Journal of Magnetism and Magnetic ]Materials 1 (1976) 241-250

© North-Holland Publishing Company

EFFECT OF SOME ADDITIONS ON THE SINTERABILITY

AND MAGNETIC PROPERTIES OF BARIUM HEXAFERRITE

A.M. GADALLA*, H.E. SCHUTZ and H.W. HENNICKE

Lehrstuhl far Glas und Keramik, TU Ciausthal, W. Germany

Received 16 October 1975

The effect of additions on the densification of previously prepared stoichiometric barium hexaferrite, during the initia!
and intermediate stages of sintering, as well as on the coercivity and remanence were studied. The effect of non-stoichio-
metry, SiO2, Al2Oa, Cr203, TiO2, SnO2, MnO.2, MgO, NiO and Bi203 is included.
While SiO2 and Bi203 form liquid phases that increase the density, Ai203, Cr203 and MnO2 form a limited solid solu-
tion and are generally beneficial when added in the proper amounts. At 1300 SiO2 up to 0.55~ and AI203 up to 17, gave
better magnetic properties. On the other hand addition of TiO2, MgO, NiO or SnO 2 has a deleterious effect.

1. Introduction of sintering thus decreasing the ,;intering temperature

In producing barium hexaferrite-which has the low-
est price per unit of magnetic energy [1 ] -- non-
stoichiometric compositions often containing inorganic
additives [2] (which may enter into solid solution or
form secondary phases) are used.
Raw materials suppliers usually recommend an
amount of SiO 2 (0.3-1%) and A120 3 to be contained
in the ferrite, which is introduced either by raw mate-
rials or added subsequently. While alkalies, manganese
and TiO 2 prese~at as impurities have negative influence
on the magnetic data, Bi20 3 is beneficial [2,3].
The role of these additives on the sinterability and
magnetic properties, is not completely understood and
apart from the effect of SiO 2, the magnetic proper-
ties were followed only by substituting part of Fe20 3
or BaO m the hexaferrite and tb~ ~;nteriog was not
followed (see later).
This paper is a part of study aiming to understand
the effect of progressive additions, of various oxides,
on previously prepared hexaferrite within and outside
the solubility range. Such a study is important to: (a)
establish specifications for raw materials required for
fabricating barium hexaferrite, (b) to increase the rate
* Associate Professor, Chemical Engineering Dept., Cairo
University.
and time and (c) to achieve better magnetic properties
by controlling the grain size and inhibiting grain growth
of the product.
2. Hypothetical changes in properties due to ~dditions
2.1. Effects outsMe the solubility range
In homogeneous material with large grains, domains
may nucleate and spread through the grains thus re-
ducing greatly the remanence and the coercive f,)rce.
Therefore, nucleation and movement of domain walls
laust be inhibited. Decreasing the grain size to the
critical value, forms single domain grains and demag-
netization occurs by coherent rotation only (since
curling and buckling are not expected in such materials
witlqh high crystal anisotropy). It should also be noted
that excessive reduction of grain size is not recom-
men,:ted since below the critical size coercivity de-
crea,~;es again. Accordingly, progressive reduction of
particle size by additions, which remain on grain
boundaries, may anchor grain growth and give high er
densities due to elimination of more pores.
One of the characteristics of hexaferrite is its
platty structure, with the larger rate of growth norraal
to the crystallographic easy axis [4- 6], thus giving a
,4.,"" /|.M. (;adaUa et al./Effect o f some additions
shape anisotropy which opposes the co, sial anisotropy
