Journal of Alloys and Compounds 461 (2008) 312315

Inuence of MoO3 and V2O5 co-doping on the magnetic properties and microstructure of a NiZn ferrite
O. Mirzaee a, , A. Shafyei a , M.A. Golozar a , H. Shokrollahi b
a

Department of Materials Engineering, Isfahan University of Technology, Isfahan 84156-83111, Iran b Materials Engineering Department, School of Engineering, Shiraz University, Iran Received 23 March 2007; received in revised form 18 June 2007; accepted 23 June 2007 Available online 27 July 2007

Abstract Effect of MoO3 and V2 O5 additions on the grain growth and magnetic properties of a NiZn ferrite was studied. The ferrites were produced by conventional powder method. The samples doped with 0.05 wt% of MoO3 in addition to 0.2 wt% of V2 O5 (V2 O5 -riched sample). For comparison, the MoO3 -riched sample which contains 0.05 wt% of V2 O5 in addition to 0.2 wt% of MoO3 and a sample without V2 O5 and MoO3 were prepared by similar process. The results showed that MoO3 and V2 O5 dopants into NiZn ferrites improved magnetic properties (such as magnetic permeability and saturation magnetization) and power loss characteristics of the materials at frequencies above 1 MHz. MoO3 and V2 O5 co-doping increased grain size (to about 20 m) and sintered density (to about 4.8 g/cm3 ) and also decreased power loss noticeably at sintering temperatures between 900 and 1200 C. 2007 Published by Elsevier B.V.
Keywords: NiZn ferrite; Microstructure; Power loss; Additive

1. Introduction The most important characteristics of soft ferrites are their high permeability, high electrical resistivity and low losses [1,2]. MnZn and NiZn ferrites are very important ferromagnetic ceramics, particularly for application at high frequencies. NiZn ferrite is characterized by its high material resistivity several orders of magnitude higher than MnZn ferrites. Because of its high resistivity, NiZn ferrite is the material of choice for operating from 12 MHz to several hundred megahertz [3]. Microstructure and magnetic properties of these ferrites are highly sensitive to preparation method, sintering conditions and amount of constituent metal oxide, including impurities or dopants. Small amounts of additives can greatly affect the properties of NiZn ferrites [4,5]. Additives can be divided into three categories. The rst group consists of additives that segregate to the grain boundaries and affect the grain boundary resistivity (such as CaO, SiO2 ). The second group consists of additives that affect microstructure development (such as SiO2 ).

The third group consists of additives that are dissolved into the spinel structure and alter the magnetic properties (such as TiO2 ) [68]. Some workers reported the inuence of V2 O5 on the grain growth and magnetic properties of NiZn ferrites [1,9,10]. The results showed that small amounts of V2 O5 can greatly affect the grain size after sintering (because of forming a liquid phase during sintering) and magnetic properties such as permeability and saturation magnetization [9,10]. In this paper, the effect of MoO3 and V2 O5 co-doping on the microstructure and power loss of NiZn ferrites was examined.
2. Experimental methods
In this study, the oxide powders including Fe2 O3 , ZnO, NiO, V2 O5 and MoO3 were supplied by Merck. The purity of ZnO, MoO3 and V2 O5 were above 99.8% and Fe2 O3 and NiO were above 99% containing 0.05% Ca, 0.03% Mg, 0.002% Ni and some oxides. The powder particle sizes were all smaller than 10 m. The ferrite (Fe2 O3 = 52, ZnO = 18 and NiO = 30 in mol%) was doped with 0.08 wt% of CaO and 0.04 wt% of SiO2 . The powders were mixed in a dry ball mill for 1 h and then calcined at 1100 C for 1 h. This condition was determined experimentally to produce the highest permeability by forming a ferrite with spinel structure as determined by XRD and lowest shrinkage at the nal sintering temperature. Fig. 1 shows the XRD pattern showing spinel structure of the ferrite. In the V2 O5 -based samples (V2 O5 -riched sample or sample 1), 0.05 wt% of MoO3 in addition to 0.2 wt% of V2 O5 was mixed

Corresponding author. E-mail address: omidmirzaee@ma.iut.ac.ir (O. Mirzaee).

