
22.50
475
2.4
BaCuxFe~2-xO19-xFx
0.35
0.63
1.14
108.0
113.5
118.0
21.66
22.72
23.72
460
450
418
3.1
2.9
-
0.3
0.4
105
108.5
21.0
21.7
470 470-
Formula
BaFez2019
BaCoxFel2-xOx9-xFx
387
References
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chapter 5

Ferromagnetic Materials, Vol. 3

A group of ferrimagnetic oxides with hexagonal structures will be described in this

1.1. Chemical composition

1.2. Phase diagram

FUNDAMENTAL PROPERTIES OF H E X A G O N A L FERRITES

BoO'Fe203 BoO-6Fe203 Fee03

FUNDAMENTAL PROPERTIES OF H E X A G O N A L FERRITES

1.2.2. SrO-Fe203 systems

FUNDAMENTAL PROPERTIES OF H E X A G O N A L FERRITES

1.2.3. PbO-Fe203 systems

,,./ ~ " (I0)

FUNDAMENTAL PROPERTIES OF HEXAGONAL FERRITES

1962, Suemune 1972, Aidelberg et al. 1974); or discontinuous grain growth

2.1. BaFele019, SrFe12019 and PbFea2019

Fig. 11. Perspective illustration of BaO.6Fe203.

FUNDAMENTAL PROPERTIES OF HEXAGONAL FERRITES

(~) Be2+ ion

(~ Fe3+ under the layer

Fig. 12. The layer sequence of BaO.6Fe203.

~'~hz ~U/~z iIz

Fig. 13. The (110) cross section of BaO-6Fe203.

FUNDAMENTAL PROPERTIES OF HEXAGONAL FERRITES

(a) Tauber et al. (1963)

FUNDAMENTAL PROPERTIES OF HEXAGONAL FERRITES

c o m p o u n d s but is shown here to illustrate the relationship a m o n g the blocks (see

2. 1.2. Magnetic structure

I" I" I" I' '~ 1'

FUNDAMENTAL PROPERTIES OF HEXAGONAL FERRITES

The total magnetization at temperature T, therefore, is expressed as

2.1.3. Saturation magnetization

Fig. 18. Saturation magnetization of BaO.6Fe203, SrO.6Fe203 and PbO.6Fe203 as a function of

FUNDAMENTAL PROPERTIES OF HEXAGONAL FERRITES

2.1.4. Magnetocrystalline anisotropy

For M-type compounds,/2,/(3 . . . . are negligible in comparison with K1 and their

Fig. 23. Magnetocrystalline anisotropy constant K~ of BaO-6Fe203 as a function of temperature: (C))

FUNDAMENTAL PROPERTIES OF HEXAGONAL FERRITES

Fig. 24. Magnetocrystalline anisotropy constant K~ of SrO.6Fe203 as a function of temperature: (O)

Buessem 1969) respectively. The broken line in fig. 27 shows HA of PbM

Since only rotation of magnetization can be expected in a particle of smaller

generally express MHc using his results:

FUNDAMENTAL PROPERTIES OF HEXAGONAL FERRITES

FUNDAMENTAL PROPERTIES OF HEXAGONAL FERRITES

temperature. He reported the temperature dependence of (KO1/2/Msas in fig. 33,

method, they may be magnetized mostly by coherent rotation, as proved by curve

2.1.6. Paramagnetic properties

and 0 can be given by

FUNDAMENTAL PROPERTIES OF HEXAGONAL FERRITES

m o l a r susceptibility XM is used i n s t e a d of XA in eq. (10), t h e n CM can b e o b t a i n e d

CA: atomic Curie constant of Fe3+ ions,

2.1.7. Magnetic aftereffect

--o-c~-c. -o-o-oc - o - o F'

FUNDAMENTAL PROPERTIES OF HEXAGONAL FERRITES

points. The ordinate of the figure is illustrated in arbitrary scale but it is

sin 0 cos 0/sin(00- 0) = HexdHa.

FUNDAMENTAL PROPERTIES OF HEXAGONAL FERRITES

single cryst, disc, d = 1 m m ,

single cryst, disc, d = 0.083 cm,

single cryst, sphere, d = 0.4 m m

oriented polycrist, slab

single cryst, sphere,

single cryst, sphere, d = 0.038~.05 cm,

* Spin wave line width