17]. Accordingly, the coercivity will never reach the
vallue of the anisotropy field: 2 K / I s for oriented
spherical non-interacting particles or 0.06 K / I s for
randomly oriented particles (where K = ariisotropy
coulstant arid I s is Ihe saturation n'iagnetizatiori'}.
Haneda and Kqiima IS] used the greatest possible cor-
rection for shape anisotropy effect and for packing
of particles and gave the following formula for the
intrinsic coercive force iHc in case of randon'lly
oriented thin plates.
ill. = 0.4S s- 4,'rls - 1.7pl s
(wl-,ere p is the volumetriic packing factor). The average
crit ~cal radius can be given by:
Re-
where k = Boitzmann constant, T c = Curie temperature
and a = distance between iron ions.
It should be noted that no finite critical size can be
given due To the shape anisotropy and as approxima-
li,'ll. Craik and Mclntyre [t~] calculated the critical
size for rectangular isolated particles (see fig. 1) and
demonstrated that the crilical size is increased by the
iT~tcraction with neighl"ouring particles and is affected
b~ h e degree of orienlatiori.
"5
.i t I
Length c alone easy axis (microns) " - ~
J lg 1. Variation ol critical size v,ith shape for isolated parti-
cles ~ rectangular barium hexaferrite crystals; length c along
•he .<:2svaxis. other dimensionsa and b [9]
2.2. ~ f f e c t s w i t h i n the solid s o l u t i o n
Ill forming a solid solution Iv K and Tc vary and
according to eqs. (1) and (2) if I s can be reduced more
than K and T c, the critical size as well as the imrinsic
coercive force should increase. This behaviour was
reported for replacing Fe 3+ by AI 3+ or Cr 3+ [811.
Referring to the hexaferrite structure, it con:~ists
of spinel blocks separated by layers containing 13a2+.
The distribution of Fe 3+ is as follows:
Spinel blocks 2 t Tetrahedral, 4 4' Octahedral
Layers 1 4' Five fold, 2 t 3 4, Octahedral.
(1) Accordingly, replacing Fe 3÷ in tetrahedral sites in
spinel blocks by non-magnetic ions would lead to an
increase in the magnetic moment of the solution and
substituting Fe 3+ in octahedral positions in spinel
blocks decreased the saturation magnetization to zero
(point of magnetic compansation) with the coercivity
(2} approaching infinity and the ferromagnetic resonance
frequencies moving to higher frequencies. The latter
case was reported for substituting Fe 3+ by A13+
[1o--12].
It should be noted that substituting one of the ions
will disturb the equilibrium between cationic and ani-
onic vacancies. This will affect the rate of diffusion
and hence the sinterabi!ity, it has been proven b'.¢
Gadalla and Hennicke [6] that the diffusion of oxygen
is the determining factor in the sintering process.
Accordingly cationic substitution by ions of lower
valence increases the available number of oxygen
vacancies and hence increases the sinterability, while
substitution by higher valence decreases the number
of oxygen vacancies and reduces the sinterability.
3. Experimental technique
/a
3.1. R a w materials
Two types of nrevimldv n r ~ a n ~ r ~ r l k , ~ r ; , , r n l~ . . . . ¢,-,-
4 - IV - :" " . . . . . j ~..,.l~[..,~,i ~,%8 q..ILItlll.~|lX ll%,A(|l~.,I °
rite powder were used as raw materials to study the
effect of additions on the densification stages (see
later) and the effect of each oxide added alone ot in
,
the presence of the impurities present in technical
iron oxide. The hexaferrite was prepared as follows:
(a) High purity o~Fe203 (~ith close particle size dis-
tribution) was prepared by heating ferrous sulphate
heptahydrate at 800°C for 3 hrs [13]. Mixing wa:;

