International Journal of Nanotechnology and Applications ISSN 0973-631X Volume 4, Number 1 (2010), pp.

51-59 Research India Publications http://www.ripublication.com/ijna.htm

Studies on Mn (1-x) ZnxFe2O4 Nanoparticles Synthesized by Co-Precipitation Method

D. Santhosh Kumar1* and K. Chandra Mouli2
1

Solid State Physics & Materials Science Research Laboratories, Dept. of Physics, Andhra University, Visakhapatnam-530003, India. * Email: dhavalasanthoshkumar@gmail.com 2 Dept. of Eng. Physics, A.U. College of Engineering, Andhra University, Visakhapatnam-530003, India. Abstract Fine Nanoscale Particles of Mn(1-x)ZnxFe2O4 were prepared by chemical route co-precipitation method. The structure of the samples are studied with X-ray diffraction (XRD) using Cu-K radiation and the Transmission Electron Microscopy (TEM).The XRD analysis confirms the formation of single phase spinel structure. The morphology of the particles formed was examined by direct observation by high resolution TEM. A narrow size distribution of the particles was observed from this TEM micrograph. This suggests that synthesis method can provide well isolated homogenous size distribution of particles, will be useful for the Electrical and Magnetic study. The magnetic properties were studied using vibration sample magnetometer (VSM) and electrical properties of the samples measured using standard two-probe method. Keywords: Co-Precipitation, Nano Particles, Hysteresis curves, soft ferrites.

Introduction
There is an intense demand for high performance and miniaturization of many electronic devices, which exclusively needs soft magnetic materials with high permeability. AB2O4 type of compounds with Spinel structure shows interesting structural, electrical and magnetic properties, which vary with the nature of the ions, their charge and site distribution amongst tetrahedral and octahedral sites [1, 2]. Various cations can be placed in A site and B site to tune its magnetic properties. Depending on A site and B site cations it can exhibit ferromagnetic, antiferromagnetic, spin (cluster) glass, and paramagnetic behaviour [3]. The general composition of such ferrites is MFe2O4. Where M represents one or several of the

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D. Santhosh Kumar and K. Chandra Mouli

divalent metals. These types of ferrites have been extensively used in many electrical devices because of its high permeability in the radio frequency region, high electrical resistivity, mechanical hardness, and chemical stability [4-6]. Among them Manganese ferrite, Nickel ferrite, Zinc ferrite and Cupper ferrite are most popular and versatile which was investigated by many researchers. In this paper magnetic and electrical properties of Mn1-xZnxFe2O4 are discussed thoroughly. The performance of any ferrite is greatly influenced by its synthesizing technique [7-13]. The conventional ceramic method of preparation which involves solid stats reaction between oxides at high temperatures is cumbersome, time consuming and does not always result in pure reproducible product. Therefore, various non-conventional processing techniques [7-9], which are mainly solution techniques are reported. In the present work nonconventional preparation method, known as co-precipitation method, was used for preparation of Mn Zn ferrite. Main advantages of this method is that it is inexpensive, time saving and results in superior properties of ferrites processed at much lower temperature. The absence of ball milling in this method leads to stoichiometric composition as there is no possibility of loss or gain of material during milling, as in case of conventional ceramic method. In the present work magnetic and electrical properties of Mn1-xZnxFe2O4 ferrite synthesized by co-precipitation method were considered. Manganese Zinc ferrites are widely used in electronic applications such as transforms choke coils and noise filters because of their higher permeabilities and low magnetic losses at high frequencies. Their properties largely depend on their microstructure [14]. So the Nano-techniques were introduced to control their ultra microstructure, instead of the traditional ceramic way. However, preparing a fine and agglomerate/aggregate-free powder is the first and perhaps the most important step towards fabricating a ceramic material of desirable microstructure and their high sintered density, small grain size and narrow grain size distribution. Fine Nanoparticles of Mn1-xZnxFe2O4 with stoichiometric proportion (x) varying from 0.2 to 0.8 were prepared by the chemical co-precipitation method. The samples were characterized utilizing x-ray diffraction (XRD), Transmission electron micrograph (TEM), vibrating sample magnetometer (VSM). The specific saturation magnetization (MS) of the particles was measured at room temperature. Electrical properties of the samples measured using standard two-probe method.

