Journal of Magnetism and Magnetic Materials 193 (1999) 288290

Fine barium hexaferrite powder prepared by the

crystallisation of glass
L. Rezlescu*, E. Rezlescu, P.D. Popa, N. Rezlescu
Institute of Technical Physics, Bd.D.Mangeron 47, 6600 Iasi, Romania

Abstract
In the present work, the glass strips (with dimensions 50 mm long, 6 mm wide and about 30100 lm thickness) of the
system Fe O BaOB O Sb O were subjected to heat treatments between 200C and 780C. The irreversible
 
 
 
structure changes on the thermal annealings were studied by X-ray diffraction and by magnetic measurements.
Crystallization of Ba ferrite at temperatures higher than 550C was observed. The magnetic properties (specific
magnetisation p and coercivity H ) in terms of the evolution of size of BaFe O crystals, dispersed in the glassy matrix

 
were discussed. The particles produced by this method satisfy the stringent requirements better than the powders made
by milling the polycrystalline materials manufactured by the usual ceramic way of preparation.  1999 Elsevier Science
B.V. All rights reserved.
Keywords: Barium ferrite; Fine particles; X-ray diffraction; Magnetization; Coercivity

1. Introduction
It has been known that the hexagonal barium ferrite
is one of the materials for magnetic media industry
[1]. For this application, particles with strictly defined
magnetic parameters, as well as size and shape distributions, are needed which in turn requires a special
technological approach. The glass crystallisation process
(GCM) has shown considerable promise due to the possibility of controlling (through thermal treatments) the
final structure and therefore the magnetic properties. The
method consists in melting the proper amounts of
the oxides with a glass forming component, rapid
quenching of the melt, controlled crystallisation of the
glass and finally chemical separation of the unwanted
components.
In the present work, the evolution with annealing
temperature of BaM ferrite fine particles crystallised in
a glass matrix and the relationship between the crystal

* Corresponding author. Tel.: #40-32-130680; fax: #40-32231132; e-mail: laura@phys-iasi.ro.

size and magnetic properties of the resulting glass

ceramic was investigated.

2. Experimental
The glass strips (with dimensions 50 mm length, 6 mm
width and about 30100 lm thickness) of the system
Fe O BaOB O Sb O were obtained by rapid quen 
 
 
ching of the liquid state between two copper rollers [2].
The obtained strips were treated successively at various temperatures, between 200C and 800C, for a long
time (2 h for each treatment). The structure and magnetic
properties of the samples were studied by X-ray diffractometry and magnetometer measurements. The average
particle size D was evaluated by Warren and Averbachs

method [3] (Fourier analysis of the profile of the maximum (11.0)).
It is known that barium hexaferrite crystallises in the
hexagonal system of the magnetoplumbite type. This is
characterised by "450C and p "68 emu/g [4]. It


should be noted that the p value measured by us at
8.8 kOe is not the saturation value.

0304-8853/99/$ see front matter  1999 Elsevier Science B.V. All rights reserved.
PII: S 0 3 0 4 - 8 8 5 3 ( 9 8 ) 0 0 4 4 2 - 9

L. Rezlescu et al. / Journal of Magnetism and Magnetic Materials 193 (1999) 288290

289

3. Results
X-ray diffraction has shown that the ribbons obtained
by rapidly cooling were essentially amorphous except for
a few very small crystallites of Ba hexaferrite (magnetoplumbite-M type) and the material exhibits a small magnetization of about 2 emu/g at room temperature. By
subjecting the ribbons to heat treatments, crystals of
BaFe O ferrite with sizes ranging from 50 to 330 nm,
 
depending on the annealing temperature, were observed.
The evolution of the size of the hexaferrite crystallites
with the treatment temperature is shown in Fig. 1. One
can observe a slight increase of D up to 700C and an

important increase at higher temperatures. The marked
increase of the crystallites can be attributed to the formation of some agglomerates of crystallites in contact where
the crystallites could be grown through a penetration
process [5] with the elimination of small crystallites.
The effect of annealing temperature on the specific
magnetization measured in an 8.8 kOe magnetic field is
also illustrated in Fig. 1. One can observe an important
increase of p after annealing at 600C. This fact points
out the existence of a critical temperature where the
crystallisation of BaM ferrite in the glass host begins
and is higher than its Curie temperature. After the final
annealing (at 780C), the glass-ceramic material obtained
has a specific magnetization of about 20 emu/g.
The dependence of the magnetic properties (p and H )

of the glassceramic on the size of BaFe O crystals,
 
dispersed in the glass matrix is revealed in Fig. 2. The
sharp increase of p for small grain size may be explained
by the multiplication of the nucleation centres that leads
to a rapid increase of the crystalline fraction in the glassy
matrix. But, another cause can be the decrease of the
number of superparamagnetic particles which can explain the coercivity curve too. H increases with increas
ing grains and then, for a further increase of the grains,
it slightly decreases. The increase of H with increasing

grains suggests a monodomain behaviour of the grains, if
the grain size does not exceed a critical value for singledomain tructure [6]. In this connection we estimate
the critical size of a single-domain particle using the
formula [4]
D
"9p /2pM,
 


where p "(2k "K "/a) is the wall density energy,

 
"K " the magnetocrystalline anisotropy constant, the


Curie temperature, M the saturation magnetization,

k the Boltzmann constant and a the lattice constant. For
D 'D
the particles are multidomains. For Ba

 
hexaferrite, using "720 K, a"3;10\ cm, "K ""