carried out with AR grade (Merck) BaCO 3 before fir-
ing 3 hrs at 1100°C to form fine active BaO • 6Fe20 3
[t4]. The ferrite reached a limiting density of
3.78 - 4.03 g/cm 3 after 6 hrs at 1300°C. The variation
of density is due to the sensitivity of the yield and its
reactivity to the fabrication process [14]. Therefore,
in studying the effect of each oxide, hexaferrite from
one homogeneous batch was used.
This material shows the effect of additions at the
beginning of the intermediate stage [6] (relative density
70-75%). This material is named "a".
(b) Bayer technical Fe20 3 produced for manufacturing
hard magnets (No. 1663) was kindly supplied by Dr.
Erzberger. It has 99% Fe203, O.l 5+-0.25 water soluble
salts, O. 1-O. 15% SO 3, 0.27-0.33% SiO2, 0.02-0.03%
Al20 3, 0.06-0.08% Cr203, 0.005-0.01% MgO,
0.04-0.06% MnO, 0.04-0.06% CuO, 0.01-0.02% CaO,
0.01-0.02% Na20 and 0.001-0.005% K 20. In this
type F e 2 0 3 was cubic of -325 mesh (0.3-0.5/a par-
ticle size). The oxide was mixed with AR grade BaCO 3
and was found to be more reactive, giving at 1 I O0°C
after only one hour the X-ray pattern of hexaferrite.
After pressing, the ferrite reached a limiting density of
4.4 g/cm 3 on firing at 1300°C for 3 hrs (relative den-
sity of 84%). Accordingly this material demonstrates
the effects of additions on approaching the density
used in service as well as the effect of impuritites
present in the technical iron oxide. This material is
named here "b".
3. 2. Preparation o f green pellets and sintering
The hexaferrite powder was pressed isostatically,
without a binder, using a pressure of 450 kp/cm 2 to
obtain isotropic material. Unidirectional pressing was
avoided since it gives preferred orientation [15]. To
avoid cracking on releasing the pressure the powder
was evacuated before pressing. Powder "a" and "b"
were sintered at 1300°C in air for 6 and 3 hrs respec-
tiVelV.
. J ttese values gave nmHing o e r l S l ( l e s (on
A , _ . _ I . . "l"Sl . . . . I . . . . Ir
. plotting
_ . ' , ,
density against sintering time) and were selected to
avoid any fluctuations in density due to slight error
in sintering temperature or time.
To investigate the effect of the early stages of sinter-
ing, materials "b" was mixed with the additions and
heated in a dilatometer with a rate of 5°/min.
Bulk densities were measured using the mercury
hydromete: and demagnetization curves for specimens,
A.M. Gadaila et al./Effect of some additions 243
with flat parallel surfaces, were drawn using the
Permagraph. To trace the distribution of the additives
(inside the lattice and/or on the grain boundaries) the
electron microprobe was used for polished and etched
specimens. Due to the low concentrations used, this
tool failed unfortunately to ascerltain the distribution.
4. Effect of non-stoichiometry
4.1. Previous work
On firing BaCO 3 and Fe203 Stuijts [I 6] found a
maximum shrink~tge at Fe203/BaO < 5.9. if BaO
enters the hexaferrite lattice, it increases both Fe 3+
and O 2- vacancies and increases the sintering rate but
it has been proven recently by various authors [171
that hexaferrite is a stoichiometric phase. Stuijts [I 6]
suggested that BaO remains as a secondary phase
(BaO • Fe203) and inhibits crystal growth. The slight
amount of this phase has practically no influence on
the magnetic properties.
While Wullkopf [I 8] showed a high coercive force.
remanence and density to occur at a ratio of 5.6,
Kojima [19] found that decreasing this ratio to 5.5
decreased the coercive force and i;ncreased slightly the
remanence. Below 5.5 both values decreased.
Recently however, Gadalla and Hennicke [14]
showed that excess BaO increases the rate of formation
of monoferrite at low temperature and that of hexa-
ferrite at high temperature and produces fine crystals
of hexaferrite in shorter time at lower temperatures.
4. 2. Results and discussions
Fig. 2 shows the results of adding BaCO 3 on pre-
viously prepared hexaferrite. It is evident that the
higher the BaO content the h i ~ e r is the initial sinter-
ing rate. On the other hand, soaki~ag results (fig. 3)
1 1 • I • .~, ,"
. 1 ,,, _
SIlOWeU a raplu U(gIISlllCa[lon tO oc, cLIr tip to a certain
limit (due to inhibiting grain growth as suggested earlier)
with a slight drop in the coercivity during th,." early
densification stages (cases "a") and a rapid drop in both
coercivity and remanence when tlJe relative densities
approach and are more than 90% (case "'b"). In the
latter case exaggerated grain grow~Eh and pore growth
was observed, indicating the movement of pore~ with
grain boundaries thus causing pore growth by coalsence
244 A.M. Gadalla et al./~ffect o[ some additio,s