Experimental
Mn- Zn ferrite of composition Mn1-xZnxFe2O4 Nano scale particles in the present work was prepared by co-precipitation method. The materials used were Manganese chloride ( 98.0% Merck, India), Zinc Chloride ( 99.1% Merck, India) Iron III chloride ( 99 % Merck, India) and Sodium chloride ( 97 % Merck, India), were weighed out in the required stoichiometric proportions and dissolved in distilled water, and NaOH solution was added to this aqueous solution under continuous stirring with a constant speed. The reaction temperature was maintained constant, with the dropping of the mixed solution to the alkaline aqueous solution. The precipitation occurred immediately and the color of suspension changed from the initially brown to dark

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brown. It was kept stirred for 2h at constant temperature then it washed with distilled water to remove sodium and chloride ions. The washed sample was dried in air. Dried sample was examined by X- Ray diffraction, Transmission Electron Microscope and Vibration Sample Magnetometer. X-Ray powder diffraction using Cu-K source and estimation mean crystallite size. The estimation is made via Debye-Scherer formula using the FWHM of the (311) peak of X- ray diffraction [14]. The morphological properties of specimens are observed by TEM. The magnetization loop for the sample was measured at room temperature using a vibrating sample magnetometer (VSM, JDM-13). Fine powders of Mn1-xZnxFe2O4 was mixed with 5% P.V.A binder and pressed into pellets of the size 10mm diameter and thickness range between 2 and 4 mm under a pressure of 50 KN applied for 3 min. these pellets were sintered in air at temperatures 900, 1000, 1100, 1200, 1300OC respectively, for 2h, by setting heating and cooling rate at 5OC per minute. The pellets were coated with silver paste on either side to establishing good ohmic contacts with the electrodes. Resistivity as a function of temperature was measure by using standard two-probe method.

Results and Discussion

The X-ray diffraction studies were carried out using Cu-K radiation with Philips powder diffractometer and determined the crystallite size. We taken X-ray diffraction at room temperature, with a copper target, the wavelength is 1.5406 , shows that the sample have formed the single-phase spinal structure. Fig.1 shows the X-ray diffraction pattern of powder samples. The diffraction peaks corresponding to (220), (311), (400), (422), (511), and (440) planes of polycrystalline MnZn phase are confirmed. The crystallite size of Mn1-xZnxFe2O4 for the most intense peak (311) plane determines from the X-ray diffraction data using the Debye-Scherrer formula. dRX = k/ cos Where dRX is the crystallite size, k = 0.9 is a correction factor to account for particle shapes, is the full width at half maximum of the most intense diffraction peak (311) plane, is the wave length of Cu target = 1.5406 , and is the Bragg angle. The average crystallite size of the prepared samples at preparation temperature is 13-19nm. Lattice constant a for the samples was calculated from the observed d values and given in the Table 1. The shape, size and morphology of the particles formed were examined by direct observation via high-resolution transmission electron microscopy. The transmission electron micrographs of the prepared samples are given in Fig. 2. Direct observations of the lattice image reveal that the particles are approximately spherical in shape and agglomerated. Agglomeration of the prepared fine particles can be clearly noticed for the larger values of zinc concentration. In other words, the decrease in particle size leads to greater agglomeration of magnetic fine particles. Because of the smaller size, (single domain) particles experience a permanent magnetic moment proportional to their volume. Hence, each particle is permanently magnetized and gets agglomerated.

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The densities of the sintered pellets were measured and kept in the Table.2. The densities of sintered Mn1-xZnxFe2O4 ferrite are found to be increased with the sintering temperature. The density may be attributed to the existence of phase transition which occurs during the crystal formation process while sintering. The investigation on fine structure of Mn1-xZnxFe2O4 ferrite clearly indicates the influence of sintering conditions on the growth [15], density of the sample and crystalline phase of the sample [16]. The usual trend in the density values is also observed in the resistivity trends of the samples. Fig.3 shows plots of Log (ohmCm) V/s Temperature 1000/T (K) for Mn1-xZnxFe2O4 ferrite. A semiconductor like general behavior is seen for the sample as the samples undergo a second order ferrimagnetic to paramagnetic phase transition. Although the trends depend on the concentration of the Zn in the sample these are more strongly dependent on the sintering temperature of the sample. Resistivity values at 300K are seen to vary between2.12 x106 ohm-cm and 1.898 x106 ohm-cm for samples sintered at different temperatures the highest and the lowest being observed for 9000C and 13000C, respectively. In ferrites electron conduction mechanisms have been studied by many investigators and reviewed by Klinger et al. various models were proposed; however, the thermally activated hopping model is found to be more appropriate in explaining qualitatively the electrical behavior of MnZn ferrites. In the hopping process the additional electron on a ferrous (Fe2+) ion requires little energy to move to an adjacent (Fe3+) on the equivalent lattice sites (B sites). In presence of the electric field, these extra electrons hopping between iron ions give rise to the electrical conduction. Therefore, any change in the (Fe2+) ion content in the spinel ferrite lattice and/or the distance between them is crucial to the intrinsic resistivity of MnZn ferrite grains, including the intrinsic grain boundaries. If the introduction of another cation into the lattice causes a change in the valency distribution on the B sites, then the number of electrons potentially available for transfer will be altered. On the other hand, the incorporation of foreign (addition of impurity) ions can change the distance between the B lattice sites, which is crucial for the conduction mechanism. Thus, the formation of an intrinsic grain boundary in doped samples by the segregation of aliovalent ions must increase the resistivity. This gives rise to polycrystalline MnZn ferrite with non-ferrimagnetic grain boundary, ferrimagnetic outer grain region and ferrimagnetic conductive core. Thus the contribution to the bulk resistivity may be considered as resistivity contribution coming from three different regions. To establish a relation between the Power loss due to eddy currents and the average grain diameter a hypothetical brick wall model is applied. As per the model each layer can be represented by a resistancecapacitance (RC) lumped circuit of high Ohmic layers. When the resistivity of the bulk is much lower than the grain boundary layers, the equivalent circuit of the ferrite can be represented by a series of lumped RC circuits of the grain boundary layers [17]. As the samples under investigation are sintered from Nanoparticle MnZn ferrite in a reducing atmosphere with no additives there is no possibility of formation of high resistivity ferrimagnetic outer grain boundary. Thus the total contribution should come only from the non-ferrimagnetic grain boundaries and ferrimagnetic conductive core.