0925-8388/$ see front matter 2007 Published by Elsevier B.V. doi:10.1016/j.jallcom.2007.06.120

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Fig. 1. XRD pattern of the NiZn ferrite after calcining at 1100 C. Ni0.64 Zn0.36 Fe2 O4 . with calcined NiZn ferrite powders. For comparison, the MoO3 -based NiZn ferrite powders (MoO3 -riched sample or sample 2) which contain 0.05 wt% of V2 O5 in addition to 0.2 wt% of MoO3 and a sample without V2 O5 and MoO3 (sample 3) were prepared by similar process. The dry powders were mixed with 3 wt% glycerin as lubricant to be pressed with 5 t/cm2 to form toroids (height 4 mm, inner diameter 16 mm and outer diameter 22 mm) for magnetic measurements. The lubricant was removed prior to sintering by heating the samples at 400 C. These samples were then sintered at 9001200 C for 2 h. The calcined powders were characterized by X-ray diffraction (XRD) (Kristaloex D5000, Cu a-Ni). The microstructure was studied using scanning electron microscopy (Cambridge Stereoscan mv2300). The concentration of atoms in the ferrite lattice and grain boundaries were measured using electronic dispersive scanning technique (EDAX). The core loss values of the toroids were measured by a B-H analyzer (Magnet Physics C-330, fully computerize). The density of samples was determined by the principle of Archimedes. Table 1 shows density, average grain size, saturation magnetization and magnetic permeability of samples sintered at different temperatures.

3. Results and discussion Fig. 2 shows the SEM micrographs. It illustrates in high amount of additives and high sintering temperatures, grain size is very large (more than 15 m) in comparison with the lower amounts of additives and sintering temperatures (about 23 m). V2 O5 and MoO3 have low melting temperatures (Tm (V2 O5 ) = 675 C and Tm (MoO3 ) = 795 C). Grain growth is rapid when a small amount of liquid wets the grain boundary area. The grain boundaries move toward their center of curvature under the inuence of surface tension forces by solution

into the liquid phase from the convex surface of the boundary and redeposition on the concave surface [11]. In Fig. 2, the grains are heterogeneous and the average grain size was taken by averaging the highest and lowest dimension for 10 different grains. According to the grain size values in Table 1, it is clear that for V2 O5 -riched samples the average grain size after sintering at 1200 C is about 18 m and for MoO3 -riched samples is a little more (20 m). The samples without V2 O5 and MoO3 have a very lower grain size (about 4 m). Electronic dispersive scanning (EDS) analysis on the ferrite samples showed that the vanadium and cobalt were located inside the grains. No considerable concentration of these materials was noticed at the grain boundaries. The sintered density and grain size of NiZn ferrites at temperature ranging from 900 to 1200 C are shown in Fig. 3. Fig. 3a shows that the density of the samples increased monotonously with the sintering temperature. Powders with V2 O5 or MoO3 additives signicantly reduce the sintering temperature. The lower sintering temperatures can be due to the liquid phase formation during sintering. Densication can be reached by the rearrangement and solution-precipitation processes. The variation of grain size with sintering temperature is shown in Fig. 3b, indicating that when the materials were sintered at 9001200 C the grain size of MoO3 -riched sample is larger than that of the V2 O5 -riched sample. Magnetic and electrical properties of ferrites depend on the control of microstructures. Among the grain and porosity microstructures, the grain size is one of the most important parameters affecting the magnetic properties of ferrites. Grain growth is closely related to the grain boundary mobility. One possible mechanism for the promotion of grain growth in NiZn ferrite is the reduction of the impurity and pore drag on the grain boundary motion. Another possible grain growth promotion mechanism is the increased pore mobility due to the creation of excess cation vacancies. Table 1 shows that when V2 O5 and MoO3 were added to the ferrites, the values of magnetic permeability and saturation magnetization increase and it can be due to the higher grain size after sintering. The magnetic permeability of polycrystalline ferrite strongly depends on the grain size. When the grain size increases in an otherwise unaltered ferrite, the permeability increases [1]. The sintering temperature dependence of the power loss for these samples is illustrated in Fig. 4. The results showed that