(see earlier). The final result of increasing grain size

and decreasing the critical size as well as adding exces-
sive nonmagnetic phase is the deterioration of the
magnetic properties.
X -

5. Effect of silica

5.1. P r e v i o u s w o r k
- 0 IOH

i \\
MOiler and Heimke [2] found that the addition of
L \\
! x x
SiO 2 up to about 1% increases the density, l he rema-
L . * 05% ~CO3 \ \
\ nence and the coercive force. Higher concentrations
! 0 , ,
..... \ "\
caused the density and remanence to drop and the
I X \,. "
!. .... -. ao"/. \ -, . coercivity to increase. After adding silica in 'various
forms they recommended using CaSiO 3 (0.4-0.8%
L \" "'*'" "1
SiO2) which caused the hexaferdte to form easily
- ~2,0~
and increased the magnetic propertieswithout the
possibility of liquid phase formation.
uoo
T£TI ~-
Fig. 2. Dilatometric changes on adding excess BaCO3 to pre- 5.2. R e s u l t s a n d discussions
siously prepared hexaferrite, 5"/rain.

5.0~ ~ - ' - - - ~ - L - _ L ' ' ' ' ' ' ' IOe'G In this study pure silica o f - 1 0 0 mesh was added in
various amounts and the early stages of sintering were
followed using the dilatometer, which proved that initially,
the higher the SiO 2 content the higher is the sinter-
ability but using excess SiO 2 caused slower shrinkage
5 ~ -, "----,. ~ 200o
at later stages (see fig. 4). Fig. 5 shows also the result
of soaking material "a" and "b" at 1300°C, iadicating
c g ~ / x-N.. that before reaching 90% theoretical density, addition
of up to 0.55% SiO 2 caused a rapid densificadon ac-
..... G • ,ooo
~,ompanied by higher coercivity and remanen:e. Higher
~ ~ ~,, content caused a slight density decrease and ~ drop in
, - ....... e_ . . . . G magnetic properties. Although it was difficult to ob-
tain the distribution of SiO 2 on polished sections
ask , , ...... ._:. ,
tO 20 3.0 using the electron probe microanalyser, a liquid phase
aaco3 was observed increasing in amount with the silica con-
Fiig.3. Effect of non-stoichiometry on density, coercivity and tent. Accordingly the initial densification is d ae to the
remanence after soaking materials a and b for 6 and 3 hrs presence of a silicate phase which increased tile particle
respectively at 1300°C.
interaction by surface tension. As the particle approach
each other, the critical size inr;eases (as explained
of pores. This implies that the impurities in technical earlier) and the coercivity increases. This effect will
iron oxide (ca'.e "b") increase the grain boundary be more pronounced at the early stages (see figs. l and
energy and their mobilit3,. 4). Excess SiO 2 will have deleterious effect due to
The higher the BaO content, the higher is dilution grain growth above the critical size and the formation
by a non-magnetic phas'~. Also excessive additions in- of intergranular, low density nonmagnetic phase.
crease the distance between the grains thus decreasing The optimum amount of SiO 2 will thus depend on
~he degree of interaction and lowering :he critical size its particle size and on the particle size of tile hexaferrite.
 A.M. Gadalla et aL /Effect of some additions 24 5

.... ~,

i
5 ~/mk~ T t300*C
4t
I,

-t~o~ \',.
t~

tt "~.

