JOURNAL OF MATERIALS SCIENCE LETTERS
Preparation of barium hexagonal ferrites by sol-gel method
P. B R A H M A , D. C H A K R A V O R T Y
Indian Association for the Cultivation of Science, Jadavpur, Calcutta 700032, India
K. S I N G H , D. B A H A D U R
Advanced Centre for Materials Science, I.I. 7. Kanpur, India
The sol-gel technique has emerged in recent years as a
versatile method for synthesizing different inorganic
materials including glasses [1]. Apart from the advan-
tage of low temperature processing a sol-gel route
makes it possible to obtain sub-micron particles so
necessary for achieving useful properties in practical
materials [2]. Though the sol-gel process has made an
impact on materials technology, the high cost of alk-
oxides appears to be a hindrance to. its large scale use
in preparing conventional materials.
Studies on the magnetic properties of hexagonal
barium ferrite have recently been carried out in our
laboratory. Both ceramic [3] as well as glass-ceramic
routes [4] have been used in making the material. We
have now adopted the sol-gel technique for prep-
aration of this ferrite because of the advantages men-
tioned earlier. We have avoided using alkoxides thereby
ensuring that the preparation cost is not high. Mag-
netic properties and microstructural characteristics of
the specimen have been studied and the results are
reported in this paper.
The starting materials are reagent grade anhydrous
FeC13, Ba(CH3COO)2 • H 2 0 and ethyl alcohol. First a
solution of FeC13 in ethanol is stirred under reflux at
78°C for 1 h and then cooled to room temperature.
Barium acetate is then dissolved in a mixture of acetic
304
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L.
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v
.IJ
~ V 1~6 1t10 101t
--
^^^ ~i27
~u ~ 126 t110 10tl
65 60 55 50
Figure 1 X-ray diffractogramsfor differentsintered samples made from sol-gelderived powder. (a) 900°C for l h, (b) 1000°C for 2h, and
(c)1100° C for 1h. (*) = unidentifiedpeaks.
1438
9 (1990) 1438-1440
acid and distilled water. The solution so obtained is
mixed in the stoichiometric ratio with the ethanol
solution of FeC13 under vigorous stirring for 20 min.
The resulting solution which has a pH of 3 is poured
into a beaker for gelation. The gel is allowed to dry
slowly by heating it at the rate of 1° C rain i to 350 ° C.
The dried gel is crushed into fine powder and is then
pressed in the form of pellets of dia. ,-, 1 cm with a
pressure of 104kg cm 2. The pellets are sintered at
temperatures ranging from 900 to 1100 ° C for a period
of 1 to 2h. The crystalline phases present are deter-
mined from the X-ray diffraction patterns taken on a
Phillips PW-1710 diffractometer using CuK~ radi-
ation. The microstructures of all the samples are
studied by a Phillips PSEM 500 Scanning Electron
Microscope. The magnetization measurements are
carried out in a PAR vibrating sample magnetometer
(model 150A) in conjunction with a Variation V-7200
magnet. Magnetization as a function of temperature is
,measured using a high-temperature oven assembly
(model 151) attached to the magnetometer.
Fig. 1 shows the X-ray diffraction patterns for the
three samples sintered at different temperatures. All of
t h e m show the presence of Ba-M ferrite. There are
also some other peaks in the diffractograms which
indicate the presence of a minor phase. The latter
t14 107
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205 101
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I I
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E
i_ (b), i , i , i , I ,
0 lO0 200 300 400 500
Temperature (°C)
Figure 2 (a) Hysteresis loop for sample sintered at 1000°C for 2h; (b) Magnetization as a function of temperature for a sample sintered at
1000°C for 2h.

could not be identified. However, it is evident from the Fig. 2a shows the hysteresis loop for one of the
trend of data that the ferrite phase grows at the samples which is typical of the others as well. Table I
expense of this phase as the heat treatment tem- summarizes the magnetization (Ms) and coercive field
perature is raised. (He) data for different specimens. It is seen that the

1439
T A B L E I Magnetic data for different heat treated sol-gel
derived samples
Heat Sample Crystalline MS
treatment label phase ( e m u g 1) at
H = 10kOe*
900 ° C (1 h) S1 Ba-M 52
1000° C (2h) S2 - 54
1100 ° C (1 h) S3 - 54
* l k O e ,.~ 7 9 . 5 8 k A m - l .
magnetization at a field of 10kOe is around 54emu
g l which is about 20% less than the saturation mag-
netization for barium hexaferrite prepared by the
ceramic route [3]. This discrepancy arises due to the
presence of an unidentified phase in the system as
mentioned earlier. This phase is nonmagnetic as is
confirmed by the magnetization against temperature
data of these samples, a typical variation being shown
in Fig. 2b. The latter gives the results obtained under
different applied magnetic fields: viz., 50kOe and
8 kOe, respectively. The figures show only one Curie
temperature at around 725 K which corresponds to
that of Ba-M phase.
Fig. 3a is the SEM micrograph for sample S~ which
shows a platelet morphology for the Ba-M particles.
The platelets have their c-axes aligned parallel to the
specimen surface as is confirmed by the low X-ray
intensity values obtained from the basal planes like
(0 0 6) and (0 0 8) [4, 6]. The average particle size cal-
culated by standard statistical technique [5] is
4.7 _ 1.3 m. The aspect ratio of the particles lies in
the range 3 to 5.
Th_e micrpgraphs Of $2 and $3 show an intercon-
nected type of morphology. We have characterized
these microstructures in terms of a fractal dimension
[7]. Table II gives the fractal dimensions of the struc-
ture obtained for samples $2 and $3, respectively.
It is evident from the results described above that
using sol-gel derived powders polycrystalline samples
possessing reasonable magnetic properties can be
prepared by sintering at a temperature lower than that
necessary in the case of conventional ceramic process-
ing [3]. Also, in the present case the value of the
coercive field H c can be altered over the range 0.6 kOe
to 2.2 kOe by a change of the heat treatment schedule
over a range of 200° C. The low Hc value observed in
the case of sample S~ can be explained on the basis of
the low aspect ratio of the crystallites [8]. Highly
reactive sol-gel derived powder presumably causes a
large cluster formation with the fusion of neighbour-
Figure 3 (a) SEM micrograph for sample S1
1440
T A B L E II Fractal dimension of microstructure of sol-gel
derived Ba-M
Hc Sample Fractal dimension D
(kOe)
S2 1.88 + 0.02
S3 1.91 + 0.01
0.6
2.2
1.2 ing grains when the samples are sintered at tem-
peratures above 1000° C as are exhibited by samples S2
and $3, respectively. The Coercive field seems to be
markedly dependent on the fractal dimension. The
latter therefore controls the effective domain wall
width in these samples. The exact mechanism however
is not clear at this stage.
In conclusion, a sol-gel technique has been devel-
oped using relatively cheap raw materials for making
barium hexaferrite (M) powders. Polycrystalline speci-
mens made from these powders show magnetic
characteristics comparable to those obtained by a
conventional route. The coercive field can be varied
over a wide range by changing the sintering tem-
perature. The microstructure of some of the samples
are found to be fractal in nature.
Acknowledgement
The investigation has been supported by the Council
of Scientific and Industrial Research of the Govern-
ment of India. The authors thank Mr D. Dasgupta,
Department of Geology, Jadavpur University, for his
help in taking some of the X-ray diffractograms.
References
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Magn. Magn. Mat. 67 (1987) 378.
Received 21 January
and accepted 30 May 1990
sintered at 9000 C for 1 h; (b) SEM micrograph for sample $3 sintered at 1100 ° C for 1 h.