3.3;10 erg/cm and M "380 Gauss [7], the value of

D
estimated was about 460 nm, which is in reason  
able agreement with the evaluation from X-ray diffraction, of 330 nm for the vitroceramic treated at 780C.

Fig. 1. Effect of the treatment temperature (for 2 h) on the

specific magnetization and on the average BaFe O grain size
 
development in the glassy matrix, measured at room temperature.

Fig. 2. Specific magnetization p and coercivity H versus aver

age grain size D for barium hexaferrite samples treated for 2 h

at different temperatures between 300C and 780C.

But, if the single domain particle size is too small, the

thermal fluctuations become important, and the magnetic behaviour called superparamagnetism appears
[8]. In this state, the volume energy can fall to a value
comparable with the thermal energy k, where k is the
Boltzmann constant. When this occurs, the magnetization vector is rotated by the thermal fluctuation and it
no longer assumes a permanent direction within the
grain. Therefore, there is an inferior limit for the single
domain particle size, D , below which a superparamag  
netic state appears, characterised by zero coercivity. For
BaFe O D +4 nm was obtained which is in agree   
ment with the value on the green material, not subjected
to thermal treatment. Similar results were already
obtained by Kubo [9] and Gornert [10,11]. The decrease
in the number of superparamagnetic particles with the

290

L. Rezlescu et al. / Journal of Magnetism and Magnetic Materials 193 (1999) 288290

4. Conclusion
Crystallisation of fine particles of BaFe O in the
 
amorphous BaOFe O B O Sb O system was evid   
 
enced with the average grain size ranging from 50 to
330 nm by thermal annealing. Thus the fine control of
crystal growth by varying the annealing temperature
can be exploited for the production of fine magnetic
powders of various sizes for a variety of practical applications.

Acknowledgements
We thank Dr. M.L. Craus for offering help with X-ray
studies and for the evaluation of the grain sizes.
Fig. 3. Specific magnetization p and average grain size D as

a function of the annealing time t . The annealing temperature is
780C.

References

increase of the single-domain particle size can explain the

abrupt increase in H .

Fig. 3 shows the dependence of p and D on the

annealing time, at "780C. The initial state of the
material is that resulting from the preceding treatment, at
750C. One can see that the specific magnetization increases abruptly after the first 10 min of the thermal
treatment while the mean size of the crystallites increases
significantly after 60 min. For larger annealing time,
magnetization increases slightly. This is due to the crystallisation of the entire amount of ferrite within the glass
host. The grain growth is slower because of the paramagnetic matrix. For ultra high density magnetic recording
media, the grain size should be small to reduce the noise
in the reproduced output. From these results it was found
that the annealing time of about 10 min at the temperature of 780C is enough to crystallise without any important grain growth.

[1] M.H. Kryder, IEEE Trans. Magn. 25 (1989) 4358.

[2] N. Rezlescu, E. Rezlescu, C. Pasnicu, M.L. Craus, J. Magn.
Magn. Mater. 131 (1994) 273.
[3] B.E. Warren, B.L. Averbach, J. Appl. Phys. 21 (1950)
595.
[4] J. Smit, H.P.J. Wijn, Les Ferrites, Dunod, Paris, 1961.
[5] N. Rezlescu, E. Rezlescu, I. Ciobotaru, M. Craus, P. Popa,
Ceramics Int. 24 (1997) 31.
[6] Y. Otani, in: G.C. Hadjipapary, G.A. Prinz (Eds.), Science
and Technology of Nanostructured Magnetic Materials,
Plenum Press, New York, 1991, p. 695.
[7] K.S. Arai, N. Tsuya, J. Phys. Soc. Japan 33 (1972)
1581.
[8] G.P. Bean, J. Appl. Phys. 26 (1955) 13.
[9] O. Kubo, T. Ido, H. Yokoyama, Y. Koike, J. Appl. Phys.
57 (1985) 4280.
[10] P. Gornert, E. Sinn, W. Schuppel, H. Pfeiffer, M. Rosler,
Th. Schubert, M. Jurisch, R. Sellger, IEEE Trans. Magn.
26 (1990) 12.
[11] P. Gornert, E. Sinn, M. Rosler, Key Eng. Mater. 58 (1991)
129.