-o,~o
t

= .0,5~, SiO2 , ,,,

* ..... o 1,3~ 5i02

..... , t,81 5 i 0 2
%
-OJ5
~q'%* "*. ~. ~. "%'%

,11 -L~

,0 . . . . . . . . . 9 ..... - ' , ' - - . " ..-'-:-

-a o ,o'oo ,ioo ,3oo t20 tSO 3~0
t PC] t l min ] --~

Fig. 4. Dilatornetric changes on adding silica.

, |~ , , w Oea

. ! "e~ form BaFel2_ x AlxOl9. Nothing was published on the

5.0 ==;,'e (a)
effect of adding alumina to previously formed hexa-
'4. 4.8 ferrite as carried out in this study. It was found that a
continuous series of solid ~,olutions exists at least up
to x = 8 in which the lattice p~,rameters a and b decrease
tO00
•- 7 ,., -...g, and the density is slightly affected. The higher the
4.4
! ~ ~n. alumina content, the lower is the curie temperature,
C~
4.2 the anisotropy constant, saturation magnetization and
the higher is the coercive force [8,10,2-,21 ]. The rapid
4.0 "'"'" ....... -o; .......
increase in coercive force 'was considered by Haneda
and Kojima [8] to be due to the increase in the critical
3a ,.'o ,is io is 3.0 size (se ~ earlier) thus approaching a single domain be-
ss o2
Fig. 5. Eifect of silica on densification and magnetic properties.
haviour at higher concent,'atio,~s. The same phenomena
was considered by Mones and Bank [20] and Van
The lower the particle size, the higher is the silica con- Uitert and co-workers [10,1 1 ] to be due to substitution
tent required to give higher packing factor. of Fe 3+ in octahedral site.,; in spinel blocks thus lowering
With high densities (case " b " ) grain growth is in.. the saturation magnetization rapidly. They also obtained
evitable and both coercive force and remanence de- evidence for the presence of a point of magnetic com-
........ J .... t ..11..
t;zeaseu ~apluty. pensation at x = 4. It '---
ua~ 'o===~
. . . . a~u
' . . . .r=pt,
. . . zt=u_~,t._,
tltiat the
higher the alumina content the higher is the tempera-
ture and the longer is the time required for sintering
6, Effect of alumina I21].
6.1. Previous work 6.2. Results and discussions

Previous work carried out on the effect of alumina In this study anhydrous extra pure 7-alumina pro-
was done by substituting part of Fe203 by Al203 to duced by Merck was used. Various amounts of alumina
 A.M. Cnldalla et al./Effect o f some midilions
246
--
,, , ,,,, !

I.

-00'.
\ x'~'~t~ T #300"C
5 " Cdm i n %

.I

. ..... . tl525~ At203

...... ~.s~s~ ~t,,o3 %. " ' - - - , . . _ _ _ _ _ , . . _ _ . . _ . . , - - . . . . . ...

"~*'--0 .... ~ ...... • . . . . . . . . . 0 . . . . . . . . "i

- 015

I , I , i - -

doo ,;oo t~o ~3oo 6o 12o ~o a~o

t [minl - --'-
T['C] • =-

Fig. 6. Dilatometric changes on adding alumina.

secondary nonmagnetic phase remaining on grain

oe e boundaries caused dilution of magnetic properties and
-- 3000 2000
has no effect on inhibiting grain growth. This con-
i'..o,. clusion was deduced since the coercivity, the remanence
iL "',. and the density decreased.
7 ,'-," -~'¢'~"-.~a"~.'::.~ ..... ll-401
2000 1000
.- 40 ~ l l ". . .i .. .. t...
Ya~--::;~k i : - - G ~,, (o)
t ~t~ -
"(b)
,~, '~
7. Effect of Cr203

