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ELSEVIER Journal of Magnetism and Magnetic Materials 196-197 (1999) 463-464

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magnetic

Magnetic glass-ceramic containing fine ferrite crystals

N. Rezlescu, L. Rezlescu*, M.L. Craus, E. Rezlescu
Institute of Technical Physics, B-dul D. Mangeron 47, 6600 lasi, Romania

Abstract
Formation of fine ferrite particles in glass ribbons by isothermal treatments and their influence on the magnetic properties of glass-ceramic system were analyzed. Two glass systems were studied: Li20-Fe2Oa-B203 and BaO-Fe203-B203-SbzO3. The magnetic behavior is discussed in terms of the evolution of the size of LiFe508 and BaFe12019 crystals with thermal annealings. 1999 Elsevier Science B.V. All rights reserved.
Keywords: Glass ceramics; Ferrites; Fine particles; Magnetic properties

Fine magnetic particles are scientifically and technologically very important. The particles are of great scientific interest in developing a better understanding of magnetic phenomena [1]. The magnetic fine particles have properties which are different from those of bulk materials. This results from reduced sizes and effects of magnetic interactions among particles. In this paper some results for the composites containing Li or Ba-M ferrite fine particles randomly dispersed in a glassy matrix are presented. The samples were obtained by glass crystallization method which permits a gradual control of the particle size [2]. The glass ribbons (30-1001xm thickness, 50mm long, 4-5 mm wide) were treated successively at various temperatures between 300 and 800C to crystallize the ferrite particles within the matrix. The glass crystallization was detected by X-ray diffraction and magnetic measurements. The mean particle size D m w a s determined using Scherrer's formula. The magnetic properties (specific magnetization cr and coercivity He) of the samples were measured with a vibrating sample magnetometer. It is known that Li ferrite crystallizes in the cubic system and it is characterized by the Curie temperature Tc = 65C and a~ = 65 emu/g and Ba hexaferrite crystallizes in the hexagonal system of the magnetoplumbite

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

type and it is characterized by T, = 450C and trs = 68 emu/g [3]. The X-ray analysis performed on the annealed Li ferrite samples revealed the start for the spinel phase crystallization after annealing at 430C. No crystalline phases were observed in the glass heat treated below 430C. For the ribbons with barium the crystallization process of the Ba hexaferrite does not occur below the Curie temperature. The evolution of the crystallite size in the glass matrix as a function of the annealing temperature is illustrated in Fig. 1 for both systems. One can observe that an important increase of the crystal size was obtained at higher annealing temperatures. Two simultaneous processes seem to take place which could be considered as controlling the grain growth: a normal grain increase due to the progressive crystallization and the formation of some agglomerated clusters in which the largest crystallites grow at the expense of the smallest ones by a 'penetrating' process. The magnetization measurements gave information on the degree of crystallization of the magnetic phase within the glass and thus the magnetic properties of the vitroceramic could be controlled by adjusting the annealing temperature. From Fig. 2 one can remark that the crystallization of Ba-M hexaferrite takes place at higher temperatures compared to Li ferrite. The temperature of 600C seems to be the beginning of the Ba hexaferrite crystallization. After the final treatment (at 780C), the glass-ceramic material has a specific magnetization much lower than that reported for Li ferrite or Ba hexaferrite

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 8 1 8-X

464

N. Rezlescu et al. / Journal qf Magnetism and Magnetic Materials 196-197 (1999) 463-464 350 --,--Liferrite 1 --m--Baferrite~ / / / 300 250 200 cE" 150 i,-i E :
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500

600 T. (C)

700

800

150 200 Dm (rim)

250

300

350

Fig. 1. The crystallites size development in the glassy matrix as a function of the annealing temperature.

Fig. 3. Specific magnetization a and coercivity H of Ba glassceramic system as a function of the mean size Dm of the Ba hexaferrite crystals.

20

16

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8

0 200

300

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Fig. 2. Effect of the annealing temperature on the specific magnetization of the glass ceramics, measured at room temperature.

single crystals due to the dispersion of the crystals in a paramagnetic matrix. Thus, the cr values can offer information on the percentage of magnetic phase crystallized in the amorphous network. The dependence of the magnetic properties (a and He) on the crystallite size, plotted in Fig. 3 for Ba vitroceramic only, suggests that the ferrite particles are m o n o d o m a i n s [2]. As a consequence, we estimate the critical size for a single-domain particle using equation

the Curie temperature, Ms is the saturation magnetization, kB is the Boltzmann constant and a is the lattice constant. For Dm > Dm(orit) the particles are multidomains and Hc decreases. For Ba hexaferrite the value of Om{erit ) estimated was about 460 nm, which is in reasonable agreement with that evaluated from X-ray diffraction (330 nm for the vitroceramic treated at 78OC). However, there is an inferior limit for the single-domain particle size, Dm(i), below which a superparamagnetic state appears [4]. In this state, the thermal fluctuations become important and the magnetization vector is rotated. For BaFe12019, D m ( i ) ~ 4 n m was evaluated, which is in agreement with the results obtained by Gotnet [5]. The decrease in the n u m b e r of superparamagnetic particles as the single-domain particle size increases may explain the abrupt increase in Hc (Fig. 3). In conclusion, the above results suggest that the microstructure and magnetic properties of the Li and Ba-M ferriglasses can be controlled by correctly selecting the heat treatments. Furthermore, the glass crystallization by heat treatments offers a facile possibility to obtain powders of very fine magnetic particles for many practical applications.

References [1] K.J. Davies et al., J. Magn. Magn. Mater. 122 (1993) 24. [2] N. Rezlescu et al., J. Magn. Magn. Mater. 131 {1994) 273. [3] J. Smit, H.P.J. Wijn, Les Ferrites, Dunod, Paris, 1961. [4] G.P. Bean, J. Appl. Phys. 26 (1955) 13. [5] P. G6rnert et al., IEEE Trans. Magn. 26 (1990) 12.

[3].
Dm~c.,> = 9aw/2=M~,
where aw = (2kBTJK1/a) 1/2 is the wall density energy, IKal is the magnetocrystalline anisotropy constant, T~ is