Journal of Magnetism and Magnetic Materials 257 (2003) 100106

Microstructures and high-frequency magnetic properties of low-temperature sintered CoTi substituted barium ferrites
Changsheng Wang*, Longtu Li, Ji Zhou, Xiwei Qi, Zhenxing Yue, Xiaohui Wang
State Key Laboratory of New Ceramics and Fine Processing, Department of Materials Science and Engineering, Tsinghua University, Beijing 100084, Peoples Republic of China Received 13 June 2002; received in revised form 26 August 2002

Abstract The CoTi substituted barium ferrites BaFe122xCoxTixO19 were prepared by chemical coprecipitation and lowtemperature sintering with Bi2O3 doping. Effects of Bi2O3 content, the temperature for barium ferrite particles fabrication and CoTi substitution amount on the microstructures and high-frequency magnetic properties were investigated by XRD, SEM, TEM and the measurements of complex permeability dispersions. Experimental results showed that the initial permeability m0 of sintered barium ferrites could be promoted effectively with Bi2O3 doping. High temperature for barium ferrite particles fabrication resulted in high permeability for sintered ferrites. Barium ferrites with initial permeability m0 > 10; magnetic resonant frequency >1 GHz were obtained when they were sintered at 9001C with 2 wt% Bi2O3 doping in the CoTi substitution range 1.201.30. The effect of Bi2O3 doping on the magnetizing process of sintered ferrites was also discussed. r 2002 Elsevier Science B.V. All rights reserved.
Keywords: CoTi substituted barium ferrites; Chemical coprecipitation; Low-temperature sintering; High-frequency magnetic properties; Complex permeability

1. Introduction In recent years, surface-mounting devices (SMDs) have been rapidly developed for electronic application. Among the three main passive SMDs, multi-layer chip inductors (MLCIs) have greatly lagged behind multi-layer chip capacitors and resistors, especially MLCIs used in hyper-frequency region of 3001000 MHz [1,2]. MLCIs are fabricated by laminating ferrite layers and internal conductors alternately, and then coring
*Corresponding author. Tel: +86-10-6278-4579; fax: +8610-6278-1346. E-mail address: wanges@mail.tsinghua.edu.cn (C. Wang).

to form the monolithic structure. Silver (melting point: 9611C) is usually used as the internal electrode material due to its high conductivity and low cost, so the ferrite powder needs to be sintered below 9501C [3]. NiZnCu spinel ferrite which has been investigated intensively cannot provide high initial permeability when applied in the hyper-frequency region; therefore, many works have been focused on hexaferrites which could be used in higher frequency region than spinel ferrite according to the Snoek law [47]. Hexaferrites are classied into ve main types depending on chemical formula and crystal structure. They are the M-type, W-type, Y-type, Z-type and X-type [4,8]. Co2Z-type is the one investigated widely in

0304-8853/03/$ - see front matter r 2002 Elsevier Science B.V. All rights reserved. PII: S 0 3 0 4 - 8 8 5 3 ( 0 2 ) 0 1 0 5 8 - 2

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the hexaferrite family for high-frequency application [9,10]; however, few investigations have been made on M-type hexaferrite, especially those sintered at temperatures below the melting point of silver. The M-type barium ferrite BaFe12O19 has strong uniaxial magnetocrystalline anisotropy and is usually used as permanent magnetic materials. However, the strong uniaxial magnetocrystalline anisotropy can be reduced by substitution of Fe3+ cations which distribute on ve distinct crystallographic sites. Different cations have been used to substitute the Fe3+ to make the barium ferrite suitable for magnetic recording and microwave applications [1113]. The typical example is the substitution of Fe3+ by Co2+ and Ti4+, which undergoes a magnetic anisotropy change from uniaxial to planar when the CoTi substitution amount is 0.91.20 [14]. Complex permeability of CoTi substituted barium ferrites have been investigated by Autissier et al. using classical ceramics method with sintering temperature 123012901C [15]. In this paper, the microstructures and high-frequency magnetic properties of CoTi substituted barium ferrites prepared by chemical coprecipitation and low-temperature sintering with Bi2O3 doping are presented.

an appropriate amount of Bi2O3. For electromagnetic properties measurement, pellets (10 mm diameter, 0.71.0 mm thickness) and toroidal samples (20 mm outside diameter, 10 mm inside diameter, about 13 mm thickness) were pressed and then sintered at 9001C and 9501C in air. The identication of the crystalline phases for ferrite particles was carried out by X-ray diffraction (XRD). To obtain detailed information on the morphology, and to verify the size of the BaFe122xCoxTixO19 particles, a set of micrographs were taken by transition electron microscope (TEM). Scanning electron microscope (SEM) was used to observe the microstructures of sintered ferrites. The high-frequency magnetic properties were measured using an HP4291B RF impedance/materials analyzer from 10 MHz to 1.8 GHz. The electrical resistivity of all ferrite samples was determined with an HP4140B meter using silver contacts.