\(a)
3 SL-----OT-----10
t:i__.. 7. Effect of AI20 3 on densification and magnetic prop-
erties.
retarded the shrinkage ,(see fig. 6 which was produced
with a heating rate of 5 °/rain). Also soaking gave
lower density as shown ~n fig. 7. With both materials
"a" and "b", up to 1% AI203 increased the coercivity
7.1. P r e v i o u s w o r k
tO00 0
~5 2.O 2.5
~At2 03 Previous work on this system was carried out by
substituting part of Fe203 by Cr203 giving the for-
mula BaFel2_xfrxOl9 • Haneda and Kojima [8,22]
found that this substitution caused lower remanence
and large increase in coercivity. This solid solution
extends at least up to 25% replacement, with decreas-
ing lattice parameter. A rapid decrease of saturation
magnetization and slow decrease of anisotropy con-
#'1

~,~,~t a-d ,.,,r;:, . . . . . ~.+-.-~ gave according to eq. l,l )

rapidly while the remancence decreased slightly. This ,.,p i , u , t t ~, It ~.t I.,i i ll't,~ i , l ~ ' i t I t . . 1 % 1 t li.l I " I ~ ' i t v

high critical radius for the substituted material and

is in agreement with previous work on solid solution
this may explain the high coercive force reported. It
a'ad is due to replacing Fe 3+ in octahedral sites of
spinel blocks [10,11] and/or due to increase in the should be noted that using the values for K, T c, I s ob-
tained by the previous authors, a theoretical curve
critical size [8]. Accord,ngly, it could be concluded
that barium hexaferrite can take a limited amount for the coercivity was plotted and was found to de-
crease up to x = 1.5 then to increase again. Excessive
of alumina in solid solution.
It seems that outside this solid solution range, the substitution results in excessively low magnetization
 A.M. Gadalla et aL /Effect of some additions 24 7

Oe.O
so i , , ,~ , , ,~41.,.s~,(b) ' 2~100 Oe.G

2400
4.8
I
.... _40,1 2400

4.6 2000
4.6 ~q~''e/ ..ID,.-(110
2000
~J
4.4 ""41" "'mOe t 1600
~d Oe --". . . . 1600 u I---i----~. ~
. .

~,. ,, \ 1200
,--2,~ ~4,,..=._ ~._._, .... ~ •~...~ . . . . .G ° ,"", "x.,,~
~ - , - - . ~ . ~ , . , - - - - ~ ) - ~ . ~)
$00 ~ 4.0 - " ~ , ~ . . . . %,,,. ~. . . . . . =~::(o1 600
~.o' Oe
.Z6 " :,:.L:--'--roJ
400
3.a 400
. . . . . . o_(oj
0.5 tO t5 20 25
d5 ,.'o ,.'s io ~s % % oa •/ . r m 2

Fig. 8. Effect of C!'203 on.densification and magnetic proper- Fig. 9. Effect of TiO 2 on densification and magnetic properties.
ties.

and curie temperature and produces a material whose

properties are highly temperature sensitive [8].
Some authors attributed the low saturation mag- ~,~.2~,_ p,,. , ~ . . oe. o
.~ ~ . ~
netization to the preference of Cr 3+ (as AI 3+) for "~ L"" "*.--..-...... 1 '°°°
octahedral coordination in the spinel lattice [10,20]. ,,,,~.orx --... '---.--.....G.... /
•. I ~,.. o "- ....0,e • 1 6°°