Table 1 Apparent density (Da ), average grain size (d), saturation magnetization (Ms ) (H = 1194 A/m), and permeability (f = 50 kHz) for samples sintered at different temperatures Sample code 1 1 1 2 2 2 3 3 3 MoO3 (wt%) 0.05 0.05 0.05 0.20 0.20 0.20 0 0 0 V2 O5 (wt%) 0.20 0.20 0.20 0.05 0.05 0.05 0 0 0 Sintering temperature ( C) 1000 1100 1200 1000 1100 1200 1000 1100 1200 d (m) 2.5 3.2 18.2 2.7 3.5 20.1 2.3 3.0 3.8 3800 5300 5500 4100 5800 5900 3300 4200 4500 Ms (emu/g) 61.2 75.6 76.3 65.1 78.3 77.8 43.2 51.6 48.0 Da (g/cm3 ) 4.3 4.7 4.8 4.2 4.6 4.8 3.8 4.3 4.5

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Fig. 3. Variation of (a) sintered density and (b) grain size of NiZn ferrite materials with sintering temperature.

higher density usually leads to lower power loss for the materials. Core loss can be divided into three contributions: eddy current loss, hysteresis loss and residual loss. At high frequencies eddy current losses begin to become an important factor [8]. Multidomain structure may occur to higher power loss for the large grain samples. Fig. 4 indicates that the power loss of the samples is maintained at low level as long as the grain size is small. Several possibilities for low melting point additives such as MoO3 and V2 O5 can be expressed. Liquid phase forming additives during sintering in small level can wet the materials and alter the densication and promote the grain growth by increasing the diffusion path between grains or can dissolve in the grains, act-

Fig. 2. SEM micrographs for samples (a) sintered at 900 C; (b) sintered at 1000 C; (c) V2 O5 -riched sintered at 1200 C; (d) MoO3 -riched sintered at 1200 C for 2 h.

Fig. 4. Variation of power loss of NiZn ferrite materials with sintering temperature at different frequencies. (a) 1 MHz and (b) 2 MHz.

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ing as aliovalent substitution dopants. Also, additives can act as an electrostatic trap by pinning the electrons at some cation sites and thus increasing the resistivity of the grains [8]. Low melting point insulating phases are formed at the grain boundaries, which increase the electrical resistivity of the material. This has as a consequence the reduction of the ohmic currents developed through the body of the material during operation under alternating currents and nally a reduction of the total power losses [12]. Fig. 4 shows that the minimum power loss at frequencies 1 and 2 MHz for all samples occurs at sintering temperature 1100 C (about 100 kW/m3 for 1 MHz and 1000 kW/m3 for 2 MHz). It can be due to the exaggerated grain growth above 1100 C and increasing the eddy current loss [1,12]. The samples doped with V2 O5 and MoO3 showed lower power loss in comparison with the samples without these dopants. It can be due to the grain growth promotion and decreasing the hysteresis loss [12]. 4. Conclusions 1. Co-doping of MoO3 and V2 O5 showed a pronounced effect on grain growth promotion and densication of NiZn ferrites. The average grain size after sintering can reach to a bout 20 m and it is about four to ve times higher than the grain size of ferrites without these additives. 2. Small amounts of MoO3 and V2 O5 can increase the apparent density of ferrite by about 8%. 3. The values of magnetic permeability and saturation magnetization increased with doping of these additives and it can be due to the higher grain size after sintering. 4. The power loss was reduced by addition of MoO3 and V2 O5 co-doping during a wide range of frequency. The minimum power loss at frequencies 1 and 2 MHz for all samples

occurs at sintering temperature 1100 C (about 100 kW/m3 for 1 MHz and 1000 kW/m3 for 2 MHz). The samples doped with V2 O5 and MoO3 showed lower power loss in comparison with the samples without these dopants. The partial diffusion of the additives in the spinel lattice of ferrite, their segregation on the grain boundaries and/or liquid phase formation can explain the obtained results. Acknowledgement The authors would like to thank the vice chancellor for research, Isfahan University of Technology, Iran, for nancial support received. References
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