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In the cubic system of ferrimagnetic spinels, the magnetic order is mainly due to a superexchange interaction mechanism occurring between the metal ions in the A and B sublattices. The substitution of non-magnetic ion such as Zn, which is having a preferential A site occupancy results in the reduction of the exchange interaction between A and B sites. Hence, by varying the degree of zinc substitution the magnetic properties of the fine particles can be varied. Fig.4 shows the room temperature hysteresis loop of the prepared powder samples for various zinc substitution. Upon increasing the partial substitution of zinc with manganese the specific magnetization (Ms), remanence (Mr), coercivity (Hc) and Curie temperature (Tc) decrease. The variation of coercivity and remanence with the increase in the zinc substitution are shown in Fig.5. The specific magnetization measured at 10 kOe was found to be maximum (47 emu/g) for x = 0.4 and decreased on further increase in Zn concentration (30 emu/g) for x = 0:8. The changes in the Saturation Magnetization and Curie temperature with the degree of zinc substitution are given in Fig.6. The changes in magnetic properties such as Ms; Hc; Mr and Curie temperature Tc are due to the influence of the cationic stoichiometry and their occupancy in the specific sites. In addition, formation of dead layer on the surface, existence of random canting of particle surface spins, non-saturation effects due to random distribution of particle size, deviation from the normal cation distribution, presence of adsorbed water, etc., were due to the reduction of magnetic properties of nanosized particles.

Table 1: Results obtained from the analysis of XRD. Name of the Sample (a) Mn0.8Zn0.2Fe2O4 (b) Mn0.6Zn0.4Fe2O4 (c) Mn0.5Zn0.5Fe2O4 (d) Mn0.4Zn0.6Fe2O4 (e) Mn0.2Zn0.8Fe2O4 (hkl) 311 311 311 311 311 d(Ao) 2.648 2.643 2.639 2.635 2.628 DaveXRR 19 17 16 14 13 ao 8.448 8.440 8.437 8.426 8.409

Table 2: Table showing density of Un-sintered samples and density of samples sintered at 900,1000,1100,1200, and 1300OC. Zinc Count (x) 0.2 0.4 0.5 0.6 0.8 Un 900OC Sintered density (g/cc) 2.7512 3.982 2.696 3.7536 2.396 3.6226 2.3941 3.5169 2.3273 3.1825 1000OC density (g/cc) 4.1854 4.1127 4.0987 3.9833 3.8471 1100OC density (g/cc) 4.3020 4.2953 4.1287 3.9909 3.8674 1200OC density (g/cc) 4.3893 4.3512 4.2163 4.1214 4.1037 1300OC density (g/cc) 4.4562 4.3623 4.2401 3.9251 3.9222

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Figure 1: Indexed XRD pattern for Mn (1-x) ZnxFe2O4 with x varying from 0.2 to 0.8., (a) Mn0.8Zn0.2Fe2O4, (b) Mn0.6Zn0.4Fe2O4, (c) Mn0.5Zn0.5Fe2O4, (d) Mn0.4Zn0.6Fe2O4 and (e) Mn0.2Zn0.8Fe2O4.