7.2. Results and discussions "I "" o. ~"-'~'t 200

05 tC ~5 2.0 2.5
Anhydrous pure chormic oxide produced by Merck X SnO 2

was used in various amounts. Fig. 8 shows that the

coercivity changes in the same way as calculated by
Haneda and Kojima using eq. (1). This shape suggests
the presence of a solid solution, the limit of which
could not be established. The pure material gave a
lower initial drop in density followed by a steady in-
crease. On the other hand, the presence of impurities
in the technical iron oxide gave the reverse effect.
8. Effect of adding TiO 2 and SnO 2
8.1. Previous work
Koiima [23] replaced part of Fe203 by TiO 2 to
have the formula B a O ' n [(Fe203)l_x(TiO2)x].
With n = 6, both remanence and coercivity decreased.
Heimke [24] found that the temperature depen-
dence of saturation magnetization is improved by sub.
stituting Fe 3+ by Ti 4+ but the crystal anisotropy
decreases. Mones and Banks [20] attributed the low
magnetization due to the entrance ol Ti 4+ in octahe-
dral positions of the spinel blocks [16].
l:ig. 10. Effect of SnO 2 on densifica:ion and magnetic proper-
ties.
8. 2. Results and discussions
Pure TiO 2 and SnO 2 produced by Merck were added
in various amounts. Fig. 9 shows the results obtained
by adding TiO 2. The results ~f pure hexaferrite were
different from that obtained using technical iron oxide.
In case of pure material the coe~'civity and ~emanence
drop (as reported by Kojima [2:3] ), with decreasing
density. With impure material a liquid phase was ob-
served to occur and caused the density to increase
rapidly. The remanence increased slightly up to 1~
then decreased again. In both cases the coercivity
drops rapidly with negligible additions of TiO 2.
Fig. 10 shows the results of adding SnO 2 which
suggests the presence of a limited solid solution taking
up to 0.3% SnO 2 with a rapid density drop and a curve
similar to Cr203 for the coe~rcivity. Above this limit
both coercivity and remanence decrease.
 ..J~8 ,,I,M. Gadalla et al./Effect o f some ~dditions

/ " • -' , .__..u,--tU Oe.O ~2 ,,.-,-.:,... . . . . oe G

$0~ m • ......... Ue ,~ 1000
"0-.0 ~" ~, •
........... 2000
o~ 40 ~,-,,o...~ " - . • . . . . e. I000 600
-o....~..
.Z.8 600 200
! ...... -32 .............. a-"-t~
0,,
I I,
3.e 0.'5 ,0 ,.5 2.~ 2.~
/ z~

t.. o. _o" d --o ~(a Fig. 12. Effect of MgO on densification and magnetic proper-
40q ties.