3. Results and discussion 3.1. Structure and morphology The XRD patterns of particle samples with Co Ti substitution amount x 1:20 obtained by chemical coprecipitation process and synthesis from NaCl melts at different temperatures are shown in Fig. 1. As can be seen, the only crystalline phase that can be detected by XRD is an Mtype hexaferrite for all particle samples, no other phases were apparently detectable. With the increase of heat-treatment temperature from 8101C to 9501C, the relative intensity increases while peaks become sharper, indicating an increase of particle size. The temperature of 8101C, which is slightly higher than the melting point (8011C) of NaCl, is much lower than (above 10001C) what is needed for complete reaction in classical ceramics method. Only the M-type hexaferrite phase formed at 8101C was thought to be from the contribution of liquid phase formation of NaCl which could make the metal ions diffusing more easily. Fig. 2 shows the morphologies of BaFe9.6Co1.2Ti1.2O19 particles prepared at 8101C (a) and 9501C

2. Experimental procedure BaFe122xCoxTixO19 particles with different target compositions were prepared by a modied ux method which combines the chemical coprecipitation process and the synthesis from salt melts [11,16]. An aqueous solution of the metal chlorides containing Ba2+, Fe3+, Co2+ and Ti4+ in the ratio required for the ferrite was stirred into an excess of an aqueous solution of NaOH and Na2CO3. All the reagents were of analytical grade. A suspension containing intermediate precipitates was formed during mixing. The product of coprecipitation was ltered off, washed thoroughly, dried and mixed with NaCl. When heated at 8109501C, ferrite particles crystallized from the NaCl matrix. When the salts were dissolved in water, BaFe122xCoxTixO19 particles were obtained. The ferrite particles were then mixed with

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810 Cx2h

850 Cx2h

Intensity (Arb. Units)

900 Cx2h

950 Cx2h

Fig. 2. TEM micrographs of the barium ferrite particles fabricated at 8101C (a) and 9501C (b).

100 80 60 40 20 0 20 30 40 50 2 (Degrees)

Intensity (%)

BaFe12 O19 27-1029

60

70

Fig. 1. XRD patterns of CoTi substituted barium ferrite particles fabricated at different temperatures.

(b) taken by TEM. It is clear that barium ferrite particles are hexagonal platelet crystals, and higher temperature corresponds to larger average size and more regular particle shape with a more perfect crystalline phase. The particle sizes are ranged in 40100 nm and 50200 nm for samples prepared at 8101C and 9501C, respectively. The microstructures and morphologies of sintered barium ferrites were studied by SEM. Fig. 3 shows the micrographs of samples sintered at 9001C for 5 h with CoTi substitution amount x 1:20: As can be seen, the microstructure of a sample sintered with Bi2O3 addition (b) is very different from that without Bi2O3 (a), although both the sintered samples were based on the same ferrite particles obtained at 9501C for 2 h. When sintered without Bi2O3 addition, sample (a) is composed of small grains with little porosity, indicating little change of particle size compared

with the original barium ferrite particles. Whereas the sample (b) that sintered with 2 wt% Bi2O3 doping is composed of much larger grains with a grain size distribution of 16 mm. The more and larger pores were formed due to the irregular alignment of larger hexagonal platelets. Effects of temperatures for barium ferrite particles fabrication on microstructures of sintered samples can also be concluded from (b)(d) micrographs in Fig. 3. It can be seen that higher particle fabrication temperature produced larger size grain and more regular grain shape when sintered at 9001C for 5 h with the same amount of Bi2O3 addition. 3.2. High-frequency magnetic properties To investigate the effect of Bi2O3 content on the high-frequency magnetic properties of CoTi substituted barium ferrites, ceramic samples were prepared by mixing the CoTi substituted barium ferrite particles which were fabricated at 9501C for 2 h, with various amount of Bi2O3 and sintered at 9501C for 5 h. The CoTi substitution amount was x 1:20 for all samples. Fig. 4 depicts the frequency dependence of complex permeability of sintered ferrites, where m0 is the real part and m00 is the imaginary part. Results revealed the tendency of an increase in initial permeability with the Bi2O3 content. For instance, the sample without Bi2O3

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Fig. 3. SEM micrographs of barium ferrites sintered at 9001C for 5 h without Bi2O3 doping with particles fabrication temperature 9501C (a); with 2 wt% Bi2O3 and particles fabrication temperature 9501C (b); with 2 wt% Bi2O3 and particles fabrication temperature 8501C (c); with 2 wt% Bi2O3 and particles fabrication temperature 8101C (d).