Figure 2: Transmission electron micrograph of the prepared samples (a) Mn0.8Zn0.2Fe2O4, (b) Mn0.6Zn0.4Fe2O4, (c) Mn0.5Zn0.5Fe2O4, (d) Mn0.4Zn0.6Fe2O4 and (e) Mn0.2Zn0.8Fe2O4.

Studies on Mn (1-x) ZnxFe2O4 Nanoparticles Synthesized

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57

9 8 7

Log (ohm - Cm)

Log (ohm - Cm)

6 5 4 3 2 1

0.2 Zn 0.4 Zn 0.5 Zn 0.6 Zn 0.8 Zn

1.0 1.5 2.0 2.5 3.0 3.5

0.2 Zn 0.4 Zn 0.5 Zn 0.6 Zn 0.8 Zn

1.0

1.5

2.0

2.5

3.0

3.5

Temperature 1000/T(K)

Temperature 1000/T(K)

Figure 3a: Plots of Log V/s 1000/T for Mn1-xZnxFe2O4 ferrites sintered at 900OC.
7

Figure 3b: Plots of Log V/s 1000/T for Mn1-xZnxFe2O4 ferrites sintered at 1000 OC.
7

Log (ohm - Cm)

Log (ohm - Cm)

0.2 Zn 0.4 Zn 0.5 Zn 0.6 Zn 0.8 Zn

1.0 1.5 2.0 2.5 3.0 3.5

0.2 Zn 0.4 Zn 0.5 Zn 0.6 Zn 0.8 Zn

1 1.0 1.5 2.0 2.5 3.0 3.5

Temperature 1000/T(K)

Temperature 1000/T(K)

Figure 3c: Plots of Log V/s 1000/T for Mn1-xZnxFe2O4 ferrites sintered at 1100 OC.

Figure 3:d: Plots of Log V/s 1000/T for Mn1-xZnxFe2O4 ferrites sintered at 1200 OC.

9 8 7

Log (ohm - Cm)

6 5 4 3 2 1 1.0 1.5 2.0 2.5 3.0 3.5

0.2 Zn 0.4 Zn 0.5 Zn 0.6 Zn 0.8 Zn

Temperature 1000/T(K)

Figure 3e: Plots of Log V/s 1000/T for Mn1-xZnxFe2O4 ferrites sintered at 1300 OC.

Figure 4: Hysteresis curve of the prepared samples Mn(1_x)ZnxFe2O4 (x = 0:2-0:8) measured at room temperature.

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Remanence magnetization (Mr) (emu/g)

D. Santhosh Kumar and K. Chandra Mouli

Saturation Magnetization (Ms) (emu/g)
400 48 46 44 42 40 38 36 34 32 30 28 0.2 0.3 0.4 0.5 0.6 0.7 0.8 150 200 250 300

14

12

10

0 0.2 0.3 0.4 0.5 0.6 0.7 0.8

Coercivity - Hc (Oe)

Mr Hc

Zinc Concentration

Zninc Concentration

Figure 5: Variation of coercivity and remanence with the increase in the zinc substitution.

Figure 6: Changes in the Saturation Magnetization and Curie temperature with the increase in the zinc substitution.

Conclusion
In the present work Mn1-xZnxFe2O4 ferrite Nanoparticles are prepared using co precipitation method. The average crystallite size of the sample is 13-19 nm. And these values are having excellent agreement with TEM image. The saturation magnetization (Ms), remenant magnetization (Mr), and coercive force (Hc) are observed. And the investigations on the resistivity of the Mn1-xZnxFe2O4 ferrite developed by sintering Nanoparticle Mn1-xZnxFe2O4 ferrite, prepared by co precipitation method, show existence of phase transitions thus contributing to amazingly high electrical resistivity in comparison to the reported values. This is a very important parameter in minimizing the eddy current losses in power applications. It is evident that the material prepared by sintering nanomaterial MnZn ferrite not only gives low loss material but also produces material with small grain size with large surface area as the grain growth is suppressed due to phase transitions. This feature can have remarkable effect on the other properties of the material. The semiconductor like behavior of the esistivity shown by this material makes it a favorable material for sensor applications.

Acknowledgement
one of the authors D. Santhosh Kumar gratefully acknowledges UGC-SAP (INDIA), for the financial assistance received through SAP Sponsored Research Fellowship in Science for Meritorious Student. And also thank full to Dr. M. R. Panigrahi, Former C S I R Scientist, Who given continues support in doing my Research work.

References
[1] G. Blasse, Philips Res. Rep. Suppl. 3 (1964) 96.

Curie Temperature (Tc) ( C)

Ms Tc

350

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