o~ ;o ,-~ .,,:o ~s
x mno2
oe o
i-re. I I. Effect of MnO 2 on densification and magnetic pro-
F,erties. tO00 1400
r .---:::e . . . . . . . . Oe
~ a,~'~.o... ~ : ~ 600 tO00
9. Effect of adding MnO 2 ca]- "'". ..... G .,.~
38 , , , 7 . . . . . ,'1 600
05 1.0 1.5 20 25
It was found that replacing part of iron with Mn 3+ ¢NiO
decreases the magnetic saturation [10]. In this study
Fig. 13. Effect of NiO on densification and magnetic proper-
precipitated active MnO 2 produced by Merck for ties.
synthesis was mixed with previously formed hexa-
fertile. It is to be mentioned that pure MnO 2 is un-
It is evident from figs. 12 and 13 that adding MgO
stable dissociating in air at 435°C to Mn203. The
or NiO decreased the density and the magnetic pro-
latter dissociates at 890°C to tetragonal Mn304 which
perties. If a solid solution was formed, the density
transforms to the spinel form at 1160°C [15]. Ac-.
should increase as explained with Mn 2+. Therefore,
cordinolv- at the sintering te~nperature (13 00 oC) the
it could be concluded that MgO or NiO forms no
solid solution formed may contain Mn 2+ and Mn 3+
solid solution and will be rejected on grain boundaries
IT, i,, evident from fig. 11 that up to 0.7~ MnO 2 (and
and seems to have no influence on controlling grain
especially at intermediate .densities), a higher den-
growth. It is also evident that NiO gives slightly higher
sities wifll increasing rema:nence and coercivity occurs
magnetic values since Mg2+ is non-magnetic.
and could be attributed to the formation of a solid
solution. Introducing divalent ions (Mn 2+) increases
the available number of Ba 2~- and 0 2- vacancies. Since
11. Effect of adding Bi 2 03
it has been proven [6] that the diffusion of oxygen
in tiffs stage is the determinivg factor, the density
Magnetic and mechanical properties of hexaferrite
is expected to increase (see fig. 11). Beyond the solid
are imporved by the proper addition of Bi203 and
solution range, inspite of tlhe rapid decrease in den-
by selecting the stoichiometric ratio and the sintering
sity the remancence was nearly the same and a slight
temperature, the saturation magnetization increased
increase in coercivity was obtained. This effect is
by 20-30% and the intrinsic coereivitv h v ~hr~,,~ aloe,/.
utc nttd~Xlt:tlCsecondary phase which separates
. . . . . . . . . . j ~ j ,.al.,,,,.,t.et l,v/~J.
......
the hexeferrite grains. If sintering was carried out above 1 I O0°C, coercivity
of stoichiometric phase drops but if Fe203 is less
than 5.5, higher coercivities are obtained [26].
I0. Effect of adding MgO and NiO Sugimoto and Takei [27] stated that the increase
in magnetic properties and lowering the ~intering
Substituting Fe 3+ by M~!2+ was found to decrease
temperature are due to the presence of a liquid phase
the magnetization and this effect was referred by
which increases the rate of formation and sintering.
Mones and Banks [20] to the revlacement of Fe 3+ in
They found also an increase in grain growth and sug-
the :~ctahedral sites of the spinel blocks.
gested the formation of limited solid solution. They
 A.M. Gadalla et cl./Effect o f some additions
• -.--a.
i it '° t400
"'-.. _t,ooo . . . . .
O2 06 LO
%ei2o3
Fig. 14. Effect of Bi203 on densifieation and magnetic proper-
ties.
found that firing above 1200°C resulted in poorer
magnetic material.
Merck Bi20 3 was added in various amounts to the
hexaferrite. It is seen from fig. 14 that at 1300°C slight
additions caused a rapid increase in density above 90%
and caused a grain growth deteriorating the magnetic
properties. When a specimen was fired to give a lower
density, an increase in both coercivity and remanence
occurred as found by the previous authors, suggesting
using lower sintering temperatures, it is also noted that
the optimum amount of Bi20 3 in this study is very low
compared to the previous authors•
12. Conclusions
1. Excess BaO increases the rate of hexaferrite forrla-
tion and produces fine crystals, it also increases the
sintering rate during early stages but excessive addi-
tions caused drop of the density and dilution of
magnetic properties due to the decreasing degree of
interaction and lowering the critical size.
2. Adding silica caused a liquid phase to form which
increased particle interaction giving rapid densifi-a-
tion during early stages of sintering accompanied
by high coercivity and remanence but SiO 2 > 0.55%
caused a ra pid urop
' in .,__
tile UellblllC~UOll
_,___:~ ._,:__ U.!...:.._
U l I l i ~ ,1..,
tJi~,
intermediate stage and drop in the magnetic pro-
perties due to grain growth and the formation of
intergranular low density non-magnetic phase•
3. Although alumina retards the sintering during early
and intermediate stages, limited amounts up to the
solubility limit (i%)increased the coercivity rapidly
and decreased the remanence slightly. Above this
amount the secondary phase has no influence on
inhibiting grain growth and both coercivity and
remanence decrease•
249
4. Chromic oxide forms a solid solution with initial
drop in coercivity followed by an increase in ac-
cordance with the previously calculated curve.
Densification is sensitive to other impurities present.
5. TiO 2 in small amounts has deleterious effect and
in the presence of impurities forms a liquid phase
that increases the densification
6. At 1300°C up to 0.3% SnO 2 and 0.7% MnO 2 can
be taken in solid solution and with the latter the
density and coercivity increase within this solution.
7. MgO and NiO are not taken in solid solution and
have deleterious effect on both densification and
magnetic properties.
8. At 1300°C Bi20 3 forms a liquid phase that increases
the density but lowers the magnetic properties•
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