has a permeability m0 of about 6; however, sample with 2 wt% Bi2O3 content has a permeability m0 of above 14 in a wide frequency range. Increasing the Bi2O3 content from 2 to 5 wt%, there is a little enhancement of both m0 and m00 : Comparing with the frequency of about 1 GHz for a sample without Bi2O3, permeability m0 of samples with Bi2O3 doping starts to decrease from 400 to 500 MHz. Permeability m00 has a maximum value at about 1 GHz for samples with Bi2O3 doping and above 1.8 GHz which is out of the measurement range for a sample without Bi2O3 doping. This behavior indicates a decreasing effect of Bi2O3 doping on cut-off frequency while the permeability m0 can be improved effectively in lower frequency range below the magnetic resonant frequency. Fig. 5 shows the effect of particles fabricating temperature on high-frequency magnetic properties of CoTi substituted barium ferrites sintered at 9001C for 5 h with CoTi substitution x 1:20 and Bi2O3 content of 2 wt%. Obviously, the magnetic properties are promoted signicantly by using the barium particles fabricated at higher temperature. The value of initial permeability m0 rises from 8 (for 8101C) to 12.5 (for 9501C). The

frequency where m0 has the maximum value shifts lower when the temperature for particles fabrication increases. The permeability m00 has little change in the frequency region below 100 MHz, but has a larger value corresponding to larger magnetic loss in relative higher frequency region of 3001000 MHz with increasing the particles fabrication temperature. The CoTi substitution dependence of complex permeability is given in Fig. 6. Samples were sintered at 9001C for 5 h with Bi2O3 content of 2 wt%, and barium particles used were prepared at 9501C for 2 h. As it shows, the magnetic resonant frequency has been greatly affected by the CoTi substitution. With the increase of CoTi substitution amount, the permeability m0 decreases and the magnetic resonant frequency increases. Barium ferrites with initial permeability m0 > 10 and magnetic resonant frequency >1 GHz could be obtained when the CoTi substitution amount was x 1:2021:30: It is known that the permeability of a polycrystalline ferrite can be described as the superposition of two different magnetizing mechanisms: spin rotation and domain wall motion [17]. Globus

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20 16 12 ' 8 4 0 1E7
Bi2O3 wt% 2 0 4 3 5

16 14 12 10 8 ' 6 4 2 0 1E8 Frequency (Hz) 1E9 1E7 950 C 850 C 810 C 1E8 Frequency (Hz) 16
Bi2O3 wt% 0 2 3 4 5

1E9

20 16 12 " 8 4 0 1E7 1E8 Frequency (Hz)

Fig. 4. Effect of Bi2O3 content on the complex permeability.

14 12 10 8 " 6 4 2 0 1E9 1E7

950 C 850 C 810 C

1E8 Frequency(Hz)

1E9

Fig. 5. Effect of magnetic particles fabrication temperature on the complex permeability.

suggested that the domain wall motion was affected by the grain size and could be enhanced with the increase of grain size [18]. Comparing the magnetic properties with the microstructures indicated in Fig. 3, it manifests that the increase in initial permeability is closely correlated to the densication and grain size of sintered ferrites. In case of ferrites composed with small grains, the relatively larger volume fraction of grain boundary and defects, where domain wall pinning could occur, would decrease the contribution of domain wall motion. In addition, small grains would make magnetization decreased due to the existence of spin canting layer [19], which also could increase the effective magnetic anisotropy eld. On the contrary, since the melting temperature of Bi2O3 is

8251C, when samples with Bi2O3 doping were sintered at above 9001C, higher density could be obtained through particle re-arrangement, solution re-precipitation and solid skeleton processes by formation of the Bi2O3 liquid phase [20]. An increase in sintered density of ferrites not only causes the reduction of the demagnetizing eld due to pores but also raises the spin rotational contribution, which in turn increases the permeability [21]. Also, as the grain size was increased with Bi2O3 doping, the multi-domain grains appeared which could result in higher permeability values due to the domain wall motion [22]. The CoTi substitution dependence of high-frequency magnetic properties was mainly due to the change of the magnetocrystalline anisotropy eld, which is

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18 16 14 12 10 ' 8 6 4 2 0 1E7 1E8 Frequency (Hz) 18 16 14 12 10 " 8 6 4 2 0 1E7 1E8 Frequency (Hz)
Fig. 6. CoTi substitution dependence of complex permeability.
x = 1.20 x = 1.25 x = 1.30 x = 1.20 x = 1.25 x = 1.30

1E9

high-frequency magnetic properties were investigated. Experimental results showed that CoTi substituted barium ferrite particles with average size range 40200 nm could be obtained when heated in NaCl matrix at 8109501C, and high temperature for barium ferrite particles fabrication resulted in high permeability for sintered barium ferrites. High-frequency magnetic properties could be improved obviously with Bi2O3 doping. The initial permeability m0 > 14 of sintered ferrites could be obtained with Bi2O3 content varying from 2 to 5 wt% compared with m0 6 without Bi2O3 doping when sintered at 9501C for 5 h. Barium ferrites with initial permeability m0 > 10; magnetic resonant frequency >1 GHz were obtained when it was sintered at 9001C with 2 wt% Bi2O3 doping in the CoTi substitution of 1.20 1.30. The electrical resistivity of all sintered ferrite samples was above 108 O cm.

Acknowledgements This work was supported by the High Technology Research and Development Project of Peoples Republic of China (Grant No. 2001AA320502).

1E9

in proportion to the magnetic resonant frequency. In addition, the electrical resistivity for all sintered samples was measured using silver contacts, and was found to be above 108 O cm. This high electrical resistivity could reduce the eddy current losses in the high-frequency range. All the electromagnetic behaviors of CoTi substituted barium ferrites showed the potential to be used for MLCIs or multi-layer chip beads (MLCBs) in the hyperfrequency range.

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